WO2008048695A2 - Synthesis and applications of nanomaterials derived from self-assembled diacetylenic triglycerides - Google Patents

Abstract

Provided are monomers, polymers and co-polymers formed from diacetylenic triglycerides. Also provided is a method for surface coating substrates which are less susceptible to oxidative damage and water contact than current substrates. The materials provided can be used for many purposes. For example, provided are nanomaterials which are prepared from the polymerization of diacetylenic triglycerides. These nanomaterials can be prepared with specific sizes, and can be used for selective trapping of materials, including hydrophobic materials. Nanomaterials having a group which is capable of chelating with silver or gold particles can be used to kill or otherwise reduce the effectiveness of bacteria, prevent bacterial attachment to surfaces, or disrupt biofilms. Also provided are biosensors prepared from diacetylenic polymers.

Description

SYNTHESIS AND APPLICATIONS OF NANOMATERIALS DERIVED FROM SELF-ASSEMBLED DIACETYLENIC TRIGLYCERIDES

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority from U.S. provisional application 60/760,191 , filed January 19, 2006, the disclosure of which is hereby incorporated by reference to the extent not inconsistent with the disclosure herewith.

BACKGROUND OF THE INVENTION

[0002] This invention relates generally to diacetylenic triglycerides and polymers formed therefrom.

[0003] Polymers and polymeric compositions are widely used in the automotive, aerospace, marine, sport, military, and industrial fields. These materials are lightweight and have demonstrated low assembly costs, excellent mechanical properties, high corrosion resistance, and dimensional stability. Polymers and polymeric compositions are generally made of synthetic chemicals derived from petroleum. Petroleum-based products are becoming increasingly undesirable for many reasons. As applications of polymers and polymeric compositions increase, alternative, non-petroleum sources are needed for these materials.

[0004] Many people have attempted to form polymers from various materials. Single-chain diacetylenic thiol-terminated compounds are reported to organize into self-assembled mono- and multi-layers on gold and polymerize using UV light (See Kim, et al., J. Am. Chem. Soc. 1995, 117, 3963-3967; Kim et al., Tetrahedron Letters 1994, 35(51 ), 9501 -9504). US patent 4562141 describes photo- polymerization of single-chain conjugated diacetylenic compounds having a polar group and a hydrocarbon chain. However, single-chain materials tend to form micellar structures, and do not form ordered single-chain structures which are necessary to position the alkyne groups in the proper position for polymerization. In addition, single-chain compounds that do polymerize form one-dimensional polymer materials which are not suitable for production of high strength materials. [0005] US patents 4933114 and 4314021 describe lipids having a hydrophobic acyl chain containing at least two conjugated acetylenic linkages for use in radiation- sensitive compositions and photographic elements. The lipids in 4933114 and 4314021 form bimolecular layer structures and are described as amphiphatic. PCT publication WO 00/56788 discloses single-chain bilayer-compatible hydrophobic chains having a conjugated diacetylenic group and a terminal amine and polymers thereof. US patent 4348329 describes phospholipids containing a conjugated acetylene group and terminal amine groups. US patent 5290960 describes phospholipids having diacetylenic groups which are used for preparing lipid vesicles and tubules.

[0006] There is a need in the art for an improved polymerization system which can utilize biorenewable materials such as soybean oil or olive oil. There is also a need in the art for biodegradable polymers. These improved polymers can be used in many applications, including surface coating.

BRIEF SUMMARY OF THE INVENTION

[0007] Provided are monomers, polymers and co-polymers formed from diacetylenic triglycerides. Also provided is a method for surface coating substrates which are less susceptible to oxidative damage and water contact than current substrates. The materials provided can be used for many purposes. For example, provided are nanomaterials which are prepared from the polymerization of diacetylenic triglycerides. These nanomaterials can be prepared with specific sizes, and can be used for selective trapping of materials, including hydrophobic materials. Nanomaterials having a group which is capable of chelating with silver or gold particles can be used to kill or otherwise reduce the effectiveness of bacteria, prevent bacterial attachment to surfaces, or disrupt biofilms. Also provided are biosensors prepared from diacetylenic polymers.

[0008] More specifically, in a specific class of compounds, provided is a diacetylenic triglyceride having the formula:

wherein two or three of Xi, X2 and X3 independently has the formula:

-OCO-{(CH₂)_n-[C_≡C-C_≡C]}_m-(CH₂)_p-CH₃,

wherein n and p are independently integers from 0 to 30, wherein the sum of p + n is at least 2; wherein m is an integer from 1 to 3;

and the other of Xi, X₂ and X₃ is selected from the group consisting of H, H₂, or an end group, provided that the end group does not contain -O-PO3- or dimethylamine.

[0009] In one embodiment, the end group is selected from the group consisting of: a halogen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorous-containing group, a carboxylic acid, -SH, -OH, -NR¹R², -COOR¹, - CONR¹R², -OSO3R¹, -SO₃R¹, and -Si(OR¹ )₃ and its silanoxide polymers, wherein R¹ and R² are independently hydrogen, halogen or C1 -C6 alkyl. Specific end groups include -SH, -O-CH₂CH₂-N(CH₃)-CH₂CH₂-N(CH₃)₂, OH, F, Cl, Br, I, -SCOCH₃, - COOR. -NH₂, -Si(OCH₃)₃, and -Si(OC₂H₅)₃.

[0010] The diacetylenic triglycerides can be photopolymerized by exposure to radiation in a wavelength range that is effective to photopolymehze at least a portion of the diacetylenic triglycerides. In one example, the diacetylenic triglycerides are polymerized under an inert atmosphere such as argon or nitrogen. "Radiation" as used herein is intended to include not only the ultraviolet, visible and infrared regions of the electromagnetic spectrum, but also electron beam radiation such as is produced by cathode ray guns, gamma rays, x-rays, beta rays, and electrical corona discharge. Methods of exposing compositions to radiation and methods of determining the effective wavelength and effective time of exposure to produce the desired amount of polymer are easily determined by one of ordinary skill in the art.

[0011] In addition, co-polymers can be prepared wherein a diacetylenic triglyceride is co-polymerized with a aryl diacetylene and/or a diaryl diacetylene using the methods described herein. As known in the art, the proportions of each component can be changed to produce the desired material.

[0012] Also provided are methods to synthesize triglycerides which involve less expensive starting materials and reagents, less-flammable reagents, and fewer steps than currently used procedures.

[0013] Also provided is a method of synthesizing a triglyceride with an amino or thiol functional group.

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 shows one example of self-assembly and irradiation of diacetylenic fatty acid 6 on an alumina surface.

DETAILED DESCRIPTION OF THE INVENTION

[0015] The description below is intended to provide non-limiting examples and explanation of certain aspects of the invention.

[0016] As used herein, "diacetylenic" means a particular structure contains at least two carbon-carbon triple bonds. A diacetylenic structure can be conjugated, where at least two of the carbon-carbon triple bonds are formed from adjacent carbon atoms (-C≡C-C≡C-), or non-conjugated. As used herein, "triglyceride" means a particular compound has the general structure shown in Scheme 1 :

Scheme 1

where the R's may be the same or different. In certain classes of triglycerides, one, two or three of the R's are hydrophobic groups. Certain classes of triglycerides are diacetylenic triglycerides, where at least one R contains at least two carbon-carbon triple bonds. Certain classes of diacetylenic triglycerides are conjugated, where at least one R contains at least one conjugated carbon-carbon triple bond pair. In certain classes of triglycerides, one or more of the hydrogens on the terminal carbons are substituted with an end group, such as a group which can form a bond to a substrate.

[0017] One class of triglycerides is not amphiphatic. One class of compounds does not form bimolecular larger structures. One class of compounds does not have a hydrophilic portion. One class of compounds does not have an ionic group. One class of compounds does not have a polar group. One class of compounds does not have a polar group on all chains. One class of compounds does not contain terminal amine group. One class of compounds is formed from biorenewable materials. One class of compounds is biodegradable polymers, where the polymer is capable of being broken down or consumed by bacteria.

[0018] As used herein, an "unsaturated fatty acid" is a group having a carboxylic acid group and an aliphatic tail having at least one double or triple bond. A "fatty acid" is a group having a carboxylic acid group and an aliphatic tail.

[0019] As used herein, a "substrate" is a material which the desired material is formed at least partially on or around or inside. Substrates can be particles, such as metal-containing particles. Particular classes of substrates are gold or silver particles. Other particular classes of particles are in a variety of size ranges, such as nanometer-scale, micrometer-scale, or larger. A particular class of substrates is a metal oxide particle. Substrates can be glass, silicon, quartz, alumina or other metal surfaces. Substrates can be a porous filter, where a layer of desired material is formed on the filter or inside a pore of the filter. Arrays of desired material can be formed using spaced-apart areas on a substrate, such as using the pores of a filter. Other substrates can be medicinal drugs, proteins, DNA, and other substances. These substrates can be encapsulated by polymers or monomers of the invention, for example. Other substrates are easily determined by one of ordinary skill in the art, depending on the desired use of the material.

[0020] As used herein, a "nanomaterial" is a material itself having overall dimensions in the nanometer scale (i.e., fractions or multiples of nanometers and all individual values and ranges therein) or present around a nanometer scale substrate. The term "nanomaterial" is not used as a definitive limit for the size of materials described herein, but rather is used to describe the relative size of the materials described herein. In specific classes of materials described herein, the diameter of the material is from 2-15 nm. In specific classes of materials described herein, the diameter of the material is less than 100 nm. In specific classes of materials described herein, the diameter of the material is less than 15 nm. In specific classes of materials described herein, the material described herein contains an inner section "pore" with a nanometer scale dimension.

[0021] As used herein, a "layer" means that one or more partial or complete monolayers of molecules or atoms are present, and is not meant to indicate that a perfect layer of molecules or atoms is formed. There may be gaps, cracks, pinholes or other defects present in a layer, as long as the gaps, cracks or other defects do not prevent the desired function.

[0022] As used herein, a "cross-linkage" is a bond between two structures. A cross- linkage can be between two groups on a single triglyceride or between two groups on different triglycerides, for example. In a particular example, cross-linking occurs between conjugated diacetylenic groups, as shown herein. In one specific example, one triple bond from two individual conjugated diacetylenic groups forms a double bond.

[0023] As used herein, a "polymer" is a structure having a unit which repeats at least three times. As used herein, "polymerization" means that a polymer is formed.

[0024] As used herein, "self-assembled monolayer" means a molecular layer of molecules is formed, where substantially all of the molecules in the self-assembled monolayer have substantially the same chemical and physical form. As known in the art, a "perfect" self-assembled monolayer is not possible using currently available synthesis and characterization techniques.

[0025] As used herein, "substantially" means that more of the given structures have the listed property than do not have the listed property. In one example, "substantially" means more than 50 % of any given structures have the listed property. In one example, "substantially" means more than 60 % of any given structures have the listed property. In one example, "substantially" means more than "substantially" means more than 80 % of any given structures have the listed property. In one example, "substantially" means more than 90 % of any given structures have the listed property. In one example, "substantially" means more than 95 % of any given structures have the listed property. In one example, "substantially" means more than 97 % of any given structures have the listed property. In one example, "substantially" means more than 99 % of any given structures have the listed property.

[0026] As used herein, "bonded" means two or more chemical or physical elements are coupled or joined. "Bonded" can include chemical bonds, chemisorptive bonds, covalent bonds, ionic bonds, van der Waals bonds, and hydrogen bonds, for example. As used herein, "group" means one or more atoms. Group includes hydrogen.

[0027] As used herein, "natural" means occurs in nature.

Monomer Synthesis

[0028] Although the synthesis reactions are shown specifically for one acid, it is understood that other acids can be used with the knowledge of one of ordinary skill in the art without undue experimentation.

[0029] This work demonstrates the conversion of natural fatty acids and triglycerides, derived from plants in one example, to useful materials. The olefinic function of the fatty acids, such as oleic acid, was used to prepare diacetylenic fatty acids. Scheme 2 summarizes a new synthesis of diacetylenic alkanoic acid 6 and its triglyceride 7 starting from oleic acid. Oleic acid (1) was methylated with oxalyl chloride in dichloromethane followed by methanol and pyridine to give methyl 9- octadecenoate (2). Double allylic bromination of alkene 2 with 2 equivalents of N- bromosuccinimide (NBS) and a catalytic amount of benzoyl peroxide in refluxing carbon tetrachloride for two hours to give methyl 8,1 i-dibromo-9-octadecenoate (3), which upon bromination with 1 equivalent of bromine in carbon tetrachloride at 25⁰C afforded methyl 8,9,10,11 -tetrabromooctadecanoate (4). It is possible to prepare compound 4 from compound 2 in one pot, in which dibromide 3 was not isolated and directly subjected to the bromination with bromine. Dehydrobromination of tetrabromide 4 with 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in benzene at 25⁰C gave methyl 9,10-dibromo-8,10-octadecadienoate (5), which was further dehydrobrominated with potassium f-butoxide in THF at 25⁰C for 4 hours to furnish 8,10-octadecadiynoic acid (6). Likely, the methyl ester function hydrolyzes under the basic conditions. Compound 6 is a known compound,¹³ which was previously prepared via a sequential alkylations of 1 ,4-bis(thmethylsilyl)butadiyne.¹² Again, it is not necessary to isolate compound 5 in the conversion of compound 4 to compound 6. The potassium t-butoxide reagent can be added to the crude product of compound 5 to obtain compound 6. Condensation of 3 equivalents of 8,10- octadecadiynoyl chloride, derived from diynoic acid 6 with oxalyl chloride in dichloromethane, with 1 equivalent of glycerol and pyridine afforded 1 ,2,3-tris(8,10- octadecadiynoyl)glycerol (7).

Scheme 2 oxalyl chloride, MeOH, pyridine "CO₂H ► "CO,CH,

[0030] The above synthesis of compound 7 begins with a fatty acid, such as oleic acid. Other fatty acids such as palmitoleic acid [cis-CH₃(CH₂)₅CH=CH(CH₂)₇COOH] can also be used to produce the corresponding 1 ,2,3-tris(7,9- hexadecadiynoyl)glycerol and 1 ,3-bis(7,9-hexadecadiynoyl)glycerol. Other unsaturated fatty acids such as linoleic, arachidonic, eracic, docasahexaenoic, eicosapentaenoic, and alpha-linoleic can be used. Also developed was a direct and shorter method to produce triglyceride 7 starting from triolein (8) (Scheme 3), a compound obtained from the chlorination of oleic acid (1) with oxalyl chloride (or thionyl chloride) followed by esterification with 0.3 equivalents of glycerol and pyridine. Similar allylic bromination and addition of bromine of triolein with NBS and Br₂ gives dodecabromide 9. Dehydrobromination of compound 9 with DBU and potassium f-butoxide afforded three moles of diacetylenic fatty acid 6. Similar treatment of 6 with oxalyl chloride and glycerol and pyridine provided diacetylenic triglyceride 7.

[0031] Olive oil and soybean oil are used similarly to produce diacetylenic triglycerides for the production of polymers. These biopolymers are biodegradable and derived from plants.

[0032] To verify the structure of compounds 6 and 7, compound 6 was independently synthesized from a known procedure¹² with minor modification (Scheme 4). Hence, 1 ,4-bis(trimethylsilyl)-1 ,3-butadiyne (10; from Aldrich Chem. Co.) was treated with CH₃Li in THF at -78⁰C followed by 7-bromoheptyl methoxymethyl ether [11 ; derived from the monoprotection of 1 ,7-heptanediol and triethylamine and chloromethyl methyl ether followed by bromination with triphenylphosphine and /V-bromosuccinimide (NBS) in dichloromethane], and potassium fluoride in DMF to give diyne 12. Deprotonation of compound 12 with n- BuLi in THF at -78⁰C followed by bromoheptane gave diyne 13. Removal of the MOM (methoxymethyl ether) protecting of 13 with 37% HCI in methanol followed by oxidation of the resulting primary alcohol with pyridinium dichromate in DMF gave diynecarboxylic acid 6. The spectral data of this compound 6 are similar to that of prepared from bromination and dehydrobromination of methyl oleoate (2).

Scheme 4

Br (CH₂)₇ — OCH₂OMe

I ) MeLi, THF 11

Me₃Sr -SiMe₃ ► Me₃Sr -Li ►

-78°C 2) KF, DMF

10 π-BuLι, THF, Br (CH₂)₆CH₃ -(CH₂J₇OCH₂OMe _► -(CH₂)₇OMOM

HMPA

12

37% HCI

MeOH₂CO — (H₂C)₇ -(CH₂J₆CH_{3 ►} HO-(H₂C)₇- -(CH₂JgCH₃

MeOH

13 14

Pyπdinium dichromate

HO₂C-(H₂C)₆- -(CH₂J₆CH₃

DMF

1) Et₃N, CH₂CI₂ ► Br (CH₂J₇ — OCH₂OMe

CICH₂OCH₃

2) Ph₃P, NBS 11

CH₂CI₂

End Group Synthesis Example

[0033] In nanomatehal fabrication, the presence of a thiol or amino functional group or other functional group in the molecule is desired in many cases. As one example, diacetylenic carboxylic acid 6 was treated with oxalyl chloride in dichloromethane followed by 0.5 equivalents of 3-bromo-1 ,2-propanediol and pyridine to give diester 15 (Scheme 5). Displacement of the bromo moiety of compound 15 with sodium thioacetate in ethanol affords thioester 16, which upon basic hydrolysis furnishes thiodiacetylenic glyceride 17. Applications of compound 17 in nanomaterials and biosensor fabrication are described in the following sections.

[0034] Other end group fabrication techniques are known in the art, and can be used with the materials described here without undue experimentation. Scheme 5

HO₂C-(H₂C)₆- -(CH₂)₆CH₃

NaSCOCH₃ ►

EtOH

16 17

Surface coating

[0035] It is known that fatty acids adsorb onto metal oxide surfaces through their carboxy group, and as a result, form films based on monomolecular layers on such surfaces via self-assembly. In previous work, such monolayers were prepared by immersing a metal oxide substrate such as glass, Siθ2 or alumina in a nonpolar organic solution such as toluene and hexane containing fatty acid for a certain period of time. Provided here are methods to fabricate nanometer-scale structure based on diacetylenic alkanoic acid or its triglyceride, for example, using nanometer-scale templates. Conditions were optimized by studying monolayer formation on alumina and then for photopolymerization of the diacetylenic alkanoic acid molecules.

[0036] Alumina is one of the materials used to prepare nanoporous filters. Such filters contain an array of cylindrical pores having a uniform diameter, and thus are suitable for size-based separation of small objects as compared with commonly used polymer-based filter papers. In addition, anodic alumina filters having pores of a different diameter (10-1000 nm) are commercially available. Thus, the methods provided here can be used to tailor the surface properties of such filters via simple monolayer formation.

[0037] Conditions for monolayer formation and polymerization of the diacetylenic alkanoic acid 6 were studied on a planar alumina surface, which is a piece of aluminum-deposited cover slip whose surface is oxidized to be AI2O3. After cleaning in UV-ozone cleaner for 90 min, the substrate was immersed in 3.6 mM toluene solution of compound 6 for one hour, washed with toluene, and dried. The monolayer formation was evaluated from water contact angle of surface (data not shown). Although alumina surface immersed in toluene (no fatty acid) was hydrophilic, the surface became hydrophobic after the alumina sample was immersed in a toluene solution containing stearic acid (C17H35COOH) or diacetylenic alkanoic acid 6. The water contact angle of the alumina surface coated with stearic acid was larger (ca. 90 °) than that coated with 6 (ca. 68°), indicating that the molecular packing of 6 is not as perfect as obtained with stearic acid.

[0038] However, the molecular packing of 6 on alumina surface is dense enough for photopolymerization. The water contact angles of the monolayer-coated surface were 68° and 91 ° measured before and after photopolymerization with UV light (254 nm, 20 mW, 6 min) under Ar, respectively (Table 1 ). It is expected that the water contact angle would increase after photopolymerization of thin film of molecules containing a diacetylenic unit. The water contact angle of the polymerized monolayer was stable in 0.2 M aqueous NH₃ solution for 3 min, where the contact angle of unpolymehzed monolayer decreased to 40° under the same conditions.

[0039] Photo-irradiation of self-assembled diacetylenic fatty acid 6 on alumina gave polymer 18 (Scheme 6 and Figure 1 ). Raman spectra of compound 6 and polymer 18 show diacetylenic absorption at 2256 cm^"1 (for compound 6) and enyne absorption at 2094 cm^"1 (for polymer 18), respectively. Results of contact angle measurements of monomers 6 and 7, and their corresponding polymers 18 and 19, along with the control, stearic acid (a saturated fatty acid was used as a negative control; before and after irradiation), glycerol thstearate (a saturated triglyceride was used as a negative control; before and after irradiation) are summarized in Table 1. The data clearly show that the polymers (more organized materials) have larger contact angles than that of monomers (less organized materials).

[0040] Using the methods and materials described here, polymers can be prepared on various surfaces, as known in the art. Modifications of the polymerization reaction (components, component amount, time of polymerization, end group, concentration of diacetylenic groups, for example), can be used as known in the art without undue experimentation. Table 1. Contact angle measurements of water on alumina surfaces after immobilizing glycehdes and unsaturated fatty acids.

Surface Surface

Polymer 19

Nanoparticles

[0041] A number of different nanoparticles such as gold, silver and metal oxide having different size and shape are used as a template for the polymers to control the size and shape of self-assembled structures as well as the efficiency of photoinitiated polymerization of the diacetylene molecules. In addition, physical properties of these self-assembled materials and their photo-induced polymers were studied. For example, diacetylene-coated nano-particles cross-linked to diacetylene- coated electrode surface covalently immobilize two- or three-dimensional nano- particle assemblies. The resulting pores from the spacing between particles are controlled by varying the size and shape of the nanoparticles. They can be used for molecular-sieving, for example. In addition, the electron transfer efficiency of the assemblies, which is important to develop energy-related devices such as solar cells, can be systematically studied by controlling the nano-particle size and shape as well as the extent of the cross-linking. These properties are measured using electrochemistry experiments and scanning tunneling microscopy.

[0042] The controlled self-assemblies of ths(diacetylenic) glycerides and bis(diacetylenic) glycerides on an alumina filter are described in Scheme 7. The Scheme describes the preparation of a specific size of nanoporous filter (having cylindrical holes of 5 - 10 nm diameter) from a photo-crosslinkage of self-assembled diacetylenic triglyceride, such as 7, on an anodic alumina filter membrane. After photopolymerization, the nanoporous polymers are obtained by washing the metal oxide filter with a solvent. The nanoporous polymers have a specific inner hydrophobic core of nanometer diameter, which can be used to selectively trap hydrophobic molecules which fit into the core. In addition, nanoparticles coated with diacetylene molecules are immobilized within such pores via photopolymerization to prepare an array of nanoparticles within such cylindrical nanopores. Catalytic reaction on the immobilized nanoparticles as well as electron transfer efficiency are studied.

cheme 7

b ^■ 10 nm >n αiametor

Manomaienais (polymerized triglyceride)

[0043] Scheme 8 shows self-assemblies of thiol diglyceride 17 on the surface of nano-gold particles. Nano-gold particles are prepared using a deposition method of gold vapor onto a frozen solvent matrix. In the solvent matrix, thiol diglyceride 17 is present as a coordinating chemical with gold nano-particles. After ultraviolet irradiation and removal of gold nanoparticle, nanotriglycerides are obtained.

Self-assembled

Nari 4omatiteria$ls (polymerized triglyceride) H C-O-C

O

HS CH-, 17 Sensors

[0044] A sensing device is prepared by depositing a specific size of macromolecule (such as prion protein; PrP, monomehc form and oligomeric form of octamer, separately) on an electrically charged gold plate (Scheme 9). Other macromolecules can be used including spore-forming bacterium, Bacillus anthracis, and other proteins which are desired to be studied. Thio-diacetylenic triglyceride, compound 17, is then added to the gold plate to fill up the vacant spaces. After photopolymerization of the diacetylenic functions of compound 17, the macromolecule is removed by washing with water. The surface of the gold plate consists of a polymer derived from compound 17 with a number of specific sized holes (marked with dotted circles; a monomeric prion for one gold chip and a separate one gold chip for octamehc prion protein). The plate can be used to trap or detect the macromolecule that is used to imprint the plate. Both monomeric PrP and octamehc PrP chips are used to analyze both forms of an equilibrated PrP. In the equilibrated PrP, a mixture of monomeric and octameric aggregate of PrP is formed. Using both sensor chips, both forms of PrP are identified. It is unlikely other proteins (not prion) have two forms with such specific sizes. Hence, the process allows a specific detection of prion proteins in minute amounts.

Scheme 9

Electrical charge

prion

Electrical charge

A current ctaartye is found

Copolymerization

[0045] Rigid co-polymers are produced from copolymerizations of either diacetylenic alkanoic acid 6 or diacetylenic triglyceride 7 with various aryl diacetylenes (such as compound 20) and diaryl diacetylenes 22 (Scheme 10). Monoaryl diacetylene 20 and diaryl diacetylenes 22 are prepared from palladium- catalyzed cross coupling of 1 -alkyl- or 1 -aryl-4-trimethylsilyl-1 ,3-butadiyne (see Scheme 4 for a similar synthesis) with aryl halides.¹⁷'¹⁸ Co-polymerization of diacetylene acid 6 with 10 - 20% of diacetylene 20 under light affords co-polymer 21 , which has a greater rigidity than that of polymer 18. Similarly, co-polymerizations of triglyceride 7 with diacetylenes 22 (10 - 20%) produce co-polymers 23, which have greater optical properties and rigidities than that of polymer 19. The conjugation from the cross linkage enyne moieties and the added aromatic rings (from compound 22) provide an extended conjugation for absorption and admission of light to longer wavelengths. Hence, these new co-polymers provide more rigid materials with a tunable optical property. [0046] It is known that concentration of the components of the solutions can be modified to provide the desired product. Such modifications can be carried out by one of ordinary skill in the art without undue experimentation.

Scheme 10

Sυrϊace Surface Co-Polymer 21

22 : R ', R^ = alkyl or H a

Co-Polymers 23

Nanostructures for Infection Control

[0047] Scheme 11 shows one example of the use of the nanostructures described here for infection control. Amino- or thiol-functionalized diacetylenic triglycerides (such as compound 24) are formed via a self-assembly into bilayer-truncated cone using known procedures and then photo-cross-linked to produce cross-linked nanostructure 26. Solution of sodium borohydhde and silver nitrate are added, and then reduced (hydroxamine) to form silver particles on the surface of nanostructure 26. This silver-containing nanostructure can be used as described earlier for infection control, using known applications. Silver nanoparticles that are currently known are difficult to use because they aggregate rapidly and are difficult to integrate into new materials. The nanoparticles described here provide discrete nanostructures that aggregate to a lesser extent.

[0048] Compound 23 is synthesized from a sequence of reactions: (i) esterification of compound 6 with oxalyl chloride followed by pyridine and 0.5 equivalents of 2- (1 ,2-dihydroxyethyl)-1 ,3-dioxolane;¹⁹ (ii) removal of the 1 ,3-dioxolane protecting group with HCI-THF-H₂O; and (iii) reduction with sodium borohydhde in ethanol.

Scheme i 1

23 24 ainirso functions

Experimental Section

[0049] General Methods. Nuclear magnetic resonance spectra were obtained from a 400 MHz or 200 MHz instrument in deuteriochloroform, and reported in ppm.

Infrared spectra are reported in wavenumbers (cm ). Mass spectra were taken from a Maldi spectrometer or an electrospray HPLC-MS instrument. Silica gel (200-425 mesh) was used for the flash column chromatographic separation. Tetrahydrofuran and diethyl ether were distilled over sodium and benzophenone before use. Methylene chloride was distilled over CaH₂ and toluene and benzene were distilled over LiAIH₄. Chemicals and reagents were purchased either from Aldrich Chemical Company or Fisher Chemical Company, and were used without purification.

Methyl 9-Octadecenoate (2)

[0050] To a solution of 10.0 g (35.4 mmol) of oleic acid in 50 ml_ of dichloromethane under argon at O⁰C, was added dropwise 5.60 ml_ (53.1 mmol) of oxalyl chloride. After stirring for 30 minutes, 20 ml_ of methanol and 20 ml_ of pyridine were added, and the mixture was stirred at 25⁰C for 30 minutes. The mixture was diluted with 100 ml_ of dichloromethane, washed with aqueous sodium bicarbonate, ammonium chloride, and water, dried over MgSO₄, and concentrated to give 9.58 g (91.3% yield) of compound 2. ¹H NMR δ 5.35 (m, 2 H, =CH), 3.67 (s, 3 H, OMe), 2.30 (t, J = 7 Hz, 2 H, CH₂CO), 2.0 (m, 4 H, CH₂C=), 1.6 (m, 2 H), 1.36 - 1.22 (m, 20 H), 0.88 (t, J = 7 Hz, 3 H, Me); ¹³C NMR δ 174 (s, CO), 130.2, 129.9, 51.6 (OCH₃), 30.0, 29.9, 29.7, 29.5, 29.34, 29.3, 29.27, 27.4, 27.3, 25.1 , 22.9, 14.3.

Methyl 8,11-Dibromo-9-octadecenoate (3)

[0051] A solution of 5.O g (17 mmol) of compound 2, 6.O g (34 mmol) of N- bromosuccinimide (NBS), and 0.15 mg (0.6 mmol) of benzoyl peroxide in 20 ml_ of tetrachloromethane was heated at reflux for 2 hours under argon atmosphere. The resulting mixture was cooled to room temperature, diluted with dichloromethane, washed twice with water and then brine, dried (MgSO₄), concentrated, and column chromatographed on silica gel using a gradient mixture of petroleum ether and ether as eluants to give 3.0 g (39% yield) of pure compound 3. ¹H NMR δ 5.81 (m, 2 H, =CH), 4.46 (m, 2 H, CHBr), 3.67 (s, 3 H, OMe), 2.31 (t, J = 7 Hz, 2 H, CH₂CO), 2.0 - 1.4 (m, 4 H), 1.62 (m, 2 H), 1.50 - 1.22 (m, 18 H), 0.88 (t, J = 7 Hz, 3 H, Me); ¹³C NMR δ the spectrum indicated four stereoisomers are presented, 174 (s, CO), 133.7, 133.7 (isomers), 133.5, 133.4, 133.3, 133.2, 133.17, 54.2 (CHBr), 54.1 (isomers), 53.9, 53.8, 51.7 (OMe), 39.2, 39.1 (isomers), 39.0, 38.9, 34.3, 34.2, 34.1 , 32.0, 31.9,

31 .8, 29.3, 29.2, 29.1 , 28.9, 28.7, 28.6, 28.0, 27.9, 27.8, 27.6, 27.5, 25.3, 25.0, 24.9,

22.9, 22.8, 22.7, 14.3. MS (electrospray), m/z 452.1 (M+1 ⁺). Methyl 8,9,10,11-Tetrabromooctadecanoate (4) [0052] To a solution of 0.10 g (0.22 mmol) of compound 3 in 8 ml_ of tetrachloromethane (freshly distilled over calcium chloride under argon) at 25⁰C, was added dropwise 35 mg (0.22 mmol) of bromine. The resulting solution was concentrated on a rotary evaporator to remove the solvent and then dried under vacuum to give a semi-solid material. Crystallization of this material in petroleum ethenether (10:1 ) at O⁰C afforded an isomer (mainly), compound 4. ¹H NMR δ 4.72 (m, 2 H, CHBr), 4.40 (s, 2 H, CHBr), 3.68 (s, 3 H, OMe), 2.32 (m, 2 H, CH₂CO), 2.15 (m, 2 H), 1.90 (m, 2 H), 1.70 - 1.24 (m, 18 H), 0.89 (t, J = 7 Hz, 3 H, Me); ¹³C NMR δ 174.4 (s, CO), 62.0 (2 C, CBr), 58.6, 58.5 (CBr), 51.5 (OMe), 39.1 , 39.0, 34.2, 31.9, 29.2, 29.1 , 29.0, 28.8, 27.5, 27.4, 25.0, 22.8, 14.3.

Methyl 9,10-Dibromo-8,10-octadecadienoate (5)

[0053] A solution of 79 mg (0.13 mmol) of compound 4 and 78 mg (0.52 mmol) of DBU in 5 ml_ of benzene was stirred under argon at 25⁰C for 4 hours. The solution was diluted ethyl acetate, washed with aqueous NH₄CI, water, and brine, dried (MgSO₄), and concentrated to give 58 mg (100% yield) of compound 5 (may contain cis and trans isomers). ¹H NMR δ 6.46 (m, 2 H, =CH), 3.67 (s, 3 H, OMe), 2.30 (m, 6 H), 1.7 - 1.2 (m, 18 H), 0.89 (t, J = 7 Hz, 3 H, Me); ¹³C NMR δ 174.4 (s, CO), 135.8, 135.7, 135.4, 135.1 , 126.1 , 125.8, 51.6 (OCH₃), 42.3, 34.3, 32.5, 31.9, 29.5, 29.3, 29.1 , 28.5, 28.3, 25.1 , 25.0, 24.9, 22.8, 14.3.

8,10-Octadecadiynoic acid (6)¹³

[0054] A solution of 58 mg (0.13 mmol; from the above crude product) and 75 mg (1.3 mmol) of potassium t-butoxide in 3 ml_ of THF was stirred under argon at 25⁰C for 4 hours, and the resulting mixture was diluted with ethyl acetate, washed with aqueous NH₄CI, water, and brine, dried (MgSO₄), concentrated, and column chromatographed on silica gel column using a gradient mixture of chloroform and methanol as eluants to give 26 mg (72% yield) of compound 6.^{13 1}H NMR δ 2.36 (t, 2 H, CH₂CO), 2.24 (t, J = 7 Hz, 4 H, CH₂C^), 1.7 - 1.21 (m, 18 H), 0.88 (t, J = 7 Hz, 3 H, Me); ¹³C NMR δ 179.9 (s, CO), 65.7, 65.6, 65.5, 65.4, 34.1 , 29.1 , 29.0, 28.96, 28.9, 28.7, 28.6, 28.5, 28.3, 24.7, 19.4, 19.3, 14.3. MS (electrospray), m/z, 277.5 (M+1 ), 553.2 (2+ charge; a tetramer of the diynoic acid). 1,2,3-Tris(8,10-octadecadiynoyl)glycerol (7)

[0055] To a solution of 32 mg (0.12 mmol) of diynoic acid 6 in 1.5 ml_ of dichloromethane under argon at 25⁰C was added 18 mg (0.14 mmol) of oxalyl chloride. After stirring for 1.5 hours, the solution was concentrated to dryness to give a liquid, the acid chloride. To the acid chloride, were added under argon a solution of 3.2 mg (0.037 mmol) of glycerol in 1 ml_ of dichloromethane and 10 mg of pyridine. The solution was stirred for 2 hours, diluted with ethyl acetate, washed with aqueous NH₄CI, water, and brine, dried (MgSO₄), concentrated, and column chromatographed on silica gel using a gradient mixture of petroleum ether and ether as eluants to give 18 mg (52% yield) of compound 7. ¹H NMR δ 5.27 (m, 1 H, CHOCO), 4.31 (d, J = 12 Hz, 2 H, CH₂OCO), 4.14 (dd, J = 12, 6 Hz, 2 H, CH₂OCO), 2.33 (m, 6 H, CH₂CO), 2.24 (t, J = 7 Hz, 12 H, CH₂C=J, 1.7 - 1.2 (m, 54 H), 0.88 (t, J = 7 Hz, 9 H, Me). MS m/z 870.33 (M+4); calcd: 867.64 (M+1 ), 868.65 (M+2), 869.65 (M+3), 870.65 (M+4)

Trioleoyl glyceride (8)

[0056] To a cold (O⁰C) solution of 20 g (70.8 mmol) of oleic acid (1) in 100 ml_ of CH₂CI₂ under argon, was added 13.5 g (106 mmol) of oxalyl chloride via syringe. After stirring the solution at O⁰C for 2 h, 2.17 g (23.6 mmol) of glycerol and 11.2 g of pyridine were added separately via syringes. The solution was stirred for 2 hours, diluted with 200 ml_ Of CH₂CI₂, and washed with aqueous NaHCO3, water, and brine, dried (MgSO₄), concentrated, and column chromatographed on silica gel using a mixture of hexane and ethyl acetate (20:1 ) as eluant to give 19.6 g (94% yield).

1,2,3-Tris(8,9,10,11-tetrabromooctadecanoyl)glycerol (9) [0057] A solution of 0.50 g (0.56 mmol) of triolein [or 1 ,2,3-tris(9- octadecenoyl)glycerol (8)], 0.59 g (3.4 mmol) of NBS, and 5.1 mg (0.022 mmol) of benzoyl peroxide in 10 ml_ of tetrachloromethane was refluxed under argon for 2 hours. The solution was cooled to room temperature, diluted with ethyl acetate, washed with water and brine, dried (MgSO₄), concentrated, and column chromatographed on silica gel using a mixture of petroleum ethenethyl acetate (10:1 ) as an eluant to give 1 ,2,3-tris(8,11-dibromo-9-octadecenoyl)glycerol. ¹H NMR δ 5.80 (m, 2 H, CH=), 5.26 (m, 1 H, CHOCO), 4.47 (m, 6 H, CHBr), 4.30 (d, J = 12 Hz, 2 H, CH₂OCO), 4.14 (dd, J = 12, 6 Hz, 2 H, CH₂OCO), 2.32 (m, 6 H, CH₂CO), 2.2 - 1.2 (m, 66 H), 0.88 (t, J = 7 Hz, 9 H, Me).

[0058] To a solution of 0.71 g (0.56 mmol) of the above bromide in 15 ml_ of tetrachloromethane under argon at 25⁰C, was added dropwise 0.25 g (1.56 mmol) of bromine. After stirring for 1 hour, the solution was concentrated to dryness to give 0.92 g crude product 9. ¹H NMR δ 5.82 (m, 1 H), 5.25 (bs, 1 H), 4.86 - 4.10 (a serious of m, 15 H), 2.32 (bs, 4 H), 2.2 - 1.2 (m, 66 H), 0.9 (t, 7 Hz, 9 H).

Conversion of compound 9 to 1,2,3-tris(8,10-octadecadiynoyl)glycerol (7) [0059] To a solution of the above crude product 9 in 10 ml_ of benzene (toluene can be used) under argon, was added 1.02 g (6.72 mmol) of 1 ,8- diazabicyclo[5.4.0]undec-7-ene (DBU). The solution was stirred at room temperature for 14 hours, diluted with ethyl acetate, washed with aqueous NH₄CI, water, and brine, dried (MgSO₄), concentrated, and column chromatographed using a gradient mixture of hexane and ether to give 74 mg (97% yield) of the hexabromide.

[0060] To a solution of 0.64 g (0.35 mmol) of the above hexabromide in 10 ml_ of THF under argon, was added 1.18 g (10.5 mmol) of potassium t-butoxide. The mixture was stirred at room temperature under argon for 14 hours, diluted with aqueous NH₄CI and ethyl acetate, the organic layer was washed with brine, dried (MgSO₄), concentrated, and column chromatographed on silica gel to give 0.189 g (65% yield) of 8,10-octadecadiynoic acid (6). NMR spectrum is identical with that prepared from compound 5.

[0061] Compound 6 was converted to triglyceride 7 by following a procedure as that described for the formation of 1 ,2,3-tris(8,10-octadecadiynoyl)glycerol above.

11-(Methoxymethoxy)-1-(trimethylsilyl)-1,3-undecadiyne (12) [0062] To a cold (-78⁰C) solution of 0.545 g (2.80 mmol) of 1 ,4-bis(trimethylsilyl)- 1 ,3-butadiyne (purchased from Aldrich Chemical Company) in 10 ml_ of THF under argon, was added 1.9 ml_ (2.80 mmol) of MeLMiBr (1.5 M in hexane) via syringe. After stirring at room temperature for 4 hours, the solution was cooled to -78⁰C, and added a solution of 0.67 g (2.8 mmol) of compound 11 in 2 ml_ of hexamethylphosphorthamide (HMPA). The solution was stirred at room temperature for 1 hour, diluted with ethyl acetate, washed with 1 N HCI, water and brine, dried (MgSO₄), concentrated to give a crude product. To this crude product, 5 ml_ of DMF and 0.5 g of potassium fluoride were added, and the solution was stirred at room temperature for 0.5 h. The solution was diluted with aqueous NH₄OH, extracted with diethyl ether, and the organic layer was washed with water and brine, dried (MgSO₄), concentrated, and column chromatographed on silica gel using a gradient mixture of hexane and ether to give 0.44 g (76% yield) of compound 12. ¹H NMR δ 4.62 (s, 2 H, OCH₂O), 3.52 (t, J = 7 Hz, 2 H, CH₂O), 3.36 (s, 3 H, OMe), 2.25 (t, J = 7 Hz, 2 H, CH₂C^), 1.90 (s, 1 H, HC=), 1.6 - 1.3 (m, 10 H); ¹³C NMR δ 96.5, 95.4, 78.5, 68.6, 67.9, 64.9, 64.6, 55.2, 29.8, 29.0, 28.9, 28.1 , 26.2, 19.1. HRMS calcd for C₁₃H₂₀O₂, 208.1463; found: 209.1477 (M+1 ).

1-(Methoxymethoxy)-8,10-octadecadiyne (13)

[0063] To a cold (-23⁰C) solution of 0.50 g (2.4 mmol) of compound 12 in 10 ml_ of THF under argon was added 1.8 ml_ (2.9 mmol) of n-BuLi (1.6 M in hexane) dropwise. After stirring at -23 ⁰C for 1 h, a solution of 0.52 g (2.9 mmol) of bromoheptane in 8 ml_ of HMPA was added via cannula under argon, and the resulting solution was stirred for 0.5 h at -23⁰C and 1 h at room temperature, diluted with aqueous HCI, and extracted with diethyl ether. The organic layer was washed with water and brine, dried (MgSO₄), concentrated, and column chromatographed on silica gel using a gradient mixture of hexane and ether as eluant to give 0.333 g (46% yield) of compound 13. ¹H NMR δ 4.62 (s, 2 H, OCH₂O), 3.52 (t, J = 7 Hz, 2 H, CH₂O), 3.36 (s, 3 H, OMe), 2.25 (t, J = 7 Hz, 4 H, CH₂C^), 1.65 - 1.24 (m, 20 H), 0.88 (t, J = 7 Hz, 3 H, CH₃); ¹³C NMR δ 96.6, 77.8, 77.6, 68.0, 65.5, 65.4, 55.3, 31.9, 29.9, 29.1 , 29.0, 28.9, 28.5, 28.4, 26.3, 22.8, 19.4, 14.3. HRMS calcd for C₂₀H₃₄O₂, 306.2559; found: 307.2563 (M+1 ).

8,10-octadecadiyn-i-ol (14)

[0064] A solution of 0.19 g (0.62 mmol) of compound 13 and 0.5 ml_ (4.3 mmol) of 37% HCI in 5 ml_ of methanol was stirred at room temperature for 14 h, diluted with aqueous NH₄OH, and extracted with ethyl acetate. The organic layer was washed with water and brine, dried (MgSO₄), concentrated, and column chromatographed on silica gel using a mixture of hexane and ether (1 :1 ) as eluant to give 0.16 g (98% yield) of compound 14. ¹H NMR δ 3.59 (t, J = 7 Hz, 2 H, CH₂O), 2.20 (t, J = 7 Hz, 4 H, CH₂C^), 2.14 (s, 1 H, OH), 1.56 - 1.20 (m, 20 H), 0.84 (t, J = 7 Hz, 3 H, CH₃); ¹³C NMR δ 77.7, 65.6, 65.5, 63.1 , 32.9, 31.9, 29.0, 28.9, 28.8, 28.5, 28.4, 25.8, 22.8, 19.4, 19.3, 14.2. HRMS calcd for Ci₈H₃₀O, 263.2297; found: 263.2301 (M+1 ).

8,10-Octadecadiynoic acid (6) from compound 14 [0065] A solution of 0.29 g (1.1 mmol) of alcohol 14 and 3.0 g (7.9 mmol) of pyhdinium dichromate (PDC) in 15 ml_ of DMF was stirred at room temperature for 14 h, diluted with 150 ml_ of water, and acidified with 3 N HCI. The mixture was extracted with diethyl ether three times, and the combined organic layer was washed with water and brine, dried (MgSO₄), concentrated, and column chromatographed on silica gel using a mixture of chloroform and methanol (50:1 ) as eluant to give 0.21 g (69% yield) of acid 6. Spectral data are similar to that described for the preparation of the compound described earlier.

1,2,3-Tris(8,10-octadecadiynoyl)glycerol (7) from compound 14

[0066] The experimental procedure is the same as that described in experiments elsewhere, and compound 7 with similar chemical yield was obtained.

3-Bromo-1,2-bis(8,10-octadecadiynoyloxy)propane (15) [0067] To a solution of 75 mg (0.27 mmol) of diyne acid 6 in 3 ml_ of dichloromethane under argon was added 0.15 g (1.16 mmol) of oxalyl chloride. The solution was stirred at room temperature for 1.5 h, concentrated on a rotary evaporator, and benzene was added. The solution was again concentrated on a rotary evaporator and then under vacuum to removal excess of oxalyl chloride. To the crude acid chloride under argon, 1 ml_ of dichloromethane, 19 mg (0.12 mmol) of 3-bromo-1 ,2-propanediol (purchased from Aldrich Chem. Co.), and 50 μl_ of pyridine were added. The solution was stirred at room temperature for 2 h, diluted with ethyl acetate, washed with aqueous NH₄CI, water and brine, dried (MgSO₄), concentrated to give 40 mg (50% yield) of compound 15. ¹H NMR δ 5.20 (m, 1 H, CHOCO), 4.25 (m, 2 H, CH₂OCO), 3.5 (m, 2 H, CH₂Br), 2.4 - 2.2 (m, 12 H), 1.7 - 1.2 (m, 36 H), 0.9 (t, J = 7 Hz, 6 H).

3-(Acetylthio)-1,2-bis(8,10-octadecadiynoyloxy)propane (16)

[0068] A mixture of 0.76 g (0.01 mol) of thioacetic acid and 0.84 g (0.01 mol) of sodium bicarbonate in 10 ml_ of ethanol was stirred at room temperature for 1 h. [0069] To a solution of 20 mg (0.03 mmol) of compound 15 in 0.5 ml_ of ethanol was added 60 μl_ (0.06 mmol) of sodium thioacetate (the above mixture). The solution was stirred at room temperature for 20 h, concentrated, and column chromatographed on a short silica gel column using hexane and ether as eluant to give compound 16.

3-Thio-1,2-bis(8,10-octadecadiynoyloxy)propane (17)

[0070] A solution of 10 mg (0.015 mmol) of compound 16 in 0.5 mL of THF and 0.5 ml_ of concentrated NH₄OH was stirred at room temperature for 10 h. The solution was concentrated to give 9 mg of compound 17 (quantitative yield).

[0071] When a group of substituents is disclosed herein, it is understood and intended that all individual members of those groups and all subgroups, including any isomers and enantiomers of the group members, and classes of compounds that can be formed using the substituents are disclosed separately. When a compound is claimed, it should be understood that compounds known in the art including the compounds disclosed with an enabling disclosure in the references disclosed herein are not intended to be included. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure.

[0072] Every formulation or combination of components described or exemplified can be used to practice the invention, unless otherwise stated. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently. When a compound is described herein such that a particular isomer or enantiomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomers and enantiomer of the compound described individual or in any combination. One of ordinary skill in the art will appreciate that methods, device elements, starting materials, and synthetic methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such methods, device elements, starting materials, and synthetic methods are intended to be included in this invention.. Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure.

[0073] As used herein, "comprising" is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of excludes any element, step, or ingredient not specified in the claim element. As used herein, "consisting essentially of does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. Any recitation herein of the term "comprising", particularly in a description of components of a composition or in a description of elements of a device, is understood to encompass those compositions and methods consisting essentially of and consisting of the recited components or elements. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.

[0074] The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.

[0075] In general the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The definitions are provided to clarify their specific use in the context of the invention.

[0076] All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. [0077] One skilled in the art would readily appreciate that the present invention is well adapted to carry out the objects and obtain the ends and advantages mentioned, as well as those inherent therein. The compounds and methods and accessory methods described herein as presently representative of preferred embodiments are exemplary and are not intended as limitations on the scope of the invention. Changes therein and other uses will occur to those skilled in the art, which are encompassed within the spirit of the invention, are defined by the scope of the claims.

[0078] Although the description herein contains many specificities, these should not be construed as limiting the scope of the invention, but as merely providing illustrations of some of the embodiments of the invention. Thus, additional embodiments are within the scope of the invention and within the following claims. All references cited herein are hereby incorporated by reference to the extent that there is no inconsistency with the disclosure of this specification. Some references provided herein are incorporated by reference herein to provide details concerning additional starting materials, additional methods of synthesis, additional methods of analysis and additional uses of the invention.

References:

1. Sagiv, J. Organized monolayers by adsorption. 1. Formation and structure of oleophobic mixed monolayers on solid surfaces. J. Am. Chem. Soc. 1980, 102, 92-98.

2. Fariss, G.; Lando, J.; Rickert, S. Electron beam resists produced from monomer- polymer Langmuir-Blodgett films. Thin Solid Films, 1983, 99, 305-315.

3. Karaman, M. E.; Antelmi, D. A.; Pashley, R. M. The production of stable hydrophobic surfaces by the adsorption of hydrocarbon and fluorocarbon carboxylic acids onto alumina substrates. Colloids & Surfaces, A: Physicochem. & Engineer. Aspects, 2001 , 182, 285-298.

4. Michalski, M. -C; Brogueira, P.; da Silva, A. G.; Saramago, B. Topography of collapsed triglyceride monolayers on glass. Eur. J. Lipid Sci. Technol. 2001 , 103, 677-682. 5. Bhattacharjee, H. R.; Preziosi, A. F.; Patel, G. N. Visual conformational transitions of water soluble polydiacetylenes: Effects of pH and electrolyte on absorption and fluorescence spectra. J. Chem. Phys. 1980, 73, 1478-1480.

6. Neumann, W.; Sixl, H. The mechanism of the low temperature polymerization reaction in diacetylene crystals. Chem. Phys. 1981 , 58, 303-312.

7. Grunfeld, F.; Pitt, C. W. Diacetylene Langmuir-Blodgett layers for integrated optics. Thin Solid Films, 1983, 99, 249-255.

8. Huang, D. -Y.; Tao, Y. -T. Self-assembled monolayer: behavior of diacetylenic amphiphiles. Bull. Inst. Chem., Academia Sinica, 1986, 33, 73-80.

9. Kim, T.; Crooks, R. M.; Tsen, M.; Sun, L. Polymeric self-assembled monolayers. 2. Synthesis and characterization of self-assembled polydiacetylene mono- and multilayers. J. Am. Chem. Soc. 1995, 117, 3963-3967.

10. Mosley, D. W.; Sellmyer, M. A.; Diada, E. J.; Jacobson, J. M. Polymerization of diacetylenes by hydrogen bond templated adlayer formation. J. Am. Chem. Soc. 2003, 125, 10532-10533.

11. Chodkiewicz, W. Synthesis of acetylenic compounds. Ann. Chem. (Paris) [13], 1957, 2, 819-869.

12. Kim, T.; Crooks, R. M. Polymeric self-assembling monolayers. 1. Synthesis and characterization of w-functionalized n-alkanethiols containing a conjugated diacetylene group. Tetrahedron Lett. 1994, 35, 9501 -9504.

13. Xu, Z.; Byun, H. -S.; Bittman, R. Synthesis of photopolymerizable long-chain conjugated diacetylenic acids and alcohols from butadiyne synthons. J. Org. Chem. 1991 , 56, 7183-7186.

14. Ulman, A. Formation and Structure of Self-Assembled Monolayers. Chem. Rev. 1996, 96, 1533-1554.

15. Martin, C. R. Nanomaterials: A Membrane-Based Synthetic Approach. Science 1994, 266, 1961 -1966.

16. Kim, T.; Chan, K. C; Crooks, R. M. Polymeric Self-Assembled Monolayers. 4. Chemical, Electrochemical, and Thermal Stability of w-Functionalized, Self- Assembled Diacetylenic and Polydiacetylenic Monolayers. J. Am. Chem. Soc. 1997, 119, 189-193.

17. Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.; Mori, A.; Hiyama, T. Coupling reactions of alkynylsilanes mediated by a Cu(I) salt: novel syntheses of conjugate diynes and disubstituted ethynes. J. Org. Chem. 2000, 65, 1780-1787. 18. Li, J.; Liang, Y.; Xie, Y. Efficient palladium-catalyzed homocoupling reaction and Sonogashira cross-coupling reaction of terminal alkynes under aerobic conditions. J. Org. Chem. 2005, 70, 4393-4396.

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Claims

CLAIMSWe claim:

1. A diacetylenic triglyceride having the formula:

wherein two or three of X-i, X2 and X3 independently has the formula:

-OCO-{(CH₂)n-[C_≡C-C_≡C]}_m-(CH₂)p-CH3, wherein n and p are independently integers from 0 to 30, wherein the sum of p + n is at least 2; wherein m is an integer from 1 to 3; and the other of X-i, X₂ and X3 is selected from the group consisting of H, H₂, or an end group, provided that the end group does not contain -0-PO₃- or dimethylamine.

2. The diacetylenic triglyceride of claim 1 , wherein the end group is selected from the group consisting of: a halogen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorous-containing group, a carboxylic acid, -SH, -OH, -NR¹R², -COOR¹, -CONR¹R², -OSO₃R¹, -SO₃R¹, and -Si(OR¹)₃ and its silanoxide polymers, wherein R¹ and R² are independently hydrogen, halogen or C1-C6 alkyl.

3. The diacetylenic triglyceride of claim 1 , wherein in at least one of X-i, X₂ and X₃, n is an integer between 4 and 10 and p is independently an integer between 4 and 10.

4. The diacetylenic triglyceride of claim 1 , wherein in at least one of X-i, X₂ and X₃, n is 6 and p is independently 6.

5. The diacetylenic triglyceride of claim 1 , wherein in all of X-i, X₂ and X₃, n is 6 and p is 6.

6. The diacetylenic triglyceride of claim 1 , wherein m is 1.

7. The diacetylenic triglyceride of claim 1 , wherein X₁ and X₂ are formed from C16-C18 fatty acids.

8. The diacetylenic triglyceride of claim 1 , wherein at least one end group is selected from the group consisting of: halide, mesylate, thiol, amine and carboxylic acid.

9. The diacetylenic triglyceride of claim 1 , wherein at least one of X-i, X₂ and X3 is an unsaturated fatty acid.

10. A nanomaterial comprising: a self-assembled layer of diacetylenic triglycerides of claim 1 on a substrate.

11. The nanomaterial of claim 10, containing one or more cross-linkages.

12. The nanomaterial of claim 10, wherein the substrate is glass, SiO₂, quartz or alumina.

13. The nanomaterial of claim 10, formed by the method comprising:

(a) self-assembling a diacetylenic triglyceride having the formula:

wherein two or three of X-i, X₂ and X3 independently has the formula:

-OCO-{(CH₂)_n-[C_≡C-C_≡C]}_m-(CH₂)_p-CH₃, wherein n and p are independently integers from 0 to 30, wherein the sum of p + n is at least 2, wherein m is an integer from 1 to 3, and the other of X-i, X₂ and X3 is selected from the group consisting of H, H₂, or an end group; and

(b) photopolymerizing the diacetylenic triglyceride.

14. The nanomaterial of claim 10, further comprising an aryl diacetylene.

15. A polymer comprising at least one cross-linked diacetylenic triglyceride.

16. The polymer of claim 15, further comprising an aryl group.

17. A method of forming a cross-linked diacetylenic triglyceride, comprising:

(a) providing a diacetylenic triglyceride having the formula:

wherein two or three of X-i, X2 and X3 independently has the formula:

-OCO-{(CH₂)n-[C_≡C-C_≡C]}_m-(CH2)p-CH_3j wherein n and p are independently integers from 0 to 30, wherein the sum of p + n is at least 2, wherein m is an integer from 1 to 3, and the other of X-i, X₂ and X₃ is selected from the group consisting of H, H₂, or an end group; and

(b) photopolymerizing the diacetylenic triglyceride.

18. The method of claim 17, wherein step (a) further comprises providing an aryl- containing fatty acid, wherein a copolymer is formed.

19. The method of claim 17, further comprising forming a self-assembled monolayer of diacetylenic triglyceride on a substrate.

20. The method of claim 19, wherein the substrate contains openings, and wherein the polymer is formed around the openings.

21. The method of claim 19, wherein the substrate is a nanoparticle of specific diameter.

22. The method of claim 21 , wherein the nanoparticle is removed after polymerization.

23. The method of claim 22, wherein the diameter is less than 5nm.

24. The method of claim 17, further comprising a first step of depositing a desired macromolecule in a desired concentration on the surface; and a last step of removing the desired macromolecule after photopolymerizing, wherein the substrate contains a template of the desired macromolecule.

25. A method of synthesizing diacetylenic fatty acids, comprising: alkylating an olefinic carboxylic acid to form an alkylated olefinic ester; tetrabrominating the alkylated olefinic ester to form a tetrabromo ester; dehydrobrominating the tetrabromo ester to form a diacetylene; condensing the diacetylene to form a diacetylenic triglyceride.

26. The method of claim 25, wherein the olefinic carboxylic acid contains from 5 to 30 carbon atoms.

27. A method of synthesizing diacetylenic triglycerides from a triglyceride having two or three chains with one or more double bonds, comprising: tetrabrominating the unsaturated triglyceride to form tetrabromo ester triglyceride; dehydrobrominating the unsaturated tetrabromo ester triglyceride to form a diacetylenic triglyceride.

28. A method of synthesizing a sulfur-containing diacetylenic triglyceride comprising: reacting a diacetylenic carboxylic acid with 3-bromo-1 ,2-propanediol, forming a brominated diacetylenic triglyceride; displacing the bromine in the brominated diacetylenic triglyceride with a sulfur- containing compound, forming a sulfur-containing diacetylenic triglyceride.