WO2020086632A1 - Procédés de nanofabrication et de nanoassemblage convergents, moyens et applications associés, produits et systèmes émanant de ceux-ci comprenant des procédés et des moyens de conversion de polluants en produits utiles - Google Patents

Procédés de nanofabrication et de nanoassemblage convergents, moyens et applications associés, produits et systèmes émanant de ceux-ci comprenant des procédés et des moyens de conversion de polluants en produits utiles Download PDF

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WO2020086632A1
WO2020086632A1 PCT/US2019/057505 US2019057505W WO2020086632A1 WO 2020086632 A1 WO2020086632 A1 WO 2020086632A1 US 2019057505 W US2019057505 W US 2019057505W WO 2020086632 A1 WO2020086632 A1 WO 2020086632A1
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materials
sub
tool
precursor
fabrication
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PCT/US2019/057505
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English (en)
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Eli Michael RABANI
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Rabani Eli Michael
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Priority to AU2019367972A priority Critical patent/AU2019367972A1/en
Priority to SG11202104122RA priority patent/SG11202104122RA/en
Priority to CA3117524A priority patent/CA3117524A1/fr
Priority to MX2021004658A priority patent/MX2021004658A/es
Priority to EP19875294.1A priority patent/EP3902767A4/fr
Publication of WO2020086632A1 publication Critical patent/WO2020086632A1/fr
Priority to PH12021550913A priority patent/PH12021550913A1/en
Priority to IL282593A priority patent/IL282593A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0004—Apparatus specially adapted for the manufacture or treatment of nanostructural devices or systems or methods for manufacturing the same
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • TITLE Convergent Nanofabrication & Nanoassembly Methods, Means &
  • This invention relates to the fields of nanotechnology, self-replicating systems, chemistry, biochemistry, medical devices, information processing and
  • Precursor or intermediate bodies comprising reactive or depassivated atoms or surfaces are positioned relative to eachother using binding means in communication with positioning means and contacted by translating same, preferably with subnanometer precision and preferably with said positioning means under control of an electronic device, more preferably under control of programmable digital logic information processing means such as a state machine or programmable digital computer.
  • These materials include diamond, silicon, b-silicon carbide, graphene and related carbon allotropes, halite structure materials including MgO, TiC, VN, HfC, TaC, Hf x Ta y C, ScN, TiN, NdN, ZrN, ZrC,
  • Novel actuator devices comprising electrical conductors situated on insulating members useful in particular in positional mechanosynthesis devices and molecular assembler systems are disclosed, as are methods and means for the fabrication thereof, preferably with graphenoid conductors linked to diamond supports. Methods and means for precise positional electrodeposition of refractory metals such as W are also disclosed.
  • Novel systems comprising energy collection and storage means, material processing means and fabrication and assembly means including same capable of self- or al lo-repl ication are disclosed, and optionally additionally feature means for collection of raw materials or capture of pollutants or both, and/or means for cultivation of living organisms or materials including for agriculture, mariculture, algaculture (e.g.
  • Modified graphenoid articles fabricated according to the present invention may also be adapted for use in photovoltaic devices, also provided. Further, arbitrary precise nanostructures and/or microstructures fabricated according to the present invention, e.g. MgO, may further be coated with metals, e.g. via the positional metal depostion methods and means disclosed herein, e.g. with Ag, to yield metamaterials featuring negative index of refraction, which has been difficult in the prior art.
  • metals e.g. via the positional metal depostion methods and means disclosed herein, e.g. with Ag
  • Figs 1A-1Y, 2A-2S, 3A-30, and 4A-4D illustrate convergent assembly of rocksalt (halite or Bl) structure materials via positioning and manipulation using both supported ligands and relief features, and means therefor including fixed and adjustable surface relief features and manipulator apparatus.
  • Fig 3H illustrates an arrangement of actuators positioning for positioning tools in opposable pairs on a surface and the assemblage of two such surfaces whereby four tools may be controllably positioned and manipulated for nanofabrication and/or nanoassembly operations.
  • Fig 3M illustrates an adjustable rod-array which can be used as a programmable relief in convergent fabrication.
  • Figs 5A-I illustrate binding and convergent reaction of acetylenes to form all-s- transoid-trans-polyenes and manipulation thereof and reactions of same with fragments representing diamondoid targets, useful for mechanosynthesis of diamondoid structures.
  • Figs 6A-H, and 6L-M show mechanosynthesis of diamondoid structures or addition thereto from tool-bound trans-polyene deposition, and means and steps of the method therefor.
  • Fig 6E shows addition of an imene substituted trans- polyene.
  • Figs 6F-H shows addition of a perfluorine derivatized trans-polyene.
  • Fig 61 shows a facial view of the perfluorine derivatized trans-polyene loaded tool shown in Figs 6F-6G and used in Fig 6H.
  • Fig 6K shows structures of various graphenoid members linked via diacetylene linkages to C a ( l l l) surfaces useful as electroactuators.
  • Figs 6J and 7A-7D show various modifications of diamondoid structural members with or for forming ligands and supported ligands, and binding of metals therewith.
  • Fig 7C shows the positioning of nitrile ligands on methyls representing diamondoid supports for binding and depositing an aluminum atom onto an aluminum workpiece, with bond formation.
  • Figs 8A illustrates a predicted side-reaction product which may form upon abstraction of the two adjacent hydrogen atoms on adjacent rings as depicted.
  • Fig 8B illustrates a hydrogen abstraction sequence which avoids formation of the side product, so that the reaction in Fig 8C can form graphenoid rings.
  • Figs 8D-8F illustrate examples of convergent fabrication and assembly of graphenoid nanostructures, with the formation of multiple aromatic rings in a single step, without rotation about bonds.
  • Figs 9A-9D depict a comb-type actuator fabricated and assembled according to the present invention useful as nanopositioning means, including as means for the present invention.
  • Fig 9A depicts one of two surface supported arrays of conductors electrically in communication to a common conductor for a comb- type capacitive actuator, schematically shown in Fig 9B, schematically shown in Fig 6C in closed position.
  • Fig 9D depicts a complete comb-type capacitive actuator comprising two facingly juxtaposed supported arrays of conductors.
  • Figs 10A-10C depicts devices and systems for conversion of wind energy to electricity and mechanical work, either or both via entrainment of charged aerosols in a windflow ascending an electrical potential gradient and/or by turning a fan or turbine, including tandem C0 2 and/or pollutant capture and for operation at high altitude, also combination with solar energy conversion means moored via tethers, cables or umbilicals including electrical transmission means for delivering electrical power to a ground or surface station.
  • Fig 11 illustrates the logic of convergent fabrication, showing one example of numbers of precursors and intermediates at succeeding steps for strict regular binary additions.
  • Fig 12 illustrates predicted excitations predicted charge surface density maps and orbitals of a graphenoid structure which may be fabricated according to the present invention and comprise trimethylamine and carboxylate functions distally located to impose a dipole, useful as absorber moieties for photovoltaic devices and optoelectronics devices.
  • Figs 13A-13F illustrate systems for the conversion of energy from the environment and the conversion of raw materials found in the environment.
  • Fig 13A depicts a system which may be fabricated and assembled according to the present invention, said system for capturing, concentrating and converting solar energy via a heat engine, distilling seawater to potable or otherwise useful form and also recovering solutes from seawater, distillation optionally availing vapor compression driven by said heat engine powered by solar energy, obtaining dissolved gases from seawater, said system situated in a floating vessel.
  • Concentrating means may be situated on solar tracking means.
  • Figs 13B-13C depict wave energy converting flotation means, suitable for supporting a platform, flotation means comprising inverted open chambers with pistons trapping air or other gases above the water level, whereby traverse traveling waves compress and expand enclosed gases and drive pistons delivering work, which may be coupled via a transmission or gearbox to an electrical generator.
  • Fig 13C depicts detail of a single pressure engine cylinder for wave energy conversion depicted in Fig 13B with a piston in communication with a gearbox; pressure develops in the cylinder as a water surface wave passes and causes the enclosed water surface to rise driving said piston or serving as a source of pneumatic power controlled by a valve; spacing between cylinders may be adjusted.
  • Fig 13D is a functional block diagram of a system for capturing and converting energy, processing various forms of matter from ambient or environmental sources including abundant materials, conversion of C0 2 to organic feedstocks, capture of methane and other hydrocarbons for lake or ocean seeps or from clathrates, purification of water, and for performing various fabrication and assembly operations on matter collected or processed, including both bulk fabrication and assembly operations and nanostructure fabrication and assembly operations.
  • Fig 13E is a functional block diagram of a system adapted for hydroponic growth of crops including food, for processing inputs to same from abundant sources and for processing products and by-products of grown plant material.
  • Fig 10G depicts a similar system adapted for deployment floating on a body of water such as an ocean or lake and for cultivating algae.
  • Fig 14 depicts addition of a first conjugated polyene to a C dia ( 110) surface and then a second conjugated polyene said first conjugated polyene and bridging to an adjacent edge of a C dia ( 110) surface forming a structure resembling a 2x1 reconstructed (100) surface perpendicular to the (110) surface.
  • Fig 15 depicts convergent fabrication of articles comprising voids.
  • Fig 16 depicts a simplified opposed STM apparatus featuring tips or probes on opposing surfaces such that two samples/workpieces may be imaged and modified using the respective opposed tip, and the two samples may be contacted with eachother under precise positional control, enabling single desired interactions to be effected by controlled positioning without causing additional undesired interactions.
  • FIG 17A-17C show methods and means for reaction of methane and C0 2 to acetate, polyketides and polyenes, suspended between metals of ligand metal complexes, which are preferably borne by nanomanipulation means.
  • FIG 17A shows a starting geometry for this reaction, and
  • FIG 17B shows that for the product.
  • FIG 18 shows nanopositioned dehydration of a tertiary alcohol reaction to an alkane, useful for the conversion of polycyclic polyols to graphenoid structure, this also works on secondary alcohols, useful for conversion of polyketones to polyenes.
  • Figs 19A-19K illustrate reactions of alkyls including methane, yielding activated methyl groups which further react with dichalcogens, dithiols, especially activated dithiols to yield compounds such as thioethers, which may further react with alcoholates or oxides to yield carbon compounds activated as electrophiles such as ketals. These may be reacted together to liberate molecular hydrogen as shown in FIG 19D.
  • FIG 19E shows conversion of thioethers and thioketals to ethers and ketals.
  • FIG 19F shows a variety of metal- ligand combinations useful for these reactions and for exchanging chalcogens and dichalcogens. Such carbon binding and activation is also predicted to operate effectively on larger alkyls including secondary and tertiary alkyl carbons.
  • FIG 20 illustrates the positional addition of butadiyne bound to a
  • This is similar to the Si and Ge based butyne binding tools of Figs 16a-d and 18 of [Rab08].
  • Said butyne may be loaded onto said silicon dimer by an intermediate binding tool, e.g. comprising one or more metals, especially Ni, as in Fig 18 of [Rab08] onto Ge surface dimer of
  • Ge(100)2xl (note that Ge could substitute for Si in the present binding tool and constitutes an alternative tool embodying this aspect of the invention).
  • the present Si ⁇ -SiC(100)2xl surface silicon dimer binding tool improves over the Ge surface dimer of Ge(100)2xl tool in mechanosynthetic operations due to greater strength. Shown are AMI optimization calculations performed with PC- GAMESS 7.01.
  • FIG 21A shows a nanopositioned metal and counterion directed hydride exchange reaction whereby a deprotonated secondary alcohol reduces the carbon of a metal bound ketone, for conversion of polyketides to polyols, alkanes and/or polyenes.
  • Ligands, ions and reactants are positioned individually by independent nanopositioning means.
  • FIG 21B shows oxidation of adjacent tertiary carbons, which here model a hydrogenated diamond (110) surface pair to be dehydrogenated.
  • a Lewis-acid tool and a base tool operate in concert at adjacent carbons to yield surface unsaturation, e.g. for subsequent carbon dimer or polyene or poly-yne addition.
  • Figs 22A-K show addition of metal-bound methyl to a monoprotonated ethylene glycol complex of Silicon, with subsequent deprotonation and
  • silacarbene complex may be reacted as shown to yield oligomers and polymers.
  • ligands esp. by concerted pulling of adjacent non-like ligands
  • poly-silacarbene fragments useful for mechanosynthesis may be obtained, the latter operations, by Zn ions bound to surface carbanions on a diamond (111) surface.
  • Figs 1A-1Y, 2A-2S, 3A-30, and 4A-4D illustrate convergent assembly of rocksalt (halite or Bl) structure materials and structures relevant to the understanding thereof. Positioning and manipulation using both ligands, supported ligands and relief features is depicted, as are means for preventing or repairing failure products of convergent fabrication bonding reactions.
  • Support- bound ligands include diamondoid and graphenoid supported fluorine atoms and dioxane and Acetylacetone analogs and derivatives, and variously occur in monodentate, bidentate and tridentate form.
  • Various spatial arrangements and motions of supported ligands for performing desired operations are shown.
  • Figs 3A-3G illustrate convergent fabrication of MgO using as means therefor MgO structural members passivated against reaction with MgO precursors or intermediates by decoration or coating with one or more graphenoid or graphene layers.
  • Fig 3H illustrates an arrangement of actuators positioning for positioning tools in opposable pairs on a surface and the assemblage of two such surfaces whereby four tools may be controllably positioned and manipulated for
  • Figs 31-30 illustrate various aspects of convergent fabrication.
  • Figs 3J-3L and 3N.vi show successive steps of convergent fabrication with motions of tools bearing precursors or intermediates denoted by arrows.
  • Fig 30 shows the use of a relief feature for manipulating precursors and intermediates for fabricating structural copies of themselves for deposition onto surfaces for forming relief structures useful as means for the convergent fabrication and assembly methods taught herein.
  • Fig 4A illustrates reaction dynamics at 300K of two Acetylacetone bound Mg(OH) ions. NVT ensemble dynamics were used with AMI as implemented in cp2k.
  • Fig 4B-D illustrates ligand contest for transferring intermediates between different types of ligands and different sets of ligands.
  • Fig 5 illustrates binding and convergent reaction of acetylenes to form all-s- transoid-trans-polyenes and manipulation thereof and methods and means for reactions of same with fragments representing diamondoid targets; the cyclohexane molecule represents a nonreacting structural member for applying directed pressure directing reactant fragment atoms to target atoms.
  • Activation in Fig 5E may be radical, cationic or anionic; with Al, a partially cationic acetylene attacks neutral singlet acetylene.
  • Figs 6A-6I and 6L illustrate mechanosynthesis of diamondoid structures or addition thereto from tool-bound trans-polyene deposition, and means and steps of the method therefor.
  • Fig 6E shows addition of an imene substituted trans- polyene.
  • Fig 6E shows a sequence of geometric optima along the trajectory of addition of an imine substituted trans-polyene reactant loaded on a trans- polyene addition tool to a bare diamond 110 surface; the first panel shows the polyene reactant pushed against target atoms before covalent bond formation commences, with reactant atom-target atom distances ranging from 231.0- 259.7pm.
  • Figs 6F-6H show addition of a perfluorine derivatized trans-polyene;
  • Fig 6F shows an isometric view of a trans-polyene addition tool loaded with a perfluorine derivatized trans-polyene
  • Fig 6G shows a molecular structure similar to that shown in Fig 6F with elements labeled (but formal double bonds not shown)
  • Fig 6H shows a sequence of geometric optima along the trajectory of trans-polyene addition to a bare diamond 110 surface as said perfluorine derivatized trans-polyene is pushed by said addition tool to a desired bare target site on said diamond 110 surface, in this instance yielding an addition product bearing a perfluorine derivatized row of added carbons with proper diamondoid bond connectivity.
  • Fig 61 shows a facial view of the perfluorine derivatized trans- polyene loaded tool used in Figs 6F-6H.
  • Fig 6K shows UFF calculated structures of various graphenoid members linked via diacetylene linkages to C a (ll l) surfaces, and various cases thereof useful for aspects of the present invention. These structures were optimized using UFF as implemented in ArgusLab version 4.01.
  • Figs 6J, 6M-6N and 7A-7D show various modifications of diamondoid structural members with or for forming ligands and supported ligands, and binding of metals therewith.
  • Fig 7C shows the positioning of nitrile ligands on methyls representing diamondoid supports for binding and depositing an aluminum atom onto an aluminum workpiece, with bond formation shown; the starting distance between tool-loaded aluminum atom and workpiece target aluminum atom is 361.9pm .
  • Figs 8A illustrates a side-reaction product which is predicted by some but not all calculation methods to form upon abstraction of the two adjacent hydrogen atoms on adjacent rings as depicted; this side product is less reactive to carbon dimer addition.
  • Figs 8B illustrates a hydrogen abstraction sequence which avoids formation of the side product; however, DFTB (as implemented in cp2k,) which appears to give reasonable agreement with density functional
  • Figs 8D-8G illustrate various examples of methods and means for convergent fabrication and assembly of graphenoid nanostructures according to these aspects of the present invention. Note the formation of multiple aromatic rings in a single step and without rotation about bonds. Calculations are optimization where times are not indicated, and in all of Figs 8A-8G were performed using PM6 as implemented in cp2k. Note also the curvature imparted by Co(ll) binding, suitable for bending graphene into configurations suitable for
  • Fig 8G follows one electron reduction of the structure shown in the second panel of Fig 8G, which speeds the final ring closure.
  • starting separation of radical centers is 268pm; in the remainder of starting structures, average separations are 290pm.
  • the system in Fig 8D is monocationic triplet; dicationic quintuplet in Fig 8E; dicationic nonalpet in Fig 8F; neutral quintuplet and then monocationic quadruplet in Fig 8G, all of which follow from ground states of isolated reactants or are ground states.
  • Fig 9A-9D depicts a comb-type actuator fabricated and assembled according to the present invention and useful also as nanopositioning means, including as means for the present invention.
  • Fig 9A depicts one of two surface supported arrays of conductors electrically in communication to a common conductor via electrical linkages (e.g. of diacetylene composition) for a comb-type capacitive actuator, schematically shown in Fig 9B, which may additionally feature a position controlled electrical switch (electromechanical switch) based on sliding contact between conductors 6470 and 6475, contact closed by translation of the subject actuator, schematically shown in Fig 9C in closed position.
  • electrical linkages e.g. of diacetylene composition
  • Fig 9D depicts a complete comb-type capacitive actuator comprising two facingly juxtaposed supported arrays of conductors (6420 which are e.g. of graphenoid composition) rigidly linked to electrically insulating support members 6430 (e.g. of diamond or b-silicon-carbide composition) by links 6440 (e.g. of diacetylene composition) with oppositely biased electrical contacts 6460 and 6465 and switch contacts 6470 and 6475.
  • 6480 is a flexural conductor serving both as a leaf spring and providing electrical communication between stationary structure and an actuating structural member.
  • Figs 10A-10C depict devices and systems for conversion of wind energy to electricity and mechanical work, either or both via entrainment of charged aerosols in a windflow ascending an electrical potential gradient and/or by turning a fan or turbine, and including adaptations thereof for tandem C0 2 and/or pollutant capture and for operation at high altitude, which is preferable because of greater wind velocity and more consistent availability of wind, and also combination with solar energy conversion means lofted above cloud-cover with concentrating means such as reflectors or lenses or instead photovoltaics, any or all of which may optionally be mounted on solar tracking means or heliostats and enclosed within a transparent shell or fuselage and lofted above cloud-cover, and moored via tethers, cables or umbilicals including electrical transmission means or wires for delivering electrical power to a ground station or marine or aquatic vessel, and optionally also sets of conduits for circulating electrolyte and/or carbonate solutions.
  • Cables or umbilicals may be carbon nanotubes or ropes made therefrom or composite materials comprising carbon nanotubes especially crosslinked therewith, may be grapheneoid, may be carbon fiber of conventional fabrication, may be ultrahigh molecular weight polyethylene (UHMWPE), or dynema or vectran or may be basalt filaments or fibers or ropes made
  • UHMWPE ultrahigh molecular weight polyethylene
  • dynema or vectran may be basalt filaments or fibers or ropes made
  • Shells may be graphene, UHMWPE, fabric of carbon fibers or composites thereof, e.g. with UHMWPE, or diamond or polymethylmethacrylate or other high strength and preferably lightweight material or any combination of the foregoing.
  • such devices and systems further comprise lightning protection means as is common for aircraft.
  • Fig 11 depicts the logic of convergent fabrication, showing one example of numbers of precursors and intermediates at succeeding steps for strict regular binary additions.
  • Fig 12 illustrates predicted excitations of a graphenoid structure which may be fabricated according to the present invention and comprise trimethylamine and carboxylate functions distally located to impose a dipole.
  • Such structures are useful as absorber moieties for photovoltaic devices and optoelectronics devices. Shown are predicted charge surface density maps for the reference state and two strong excitations predicted by ZINDO-CI spectral calculations for singlet excitations (as implemented in ArgusLab 4.01.) Charge densities of excited states of interest show favorable locations for forming electrical contacts to absorber moieties )for photovoltaic and optoelectronic applications,) of which the structure shown is an example. Bottom panel shows orbital maps for orbitals 187 and 189 for comparison to excited state 8, predicted for absorption of a 629nm wavelength photon.
  • Fig 13A depicts a system which may be fabricated and assembled according to the present invention, said system for capturing, concentrating and converting solar energy via a heat engine, distilling seawater to potable or otherwise useful form and also recovering solutes from seawater, distillation optionally availing vapor compression driven by said heat engine powered by solar energy, obtaining dissolved gases from seawater, said system situated in a floating vessel. Concentrating means may be situated on solar tracking means.
  • Fig 13F depicts a similar system adapted for deployment floating on a body of water such as an ocean or lake and for cultivating algae, e.g. for biofuel, bioplastic or, for Arthrospira platensis cultivation, also food use. Culture vessel shown here submerged near water body surface could alternatively be supported on a platform as that of Figs 13B-13C, whereby wave power could additionally be exploited by the corresponding system.
  • Figs 13B-C depict wave energy converting flotation means, suitable for supporting a platform, flotation means comprising inverted open chambers with pistons trapping air or other gases above the water level, whereby traverse traveling waves compress and expand enclosed gases and drive pistons delivering work, which may be coupled via a transmission or gearbox to an electrical generator.
  • Optional mooring means provided.
  • Also shown are means for diverting pressurized gas for pneumatic power, facilitated by downshifting or locking gears to slow or lock piston motions.
  • Fig 13C depicts detail of a single pressure engine cylinder (or chamber) 10401 of the system for wave energy conversion depicted in Fig 13B.
  • Piston 10410 is in communication with gearbox 10420 via rod 10430 passing through gas-tight seal 10435 and rack 10440.
  • Gearbox 10420 may controllably engage work output by said pressure engine to electrical generator 10445 or rotary work output shaft 10450.
  • Pressure develops in cylinder 10401 as a water surface wave 10460 with transverse displacement passes and causes enveloped water surface 10465 enclosed by said cylinder to rise, said pressure driving said piston, or alternatively serving as a source of pneumatic power controlled by a valve at pneumatic output 10455.
  • Translation control means 10470 enable adjustment of positions of support rods 10475 whereby position of supported platform
  • Sliding members 10485 permit motions compensating for shifts in positions of cylinders relative to said supported platform as the spacing of said cylinders is adjusted.
  • Piston stops 10490 restricts motion of piston such that piston cannot be drawn out of cylinder or compress working fluid enclosed in cylinder 10401 by piston 10410 beyond a minimum volume.
  • Fig 13D depicts a functional block diagram of a system for capturing and converting energy, processing various forms of matter from ambient or environmental sources including abundant materials such as salts from seawater including magnesium, including basalts and manganese nodules or polymetallic nodules, conversion of C0 2 to organic feedstocks, capture of methane and other hydrocarbons for lake or ocean seeps or from clathrates, purification of water, and for performing various fabrication and assembly operations on matter collected or processed, including both bulk fabrication and assembly operations and nanostructure fabrication and assembly operations.
  • Advantages attained with this class of system include flexibility of material source and generality of capability, and enhanced utilization of energy and prevention of waste by maximizing the utilization of by-products in other operations of the system.
  • modules only require relatively simple structural means such as vessels, pistons and chambers which may also serve as pumps or valves, conduits which may also house filtration media or catalyst beds or form
  • Fig 13E shows a functional block diagram of a system adapted for hydroponic growth of crops including food crops, for processing inputs to same from abundant sources and for processing products and by-products of grown plant material.
  • Such a system may be combined with flotation means as in Fig 13B- 13C whereby crops may be grown over the surface area of the ocean,
  • Fig 13F depicts a system for capturing and controllably directing solar energy to an algaculture growth vessel 10701, a water distillation still 10705 and a solar engine 10710, wherein incident solar radiation is captured by solar concentrating means 10712 wherein light is directed by light concentrating partial reflectors 10715 oriented by solar trackers 10720 to converge on a subsystem for solar energy utilization.
  • Solar engine 10710 may drive an electrical generator 10725 or rotational work output shaft denoted by semicircular arrow.
  • Heat exchanger 10730 may recover heat from distillate condensation in the case of a low temperature engine operation for transferring recovered heat energy to said engine, or for the case of high temperature engine operation may recover exhaust heat from said engine and transfer heat energy to said water distillation still 10705 for distilling water.
  • a water filter 10735 is provided for filtering intake water for distillation and/or algae growth.
  • An algae collection filter 10740 is provided for harvesting algae prior to medium discharge at outflow 10745.
  • the system depicted in this figure is preferably partially submerged below water- body surface 10750, and is preferably supported by flotation means 10755 and secured by mooring 10760.
  • Fig 14 depicts the addition of a conjugated polyene to an edge of a C dia ( 110) surface forming a structure resembling a 2x1 reconstructed (100) surface perpendicular to the (110) surface.
  • Fig 15 depicts convergent fabrication of articles comprising voids including internal voids.
  • Blocks of sacrificial material or alternatively passive or passivated spacers, preferably which display attractive surface interaction with the material being fabricated, are interposed between the material, preferably in linear subassemblies as shown, which are then bonded to other linear (or alternatively onto planar) subassemblies, whereafter spacers or sacrificial materials are removed.
  • Articles comprising voids may then be stacked onto other such articles or onto articles without voids for forming extended 3-dimensional structures.
  • Fig 16 depicts a simplified opposed STM apparatus featuring tips or probes on opposing surfaces such that two samples/workpieces may be imaged and modified using the respective opposed tip, and the two samples may be contacted with eachother under precise positional control. Samples/workpieces may be mounted while in opposing contact to ensure proper relative allignment. Such an apparatus may additionally be fitted with valved inlets for admitting vapors.
  • the opposed STM system depicted comprises a 3-dimensional nanopositioning stage 13010 and opposed tips 13020A and 13020B useful for performing surface modifications on workpieces 13001A and 13001B and verifying and/or determining the precise location of modifications or other surface features (e.g.
  • first workpiece 13001A or second workpiece 13001B which may themselves be mutually juxtaposed whereby surface modifications on a first workpiece may in turn interact with a desired surface site on a second workpiece.
  • Each tip is in electrical communication with a picoammeter 13030A and 13030B and bias generator 13040A and 13040B for STM imaging and surface modification.
  • the opposed STM configuration shown enables a single desired interaction to be effected by positioning stage 13010 without causing additional undesired interactions.
  • Figs 17A-17C shows methods and means for reaction of methane and C0 2 to acetate, polyketides and polyenes, suspended between metals of ligand metal complexes, which are preferably borne by nanomanipulation means.
  • Fig 17A for views of a starting geometry for this reaction
  • Fig 17B for the product
  • Fig 17A-17B are AMI geometries, subjected to optimization using cp2k to reveal a minimal energy reaction path for the exothermic reaction, rendered using Jmol.
  • FIG 18 shows a nanopositioned metal and counterion directed hydride exchange reaction whereby a deprotonated secondary alcohol reduces the carbon of a metal bound ketone, useful for conversion of polyketides to polyols, alkanes and/or polyenes.
  • Ligands, ions and reactants are positioned individually by independent nanopositioning means.
  • Figs 19A-19K illustrate reactions of alkyls including methane, yielding activated methyl groups which further react with dichalcogens, dithiols, especially activated dithiols to yield compounds such as thioethers, which may further react with alcoholates or oxides to yield carbon compounds activated as electrophiles such as ketals. These may be reacted together to liberate molecular hydrogen as shown in FIG 19D.
  • FIG 19E shows conversion of thioethers and thioketals to ethers and ketals.
  • FIG 19F shows a variety of metal- ligand combinations useful for these reactions and for exchanging chalcogens and dichalcogens. Such carbon binding and activation is also predicted to operate effectively on larger alkyls including secondary and tertiary alkyl carbons.
  • FIG 20 illustrates the positional addition of butadiyne bound to a
  • This is similar to the Si and Ge based butyne binding tools of Figs 16a-d and 18 of [Rab08].
  • Said butyne may be loaded onto said silicon dimer by an intermediate binding tool, e.g. comprising one or more metals, especially Ni, as in Fig 18 of [Rab08] onto Ge surface dimer of
  • Ge(100)2xl (note that Ge could substitute for Si in the present binding tool and constitutes an alternative tool embodying this aspect of the invention).
  • the present Si : b- SiC(100)2xl surface silicon dimer binding tool improves over the Ge surface dimer of Ge(100)2xl tool in mechanosynthetic operations due to greater strength. Shown are AMI optimization calculations performed with PC- GAMESS 7.01.
  • FIG 21A shows a nanopositioned metal and counterion directed hydride exchange reaction whereby a deprotonated secondary alcohol reduces the carbon of a metal bound ketone, for conversion of polyketides to polyols, alkanes and/or polyenes.
  • Ligands, ions and reactants are positioned individually by independent nanopositioning means.
  • FIG 21B shows oxidation of adjacent tertiary carbons, which here model a hydrogenated diamond (110) surface pair to be dehydrogenated.
  • a Lewis-acid tool and a base tool operate in concert at adjacent carbons to yield surface unsaturation, e.g. for subsequent carbon dimer or polyene or poly-yne addition.
  • FIG 22A-K shows addition of metal-bound methyl to a monoprotonated ethylene glycol complex of Silicon (as studied by R. Laine and coworkers), with subsequent deprotonation and protonation steps yeilding lingand release and SiC unsaturation.
  • the resulting silacarbene complex may be reacted as shown to yield oligomers and polymers.
  • ligands esp. by concerted pulling of adjacent non-like ligands
  • poly-silacarbene fragments useful for mechanosynthesis may be obtained.
  • the latter operations by Zn ions bound to surface carba ions on a diamond (111) surface.
  • Figs 23A-D show the convergent fabrication of hexagonal-boron-nitride (hBN) atarding with dehydrogenated borazine (B3N3) and dehydrogenated p-di- borazine, to yield a B9H9 structure comprising 3 six-membered rings fused together forming a fourth central ring and having edges that approximate the armchair structure found in some carbon nanostructures.
  • hBN hexagonal-boron-nitride
  • B3N3 dehydrogenated borazine
  • p-di- borazine dehydrogenated p-di- borazine
  • these percursors and intermediates may be bound by a variety of tools (not shown) situated on structural supports or nanopositioning means, for example; most preferably, heteroaromatic nitrogen such as in a pyridine skeleton conveniently bind boron atoms, and zinc atoms bound by double deprotonated ethylene diamine skeletons or bound by phenanthroline skeletons may bind to nitrogens; these are preferably used to bind edge atoms, though they may also be used to bind internal (non-edge) atoms.
  • tools may be conveniently situated on graphenoid structures, or on other hBN nanostructures.
  • Fig 24A illustrates convergent assembly of diamond or b-Silicon-Carbide rhombohedron blocks, yielding a final block (after 3 steps from the starting blocks) which is eight times the volume of the starting reactant blocks provided, and all-bulk-like bonding for non-surface atoms results. Note that all surfaces undergoing bonding in each step are parallel. Note that in the assembly of more complicated articles, not all faces in an individual reactant need be coplanar in any bonding step, but to ensure correct resulting bonding, all faces being bonded should lie in parallel planes, and preferably be bonded by being facingly juxtaposed by transtlation normal to these planes, such that maximum distance between atoms not to be bonded is maintained.
  • Fig 24B shows the comparable process for cubic blocks. As shown, the top and bottom surfaces of these cubes are 100(2x1) for the case of diamondoid materials. Where bulk-like bonding geometry is desired at bonded interfaces, assuming that bonding of 100(2x1) surfaces does not yield bulk-like bonding geometry, the resulting limitation becomes evident in comparison.
  • Figs 25A-H relate the geometrical depictions of Fig 24A to small diamond molecules having rhombohedral bounds.
  • Fig 25H shows the facing juxtaposition of two such 32 carbon blocks via translation normal to the facing surface planes, the optimal path for contacting rhombohedral blocks to yield bulk-like bonding. (Shown is the onset of bonding, so not all bonds formed are depicted.)
  • Fig 26 shows bicyblo[1.3.3]nonane and derivatives including bridging
  • unsaturations such as radicals, carbenes (triplet carbenes where unbound by metals) and alkenes, alone or bound by metals in metal-ligand complex tools which may be used to position and adjust the reactivity of these, and a scheme for fabricating linear rigid polymers of these joined by spirocarbons featuring adamantane units.
  • the resulting surfaces normal to the polymer axis are 110-like, and hence passivating hydrogens may be removed from one such surface of each of two such molecules, and these may be contacted as shown to bond into larger diamond-like structures.
  • Figs 27A-B show convergent reaction schemes from butane, butane radicals or butadiene, to yield products comprising rings, which then are combined to yield products with a diamantane core structure, useful in further convergent reactions.
  • ligands are moved to translate reactants and/or apply forces to drive the desired reaction. Similar reactions may be used to produce the blocks of Fig 25.
  • Fig 27B shows bond formation progressing after two bonds already formed between C8 reactants (the first two are formed analogously to bonds formed in Fig 27A from similar reactants, but said reactants in Fig 24B are produced by contacting said similar reactants to form a 1,4 substituted 6 member ring instead of a 1,2 substituted 6 member ring, and transmetallation replaces V with Al, and hydrogens donated and abstracted, and metal-ligand tools translated, to yield the intermediates shown.)
  • cyclopentanes serve as pressure application means (under positional control, driven by actuators, preferably operating according to a program to execute desired motions) and reactant contraining means, and tert-butanes (and in particular the secondary methyls projecting towards reactants) serve as reactant contraining means.
  • cyclopentanes would be diamond surfaces or corners formed by the intersection of diamond surfaces, and tert-butanes would be replaced by diamond surfaces with surface methyls similarly projecting towards reactants.
  • Figs 28A-C show the calculated reaction, with reactants under independent positional and orientational control by binding tools comprising active structural members which are metal-ligands (here, UCr-, L 2 AI-) of precisely
  • Figs 28A-B show different isometric views of the starting configuration, with 320pm internuclear separation of reacting carbons.
  • Fig 25C shows the reaction product with desired bonds consistent with bulk-like diamond structure formed.
  • the products shown could favorably be further dehydrogenated (e.g. by hydrogen abstraction tools, hydride removal tools or base reagent tools as in other aspects of the present invention) to provide sites for addition of conjugated polyenes (e.g. butadiene fragments in the case shown) to build up further bulk-like diamond structure, as for polyene additions in other aspects of the present invention.
  • conjugated polyenes e.g. butadiene fragments in the case shown
  • binding tools shown are fragments of those which would be actually used; such tools would ordinarily be bound to structural members exerting positional and orientational control, for example, the UCr binding tools would have 2 or more hydrogens on butyl carbons and also preferably one or more hydrogen on the methyl ligand replaced by covalent bonds to structural supports, and the L 2 AI binding tools would have 2 or more hydrogens on the cyclopentyl moiety and preferably also one or more hydrogens on the ring formed by metal binding replaced by covalent bonds to structural supports for positional and orientational control.
  • controlled translation or trajectories of structural supports provideaki control over the reaction, enabling high yields of desired precise products from straightforward and highly adaptable operations, preferably under programmable automatic control, e.g. by information processing devices and actuators in communication with said structural members and hence reactant species..
  • Figs 28D-F show exemplary novel ligands which proved favorable to this reaction, featuring extensive conjugation and also various means of control over both polarization of metal-carbon or metal-reactant-atom (e.g. for reactants with B,N,Si,Ge,P,0,Sn or other substitutions to be directly involved in bond-forming reactions such as these).
  • the metal-ligand complex has a number of degrees of freedom concerning charging state, polarization and charge
  • linker length may vary from zero to many atoms, may involve substitutions such as nitrogen (especially for modulation of properties by protonation thereof)
  • this new ligand could also be used with metals other than Aluminum and could replace the alkyl-ligands used in these reactions for the Chromium complex binding tools shown.
  • Figs 29A-B show the reaction between B 4 clusters bound to a pyridine skeleton tool as these are brought into proximity forming a B 8 cluster bound to these tools.
  • Figs 29C-D show the reaction between B 8 clusters bound to the
  • Figs 29E-F show two views of B I6 clusters bound to the nitrogens of pyridine skeleton tools.
  • apical boron atoms stabilized by weakly bound carbons of neutral alkyls (here, methane).
  • Figs 2-H show two views of the product which forms from the starting configuration in E and F. Note the geometry matches that of striped borophene, which is a metallic conductor. One of the desired bonds does not form ; this can be formed by susequently pushing the to borons together from opposing sides with alkyl-functionalities of tools (as was the case for MgO in Fig FIG.lH.ii. ).
  • Figs 30A-E show interpenetrating graphene-halite composite structures and components thereof.
  • Fig 30A shows a 64 atom TiC nanostructure
  • Fig 30B shows a 64 atom TiC nanostructure bound by a diazagraphenoid nanostructure, which features nitrogens speced to bind in register with titanium atoms in this structure.
  • This structure is useful as a substructure in comb-type actuators since the grapphenoid structure (or a larger structure of which it may be a substructure) is electrically conductive.
  • Figs. 30C-E show graphenoid structures which comprise a pore and illustrate different molecular tools situated on the zig-zag and armchair edges thereof.
  • Tools shsown include a phosphate group, a cyano group,, a diamine ligand, a catechol skeleton, a pyridine skeleton, a
  • phenanthroline skeleton an ethynyl-radical bound via a methylene bridgin arm- chair edge rings, a keto group, and a dimethylene-boron bridging a thadjacent carbons of an apical aromatic ring, forming a five-membered ring thereon.
  • Figs 31A-B show cobalt catalysis of aryl bond formation under electronic control.
  • Fig 31A shows a cobalt-catecholate tool h-6 bound to a phenyl anion, opposed to a phenyl radical; this system is monoanionic quintuplet, formed by adding an electron to the neutral quadruplet, which causes this reaction to commence, such that the reaction may be under electronic control.
  • Fig 31B shows the product formed.
  • Figs 32A-B shows two Ti4C4 intermediates bound by 1,2-difluorobenzene ligand skeleton binding tools with bidentate binuclear binding.
  • Fig 32A shows the configuration at 37fs after the calculation started;
  • Fig 32B shows the configuration at 1037fs. This shows that the tool and precursor arrangement shown is suitable for contacting these intermediates to yield the desired reaction product, Ti8C8. (computed by M06-L using cp2k, double-zeta basis on Ti, TZVP basis for C and H.)
  • Figs 33A-P concern interpennetrating structures of different materials, for example layer compound-halite structures such as TiC-graphene structures.
  • Layer materials such as graphene, BC3, hBN, borophene, silene, germene, stanene, etc., and three dimensional material structures such as halite
  • CaO, CaS, BaO, SrO, FeO, Li F, ZrC, ZrN, HfN, etc. may be fabricated into structures comprising protuberances, holes or vias.
  • Protruberances may be as small as one to three rings (for layer materials) or one or two atomic layers (for three
  • Fig 33A shows optimal contact between a Ti4C4 complex and an aromatic compound , pyrene as a minimal example (computed by M06-L using cp2k, double-zeta basis on Ti, TZVP basis for C and H.)
  • This structure informs the design of subsequent structures depicted in this Figure; the BSSE corrected interaction energy for this structure is -10.53 kcal/mol.
  • Fig 33B-P show different views and renderings (ball- and-stick or van-der-Waals) of structures which illustrates how aceneoid or graphenoid nanostructure molecules may penetrate TiC nanostructures, or vice- versa or both;
  • Fig 33G shows how halite material may penetrate a graphenoid sstructure fabricated with a hole rather closely matched to the dimensions of the halite structure; The halite would in practice be situated on a halite surface forming a protuberance thereon, the graphenoid placed on the halide surface around the protuberances, and further halite material bonded onto the exposed surface of said protuberance and extending further than the dimensions of the hole through which said protuberance was inserted, whereby said aceneoid or graphenoid nanostructure molecules become interlocked with said halite structure, yielding strong mechanical linkage.
  • junctions between zig- zag acene or graphenoid regions and armchair graphenoid regions preferably replace one or more
  • Fig 34A-H show several views and renderings of a composite structure of perijunctional nitrogen substituted graphenoid structures interlocked with a TiC structure which extends to sandwich the polybenzobenzene-like structure which features functional groups useful as tools.
  • these are: an alkly-ethynyl radical (an ethynyl group situated on a methylene brige between armchair graphenoid rings), or alternatively an ethide anion useful as a base reagent tool; and, adjacent deprotonated hydroxyls useful as a ligand (metal binding tool).
  • the halite structure extends further to sandwich the polybenzobenzene-like structure to afford additional positional stabilization against thermal or accoustic vibrations or applied stresses, to increase positional accuracy of tools or the functional groups thereof.
  • the halite structure shown may be continuous with the structure of a TiN-based comb actuator; the polybenzobenzene-like/armchair-edge structure shown on the bottom of the figure may be extended, for instance, to form a graphenoid spring which resists the electromotive force of the comb capacitor of a comb actuator.
  • Fig 35A and Fig 35B show the AMI calculated structures for the reaction of two neutral triplet molecules (thus the reaction is neutral quintuplet, and the product will relaxx to a more stable triplet with nearly identical shown in structure Fig 35C) the exocyclic diboron analog of the p-xylylidenyl diradical (that used herein for unmodified graphenoid fabrication) to yield a larger intermediate for use in fabrication of larger BC3 graphenoid analogs.
  • the circled hydrogens in Fig 35C would be abstracted to yield reactants for larger BC3 structures;
  • dehydrogenated carbons reacting with dehydrogenated borons This reaction ensues without metal catalysis; in practice, the reactants may be bound to metals (with a wider range being suitable for this reaction than for the analogous graphenoid fabrication reactions because the spin-up [alpha] phenyl radical reacts with pi-orbital electron on the dehydrogenated boron, and so no spin- down [beta] density need be induced here) in metal-ligand complexes by h-6 bonding and/or to aromatic nitrogens (e.g. in pyridine skeletons in graphenoid nanostructures in communication with nanopositioning means) at non-reacting borons.
  • the BC3 monolayer is a semi-conductor [Lau09], which may be precisely doped by the methods taught herein to fabricate electronic devices further including sheets comprising hBN insulating regions, zig-zag graphenoid wires, etc.,.
  • Figs 36A-B show the positionally controlled reaction of two Sr 4 0 4 molecules to form a precise Sr 8 0 8 structure.
  • Fig 36A shows two Sr 4 0 4 molecules situated 360pm apart;
  • Fig 36B shows the result 1700fs later as predicted by NVT Nose- Hoover molecular dynamics (M06-L density functional with DZVP basis set, carried out with cp2k-6.1).
  • M06-L density functional with DZVP basis set carried out with cp2k-6.1
  • no hexagonal structures are formed by irreversible bond-breaking, so that this material may be formed by convergent fabrication without the need for the application of pressure to close hexagonal structures to yield the halite structure.
  • the reactants and products would be bound by binding tools such as the ligands in Figs 32A-B, for example.
  • Figs 37A-C shows the result of convergent fabrication together of two Al 4 0 6 molecules.
  • Fig 37A shows the result of convergent fabrication together of two Al 4 0 6 molecules (themselves each produced from two bicycllic [closed] Al 2 0 3 molecules) manipulated by difluorobenzene skeleton structure tools; note that bulk-like bonding is achieved, which has been difficult in other approaches.
  • Fig 37B shows this product without associated tools.
  • Fig 37C shows the product of two generations of convergent fabrication starting from “boomerang” Al 2 0 3 molecules [two terminal oxygens and an apical oxygen and two aluminum cations therebetween] which is shown here to also yield bulk-like bonding with two bicycllic [closed] segments at sites where precursors bonded together.
  • Figs 38A-H shows polyketide fabrication from acetate precursors held by a imidazole skeleton fragment tool and a Zn-ethylene glycol fragment tool being contacted and caused to react with a polyketide workpiece held by Mg-ethylene glycol fragment tools.
  • Alpha carbons are deprotonated by base tools and the resulting carbanion attacks the imidazolide carbonyl to yield the desired bond to form a 6-membered ring.
  • molecules may be precisely fabricated; these may be subjected to protonation by acid tools, precisely reduced using hydride tools such as ethylene-diamine borohydride in conjuction with base tools to remove hydroxyls and yield graphene-type structures, including in predetermined patterns, whereby conductive patterns may be formed in insulating sheets.
  • hydride tools such as ethylene-diamine borohydride in conjuction with base tools to remove hydroxyls and yield graphene-type structures, including in predetermined patterns, whereby conductive patterns may be formed in insulating sheets.
  • Fig 39A-G show graphenoid nanofabrication steps from triphenylene molecule precursors or intermediates; such materials built up from triphenylene
  • triphenyloid materials precursors or intermediates are refered to herein as triphenyloid materials.
  • reactants, intermediates and/or products may be held by any suitable binding tool and interaction which does not disrupt the electronic configuration of the benzyne functionalities or the singlet carbons (for example, two or more carbons distal in reactant structures to reacting carbons may be deprotonated or have hydrogens abstracted and then be bound by a ligand-tool bound metal such as an aluminum atom bound by oxygens of a ligand, such as that in Fig 7D).
  • a ligand-tool bound metal such as an aluminum atom bound by oxygens of a ligand, such as that in Fig 7D).
  • Fig 39A shows a triphenylene molecule from which three hydrogens (adjacent hydrogens are first abstracted from carbons bonded together to yield benzyne functionality [refering to a dehydrogenated aromatic carbon-carbon bond in analogy to benzyne as a chemical functionality] before a hydrogen is abstracted to form an adjacent carbon radical) have been removed is positioned to react with a second triphenylene molecule from which four hydrogens have been removed to form two adjacent benzyne functionalities; the carbons are at least 300pm apart.
  • Fig 39B shows the structure at 166fs- note that by this time all three bonds required for continuous graphenoid structure have already been formed;
  • Fig 39C shows the structure at lOOOfs;
  • Fig 39D shows the structure (depicted in rotated orientation relative to Fig 39C to facilitate comparison with subsequent drawings) at 1178fs (at which the calculation was terminated as recoil vibrations declined in amplitude).
  • Fig 39E shows the result of a similar set of steps and reaction as depicted in Figs 36A-D using the product in Fig 39D as the two starting reactants dehydrogenated in analogy to Fig 39A, such that the structure in Fig 39E comprises four
  • Fig 39F similarly shows the product formed from two reactants which are products shown in Fig 39E (though rotated and flipped, as depicted).
  • Fig 39G similarly shows the product formed from two reactants which are products shown in Fig 39E, but dehydrogenated and positioned to yield the elongated product shown, which may be regareded as a graphenoid nanoribbon or triphenyloid nanoribbon.
  • the present invention features methods and means for nanofabrication and convergent assembly applicable to a broad range of materials and which may be adapted to fabrication of nanoscale objects and molecules as well as microscale and macroscale objects and bulk materials; assembly of objects thus fabricated into multicomponent objects, devices and systems is likewise accomplished when bonding steps are selectively omitted.
  • an important feature of aspects of the present invention is that systems for performing convergent fabrication and convergent assembly may themselves be fabricated and assembled largely or completely by the same methods which they are designed to perform. Automation, and either programmable control (e.g. by control of operations by a programmable computer system) or sense-response state- machine operation may reduce or eliminate requirement for labor inputs for system or desired end-product production.
  • the methods and means of the present invention may be adapted and applied to a very large subset of all material products, from nanoscale devices including information processing devices and nanocybernetic systems, to medical robotics (and sensors and diagnostics including implantable or injectable versions thereof), to agricultural robotics (especially operatively coupled to or operating within the same system as means for providing irrigation and fertilizer, e.g. water desalination means and nitrogen fixation means, abd also especially growth substrates or matrices), to energy conversion and storage systems, to architectural structures and infrastructure, to transportation systems including submarines, watercraft, aircraft and spacecraft, as well as systems for environmental restoration and modifying the climate of wide areas including also extraterrestrial bodies and planets.
  • irrigation and fertilizer e.g. water desalination means and nitrogen fixation means, abd also especially growth substrates or matrices
  • energy conversion and storage systems to architectural structures and infrastructure, to transportation systems including submarines, watercraft, aircraft and spacecraft, as well as systems for environmental restoration and modifying the climate of wide areas including also extrater
  • automated and especially programmable control, of both systems therefor (capability replication) and also desired products generally operatively coupled to means for processing raw materials into feedstocks for fabrication and generally operatively coupled to means for conversion of energy especially ambient sources of energy such as solar irradiation, fluid motion such as wind or wave energy, and/or thermal gradients (e.g. of geothermal origin, due to nuclear decay, or from thermal energy stored in thermal energy storage means).
  • energy especially ambient sources of energy such as solar irradiation, fluid motion such as wind or wave energy, and/or thermal gradients (e.g. of geothermal origin, due to nuclear decay, or from thermal energy stored in thermal energy storage means).
  • Systems comprising fabrication means, materials processing means and energy conversion means, capable of producing systems comprising fabrication means, materials processing means and energy conversion means and also capable of producing a predetermined desired product.
  • systems for performing fabrication and/or materials processing and/or energy conversion may be fabricated by either or both atomically precise methods or conventional bulk fabrication techniques or combinations of both.
  • a most preferred class comprises the precise
  • a preferred class of embodiments of the present invention is fabrication and assembly systems comprising means for fabrication via
  • positional chemistry e.g. positional mechanosynthesis or precise
  • a further preferred class of embodiments of the present invention is fabrication and assembly systems of the foregoing type further comprising means for processing raw materials; more preferred embodiments of this latter class include systems capable of taking in raw materials or pollutants found in the environment, especially either by capture from a fluid stream or by retrieval using grasping or digging means. Additionally, any of the foregoing systems may be used to produce functionally similar systems using only bulk fabrication techniques, which are likewise embodiments of the present invention.
  • embodiments of the present invention is any of the foregoing further comprising means for concentrating solar radiation for providing thermal energy to one or more materials processing operations, including but not limited to melting operations, boiling or vaporization or distillation operations.
  • a further preferred class of embodiments of the present invention is any of the foregoing, with or without solar energy concentrating means further comprising means for converting the energy of a flowing fluid (e.g.
  • a preferred subclass of embodiments of the latter class further comprises means for capturing a component of or pollutant occurring in a fluid inflow stream or portion thereof; a preferred subclass of embodiments of the latter subclass further comprise means for causing a transformation of said component or pollutant into a more desired or at least sequestrated form.
  • systems according to the preceding subclass but without means for converting the mechanical energy from said fluid inflow stream are embodiments of the present invention.
  • parts are most preferably transferred directly from one assembly means to a subsequent assembly means, preferably but not necessarily with concurrent bonding to or assembly with another part or intermediate assembly.
  • Conveyance of precursor materials or feedstocks to fabrication or assembly means may be by conveyor chains or belts or conduits or alternatively or additionally via a plurality of manipulators situated along a path in bucket-brigade-type operations, and intermediate products or intermediate assemblies may similarly be conveyed according to the foregoing from one part of a fabrication and assembly system to another.
  • embodiments of the present invention are simple polyhedra such as prisms, pyramids, parallelipipeds and cubes, although a vast range of sets of three- dimensional solids (or their geometric idealizations) capable of tiling into desired target shapes may be used; accordingly a critical obstacle faced in the few concretely proposed self-replicating systems is avoided, as is the need for any specialized capital equipment for many embodiments.
  • means for processing, fabricating, manipulating and and assembling components are simplified, and methods comprising simple operation rules are provided to overcome limitations of prior art. Control over passivation and bonding is exerted in a variety of ways according to materials used, construction-system composition, desired product properties and
  • subsystems which themselves are means for useful purposes enables a class of replicating systems which are not programmable in the ordinary sense but nonetheless produce useful products; fabrication and assembly of subsystem modules may be conducted in ratios other than those strictly required for self- replication (whether under conditional control of a switch or external stimulus received by the system, or as an invariant consequence of mechanistic design) with surplus modules thus available as useful end products. Included are methods and means for fabricating such polyhedra from simple organic or inorganic compounds which are readily available.
  • materials are fabricated into desired structures or bodies, and operations for such fabrication may include convergent assembly operations novel to the present invention, and such structures or bodies may then be assembled together with other such structures or bodies into devices,
  • Convergent assembly may be used either to fabricate a body comprising a material or to assemble distinct components into a device, depending on whether fusion or bonding occurs;
  • distinct parts of a mechanical watch for example, if they are not fabricated in situ as in MEMs fabrication from a monolithic wafer, must be assembled together such that the desired articulations occur in the final product, but must not be fused. Fabrication involves changes in chemical bonds whereas generalized assembly need not; in this respect, bonding or fusion of bodies by convergent assembly according to embodiments of the present invention is properly fabrication, whereas assembly together of distinct parts which remain distinct bodies after assembly is properly assembly even when the manipulations involved are superficially similar; for example, it would be possible to fabricate a silicon wafer or a magnesium oxide crystalline prism according to the present invention via convergent assembly, such that it would be difficult or impossible to distinguish which silicon atoms arose from different components, and (apart from relative perfection) it would likewise be difficult to know that these arose from convergent assembly rather than some other crystal-lization process, while parts of a mechanical assembly like a mechanical watch are readily
  • Fabrication via convergent assembly permits the rapid and efficient and precise fabrication of structures, which may additionally be assembled together via similar types of operations without the formation of chemical bonds whereby mechanical assemblies may be produced; accordingly, similar or ident-ical means and similar processes may be used to accomplish both fabrication and assembly processes in the course of producing final products from raw materials or feedstocks.
  • One example of a subsystem or module useful in a self-replicating system which processes raw materials present in input feeds or intake streams into materials for fabrication of components and assembly thereof into useful devices and systems, (whether limited to being like systems and/or subsystem modules thereof or instead producing products according to fabrication and assembly programs [which programs may further be modifiable] or according to other methods and means of specification and control,) particularly suited for operation in aquatic or marine environments, is a module for separation of particles and dissolved materials from an input solution or inflow thereof, such as a distillation module.
  • a distillation module may be fitted with one or more pumping and filtration means and comprise a chamber for collecting filtrate and eluate, preferably thermal regeneration means such as a counterflow heat exchanger, a distillation chamber, energy delivery means, condensing means (such as a condenser coil,) a condensate collection chamber or distillate collection means and preferably also a valve between said distillation chamber and said condensing means.
  • thermal regeneration means such as a counterflow heat exchanger
  • a distillation chamber preferably a counterflow heat exchanger
  • energy delivery means condensing means (such as a condenser coil,) a condensate collection chamber or distillate collection means and preferably also a valve between said distillation chamber and said condensing means.
  • said energy delivery means may be solar energy concentration means such as a curved reflector, a lens, a fresnel lens or a fresnel reflector, or combinations thereof, preferably aimed by tracking means, preferably arranged so as to deliver concentrated solar energy to an absorber such as a black-body situated near the surface of the liquid to be distilled (e.g.
  • said energy delivery means may be heat transfer means such as a thermal conductor, such as a heat pipe or more preferably a loop heat pipe for transferring heat from a different process of the system such as the crystallization of a melt or an exothermic chemical reaction or some other heat generating process.
  • a thermal conductor such as a heat pipe or more preferably a loop heat pipe for transferring heat from a different process of the system such as the crystallization of a melt or an exothermic chemical reaction or some other heat generating process.
  • a distillation module may further comprise pressure reduction means for reducing the pressure of liquid to be distilled such that the boiling point thereof is slightly depressed; vapor so obtained is then pumped to a condensate collection chamber, where preferably, during repressurization, negative
  • differential pressure contributes to pressure reduction of the distillation chamber for further vaporization, whereby some of the energy for pressure reduction is recovered form condensing vapor and reused.
  • a dual-acting piston pump between said distillation chamber and said condensate collection chamber which reciprocates (with check valves or reed valves enforcing vapor flow direction from said distillation chamber to said condensing means) to reduce the pressure of the distillation chamber while compressing the contents of the condensate collection chamber (note that other expansion-compression means or pumping means may substitute as equivalents.)
  • mechanical energy for driving said piston is provided by a heat engine heated either by thermal energy from another process of the self replicating system or by solar energy, preferably concentrated either by the foregoing solar energy
  • a preferred embodiment comprises a heat engine comprising structural members composed of high temperature ceramic or refractory material (e.g. MgO) preferably comprising protective layers (e.g. graphite or graphene); if produced by the nanofabrication methods of the present invention or equivalents, these may be atomically flat and oriented for superlubricity of sliding of similarly coated bodies, e.g. solid superlubricated sliding, e.g. of a piston ring and an engine chamber or cylinder, and utilizing a noble gas working fluid (e.g.
  • argon preferably situated in an enclosure which is evacuated or filled with an inert gas, preferably a noble gas, (more preferably argon,) the foregoing enabling high temperature operation (when protected from gases reactive at high temperatures such as 0 2 , H 2 0 by said enclosure, limited only by working strength at temperature and formation of carbon monoxide from reaction of MgO and carbon, which should not be appreciable below about 1500K, with higher operating temperatures being likely achievable) and hence improving efficiency; preferred absorbers for conversion of incident light to thermal energy include carbon black, soot, graphene polymers, carbon nanotubes, aligned carbon nanotube thick films.
  • MgO materials may be reinforced by the inclusion of carbon nanotubes or graphene fibers to form a composite, especially by co-assembly thereof according to an aspect of the present invention.
  • Heat engines comprising MgO:C composite and graphene coated MgO structural members enable operation at higher temperatures than most conventional engines comprising conventional alloys and especially using reactive working fluids or internally combusted fuel, and so enable improved thermodynamic efficiency, a further advantage being that this result is realized using abundant materials.
  • heat engine structural members fabricated according to one or more methods of the present invention and/or included in a system embodying devices of the present invention may comprise structural members composed of pure or modified graphene, or or composites of graphene and other refractories, including but not limited to graphene and TiC, graphene and VN, graphene and HfC, graphene and TaC, graphene and Hf x Ta y C, graphene and ScN, graphene and TiN, graphene and ZrN, graphene and ZrC, graphene and one or more halite-structured material, where the term composites may also denote graphenoid coatings on a body of the corresponding material (e.g.
  • such a heat engine pumps heated working fluid to a heat exchanger, preferably a countercurrent heat exchanger with compression for heat ejection, with low grade ejected heat recovered and used for some other purpose, e.g. water distillation, or stored in heat storage means for later use, e.g. to continue distillation when solar irradiance is insufficient.
  • a heat engine according to the foregoing comprises pairs of chambers or cylinders each featuring pairs of pistons (e.g.
  • each of the pair of chambers or cylinders are connected together via a conduit from a valve to a counterflow heat exchanger to a conduit to a port of the other chamber or cylinder, whereby, following a work stroke, a piston is translated to open a valve, working fluid is pumped by engine compression through said heat exchanger where heat is removed and exchanged to working fluid flowing into the other chamber or cylinder of the pair, where further thermal energy is received and the complementary cycle completed.
  • heat arising from some other process of the self- replicating system is used to power said heat engine, especially when solar irradiance is insufficient, or other sources of mechanical energy may used instead of a heat engine, such as a wind-driven turbine, a wave-driven turbine, a flow-driven turbine, an electrical motor, etc.,.
  • a heat engine such as a wind-driven turbine, a wave-driven turbine, a flow-driven turbine, an electrical motor, etc.,.
  • Work e.g. from the foregoing heat engine, powered by solar energy or waste heat from some other process, drives vapor expansion and vapor compression means for facilitating efficient distillation. Differential pressure caused in the foregoing arrangement enables the recovery of the heat of vaporization from condensation at a higher
  • distillation may be partial or complete, depending on whether it is desired to recover salts or other solutes and in what form.
  • distillation pressure is progressively reduced during subsequent depressurization-repressurization cycles without additional intake of liquid, whereby the boiling temperature is maintained below the condensation temperature in spite of increasing solute concentration. Filtration, especially using filters prepared by nanofabrication according to the present invention or equivalent methods (e.g.
  • salts and residues may be recovered for potential use.
  • recovered material comprises elements or compounds useful as material or raw materials for fabrication, these may advantageously be recovered, processed and used or stored by a self-replicating system or a module therefor or delivered for transfer to other systems.
  • salt residues from seawater comprise magnesium, which may be separated or purified as in methods of established art implemented by a module or
  • MgO materials which may then be cleaved or cut and polished into polyhedra such as parallelipipeds or cubes, or in the case of sintering pressed at elevated temperature into masses such as bricks or other geometrical solids defined by press geometry) which may then be assembled and bonded together (e.g. via bonding agents, adhesives, polyelectrolytes [e.g. polycations, or polyanions, as in nacre,] surface
  • nanofabrication methods e.g. magnesium cations may be bound by ligands [e.g. exchanged for counterions] said ligands bound or linked to structural members for manipulating said ligands, said structural members preferably in communication with positioning means, for positional nanofabrication of MgO materials.
  • MgO in particular features a high melting point (as a refractory) as well as transparency to a relatively broad portion of the visible and infrared spectrum for the crystalline material, making this material suitable for both optical and structural components of solar-thermal systems, and further for structural members or means for devices useful for performing other high-temperature processes;
  • halite lattice rocksalt or B1 lattice
  • the halite lattice features three orthogonal (100) surfaces which in general do not reconstruct and are capable of direct surface bonding, is conceptually simple and easily visualized by untrained designers, lends itself to the fabrication of orthogonal structures, and shared by a wide range of other materials., such that fabrication methods and operation sequences therefore may be adapted as well to these.
  • Optical surfaces exposed to moisture are preferably coated with a sealant or protective layer to prevent damage; suitable coatings include films or thin films of polymethylmethacrylate,
  • polyhexylmethacrylate polyallyl, polystyrene, polyacrylonitrile, vinyl polymers, polyvinylidene chloride, polyvinyl chloride, polytetrafloroethylene (especially further comprising chloride containing monomers or modifications for enhancing bonding to magnesium,) corundum or aluminum oxide, silicon dioxide, or other protective coatings known in the arts. Further functional coatings such as anti reflective coatings are fully within the scope of the invention.
  • self-assembled monolayers may serve to provide similar protection; various calculations (not shown) predict stable adsorption of ether oxygens (e.g of 7- oxo-[2.2.1]-bicycloheptane and the corresponding polyfuran Diels-Alder oligomers) although any compound stably forming self-assembled monolayers on MgO surfaces (or in general other metal oxide, metal nitride, transition-metal oxide, transition metal-nitride or other related material surfaces) may be used to provide varying degrees of protection or impart other desired surface properties such as lubricity, passivation, hydrophilicity, hydrophobicity, etc.,.
  • Carbon films one example being that film produce by heating MgO under a carbon dioxide atmosphere
  • solid lubricants such as polyaromatic lubricants or graphite-based lubricants.
  • Materials of this class include TiC, ScN, MgS, MgSe, MgTe, CaO, SrO, BaO, CaS, SrS, SrSe, SrTe, BaS, BaTe, b-AIN, NiO, FeO, TiO, MnN, MnO, MnS, MnSe, YN, ZrN, ZrC, HfC, TaC, NdN, NdP, VN, V-N, VC, epsilon-VC, VO, CrN, CoO, EuS, AgF, AgBr, PbS, PbSe, PbTe, SnAs, NdAs, PrAs, LaAs, As, CdO, LaBi, CaNH, SrNH, BaNH, KH, KF, KCI, KBr, Kl, KCN, RbH, RbCI, RbBr, Rbl, LiH, LiF, LiCI, LiB
  • photoluminesent, magnetic and spin, catalytic, chemical, surface and other properties may be fabricated and assembled with nanoscale accuracy and also precision doping according to the present invention; applications include hydrogen storage in the form of the above listed hydrides or amides, storage of hazardous materials including As, Pb, Cr, Cd and CN (especially where these are doped into or encapsulated by other materials for preventing dissolution or diffusion of hazardous constituents from such a storage body, preferably where two or more protective coatings or layers are applied, preferably where
  • protective materials and hazardous materials are fabricated into a cellular structure whereby any damage to a protective material will only permit the escape of only a small fraction of hazardous materials, so, for example PbS or SnAs may be fabricated into nanosized cubes of a size to limit lattice mismatch with NaCI [used as a primary coating] which is further encased in MgO of a thickness to resist high temperatures] which is further encased in a solvent resistant material or multilayers of materials imparting resistance to multiple solvents or liquids, e.g.
  • embodiments may in turn be in communication with positioning means or alternatively said structural support may be the body or surface of one of the foregoing or a similar protective material, e.g. intermediate to the construction of a cellular structure.) Fabrication and assembly of such a wide range of materials enables improvements in a vast range of technological applications as well as new applications, and also efficient utilization of a broad range or raw or reclaimed materials, the construction of systems useful for a far broader range of material processing than possible heretofore, particularly in self-replicating or al lo-repl icating systems or modules therefore, and also atomically precise fabrication of complicated devices capable of operating in quantum regimes (e.g. spintronic devices featuring heterostructures of ScN with Mn doped ScN, including quantum dot or quantum wire type structures, useful for information processing, information storage, spintronic devices, display devices, photovoltaic devices, etc., .)
  • quantum regimes e.g. spintronic devices featuring heterostructures of ScN with Mn doped ScN, including quantum
  • MgO is a preferred material for general structural purposes, high temperature applications and optical applications, various processing,
  • fabrication, manipulation, bonding and assembly methods disclosed and/or combined herein, as well as devices, subsystems or systems for performing same, may also be applied to other materials including other halite structure materials, other binary oxides, other binary materials, adamantine materials and still other materials.
  • direct bonding methods as applied in the art of wafer bonding, or alternatively or additionally as in the vacuum welding of metal surfaces free of passivating materials
  • Materials of the halite or B1 class include MgO, TiC, ScN, TiN, MgS, MgSe,
  • halite or distorted-halite structural materials e.g. body centered tetragonal [bet] structures might be viewed as a severe distortion of a halite structure but in some instances would only require small differences in design and in the actual operations performed during fabrication to allow for the structural difference) are entirely within the scope of these aspects of the present invention.
  • materials include oxides, nitrides, sulfides, carbides, selenides, tell urides, phosphides, arsenides, halides, and hydrides, comprise halite materials comprising three or more elements, comprise elements from transition metals (including early-, middle- and late-transition metals,) main-group metals, lanthanides, actinides; these also show the feasibility of including molecular cations (e.g. in NH 4 I) and molecular anions (e.g.
  • Notable desirable properties of materials of the foregoing list include: hardness and/or strength (TiC, ScN, b-AIN, YN, ZrN, NbN, ZrC, HfC, TaC,) thermal resistance and/or high melting point (e.g. MgO, CaO,) phospholuminesence (e.g. for nanostructures or quantum dots or quantum rods useful for photonic energy absorption yielding triplet excitons with extended lifetimes for reducing
  • implantable devices TiN, also TiC, and perhaps MgO, or e.g. TiN encapsulated or coated MgO,
  • magnetic material properties e.g. CrN, Mn doped ScN,
  • semicoductor material properties e.g. CrN, ScN,
  • metallic conduction e.g. CrN below 260K,
  • supercoductivity e.g. NbN, used also in superconducting single photon detection devices,
  • electron emission SrO, BaO;
  • halite structured materials are variously abundant or relatively abundant in seawater, manganese nodules, volcanogenic massive sulfide ore deposits, black smokers, sediments (ocean, abyssal plane, shore, silt or on land,) basalt or rocks, or extraterrestrial bodies, and nitrogen, of course, is abundant in air.
  • inventions may in turn be in communication with positioning means or alternatively said structural support may be the body or surface of one of the foregoing or a similar protective material, e.g. intermediate to the construction of a cellular structure.)
  • convergent fabrication and assembly may be performed by situating precursors or intermediates adjacent to corners or ridges in relief structures (e.g. as shown at the bottom of FIG lP.vii) and facingly juxtaposing two such precursors or intermediates by facingly juxtaposing two such relief structures.
  • said relief structures may themselves be fabricated and assembled according to the convergent fabrication and assembly methods taught herein, and so these methods provide for fabricating and constructing means suitable therefor.
  • exactly one precursor or intermediate is situated on one relief surface.
  • relief structures are designed to comprise structures for aligning the relative translation of juxtaposed reliefs for proper registry of contact of precursors or intermediates.
  • relative motions of facingly juxtaposed reliefs for contacting precursors or intermediates are chosen to avail alignment for proper registry of contact of precursors or intermediates.
  • relief structures or surfaces are passive or passivated to prevent reaction with precursors or intermediates.
  • relief structures or surfaces comprise atomic substitutions or decoration with ligands adducted thereto for binding to precursors or intermediates.
  • relief structures may be designed such that contact areas of bound reactants differ, or contact areas of a product to each of the two reliefs differ, such that van der Waals forces attracting a product to each of the two reliefs differ and the relief featuring the stronger interaction with said product thus retains said product as said reliefs are withdrawn from eachother.
  • precursors or intermediates which are bonded by chemical reactions which may operate in the presence of solvents or instead are bonded by adhesives may similarly be held on a relief by capillary forces, with contact area determining bonding strength, a fact which may be exploited as for van der Waals binding.
  • additional manipulator(s) may contact products of contacting steps while a first relief is slid relative to the second relief and manipulators and said product of contacting steps where said maipulator(s) obstruct translation of said product with said first relief, whereby product may controllably be retained by a desired relief for subsequent manipulations and/or contacting steps.
  • small articles are fabricated and assembled according to the present invention using supported ligands positioned by nanopositioning means as means for performing positional convergent fabrication and assembly, and products thereof are further used as inputs for convergent fabrication and assembly according to the present invention utilizing relief structures as positioning means, most preferably said relief structures further comprising features for aligning desired registry of contact of precursors at each step, or alternatively so utilized through choice of motions or relative trajectories and points of contact to effect aligning desired registry of contact of precursors at each step.
  • FIG lP.vi for examples of trajectories facilitating desired alignment of registry between precursors of a bonding step by means of alignment by sliding of passivated or nonreacting surface features; additionally, surfaces of relief features of a first relief surface may be slid along relief features of a second, juxtaposed surface for causing aligned, spatially precise trajectories of relative motions of relief surface in the course of translations or motions for performing convergent fabrication and assembly operations of the present invention.
  • halite materials may be fabricated assembled according to the present invention into arbitrary structures useful as left-handed materials or metamaterials, materials featuring negative index of refraction or having unusual electromagnetic permitivities or
  • halite materials and more preferably ScN and Cu coated ScN materials may be fabricated and assembled according to the present invention into three dimensional microstructured or nanostructured bodies with cellular structures such as grid-like structures and gapped-gridlike structures and more preferably still with significant void volume or vias incorporated therein (either open to surroundings or enclosed therein.)
  • Objects to be shielded or obscured from electromagnetic radiation may be shielded by bodies of the foregoing composition or construction, and more preferably may be substantially surrounded by metamaterial structural members of the foregoing composition or construction fabricated and assembled according to the present invention.
  • Fig 1 illustrates convergent assembly of rocksalt (halite or Bl) structure materials and structures relevant to the understanding thereof.
  • the process is a fabrication process, while where heterogeneous, aperiodic or precise but irregular structures are assembled, then such a process is an assembly process per se even when assembly results in bonding with the formation of covalent bonds as shown; this relates to the distinction between material masses which might be fabricated by bulk processes and those requiring precise structural control over three dimensional distributions of mater, the later being realized by bonding via convergent assembly including omission of blocks from predetermined positions in a lattice being assembled.
  • the first two panels show the initial and resulting structures if one attempts to bond two Mg 4 0 4 species simply by positioning these at a separation close to the threshold for attraction to overwhelm repulsion; other calculations with other methods show similar products including products with scission of two additional bonds from the unbroken reactant shown yielding two overlapping perpendicular hexagonal prism structures, and reducing temperature to 8K yielded no significant improvement; AMI appears to yield a higher estimate of the stabilization of such bond scission products compared to the all-halite structure product compared to higher level calculations (not shown) so selection of AMI should yield
  • the next two panels show the effect of adding a physical restraint to the same starting geometry, con-straining lateral motions of atoms undergoing bonding (the cycloeicosa-l,3,6,8, ll, 13, 16,18-octayne macrocycle serving as constraining means held stationary by methylene hydrogens) showing that lateral constraint is effective at preventing or impeding reactant or inter-mediate bond scission.
  • This lateral constraint is a specific example of the more general principle of steric constraint, where firmly held non-reactive barriers (termed barrier members) are positioned or prepositioned to impede unwanted motions of reacting fragments or species.
  • an aspect of the present invention concerns positioning or prepositioning a steric barrier for preventing motions of reactant or reactant fragment atoms during the course of a bond forming reaction for stabilizing a desired reaction path to form a desired product, especially for reactions for convergent assembly of nanostructures.
  • the following three panels show two Mg 2 0 2 square reactants held by 1,3- difluoropropane ligands, each held by the circled hydrogens shown for one ligand in the center panel, representing at least the carbon and fluorine skeleton thereof held stationary by support means used in practice to position and move said skeleton.
  • This starting configuration was chosen in attempt to form an Mg 4 0 4 cube, but illustrates the reluctance to form fully closed product structures; nonetheless, the process shown is useful for forming planar structures of monoatomic thickness, useful with convergent assembly methods of the present invention for forming films including unsupported films, which in turn may themselves be combined by the same methods to form thicker films with exponential increase in thickness per step (i.e.
  • the following two panels show ligands which are readily incorporated in the structure of graphene or diamondoid supports, the left being a 1-fluoronaphthalene skeleton and the right being the Diels-Alder adduct of glyoxal with a dehydrogenated carbon surface-dimer of a 2x1 reconstructed diamond (100) surface (which may arise from a preformed diamond surface subjected to hydrogenation and then positional abstractions of hydrogens from a dimer near an edge of a (110) face or step edge, with the adduct structure then subjected to reduction with hydrogen of the resulting double bond, the net result being a dioxane skeleton fused to a diamondoid support, other dioxane and dioxene fusions to diamondoid structures or equivalent structures entirely contemplated within the present invention.)
  • the next panels show, respectively, the AMI optimum structure (10 4 heartree/Bohr) of an Mg 2 0 2 square
  • the following two panels show the optimal structure with 75% van der Waals radii.
  • the following two panels show how two such ligand-reactant complexes are positioned for convergent assembly into an Mg 4 0 4 cube (the starting structure is two AMI optimized geometries [ 10 5 hartree/Bohr, with PC-GAMESS,] and the following structure is of an intermediate in the optimization of that structure;) the most important conclusions from this calculation are that the ligands used permit the desired starting configuration, and that there exists a favorable path towards the desired product.
  • the following two panels show two additional types of ligands, fluorine modified (111) diamond similar to the foregoing 1,3-difluoropropane ligands but additionally with a surface carbon substituted by nitrogen to permit the binding conformation shown (this may be produced from a preformed diamond (111) surface from a nitrogen doped sample, by finding a nitrogen substitution site [e.g. via chemical force microscopy or analogous physical interactions or processes] and abstracting hydrogens and fluorinating at appropriate surface sites relative to nitrogen substitutions, or directly by nanofabrication methods according to the present invention;) shown also are aromatic moieties (benzene here, representing, e.g.
  • the resulting structure completely surrounds and constrains the ligand- bound reactants, and for the case of diamond and graphene provides high thermal conductivity paths for conducting evolved heat away from the reaction site, both reducing thermal destabilization of desired products or reaction paths and additionally conducting thermal energy to energy recovery means or exhaust means.
  • the right panel shows a further ligand comprising fluorine, oxygen and hydrogen atoms all of which cooperate to bind a reactant fragment in a desired orientation, energetically distinguishing in particular the configuration shown from binding of MgO only to a fluorine and a hydrogen.
  • the following panels pertain to the use of dioxane-based ligands to assemble Mg 2 0 2 squares into an Mg 4 0 4 cube.
  • Hydrogens circled for one dioxane molecule in the first panel of this series represent atoms which are preferable substituted by support atoms, and all of the ligands in this series would be similarly bound to supports for positioning ligand skeletons, except for the panel immediately to the right of the first panel which shows a configuration at 340fs with dioxane molecules unconstrained.
  • 7AN 7-aza-norbornane
  • 7AN 7-aza-norbornane
  • the most notable and desirable feature of this compound is the gauche configuration bridging ethyl fragment, suitable for evenly applying pressure to a large fraction of the adjacent reactant fragment; whether this is critical has not been tested but this performed quite satisfactorily so is preferred, but other alkyl fragments or groups or other compounds or materials which may serve to apply required force without causing unwanted reactions or themselves bonding to reactive fragments or their products are entirely contemplated as within the scope of this aspect of the present invention.
  • the third panel shows the configuration after 500fs at 80K, which is little changed; thereafter, each force-applying means is advanced towards reactive fragments (in one instantaneous 20pm translation each,) which cleanly leads to the desired product, shown at 500fs and then 3000fs.
  • the next four panels concern removing a dioxane ligand by pulling, most preferably in the directions indicated by arrows, in the increments listed and times indicated in the legends; a total of 80pm in the Z direction followed by 100pm in the X direction were necessary for release.
  • ligands could be translated in the Y direction (for the configuration shown,) individually, to shear bonds to bound product, which in that case would be restrained by (7AN) pressure-applying means, until all ligands which are desired to be removed are removed.
  • (7AN) pressure-applying means 7.
  • Minimization of kinetic energy in the mutual approach of reactant fragments minimizes the energy available to cause reactant atoms to stray onto unwanted reaction paths, such as in the present case, scission or breakage of reactant fragment bonds which are desired to be retained in a product species.
  • the left panel shows two optimized structures positioned slightly closer than the repulsive barrier distance; note that reactant fragments are deliberately set partially askew in this calculation to show that some positional error is tolerated by the desired reaction.
  • the right panel shows the product formed, seen 2500fs after the start of this dynamics calculation.
  • binding restraint and barrier members to favor the formation of desired products by two different, cooperating sets of methods and means.
  • binding atoms e.g. chlorine or fluorines
  • tools comprising structural members for serving as barrier means, for example, a diamond nanostructure comprising chlorine or fluorine surface substitutions and a structure which bounds a desired spatial reaction path.
  • the following two panels show similar dynamics calculation for the 1,3- difluoropropane ligands.
  • the starting structure was obtained by replacement of chlorine atoms in the preceding structure with fluorine atoms, and partial optimization holding the same ligand hydrogens and also medial magnesium and oxygen atoms fixed.
  • Convergent assembly according to the present invention may be of a variety of materials which are provided as or fabricated into a variety of precursor shapes or geometrical solids, chosen to permit tiling (e.g. three dimensional tiling) into a desired structure.
  • suitable types are: prismatoids: cubes, cuboids, parallelepipeds, frusta, prisms, antiprisms, wedges; prisms: hexagonal prisms, pentagonal prisms, trigonal prisms, square prisms, octagonal prisms, heptagonal prisms; pyramids: square pyramids, tetrahedrons; parallelepipeds: hexagonal parallelepipeds, pentagonal parallelepipeds, trigonal parallelepipeds, square parallelepipeds, octagonal parallelepipeds, heptagonal parallelepipeds; among others, and any combination of the foregoing useful or convenient for the fabrication of a desired product or intermediate.
  • Sets of the foregoing may be fabricated or provided in two or more different sizes, scales or aspect ratios with the composition of such sets preferably chosen to facilitate assembly of the desired product (e.g. enable assembly in a reduced or minimal number of steps.)
  • tools for manipulating or operating on precursors and intermediates assembled from precursors and/or sub-assemblies or assemblies thereof comprise or more preferably consist of assemblies of precursors like those which they are used to assemble.
  • halite structured materials represent the simplest case of this class, and such materials include NaCI, MgO, CaO, BaO, SrO, MgS, CaS, TiC, HfC, TaC, Hf x Ta y C, ScN, TiN, and VN, among others.
  • magnesium atoms or cations are permitted to associate with ligands, at least some of which are bound or linked to one or more structural members; preferably, at least one ligand is removed, withdrawn (by withdrawing a first structural member to which a first ligand binding a bound species is linked or bound from a second ligand [which may be of similar or different composition of structure as said first ligand] also binding said bound species, said second ligand linked or bound to a second structural member, whereby said first and said second ligand are pulled apart, a process here named
  • ligand-bound MgO may then be contacted either with a second ligand-bound MgO molecule or with a larger MgO structure, whereby either convergent-type fabrication or assembly may be conducted (with selective removal of
  • predetermined ligand molecules from workpieces via translation of structural members to which said ligand molecules are attached during a fabrication or assembly process) or depositon-type fabric-ation onto workpieces (analogous to diamond mechanosynthesis via carbon dimer deposition.)
  • Suitable ligands include derivatives of: o-quinone, catechol, ethylene glycol, ketones, organohalides, alkyl halides, chloromethane, 1,2-dichloroethane, 1,3- dichloropropane, 1,3-difluoropropane, 1,3-dihalocyclopentane, 1,3- dichlorocyclopentane, 1,3-difluorocyclopentane, 1,3-dichlorocyclohexane, 1,3- difluorocyclohexane, 1,3-dihalocyclohexane, 1,3,5-trihalocyclohexane, 1,3,5- trifluorocyclohexane, 1,3,5-trichlorocyclohexane, pentane-2, 4-dione, benzene (as an h-l through h-6 facial complex,) polyphenyls, phenol, pyridine, 1- fluoronaphthalen
  • a structure with two hydroxyl functions situated in sufficient proximity on a diamond, diamondoid or polymantane surface, e.g. on adjacent dimers on a hydrogenated (2x1) reconstructed C(100) diamond surface may comprise the 1,3-propane-diol skeleton, suitably arranged for use as a ligand (preferably in this case nitrogens may be substituted to at least the proximal position of the neighboring colinear dimers to both cooperate with binding and also permit deprotonation of hydroxyls without subsequent intramolecular deprotonation of adjacent tertiary carbons, an unfavorable basic reaction which might, however, occur due to proximity.)
  • a hydrogenated (111) diamond surface may have two adjacent hydrogens substited by fluoromethyl groups whereby the resulting structure comprises a 1,5-fluoropentyl skeleton, useful as a ligand bound to a structural member; likewise for the hydrogenated un
  • diethylaminosulfurtrifluoride [Et 2 NSF 3 ,] Si F 4 , CoF 3 , AgF, AgF 2 , SF 4 , any alkyl- amineosulfurtrifluoride or alkyl-amineosulfurtetrafluoride or related selenium or tellurium compounds, azahexane-N-sulfurtrifluoride etc.,) to yield a surface bearing a 1,3-difluoropropane skeleton (or equivalently a 1,3- difluorocyclohexane skeleton) embedded in said unreconstructed (111) diamond surface; the 1,3,5-trifluorocyclohexane skeleton embedded in the
  • unreconstructed (111) diamond surface is likewise realized by abstracting three surface hydrogens from the same six membered carbon ring comprised by the (111) surface, to yield another particularly useful surface embedded ligand.
  • Such ligands disclosed herein are also useful for binding organic precursors, feedstocks or reagents, into complexes with supported ligand-bound metals, including for the positional mechanosynthesis of diamondoid and graphenoid materials, by methods taught in [Rab08] and also disclosed herein.
  • an aqueous solution of MgCI 2 is contacted with the Diels-Alder syn bis-adduct of dioxin (C 4 H 4 0 2 ) with benzofuran (or o-xylylene, e.g. via photolysis of benzocyclobutane) terminated polyacene, graphenoid, polyaromatic or polyheterocyclic structural members, whereby a dioxane fragment bound to a structural support is permitted to bind a magnesium cation, and withdrawn from said aqueous solution.
  • anionic functional groups on structural members are colocalized with said dioxane fragment during withdrawal from said aqueous solution to maintain electrical neutrality, although this may not be strictly required.
  • dioxane fragment-MgCI 2 complexes For the case of concentrated solutions, it is likely that dioxane fragment-MgCI 2 complexes will be obtained, while dilute solutions are expected to mainly yield aqua complexes.
  • the complex is contacted with NaOH to yield dioxane fragment-Mg(OH) 2 and NaCI (which is washed away;) dioxane fragment-Mg(OH) 2 is protonated, contacted with a dehydration reagent (e.g. P 2 0 5 or substituted P 2 0 5 bound to a support, e.g. RP 4 0 9 where R is a support linked to phosphate via, e.g.
  • a dehydration reagent e.g. P 2 0 5 or substituted P 2 0 5 bound to a support, e.g. RP 4 0 9 where R is a support linked to phosphate via, e.g.
  • a carbon atom thereof to remove water, one equivalent of hydroxide, and a strong base tool (e.g. an acetylide anion) to remove a proton, yielding a support-borne dioxane fragment- MgO complex.
  • a strong base tool e.g. an acetylide anion
  • coordinating waters may be removed by contact with another cation, or the formation of aqua complexes may more preferably be avoided by fully coordinating the magnesium cation with multiple support bound or tethered ligands as outlined in the foregoing description of ligand contests, then reacted with one equivalent of hydroxide and deprotonated to yield the same support-borne dioxane fragment-MgO complex.
  • two support-borne dioxane fragment- MgO complexes are contacted to yield an Mg 2 0 2 square bound by two support- borne dioxane ligands, useful as a precursor for further fabrication of larger MgO bodies such as sheets or cuboids, or as a precursor for assembly of
  • a further example of a ligand in communication with a structural member is an oligo-p-phenylene or poly-p-phenylene molecule (l,4-oligo-/poly-phenylenes) having one or more phenyl units substituted at phenyl ring positions 2 and 3 by hydroxyl to give a catechol unit, or the same oxidized to quinoid form to yield an o-quinone unit; these examples represent substitution of a ligand monomer into an oligomer or polymer serving as a structural member.
  • Preferably structural members of these embodiments are in communication with positioning means for controllably positioning or translating ligands for controllably positioning or translating ligand-bound species relative to a workpiece or other ligand-bound species.
  • catechol or quinone units e.g. at positions 5 or 6 with further structural members, such as a further oligo-p-phenylene chain itself either in communication with separate positioning means for controlling the rotation of said catechol or quinone unit, or fixed relative to the main polymer backbone for fixing the rotational orientation of said catechol or quinone unit.
  • structures such as 4,5-bis(oligo/poly-p-phenylene)-benzene-l,2- diol (optionally bearing solubilizing groups) may both position and constrain the rotation of catechol or quinone units (i.e. the catechol or quinone unit in this case is at the apex of angularly disposed poly-p-phenylene chains, projecting oxygens at a vertical angle to the angle formed by the poly-p-phenylene chains.
  • metals or cations other than magnesium such as transition metals or other main-group metals, often affording binding selectivity, for example, iron with catechol or tiron derivatives, phosphines with palladium or nickel, amines with copper, etc., as known in the associated arts.
  • structural members comprising ligand skeletons or to which ligands are linked or bound are electrically conductive or semiconductive, or alternatively or additionally, ligands (with or without bound species according to the specific case) are contacted with reducing agents, or alternatively or additionally, a workpiece is electrically conductive or semiconductive, electron transfer may be effected to cause changes in the strength of ligand binding, and also reaction of bound species with other such species or workpieces.
  • ligands may be derivatized with a molecular wire, e.g. catechol may be substituted at positions 3, 4, 5 or 6 with a conjugated polyene for conducting electrons.
  • a ligand bound to a structural member which is under positional control may be used to position a metal atom or a metal cation in close proximity to a target site on a metal workpiece to which it is desired to bond said metal cation, an electrical potential is applied to said metal workpiece whereby deposition of said metal atom (for a positive electrical potential applied to workpiece) or said metal cation (for a negative electrical potential applied to workpiece) at said target site is facilitated.
  • direct contact of the atom to be added and one or more atoms at a target site may be possible or necessary. Note that similar deposition methods may be applied to
  • semiconductive materials such as semiconductive metal oxides or
  • semiconductive metal nitrides Preferably, such depositions are conducted at reduced temperatures to minimize surface diffusion of deposited atoms.
  • the foregoing may be applied or extended to the deposition of metals from binuclear or polynuclear complexes, such as ditungsten- tetrakis(hexahydropyrimidopyrimidine) (W 2 hpp 4 ) or derivatives or analogs thereof, especially to workpieces comprising metallic members; in this case, at least one hpp ligand (or alternative ligands, e.g.
  • a deprotonated guanidino skeleton or a deprotonated 1,3-diaza substitution is preferably bound to a structural member for positioning said skeleton or said ligand in fixed relative orientation by two or more covalent bonds, and the remaining hpp ligands or alternative ligands are linked to at least a second structural support (and more preferably, to a second, a third and a fourth structural member for positioning the linked ligand or skeleton), whereby, a ditungsten species may be added to a tungsten workpiece by: first, two ligands or skeletons may be pulled away from the complex to expose the ditungsten, second, the remaining complex may be positioned near a target site in a predetermined orientation and preferably also advanced to contact one or more atoms at said target site, and optionally, third, an electrical potential is applied to said workpiece or
  • ligands or coordinating atoms thereof are retracted in a sufficiently low rat in terms of ligands or coordinating atoms per step that retracting tool avidity to deposited metal atoms is less than the avidity of the target site.
  • a similar ligand supported on a diamondoid structure is shown in Fig 3L and may be fabricated by the reaction scheme shown in Fig 3J by operations similar to those of Example XII. Deposition of metal atom dimers via binuclear complexes involving ligand-based molecular tools or molecular tools comprising ligand skeletons to body-centered-cubic (bcc) structure metals (e.g.
  • Tungsten may conveniently deposit to the positions forming the bounding box of a unit cell edge at the metal surface, said surface preferably including a face of said unit cell; for face-centered-cubic (fee) structured metals (e.g. nickel, titanium, palladium, platinum, aluminum,) deposition of metal atom dimers via binuclear complexes involving ligand-based molecular tools or molecular tools comprising ligand skeletons is preferably to target sites on a metal surface which will constitute a corner atom and a center atom of the bounding box of a unit cell in the finished structure, said metal surface preferably including a face of said unit cell; for hexagonal structure metals (e.g.
  • the preferred target sites are any adjacent pair of atoms in the unit cell on the metal surface, preferably colinear with a previously deposited metal dimer, most preferably adjacent a step edge.
  • the foregoing is preferably conducted in high vacuum, hard vacuum, or more preferably ultrahigh vacuum, although inert gas atmospheres (e.g. He (g) , Ne (g) or Ar (g) ), liquefied noble gases (e.g.
  • Preferred target sites are step edges and especially step edges adjacent to atoms previously deposited.
  • Tungsten adopts a body-centered cubic structure and flat surfaces along a plane of the unit cell are not expected to reconstruct, although they may relax; each tungsten atom to be added would bond to four surface atoms at an isolated flat site, five surface atoms isolated at an edge and six surface atoms at an edge adjacent a previously added atom or dimer; in all cases an added dimer forms eight or more bonds, and so should be quite stable at low to moderate temperatures, especially adjacent to step edges (for high melting point materials such as W, it is possible that ligand-reactant atom bonds become increasingly destabilized with increasing temperature more quickly than do desired reactant atom-workpiece bonds, so particularly in these cases it is possible that reactant-fragment release from tool atoms occurs more readily or with lower mechanical work or yielding lower target or product errors, so experimentation varying temperature for any given type or identity of tool or tool-atom and any given target atom type and configuration and any given reactant fragment
  • refractory metal which should also be applicable to other metals, transition metals and alloys, and may be performed with other ligands.
  • alloys comprising multiple metallic elements including those comprising transition metals or lanthanides or actinides may similarly be fabricated, including structures with predetermined elements at predetermined lattice sites such as would be impossible heretofore.
  • Notable metals which are expected to be acceptably deposited according to the foregoing include bcc structure metals, fee structure metals, hexagonal structure metals, nickel, titanium, scandium, zirconium, palladium, platinum, aluminum.
  • Workpieces thus fabricated may be fabricated to have one or more flat metal surfaces or metal surfaces with predefined contours which may be designed to be complementary to other metal surfaces so fabricated, such that in the case of fabrication in hard vacuum, workpieces bearing complementary or flat surfaces may be manipulated according to the various respective methods of the present invention to be contacted in a predetermined desired relative orientation whereby bonding or vacuum welding of surfaces so juxtaposed is caused to occur; note that workpieces comprising metallic members may be manipulated by the bonding thereto of ligands or analogous skeletons in communication or embedded in, respectively, structural members in communication with
  • manipulation for contacting metal bodies for vacuum welding preferably further comprises providing one or more alignment means for aligning the approach of bodies to be vacuum welded, and preferably further comprises contacting a first body to be welded or a tool holding same against said alignment means towards a second body to be welded directly or indirectly contacting said alignment means.
  • ligands or skeletons are pulled away from a workpiece or assemblage or workpieces preferably one by one or at least in successive minorities, such that the workpiece or assemblage or workpieces is retained by a predetermined subset of ligands or skeletons according to the collective binding strength and rigidity of positional constraint of each subset of ligands or skeletons being pulled apart (e.g.
  • a tungsten nanostructure may be bonded by a structural- member bound hpp-like ligand and four structural members each presenting a nitrile functionality; successively, first a subset consisting of two nitrile bearing structural members may be withdrawn whereby the workpiece is retained by a subset consisting of two nitrile-bearing structural members and an hpp-bearing structural member; second, a nitrile-bearing structural member may be
  • a nitrile-bearing structural member may be withdrawn whereby the workpiece is retained by the remaining hpp-bearing structural member.
  • Composite materials and structures and devices comprising same may likewise be fabricated and assembled according to the present invention.
  • a preferred example is a composite of carbonaceous material (graphene or carbon nanotubes or carbon fibers) and a refractory material, such as magnesium oxide.
  • Carbon materials provide tensile strength and thermal as well as electrical conductivity, while refractory materials provide thermal mass and high
  • such materials may comprise a sufficient proportion of carbon to impart thermal absorptivity (e.g. dark or black color, infra-red absorptivity) such that a
  • a combined solar thermal energy absorber and storage means of the present embodiment is used with a noble gas (e.g. argon) as a heat transfer fluid, preferably at substantially constant volume, which may be caused to flow through channels or interstices in said composite material to take on heat, and flowed either to a heat exchanger for delivering thermal energy to a heat engine or directly into a heat engine where it serves as a working fluid and is permitted to expand, delivering work.
  • a noble gas e.g. argon
  • the nanofabrication capabilities of the present invention (or equivalents) further permit conduit surfaces to be precisely structured to cause optimal turbulence at a given desired flow rate to ensure efficient heat transfer from such storage means to a heat transfer fluid.
  • MgO decorated or coated by graphene with structures both of these materials nanofabricated according to the present invention is preferably substituted by nitrogens at zig-zag edges (which are in any case the edges prefered for the principal graphene fabrication methods taught herein and shown in Fig 5 and Scheme III) to yield pyridine rings, wherein nitrogen bonds to magnesium upon placement by nanomanipulation thereof at step edges, or by inclusion of adducted structures comprising the skeleton of benzofuran Diels-Alder adducts or bis-adducts, e.g.
  • the present invention features an aspect for fabricating diamondoid nanostructures and materials and also related materials from conjugated trans- polyenes.
  • conjugated trans-polyene is taken as analogous to a Pandey chain of diamond (110).
  • This class of reaction at least when driven by pressure and in some cases and for some calculation methods without extremes of pressure, was found to be widely successful for different metals (B, Al, Ga, In, Tl, Cr, Ti, Ni, among others) and also Group 14 elements (Si, Ge, Sn, Pb) and different designs of binding tools including metals directly bound to diamondoid structure (both (110) and (111) surfaces, with two or three bonds between tool and metal center depending on metal valence) and reactants, via methylene functional groups, via amine or amide (RHN ) or hydroxyl or oxide or sufile or tell uride or phosphine or arsine or antimonide functionalizations.
  • metals B, Al, Ga, In, Tl, Cr, Ti, Ni, among others
  • Group 14 elements Si, Ge, Sn, Pb
  • binding tools including metals directly bound to diamondoid structure (both (110) and (111) surfaces, with two or three bonds between tool and metal center depending on metal valence) and reactants
  • relief structures for performing convergent fabrication and assembly as taught herein may be fabricated on diamondoid surfaces by forming surface features from conjugated all-trans-polyene
  • surface sites near relief features may be modified with directly bound or ligand-bound metals for binding diamondoid precursors or intermediates for convergent fabrication or assembly at surface sites from which hydrogen is absent (reliefs of diamondoid
  • composition being particularly preferred since these will be suitable for applying even extremely high pressures for causing bonding to occur even in products where strained structures are desired to be produced, and also since these may serve for the fabrication and assembly of like tools.
  • An aspect of the present invention concerns adaptations of conventional methods and means used in surface science and technology to the preparation of molecular tools useful for the present invention.
  • An opposed STM is a device featuring two opposed surfaces onto each of which one or more samples may be situated, each of which supports an STM tip for imaging, manipulating and/or modifying samples, and each of which is under translational control of a two- dimensional nanopositioner, said two opposed surfaces relatively advanced or withdrawn from eachother by a depth positioner featuring subangstrom
  • each sample is within operating positional range of the STM tip on the opposing surface and also samples may be positioned in proximity and contacted with eachother with angstrom or
  • Chemisorbed modifications may act as inverse STM tips in imaging eachother especially when sensitive electrometric detection is utilized
  • opposed STMs used are situated in individual chambers capable of containing fluids and being evacuated to ultra-high vacuum (UHV.)
  • UHV ultra-high vacuum
  • a plurality of ports featuring valves for pumping in or out gases or liquids are provided, preferably a heating element is provided, preferably a cooling element is provided or conduits for coolant are included in the structure of said chambers.
  • opposed STM devices additionally feature means for
  • SPM probes are included, such as a single electron transistor or a single electron transistor field effect transistor probe whereby surface charge may be mapped; useful for determining the presence of surface anions, especially ethide modifications and amide (e.g. RHN ) modifications, and the successful formation and location thereof.
  • said opposed STM is controlled and
  • the foregoing devices additionally feature storage chambers for storing tools and protecting same from the ambient atmosphere, i.e. storage is preferably under inert gas such as argon or under UHV, and also transfer means for transferring samples or tools from said opposed STM chamber and the surfaces thereof to storage chambers.
  • storage chambers for storing tools and protecting same from the ambient atmosphere, i.e. storage is preferably under inert gas such as argon or under UHV, and also transfer means for transferring samples or tools from said opposed STM chamber and the surfaces thereof to storage chambers.
  • samples may be covered with a protective lid or shell and remain mounted in said STM chamber until spent or regenerated/recycled/reloaded.
  • One preferred embodiment features an opposed STM in a chamber, additional probes such as a probe comprising a single electron transistor, a chamber for performing plasma and gas reactions, a chamber for performing solvent-based surface modifications, means for pumping and controlling the flow of gases and liquids, temperature regulation means, and means for transfer of samples between chambers
  • additional probes such as a probe comprising a single electron transistor, a chamber for performing plasma and gas reactions, a chamber for performing solvent-based surface modifications, means for pumping and controlling the flow of gases and liquids, temperature regulation means, and means for transfer of samples between chambers
  • metal atoms e.g. bound by ligands, or alternatively
  • inorganic nanostructures such as a corner atom in a cubic metal nitride or metal carbide
  • h-2 to h-6 complexes with aromatic and
  • heteroaromatic rings with ligands or other supporting structures in
  • a hydrogen abstraction tool e.g. a nanopositioner-bound alkyne-radical tool,
  • a hydrogen abstraction tool e.g. a nanopositioner-bound alkyne-radical tool,
  • a radical site of a phenyl radical towards the carbon of said benzene from which said hydrogen was abstracted such that the radical atom of said phenyl radical is most closely juxtaposed to said carbon of said benzene from which said hydrogen was abstracted, whereby the desired bond-forming reaction is permitted to occur.
  • poly[n]acenes including precisely branched poly[n]acenes may be fabricated.
  • cobalt, manganese, niobium and tungsten significantly bend rings to which they bind, while others do so only slightly or not at all.
  • cobalt and tungsten are useful for forming products comprising bent or curved structures such as nanotubes or nanorings.
  • Binding of 2,6-dimethene-poly[n]acenes by multiple cobalt catecholate (CoCat) complexes (which appear to favor h-3 and h-4 binding to aromatic rings) on the same face facilitates curvature for cyclization; abstraction of hydrogens from the two methenes and positons 3 and 7 with CoCat complexes bound to the terminal rings provides the necessary reactivity and effects the desired positioning using nanopositioning means.
  • CoCat cobalt catecholate
  • multiple ligand-metal complexes which bend aromatic rings to which they bind may be bound, preferably in alternation, to opposite faces of a graphenoid structure adjacent to the edge to be bonded to another graphenoid structure so as to cancel or reduce displacements due to bending of rings whereby two edges to be fused may be juxtabosed along their full length.
  • two edges to be fused may be bound by multiple ligand-metal complexes in complementary or mirror image arrangements such that edges to be fused may be justaposed along their full length in spite of bending by metal binding.
  • catechol is an aromatic compound, and so precursors comprising one or more catechols are susceptible to nanofabrication according to the foregoing, whereby catechol ligands may be precisely
  • Precursors bearing functional groups or substituents or atomic substitutions at specific positions may be used as reactants to yield products comprising the respective modification at a predetermined location of the desired product.
  • Preferred functional group substituents include ethyne groups,
  • dialkylphosphines diarylphosphines, keto groups, carboxyl grooup, hydroxyl groups, amino groups.
  • Preferred atomic substitutions include nitrogen, boron, phosphorus.
  • the foregoing may serve as molecular tools or portions thereof, integrated at predetermined locations into the structure of graphene structural members; for example, hydroxyls, phosphines or amines may yield ligand structures for binding metal atoms, while ethyne may serve as a hydrogen abstraction tool or a deprotonation (base) tool, depending on oxidation state, and carboxyl groups may serve as a protonation tool (acid.)
  • Up to four colocalized basic carboxymethyl groups (or fewer in combination with acetate or other carboxylate molecules) may serve to bind two copper(ll) ions in a Chinese lantern structure for oxidizing deprotonated ethyne groups (anion to radical.)
  • the present method for bond formation via metal-facilitated radical-radical coupling permits both the addition of monomeric precursors (e.g. benzene, benzoate, aniline, phenol, pyridine, catechol, phenanthrene, phenanthroline, naphthalene, anthracene, tetracene, p- xylylidene, 2,6-dimethyl-anthracene, 9,10-substituted 2,6-dimethyl-anthracenes, 9,10-modified 2,6-dimethyl-anthracenes, pyrene, , -dimethyl-pyrene, indene, -methyl-indene, 5-methyl-cyclopentadiene, among many others) to larger structures, as well as fabrication according to convergent synthetic schemes, e.g.
  • monomeric precursors e.g. benzene, benzoate, aniline, phenol, pyridine, catechol, phenanthrene, phenanthroline
  • p-xylene may be viewed as a "simplest monomer” in many variations of these syntheses, although there is no limitation to the use of other precursors.
  • carbon nanotubes, especially zig-zag carbon nanotubes and/or branched nanotubes may be combined to form longer carbon nanotubes, with the advantages that atomically precise structures including network structures may be obtained, and that great lengths of single molecule
  • (monomolecular) carbon nanotubes or substituted carbon nanotubes may be produced in a small number of steps, e.g. each step doubling the lengths yielding a geometric rate of growth in length.
  • polyheteroaromatic structures comprises combining aromatic molecules each comprising two exocyclic carbon atoms or heteroatoms wherein at least one exocyclic atom on each reactant molecule is provided or prepared for reaction in radical form.
  • p-xylylene biradical having two hydrogens abstracted from a methyl group of xylene, one hydrogen abstracted from the other methyl group and one hydrogen abstracted from an adjacent carbon of the ring, bound to a vanadium catecholate cation (alpha, alpha, beta, 2-tetradehydro-l,4-xylene-r
  • aromatic molecules comprising two distal exocyclic carbons or heteroatoms represents a composition of matter useful as precursors or intermediates in the convergent synthesis of poly[n]acene and graphene (or graphenoid) structures or nanostructures.
  • graphene quantum dots, or poly[n]acene or graphene nanowires may be fabricated according to the foregoing, including in situ for device or system fabrication; accordingly, a wide range of electronic and optoelectronic devices may be fabricated with the present invention; of course, integrated or complex systems comprising a large plurality of devices are most preferably fabricated by a plurality of fabrication means operated in parallel or simultaneously.
  • this method enables the convergent fabrication of single-wall nanotube of precise diameter and length and atomic substitution of lengths greater than a micron, greater than a millimeter, greater than a centimeter, greater than a meter, greater than 100 m, greater than 1 kilometer, greater than 1,000 km, greater than 36,000 km, greater than 134,217 km.
  • Multiwall nanotubes may be combined by sliding successive tubules from inner to outer of each multiwall nanotube to be joined into contact with the matching tubule, whereby access to reacting atoms by metal atoms is possible for reacting atoms which ultimately become internal to the product multiwall nanotube. Accordingly, carbon nanotubes or nanonets, including multiwall nanotubes of length sufficient to serve as a cable for a geosynchronous orbital elevator may be fabricated according to the present invention and such products are a distinct embodiment of the present invention.
  • the present invention permits the construction of a geosynchronous orbital elevator comprising a cable which is a single molecule; and which more preferably may have a network topology comprising carbon nanotube segments; most preferably, said cable is free from edge structures, which are more reactive to potentially damaging species.
  • Network structures e.g. formed by joining branched nanotubes with linear nanotubes, are more preferred as these are more tolerant to damage before losing strength under load.
  • a particular advantage of single molecule network carbon nanotube cables is that a single cable may weigh significantly less than one gram or even less than one milligram, but be strong enough to support a multiple of its own weight and the tension from a small
  • geosynchronous orbital ballast as well as the weight of a crawler micromachine or nanomachine for ascending a first cable molecule, drawing up a second cable (e.g. via one terminus or alternatively via a central portion thereof.)
  • a crawler micromachine or nanomachine for ascending a first cable molecule, drawing up a second cable (e.g. via one terminus or alternatively via a central portion thereof.)
  • graphene quantum structures including graphene quantum dots and graphene quantum wires is enabled. These structures have a wide range of applications including in the areas of photovoltaic and electrooptical devices, electronic devices, spintronic devices, antenna devices.
  • Atomically precise antenna devices offer the prospect of improved quality factors, enabling narrower tuned bandwidth and thus greater efficiency both in terms of communications spectrum utilization and energy efficiency and sensitivity; cross-sectional anisotropy of graphenoid structures (contrasted to the cross-sectional isotropy of nanotubes) enables polarization selectivity, since resonant modes normal to a graphene sheet differ markedly from lateral modes; different modes are therefore excited with markedly different efficiencies according to the orientation of the graphenoid structure.
  • Atomically precise graphene structures including structures comprising multiple graphenoid layers may serve as resonant beams in such sensor devices, yielding improved mechanical properties and higher quality factors and sensitivity to smaller forces or masses, whereby improved sensor devices are enabled.
  • binding sites e.g. ligands or functional groups for coupling to biological molecules such as immunoglobulins, haptens, oligonucleotides or other biomolecules
  • binding sites may be positioned at precise locations, with precise number and density, whereby reproducibility is greatly enhanced.
  • graphenoid beams may serve as improved cantilevers for scaning probe microscopies such as scanning force microscopy (SFM/AFM), resonant scaning force microscopy (RSFM/tapping SFM), magnetic force microscopy, etc.,.
  • SFM/AFM scanning force microscopy
  • RSFM/tapping SFM resonant scaning force microscopy
  • magnetic force microscopy etc.
  • graphene is electrically conductive
  • such probes are suitable for concurrent SFM and scanning tunneling microscopy/spectroscopy (SFM+STM or SFM+STS) and also concurrent RSFM and scanning tunneling microscopy/spectroscopy (RSFM+STM or RSFM+STS.) Atomic precision of such structures enabled with the present invention greatly improves the
  • Actuators useful as nanopositioning means may comprise comb-type actuators or related topologies fabricated and assembled according to the present invention and comprising graphene as conductive members thereof.
  • the lattice spacing of diamond is about 3% larger than graphite and graphene, but this small degree of mismatch still permits suitbly designed nanostructures of these two materials to be bonded together at multiple locations without significant distortion, stress or bending.
  • Convenient linkages accommodating hydrogens terminating diamond and graphene include acetylene and diacetylene linkages.
  • Diacetylene linkages may be formed with good yield via Eglinton coupling or Glaser coupling, or related reactions catalyzed by ligand-metal complexes bound to nanopositioning means.
  • ethyne substitutions are formed at desired sites on a diamond nanostructure, and these are coupled to juxtaposed ethyne substituents on a graphenoid nanostructure, most preferably using a nanopositoned catalyst such as copper acetate and a base.
  • hydrogen is abstracted from two or more sites on a diamond surface using nanopositioned hydrogen abstraction tools, surface tertiary radicals are brominated or iodinated either using a nanopositioned bromination tool (e.g.
  • a nanopositioned metal bromide such as aluminum bromide catecholate or aluminum iodine catecholate
  • a metal acetylide e.g. NaCCH
  • an acetylide bound to a nanopositoned metal-ligand complex e.g. in vacuum phase, or contacted directly with negatively charged ethide groups (arising from deprotonation and oxidation or electrooxidation of ethyne groups)
  • nanostructures via linking moieties such as diacetylene may avail diacetylene derivatives of the graphenoid member, which are deprotonated (e.g. by amine base, assisted by Cu(l) pi bonding to the terminal triple bond) to yield anionic acetylide functionalities and advanced via nanopositioning to juxtapose cationic sites of the diamondoid member formed as above.
  • graphenoid members are paired and more preferably bound adjacent to eachother, and more preferably still members of each pair are of similar or identical structure or at least have at least partially matching edges, which most preferably are further modified by the addition of cross-linking moieties bridging members of each pair opposite the side by which graphenoid members are bonded to diamondoid members.
  • Bridging or crosslinking enhances mechanical rigidity and also may enforce canceling between members of each pair of buckling or warping due to mismatch between the graphenoid and diamondoid lattices.
  • cross-linking or bridging counteracts bending of conductive paths into local increased proximity which might give rise to local deviations from desired or expected forces or even contact and attendant short-circuit.
  • edge-bonding to supports may also eliminate effects from facial disposition of graphene samples onto substrates, further distinguishing these cases, as may other specifics arising for any specific structure, so although relevant and possibly useful, the effect of pairing on conductivity and noise must be tested on a case-by-case basis.
  • Bridging or crosslinking moieties may be chosen to have various electronic properties; for example, unsaturated or conjugated bridging or crosslinking moieties may provide conductive paths or electrical communication between different graphenoid members, either those of a pair when pair members are spaced apart, or between non-paired graphenoid members or graphenoid members of different pairs or groups.
  • unsaturated or conjugated bridging or crosslinking moieties may provide conductive paths or electrical communication between different graphenoid members, either those of a pair when pair members are spaced apart, or between non-paired graphenoid members or graphenoid members of different pairs or groups.
  • each of a pair of half-actuator members may comprise parallel pairs of graphenoid strips each bound at two or more atoms of one edge to a diamondoid support via diacetylene linkages, with each graphenoid strip bridged (e.g.
  • Electromechanical actuators comprising a translating structural member actuated thereby in communication with an electrical member (e.g. electrical conductor or at least an electrical resistor or other electrical component) other than those conductors most directly controlling said electromechanical actuators may serve to make and break electrical contact of said electrical member with some other electrical component (e.g. a conductor,) such that switching functions may be realized.
  • an electrical member e.g. electrical conductor or at least an electrical resistor or other electrical component
  • some other electrical component e.g. a conductor,
  • Structures such as IX may be further derivatized with (or alternatively formed via reactions similar to the foregoing but including derivatized precursors to yield functional substituents at desired positions in the obtained product having) pairs of oppositely charged functional groups to yield dipoles or multipoles. Similar to the situation with organic dyes, imposition of a dipole or multipole on an extended aromatic system yields enhanced photophysical responsivity; thus the foregoing methodology enables the precise nanofabrication of absorber moieties for photovoltaic devices. The resultant intrinsic electric field facilitates oriented dissociation of the quasiparticles (arising from photon absorption) to yield charge separation which is efficiently coupled into electrical contacts oriented
  • one or both electrical contacts may be via graphenoid
  • nanostructures which are pi-stacked with a portion (preferably less than one half the area of one side) of said absorber moieties and one or both of said
  • selective optical receiver devices for optoelectronic applications and especially multiplexed variations thereof.
  • a plurality of arrays of such optical absorbers coupled with electrical contacts and tuned to specific frequencies, especially with the position of said arrays ordered in space such that higher frequencies are received first along the path of incident radiation and electrical contacts to each such tuned array are regulated at electrical potential such that obtained current (of photoelectrons) is available at the highest electrical potential possible from the incident frequency of photon from which it arose and energy obtained is maximized; before conversion, energy output from such a device features a range of voltage outputs delivered at multiple contacts.
  • the particular combination of this property with the high conductivity (high electron and hole mobilities) of graphene further enhances photovoltaic applications.
  • each single graphene layer (one atom thick) attenuates visible light by about 2%, so in combination with the strength of graphene, these properties enable the use of one or a few layers of graphene as a transparent electrode for photovoltaic devices according to the present invention; since the graphene fabrication methods disclosed herein also enable the predetermined incorporation of arbitrary voids, and since such an electrode need not be continuous, more preferably a large fraction of the area of such an electrode instead is omitted as void area, whereby such transparent electrodes absorb less incident light.
  • Ferromagnetic graphene may be produced similarly to the foregoing by designing voids internal to a graphenoid structure comprising a radical site an an atom on the periphery of said void; a pluraity of such voids in proximity increase the areal magnetic moment.
  • nanotube conduits may be oriented or directed such that flow from orifices thereof converges, the number and relative angular orientation of a plurality of nanotube conduits being adjusted, most preferably dynamically by actuators of the present invention, according to desired droplet size and flow rate as well as liquid properties.
  • Marks may be realized by utilizing different methods and means to cause charge separation for obtaining charged aerosols.
  • an aqueous electrolyte such as seawater, a sodium chloride solution, a sodium hydroxide solution or a calcium hydroxide solution or an ammonium hydroxide solution or another electrolyte is subjected to
  • a Kelvin water-dropper arrangement is utilized to obtain net charged solutions from one of the
  • one of the two obtained net charged solutions is aerosolized and caused to ascend an electrical potential (e.g. by entrainment in wind or another fluid flow, or from initial velocity, e.g. caused by descent of the liquid in a gravitational potential) whereafter particles are collected on a collector.
  • Said collector may itself be an electrode or alternatively only means for mechanically capturing particles and causing same to flow to a collection reservoir.
  • the second net-charged solution generally is retained at the original electrical potential, although some embodiments may also aerosolize this solution and cause it to traverse an electrical potential opposite in sign to that traversed by the first net charged solution; for example a net charges are separated, a first net charged solution having excess negative charge is caused to traverse a potential difference to a more negative electrical potential and a second net-charged solution having excess positive charge is caused to traverse a potential difference to a more positive electrical potential; a switch may be closed to permit current to flow across a load between said negative electrical potential and said positive electrical potential, whereby electrical energy may be utilized.
  • Marks Further improvements possible over Marks include the exploitation of wind energy at high altitudes, where winds are typically more available and
  • a Marks-type wind/electrical generator may be housed in a lofted structure which is preferably tethered or secured (e.g. maybe secured to the ground or to a floating vessel on a body of water or may be moored to the bottom of a lake or ocean or other body of water )by high-strength cables, e.g. comprising graphene or nanotube
  • said cables further comprise insulated wires (which may themselves be graphene, carbon nanotubes or other conductive nanotubes, generally bundles thereof) for transmitting electrical energy to a point of use or a transmission network.
  • tether cables preferably further comprise conduits for conveying liquids to and from said lofted structure.
  • said lofted structure comprises structural members for providing lift in a fluid flow and for controlling aerodynamics.
  • said lofted structure comprises enclosed volumes which may either be rigid or mechanically persistent bodies enclosing an evacuated space or alternatively filled or inflated with a lighter than air gas such as helium or hydrogen.
  • nanofabricated diamond sheeting of one micron thickness is reputedly sufficient to resist atmospheric pressure, such that relatively small total masses may enclose significant volume of evacuated space, providing buoyant lift in the atmosphere (although greater thicknesses may certainly be used.)
  • high strength sheeting such as graphene sheeting may be stretched across a rigid frame (more preferably of steel or of tungsten or of titanium or an alloy or most preferably of diamond or b-silicon- carbide construction) to yield and enclosed space which is evacuated;
  • balloon filled with lighter than air gas may be used.
  • the foregoing type structure featuring droplets entrained in a gas flow resembles industrial contactor devices for capturing components of a gas stream via interfacial transport from gas to liquid phase across the large aggregate surface area summed over the number of droplets, and this fact is a particular reason for interest in this class of device, i.e. if appropriate aerosol composition is chosen, carbon dioxide or other pollutants may be captured in tandem with electricity generation with only modest additional cost or effort.
  • hydroxide electrolytes e.g. sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide
  • solutes comprising amines especially at high pH are among those liquids or solutions capable of capturing C0 2 .
  • aerosols of sorbent materials such as amine-based liquid sorbents may be generated in tandem with charged aerosols, or may themselves be charged as in Marks' original methods.
  • the application of functionally similar to this type to the capture of C0 2 from the atmosphere, in particular using NaOH and CaOH droplets, but falling under gravitation were studied and developed by J.K.
  • said lofted structure is of a design similar to flying-wing aircraft but more preferably featuring larger than
  • Choice of altitude is determined by factors most desired to be optimized: for instance, reduced loss of water to evaporation will occur at lower temperatures and higher altitudes, while capture of C0 2 from the atmosphere will probably be greater at greater temperatures where water is liquid, and altitudinal wind velocity distributions vary both geographically and temporally; preferably, altitudes of lofted generators and/or capture devices may be adjusted
  • two or more lofted bodies may be secured by one or more common tethers, cables or umbilicals, and held a different altitudes and operated to optimize a different result (e.g. by modifying one or more operating parameter, preferably under automated [e.g. computer] control.)
  • a further improvement possible with the foregoing system presenting substantial surface area at high altitude relates to the fact that one major limitation of photovoltaic electricity generation is scattering and attenuation of solar radiation by clouds.
  • the foregoing lofted systems are expected to frequently be deployed at altitudes greater than those of typical cloud-cover, and so constitute convenient platforms for the deployment of photovoltaic devices above typical cloud-cover levels for increasing duration of photovoltaic electricity generation.
  • the photovoltaic devices are mounted on solar tracking means atop said lofted system and more preferably in this case, ailerons are provided on the bottom surface of said lofted system and operated to compensate for aerodynamic forces arising from the positioning of said solar tracking means.
  • the foregoing systems may be housed in an outer shell at least the top surface of which is transparent to solar radiation, and photovoltaic devices are mounted on solar tracking means housed inside the outer shell such that solar tracking does not lead to forces due to aerodynamic forces from wind on surfaces not aligned with the direction of wind flow.
  • said photovoltaic devices are lightweight; most preferably, said photovoltaic devices comprise at least one of: graphenoid absorber moieties, a graphene electrode, an aluminum electrode, nanotubes, oligoacenes, nanostructured silicon.
  • reduced temperature at high altitude additionally favors the absorption of atmospheric methane by water droplets, and may cause the formation of clathrates.
  • Inclusion of tertiary amines may likewise favor methane absorption [ Fei 72 ] as well as reduce the freezing point of droplets, so collection of liquid from electrodes followed by degassing with collection of gas, warming to boil off methane with collection thereof or alternatively filtration of clathrates therefrom represent preferred embodiments of this aspect of the present invention, and addition of tertiary amines, e.g. Tetrabutylammonium, to solutions for atomization to droplets used in conversion of wind energy to electrical energy are further preferred.
  • tertiary amines e.g. Tetrabutylammonium
  • systems according to this class of embodiments of the present invention may comprise functions including the 16 combinations of: wind powered electricity generation, C0 2 capture, atmospheric methane capture, pollutant capture, solar energy conversion lofted above cloud-cover.
  • High altitude as used herein is defined as approximately 250m above ground level unless otherwise indicated.
  • This enables the performance of sequencing by synthesis on single molecules (similarly to the method as disclosed by E.M. Rabani, WO 96/27025 but with programmable positional control over individual molecules and reagents.)
  • a limitation of sequencing by synthesis has been either harsheness of deprotection chemistries or expense of reagenst.
  • triphosphate serves as a base for driving this reaction, in a manner that depended on correct base-paring of the incoming nucleotide triphosphate with the templating base.
  • this reaction instead turns the tightly bound water to a base well positionned to attack the protecting-group ester, explaining the behavior of T7 DNA polymerase with these modified nucleotides.
  • This situatiobn can be exploited to form a reagent that serves as a mild, sequence specific, enzymatic deprotection reagent as follows. 3' protected dNTPs of a single base moiety are linked (e.g.
  • T7 DNA Polymerase may be immobilized to a mannipulator by BIOTRYX (via thioredoxin linked to biotin-streptavidin), and a primer is likewise tethered to a manipulator, preferably comprising a force sensor (e.g.
  • a moleucular cantilever that closes as a break-junction switch, combined with a single-electron transister, for electrical detection).
  • Such an elongation complex is contacted with different regions bearing each 3' protected dNTPs and when force is detected (e.g. as en electric signal) as the primed complex is withdrawn, base addition is detected and the identity of the base at the contacted region is recorded.
  • a manipulator to which non-hydrolyzable deoxynucleotide triphosphates (which may similarly be segregated to detect the identity of the next templating base— matching when the elongation complex is released from the previously added 3' protected dNTP, and the cycle is repeated.
  • an embodiment of the methods, means and systems of the present iinvention enables an efficient method for polynucleotide sequence
  • each tool or reactant or intermediate or workpiece is situated on a separate body, structural member, or carrier.
  • a clean, flat hydrogenated Si(100):2xl surface under UHV is specifically dehydrogenated using an opposed STM at specific sites for anthracene
  • This vapor is removed or flushed out with argon, and a vapor of sodium acetylide is introduced for a time sufficient for reaction with chemisorbed 9-chloro-9,10- dihydro-Anthracene to yield ethyne functionalization thereof.
  • a clean, flat hydrogenated Si(100):2xl surface under UHV is specifically dehydrogenated using an opposed STM at specific sites for anthracene
  • Example III Supported base regeneration tool nanofabrication:
  • a clean, flat hydrogenated Si(100):2xl surface under UHV is specifically dehydrogenated using an opposed STM at specific sites for anthracene
  • a clean, flat hydrogenated C a ( l l l) surface is briefly subjected to plasma etching with hydrogen plasma for a period sufficient only for a small fraction (e.g. 1%) of surface hydrogens to be abstracted (yielding H 2 molecules and tertiary surface radicals.)
  • Plasma is cleared, and the surface is exposed to I 2(9) to yield an unstable surface iodination (other halogens, e.g. Br 2 , Cl 2 , F 2 , may be used when lower reactivity is preferred, or, in the case of F 2 , to yield a
  • Example IVb C dia (lll) Supported ethyne/ethide tool fabrication:
  • Example IVa The product from Example IVa is contacted with a dilute solution of sodium acetylide (NaCCH, or other metal acetilide, including e.g. LiCCLi) preferably in a polar solvent such as dioxane or methyl ether to facilitate halide bond- dissociation and S N 1 reaction.
  • NaCCH sodium acetylide
  • LiCCLi metal acetilide
  • the product from Example IVa is contacted with a dilute solution of sodium amide or ammonia base, preferably in a polar solvent such as dioxane or methyl ether to facilitate halide bond-dissociation and S N 1 reaction.
  • a polar solvent such as dioxane or methyl ether
  • the product from Example IVa is contacted with a solution of an aliphatic ester of glycine, such as the glycine methyl ester preferably in the presence of a hindered base such as triisopropyl amine, preferably in a polar solvent such as dioxane or methyl ether to facilitate halide bond-dissociation and S N 1 reaction.
  • a nucleophile such as sodium hydroxide (e.g. at pH 9) to hydrolyze the ester to yield a surface bound carboxylate.
  • Example VII C dia (lll) Supported metal ligand complex tool fabrication:
  • Example VI The product from Example VI is contacted with a solution of Cu(l)CI in a polar solvent for a sufficient time for binding Cu(l) to surface-linked carboxylate, rinsed and then contacted with a disproportionation solution comprising
  • Cu(l)Acetate and Cu(ll)Acetate rinsed and then contacted with a solution of Cu(ll)Acetate.
  • Most surface carboxylates should be involved in Cu(ll)Acetate complexes (R-A/-Glycinate(Cu(ll) 2 Acetate 3 ,) useful as an oxidation tool.
  • Example Villa C dia (lll) Supported ethynyl radical tool fabrication:
  • Example IVb A product from Example IVb prepared using sodium acetylide is contacted with a solution of Cu(l)Acetate, Cu(ll)Acetate, and an amine base analogous to [CN63] but omitting any dissolved ethynylic species, to yield the oxidized surface-bound ethynyl radical.
  • copper amide species are generated via disproportionation of Cu(l) to Cu(0) and Cu(ll) with the binding of the neutral metal to nitrogen reducing the barrier to deprotonation of nitrogen, e.g. by other amines or ammonia or hydroxyls arising from disproportionation of water.
  • nanopositioned supports and preforming the foregoing reaction under positional control which is made straightforward by the methods and means of the present invention.
  • Example Vlllb C dia (lll) Supported ethide tool nanofabrication:
  • a product from Example IVb prepared using sodium acetylide is mounted in an opposed STM on a first surface.
  • a product from Example V prepared using sodium amide at higher concentration is mounted on a second surface opposed to said first surface, and the relative positions of modification sites are
  • a solution of Cu(l)Acetate is optionally added as a catalyst.
  • Amine/amide modification sites are contacted to ethyne modification sites to permit deprotonation of ethyne modifications to yield ethide modifications. If Cu(l)Acetate was used, extensive rinsing of samples is done, including ammonia to remove copper.
  • a product from Example VII is mounted in an opposed STM on a first surface.
  • a product from Example VI 11 b is mounted on a second surface opposed to said first surface, and the relative positions of modification sites are determined. (R- A/-Glycinate(Cu(ll) 2 Acetate 3 ,) modification sites are contacted to ethide
  • Example VI I Id C d ia ( 111) Supported ethynyl radical tool nanofabrication:
  • a product from Example VII is mounted in an opposed STM on a first surface, and the relative positions of modification sites are determined.
  • direct electrooxidation is performed using the STM tip, at a positive bias, preferably above +2V or at leased pulsed to such a bias, whereby ethide modifications or a predetermined fraction and spatial distribution thereof are oxidized to ethyne radical modifications, useful as hydrogen abstraction tools and halogen abstraction tools.
  • Example IX C dia (l ll) Supported ligand tool nanofabrication:
  • a clean, flat hydrogenated C dia (lll) surface is mounted in an opposed STM on a first surface.
  • a product from Example VI I lc or Example VI I Id is mounted on a second surface opposed to said first surface, and the relative positions of modification sites are determined. Pairs of adjacent C dia (lll) hydrogens are abstracted, in patterns suitable for forming all-trans-all-s-trans-polyene omega binding ligands for binding polyenes of desired length, most preferably in most extended conformation, drawn taught by ligands.
  • the sample is removed to a different chamber away from ethyne radicals, and the surface comprising dehydrogentated sites (surface radicals) is exposed to I 2 ⁇ 9) to yield an unstable surface iodination (other halogens, e.g. Br 2 , Cl 2 , may be used when lower reactivity is preferred.)
  • Gas is flushed with inert gas, e.g. Argon, and then the sample is contacted with (NH 2 ) 3 AIBr vapor or a solution thereof, preferably in a polar solvent such as dioxane or methyl ether to facilitate halide bond- dissociation and S N 1 reaction, to form R(NH 2 )AIBr(NH 2 ).
  • amines are further deprotonated, e.g. using a base tool as from Example V is used similar to use in Example VII lc to remove protons from nitrogens to yield R(NH)AIBr(NH).
  • Example X C dia (l ll) Supported polyene addition tool:
  • a product from Example IX is contacted with a solution or vapor of all-trans- Li(CH) n U. Solvent, if any is removed, and the sample is thermally annealed to facilitate trapping of the desired ligand relative configuration (aluminum atoms in closest possible configuration) and also taught spanning of ligands by the polyene transmetalating thereonto. Multiple thermal annealing .cycles may be performed to ensure displacement and migration of Li Br away from loaded tool.
  • Example XI C dia (110) preparation for polyene addition:
  • a clean, flat hydrogenated C dia (110) surface is mounted in an opposed STM on a first surface, with the 110 crystallographic axis of the C dia (110) in
  • oxidized modification sites i.e. ethynyl radicals useful for hydrogen abstraction
  • hydrogens are abstracted by contacting an unused ethynyl radical therewith, recording the usage of the ethynyl radical used so it is not attempted to reuse same without regeneration thereof, and repeating the foregoing for other hydrogens at said location, and, according to the precise reaction mechanism desired, optionally also abstracting target atom adjacent hydrogens (see Fig. 6A and Fig. 6B for two important alternatives) by performing similar steps therefor.
  • a product from Example XI mounted in an opposed STM on a first surface, with the crystallographic axis of the C dia (110) in predetermined orientation is translated into facing juxtaposition with a product from Example X mounted in predetermined. orientation on a second surface opposed to said first surface such that the long axis of the polyene thereon is parallel to the 110 axis of said product from Example XI. If they are not already known, position of loaded polyene binding tool mounted on said second surface is first determined and necessary trajectory for positioning said polyene binding tool relative to dehydrogenated target site is computed.
  • Said loaded polyene binding tool is translated into facing juxtaposition with said target site and advanced thereto and contacted therewith, as necessary pressure is applied to drive polyene carbons to form bonds with surface target atoms; pressures applied may exceed lOGPa but preferably are more than at least lOOMPa (due to the small contact areas involved, these represent only modest forces.)
  • Opposed surfaces are then withdrawn from eachother, breaking metal-carbon atoms and leaving polyene adducted to surface target atoms as a saturated, hydrogenated row (see Fig. 6E for a series of images of AMI predicted optimal structures of a reaction like the foregoing but with a nitrogen substitued polyene to yield a product substituted by nitrogen at a predetermined site).
  • the foregoing may be repeated at adjacent rows or other desired sites to fabricate up bulk diamondoid materials or diamond nanostructures.
  • Example XI la Diamond color center fabrication, fabrication of component devices for quantum computation and information storage:
  • Color centers comprise an atomic substitution (e.g. nitrogen substituting for a carbon atom) adjacent to an atomic vacancy. Desirable color centers may additionally comprise isotopic carbon substitution (e.g. 13 C) at positions near or adjacent to vacancies or atomic substitutions, whereby nuclear spin may be coupled to electron spin.
  • atomic substitution e.g. nitrogen substituting for a carbon atom
  • Desirable color centers may additionally comprise isotopic carbon substitution (e.g. 13 C) at positions near or adjacent to vacancies or atomic substitutions, whereby nuclear spin may be coupled to electron spin.
  • Such features may be fabricated at precisely desired positions in a nanostructure or bulk material, e.g. in predetermined patterns, as in Example XI but using atomically substituted polyene.
  • Sub-stitution may be internal or terminal. In a convenient case, substitution is terminal, e.g.
  • N- substitution (1-aza-polyene or 1-imene-polyene) and a second polyene is similarly added along the same 110 trough colinear to the substituted polyene but displaced by one carbon atom to leave the desired vacancy. Further polyenes are similarly added to surround the substitution and vacancy. Where isotopic substitution is desired, polyene reactants must be provided with corresponding position substituted with the desired isotope. Although various schemes for heterofunctional terminally modified polyenes with isotopic substitution at a non-central position may accomplish this, especially using heterometallic metal ligands complex pairs for binding thereof in a binding tool, most target structures and device designs could either tolerate additional isotopic substitutions more than about 600pm away from that most strongly coupled to a color center.
  • Example XI lb Diamond color center fabrication, fabrication of component devices for quantum computation and information storage, from non-colinearly placed precursors:
  • Similar structures as those fabricated in Example XI la may be fabricated again through polyene addition but forming a vacancies between colinear polyene adducts along a 110 trough by shifting addition by one atom to leave a gap and adding a second, atomically substituted polyene with the substituted atom adjacent to the vacancy; alternatively, said atomically substituted polyene may be deposited first and polyenes for forming a gap may be deposited with terminal carbons thereof targeting carbon atoms of said atomically substituted polyene adjacent to the substituted atom and leaving a vacancy or gap where there would otherwise be an atom bonded to the substituted atom in bulk diamond.
  • Example Xllc Diamond color center fabrication, fabrication of component devices for quantum computation and information storage:
  • color centers may be fabricated from one or more subtituted cumulene deposited as in embodiments of [Rab08] or similarly from carbon dimers and substituted carbon dimers as in [Rab08], with the additional reactant of 13 C monosubtituted carbon dimers being useful in the later case where isotopic substitution is also desired.
  • Example XIII Loaded polyene addition tool from a,w-dihalo-n-alkyl
  • a a,w-dihalo-n-alkyl compound is treated with an alkaline or alkaline earth metal (e.g. Li, Mg, etc.,) to form a terminally dimetallated intermediate.
  • an alkaline or alkaline earth metal e.g. Li, Mg, etc.
  • This is contacted (either as vapor or in solution) with the product of Example IX or an analogous binding tool bound to a structural support positioned by positioning means to become bound thereto via transmetallation.
  • thermal annealing or rinsing or flowing of a gas stream is performed to displace any Alkaline halide salt which remains bound.
  • Hydrogen abstraction tools such as prepared in Example VII Id are used in similar to use in Example XI but to abstract hydrogens from the supported-ligand-bound n-alkyl chain, preferably from pairs of adjacent carbon atoms starting either with a terminal carbon or a carbon adjacent thereto in the alkyl chain, such that, in the preferred case of paired abstraction steps from adjacent carbons double bonds are formed upon intersystem crossing. Note, however, that abstraction could instead be done on alternating carbon atoms or in arbitrary order, probably without ill effects, although care should be taken to avoid contact between an active abstraction tool and a radical site or unsaturated site to avoid undesired bond formation through radical attack.
  • a loaded tool as prepared in Example XIII comprising metals of a first type, e.g. Magnesium, may be facingly juxtaposed to a similar unloaded tool prepared in Example IX having metals of a second type, e.g. Aluminum, capable of causing transmetallation thereonto of the reactant loaded in Example XIII now
  • a first type e.g. Magnesium
  • a second type e.g. Aluminum
  • one binding tool may be used to prepare and transport reactants or precursors thereof and transfer reactants so transported to binding and deposition tools at a site of use in deposition operations.
  • Example XIV Convergent synthesis or polyaromatic compounds: Parylene vapor is heated to dissociation to p-xylylene in the presence of a nanopositioned support-bound V(lll)catecholate complex or Cr(ll)catecolate complex. A boron radical situated on a said nanopositioned support located to face one of the xylylene double bonds to associate therewith, whereby said xylylene is bound in a definite orientation in a heterobinuclear complex, whereby positions of methene hydrogens of said xylylene are held in a fixed and
  • a first abstraction tool e.g. an ethynyl radical (e.g. as prepared in Example VII Id) is used to abstract a hydrogen from the position on xylylene ortho to the methene not bound by boron.
  • a second abstraction tool e.g. as prepared in Example VI I Id is used to abstract a hydrogen from the methene not bound by boron.
  • the foregoing is performed with an additional set of ligands and tools on a second p-xylylene molecules, preferably in tandem with the foregoing.
  • Structural members supporting ligands are translated by nanopositioning means causing radical sites to be contacted to form bonds yielding a product comprising a newly formed aromatic ring, as shown in FIG.
  • Example XV Graphenoid addition to diamondoid:
  • a hydrogenated Cdia(lll) surface of a sample is subjected to H-abstraction at desired sites using nanopositioned ethyne radical tools and ethyne modification as in preceding examples to yield ethyne modifications at sites where linkage to graphenoid members is desired.
  • Graphenoid members are modified with ethyne groups at sites to which linkage to diamondoid member is desired.
  • Graphenoid members are manipulated by nanopositioned V(lll)Catecholate cation facially bound, e.g. as in FIG. 8F and translated such that ethynes desired to react together to form diacetylene linkages are held in close proximity.
  • bilayer structures may be fabricated.
  • bilayers may be crosslinked, e.g. as shown in FIG 6K, e.g. by abstracting selected hydrogens and contacting with a crosslinking reagent comprising at least two unsaturations.
  • Example XVI Graphene supported catecholate ligand assembly:
  • 4-methyl-Catechol is used as a reactant in the fabrication of graphene to yield 1,2-dihydroxyl substitution at a desired edge location.
  • 4-methyl- Catecholate may be bound as a ligand to a nanopositioned AI(lll)Caetechol in a dicatecholate complex, or to one of the supported Al(lll) complexes shown in FIGS. 7D or 6J operatively coupled to nanopositioning means.
  • the reactant is additionally bound facially by a nanopositioned V(lll)Caetechol, e.g. similarly to FIG. 8E.
  • Hydrogen is abstracted from position 5 and from the methyl group, and this reactant is reacted with another reactant comprising one or more aromatic rings and preferably also one or more exocyclic methenes from which hydrogens have been abstracted, e.g. as in FIG. 8E.
  • Another reactant comprising one or more aromatic rings and preferably also one or more exocyclic methenes from which hydrogens have been abstracted, e.g. as in FIG. 8E.
  • functionalized aromatic compound is then preferably modified to comprise two or more ethyne functionalities along an edge and linked as in Example XV to a C dia ( l l l) surface to yield a supported and stably oriented ligand useful, e.g. for binding metals for binding aromatic rings for causing convergent fabrication of graphenoid materials as taught herein.
  • Example XVI I C dia ( l l l) supported Graphene actuators:
  • C dia ( l l l) is linked to graphenoid members as in Example XV, said graphenoid members for serving as wires and electrodes for comb-type actuators as depicted in FIG. 9A.
  • Electrical contacts analogous to vias of conventional circuits may be formed between graphenoid ribbons by diacetylene or acetylene linkages.
  • Diamondoid supported graphenoid actuator members are manipulated as taught in [Rab08] and facingly juxtaposed with graphenoid members interdigitated as shown; alternatively, manipulation may be via the
  • the device thus formed may be charged to facilitate release of one actuation member from the manipulator, yielding a device as shown in FIG. 9D.
  • Example XVI I C dia ( l l l) actuator supported Graphene supported ligand:
  • One or more graphenoid members of Example XVI is prepared from reactants comprising catecholate reactants as in Example XVI, fabricated to bear oxygens at a desired pre-determined site thereon, is used as a graphenoid member as in Example XV to form an actuator as in Example XVII for nanopositioning the supported catecholate ligand thus created.
  • Example XVIII C dia (lll) actuator supported Graphene supported ligand metal complex:
  • Example XVII A product obrtained in Example XVII is contacted with a solution comprising a metal cation such as V(lll) solvated with dioxane, forming a catecholate-type ligand-metal complex therewith.
  • a metal cation such as V(lll) solvated with dioxane
  • the obtained complex is useful for binding to aromatic species, manipulating same and modifiying the reactivity of same, and also performing reactions and fabrication and assembly operations as taught herein.
  • X is a halide
  • X is treated with an alkaline metal to yield a,w- metalated intermediate, and then caused to bind (as in ) to a tool as prepared in Example IX and dehydrogenated to yield the conjugated polycarbosilene analogous to a polyene as done for n-alkyl precursors in Example XIII.
  • a target site on a hydrogenated ( 110) surface of a b-Silicon-Carbide body is prepared by hydrogen abstraction as done for C dia (110) in Example XI.
  • the tool-bound conjugated polycarbosilene is used to add the unsaturated fragment loaded thereon to said target site, as done for conjugated polyene deposition onto C dia ( HO) in Example XXII but accounting for differences in lattice constant.
  • a bare ( 110) surface of a b-Silicon-Carbide body may be used, particularly for smaller bodies less likely to undergo any long-range surface reconstructions.
  • Example XX b-Silicon-Carbide tools for carbon dimer and cumulene binding and deposition, hydrogen abstraction, oxidation, use therof, systems comprising, and operation of systems comprising same:
  • a b-Silicon-Carbide body is prepared according to Example XIX comprising a (100) face of Silicon atoms, e.g. as shown for fabrication of diamondoid
  • dehydrogenated (100)2x1 silicon dimers as in [Rab08], or binding sites for carbon dimers comprising two adjacent colinear silicon dimers comprising distal silicon atoms which bear hydrogen passivation and comprising proximal silicon atoms from which hydrogen is abstracted to form the desired binding site as in [Rab97] and [Rab08].
  • Such carbon dimer binding tools may additionally be used as tools for nanomanipulation as in [Rab97] and [Rab08].
  • Tools thus fabricated may be fabricated and/or assembled onto structural members in communication with nanopositioning means and used for carbon deposition operations, as in [Rab97] and [Rab08] and elsewhere herein.
  • two hydrogens are abstracted (e.g. by FCL as by [Lyd98] or using a hydrogen abstraction tool from an Example herein) from a single (100) silicon dimer on the at a site for forming this tool, and this site is contacted with 1,3-butadiyne (e.g. as vapor or bound to a binding tool or in solution) whereby a [2+2] cyclization product thereof (as found by )with the bare silicon dimer is obtained.
  • 1,3-butadiyne e.g. as vapor or bound to a binding tool or in solution
  • the projected ethyne which result is treated as in foregoing examples to yield an ethide (base) or ethynyl radical and used as in foregoing examples.
  • Ethides so formed may be used as nucleophilic attachment sites for linking other molecules or chemical functionalities to predetermined sites on b-Silicon-Carbide bodies, including haloalkylcarboxylic acids such as 2- bromoacetic acid or 3-bromopropionic acid, serving as ligands especially for participating in Cu 2 Ac 4 complexes especially for use as an oxidation reagent, or ethide may be reacted with haloamines such as CINH 2 or azaalkylhalides such as 3-chloro-azacyclopentane for forming nitrogen containing tools which may be treaded with NaNH 2 to form amide base tools, for example.
  • haloalkylcarboxylic acids such as 2- bromoacetic acid or 3-bromopropionic acid
  • ethide may be reacted with haloamines such as CINH 2 or azaalkylhalides such as 3-chloro-azacyclopentane for forming nitrogen containing tools which
  • b-Silicon-Carbide bodies fabricated as in Example XIX may be fabricated using polycarbosilene precursors comprising atomic substitutions (e.g. B, N, P) for effecting doping, whereby semiconductivity may be imparted in a precisely positionally controlled manner for forming conductive paths and switching devices such as transistors and whereby members may be used for electrooxidation, e.g. of tools or of bound reactants or of workpieces.
  • comb-type actuators may be similarly fabricated and assembled, including with tools of the present Example situated at precise locations thereon.
  • switching means may be combined as in prior art to form programmable computational means having program and information storage means, which in turn may control switching means controlling actuators and nanopositioning means for nanomanipulation and positional mechanosynthesis, current flow to electrodes for electrooxidation and electroreduction.
  • switching means controlling actuators and nanopositioning means for nanomanipulation and positional mechanosynthesis, current flow to electrodes for electrooxidation and electroreduction.
  • tools for performing all of the necessary mechanosynthesis operations for positional mechanosynthesis of diamondoid materials are prepared on one or more b-Silicon-Carbide bodies, which additionally are adapted for use as nanopositioning means and control means.
  • fabrication and assembly systems capable of producing systems capable of performing fabrication and assembly are enabled, including for the fabrication of two or more distinct material compositions, thus enabling self-or al lo-repl icating systems capable of fabrication and assembly with atomic precision.
  • nanofabrication and/or nanoassembly including by the convergent methods taught herein, said means preferably being fabricated and assembled by systems of the present example, enables fabrication and assembly of such systems from stored precursors or raw materials occurring in the environment.
  • Geometric increase in number of such systems producing similarly capable system enables the construction of systems for performing a variety of useful functions, said systems having overall dimensions ranging from below one micron to exceeding 1000km (and in the case of graphenoid space elevator cables fully extended, exceeding 10,000km or even 30,000 or 36,000km) and having areas up to or exceeding 1,000,000 km 2 , such as for capturing and converting solar energy, converting wave energy (e.g. via pistons as shown herein or by other devices fabricated by methods and means of the present invention) and/or wind energy (especially high altitude wind energy as taught herein,) growing crops or algea, providing potable water, constructing dwellings and architectural constructions, and capturing and converting pollutants including C0 2 . Given that actuator velocities may exceed lOOm/s and
  • said means for retrieving manganese or polymetallic nodules comprises a cable or umbilical or conveyor belt or conveyor chain of length greater than 1000m, and more preferably greater than 6000m.
  • said means for retrieving manganese or polymetallic nodules comprises a grasping means for grasping manganese or polymetallic nodules and more preferably means for recognizing nodules operatively coupled to said grasping means.
  • said means for recognizing nodules comprises sensing means selected from: sound imaging or sonar, tactile sensing, whiskers for tactile profiling, metal detector means.
  • said means for retrieving nodules comprise graphenoid articles, and more preferably comprise a graphene cable, rope, belt or chain.
  • a vast array of simple structures may be fabricated and assembled according to the present invention, including a very large subset of known devices and systems established in a wide range of useful arts; these may be combined into supersystems comprable in complexity to conventional chemical processing plants or the like.
  • a system such as that of Example XXI or Example XX may comprise structures serving as flotation means may be fabricated via methods and means of the present invention and combined with any combination of the foregoing to enable the facile construction of ocean or aquatic based facilities for energy conversion, materials processing, pollutant capture and conversion, water purification (e.g.
  • aquaculture, mariculture, agriculture, hydroponic agriculture, and/or human habitation up to and including floating cities (which are thereby self-sufficient) which preferably may further comprise means of propulsion and may further include means for watertight enclosure to enable submersion, e.g. to avoid turbulent weather or conditions.
  • Methane clathrates may be collected mechanically e.g. by digger devices, or alternatively methane released by cold seeps or liberated by arctic lakes or melting tundra may be captured by sheets, e.g. graphene sheets, operatively coupled to collecting ducts and pumping means to obtain methane, especially methane which poses a danger of liberation to the atmosphere and potentially driving climate forcing.
  • Collecton may be accomplished by bubbling a gas stream which may contain methane to be captured through chilled liquid water under conditions suitable for methane clathrate formation to occur, with collection either by settling due to gravity or by filtration after sufficient time for crystals to grow, preferably in a continuous process. This may be converted to CO and H 2 via steam methane reforming, preferably in heated reactors
  • MgO walls which may optionally further be coated with protective surfaces such as silicon carbide (fabricated and assembled e.g. according to the present invention,) with suitable catalysts e.g. on reactor walls or provided as an aerosol in a fluid stream.
  • Heat to drive the desired reaction may be obtained either by solar concentrating means or, less preferably, by combustion of methane if no other heat source is convenient.
  • CO and H 2 yielded may be optionally separated and may further be combined to yield methanol.
  • Methanol may either be reacted with more CO to yield acetic acid directly or be
  • halogenated using hydroiodic acid contacted with metallic sodium and C0 2 to yield acetate.
  • two species which pose danger to the climate may be combined to yield a useful feedstock.
  • collected methane is boiled off, dehumidified, and utilized as a feedstock for cationic or metal catalyzed or Lewis-acid catalyzed reactions disclosed herein (e.g. as in Example XXIVc below) for production of esters, polyketones, polyenes, diamond, graphene, b-SiC, etc. more preferably with concurrent energetic yield, and most preferably combined with at least 1 mole-percent C0 2 in the foregoing process.
  • Atmospheric methane may be captured concurrent to C0 2 capture in a high altitude Marks generator with collection of deposited droplets as liquid followed by degassing, boiling off methane or filtering for clathrates. Methane thus captured may be used as in Example XXIII.
  • Acetate or acetic acid e.g. produced as in Example XXIII, is esterified to a hydroxyl, thiol, selenol or tellurol or other heteroatom situated on a
  • nanomanipulator e.g. a graphenoid structural member, preferably linked via one or more aliphatic carbons such as a methylene, in communication with
  • a base tool Under conditions suitable for aldol reactions or Claisen condensation, a base tool is contacted with a hydrogen of the alpha carbon of the acetyl group to yield a carbanion. Said carbanion is constacted with the carboxy carbon of another molecule esterified to a similar nanomanipulator, whereby said another molecule is displaced from said similar nanomanipulator and extended by two carbons.
  • a second hydrogen on the alpha carbon deprotonated and reacted previously is removed with a second base tool, and the protonated base may be contacted with the beta hydroxyl, whereby dehydration is facilitated.
  • conjugated polyenes of desired length under mechanical control, from acetic acid or acetate feedstocks, most preferably comprising carbon atoms arising from methane clathrates, cold seeps and/or carbon dioxide, most preferably collected from the environment.
  • Polyene species of desired length are synthesized according to Example XXIVa with the modification that said another molecule is an acetyl or an n-alkanoate with a hydrogen of the terminal methyl group removed (using a base tool) and bound by a metal held by a ligand situated on a structural support which preferably is under positional control by nanopositioning means. Operations are preferably conducted by positioning reactants/intermediates such that the product is all-trans, all s-transoid polyene, bound on one terminus by a
  • said ligand binding said metal bound to said terminal methyl is oriented relative to the polyene and in relation to the terminal ester such that the metal-carbon bond is like that of the surface bound polyenes of Figs. 5G-5I or Figs. 6A-I or obtained in Example XII.
  • a Lewis base or nucleophile e.g. a deprotonated thiol, deprotonated selenol, deprotonated tellurol, deprotonated hydroxyl
  • a Lewis Acid or electrophile e.g.
  • Zinc(ll) or Cadmium(ll) or Magnesium(ll) or other cation bound to a ligand comprising a deprotonated acetylacetonate ligand skeleton or an ethylene diamine ligand skeleton or a deprotonated ethylene diamine ligand skeleton, situated on a support or linked via a linker to a structural member.
  • a ligand comprising a deprotonated acetylacetonate ligand skeleton or an ethylene diamine ligand skeleton or a deprotonated ethylene diamine ligand skeleton, situated on a support or linked via a linker to a structural member.
  • a deprotonation tool and an electron withdrawing tool respectively.
  • said ligand skeleton is in communication with nanopositioning means.
  • Methane used is most preferably obtained from oceanic methane clathrates, permafrost methane clathrates, cold seeps, peat bogs or peat, or other environmental sources, whereby these may be prevented from release to the atmosphere.
  • a methane molecule binds either said Lewis Acid or nucleophile or said Lewis base or electrophile, forming a methane loaded tool, and if not yet present, the other of the foregoing not having methane bound thereto is translated into proximity with the methane loaded tool, such that said methane molecule is situated between said Lewis base or nucleophile and said Lewis base or nucleophile, with weak bonding to both; this may be accomplished either by direct translation using
  • nanopositioning means in communication with supports or structural members, or, for linker bound deprotonation tools and/or electron withdrawing tools, simply permitting (if it does not initially obtain) linker motion and passive diffusion to permit contact between the two types of tools and a bound methane molecule, although in this case linker length and location should be predefined to prevent direct bonding of these.
  • spectator ions e.g.
  • deprotonated carboxylates such as 2-Methyl-2-nitrile-propionate or more preferably a skeleton thereof bound to a support or nanopositioner
  • tertiary amines such as tetramethylamine or more preferably a skeleton thereof bound to a support or nanopositioner
  • methane is deprotonated and forms a bond with said electron withdrawing tool, e.g.
  • Two ligand-metal complexes each having a net formal charge of at least +1, (e.g. Zn(ll), each bound by a single acetylacetonate ligand skeleton, each ligand skeleton situated on independent nanopositioning means,) are situated such that the metal centers are about 300-600pm apart, with space empty therebetween in an enclosed vessel or volume, which is preferably evacuated.
  • At least one C0 2 molecule is admitted, whereupon oxygens bind to metals and is suspended therebetween.
  • C0 2 is C0 2 obtained from the environment or from industrial processes, most preferably from dissolved C0 2 or carbonate species from an ocean, whereby atmospheric buildup of C0 2 and also ocean acidification may be counteracted.
  • FIG. 17A shows such a complex as a reactant in the reaction of the following Example.
  • a tool loaded with a methyl carbanion obtained in Example XXIVe and the C0 2 containing complex obtained in Example XXIVd are translated relative to eachother to advance said methyl carbanion towards said C0 2 carbon,
  • One of the nanopositioning means in communication with one of the ligand- metal portions of said acetate containing complex in communication with nanopositioning means obtained in Example XXIVe is withrawn and replaced with a ligand-metal complex having a neutral formal charge (e.g. Mg(ll)catecholate or the corresponding ligand skeleton) in communication with independent
  • nanopositioning means preferably in concerted motions of the withdrawing and replacement complexes.
  • the resulting complex has a neutral formal charge.
  • an oxygen of the acetate molecule from which a metal ligand complex has been or is concurrently being withdrawn may be protonated (e.g. using an acid tool) to obtain an acetic acid containing complex having a formal positive charge.
  • a metal ion in either a neutral or positively charged metal ligand complex situated on nanopositioning means is contacted with the protonated acetic acid oxygen, whereby an acetic acid containing complex bearing a hydroxyl activated as a leaving group is obtained.
  • a deprotonation tool situated on nanopositioning means is advanced towards hydrogens of the alpha carbon of the acetate in the complex obtained in
  • Example XXIVf to obtain the deprotonated alpha carbanion in a resulting alpha- carbanionic acetate containing complex with a formal charge of -1 situated between two nanopositioning means.
  • the alpha-carbanionic acetate containing complex situated between two nanopositioning means obtained in Example XXIVg and the activated acetic acid containing complex suspended between two nanopositioning means, preferably of type bearing a hydroxyl activated as a leaving group, obtained in Example XXIVe are relatively translated towards eachother such that the carbanionic carbon in the complex from Example XXIVg contacts and is able to form a bond with the carbonyl carbon in the acetic acid containing complex bearing a hydroxyl activated as a leaving group from Example XXIVe.
  • a nanopositioner-ligand-metal-hydroxide is withdrawn.
  • the oxygen deriving from the carbonyl to which the carbanion bonded is bound by a neutral metal-ligand, which is more easily withdrawn after this reaction.
  • a metal cation e.g. bound by a further ligand in communication with nanopositioning means
  • the product is a beta-keto four carbon carboxylate species including a terminal methyl which is alpha to a carbonyl (i.e. an alpha carbon.)
  • a product complex from Examples XXIVe-h may be deprotonated at terminal methyl groups alpha to carbonyls using an base tool to yield a terminal carbanion.
  • a product complex from Examples XXIVe-h may be protonated at a carboxyl oxygen using an acid tool to yield a highly activated electrophilic carboxyl as in Example XXIVf. As in the preceding examples, these are relatively translated to advance said carbanion to said electrophilic carboxyl to form a bond therebetween.
  • Complexes comprising polyketides, most preferably but not necessarily linear polyketides may be so obtained.
  • a first complex comprising a polyketide obtained in Example XXIVi is activated or deprotonated and added to a second complex comprising a polyketide obtained in Example XXIVi (which may have the same or a different structure or length as said first complex of this Example) or instead a complex from Examples XXIVe-g which has been deprotonated at an alpha carbon by a nanpositioned base tool, by advancing the carbanion and activated carbonyl towards eachother, to yield larger polyketide products of predetermined defined structure.
  • Example XXIVj Repetitive cycles of Example XXIVj are performed, preferably in convergent fashion and most preferably in maximally convergent fashion in analogy to Fig. 11. to yield extended polyketide products, most preferably linear polyketides for dehydration to linear polyenes of predetermined length suspended between nanopositioning means and added to specifically dehydrogenated or bare diamond 110 surface or specifically dehydrogenated or bare Si:SiC[3C](110) target sites.
  • Examples XXIVj-k and any incorporated preceding examples are performed with at least one reactant in at least one reaction comprising an atomic substitution or functional group substituent (e.g. using preformed precursors obtained through conventional synthesis) to obtain extended polyketide products featuring atomic substitutions or functional group substituents of predetermined desired type at predetermined locations, e.g. in predetermined sequence for linear products, most preferably linear polyketides featuring atomic substitutions or functional group substituents in predetermined sequence, which may further be subjected dehydration to linear polyenes of predetermined length suspended between nanopositioning means and added to specifically dehydrogenated or bare diamond 110 surface or specifically dehydrogenated or bare Si:SiC[3C](110) target sites.
  • an atomic substitution or functional group substituent e.g. using preformed precursors obtained through conventional synthesis
  • Polyketides obtained in the foregoing examples are dehydrated as follows: a hydrogen atom from LiiHi bound to a ligand skeleton such as dimethylpyrazine or 1,4-dioxane, or other hydrogen containing recuction tools in communication with nanopositioning means, is contacted to a carbonyl which is beta to a second carbonyl has a cation bound oxygen at the position of the polyketide to be dehydrated, to form a secondary oxide (R 1 C(0)CH 2 C(0 M + L k )R 2 ).
  • One or two additional cations, preferably metals in positively charged ligand-metal complexes positioned by nanopositioning means are contacted to the oxide oxygen atom, and a base tool (e.g.
  • a deprotonated ethynyne base tool e.g. from a tool comprising a phenylacetylene skeleton deprotonated as in [Rab07,Rab08] positioned via nanopositioning means
  • a hydrogen atom between the carbonyl being dehydrated and the carbonyl at the respective beta position.
  • polyketides suspended drawn tight between two independent nanopositioning means most preferably, ligand-bound metals bind with ligand skeletons oriented such that metal bonds are directed to properly constrain and orient polyenes suspended therebetween in a defined orientation (constrained e.g. as if the metal atoms continue the linear all-s-transoid-all-trans pattern), to yield a linear all-s-transoid-all-trans polyene, which is useful for addition to specifically dehydrogenated or bare diamond 110 surface or specifically dehydrogenated or bare Si:SiC[3C](110) target sites as disclosed herein.
  • Deprotonated metal-bound methyl group from Example XXIVc (e.g. CH 3 Zn +2 L 2 ) is contacted with a sulfur atom of a dithiol (each sulfur atom of which is preferably covalently bound to a separate nanopositioner whereby each may be controllably positioned, and preferably the sulfur atom distal from said methyl group is either protonated or in contact with a cation such as an ionized metal, e.g. especially Zn +2 L _1 or polarized by a positive electrical field whereby
  • nucleophilic attack on the disulfide is promoted) most preferably as shown in Figs. 19A and 19E.
  • a methyl ether is formed and the dithiol is reduced, directly or indirectly yielding a thiol or thiolate.
  • Sulfur containing products may be recycled to the dithiol as shown in Fig. 19D with liberation of molecular hydrogen .
  • Example XXIVb,m or n suspended between two positioning means with ligands directed as in and drawn tight, is abutted with a hard tool surface such as a diamond tool surface. This is then positioned relative to a target site and pressed against a bare, partially dehydrogenated or stepped diamond 110 surface analogous to any Example XII. See, for example, FIGS. 5G-5I, and also FIGS. 5E-5F for obtaining this from carbon dimer precursors.
  • said tool surface is of a width exactly matching the length of said polyene, with said polyene positioned across the width of said tool surface with said ester and said metal extending past the edges of said surface, such that only the polyene and not the ester or the metal are pressed onto the workpiece; most preferably, said polyene is of a length exactly matching that of the workpiece surface along the trough over which addition is done, plus or minus any terminal carbons in the row thus added which are required in the desired product or succeeding intermediate structure— fabrication of a
  • Pandey chains correspond to entire rows of Pandey chains, including with predetermined sequences of atomic substitutions (e.g. B, N, P, etc.) or, for desired positions of precursors ultimately resulting in surface regions, functional substituents (e.g. hydroxyls, thiols, selenols, tel lurols, methyls, boranyls, phenylenes, ethynes, nitriles, amines, phosphines, carboxyls, etc.) including pluralities thereof which may further be form fused ring systems comprising a segment of the polyene chain to be added over a 110 trough (e.g.
  • acetylacetonate fused via three alternating polyene carbons most preferably with addition to a partially dehydrogenated surface with surface atoms near functional groups remaining passivated to prevent unwanted reactions with functional groups during addition (see, for example, FIGS. 6M-6N and FIG. 7 A for examples of additions of polyenes having atomic and functional substitutions which may or may not include fused rings, but note that in this Example polyenes to be added are suspended between positioning means.) Note that alteratively polyenes may be suspended between fixed arms or structural members serving as suspension means, rather than two independent positioning means.
  • ligand- bound metals bind polyene to be added, with metal bonds directed to properly orient polyenes suspended therebetween in a defined orientation (constrained to be the case e.g. as if the metal atoms continue the linear all-s-transoid-all-trans pattern, and the chain abuts said counterpressure surface,) and the distance between metal atoms is such that polyene suspended therebetween is drawn tight to avoid rotations deviating from planar all-s-transoid-all-trans
  • the wind energy conversion subsystem adapted for concurrent C0 2 capture illustrated in FIGS 10B-C is fabricated featuring skin which may comprise one or more of diamondoid, graphene, graphite, C 3 B, hexagonal-BN, TiC, ScN, VN, b-SiC, polyketides, polyenes, polyphenylene, TaC, HfC, Hf x Ta y C, aluminum, or steel .
  • the subsystem preferably comprises one or more evacuated (or at least enclosing a reduced pressure and/or density gas), cellular, membrane-bounded structure, with interpenetrateing channels or interstices exposed to atmospheric pressure for providing buoyancy and serving as lofting means or lighter-than air
  • said membrane preferably being supported by an internal skelleton or structural framework to prevent collapse against atmospheric pressure, said membrane being of diamondoid, TiC, ScN, VN, b-SiC, or most preferably graphenoid material, and said internal skelleton or structural framework being of MgO, W, TiC, ScN, VN, b-SiC, diamond, diamondoid, graphene, graphite, carbon nanotubes, polyketides, polyenes, polyphenylene, TaC, HfC, Hf x Ta y C, aluminum, steel, of sufficient thickness to support said membrane across areas exposed to atmospheric pressure.
  • said cellular structure comprises linear rods composed of edge-sharing regular tetrahedra (where shared edges balance stresses on edge framework structures, said tetrahedra having
  • the reaction depicted in Fig 25A-C herein, as described above, shows the convergent assembly of (fragments representing dimethyl functionalized tertiary carbons, in anti- positions, of diamantane cages) intermediates themselves formed by reaction of precisely dehydrogenated butadiene moieties to 1,4- dimethylenyl-cyclohexenyl moieties themselves dehydrogenated and reacted to form precisely functionalized diamantane species, suitable for further
  • impossible devices such as strong, thermally conducting negative index of refraction devices featuring also, for example, fluorescence or phosphorescence.
  • Silicate containing materials e.g. sand, clays or other minerals
  • digger means especially e.g. a robot comprising digger means and a storage compartment for transporting collected material
  • filtration from a fluid stream in which they are entrained These are transported to an enclosed vessel wherein they are deposited and held by constraining features on a surface and optionally impacted by hard tools (e.g. diamond, titanium carbide or b-SiC, or chitin containing structures, blades or indentation tools or alternatively such features situated on millstone or grinding apparata to at least create cracks in said material whereby surface area is increased).
  • hard tools e.g. diamond, titanium carbide or b-SiC, or chitin containing structures, blades or indentation tools or alternatively such features situated on millstone or grinding apparata to at least create cracks in said material whereby surface area is increased.
  • Said material is then contacted by a plurality of slicate binding tools which may comprise phosphate groups, sulfate groups, hydroxyl groups, deprotonated hydroxyl groups, thiolate groups, thiols, sulfur anions or oxygen anions such as oxygen anions bound to metal atoms in ligand-metal based binding tools (e.g. a water molecule is bound to a monocationic zinc-ethylene-diamine complex is doubly deprotonated by base reagent tools to yield the bound oxyanion).
  • a water molecule is bound to a monocationic zinc-ethylene-diamine complex is doubly deprotonated by base reagent tools to yield the bound oxyanion.
  • acid reagent tools or or alkali metal cations bound to ligands in binding tools are also contacted to said material near sites contacted by silicon binding tools whereby Si-0 bonds may be further weakened.
  • a silicon binding tool may bind said cations, e.g. as would be the case for a binding tool comprising a catecholate structure previously treated with NaOH to yield the disodium catecholate form; similarly, a tool comprising a disodium ethylene glycolate structure could be used.
  • Withdrawn tools are transported out of said vessel and are replaced with fresh binding tools and fresh reagent tools and the foregoing steps of binding tool and reagent tool contacting and withdrawal are repeated to obtain more silicon atoms from said material.
  • tools transit said vessel situated on a conveyor chain, conveyor belt, rack or other transport means to enable efficient transport, and therefrom are preferably transported to a storage space or a reaction vessel or volume for subsequent mechanosynthetic operations whereby silicon atoms obtained from said materials may be used as feedstocks for nanofabrication of desired articles.
  • Graphenoid nanostructures may be produced by convergent positional mechanosynthesis without metal catalysis (although metal-ligand binding tools may bind reactants, intermediates or products for manipulation thereof without altering electronic structure or reactivity compared to the corresponding unbound species [not dehydrogenated or deprotonated solely for attachment of binding tools]).
  • metal-ligand binding tools may bind reactants, intermediates or products for manipulation thereof without altering electronic structure or reactivity compared to the corresponding unbound species [not dehydrogenated or deprotonated solely for attachment of binding tools].
  • metal-ligand binding tools may bind reactants, intermediates or products for manipulation thereof without altering electronic structure or reactivity compared to the corresponding unbound species [not dehydrogenated or deprotonated solely for attachment of binding tools]
  • Fig 39A-G show graphenoid nanofabrication steps from triphenylene molecule precursors or intermediates; such materials built up from triphenylene precursors or intermediates are refered to herein as triphenyloid materials.
  • triphenyloid materials are analogs of the structures in Figs 23A-D, although electronic structures and reaction mechanisms differ.
  • the reaction depicted does not require catalysis; the reacting edges are all of the graphene armchair type, and products produced in these convergent reactions or recurrent cycles thereof may have all-armchair edges; this enables this single reaction type to be the basis of convergent graphenoid nanofabrication.
  • reactants, intermediates and/or products may be held by any suitable binding tool and interaction which does not disrupt the electronic configuration of the benzyne functionalities or the singlet carbons (for example, two or more carbons distal in reactant structures to reacting carbons may be deprotonated or have hydrogens abstracted and then be bound by a ligand-tool bound metal such as an aluminum atom bound by oxygens of a ligand, such as that in Fig 7D).
  • a ligand-tool bound metal such as an aluminum atom bound by oxygens of a ligand, such as that in Fig 7D).
  • Fig 39A shows a triphenylene molecule from which three hydrogens (adjacent hydrogens are first abstracted from carbons bonded together to yield benzyne functionality [refering to a dehydrogenated aromatic carbon-carbon bond in analogy to benzyne as a chemical functionality] before a hydrogen is abstracted to form an adjacent carbon radical) have been removed is positioned to react with a second triphenylene molecule from which four hydrogens have been removed to form two adjacent benzyne functionalities according to the pattern shown in Fig 8B to avoid formation of undesired four-membered rings or bonds; the carbons are at least 300pm apart.
  • Fig 39B shows the structure at 166fs--note that by this time all three bonds required for continuous graphenoid structure have already been formed;
  • Fig 39C shows the structure at lOOOfs;
  • Fig 39D shows the structure (depicted in rotated orientation relative to Fig 39C to facilitate comparison with subsequent drawings) at 1178fs (at which the calculation was terminated as recoil vibrations declined in amplitude).
  • Fig 39E shows the result of a similar set of steps and reaction as depicted in Figs 36A-D using the product in Fig 39D as the two starting reactants
  • Fig 39E comprises four triphenylene skeletons.
  • Fig 39F similarly shows the product formed from two reactants which are products shown in Fig 39E (though rotated and flipped, as depicted).
  • Fig 39G similarly shows the product formed from two reactants which are products shown in Fig 39E, but dehydrogenated and positioned to yield the elongated product shown, which may be regareded as a graphenoid nanoribbon or triphenyloid nanoribbon.
  • triphenylene reactans may be modified structures, e.g.
  • substituted through atomic replacements] such as by nitrogen, boron, phosphorous, oxygen, sulfur, etc., or those destined to be situated at edges of product structures may be chemically functionalized, e.g. with one or more hydroxyls, ethynes, amines, carbonyls, carboxyls, thiols, alkyls, methylenes, phosphines, oximes, cyano- groups, halogens, fluorines, boranes, aminoboranes, alkylethynes, functionalized alkyls (e.g. ethylene bridges themselves additionally bearing any of the
  • Articles substantially composed of three-dimensionally interlocked layer compouns e.g. graphenoid structures, h-BN, borophene, silicene, germylene, stannylen, phosphorene, two-dimensional transition metal-dichalconides,
  • rods, polymers, looped, cyclic or otherwise topologically closed structures such as washers or rings may be formed from two-dimensional nanostructures threaded through pores or voids of sheets and covalently closed or locked.
  • stacks of two dimensional compound nanostructures may be bound together without disrupting the bulk-like structure or properties thereof into stable structures that, for example, display greater hardness than the bulk layered compound and will not slide or lubricate.
  • Composite structures of the present example may display both hardness and tensile strength which although anisotropic is greater in all directions than the corresponding bulk compound.
  • interlocked metamaterials composed of two-dimensional materials may be fabricated and bring the properties of said two-dimensional materials to the physical effects which may be realized in metamaterials such as negative index of refraction.
  • chemical functionalities situated on the edges of two-dimensional layers may be covalently crosslinked or crosslinked by salt bridges, hydrogen-bonds or metals in ligand-metal interactions to stably organize and order precisely stacked two-dimensional layer nanostructures, which may all be of similar atomic, chemical or material composition.
  • layers of different two-dimensional compounds may be interlocked or crosslinked to form stable precise three- dimensional nanostructures or systems
  • layers of graphenoid composition may be interspersed in layers of h-BN whereby two or more electrically conducting layers are separated by tunnel bariers (for one or a few layers of h-BN therebetween) or insulating layers (for several of h-BN
  • Nanostructures of Examples XXXa-d comprise within their structures nanopositioners (e.g. comb actuators, pneumatic or hydraulic cylinders and pistons, etc.) and binding tools. These may be used to perform the
  • nanofabrication and/or nanoassembly methods of the present invention including fabricating systems or subsystems according to the present example, enabling self-replication or al lo-repl ication of systems or subsystems composed of substantially one material (e.g. greater than 90% by mole fraction graphenoid carbon).
  • a system or subsystem of Example XXXe may be used to fabricate and assemble a system or subsystem comprising two or more different materials comprising within their structures nanopositioners (e.g. comb actuators, pneumatic or hydraulic cylinders and pistons, etc.) and binding tools.
  • nanopositioners e.g. comb actuators, pneumatic or hydraulic cylinders and pistons, etc.
  • binding tools e.g. comb actuators, pneumatic or hydraulic cylinders and pistons, etc.
  • a system or subsystem composed of substantially one material may fabricate and assemble a system or subsystem comprising two or more different materials for nanofabrication and/or nanoassembly, including self-replicating or al lo-repl icati ng systems.
  • a system or subsystem comprising two or more different materials comprising within their structures nanopositioners (e.g. comb actuators, pneumatic or hydraulic cylinders and pistons, etc.) and binding tools may be used to fabricate and assemble a system or subsystem of Example XXXe comprising within their structures nanopositioners and binding tools.
  • a system or subsystem composed of two or more different materials may fabricate and assemble a system or subsystem substantially composed of one material for nanofabrication and/or nanoassembly, including self-replicating or al lo-repl icati ng systems.
  • Atomic substitutions, functional group derivatives (e.g. exocyclic chemical functional groups) for use as molecular binding tools, reagent tools are situated at precise predetermined desired locations on structural members (during the fabrication thereof according to the nanofabrication and nanoassebly methods of the present invention) in communication with nanopositioning means which are under programmable computer control (e.g. electrostatic or comb actuators controlled by an electronic and preferably digital finite state-machine or digital computer, or pneumatic, fluidic or hydraulic actuators comprising valves, cylinders or pistons and controlled, e.g.
  • programmable computer control e.g. electrostatic or comb actuators controlled by an electronic and preferably digital finite state-machine or digital computer, or pneumatic, fluidic or hydraulic actuators comprising valves, cylinders or pistons and controlled, e.g.
  • Nanopositioning means are operated to conduct mechanosynthetic operations, chemical transformations of individual molecules or assemblages, and/or convergently assemble nanostructures similarly produced.
  • raw materials may include: carbon dioxide, ammonia, methane, sand or silicate, phosphate, magnesium salts or oxides, manganese nodules or polymetallic nodules, minerals, metal ores.
  • Raw materials may be entrained in a fluid stream (e.g. air, wind, exhaust, or liquid streams including, for example, drainage) or transported by conveyors, belts, pulleys, cords or tethers, etc., or may passively diffuse into systems or subsystems through a pore, anulus or conduit or enter due to motion from environmental agitation such as waves in a body of water.
  • Systems or subsystems comprising said structural members and positioning means of Example XXXh further also comprise leaf springs or sheet springs, which optionally further comprise electrically conductive regions and electrically insulating regions.
  • these may be hexagonal boron-nitride regions fused with graphene regions of a nanostructure of 2-dimensional hybrid material (hBN/graphene hybrids).
  • these may be sheets consisting of a few atomic layers (e.g. less than 33 but more preferably only 2) of halite materials such as SrO insulating regions and TiC or TiN conducting regions, fused together in a desired predetermined pattern.
  • Leaf springs in this example may be parts or systems of flexible electronics, or may be articles serving as both mechanical and electrical parts, e.g. means for restorative mechanical force which communicate one or more electrical signal or provide electrical energy via a mechanically compliant coupling; thee may be used in arrangements such as those shown in Fig. 9D, for example, serving as parts of comb-actuator
  • nanopositioners so that e.g. 6480 could serve as a leaf spring carying a number of signals or energizing different conductive members differently to effect particular motion dynamics.
  • Oceanic gas hydrates are collected by first encasing layers of deposits thereof in enclosing membranes two-dimensional materials (such as graphene or hBN) which are strong enough to contain enclosed material in approximately the original volume enclosed outside the gas-hydrate stability zone, whereby destabilization is prevented. Top layers of deposits are covered with
  • impermeable membranes of similar composition onto which sediment from away from gas-hydrate deposits are gradually loaded at a suitable rate to compensate for removed material and maintain the load and pressure stabilizing underlying gas hydrates or gas trapped thereunder, preventing methane release into the ocean or atmosphere.
  • Subsystems of the present invention for programmable nanofabrication and nanoassembly are provided in sufficient numbers for high degrees of parallelism (e.g. 128 or more, 1024 or more, 1048576 or more, 10 9 or more, 10 12 or more) to effect a 3D-printer.
  • a system of Example XXXIIa is provided with an inlet for natural gas, filtration means therefor, dehydration means therefor (which may comprise refrigeration means, a cold trap and a drain or waste liquid receptacle), and dried methane filtered from said natural gas is used as a raw material for printing of articles comprising carbon.
  • a system of Example XXXIIa or Example XXXIIb is connected to a network and communicates thereby with a computer server which communicates instructions and authorization codes or license codes to said 3D-printer.
  • a system of Example XXXIIc is connected to a network and communicates thereby with a computer server which communicates information concerning results of operations of said 3D-printer to said computer server, and said computer server records said information or information processed therefrom on a block-chain or open ledger.
  • user account balances may be adjusted for license fees or authorizations to receive digital currency from users of said 3D-printer (or recipients of products thereof) may be recorded on said block- chain or open ledger.
  • a system of Example XXXIId may be equipped with means for communicating with a smartphone application or digital wallet on a digital computer, housed in a tamper resistant enclosure or cabinet, provide means for a user to select desired products to be produced, whereby the system of the present example
  • a system of Example XXXIIa or Example XXXIIb is connected to a network and communicates thereby with a computer server which hosts an online forum for sharing designs or a store for downloading instructions and license
  • One or more systems of any of Examples XXXIIa-f are operated to produce a building, architectural structure or dwelling.
  • One or more systems of any of Examples XXXIIa-f are operated to produce an automobile, bicycle, boat, ship, aircraft or spacecraft.
  • Comb actuators may conveniently be assembled from nanofabricated TiN or graphenoid, BC3 nanolayers or striped borophene, with SrO, MgO. BaO or hBN insulators, one or more 2D leaf springs including wires (e.g. graphene or C 3 B in hBN or TiC, TiN, ZrC, ZrN, HfN or doped TiN in SrO, MgO. or BaO [as necessary with interfacial gaps to prevent strain due to lattice mismatch, e.g. interfacial contacts of 16-atoms regularly spaced with gas therebetween]), one or more wire per leaf spring; multiple electrical contacts enabling further comb actuators to be situated on comb actuators.
  • wires e.g. graphene or C 3 B in hBN or TiC, TiN, ZrC, ZrN, HfN or doped TiN in SrO, MgO. or BaO [as necessary with interfacial gaps to prevent strain
  • a first subset of electrical conductors in one or more springs provide electrical connections to a first actuator member provide electrical potential bias for the actuation of said first actuator member (said first actuator member opposed to a first actuator counter-member comprising an electrically conductive region and situated on said support for the actuator assembly) and a second subset of electrical conductors in said one or more springs provide electrical connections to a electrical conductors in one or more springs between said first actuator member and said second actuator member to provide electrical potential bias for the actuation of said second actuator member, said second actuator member opposed to a second actuator counter-member which is at the electrical potential of the main conductive regions of said first actuator member, said first and said second actuator members preferably oriented to cause translation in different directions.
  • Programmable molecular assembler comprising molecular binding tools, reagent tools as atoms situated on structural members in communication with nanopositioning means
  • actuators selected from the group consisting of: capacitive actuators; comb actuators; electromagnetic actuators (e.g. comprising ferromagnetic graphenoid strutures); and, hydraulic actuators comprising fluid conduits, pistons and cyclinders. further comprising an input port and an output port for materials and products; further comprising a radio, (wired) electrical, optical (fiber or free- space), or acoustic communications link,
  • ferromagnetic graphene by designin voids internal to a graphenoid structure comprising a radical site an an atom on the periphery of said void; a pluraity of such voids in proximity increase the areal magnetic momment.
  • Subsets of the various fabrication methods and means of the present invention may be used to fabricate and assemble any devices or systems of prior art or of future development, in most instances improving same through improved precision, improved materials, improved efficiency, reduced defects, reduced effort and reduced cost.
  • devices and systems useful especially as subsystems of systems of the present invention for the processing of raw materials and pollutants and the conversion and storage of energy are useful especially as subsystems of systems of the present invention for the processing of raw materials and pollutants and the conversion and storage of energy.
  • a trivial example is use of MgO bodies featuring conduits for circulating heat transfer fluid therethrough as thermal energy storage means.
  • Other examples are the teaching of U.S. Patents Nos. 2,594,998, 3,080,583 (Submarisle
  • Feillolay A.; Eucas, M.; 1972. "The Solubility of Helium and Methane in Aqueous Tetrabutylammonium Solutions at 25° and 35°", Journal of Physical Chemistry 76(21):3068.
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  • Systems, subsystems and articles of the present class of embodiment may substantially consist of bulk or macroscale fabricated materials and parts, but the properties or functions of these may be improved by addition or
  • nanofabricated materials e.g., bulk fabricated optical components (e.g. of cellulosic composition, e.g. cast from cellulose carbamate or cellulose dissolved in acetamide-lithium chloride mixtures) or vessels may be coated with nanofabricated materials such as graphene to confer gas
  • impermeability or nanofabricated metamaterials to confer antireflectivity for example.
  • These embodiments do not strictly depend on positionally controlled mechanosynthetic nanofabrication, since they may use, for example, bulk fabricated graphene-oxide which is reduce to graphene and deposited in thin layers, and also these enhancements are dispensable to operative function.
  • Systems of the present embodiments of the present invention comprise subsystems for converting carbon dioxide (C0 2 ), methane, dinitrogen (N 2 ), petroleum (whether from seeps or oil spills or other origin in the environment) or pollutants (e.g. agricultural runoff), or other raw materials found in the
  • cellulose including bacterial nanocellulose, or sugars such as sucrose e.g. cellulose including bacterial nanocellulose, or sugars such as sucrose (as products or for concurrent or subsequent in metabolic-engineering-based production of other biological products), bioplastics such as poly-3-hydroxy-butyrate
  • bioplastics such as poly-3-hydroxy-butyrate
  • algaculture particularly of microalgae such as chlorella and nanochloropsis, nanoalgae and picoplanktons such as nanochlorous and synnecococcus, or foods or agricultural feed such as cyanobacteria (e.g. spirulina platensis) or other algae (including macroalgae such as ulva ), with other biological compounds (e.g.
  • amino acids, vitamins, bioplastics possibly being concomitantly produced and collected.
  • Further examples include: anabaena for fixing nitrogen; or Chlamydomonas reinhardtii, photosynthetic purple bacteria, or anaerobically grown cyanobacteria (i.e.
  • molcular oxygen must be efficiently removed from or consumed in the growth medium) for producing molecular hydrogen (H 2 ).
  • Biomass thus produced or residual biomass from various processes utilized in systems of the present invention may further be fermented in susbystems for fermentation and distillation to yield alcohols such as ethanol which may be used as a feedstock or solvent in other subsystems or processes of the present invention, or may be a liquid fuel product, which may be either used in the operations of systems of the present invention or constitute a product of systems of the present invention.
  • alcohols such as ethanol which may be used as a feedstock or solvent in other subsystems or processes of the present invention, or may be a liquid fuel product, which may be either used in the operations of systems of the present invention or constitute a product of systems of the present invention.
  • biomass may be produced by the cultivation of macroalgae such as seaweed, most preferably using the rope- based cultivation methodology, e.g. , and also reviewed in [Ferl7], or the screen based cultivation methodology, e.g. [Ade93].
  • macroalgae such as seaweed
  • Macroalgae thereby produced may themselves be a desired procuct (food or agricultural feed), input for the purification of desired compounds (carageenan, alginate, agar, agarose, etc.,) or may be subjected to hydrous pyrolysis (preferably using a solar furnace) to yield pitch; hydrous pyrolysis may preferably be effected using concentrated solar irradiation or infrared radiation derived therefrom.
  • Pyrolytic products of biomass may be fibers; or pyrolytic fibers may be laid up and acreted with further pyrolysis gases to form carbon composites or the like; pyrolytic fibers may be formed into ropes or used in the construction of screens, and ropes or screens produced thereby may be used in the cultivation of macroalgae.
  • Frames of screens may be made from carbon composite beams; ropes may be suspended on pulleys which are carbon composite articles situated on beams which are also carbon composites.
  • ropes or screens produced and employed in this way constitute means for the cultivation of a material input for the fabrication of like articles, and so cultivation directly supplies material inputs for the production of further cultivation subsystems.
  • two or more distinct species of macroalgae are interspersed together during cultivation.
  • multiple individuals of a first species of macroalgae are grown on a first rope
  • multiple individuals of a second species of macroalgae are grown on a second rope.
  • Said first rope and said second rope are supported in seawater or freshwater by independent pulley systems, such that the two may independently be translated and processed, for example to accommodate different growth rates of said first species of macroalgae and said second species of macroalgae.
  • preindustrial ocean pH can be achieved by fixation of about 0.3 mM or less marine inorganic carbon.
  • oceanic stratigraphy does not distribute non-precipitated carbonates uniformly and precipitated carbonates account for a large portion of anthropogenic protons, so in practice, carbonates (including bicarbonates) will need to be transported from below the photic layer of the ocean for consumption via transformation to biomass, and extensive monitoring of the effects of operations to avoid localized hyper-alkalinization or excessive localized depletion of inorganic carbon.
  • Systems of the present invention comprise subsystems for fabrication wherein materials collected from the environment or produced via algaculture, agriculture or mariculture in subsystems therefor may be utilized.
  • Generally products produced by systems of the present invention are completely or mostly composed of materials produced or collected from the environment by said systems, or at least mostly from materials transferred directly or indirectly from cooperating systems which are generally similar in comprising subsystems for collection and/or transformation of raw materials from the environment into feedstocks for production of desired articles.
  • cellulose may be dissolved to create vicose solutions; more preferably cellulose is converted to cellulose acetates or more preferably still cellulose carbamates by reaction with urea and then dissolved in sodium hydroxide solutions according to the teachings of Zimmer in US6590095 for spinning into fibers or deposition of films, etc.,.
  • a preferred cellulose may be dissolved to create vicose solutions; more preferably cellulose is converted to cellulose acetates or more preferably still cellulose carbamates by reaction with urea and then dissolved in sodium hydroxide solutions according to the teachings of Zimmer in US6590095 for spinning into fibers or deposition of films, etc.,.
  • embodiment for the production and transformation of cel I ulosic biomass is to form desired articles of cellulose composite materials according to the teachings of [Soy09], wherein bacterial cellulose (which includes cyanobacterial cellulose) in fiber form is treated with solutions of lithium chloride and N,N-dimethyl- acetamide to effect surface-selective dissolution of cellulosic fibers whereupon reprecipitation of dissolved cellulose forms a matrix around undissolved cellulose.
  • Bacterial cellulose sheets are formed by flotation, and then
  • the prior art method may be improved upon to form articles of desired shape by assembling partially dissolved BC sheets (optionally with compression) prior to methanol immersion, such that reprecipitation of cellulose between BC sheets fuses them together in areas of contact.
  • Such cellulose derived composite materials may be used in structural members of systems or subsystems of the present invention, or may be a product produced thereby, for instance as boards for use in construction substituting for lumber, and hence reduce human population pressure on forestry resources facilitating rewilding.
  • Cellulose is favorably obtained from cyanobacteria and more particularly cyanobacteria modified for high cellulose biosynthesis as taught by [Zhaol5].
  • Overexpression of six genes for cellulose biosynthesis from Gluconacetobacter xylinus namely cmc-ccp-cesAB-cesC-cesD-bgl
  • cmc-ccp-cesAB-cesC-cesD-bgl a Synechococcus sp.
  • PCC 7002 mutant with the native cesA gene inactivated resulted in cellulose production reaching 14% of biomass when cells were grown at low salinity.
  • Cellulose may alternatively be obtained through cocultivation of cyanobacteria modified to secrete sugars such as sucrose with heterotrophic bacterial strains which produce cellulose.
  • biomass or fractions thereof including, for example, glycerol or acetate
  • biomass or fractions thereof may be provided as a nutrient source for the heterotrophic cultivation of bacterial strains which produce cellulose (e.g. Gluconacetobacter xylinus)
  • fungi may be cultivated using biomass or fractions thereof as a nutrient source may be cultivated to harvest biopolymers or biochemicals therefrom, including cellulose, chitin, and chitosan.
  • Films or other optical materials having dispersion of the refractive index thereof may be used to separate different wavelength photons from a light source, such as from the sun, i.e. acting as a beam-splitter.
  • a light source such as from the sun, i.e. acting as a beam-splitter.
  • PAR photosynthetically active radiation
  • thermal radiation for instance, to enable greater utilization of incident energy by directing PAR to cultures comprising cultivated algae, plankton, moss, microalgea, nanoplankton, macroalgae or to terrestrial plants (grown, e.g. in subsystems of the present invention for hydroponic or aeroponic cultivation) while simultaneously directing thermal radiation (e.g.
  • thermal absorber means for capturing and/or storing thermal energy
  • thermal concentrator means or to a thermal fluid or heat transfer fluid, or directly to a heat engine, or to subsystems for thermal material or chemical processing (such as subsystems of the present invention for pyrolysis), or alternatively directing said thermal radiation (directly or indirectly) back through the atmosphere into space (whereby total solar heat absorbed by the earth, and hence any radiative forcing effected by anthropogenic emissions, is counteracted, effectively increasing the albedo of the earth specifically for thermal radiation; in this case, the optical path of reflected thermal radiation must be directed to avoid clouds).
  • optical films having dispersion such that the refractive index decreases with increasing wavelength permit the fabrication of structured optical films or articles which, when situated at an appropriate angle to the direction of travel of incident light, are capable of reflecting visible radiation or PAR, but transmit thermal radiation, similarly to a cold-mirror.
  • optical films having dispersion such that the refractive index increases with decreasing wavelength permit the fabrication of articles which function similar to a hot-mirror; the adjustments to be made to accomplish this relative to accomplishing the functionality of a cold-mirror as described here will be obvious to those skilled in the arts of optics).
  • Optical films or articles perform the desired function in these embodiments of the present invention by being situated at an appropriate angle relative to an incident optical path such that the angle of a beam of light from air or vacuum or another optical medium with a refractive index lower than the refractive index of said optical films or articles, refracted by the front surface of said optical films or articles, is incident on a back surface of said optical films or articles at an angle relative to the selected critical angle for total internal reflection (at a wavelength chosen to be the lower limit for the wavelength of transmitted photons [in the case of cold-mirror-like functionality]), so that photons having a larger
  • wavelengths having a larger critical angle are transmitted through the back surface of said optical films or articles to a lower refractive index optical material, while photons of lower wavelength, having a smaller critical angle (due to a higher refractive index at that wavelength) are reflected from said back surface.
  • tolerances for angles must be very small, less than about 0.05 degrees, so rigid structures must be used to align all elements to incident light paths with high precision.
  • heliostat or solar tracking means comprise detectors for detecting optimality of aim (e.g. photodetectors, thermometry devices), information processing means for calculating adjustments to heliostat or solar tracking means aim or position, and motors or actuators for adjusting heliostat or solar tracking means aim, whereby feedback control maintains aim
  • response rates of heliostat or solar tracking means should be fast relative to motions or vibrations which may be caused by such disturbances.
  • response rates of heliostat or solar tracking means of systems or subsystems of the present invention lofted in air should be fast relative to motions or vibrations which may be caused by wind or air turbulence other atmospheric disturbances.
  • cellulose films are used to both effect beam-splitting of PAR photons (which are captured by total-internal-reflection such that the film acts as a waveguide) from thermal photons (which pass through the film).
  • the film may be described as an infra-red transmitting, PAR receiving film, and said film is in optical communication with a photobioreactor, further light processing means, or light receiving means for a photobioreactor.
  • Aerogels of cellulose, phenol-formaldehyde aerogels or carbon aerogels derived therefrom may be used as insulation for photobioreactors, at least for surfaces thereof through which light need not be transmitted.
  • Such aerogels are produced from materials derived from biomass produced according to the present invention.
  • Such aerogels provide thermal insulation to maintain desired temperatures for algae or microalgae growth, or for thermal insulation in other subsystems of the present invention, such as subsystems for pyrolysis or heat engines such as solar-thermal Stirling engines or Erikson engines.
  • Such aerogels are also useful as protectants against flame.
  • Such aerogels may be used in systems or subsystems of the present invention, or may be a product produced thereby, for instance as boards for use in construction substituting for insulation such as fiberglass insulation.
  • Phenol, resorcinol, acetic acid and methanol may be obtained from fractional distillation of the liquid products of hydrous pyrolysis of biomass or volatiles from torrefaction of biomass.
  • Means for distillation may be fabricated in the present invention from extruded tubing composed of pyrolytic carbon (e.g. extruded pitch), or tubing formed from carbon reinforced carbon.
  • Formaldehyde may be obtained from the enzymatic or chemical oxidation of methanol, including catalytic oxidation using catalysts (iron oxide with V or Mo).
  • Iron oxides and impurities including V and Mo may be obtained from polymetallic nodules or manganese nodules from the ocean floor, or ocean sediment or may be provided to systems or subsystems of the present invention exogenously.
  • a preferred embodiment of the present invention is a system comprising a subsystem for algaculture, a susbsystem for hydrous pyrolysis (preferably comprising a solar furnace) of biomass produced in said subsystem for algaculture to yield pitch, a subsystem for producing carbon fiber from said pitch (preferably comprising a solar furnace for thermal processing of fibers), a subsystem for laying up said carbon fiber into desired shapes or weaving said carbon fiber into fabric or twill.
  • Nanocellulose may be purified from biomass, e.g. from Gluconacetobacter xylinus modified to overproduce cellulose [] cocultivated with Synecococcus modified to secrete sucrose [], and processed into rayon fibers, which are then thermally processes (preferably in a solar furnace) into carbon fibers.
  • acryonitrile is produced from biomass, as by [], said acrylonitrile is polymerized and spun (e.g.
  • Acrylonitrile may be obtained by the thermal decomposition of glycerol (obtained from biomass) to acrolein, followed by amination (at the aldehyde function) with ammonia (e.g. arising from cultivation of anabaena by the microalgae cultivation methods and subsystems of the present invention), followed by oxidation to the nitrile ().
  • acrylonitrile may be obtained through the (double) decarboxylation of glutamate (obtained from biomass).
  • systems preferably comprise subsystems for separating toxic byproducts from desired products and
  • gaseous or liquid byproducts e.g. exhausted from a pyrolysis chamber or cleared with an inert sweep gas or collected by drainage
  • gaseous or liquid byproducts may be captured by sorbents or may be subjected to liquid extraction (with recycling of sorbents or solvents as byproducts are concentrated).
  • Byproducts are then neutralized or encapsulated; these may be further purified to capture useful species such as H 2 , phenol, etc., and toxic species isolated for treatment or carbonization.
  • pyrolysis product articles produced according to the present invention may degrade or neutralize the toxicity or any surface adsorbates arising during pyrolysis. Such measures are preferred to minimize toxic species which could leach from pyrolysis product articles.
  • An alternative or additional measure to prevent leaching of toxic pyrolysis product species from pyrolysis product articles is to coat said articles with any of a number of coating materials forming a barrier to escape of any potential leachates during the useful life of the article. While such coatings could be as simple as paint, coatings preferred for articles to be deployed in the environment are preferably of composition similar or identical to natural materials.
  • a simple but particularly useful example is bioplastic coatings, and most particularly polyhydroxybutyrates.
  • polyhydroxybutyrates are naturally produced by spirulina platensis, which may be cultivated by cyanobacteria cultivation subsystems of the present invention polyhydroxybutyrates may be extracted from spirulina using organic solvents; for purposes of the present invention, it is preferable to use solvents derived from acetic acid or short-chain fatty acids (e.g. by esterification with ethanol or reduction of lipids to n-alkanes) which are obtained by purificaiton from biomass instead of the halogenated solvents which are conventionally used for the extraction of polyhydroxybutyrates.
  • solvents derived from acetic acid or short-chain fatty acids e.g. by esterification with ethanol or reduction of lipids to n-alkanes
  • Manifolds comprising tubular vias or fibers are useful in multiple aspects of the present invention. For example, these may serve as layups for deposition of pyrolytic carbon to form carbon composite materials, such as reinforced carbon- carbon, when the fiber materials comprise carbon fibers.
  • Manifolds may instead comprise tubules which define tubular voids in materials deposited thereon; when cellulose is precipitated or deposited onto manifolds of tubules, a lignin-free wood-substitute material comprising structural voids mimicking xylem is formed. Such a material may be more resilient to recovery from bending stressed than the corresponding continuous solid lacking xylem- like voids.
  • Manifolds may instead comprise optical fibers and especially luminous fibers. These are useful as optical distribution means for high light efficiency luminous- fiber bioreactors such as those disclosed by [Tak92] or [Xuel3]. Additionally, manifolds comprising optical fibers or luminous fibers may additionally comprise membranous tubular structures wherein membrane materials are permeable to gases desired to be exchanged with the growth volume of a bioreactor, such as C0 2 and/or 0 2 . (Similarly, when nitrogen fixing organisms are grown or NH 3 is otherwise evolved, N H 3(g) may be exchanged.
  • Optical fibers and luminous fibers may utilize liquids as a high-refractive-index optical material; in this case optical fibers comprise a tubular sheath into which a high-refractive-index liquid optical material is introduced.
  • higher refractive index materials is glycerol; this is a common byproduct of microalgae growth and in particular a byproduct of production of algae derived liquid fuels.
  • Luminous fibers are optical fibers which partially scatter light conducted thereby out into the surrounding volume. In [Tak92], these were produced by damaging the cladding of conventional optical fibers; in [Xuel3] the luminous fibers utilized comprised luminescent particles within the high-index optical core, whereby emitted photons are emitted at random angles, many of which are not totally internally reflected back into the fiber.
  • Pyrolysis may be carried out in pyrolysis chambers which are themselves composed of pyrolytic carbons such as RCC.
  • chambers may be assembled from panels and edge brackets or frames, which may be smaller in largest dimension than the largest internal dimension of said pyrolysis
  • degassed organic polymer melts or degassed pitch or tar from hydrous pyrolysis are applied to articulating surfaces of panels and brackets or frames which are then assembled together to the final desired structure, which is then thermally treated under non-oxidizing conditions (optionally with additional pyrolysis gases) to effect pyrolysis of the applied material forming solid and gas-tight joints.
  • Panels may be pyrolyzed and/or thermally treated in such chambers in a series of steps wherein at the final step a panel is moved against a panel serving as a wall of the pyrolysis chamber such that additional pyrolysis gases react with one side of a panel being processed rather than the walls of the pyrolysis chamber.
  • pyrolysis chambers provide ready accessibility of workpieces for pyrolysis; although any shape pyrolysis chamber could be used in pyrolysis subsystems of the present invention, this is best enabled by choosing a design for pyrolysis chambers having two or more appreciably flat faces where preferably one of the larger faces is closed by a lid or pressure plate, which may be removed, rotated or translated to enable grippers, tongs, manipulators or robotic arms to place, move or remove workpieces.
  • Pyrolysis chambers additionally feature a port (preferably further comprising a valve or structural members for mounting a valve) for introducing pyrolysis gases and for exhausting same and/or pyrolysis product gases.
  • panels or panels and frames may comprise within their structure channels for flowing a heat transfer fluid, and on assembly into a pyrolysis chamber, said channels may be in fluid communication with a heat transfer fluid pump and one or more heat reservoir or recuperator.
  • a plurality of heat reservoirs are included in a pyrolysis subsystem and valves or fluidic logic gates control the sequence of steps of flow of said heat transfer fluid.
  • Said plurality of heat reservoirs provide a set of increasing temperatures from ambient to the hottest working temperature reached by the pyrolysis subsystem and are accessed sequentially during heating of the pyrolysis chamber to provide heat to increase the temperature of the pyrolysis chamber in succeeding steps, after each of which, flow is switched to the next hotter heat reservoir.
  • Heat reservoirs comprise materials with significant thermal mass with one or more channels for flowing heat transfer fluid therethrough; depending on materials and design chosen, heat reservoirs may be enclosed in a containment structure
  • heat transfer fluids may be used, including inert gases, noble gases, molten salts and molten metals, although in the latter two instances care must be taken to select compatible materials that are not eroded, corroded or dissolved.
  • Ar (g) is a most preferred heat transfer fluid; dinitrogen gas ( N 2(g) ) is also relatively inert and less prone to diffuse into materials, although it might be less inert at the highest pyrolysis temperatures, so although this may be used as a heat transfer fluid, suitability should be verified for uses at higher temperatures.
  • An exemplary heat reservoir is composed of (preferably porous) sinterred MgO comprising a channel for flowing Ar (g) heat transfer fluid enclosed in a jacket composed of pyrolized carbon or fiber reinforced carbon.
  • a further class of fabrication techniques and subsystems useful for the present invention is a modification of filament-based three-dimensional printing wherein polyacrylonitrile fibers (e.g. produced by electrospinning) are used as filament. These may be thermally fused (partially melted or annealed together in contact) during the three-dimensional printing operation to form an intermediate layup.
  • polyacrylonitrile fibers e.g. produced by electrospinning
  • solvent softening may be used by providing a solvent channel through which a solvent which softens polyacrylonitrile flows to an orifice adjacent to the position at which the fiber emerges from the print head such that said solvent wets said fiber.
  • Embodiments of this class avoid the topological constraints of weaving or knitting, and while the intermediate layups composed polyacrylonitrile fibers which are precursors in this usage do not enjoy the topological strengthening which results from internal tensions, reptations and constraints under applied forces (which are thus redistributed), a significant portion of the same effects other than reptation are realized upon pyrolysis and carbonization of three-dimensional printed polyacrylonitrile fiber layups.
  • Pyrolyzed or carbonized three-dimensional printed polyacrylonitrile fiber layups may subsequently be pyrolyzed in the presence of pyrolysis gases to infiltrate same to from the carbonaceous host material of the reinforced carbon-carbon article thus produced.
  • improved pyrolytic product composites are produced with layup intermediates designed such that even complete pyrolysis yields a product having channels or pores for permitting the escape of pyrolysis product gases. More preferably, channels are designed in a hierarchial dentritic pattern throughout the body of an article, part, block, sheet or rod produced by pyrolysis such that gaseous pyrolysis products formed throughout the volume of the article have a sufficiently high likelihood of graceful escape.
  • corral biomass growth in the open ocean typically does not exceed 20-26g/(d)(m 2 ) winter and summer average bioproductivity [Odu55].
  • Adey et al. have shown that raceway cultivation of macroalgae can attain annual average bioproductivity of 35g/(d)(m 2 ) when nutrients such as phosphorous, nitrogen and iron are non-limiting [Adell].
  • a principal aim of that work was demonstration that excess nutrients could be removed from effluent streams to avoid eutrophication.
  • C0 2 sequestration through iron and/or phosphate ocean fertilization Although these have been questioned both in terms of efficacy and with respect to potential ecological impacts.
  • embodiments of the present invention comprising subsystems for open rope-, mesh- or frame-supported macroalgae cultivation may feature means for releasing nutrients at a central near-surface location surrounded by sufficient quantities of macroalgae to consume substantially all added nutrients during the course of their growth.
  • supports on which algae are supported may be progressively moved from zones of higher nutrient concentration early during their growth progressively further away as new supports for younger algae are introduced to the higher nutrient zone; at final phases of growth before harvest, supports and alge thereupon will have been moved to the periphery of the cultivation zone where nutrient levels are little higher than natural nutrient levels in the local environment, such that mature cultivated algae essentially scavenge any added nutrients before they can diffuse to the surrounding environment to any significant extent.
  • cultivation is conducted such that nutrient consumption at least equals nutrients supplied for fertilization.
  • nutrients may be recycled by purifying proteins, minerals and nucleic acids from biomass prior to biomass utilization, and said proteins, minerals and nucleic acids may be hydrolyzed and provided as nutrients for subsequent cultivation.
  • such subsystems for supported growth of macroalgae may be operated in locations subject to eutrophication or nutrient runoff, cultivated macroalgae therefrom similarly separated into nutrients for recycling and biomass for utilization, and nutrients thus obtained transported by transporting means to supported cultivation subsystems not in locations subject to eutrophication or nutrient runoff, whereby bioproductivity higher than that naturally possible in the open ocean (or in open waters of freshwater bodies of water) may be sustained while remediating nutrient pollution.
  • Said transporting means are preferably autonomous vehichles but may also be conduits such as tubing, pipes or pipelines.
  • nutrients recovered from macroalgae cultivated on supports in open- waters with high nutrient concentrations may be utilized in the cultivation of microalgae, microplankton, nanoplankton or the like in subsystems therefore in other embodiments of the present invention.
  • photobioreactor 30 x 10 cm 2 , 2-6 cm apart, but would scale to 100 x 10 cm 2 , 2-6 cm apart for 1 m wide photobioreactors; at 2 cm separation with both surfaces of each curtain supporting biofilms, the light dilution rate is 10, meaning that 10 m 2 of biofilm grow for every 1 m 2 of incident sunlight, both increasing
  • systems of the present invention may comprise subsystems for cultivation of plants or algae and subsystems for transforming input materials into C0 2 or concentrating C0 2 for providing C0 2 enriched atmospheres, such as a subsystem for calcining calcium carbonate (CaC0 3 ) to CaO and C0 2 using solar thermal energy or process heat above 840°C; in that specific case, CaC0 3 may be obtained from ocean sediment by that or another subsystem of the present invention or as in [Rab09] or
  • the support can be both simplified and constructed from materials readily produced according to the present invention.
  • textiles or meshes (which may be sparse) of strong fibers such as carbon fibers may support films of cellulose acetate,
  • each curtain can be less than 1 mm thick, and more favorably less than 100 pm thick, and most preferably less than 50 pm thick.
  • This arrangement utilizes high-strength-to-mass ratio materials to substitute for the heavier glass supports used in [Liul3], such that this contribution to the areal mass density of
  • subsystems for algal growth as biofilms can be low. Reduced areal mass density entails lower materials requirements to produce a given subsystem area, and also entails reduced system mass. Among other advantages, these reduced requirements enable faster rates of subsystem growth/rates of production of subsystems and lower times necessary to grow the biomass required as material inputs. Light management for high bioproductivity photosynthetic growth:
  • light management may permit reduction in heating by redirecting infrared wavelengths (for utilization elsewhere, such as in thermal processing or in a heat engine), redirection of ultraviolet radiation for use in fabrication (e.g. photocuring polymers), managing growth dynamics of algae (e.g. certain algae have been shown to divide under red light but accumulate mass under blue light []).
  • infrared wavelengths for utilization elsewhere, such as in thermal processing or in a heat engine
  • ultraviolet radiation for use in fabrication e.g. photocuring polymers
  • managing growth dynamics of algae e.g. certain algae have been shown to divide under red light but accumulate mass under blue light [].
  • Various trade-offs are involved in light management.
  • Incident solar irradiation is received by receiving means, which may be selected from: a lens, a Fresnel lens, a Fresnel cylindrical lens, a Fresnel cylindrical lens with backside relief features and frontside antireflective features or coating (for maximizing utilization of incident radiation), a concentrating mirror (especially frontside silvered via vacuum coating).
  • Receiving means are thus capable of concentrating incident radiation. Concentrated incident radiation may optionally be transmitted to a lens or mirror to generate a beam therefrom or otherwise spatially redistribute received irradiance.
  • photosynthetically active radiation (PAR) and actinic radiation may be separated from infrared radiation using either a hot-mirror (including a concave hot-mirror for focusing thermal radiation) or a cold-mirror.
  • Received irradiance may be processed to separate ranges of wavelengths by passage through a prism or wire diffraction grating, a transmissive diffraction grating (e.g. a replicated optics diffraction grating), or by reflection from a reflective grating (e.g. a metalized replicated optics grating such as a blazed grating, especially in the
  • Liu 13 Liu, T; Wang, J . ; Hu, Q.; Cheng, P; Ji, B. ; Liu, J.; Chen, Y. Zhang, W.; Chen, X.; Chen, L. ; Gao, L. ; Ji, C.; Wang, H.; 2013. "Attached cultivation technology of microalgae for efficient biomass feedstock production”; Bioresource Technology 127:216-222.
  • photobioreactor structure using optical fibers as inner light source to fulfill flashing light effects of microalgae Bioresource Technology 138:141-147.
  • silver catalyst copper catalyst; CuO; CuO + ZnO;
  • photoactive additive e.g. UV cured with _

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Abstract

L'invention concerne de nouveaux procédés et moyens de nanofabrication et de nanoassemblage convergents, et des systèmes produits par ceux-ci et leur mise en œuvre qui sont dirigés vers une large gamme d'applications. Des molécules et/ou des nanostructures sont liées à des moyens de liaison supportés et manipulées pour translater de tels précurseurs ou intermédiaires pour qu'ils se lient ensemble dans des emplacements et des orientations souhaités de manière précise pour produire les structures précises souhaitées. L'invention concerne également des procédés et des moyens appropriés pour la fabrication précise d'une gamme de matériaux comprenant du diamant, du carbure de silicium β et des matériaux apparentés, et des modifications précises de ceux-ci telles que des centres colorés dans une configuration prédéfinie pour des applications d'informatique quantique et de traitement et de stockage de l'information, et pour la fabrication précise de matériaux structurés à base d'halite comprenant du MgO, du MgS, du TiC, du VN, du ScN, du ScN dopé par du Mn de manière précise, du NbN, du HfC, du TaC, du HfxTayC, de l'AI2O3, du SrO, du BaO, du ZrO2, du ZrC, du ZrN, du HfN, ainsi que des métaux y compris des métaux réfractaires tels que le W, ce qui permet d'obtenir une gamme extrêmement large de matériaux et de propriétés de matériaux qui peuvent être mis à disposition ou utilisés.
PCT/US2019/057505 2018-10-22 2019-10-22 Procédés de nanofabrication et de nanoassemblage convergents, moyens et applications associés, produits et systèmes émanant de ceux-ci comprenant des procédés et des moyens de conversion de polluants en produits utiles WO2020086632A1 (fr)

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AU2019367972A AU2019367972A1 (en) 2018-10-22 2019-10-22 Convergent nanofabrication and nanoassembly methods, means and applications thereof, products and systems therefrom including methods and means for conversion of pollutants to useful products
SG11202104122RA SG11202104122RA (en) 2018-10-22 2019-10-22 Convergent nanofabrication & nanoassembly methods, means & applications thereof, products & systems therefrom including methods and means for conversion of pollutants to useful products
CA3117524A CA3117524A1 (fr) 2018-10-22 2019-10-22 Procedes de nanofabrication et de nanoassemblage convergents, moyens et applications associes, produits et systemes emanant de ceux-ci comprenant des procedes et des moyens de con version de polluants en produits utiles
MX2021004658A MX2021004658A (es) 2018-10-22 2019-10-22 Metodos, medios y aplicaciones de nanofabricacion y nanoensamblaje convergentes, productos y sistemas de los mismos, incluidos metodos y medios para la conversion de contaminantes en productos utiles.
EP19875294.1A EP3902767A4 (fr) 2018-10-22 2019-10-22 Procédés de nanofabrication et de nanoassemblage convergents, moyens et applications associés, produits et systèmes émanant de ceux-ci comprenant des procédés et des moyens de conversion de polluants en produits utiles
PH12021550913A PH12021550913A1 (en) 2018-10-22 2021-04-22 CONVERGENT NANOFABRICATION and NANOASSEMBLY METHODS, MEANS and APPLICATIONS THEREOF, PRODUCTS and SYSTEMS THEREFROM INCLUDING METHODS AND MEANS FOR CONVERSION OF POLLUTANTS TO USEFUL PRODUCTS
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CN114455894A (zh) * 2022-02-23 2022-05-10 日照弗尔曼新材料科技有限公司 一种水泥基轻质灭火砂浆及其制备方法

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CN114455894A (zh) * 2022-02-23 2022-05-10 日照弗尔曼新材料科技有限公司 一种水泥基轻质灭火砂浆及其制备方法
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MX2021004658A (es) 2021-08-16
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IL282593A (en) 2021-06-30
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CA3117524A1 (fr) 2020-04-30
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