MXPA04005698A - Stabilized biocompatible membranes of block copolymers and fuel cells produced therewith. - Google Patents

Abstract

The present invention relates to a stabilized biocompatible membrane useful in fuel cells. A perforated substrate (42) having perforations (49) forms perforated anode (44) and perforated cathode (45). A biocompatible membrane (61) is formed across the apertures and is flush with anode (44) or can be attached to adjacent cathode (45). Biocompatible membrane (61) can include one or more polypeptides (62) and (63).

Description

STABILIZED BIOCOMPATIBLES MEMBRANES OF COPOLYMERS IN BLOCK AND FUEL CELLS PRODUCED WITH THEM BACKGROUND OF THE INVENTION In a series of articles by Meier et al., Several constructions were proposed for polymer-based membranes, which included functional proteins. Although such membranes have been the subject of speculation in the past, it is believed that this is the first polymer-based membrane containing successful biological proteins that included an impregnated enzyme that Corinne Nardin, Wolfgang Meier et al., 39 Angew Chem. Int. Ed., 4599-602 (2000); Langmuir, 16 1035-41 (2000); and Langmuir, 16 7708-12 (2000). These articles describe a triblock copolymer of poly (2-methyloxazoline) -block-poly (dimethylsiloxane) -block-poly (2-methyloxazoline) functionalized in which a protein (a "porin" - a passive pore forming molecule) is impregnated. , not selective). The work of Meier and collaborators is unique and limited in scope. The use of polymers is not widely discussed, nor is it suggested that the polymer membrane described could also be used in conjunction with other similar enzymes. Certainly none of these articles suggests the possibility of creating a synthetic membrane that contains an impregnated biological species capable of participating in oxidation or reduction, or in "the transport mediated by polypeptides of molecules, atoms, protons or electrons active through the membrane. " Indeed, the narrowness of the description and the lack of other successes offer little reason for the optimism that other biological materials could be successfully impregnated into polymer membranes. The creation of membranes for the study of proteins associated with membranes has been known for a long time. See- Filed onaJL Assembly_of Membrane Proteins in Planar Lipid Bilayer, 14 Quart. Rev. Biophys. 1-79 (1981). Actually, the redox and transmembrane proteins were impregnated in biologically based membranes, for example, membranes produced from molecules found in cells or living organisms, for purposes of studying their structure and mechanism. The use of lipid bilayers containing impregnated enzyme complexes such as NADH dehydrogenase from E. Coli, which can transport protons through the membrane and / or participate in redox reactions, has also been described. See Liberatore and collaborators, Publication of Request for U.S. Patent No. 2002/0001739 Al, published on January 3, 2002. Actually, Liberatore and colleagues described the use of such membranes as part of a battery. Neither the existence of biological membranes containing enzymatic complexes nor the discovery of a unique combination of a polymer membrane and a specific enzyme offers much hope for the development of a broad class of synthetic, biocompatible, polymeric membranes that are stable and functional. See also G. Tayhas et al. "A Methanol / Diogen Biofuel Cell That Uses NAD + -Dependent Dehydrogenase as Catalysts: Application of an electro-¾n-z ^ ymatis- -Me ±± LoL_to_ Regenérate Nicotinamide Adenine Dinucleotide at Low Overpotentials", 43, J. Electroanalytical Chem. 155-161 (1998).

SUMMARY OF THE INVENTION The present invention concerns a biocompatible membrane that includes at least one layer of a synthetic polymeric material having a first side and a second side. The biocompatible membrane includes at least one polypeptide associated therewith. In a preferred aspect, the present invention relates to a biocompatible membrane wherein the polypeptide is capable of participating in a chemical reaction, participating in the transport of molecules, atoms, protons or electrons from the first side of the at least one layer to the second side of the same layer or participate in the formation of molecular structures that facilitate such reactions or transport. In an even more particularly preferred aspect of the invention, the polypeptide is a redox enzyme and / or is an enzyme capable of participating in the transmembrane transport of protons. Actually, the polypeptide can have both the ability to cause the release of electrons and to participate in the transport of electrons through the membrane. When discussing the transport of protons through a steffibfaaa-jJDr, it will be appreciated that neither the exact mechanism nor the exact species transferred is known. The transferred species can be a proton per se, a positively charged hydrogen, a hydronium ion, ¾0 + or actually some other charged species. For convenience, however, this will be discussed collectively herein as "protons." Any synthetic polymeric material that is a block copolymer, copolymer or polymer or mixtures thereof may be used in accordance with the present invention so long as they are capable of forming the biocompatible membrane. In a preferred aspect of the present invention, the synthetic polymeric material consists exclusively of at least one block copolymer. Mixtures of block copolymers are also contemplated. Optionally, the synthetic polymeric material will include at least one additive. In a second preferred embodiment according to the present invention, the synthetic polymeric material includes at least one polymer, copolymer or block copolymer. However, if a block copolymer is present, the synthetic polymeric material also includes at least one polymer or copolymer. An optional additive is also contemplated. In another preferred embodiment of the present invention, the synthetic polymeric material may be any material that is capable of forming a biocompatible membrane and includes in addition thereto at least one stabilizing polymer. In another aspect of the present invention, the synthetic polymeric material is a block copolymer, a mixture of block copolymers or a mixture of one or more block copolymers and a stabilizing polymer rich in hydrogen bonds. Preferably, the polypeptide is impregnated in a synthetic polymeric material to thereby form a biocompatible membrane. "Biocompatible membrane" as used herein is one or more layers of a synthetic polymeric material that forms a sheet, cap or other structure that can be used as a membrane and is associated with a polypeptide or other molecule, often of origin biological. By "biocompatible", it is meant that the membrane itself is made of synthetic polymeric materials that will not incapacitate or otherwise block all functionality of a polypeptide when associated with each other. A "membrane" as used herein is a structure such as a sheet, layer or plug of a material that includes, at least its main structural component, synthetic polymeric materials and can be used to selectively segregate space, fluids (liquids) or gases), solids and the like. A membrane as used herein may include permeable materials that allow passage or diffusion of some species from one side to the other. A membrane used in a fuel cell, for example, prevents the passage of some components from inside the cathodic compartment to the anodic compartment and / or prevents the passage of some components into the anodic compartment into the cathodic compartment. However, other components can pass freely. At the same time, as exemplified in a mode of a membrane according to the present invention, it will allow and actually facilitate the passage of protons from the anodic compartment to the cathode compartment. "Associate" in accordance with the present invention can mean a number of things that depend on the circumstances. A polypeptide may be associated with a biocompatible membrane because it is linked to one or more of the surfaces thereof, and / or squeezed or bonded on one or more of the surfaces of the membrane (such as in slots or pores). The "associated" polypeptide can be arranged inside the membrane or in a vesicle or lumen contained in the membrane. The polypeptides could also be arranged between successive layers. The polypeptides may be impregnated in the membrane as well. Really, in a particularly preferred embodiment, the polypeptide is impregnated or integrated into the membrane in such a way that it is at least partially exposed through at least one surface of the membrane and / or can participate in a redox reaction or in the transport of a molecule, atom or electron mediated by the polypeptide from one side of the membrane to the other. The term "participates", in the context of transporting a molecule, atom, proton or electron, from one side of the membrane to the other, includes active transport, where, for example, the polypeptide "pumps" the molecule physically or chemically. , atom, proton or electron through the membrane, usually, but not exclusively, against a pH, concentration or charge gradient, or any other active transport mechanism. However, participation does not need to be limited in that way. The mere presence of the polypeptide in the membrane can alter the structure or properties of the membrane sufficiently to allow a proton, for example, to be transported from a relatively high proton concentration to a relatively low proton concentration on the other side of the membrane. This is not exclusively a non-selective, passive process such as can result from the use of passive, non-selective pore formers or simple diffusion. Actually, in some cases, the inactivation of the polypeptides in a membrane provides results that are inferior to those of similar membranes made without polypeptides in all. These processes (which exclude passive diffusion) are collectively referred to as "polypeptide-mediated transport" where the presence of the polypeptide plays a role in the transport of a species across the membrane, differently from the merely structural one that provides a static channel . Stated another way, "polypeptide mediated transport" ', means that the presence of the polypeptide results in effective transport from one side of the membrane to the other in response to some very different concentrations. "Participa", in the context of a redox reaction, means that the polypeptide causes or facilitates the oxidation and / or reduction of a species, or leads to or from the reaction protons, electrons or oxidized or reduced species. "Polypeptide (s)", include at least one molecule composed of four or more amino acids, which is capable of participating in a chemical reaction, often as a catalyst, or participating in the transport of a molecule, atom, proton or electron from one side of a membrane to the other, or participate in the formation of molecular structures that facilitate or enable such reactions or transport. The polypeptide can be single-stranded, multi-stranded, can exist in a single subunit or in multiple subunits. It can be made from exclusively amino acids or combinations of amino acids and other molecules. These may include, for example, PEGylated peptides, peptide nucleic acids, mimetic peptides, nucleoprotein complexes. Also contemplated are strands of amino acids including modifications such as glycosylation. The polypeptides according to the present invention are generally biological molecules or derivatives or conjugates of biological molecules. Accordingly, the polypeptides can include molecules that can be isolated, as well as molecules that can be produced by recombinant technology or that must be, totally or partially, chemically synthesized. Accordingly, the term encompasses proteins and enzymes as found naturally, mutants thereof, derivatives and conjugates thereof, as well as fully synthetic amino acid sequences and derivatives and conjugates thereof. In a preferred embodiment, the polypeptides according to the present invention can participate in the transport of molecules, atoms, protons and / or electrons from one side of a membrane to another side thereof., can participate in oxidation or reduction, or are charge activating protons that pump polypeptides such as Complex I DH- (also referred to as "Complex 1"). The present invention originates in the recognition that it is possible to create biocompatible membranes using a wide range of synthetic polymeric materials and polypeptides. Biocompatible membranes, when produced in accordance with the present invention, can have advantages over their fully biological counterparts in that they can be more stable, have a longer life, are more durable and capable of being placed in a wider range of useful environments. Actually, some of the biocompatible membranes of the invention can operate when contacted with solutions that have very extreme and very different pHs on one or the other side. They can also be formulated to be stable in the presence of certain oxidizing and / or reducing agents and be useful at relatively extreme temperatures or other storage and / or operating conditions. They will facilitate the passage of current to a degree at least greater than that which could take place using the identical membrane without a polypeptide. Preferably, the biocompatible membranes of the present invention will provide at least about 10 picoamperes / cm2 (such as when the biocompatible membrane is used in a sensor) more preferably at least about 10 milliamperes / cm2 and even more preferably about 100 milliamperes / cm2 or more . These biocompatible membranes are also, generally, but not exclusively, self-stable as an air membrane and thus can be at least partially desolventized. When used in a fuel cell, these biocompatible membranes will have a useful operating life of, preferably, at least 8 hours, more preferably, at least 3 days, and even more preferably one month or more, and even more preferably, six months or more Synthetic polymer membranes that are biocompatible and that contain polypeptides capable of participating in a redox reaction and / or participating in the transport of a molecule, atom, proton or electron from one side of the membrane to the other are particularly advantageous because they can be used in the creation of a wide range of batteries or fuel cells. These include batteries that are environmentally friendly, lightweight, compact, and easily transportable. It is also possible to produce fuel cells that are very high in terms of output power. Preferably a fuel cell produced in accordance with the present invention can generate at least 10 milliwatts / cm 2, preferably at least about 50 milliwatts / cm 2 and more preferably at least about 100 milliwatts / cm 2, when a circuit, usually with a load or resistance , is created between the anode and the cathode. This also refers to when it is an electrical contact. Accordingly, another aspect of the present invention is a fuel cell. The fuel cell includes an anode compartment having an anode and a cathode compartment having a cathode. The fuel cell also includes at least one biocompatible membrane, which can be arranged in the anodic compartment, in the cathode compartment or between the anodic and cathodic compartments. The biocompatible membrane, as discussed previously, may include at least one layer of a synthetic polymeric material and at least one synthetic polypeptide associated therewith. Preferably, the polypeptide has the ability to participate in a redox reaction and / or to participate in the transport of molecules, atoms, protons or electrons from one side of the membrane to the other. In a particularly preferred embodiment, the polypeptide can participate in both a redox reaction and in the transport of a molecule, atom, proton or electron. Such a fuel cell can also include an electron carrier and a second polypeptide, both being arranged in the anodic compartment. Another aspect of the present invention is the creation of solutions that are themselves useful for producing biocompatible membranes in accordance with the present invention. The solutions include at least one synthetic polymeric material and at least one polypeptide in a solvent system that often includes both organic solvents and water. Synthetic polymeric materials, preferable, are present in an amount of between about 1 and about 30 weight percent / volume, and more preferably, and between about 2 and about 20 weight% / volume and more preferably between about 2 and about 10% in weight / volume. Similarly, the polypeptide is present in the solution in an amount of between about 0.001 and about 10.0% w / v, more preferably between about 0.01 and about 7.0% w / v, and even more preferably between about 0.1 and about 5.0% in weight / volume. The solution may also include a solubilizing detergent additive and other materials if desired. The synthetic polymeric material, in a preferred embodiment, consists of at least one block copolymer. In another preferred embodiment, the synthetic polymeric material includes at least one polymer, copolymer or block copolymer with when the synthetic copolymer materials include at least one block copolymer, the synthetic polymeric material also includes at least one polymer or copolymer. In another particularly preferred embodiment, the synthetic polymeric material includes at least one stabilizing polymer.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a fuel cell according to the present invention. Figure 2 is a schematic representation of the transfer of electrons and protons in an anode compartment of a fuel cell, in an embodiment of the present invention.

Figure 3a illustrates an anode and a cathode disposed on opposite sides of a dielectric spacer. Figure 3b illustrates, in cross-section, a distribution of a dielectric separator, an anode, a cathode and a biocompatible membrane in accordance with the present invention. Figure 3c schematically shows a view of a fuel cell including the separator, the anode, the cathode and the membrane of Figure 3b. Figure 3d is a second embodiment of a membrane in accordance with the present invention ilusiraia ^^ schematically as it was disposed in the perforations contained in a dielectric substrate. Figure 3e is a second embodiment of a membrane in accordance with the present invention, schematically illustrated as being disposed in the perforations contained in a dielectric substrate. Figure 4a is a cross-sectional view of an opening having a beveled edge and a biocompatible membrane. Figure 4b is a cross-sectional view of an opening having a beveled edge and a biocompatible membrane. Figure 4c is a cross-sectional view of an opening having a beveled edge and a biocompatible membrane.

DETAILED DESCRIPTION OF THE INVENTION The biocompatible membranes according to the present invention can be formed from any synthetic polymeric material which, when associated with one or more polypeptides as described herein, satisfy the objectives of the present invention. Synthetic polymeric materials can include polymers, copolymers and copolymers and block and mixtures thereof. These can be linked, cross-linked, J nr.i onaj i ^ dos__n ^ otherwise associated with each other. "Functionalized" means that polymers, copolymers and / or block copolymers have been modified with end groups that are selected to perform a specific function, if polymerization is carried out (cross-linking blocks, for example), anchoring to a chemical surface particular (use of, for example, certain sulfur bonds), facilitates electronic transport via a covalent link to an electron carrier or an electron transfer mediator, and the like known in the art. Typically, these terminal groups are not considered a constituent of the polymer or of the block itself and are often added at the end or after the synthesis. Synthetic polymeric materials are generally present on the finished membrane (the membrane under conditions for use) in an amount of at least about 50% by weight of the finished membrane, more typically at least about 60% by weight of the finished membrane and often between about 70 and about as much as 99% by weight thereof. A portion of the total amount of the synthetic polymeric material may be a stabilizing polymer, generally up to about one third, by weight based on the weight of the synthetic polymeric material in the biocompatible membrane. The biocompatible membranes of the invention are preferably produced from one or more block copolymers such as block copolymers AB, ABA or ABC, with or without other synthetic polymeric materials such as polymers or copolymers, and with or without additives.

A block copolymer is described in a series of articles by Corinne Nardin, Oliggang Meier and others. Angew Chem Int. Ed. 39: 4599-4602, 2000; Langmuir 16: 1035-1041, 2000; Langmuir 16: 7708-7712, 2000. The triblock copolymers of poly (2-methyloxazoline-block-poly (dimethylsiloxane) -block-poly (2-methyloxazoline) functionalized described are as follows: C In the above chemical formula, the average value of x is 68, and the average value of y is 15. This is in an ABA block copolymer in which WC "mentioned in the formula does not necessarily equate to the designation" C "of an ABC block copolymer can provide relatively large membranes that can incorporate functional proteins." The methacrylate portions at the ends of the polymer molecules consider cross-linking mediated by the free radical after incorporating the protein to add greater mechanical stability. such as these, particularly those which are non-ionic, have greater stability at higher voltage differences between the anode and the cathode.The triblock copolymer poly (2-methyloxazoline) - tjj3o¾ej ^ l dimethylsiloxane) -block-poly (2-methyloxazoline) ) functionalized discussed above is an example of a synthetic polymeric material that can be used. Exemplary block eroses include, without limitation: amphiphilic block copolymers [The triblock copolymer layers of the vesicles can be considered as an imitation of biological membranes although they are 2 to 5 3 times thicker than a conventional lipid bilayer. However, they can serve as a matrix for integral proteins of the membrane. Surprisingly, the proteins remain functional despite the thickness of the end of the membranes and even after polymerization 10 of the reactive triblock copolymers]; The triblock copolyanfolides of 5- (N, N-dimethylamino) [Bieringer et al., Eur Phys. J.E. 5: 5-12, 200 1. Among said polymers are A14S63 23 / i3iS23 46 / A1422323 35, 15 AÍ56S23A2i, A57S11A32]; styrene-ethylene / butylene-styrene triblock copolymer [(KRATON) G 1 650, a 2 9% styrene, solution viscosity 8,000 (2 5% by weight polymer), triblock block copolymer at 100% % styrene-ethylene / butylene-styrene (S-EB-S); (KRATON) G 20 1 652, a styrene at 2 9%, viscosity of the solution of 1 350 (25% by weight of polymer), block copolymer of triblock at 1 00% of S-EB-S; (KRATON) G 1 657, a viscosity of the solution of 4200 (25% by weight of polymer), block copolymer of the diblock to 35% of S-25 EB-S; all available from Shell Chemical Company. The preferred block copolymers are styrene-ethylene / propylene (E-EP) types and are commercially available under the trademarks (KRATON) G 1726, a 28% styrene, viscosity of the solution of 200 (25 5% by weight of polymer), block copolymer of 70% diblock of S-EB-S; (KRATON) G-1701X a styrene at 37%, viscosity of the solution of > 50,000, block copolymer of 100% S-EP diblock, and (KRATON) G-1702X, a styrene at 28, viscosity of the solution of > 10 50,000, 100% diblock block copolymer of S-EP also available from the Shell Chemical Company, Houston, __J? EjcajL? JJSA _ copolyme or triblock siloxane Siloxane block copolymers containing nitrile were developed as stabilizers for fluids 15 magnetic siloxane. Magnesium siloxane fluids have recently been proposed as internal tampons for retinal detachment surgery. PDMS-b-PCPMS-b-PDMSs (PDMS = polydimethylsiloxane, PCPMS = poly (3-cyanopropylmethyl-cyclosiloxane) were prepared 20 successfully through the kinetically controlled polymerization of hexamethylcyclotrisiloxane initiated by macroinitiators of PCPMS coverted by lithium silanolate. The macroinitiators were prepared by equilibrating mixtures of 3-25 cyanopropylmethylcyclosiloxanes (DxCN) and dilithium diphenylsilandiolate (DLDPS). DxCNs were synthesized by hydrolysis of 3-cinaopropylmethyldichlorosilane, followed by cyclization and equilibrium of the resulting hydrolysates. DLDPS was prepared by deprotonation of diphenylsilandiol with diphenylmethyl lithium. It was found that mixtures of DxCN and DLDPS could be equilibrated at 100 ° C in 5-10 hours. By controlling the DxCN-to-DLDPS relationship, macroinitiators of different molecular weights could be obtained. The main cyclics in the balanced macroinitiator are tetramers (8.6 ± 0.7% by weight), pentamers (6.3 ± 0.8% (2.1 ± 0.5% by weight). Copolymers were prepared in triblocks of 2.5 k - 2.5 k - 2.5 k, 4 k - 4 k- 4 k, and 8k- 8k- 8k and characterized These triblock copolymers are transparent, separated microphase and highly viscous liquids It was found that these triblock copolymers can stabilize nanometer range-Fe203 and cobalt particles in octamethylcyclotetrasiloxane or hexane, therefore PDMS-b-PCPMS-B-PDMSs represents a class of promising steric stabilizers for magnetic fluids of silicon]; the triblock copolymer of DEO-CPPO-CPEO; the triblock copolymer of PEO-PDMS-PEO [polyethylene oxide (PEO) is soluble in the aqueous phase, while the poly-dimethyl siloxane (PDMS) is soluble in oil phase]; the copolymer in triblock of PLA-PEG-PLA; poly (styrene-b-butadiene-b "styrene) triblock copolymers [commonly used thermoplastic elastomers, include Styrolux from BASF, Ludwigshafen, Germany]; poly (ethylene oxide) / poly (propylene oxide) triblock copolymer films ) [pluronic F127, Pluronic P105, or Pluronic L44 of BASF, Ludwishafen, Germany]; copolymer in triblock of poly (ethylene glycol) -poly (propylene glycol); copolymer in triblock of PDMS-PCPMS-PDMS (polydimethylsiloxane-polycyanopropyl methyl siloxane) ) [a series of epoxy and vinyl triblock copolymers with systematically varied molecular weights were synthesized via anionic polymerization using LiOH as an initiator.Nitrile groups in the block of the central copolymer are thought to be absorbed on the surfaces of the particles, while that terminal blocks of PDMS stand out in the reaction medium], the copolymer in triblock of styrene-butadiene-azo-functional HEMA, triblock copolymers in amphiphil Ilic carrying polymerizable terminal groups; triblock copolymer of polymethylmethacrylate (sPMMA) -polybutadiene (PBD) - syndiotactic sPMMA, triblock of tertiary amine methacrylate [copolymer in AB diblock that can form both micelles (block B in the nucleus) and inverted micelles (block A in the nucleus) ) in water at 20 ° C]; triblock copolymer of PLGA-b-PEO-b-PLGA biodegradable; triblock copolymer of polylactide-b-polyisoprene-b-polylactide; triblock copolymer of PEO-PPO-PEO [same as Pluronic of BASF]; triblock copolymer of poly (isoprene-block-styrene-block-dimethylsiloxane); triblock copolymer of poly (ethylene oxide) -block-poly (polystyrene) -block-poly (ethylene oxide); triblock copolymer of poly (ethylene oxide) -poly (THF) -poly (ethylene oxide); triblock of ethylene oxide; E-caprolactone poly (Birmingham Polymers); cop lactide) [Birmingham Polymers]; poly (L-lactide) [Birmingham Polymers]; poly (glycolide) [Birmingham Polymers]; poly (DL-lactide-co-caprolactone) [Birmingham Polymers]; styrene-isoprene-styrene triblock copolymer [Japan Synthetic Rubber Co., MW = 140 kg / mol, PS / PI block ratio = 15/85]; PEO / PPO triblock copolymer; P MA-b-PIB-b-PMMA [TPE in linear triblock]; triblock copolymer of PLGA-block-PEO-block-PLGA (polymeric proton membrane of TBC styrene / ethylene-butylene / sulfonated styrene (S-SEBS)). Available as Protolyte A700 from Dais Analytic, Odessa FL]; triblock copolymer of poly (l-lactide) -block-poly (ethylene oxide) -block-poly (l-lactide); triblock copolymer of poly ester ester ester; triblock copolymer of PLA / PEO / PLA [Synthesis of triblock copolymers will be prepared by means of ring-opening polymerization of DL-lactide or e-caprolactone in the presence of poly (ethylene glycol), using calcium hydride or non-toxic metallic Zn as co-initiators instead of stannous octanoate. The composition of the copolymers will vary when adjusting the polyester / polyether ratio]; triblock copolymer of PCC / PEO / PCC [The above polymers can be used in mixtures of two or more. For example, in two polymer blends measured in percent by weight of the first polymer, said blends can comprise 20-25%, 25-30%, 30-35%, 35-40%, 40-45% or 45-50% ]; poly (methyl t-butyl-b-methacrylate-b-t-butyl acrylate) [Polymer Source, Inc., Dorval, Quebec, Canada]; poly (t-butyl-b-styrene-b-t-butyl acrylate) [Polymer Source, Inc.]; poly (t-butyl-b-acrylate t-butyl-b-methacrylate t-butyl methacrylate) [Polymer Source, Inc.]; poly (t-butyl-b-methyl methacrylate-t-butyl methacrylate methacrylate) [Polymer Source, Inc.]; poly (t-butyl-b-styrene-b-t-butyl methacrylate methacrylate) [Polymer Source, Inc.]; poly (methyl methacrylate-b-butadiene (addition in 1,4) -b-methacrylate of n-butyl-b-methyl methacrylate b-acrylate) [Polymer Source, Inc.]; poly (methyl methacrylate-methyl t-butyl-b-methacrylate acrylate) [Polymer Source, Inc.]; poly (methyl methacrylate-b-methyl t-butyl-b-methacrylate methacrylate) [Polymer Source, Inc.]; poly (methyl methacrylate-b-dimethylsiloxane-b-methyl methacrylate) [Polymer Source, Inc.]; poly (methyl methacrylate-b-styrene-b-methyl methacrylate) [Polymer Source, Inc.]; poly (methyl methacrylate-b-2-vinyl pyridine-b-methyl methacrylate) [Polymer Source, Inc.]; poly (butadiene (1, 2) -b-styrene-b-butadiene addition (addition in 1.2)) [Polymer Source, Inc.]; poly (butadiene (addition in 1,3) -b-styrene-b-butadiene (addition in 1.4)) [Polymer Source, Inc.]; poly (ethylene oxide-b-propylene oxide-b-ethylene oxide) [Polymer Source, Inc.]; poly (ethylene-b-styrene-b-ethylene oxide) [Polymer Source, Inc.]; poly (lactide-b-ethylene oxide-b-lactide) [Polymer Source, Inc.]; poly (lactone-b-ethylene oxide-b-lactone) [Polymer Source, Inc.]; poly (lactide-b-ethylene-b-lactide) terminated in w-diacrilonyl [Polymer Source, Inc.]; poly (styrene-b-acrylic acid-b-styrene) [Polymer Source, Inc.]; poly (styrene-b-butadiene (1, 4) -b-styrene addition) [Polymer Source, Inc.]; poly (styrene-b-butylene-b-styrene) [Polymer Source, Inc.]; poly (styrene-b-n-butyl-b-styrene-acrylate) [Polymer Source, Inc.]; poly (styrene-b-t-butyl-b-styrene acrylate [Polymer Source, Inc.], poly (styrene-b-ethyl acrylate-b-styrene) [Polymer Source, Inc.]; poly (styrene-b) -ethylene-b-styrene) [Polymer Source, Inc.]; poly (styrene-b-isoprene-b-styrene) [Polymer Source, Inc.]; poly (styrene-b-ethylene oxide-b-styrene) [ Polymer Source, Inc.]; poly (2-vinyl pyridine-b-t-butyl-b-2-vinyl pyridine acrylate) [Polymer Source, Inc.]; poly (2-vinyl pyridine-b-butadiene (added in 1, 2) -b-2- vinyl pyridine) [Polymer Source, Inc.]; poly (2-vinyl pyridine-b-styrene-b- 2-vinyl pyridine) [Polymer Source, Inc.]; poly (4-vinyl pyridine-b-t-butyl-b-4-vinyl pyridine acrylate) [Polymer Source, Inc.]; poly (4-vinyl pyridine-b-methyl methacrylate-b-4-vinyl pyridine) [Polymer Source, Inc.]; poly (4-vinyl pyridine-b-styrene-b-4-vinyl pyridine) [Polymer Source, Inc.]; poly (butadiene-b-styrene-b-methyl methacrylate) [Polymer Source, Inc.]; poly (styrene-b-acrylic acid-b-methyl methacrylate) [Polymer Source, Inc.]; poly (styrene-b-butadiene-b-methyl methacrylate) [Polymer Source, Inc.]; poly (styrene-b-butadiene-b-2-vinyl pyridine) [Polymer Source, Inc.]; poly (styrene-b-butadiene-b-4-vinyl pyridine) [Polymer Source, Inc.]; poly (styrene-b-t-butyl-2-vinyl pyridine methacrylate) [Polymer Source, Inc.]; poly (styrene-b-t-butyl-b-4-vinyl pyridine methacrylate) [Polymer Source, Inc.]; poly (styrene-b-isoprene-b-glycidyl methacrylate) [Polymer Source, Inc.]; poly (styrene-b-a-methyl styrene-t-butyl acrylate) [Polymer Source, Inc.]; poly (styrene-b-a-methyl styrene-b-methyl methacrylate) [Polymer Source, Inc.]; poly (styrene-b-2-vinyl pyridine-b- ethylene oxide) [Polymer Source, Inc.]; poly (styrene-b-2-vinyl pyridine-b-4-vinyl pyridine) [Polymer Source, Inc.]. The above block copolymers can be used alone or in mixtures of two or more in different or equal classes. For example, in mixtures of two block copolymers measured in percent by weight of the first polymer, said mixtures may comprise 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, -40%, 40-45% or 45-50%. Where three polymers are used, the former may comprise 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, 35-40%, 40-45% or 45-50% of the total polymer components, and the second can be 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, 35-40%, 40-45% or 45-50% of the remnant. In other words, the amount of each block copolymer in a mixture can vary considerably with the nature and number of the block copolymers used and the properties desired. However, generally, each block copolymer of a mixture according to the present invention will be present in an amount of at least about 10% based on weight of the total polymers in the membrane or solution. These same general ranges would apply to membranes produced from one or more polymers, copolymers and / or mixtures with block copolymers. There may also be cases where a polymer, single copolymer, or block copolymer can be "doped" with a small amount of a different block polymer, copolymer or copolymer, even as little as 1.0% by weight of the membrane to adjust the properties specific to the membrane. The embodiments of the invention include, without limitation, the block copolymers A-B, A-B-A or A-B-C. The average molecular weight for triblock copolymers of A (or C) is, for example, 1,000 to 15,000 daltons, and the average molecular weight of B is 1,000 to 20,000 daltons. More preferably, block A and / or C will have an average molecular weight of about 2,000-10,000 daltons and block B will have an average molecular weight of about 2,000-10,000 daltons. If a diblock copolymer is used, the average molecular weight for A is between about 1,000 to 20,000 Daltons, more preferably about 2,000-15,000 Daltons. The average molecular weight of B is between about 1,000 to 20,000 Daltons, more preferably about 2,000 to 15,000 Daltons. Preferably, the block copolymer will have a hydrophobic / hydrophilic balance that is selected in (i) to provide a solid at the storage and anticipated operating temperature and (ii) to promote the formation of structures similar to the biomembrane instead of micelles. More preferably, the hydrophobic (or block) content should exceed the hydrophilic (or block) content. Therefore, at least one block of the diblock or triblock copolymers is preferably hydrophobic. Although wettable membranes are possible, preferably the content of hydrophilic and hydrophobic synthetic polymeric materials will render the membrane poorly wettable. As described above, in a preferred embodiment of the present invention, a biocompatible membrane produced using a mixture of synthetic polymeric materials is provided. Said mixtures may be a mixture of two or more block copolymers which are identical but for the molecular weight of their respective blocks. For example, a biocompatible membrane can be produced using a mixture of two block copolymers, both of which are poly (2-methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline), one of which having an average molecular weight of 2. kD- 5 kD- 2 kD and the other 3 kD- 7 kD-3 kD and the ratio of the first block copolymer to the second is from about 67% to 33% by weight of the total synthetic polymeric material used. This, of course, means that most of the first blocks of the block copolymer have a molecular weight of about 2 thousand Daltons, the second block has a molecular weight of 5 thousand Daltons and the third block has a molecular weight of 2 thousand Daltons. The smallest part of block copolymers have blocks of approximately 3,000, 7,000 and 3,000 Daltons. Of course, it is also contemplated to be able to use two or more completely different block copolymers and mixtures of different block copolymers and identical block copolymers. that differ only in the size of their respective blocks. But the mixtures are not limited to block copolymers. Polymers and copolymers can be used, alone, in combination, and in combination with block copolymers according to the present invention to produce biocompatible membranes having the properties described herein. Useful polymers and copolymers are preferably solids at room temperature (25 ° C). They can be dissolved in solvents or solvent systems that can accommodate any other synthetic polymeric material used, any additives used, and the polypeptide used. Polymers and copolymers useful in producing biocompatible membranes can include, without limitation polystyrenes, polyalkyl and polydialkyl siloxanes such as polydimethylsiloxane, polyacrylates such as polymethacrylate, polyalkenes such as polybutadiene, polyalkylene and polyalkylene glycols, sulfonated polystyrene, polydienes, polyoxins, poly (vinyl pyridines) ), polyolefins, alcohol copolymers alkylene vinyl / polyolefins, copolymers of ethylene-buten-propylene, copolymers of ethyl vinyl alcohol, perfluorinated sulfonic acids, polymers and copolymers of vinyl halogen such as copolymers of vinyl chloride and acrylonitrile, copolymers of ethylene / methacrylic and other soluble polymers and copolymers but generally hydrophobic all with a molecular weight between about 5,000 and about 500,000. Particularly preferred polymers include: poly (n-butyl acrylate); poly (t-butyl acrylate); poly (ethyl acrylate); poly (ethyl hexyl acrylate); poly (hydroxy propyl acrylate); poly (methyl acrylate); poly (n-butyl methacrylate); poly (s-butyl methacrylate); poly (t-butyl methacrylate); poly (ethyl methacrylate); poly (glycidyl methacrylate); poly (hydroxypropyl methacrylate); poly (methyl methacrylate); poly (n-nonyl methacrylate); poly (octadecyl methacrylate); polybutadiene (addition in 1, 4); polybutadiene (addition in 1, 2); Polyisoprene (addition in 1, 4); polyisoprene (addition in e, 2 and addition in 1.4); polyethylene; poly (dimethyl siloxane); poly (ethyl methyl siloxane); poly (phenyl methyl siloxane); Polypropylene; poly (propylene oxide); poly (4-acetoxy styrene); poly (4-bromo styrene); poly (4-t-butyl styrene); poly (4-chloro styrene); poly (4-hydroxyl) styrene); poly (4-methoxy styrene); polystyrene; isotactic polystyrene; syndiotactic polystyrene; poly (2-vinyl pyridine); poly (4-vinyl pyridine); poly (2-6-dimethyl-p-phenylene oxide); poly (3- (hexafluoro-2-hydroxypropyl) -styrene); polyisobutylene; poly (9-vinyl anthracene); poly (4-vinyl benzoic acid); poly (sodium salt of 4-vinyl benzoic acid); poly (vinyl benzyl chloride); poly (3 (4) -vinyl benzyl tetrahydrofurfuryl ether); poly (N-vinyl carbazole); poly (2-vinyl naphthalene) and poly (9-vinyl phenanthrene). Since the polymers and copolymers are generally synthetic polymeric materials, they can be used in the same amounts previously described for block copolymers and blends. In a particularly preferred aspect of the present invention, the biocompatible membrane includes a synthetic polymeric material, preferably at least one block copolymer (most preferably one that is at least partially amphiphilic) and a synthetic polymeric material that can stabilize the membrane biocompatible It has been found that certain polymers, most notably, hydrophilic polymers and copolymers capable of forming a plurality of hydrogen bonds ("hydrogen bond rich") can stabilize the mem ^^ a ^^ E ^ n ^ e ^ ^ context of stabilizing polymers, the term "polymer includes monomers, polymers and copolymers." "Hydrophilic", in this context, means that the stabilizing polymer will dissolve or be solubilized in water or water-miscible solvents. Without wishing to adopt any theory of operation, it is believed that the use of such polymers can aid in functionally integrating polypeptides into the biocompatible membrane structure.A stabilizing polymer imparts to a biocompatible membrane longer operating life and / or greater resistance to mechanical failure when compared to an identical bicompatible membrane produced without the Stabilizing polymer when exposed to the same conditions A biocompatible membrane stabilized in C In the synthetic polymeric material includes a stabilizing polymer, used in a fuel cell, for example, it may have an increased operating life of at least about 10%, more preferably at least about 50%, more preferably at least about 100% Particularly preferred polymers capable of stabilizing the polypeptides in the biocompatible membranes of the present invention include: 10 dextrans, polyalkylene glycols, polyalkylene oxides, polyacrylamides, and polyalkyleneamines. These polymers ___ is] oi-zados (again including copolymers) have an average molecular weight that is generally lower than polymers and copolymers used as materials 15 polymeric synthetics. Their molecular weight generally ranges from about 1,000 daltons to about 15,000 daltons. Particularly preferred polymers, capable of stabilizing biocompatible membranes include, without limitation, polyethylene glycol Having an average molecular weight of ben about 2,000 and about 10,000, polyethylene oxide having an average molecular weight of ben about 2,000 and about 10,000, polyacrylamide having an average molecular weight of 25 ben approximately 5,000 and 15,000 daltons. Other stabilizing polymers include; polypropylene, poly (n-butyl acrylate); poly (t-butyl acrylate), poly (ethyl acrylate); poly (2-ethylhexyl acrylate); poly (hydroxy propyl acrylate); poly (methyl acrylate); poly (n-butyl methacrylate); poly (s-butyl methacrylate); poly (t-butyl methacrylate); poly (ethyl methacrylate); poly (glycidyl methacrylate); poly (2-hydroxypropyl methacrylate); poly (methyl methacrylate); poly (n-nonyl methacrylate); and poly (octadecyl methacrylate). The amount of stabilizing polymers used in biocompatible membranes is not critical as long as some measurable improvement is made in the properties and functionality of the biocompatible membrane is not unduly impeded. Some functionality and commercial longevity is expected. However, generally, the amount of stabilizing polymer used as a function of the total amount of synthetic polymeric material found in the finished biocompatible membrane (by weight) is generally no more than one third, and typically 30% by weight or less. Preferably, the amount used is between 5 and about 30 ¾, more preferably between about 5 and about 15% by weight of the synthetic polymeric material in the finished membrane is used.

In addition to one or more polymers, copolymers and / or block copolymers, and / or stabilized polymers, TG synthetic polymeric material of the invention may include at least one additive. The additives may include crosslinking agents and lipids, fatty acids, sterols and other components of the natural biological membrane and its synthetic analogs. These are generally added to the synthetic polymeric material when it is in solution. These additives, if present in the whole, would generally be in an amount of between about 0.50% and about 30%, between about 1.0% and about 15 ¾, based on the weight of the synthetic polymeric material. When the cross-linked portions are incorporated into the biocompatible membrane, the methods useful for polymerization include chemical polymerization with propagating or radical-forming agents and polymerization via photochemical generation of the radical with or without additional radical propagating agents. The parameters can be adjusted depending on conditions such as the membrane material, the size of the biocompatible membrane segments, the structure of the support, and the like. Care will be taken to minimize damage to the polypeptide. A particularly useful method involves the use of peroxide at a neutral pH, followed by acidification. Examples of useful polypeptides that may be associated with a synthetic polymeric material, such as to form a biocompatible membrane in accordance with the present invention, and that may participate in one or both of the functions of oxidation / reduction and transmembrane transport (molecules , atoms, protons, electrons) include, for example, NADH dehydrogenase ("complex I") (eg, from E. Coli, Tran et al., "Requirement for the proton pumping NADH dehyd Ogenase l of Escherichia coli in respiration of NADH to fumarate and its bioenergetic implications ", Eur. J. Biochem 244: 155, 1997), NADPH transhydrogenase, proton ATPase, and cytochrome oxidase and several of its forms. Additional polypeptides include: glucose oxidase, (using NADH, available from several sources, including numerous types of this enzyme available from Sigma Chemical), glucose-6-phosphate dehydrogenase (NADH, Boehringer Mannheim, Indianapolis, IN), 6-phosphogluconate dehydrogenase (NADPH, Boehringer Mannheim), malate dehydrogenase (NADH, Boehringer Mannheim, glyceraldehyde-3-phosphate dehydrogenase (NADH, Sigma, Boehringer Mannheim), isocitrate dehydrogenase (NADH, Boehringer Mannheim; NADPH, Sigma), a-ketoglutarate oxidoreductase complex , also referred to as "Complex II", "A structural model for the membrane-integral domain of succinate: quinone oxidoreductases" Hagerhall, C. and Hederstedt, L. FEBS Letters 389; 25-31 (1996) and "Purification, crystallization and preliminary crystallografic studies of succinate: ubiquinone oxidoreductase from Escherichia coli "Tornroth, S., et al., Biochim, Biophys, Acta 1553, 171-176 (2002), heterodisulfur reductases , F (420) H (2) dehydrogenase T (-Baumer - _ ^ oJ ^ orators, "The F420H2 dehydrogenase from Methanosarcine mazei is a Redox-driven proton pump closely related to NADH dehydrogenases. "275 J. Biol. Chem. 17968 (2000)) or a hydrogen formate (Andrews, et al.," A12-cistron Escherichia coli operon (hyf) encoding a putative proton-translocating form hydrogenlyase system. "143 Microbiology 3633 (1997) ), nucleotides nicotinamide transhydrogenases: "Nicotinamide nucleotide transhydrogenase: a model for utilization of substrate binding energy for proton translocation." Hatefi, Y. and Yamaguchi, M., Faseb J., 10: (1996) _, _______ proline dehydrogenase: "Proline Dehydrogenase from Escherichia coli K12"Graham, S., et al., J. Biol. Chem. 259; 2656-2661 (1984), and Cytochromes including, without limitation, cytochrome C oxidase (crystallized with either undecyl-PD- maltoside or cyclohexyl-hexyl-pD-maltoside), Cytochrome bci: "Ubiquinone at Center N is responsible for triphasic reduction of 5 cytochrome bci complex." Snyder, CH, and Trumpower, BL, J. Biol. Chem. 274; 31209- 16 (1999), Cytochrome bo3: "Oxygen reaction and proton uptake in hel ix VIII mutants of cytochrome bo3. "Svensson, M., et al., Biochemistry 34; 5252-58 (1995), "Thermodynamics of 10 electron transfer in Escherichia coli cytochrome bo3." Schultz, B. E., and Chan, S. I., Proc. Nati Acad. Sci. USA ___ 9 ^ 5 ^ JJ ^ 4 ^ z4 ^ JJ1998 L and Cytochrome d: "Reconstitution of the Membrane-bound, ubiquinone-dependent pyruvate oxidase respiratory chain of Escherichia coli with the cytochrome 15 d terminal oxidase". Koland, J. G. et al., Biochemistry 23; 445-453 (1984), Joost and Thorens, "The extended GLUT-family of sugar / polyol transport facilitators: nomenclature, sequence characteristics, and potential function of its novel members (review)" 18 Mol. 20 Membr. Biol. 247-56 (2001), and selector channel proteins including those described in Goldin, A.L., "Evolution of voltage-gated Na (+) channels". J. Exp. Biol. 205; 575-84 (2002), Choe, S., "Potassium channel structures". Nat. Rev. Neurosci. 3; 115-21 (2002), Dimroth, P., "Bacterial 25 sodium ion-coupled energetics". Antonie Van Leeuwenhoek 65; 381-95 (1994), and Park, J.H. and Saier, M. H. Jr. , "Phylogenetic, structural and functional characteristics of the Na-K-Cl cotransporter family". J. Membr. Biol. 149; 161-8 (1996). All of the foregoing are incorporated herein by reference. Methods of isolating such an NADH dehydrogenase ee are described in detail, for example, in Braun et al., Biochemistry 37: 1861-1867, 1998; and Bergsma et al., "Purification and characterization of NADH dehydrogenase from Bacillus subtilis", Eur. J. Biochem. 128: 151-157, 1982. As described by Spehr et al., Biochemistry 38: 16261-16 ^ 267 ^^^ 3 ^^ _? 1 complex I NADH dehydrogenase (or, NADH: ubiquinone oxidoreductase), which is expressed from a operon, can be overexpressed in E. coli by replacing a T7 promoter in the operon to provide useful amounts for use in the invention. Complex I can be isolated from over expression in E. coli by the method described by Spehr et al. Using solubilization with dodecyl maltoside. The complex I can be managed so that the NADH dehydrogenase activity is eliminated or greatly reduced. As described in Bottcher et al, "A Novel, Eatically Active Conformation of the Escherichia coli NADH: Ubiquinone Oxidoreductase (Complex I)", published on the web as it was accepted for publication at www. jbc org, 2002 (manuscript M112357200), in Complex I in solution high in salts or at high pH changes the conformation so that the transport of protons is not coupled to the NADH dehydrogenase activity, creating the DH- form. Applicants have used these conditions and combinations of these conditions to show that the fuel cell of the invention can operate without NADH dehydrogenase activity in the anode / cathode separator.These conditions include concentrations of anodic or anolyte salt of 200 nm. at 2 M, and pH of 8.0 or higher It is believed that the transporter activity operates according to load imbalance between the anodic and cathodic sides The proton transport activity of the DH- form has been confirmed by the maintenance of the generation of current in fuel cells in which the biocompatible membranes interrupted by their shape provided the only avenue to release the load imbalance (It is noted that with the inverse proton transport of complex I has been further controlled against conditions of use over the cathodic side that maintains the coupling of NADH dehydrogens of any complex I oriented inversam This is why the blocking of reverse transport due to lack of the NADH substrate. It will be recognized that the source of any ee used in the invention can be a thermophilic organism that provides an ee more stable at temperature. For example, complex I can be isolated from Aquifex aelicus in a form that operates optimally at 90 ° C, as described in Scheide et al., FEBS Letters 512: 80-84, 2002 (which describes a preliminary isolation using the type of extraction of detergent used elsewhere for complex I). Additionally, it is contemplated that genetically modified polypeptides, such as modified enzymes, can be used. A commonly applied technique for genetically modifying an enzyme is to use recombinant instruments (e.g., exonucleases) to eliminate the N-terminal, C-terminal or internal sequence. These elimination products are created and tested systematically using ordinary experimentation. As is often the case, it can be found that significant portions of the gene product have an effect on the commercial function of interest. More focused eliminations and substitutions can increase the stability, operating temperature, catalytic velocity and / or solvent compatibility provided by the enzymes that can be used in the invention. Of course it is possible to use mixtures of various polypeptides described herein, as may be desirable. The amount of polypeptide used will vary with the type of polypeptide used, the nature and function of the biocompatible membrane, the environment in which it will be used, etc. The amount of polypeptide may be important for certain applications such as fuel cells where, in general, the highest concentration of polypeptide per square centimeter of surface area, the highest rate of proton transfer per unit area (in terms of current) . In general, no olisiaiitej_cji_ta-_de that any polypeptide is present and functional, and provided that the amount of polypeptide used does not prevent the formation of membrane or convert the unstable membrane, then any amount of polypeptide is possible. Generally, the amount of polypeptide will be at least about 0.01%, more preferably about 5%, even more preferably 10%, and even more preferably at least about 20% and more preferably 30% or more by weight based on the final weight of the biocompatible membrane. The amount of polypeptide to solvent can be as low as 0.001% weight / volume and as high as 50.0% weight / volume. Preferably, the concentration is from about 0.5% to about 5.0% weight / volume. More preferably the concentration is from about 1.0% to about 3.0 ¾ ~ erT w / v. Suitable solubilizers and / or stabilizers may also be necessary such as co-solvents, detergents and the like, particularly in connection with the polypeptide solution. Solubilizing detergents are commonly found at the concentration level of 0.01% to 1.0%, and more preferably are contemplated up to about 0.5%. Said detergents include ionic detergents: sodium dodecyl sulfate, sodium N-dodecyl sarcosinate, N-dodecyl Beta-D-glucopyranoside, Octyl-Beta-D-glucopyranoside, dodecyl-maltoside, decyl, undecyl, tetradecyl-maltoside (in general, an alkyl chain of about 8 carbons or more bonded to a sugar as a general form of an ionic detergent) octyl-beta-D-glucoside and polyoxyethylene (9) dodecyl ether, C12E9, as well as non-ionic detergents, such as triton X-100, or Nonidet P-40. Also useful are certain polymers, typically diblock copolymers that exhibit surfactant properties, such as the Pluronic series from BASF, or Disperplast (BYK-Chemie). The solvent used in producing the solution of synthetic polymeric material is preferably selected to be miscible with both the water used (the polypeptide solution often includes water) and with at least one of the synthetic polymeric materials (polymer, copolymer and / or copolymer). block). However, as described above, it is possible to form membranes using solvents or mixtures that are not miscible in water. It is noted that while the use of solvents to produce solutions is preferred, the term "solution" as used herein also encompasses suspensions. When a block copolymer is used, the solvent could solubilize these synthetic polymeric materials. While the synthetic polymer material may be relatively sparingly soluble in the solvent (less than 5% w / v), it is preferable more soluble than 5% w / v and generally, the solubility is at least 5 to 10 ¾ in weight volume, preferably more than 10% by weight volume of the synthetic polymer material to the solvent. Suitable solvents may include, without limitation, low molecular weight aliphatic alcohols and diols of between 1 and 12 carbons such as methanol, ethanol, 2-propanol, isopropanol, 1-propanol, aryl alcohols such as phenols, benzyl alcohols, aldehydes low molecular weight and ketones such as acetone, methyl ethyl ketone, cyclic compounds such as benzene, cyclohexane, toluene and tetrahydrofuran, halogenated solvents such as dichloromethane and chloroform, and common solvent materials such as 1,4-dioxane, normal alkanes (C 2 - C12) and water. Solvent mixtures are also possible as long as the mixtures have the appropriate miscibility, evaporation rate and other appropriate criteria, described for the individual solvents, (components of solvents that have some tendency to form destructive protein contaminants such as peroxides. they can be used as long as they can be purified and handled properly). The solvent typically comprises 30% by volume or more of the solution of synthetic polymeric material / polypeptide, preferably 20% by volume or more, and usually of at least 10% by volume or more. If the membranes are to include "other materials" such as detergents, lipids (e.g. cardiolipin), sterols (e.g. cholesterol) or regulators and / or salts, which could also be added prior to membrane formation and could be present in an amount of between about 0.01 and about 30%, preferably between about 0.01 and about 15% based on the weight of the finished biocompatible membrane. Other materials, when opposed to additives, are often mixed with polypeptide solutions, not synthetic polymer solutions. Biocompatible membranes according to the present invention can be produced using any one of the numerous conventional techniques used in the production of membranes from synthetic polymeric materials and even lipid bilayers, provided that the resulting biocompatible membranes are useful as described in I presented. A method of forming a biocompatible membrane, which is preferred for use with membranes based on block copolymers, is as follows: 1. Form a solution or suspension of synthetic polymeric material in a mixed solvent or solvent system. The solution or suspension may be a mixture of two or more block copolymers, although it may contain one or more polymers and / or copolymers. The solution or suspension preferably contains 1 to 90% w / v of synthetic polymeric material, more preferably 2 to 70%, or even more preferably 3 to 20% w / v. Seven% by weight / volume is particularly preferred. 2. One or more polypeptides (typically with solubilizing detergent) are placed in solution or suspension, either separately or added to the existing polymer solution or suspension. When the solvent used to solubilize the synthetic polymeric materials is the same, or of similar characteristics and solubility in which the polypeptide can solubilize, it is usually more convenient to add the polypeptide to the polymer solution or suspension directly. Otherwise, the two or more solutions or suspensions containing the synthetic polymeric materials and the polypeptide should be mixed, possibly with an additional cosclose or solubilizer. More often, the solvent used for the polypeptide is aqueous. The mixing of these solutions and / or suspensions is often a relatively simple matter and can be achieved manually or with automatic mixing tools. Heating or cooling may also be useful in forming the membrane depending on the solvents and polymers used. In general, solvents that evaporate rapidly tend to form better membranes with cooling while solvents that evaporate extremely slowly would most likely benefit from a slight degree of heating. One can examine the boiling point of solvents used to select those with the most favorable characteristics provided they are appropriate for the polymer used. However, one must, of course, also consider the need to incorporate the polypeptide into the mixture of the polymer and the solvent, which can be a non-trivial matter. It is possible, for example, to mix 5 microliters of Complex I solubilized in detergent (dodecyl maltoside at 0.15% w / v) having 10 mg / ml of Complex I in 95 microliters of a mixture of a polyblock-polybutadiene triblock copolymer -polystyrene at 3.2% w / v (a fully hydrophobic triblock marketed under the trademark STYROLUX 3G55, Lot No. 7453064P, available from BASF in a 50/50 mixture of acetone and hexane and deposited in the same manner as for the formation of In this case, the final mixture includes approximately 5% by volume of water, and 0.75% by weight of Complex I in relation to the weight of the synthetic polymeric material, In general, the solutions are sufficiently stable at room temperature to be useful for at least 30 minutes, provided that the solvents do not evaporate during that time.They can be stored overnight, or longer, generally under refriger conditions 3. A volume of the final solution or suspension that includes both the polypeptides and the synthetic polymeric materials is formed into a membrane and allowed to dry at least partially, whereby at least a portion of the solvent is removed. It is possible to completely dry some of the membranes produced according to the invention or to dry substantially the same. By substantially drying it is meant that there may be some residual solvent up to about 15%, which is often retained even if it is left out of room temperature for several hours. In a particularly preferred embodiment, substantially all of the weights of the finished membrane will be either polypeptide or polymeric material. In this case, the amount of synthetic polymeric material, including additives and stabilizing polymers, ranges from about 70% to about 99% by weight. weight of the finished membrane. However, it may be desirable to have an even higher polypeptide content or it may be necessary to retain some solvent, therefore the amount of synthetic polymeric material may be reduced. Generally, however, at least about 50% by weight of the finished biocompatible membrane will be synthetic polymeric material. When the synthetic polymeric material is a mixture that includes a block copolymer and a polymer or copolymer, other than a stabilizing polymer, the block copolymer may be present in an amount of at least about 35% by weight of the biocompatible membrane. Up to about 30% by weight of the biocompatible membrane can be "additives" and "other materials" (collectively) as defined herein. More preferably the amount of additives and other materials is up to 15% by weight of the biocompatible membrane. Up to about 30% by weight of the synthetic polymeric material can be stabilizing polymer. Generally, the stabilizing polymer will be present in an amount of between about 5 and about 20% of the weight of the polymeric material: used. Identifying which solvents are particularly useful in accordance with the present invention and which combination of polymers and polypeptides and solvents could be used depends on numerous factors, some of which have already been discussed in terms of miscibility., evaporation and the like. The polymeric constituents and the protein must be capable of being completely dissolved in the solvent or solvent mixtures. The evaporation rate must be sufficiently long to allow a time to produce a membrane. However, the amount of time should not be so long as to make the manufacturing impractical. While apolar solvents may be useful, generally more apolar solvents may not be useful in certain circumstances as hydroxyl or ionic components of the polymer that may be poorly soluble in completely apolar solvents. Accordingly one may be able to dissolve a very rigid hydrophobic component such as polystyrene and be unable to simultaneously dissolve a very ionic component such as acrylic acid. However, with polymers of completely hydrophobic character, apolar solvents are then preferred. Solvents should generally be, in part, non-aqueous when the solvent is at least partly dissolvable in non-aqueous.

And although the miscibility in water for the reconstitution of the membrane protein is not desired, it is not a strictly limiting factor. Accordingly, preferably all solvents are non-aqueous. The solvent for the polypeptide and the stabilizing polymers, however, is predominantly water or at least miscible in water. Preferred methods of forming biocompatible membranes including both at least one synthetic polymeric material and a stabilizing polymer include the step of making an appropriate solution of block copolymer and, usually separately, stabilizing polymers and polypeptides. As described elsewhere, the polypeptide may include one or more detergents or surfactants and is typically in an aqueous solution. Once the appropriate solutions are worked up and mixed, the membranes can be made by any of the techniques described herein or known in the art, including, for example, coating a perforated dielectric substrate with the solution followed by at least evaporation partial of the solvents. Said evaporation can be facilitated in vacuum. One method of forming a biocompatible membrane, which includes a stabilizer polymer rich in hydrogen bonds, is as follows: 1. A solution or suspension of the Protolyte A700 block copolymer in a solvent as supplied is diluted with an equal volume of ethanol (water 5% by weight / volume). The solution contains approximately 5% weight / volume of block copolymer. 2. Separately, an aqueous solution or suspension of the stabilizing agent is made by mixing 943 mg of polyethylene glycol (PEG) 8000 to produce a solution having a concentration of about 2.3% w / v. The concentration of the stabilizing agent in solution is close to the saturation limit. 3. Next, 4 microliters of a solution including 10 mg / ml of Complex I derived from E. Coli is added along with 0.15% w / v dodecyl maltoside to 6 microliters of the PEG solution and then mixed to generate a solution or suspension. 4. The 10 microliters of the solution are then mixed with 10 microliters of the solution including the block copolymer. 5. A small volume (eg, 4 microliters) of the resulting solution is dripped onto the openings of a subset of openings (holes drilled through the support) of a perforated substrate 1 mil (25.4 microns) thick. ??? , a polyimide strand, having openings that are 100 micrometers in diameter and 1 thousand in depth. 6. The solution is allowed to air dry in a hood thus removing the solvent. 7. Steps 5 and 6 are repeated as necessary to cover all openings. The method described above of introducing the polypeptide into a solution containing a stabilizing polymer before mixing with nonaqueous solvents in the presence of block copolymers is believed to stabilize the function of the polypeptides used in the biocompatible membrane. However, the polymer and the block copolymer could also be mixed and the resulting solution could be mixed with a generally aqueous polypeptide solution. Optionally, each opening could be checked to ensure membrane formation, or to verify at least a number of microscopically relevant openings statistically. If the openings do not contain a membrane, reset the holes using additional solution and a pipetting device to micropipette scale. Typically, only a very small volume of solution is required to restore said holes. The membranes can be dried completely or substantially in a vacuum equipment, or ___ of ^ eoa ^ Lo ^ __ The membranes thus formed can be stored vacuum dried or dried, if desired. Where the biocompatible membrane incorporates crosslinked portions, such as methacrylates, and will be used in a fuel cell, the following procedure can be used: Prepare the biocompatible membrane in a support that will form the cathode / anode separator. Assemble a cell with a biocompatible membrane on the anode / cathode separator support, electrodes and regulators only. Connect the two electrodes to a high load, such as approximately 150 kilo-Ohms. Add hydrogen peroxide to the cathode side to initiate the crosslinking process, for example so that the concentration of the peroxide will be 1% by volume. Let the fuel cell rest under load for a period of time, for example 1 hour (± 10%). Adjust the pH of the cathode side to pH less than 5 to stop crosslinking. The parameters can be adjusted depending on such conditions as the material of the membrane, the size of the biocompatible membrane, the thickness of the biocompatible membrane, the structure of the support, and the like. Once the synthetic material / polypeptide has been produced, it can be formed into a membrane. The biocompatible membranes according to the present invention can be self-stable membranes. Said membranes can be formed by pouring the solution in a tray or on a sheet in order to achieve the desired thickness. Once the solution has dried and the solvent has been removed by drying, the dried membrane can be removed from the tray or detached from the backing layer. Suitable anti-tack agents can be used to aid in this process. The biocompatible membranes can be formed against a solid material, such as by coating on glass, carbon that is surface modified to increase hydrophobicity, or a polymer (such as polyvinyl acetate, PDMS, Kapton®, a perfluorinated polymer, PVDF, PEEK, polyester, or UHMWPE, polypropylene or polysulfone). Polymers such as PDMS provide excellent support that can be used to establish openings in which biocompatible membranes can be formed. The membrane can then be cut or shaped as necessary or used as is. Furthermore, to facilitate the use of the membrane, it can be physically fixed or through some kind of fastening device or adhesive to a carrier if desired. This can be explained as stretching a canvas over a frame before painting a painting when the frame is the support and the membrane is the canvas. Alternatively, the membrane can be formed with such a structure. A suitable analogy could be a child's bubble rod, used to blow bubbles, and add it to a soap and water solution. A film of soap and water is formed through the opening of the rod. The structural material used in the periphery allows the film to be handled and manipulated and provides rigidity and strength. It also helps to provide the desired shape of the film. The same kind of process can be employed using a physical structure and the membrane-forming solutions of the present invention.

In a preferred embodiment according to the present invention, a biocompatible membrane can be disposed and / or formed in or through the openings of various perforated substrates that preferably include dielectric substrates. "Perforated substrates" mean that they have at least one hole, opening (synonymous with hole as used herein) or pore in which, or on which, a biocompatible membrane could be disposed. For example, Figure 3b shows one embodiment of a useful membrane construction in a fuel cell. A perforated substrate 42, which leaves many perforations 49, has its metallized surfaces to form a perforated anode 44 and a perforated cathode 45. It is also noted that the perforated substrate 42 can be a porous substrate without, for example, perforated holes. In such cases, the perforations 49 are understood to be pores. A biocompatible membrane 61 in accordance with the present invention is formed through apertures or perforations 49 of perforated substrate 42, and is fixed directly to the surface of the anode. The biocompatible membrane 61 can also be disposed in the perforation and be leveled with the anode 44 or it can be fixed to or be adjacent to the cathode 45. Two membranes 61 can be provided, one, for example, disposed through the anode as illustrated and a in the perforation 49 of the substrate 42, leveled with the anode 45, etc. (not shown). The membranes 61 may be the same or different in terms of the synthetic polymeric materials used, the polypeptides used or both. Actually, a plurality of said membranes 61 and indeed, the layers of the biocompatible membranes 61 can be used in conjunction with other types of membranes, diffusion separators and the like. While the foregoing has been explained in the context of Figure 3b, it is equally applicable to other constructions and, in particular, to any type of fuel cell construction. The biocompatible membrane 61 may include one or more polypeptides 62 and 63 as illustrated. Coating methods that can be used to form electrodes (44, 45) on a substrate include a first coating or conductor lamination, followed by plating, sputtering metals or using another coating method for coating with titanium or with a noble conductor such as gold or platinum. Another method is to cathodically spray a metal directly a fixing layer, such as chromium or titanium onto the support, followed by plating, sputtering metals or other coating method to fix a noble conductor. The outer metal layer can be favorably treated to increase its hydrophobicity, such as with dodecane thiol. Substrates or substrates with high natural surface charge densities, such as Kapton and Teflon, are in some preferred embodiments. As noted above, these can be used to form the anode / cathode separator without the use of surface electrodes. The substrate 42 is often preferably dielectric. The perforations or pores 49 and metallized surfaces (anode 44 and cathode 45 (for modes using electrodes so located)) of the substrate 42 can be constructed, for example, with photolithography corrosion or concealment techniques well known in the art. The perforations can also be formed, for example by drilling, drilling, laser drilling, elongation, and the like. Alternatively metallized surfaces (electrodes) can be formed for example by (1) deposit in thin film through a filter, (2) apply a thin layer metallization cover coating then photo-define, selectively corrode a pattern in the metallization , or (3) photo-define the metallization pattern directly without corrosion using an insulating separating material impregnated with metal (Fodel Dupont process, Drozdyk et al., "Photopatternable Conductor Tapes for PDP Applications", Society for Information Display 1999 Digest, 1044 - 1047; Nebe et al., US Patent 5,049,480). In one embodiment, the perforated or porous substrate is a film. For example, the dielectric may be a porous film that becomes impermeable outside of the "perforations" by the metallizations. The surfaces of the metal layers can be modified with other metals, for example by electroplating. Said electroplaqueos are, for example, with titanium, gold, silver, platinum, palladium, mixtures thereof, or the like. AdejnáSj__ For metallized surfaces, the electrodes can be formed by other suitable conductive materials, said materials can be modified on the surface. For example, the electrodes may be formed of carbon (graphite), including graphite fiber, which may be applied to the dielectric substrate, for example by evaporation of the electron beam, chemical vapor deposition or pyrolysis. The surfaces to be metallized can be cleaned with solvent and corroded with oxygen plasma. Useful means for forming hydrophilic electrodes are described for example in Surampudi, US Patent 5,773,162, Surampudi, US Patent 5,599,638, Narayanan, US Patent 5,945,231, Kindler, US Patent 5,992,008, Surampudi, WO 96/12317, Surampudi, WO 97/21256 and US Pat. Narayanan, WO 99/16137. The biocompatible membranes used in the invention are optionally stabilized against a solid support. One method of achieving such stabilization uses sulfur-mediated bonds or lipid-related molecules to bond, fix or bond metal surfaces or other solid support surfaces to biocompatible membranes. For example, a porous support can be coated with a removable filler layer or 10 sacrifiable, and the coated surface smoothed by, for example, polishing. Such a porous support can include ___cjj jguiera of the proton-conducting polymeric membranes discussed, typically provided that the proton-conducting polymeric membrane can be 15 smoothed after coating, and is stable to the process described later. A useful porous support is sintered glass. The smoothed surface is then coated (with pre-cleaning when necessary) with metal, such as with a first chrome layer and an overcoat of gold.

The sacrificial material is then removed, such as by dissolution, taken with the metallization over the pores but leaving a metallized surface surrounding the pores. The sacrificial layer may comprise insulating photoprotective material, paraffin, cellulose resins 25 (such as ethyl cellulose), and the like.

The fixation or glue comprises alkyl thiol, alkyl disulfides, thiolipids and the like adapted to fix a biocompatible membrane as illustrated in Figures 7A and 7B. Such fixations are described for example in Lang et al., Langmuir 10: 197-210, 1994. Additional fixings of this type are described in Lang et al., US Patent 5,756,355 and Hui et al., US Patent 5,919,576. Figure 3d includes a similar distribution. However, unlike Figure 3b, where the biocompatible membrane 61 is currently fixed to the metallized surface of the anode 44, in Figure 3d, the membrane 61 is formed in the opening 49 in the perforated substrate 42, so that It necessarily makes contact with either the anode 44 or the cathode 45. It is noted that these figures are not to scale and that the membrane may be thicker or thinner than the electrode and may be thicker or thinner than the electrode. perforated substrate 42. It is also noted that in Figure 3b, the biocompatible membrane 61 is not disposed between the anode 44 and the cathode 45. However, the biocompatible membrane 61 is disposed between the anode 44 and the cathode 45 in the Figure 3d In each of Figures 3b and 3d, the combination of the substrate 42 and the biocompatible membrane 61 (together with the anode 44 in Figure 3b) forms a structure that can also be referred to as a separator. Figure 3e illustrates a preferred embodiment for fuel cells. In this figure, the distribution of the membrane 61 and the perforated substrate 42 (a substrate containing pores, perforations or openings) is as previously described in connection with Figure 3d. However, the cathode and the anode are spaced apart from the perforated substrate. They may be plated electrodes, but they are not plated on the surface, or even in contact with the substrate 42 or the membrane 61. In this case, the membrane 61 and the substrate 42 are the separator. ^^^^^^^^^^^^^^ orcomable can be formed through pores, perforations or openings 49 and the enzyme incorporated therein, for example, by the methods described in detail in Niki et al., US Patent 4,541,908 (cytochrome C fortified in an electrode) and Persson et al., J. Electroanalytical Chem. 292: 115, 1990. Said methods may comprise the steps of: making an appropriate solution of polypeptide and synthetic polymeric material as discussed previously, the perforated substrate Preferably a dielectric substrate is immersed in the solution to form the biocompatible membranes containing enzyme. Sonication or detergent dilution may be required to facilitate the incorporation of the enzyme into a biocompatible membrane. See, for example, Singer, Biochemical Pharmacology 31: 527-534, 1982; Madden, "Current concepts in membrane protein reconstitution", Chem. Phys. Lipids 40: 207-222, 1986; Montal et al, "Functional reassembly of membrane proteins a planar lipid bilayers", Quart. Rev. Biophys. 14: 1-79, 1981; Helenius et al., "Asymetric and symetric membrane reconstitution by detergent elimination", Eur. J. Biochem. 116: 27-31, 1981; Volumes on biomembranes (for example, Fleischer and Packer (eds.)), In Methods in Enzymology series, Academic Press. Alternatively, a fine division made (preferably but not necessarily) of a hydrophobic material such as Teflon with a small opening has a small amount of introduced amphiphilic material. The coated opening is immersed in a diluted electrolyte solution in which the droplets will be fine and spontaneously self-orienting the extension of the opening. The biocompatible membranes of substantial area have been prepared using this general technique. "Two common methods for the formation of the biocompatible membranes themselves are the Langmuir-Blodgett technique and the injection technique.The Langmuir-Blodgett technique involves the use of a Langmuir-Blodgett depression with a division, such as a TeflonT polymeric division in the center.The depression is filled with aqueous solution.The opening of the polymer division is placed above the water level.The solution containing the polypeptide and the Synthetic polymeric material is spread over the surface and the polymeric partition is slowly lowered into the aqueous solution forming a biocompatible membrane over the opening.The injection method is similar except that the polymeric partition is kept fixed.In this method the aqueous phase is filled just below the opening, the solution is introduced on the surface and then the the liquid one is raised above the division by injecting additional electrolyte solution from below. Another method to form biocompatible membranes is to use self-assembly technique. This is a variation of the two previous techniques described and was in fact the first technique to be used successfully to manufacture synthetic lipid membranes. The technique involves the preparation of a membrane forming solution as described above. A drop of the solution is introduced into a perforated substrate 42, often a hydrophobic substrate. The substrate 42 is then immersed in a dilute aqueous solution of electrolyte wherein the droplet will become thin and spontaneously oriented. The remaining material migrates to the perimeter of the layer where it forms a deposit called the Plateau-Gibbs boundary. The thickness of the substrate 42, is a perforated substrate having apertures or porous material, is for example from about 15 micrometers (um) to about 5 millimeters, preferably from about 15 to about 1,000 micrometers, and more preferably, from about 15 micrometers at approximately 30 micrometers. The width of the perforations or pores is, for example, from about 1 micrometer to about 1,500 micrometers, more preferably 20 to about 200 micrometers, and even more preferably, about 60 to about 140 micrometers. About 100 microns is particularly preferred.

Preferably, the perforations or pores comprise in excess of about 30% of the area of any area of the dielectric substrate involved in transport between the chambers, such as from about 50 to about 75% of the area. In certain preferred embodiments, the substrate is glass or a polymer (such as polyvinyl acetate, polydimethylsiloxane (PDMS), Kapton® (polyimide film, Dupont de Nemours, Wilmington, DE), a perfluorinated polymer (such as Teflon, from DuPont). from Nemours, Wilmington, DE), polyvinylidene fluoride (PVDF, for example, a semi-crystalline polymer containing approximately 59% fluorine marketed as Kynar by Atofina, Philadelphia, PA), PEE (defined below), polyester, UHMWPE (described below), polypropylene or polysulfone), soda and lime glass or borosilicate glass, or any of the foregoing coated with metal. The metal can be used to anchor the biocompatible membrane (such as a monolayer or bilayer of amphiphilic molecules). The metal coating can be removed from some joints in which they also probably provide an electrically conductive route for a short between the anodic and cathodic compartments. In a particularly preferred aspect of the present invention, the perforated substrate 42 is made of a dielectric material. The polypeptide 62 can be immobilized on the biocompatible membrane in the proper orientation to allow access of the catalytic site for the oxidative reaction to the anodic compartment and the asymmetric pumping of protons. However, if the polypeptide is not asymmetrically oriented, the polypeptide oriented to the contrary is not harmful for a variety of context-dependent reasons. First, the imbalance of the charge created by the fuel cell on the anodic side activates the transport of protons to the cathode side "even against a proton concentration gradient.In situations where pumping is conditioned by the use of a reduced electron carrier, the counter pumping did not have such a carrier since the electron carrier is substantially insulated in the anodic compartment 41. (By "substantially isolated" those skilled in the art will recognize sufficiently isolated to allow operation of the fuel cell.) In one embodiment, as shown in Figures 4a to 4 The biocompatible membrane 61 contains crosslinked portions and is formed through an aperture with bevelled edges on the substrate 42. The degree of beveling can be any degree that increases the stability of the biocompatible membrane. When the crosslinked block copolymer is relatively less rigid, higher bevel can be used to increase stability, while a smaller amount of bevel may be appropriate for the more rigid cross-linked block copolymer. As illustrated, numerous forms of bevels can contribute to increase stability. In another alternate embodiment in accordance with the present invention, the solution containing the polypeptide and the synthetic polymeric material can be conducted through a surface of a porous support material, instead of a perforated material as illustrated in Figure 3b . Once the protons, for example, were pumped through the membrane, they could migrate through the pores of the support spacer material. If a substrate is perforated or porous, it is not necessary for a membrane to be formed through its entire surface. For example, although it may be desirable to form a membrane across the entire surface of a perforated substrate, it may be preferred to selectively introduce a solution containing polypeptide and synthetic polymeric material into the perforations or merely through the perforations. The thickness of the biocompatible membrane according to the present invention can be adjusted by means of known techniques such as controlling the volume introduced to a particular pore size., perforation, compartment or tray, etc. The thickness of the membrane will be dictated widely by its composition and function. A membrane is intended to include a transmembrane proton transporter complex such as Complex I must be thick enough to provide sufficient support and orientation to the enzyme complex. However, it should not be so thick as to prevent the effective transport of the proton through the membrane for an opening or perforation of approximately 100 microns in diameter in a distribution of 100 openings and a solution that includes the complex I in an amount of about 4 microliters in a copolymer solution containing about 7% w / v of the copolymer copolymer of poly (2-methyloxazoline) -block-poly (dimethylsiloxane) -block-poly (2-methyloxazoline), described in one of the articles of Meier and collaborators previously identified, a membrane of adequate thickness can be obtained.The thickness of the membrane can vary widely depending on the necessary longevity, its function, etc. The membranes that are designed for the transport of protons for example They are often thinner than the membranes to which an enzyme that can oxidize something is fixed, however, in general, the membranes will will run from about 10 nanometers to 100 micrometers or even thicker. Actually, biocompatible membranes useful for transporting protons in a fuel cell have been successful at thicknesses of 10 nanometers up to 10 micrometers. Again, thicker membranes are possible. In certain embodiments of the present invention, particularly useful in the creation of fuel cells, the biocompatible membranes of the present invention are capable of transporting protons against a pH gradient. This concept will be discussed further in the present. However, conceptually, on the cathodic side of the biocompatible membrane, the pH of any medium, electrolyte or the like is acidic while on the anodic side of the membrane the pH is basic. This is contrary to what is found in most fuel cells. Generally, such conditions would favor the proton regulation from the proton-rich acid side to the relatively poor basic side in protons. The use of membranes in accordance with the present invention can, however, pump current up from the poor side of protons to the rich side in protons. This highlights another aspect of the present invention that may be particularly useful. The membranes of the present invention can also be active and functional despite relatively wide variations in pH conditions on opposite sides thereof. For example, membranes in accordance with the present invention can catalyze proton transfer where the pH in an anodic compartment is at least 0.5 units higher than the pH in the cathode compartment. In many fuel cells, the pH in the anodic compartment is lower than the pH found in the cathode compartment due to the higher concentration of protons. However, fuel cells produced in accordance with the present invention need not depend on differences in proton concentration to drive the protons across the membrane by diffusion. This can be a particularly important advantage because species used as electron carriers and / or electron transfer mediators often work more efficiently at relatively alkaline pH. The fuel oxidation reactions can also be more efficient under said pH conditions. The differential of pH, based on electrolytes used, etc. it may not need to be adjusted during the life of a fuel cell. Alternatively, a regulatory system can be added, and additional regulator added if necessary, in the anodic / cathodic compartment during the operation. Preferably, the anodic compartment will have a pH that is at least about one pH unit higher than the pH in the cathode compartment, more preferably 2 units of higher pH. In a particularly preferred embodiment, the pH of the anodic compartment is 8 or higher and the pH in the cathode compartment is 5 or less. See Example No. 59. "Another aspect of the present invention is a fuel cell produced using a biocompatible membrane as described herein Without being limited to other appropriate definitions known in the art, a fuel cell is a device that generates electrical energy through the chemical conversion of a fuel The specific type of fuel cell, in terms of the type of fuel used, the type of electron transporting species (electron carriers, soluble enzymes, transfer mediators and the like ) or used electrolytes, the types of electrodes used and the like are subject to wide variations and all are contemplated as long as they are capable of meeting the appropriate criteria.For example, the systems used must be compatible with the biocompatible membrane. are, for example, corrosive to the membrane, then the life of the fuel cell can be unusually cor ta (less than 8 hours of useful life). If the materials used cause sufficient instability, then it may also be the reason why the particular fuel, for example, can not be useful in accordance with the invention. Particularly preferred are fuel cells that are small and light enough to be used in portable electronic devices such as computers, PDAs, cell phones, people locators, personal entertainment systems, Game Stations 2, Kid Games, portable DVD players, power tools, toys, stereo equipment, radios, cameras and video recorders, digital recorders and cameras, instant lighting, cars, trucks, boats, airplanes, etc. The fuel cells are preferably "green" which means that they can be easily disposed of because they do not contain corrosive or dangerous chemicals, either as fuel or waste. In addition, these fuel cells can be refillable (addition of additional fuel, etc.) or can only be used / disposed of.

As illustrated in Figure 1, a fuel cell according to the present invention can include an anode compartment 1 having an anode 4 and a cathode compartment 3 having a cathode 5. The assembly also includes a perforated or porous dielectric substrate 2. The fuel cell also includes at least one biocompatible membrane 61 as previously described (not shown in Figure 1). The anode 4 has a conduction or electrical contact 6 and the cathode 5 has a conduction or electrical contact 7 that can be electrically connected, or joined in an electric circuit through a load or resistance to place them in an electrical contact. The biocompatible membrane 61 may be disposed in the anodic compartment, as is the case in Figure 3b, in the cathode compartment or between the anodic and cathodic compartments as shown in Figures 3d and 3e. The biocompatible membrane is also disposed between the anode and the cathode in Figures 3d and 3e and may even be as defined by the boundary between the anodic compartment and the cathode compartment in the illustration. The fuel cell usually includes electrical contacts that make it possible to form a circuit between the two electrodes. The anodes and cathodes can be made from any electrically conductive material that is otherwise generally unreactive with the elements of the fuel cell. The anode and the cathode are preferably made of metals or carbon as previously described. The size and shape of the anode and cathode can be elaborated to fit the necessary dimensions of a fuel cell and allow the passage of several chemical species. Figure 3c illustrates a fuel cell produced in accordance with the present invention comprising a housing of the cell 51 and a perforated substrate 42 that includes in its perforations a biocompatible membrane as described in present 61. The anode and the cathode are plated onto the substrate as previously described and not shown individually, however, as shown in Figure 3c, the anodic contact 54 and the cathode contact 55 are fixed to the relevant electrodes in the fuel cell. An electrode as part of the support system for a biocompatible membrane, as illustrated in Figure 3b, then the electrode must have enough perforations or other means of providing access to molecules, atoms, protons or electrons to flow through it. When the fuel cell has a configuration similar to Figure 3e, however, it is possible that the electrodes are complete amente solids. However, it may still be desirable to have fuel or other components of a fuel cell capable of passing through and around the electrode and therefore, it is possible to provide perforations in any case. The biocompatible mmebrana useful in the fuel cell according to the present invention has already been discussed. The biocompatible membrane will preferably facilitate the passage of current in an amount that is greater than that which would result from the use of the same membrane without the polypeptide. More preferably, the biocompatible membrane will facilitate the flow of at least about 10 milliamperes / cm2, more preferably at least about 50 milliamperes / cm2, and more preferably at least about 100 milliamperes / cm2. In the simplest mode, the biocompatible membrane is itself self-supporting and capable of supporting itself or being supported by a peripheral structure and is disposed through an opening or disposed between an anode and a cathode. It is also important in this case that the basic membrane is at a dielectric and that it avoids the free flow of certain components between the anodic and cathodic compartments such as catholytes, electrolytes, cathodic fuel., anodic fuel, anolytes, other ions, etc. The following less complicated modality would involve the use of a similar biocompatible membrane, but one that is unable to prevent the complete intermixing of the necessary or non-dielectric species. In which case, an additional separator may be necessary. Said separators can be made of the same materials used to produce the substrate 42 described above or, in the alternative, as illustrated in Figures 3d and 3e, the membrane can be disposed either on or covering the perforations or pores in the Substrate 42. Useful materials for the substrate and the methods of preparing them have already been discussed. The anodic electrode can be coated with an electron transfer mediator such as an organometallic compound which functions as a substitute electron receptor for the biological substrate of the redox enzyme. Similarly, the biocompatible membrane of the embodiment of Figure 3 or structures adjacent to the biocompatible membrane can incorporate said transfer mediators.

The electron transfer mediators may be more generally available in the anodic chamber. Such organometallic compounds may include, without limitation, dicyclopentadienyl iron (CioHioFe, ferrocene, available together with substitutable analogs, from Aldrich, Milwaukee, WI), platinum on carbon, and palladium on carbon. Additional examples include ferredoxin molecules of appropriate oxidation / reduction potential, such as the ferredoxin formed from rubedoxin and other ferredoxins available from Sigma Chemical. Other electron transfer mediators include organic compounds such as quinone and related compounds. Still additional electron transfer mediators are ethylviologen, ethylviologen or benzylviologen (CAS 1102-19- dipyridinium), and any subsequent listing in the definition of electron transfer mediators. The anodic electrode (as opposed to the biocompatible membrane) can be impregnated with an enzyme, which can be applied before or after the electron transfer mediator. One way to ensure the association of the enzyme with the electrode is simply to incubate a solution of the enzyme with an electrode for a sufficient time to allow the associations between the enzyme and the enzyme, such as Van der Waals associations, to mature. Alternatively, a first binding portion, such as biotin or its avidin / streptavidin binding complement, can be attached to the electrode and the enzyme linked to the first binding portion by means of a fixed binding complement molecule. Additional methods of attaching the enzyme to electrodes or other materials, and additional electron transfer mediators are described in Willner and Katz, Angew. Chem. Int. Ed. 39: 1181-1218, 2000. The anodic chamber may include enzymes adjacent to or associated with or separated from the anodic electrode. For example, a redox enzyme can be attached to the side of the anode chamber of a polymer that forms an anode / cathode conductor proton separator, with a layer of conductive material on the anodic side that the anodic electrode supplies. In some embodiments of the invention, it is anticipated that the electron carrier will be effective to transfer electrons to the anodic electrode in the absence of the redox enzyme. Some embodiments of the invention may, moreover, use a traditional form of an anode / cathode separator: a polymeric membrane selected for its ability to passively conduct protons in conjunction with the biocompatible membrane of the invention. The separator is effective for pumping against a proton gradient. The dual membranes may be disposed through and / or in the perforations or pores of an anode / cathode separator or they may be placed between the anodic and cathodic compartments. These membranes can be of the traditional composition or biocompatible membranes. A context in which said dual membranes are observed is one in which the pores are of relatively narrow diameter. Another context is one in which the anode cathode separator is formed of sandwiched materials so as to separate the junctions between nucleated materials that differ from the formation of biocompatible membranes separated through the pore.

Without being limited to theory, it is believed that the second, biocompatible membrane closest to the cathode, operates to some degree passively, when the pumping of the first biocompatibile membrane creates a high proton concentration, activating passive transport to the cathode compartment. Thus, to the extent that the cathodic compartment contains peroxide that could potentially damage the transport protein, the active transport function can be damaged, while the second biocompatible membrane isolates the former from higher concentrations of the peroxide. In one modality, the advantage of the dual membrane is obtained with one or more biocompatible membranes, the first of which (on the anodic side) incorporates the polypeptide and a proton-conducting polymer membrane adapted to the side of the cathode chamber to limit the peroxide transit to the biocompatible membranes. Again, an intermediate zone between the biocompatible membranes and the proton-conducting polymer membrane gains a high proton concentration due to active transport, which further activates the transit along a concentration gradient in the cathode compartment. In one embodiment, the substrate in which the pores are formed is a dielectric Kapton sandwich, and conductive Kapton sandwich (conductor through the presence of incorporated graphite). The conductive Kapton can form the anodic electrode, or be properly metallized to form the anodic electrode. The three layers are relatively hydrophilic, relatively hydrophobic, then relatively hydrophilic. Figure 2 shows a schematic block diagram representation of an anode side mode of a fuel cell according to the present invention. The anodic compartment contains the fuel. The fuel is an organic molecule that is depleted according to the present invention and consumed. However, its consumption generates protons and electrons. Preferred fuels in accordance with the present invention are compounds that are or can be transformed into single carbon compounds. Preferred among these is methanol. However, fuels can include, without limitation, oxidizable sugars and sugar alcohols, alcohols, organic acids such as pyruvates, succinates, etc., fatty acids, lactic acids, citric acid, etc., amino acids and short polypeptides, aldehydes, Ketones, etc. The fuel in this embodiment is first activated by means of soluble enzymes which, in the case of methanol, can be an alcohol dehydrogenase. As will be seen later, other dehydrogenases such as aldehyde dehydrogenase and formate dehydrogenase may also be used or may be used with one another. These soluble enzymes are capable of acting from the fuel to generate electrons and protons. Soluble enzymes are generally present in a range of from about 0.001 to about 25,000 units, more preferably from about 0.1 units to about 12,500 units, and more preferably from about 1 unit to about 12,500 units. Units, in this context refer to the specific activity of the soluble enzyme and one unit of activity is the amount required to convert 1 micromole of fuel (or substitution of the enzyme in other contexts) per minute at 25 ° C, "Soluble enzymes "It is a fragment of an incorrect name as these compounds do not need neither to be soluble nor to be enzymes. These compounds can be suspended or emulsified and / or immobilized on beads or some other solid support. It does not really matter as long as they are functional, can act from the fuel, and allow carriers and / or electron transfer mediators to carry protons to the biocompatible membrane and electrons to the anode. The protons and electrons are transferred by means of the coordinated action of soluble enzymes in the fuel to an electron carrier also mentioned as a cofactor. Such an electron carrier is NAD "1" / NADH. Electron carriers may include, without limitation, reduced nicotinamide adenine dinucleotide (mentioned NADH; the oxidized form mentioned as NAD or NADH +), reduced nicotinamide adenine dinucleotide phosphate (mentioned NADPH, the oxidized form mentioned as NADP or NADP *), reduced nicotinamide mononucleotide (MH, oxidized MN form), reduced flavin adenine dinucleotide (FADH2, oxidized form of FAD), reduced flavin mononucleotide (FMNH2, form of oxidized FMN), reduced coenzyme A, and the like. Electron carriers include proteins with incorporated electron donating prosthetic groups, such as coenzyme A, protoporphyrin IX, vitamin B12, and the like. All of the above are believed to carry both electrons and protons that can be generated by the action of soluble enzymes in the fuel. However, not all electron carriers will drive protons. It will be recognized that the Ci compounds comprising carbon, oxygen and hydrogen are electron carriers. However, these are also combustible. Also in the definition of electron carrier are the electron transfer mediators, as specified below. Electron carriers, when present, are generally provided in concentrations of between about 1 microMolar to about 2 Molar, more preferably about 10 microMolar to about 1 Molar, and more preferably about 100 microMolar to about 500 milliMolar. Under the influence of soluble enzymes, protons and electrons, NAD + is converted to NADH. From this point, the electrons and / or protons can be transferred and labeled among a number of additional cofactors and / or transfer mediators. An electron transfer mediator is a composition that facilitates the transfer of electrons released from an electron carrier to another molecule, typically an electrode or other electron transfer mediator with a reduction potential of less than or equal. Examples, in addition to those previously identified, include phenazine methosulfate (PMS), pyrroloquinoline quinone (PQQ, also called methoxatin), hydroquinone, methoxyphenol, ethoxyphenol, or other typical quinone molecules, methyl viologen, 1,1-dibenzyl dihydrochloride -4,4 '-dipyridinium (benzyl viologen), N, N, N', N '-tetramethylphenylenediamine (TMPD) and dicyclopentadienyl iron (Ci0Hi0Fe, ferrocene).

Electron transfer mediators, when present, generally provide erT concentrations of between about 1 microMolar to about 2 Molar, more preferably between about 10 microMolar and about 2 Molar, and even more preferably between about 100 microMolar and about 2 Molar. However, for simplicity, and as illustrated in Figure 2, the reduced cofactor or electron carrier can then interact with the polypeptides, in this case, the dehydrogenase function of Complex I impregnated in a biocompatible membrane in accordance with the present invention. . Complex I releases protons from the NADH molecule, as well as electrons. The electrons must flow directly to the anode. However, more often, they are picked up by a transfer mediator, which then transports the electrons to the anode. Complex I of NADH dehydrogenase is an interesting polypeptide because it can also participate in the transport of protons through the biocompatible membrane. What is particularly interesting, however, is that the transferred protons are not necessarily the protons released by the action of the dehydrogenase portion of Complex I. Therefore, it is more successful, a fuel cell in accordance with this particular aspect of the invention contains additional proton species in the anodic compartment.The proton transporter function of Complex I is illustrated in Figure 2 as the redox function.When the transfer mediator transfers its electrons to the anode, it has oxidized it, allowing it to to be able to obtain additional electrons released by oxidizing other electron carriers The oxidized cofactor (NAD +) is now also ready to receive protons and electrons under the influence of fuel and soluble enzymes The reactions described below take place at the electrode anodic and in the anodic compartment and can be chemically exemplified as follows : H20 + NADH NAD + + H30 + 2e ~ (3) This reaction can be fed by the following reactions: ADH CH3OH + NAD + HCHO + H + + NADH (4) ALD HCHO + H20 + NAD + ¾ HC02H + H + + NADH (5) FDH HC02H + NAD + ¾ C02 + H + + NADH Total: CH3OH + H20 + 3 NAD + ¾ C02 + 3H + + 3 NADH (7) Thus, the reactions and the electron-generating reaction sum up as follows: 3 NADH? 3 NAD + 3 H + + 6e "(3 *) CH3OH + H20 + 3 NAD + t? C02 + 3 H + + 3 NADH (8) Total: CH3OH + ¾0 ¾ C20 + 6 H1 + 6e ~ (9) Soluble enzymes that they can be used to generate a reduced electron carrier (such as NADH as illustrated above) of an organic molecule such as methanol can be initiated with a form of alcohol dehydrogenase (ADH). Suitable ADH enzymes are described for example in Ammendola et al. "Thermostable NAD (+) -dependent alcohol dehydrogenase from Sulfolobus solfataricus: gene and protein sequence determination and relationship to other alcohol dehydrogenases", Biochemistry 31: 12514-23, 1992; Cannio et al, "Cloning and overexpression in Escherichia coli of the genes encoding NAD-dependent alcohol dehydrogenase from two Sulfolobus species ", J. Bacteriol 178: 301-5, 1996; Salióla et al.," Two genes encoding putative mitochondrial alcohol dehydrogenase are present in the yeast Kluyveromyces lactis ", Yeast 7: 391- 400, 19 91; and Young et al., "Isolation and DNA sequence of ADH3, a nuclear gene encoding the mitochondrial isozyme of alcohol dehydrogenase in Saccharomyces cerevisiae", Mol. Cell Biol. 5: 3024-34, 1985. If the resulting formaldehyde is oxidized, an aldehyde dehydrogenase (ALD) is used. Suitable ALD enzymes are described, for example, in Peng et al., "CDNA cloning and characterization of a rice aldehyde dehydrogenase induced by incompatible blast fungus", Accession No. of GeneBank AF323586; Sakano and collaborators, "Arabidopsis thaliana [Thale cress] aldehyde dehydrogenase (NAD +) - like protein" Access Number to GeneBank AF327426. If the resulting additional formic acid is oxidized, a formate dehydrogenase (FDH) is used. Suitable FDH enzymes are described for example in Colas des Francs-Small, et al, "identification of a major soluble protein in mitochondria from nonphotosynthetic tissues as NAD-dependent form dehydrogenase [from potato]", Plant Physiol. 102 (4): 1171-1177, 1993; Hourton-Cabassa, "Evidence for multiple copies of form dehydrogenase genes in plants: isolation of three potato genes, fdhl, fdh2, and fdh3", Plant Physiol. 117: 719-719, 1998. For the reasons discussed below, it may be useful to use soluble enzymes that are adapted to use or otherwise be able to carry settled quinone-based electrons. Such enzymes are, for example, described in: Pommier et al., "A second phenazine methosulphate-linked form dehydrogenase isoenzyme in Escherichia coli", Biochim Biophys Acta. 1107 (2): 305-13, 1992. ("The diversity of reactions involving form dehydrogenases is apparent in the structures of electron acceptors which include pyridine nucleotides, 5-deazaflavin, chiñones, and ferredoxin "); Ferry, J. G. "Form dehydrogenase" FEMS Microbiol. Rev. 7 (3-4): 377-82 ^ __ 1990. (formaldehyde dehydrogenase with quinone activity); Klein and colleagues, "A novel dye-linked formaldehyde dehydrogenase with some properties indicating the presence of a protein-bound redox-active quinone cofactor" Biochem J. 301 (Pt 1): 289-95, 1994. (representative of numerous articles on dehydrogenases with linked quinone cofactors); Goodwin et al., "The biochemistry, physiology and genetics of PQQ and PQQ-containing enzymes" Adv. Microb. Physiol. 40: 1-80, 1998. (on alcohol dehydrogenases using quinones); Maskos et al, "Mechanism of p-nitrosophenol reduction catalyzed by horse liver and human pi-alcohol dehydrogenase (ADH)" J. Biol. Chem. 269 (50): 31579-84, 1994 (example of electron transfer catalyzed by mediator from NADH to an electrode after the reduction of NADlT by an enzyme); and Pandey, "Tetracyanoquinodimethane-mediated flow injection analysis electrochemical sensor for NADH coupled with dehydrogenase enzymes" Anal. Biochem. 221 (2): 392-6, 1994. The reaction corresponding to the cathode in the cathode compartment can be any reaction that consumes electrons produced with a useful redox potential. Using oxygen, for example, the reaction can be: 2 H3Cf + ½ 02 + 2e "? 3 H20 (2) Using reaction 2, the catholyte solution (an electrolyte used in the cathode compartment) can be regulated to explain the consumption of hydrogen ions, hydrogen ion donor compounds can be supplied during the operation of the fuel cell, or more preferably, the separator between the anodic and cathodic compartments is sufficiently effective to release the neutralizing hydrogen ions (hydrogen ion or proton) In one embodiment, the reaction corresponding to the cathode is: H202 + 2 H + + 2e "« 2 H20 (10) The cathodic reactions result in a net production of water, which, if significant, can be reduced by, for example, providing it for space for overflow liquid, or by providing it for the phase of steam depletion. A number of electron receptor molecules are often solid at operating temperatures or solutes in a carrier liquid, in which case the cathode chamber could be adapted to conduct said non-gaseous material. Where, as possibly the case with hydrogen peroxide as the electron receptor molecule, the electron receptor molecule can damage the polypeptides of the biocompatible membrane and any other species in the anodic chamber, and a scavenger can be used in the fuel cell said electron receptor molecules to prevent the peroxide or harmful electron receptor molecules from entering the anodic chamber. Such a scrubber can be, for example, the catalase enzyme (2 H202 ™ 2H20 + 02), especially where the conditions at the anodic electrode are not effective to catalyze the transfer of electrons to 02. Alternatively, the scrubber can be any noble metal , such as gold or platinum. Such a scrubber, where there is an enzyme, can be covalently bound to a solid support material. Alternatively, a separator is provided between the anodic chamber and the cathodic chamber and has greater limited permeability to hydrogen peroxide. Solid oxidants such as calcium peroxide, potassium perchlorite (KCIO4) or potassium permanganate (KMn04), can be used as the electron receptor. The fuel cell operates in a temperature range appropriate for the operation of the redox enzyme or proton transporter. This temperature range typically varies with the stability of the enzyme, and the source of the enzyme. To increase the appropriate temperature range, one can select the appropriate redox enzyme from a thermophilic organism, such as a microorganism isolated from a volcanic wind or hot spring. Additionally, genetically modified enzymes can be used. However, preferred operating temperatures of at least the first electrode are about 80 ° C or less, preferably 60 ° C or less. Preferred fuel cells according to the present invention include an anodic compartment, a cathode compartment, an anode and a cathode, as well as a biocompatible membrane disclosed herein that includes a polypeptide capable of participating in proton transfer from a side of the membrane to the other. At least one of the electron transfer mediators and a carrier electrode are also found in the anodic compartment. The fuel cells of the present invention can preferably generate at least about 10 milliwatts / cm 2, more preferably at least about 50 milliwatts / cm 2 and more preferably at least about 100 milliwatts / cm 2 during their useful life (there will be some diminished output towards the end of their life) . The fuel cell will preferably generate said energy density until its fuel is finally exhausted (unless it is refillable), but generally at least eight hours, preferably one week, more preferably one month and more preferably six months or more. EXAMPLES Example No. 1 It was produced as follows, a useful solution for producing a biocompatible membrane according to the present invention: a block copolymer at 7% w / v (70 mg) (poly (2-methyloxazoline) -polydimethyl siloxane-poly (2-methyl (oxazoline) ) having an average molecular weight of 2 KD-5 KD-2 KD was dissolved in a mixture of ethanol solvents 95% by volume / 5% by volume with stirring using a magnetic stirrer Six microliters of this solution were removed and mixed with four microliters of a solution containing 0.015% w / v dodecyl maltoside, 40 micrograms of Complex? (? mg / ml) in water, these were then mixed in. The resulting solution contained 4.2% w / v polymer. , 55% by volume of EtOH, 45% by volume of H20, 0.06% by weight / volume of dodecyl maltoside and the protein / polymer ratio is 6% by weight Example No. 2 A useful solution was prepared to produce a biocompatible membrane in accordance with the present invention, generally as described in Example No. 1 with the following changes: less polypeptide solution was used to provide a final solution including 0.015% w / v of dodecyl maltoside and 1.5% by weight of polypeptide relative to the synthetic polymeric materials. Example No. 3 A solution useful for producing a biocompatible membrane was prepared in accordance with the present invention, generally as described in Example No. 1 with the following changes: less polypeptide solution was used to provide a final solution which included 0.03 % by weight / volume of dodecyl maltoside and the final solution contained 3.0% by weight of polypeptide relative to the synthetic polymeric materials.

Example No. 4 A solution useful for producing a biocompatible membrane was produced according to the present invention, generally as described in Example No. 1 with the following changes: less polypeptide solution was used to provide a final solution including 0.045% weight / volume of dodecyl maltoside and the final solution contained 4.5% by weight of polypeptide relative to synthetic polymeric materials. Example No. 5 A solution useful for producing a biocompatible membrane was prepared in accordance with the present invention, generally as described in Example No. 1 with the following changes: less polypeptide solution was used to provide a final solution including 0.0075 % by weight / volume of dodecyl maltoside and the final solution contained 0.75% by weight of polypeptide relative to synthetic polymeric materials. Example No. 6 A solution useful for producing a biocompatible membrane was prepared in accordance with the present invention, generally as described in Example No. 5 with the following changes: the synthetic polymeric material was originally present in a 5% solution in weight / volume Sufficient polypeptide solution of the type described in Example 1 was added to produce a final solution including 0.0075% w / v of dodecyl maltoside and 0.75% by weight of polypeptide relative to the synthetic polymeric materials. Example No. 7 A solution useful for producing a biocompatible membrane was prepared in accordance with the present invention, generally of the type described in Example No. 6 with the following changes: sufficient polypeptide solution was included as described in Example 1 to_produce a final solution including 0.015% weight / volume of dodecyl maltoside and the final solution contained 1.5% by weight of polypeptide relative to the synthetic polymeric materials. Example No. 8 A solution useful for producing a biocompatible membrane was prepared in accordance with the present invention, generally of the type described in Example No. 6 with the following changes: sufficient polypeptide solution was included as described in Example 1 for produce a final solution that includes 0.03% weight / volume of dodecyl maltoside and the final solution contained 3% by weight of polypeptide relative to the synthetic polymeric materials.

Example No. 9 A solution useful for producing a "biocompatible membrane" according to the present invention was prepared, generally of the type described in Example No. 6 with the following changes: sufficient polypeptide solution was included as described in Example 1 to produce a final solution including 0.045% weight / volume of dodecyl maltoside and the final solution contained 4.5% by weight of polypeptide relative to the synthetic polymeric materials Example No. 10 J5e prepared a solution useful to produce a biocompatible membrane of according to the present invention, generally of the type described in Example No. 6 with the following changes: sufficient polypeptide solution was included as described in Example 1 to produce a final solution including 0.06% w / v dodecyl maltoside and the final solution contained 6.0% by weight of polypeptide relative to the synthetic polymer materials. Examples Nos. 11-15 Useful solutions were prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 1-5 respectively except that the amount of the synthetic polymeric material used in each solution was originally of 10% in weight / volume. When ? microliters of the solution were mixed with sufficient polypeptide solution of the type described in Example 1 a final solution was produced which included 0.06, 0.15, 0.03, 0.045 and 0.0075% w / v of dodecyl maltoside and 6.0, 1.5, 3.0, 4.5 and 0.75% by weight of polypeptide relative to synthetic polymeric materials, respectively. Example No. 16 A solution useful for producing a compatible compound according to the present invention was prepared generally as described in Example No. 3, however, the solvent used to dissolve the synthetic polymeric material included ethanol, 25% methanol in volume and amount of water indicated in Example No. 3. Enough polypeptide solution was used to provide a final solution that included 0.03% w / v dodecyl maltoside and 3.0 wt% polypeptide relative to synthetic polymeric materials . Example No. 17 A solution useful for producing a biocompatible membrane according to the present invention was prepared generally as described in Example No. 2, however, the solvent used to dissolve the synthetic polymeric material included ethanol at 47.5% by volume, 2.5% by volume water, 25% by volume Tetrahydrofuran ("THF"), 25% by volume dichloromethane. Enough polypeptide solution was used to provide a final solution that included 0.015 w / v% dodecyl maltoside and 1.5 wt% polypeptide relative to the synthetic polymeric materials. Example No. 18 A useful solution can be prepared to produce a biocompatible iodide according to the present invention generally as described in Example No. 6, however, the solvent used to dissolve the synthetic polymeric material included 9.5% ethanol in volume, 0.5% by volume of water, 40% by volume of acetone and 40% by volume of exone. Examples 19-24 Useful solutions for producing a biocompatible membrane were prepared in accordance with the present invention, generally as described in Examples Nos. 11-15 above, however, the final concentration of dodecyl maltoside was 0.15% by weight / volume. Example 25 A solution useful for producing a biocompatible mixture according to the present invention was prepared, generally as described in Example No. 4 above, however, the equilibrium of the surfactant used in the polypeptide solution is dodecyl β-D- glucopyranoside and the final concentration of the surfactants is 0.15% weight / volume. Example No. 26 A solution useful for producing a biocompatible membrane was prepared in accordance with the present invention, generally as described in Example No. 9 above, however, the surfactant used in the polypeptide solution included a mixture of a surfactant polymer sold under the trademark PLURONIC L101, lot WPDX-522B of BASF, Ludwigshafen Germany and the same concentration of dodecyl maltoside specified in Example No. 9. The polymeric surfactant was diluted to 0.1% by volume of its concentration supplied in the solution final. Example No. 27 A solution useful for producing a biocompatible membrane was prepared in accordance with the present invention, generally as described in Example No. 2 above, however, the surfactant used in the polypeptide solution included a mixture of a surfactant polymer sold under the trademark DISPERPLAST, lot No. 31J022 of BYK Chemie, Wallingford CT and the same concentration of dodecyl maltoside specified in Example No. 2. The polymeric surfactant was diluted to 0.135% by volume of its concentration supplied in the solution final. Examples 28-32 Useful solutions for producing a biocompatible membrane were prepared in accordance with the present invention, generally as described in Examples 6-10 respectively, however, the synthetic polymeric material used may be a poly (2-methyloxazoline) - p ^ l ^ idimethylsiloxane-poly (2-methyloxazoline) (5% w / v) having an average molecular weight of 3 kD- 7 kD-3 kD. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.60% w / v dodecyl maltoside and 0.75, 1.5, 3.0 , 4.5 and 6.0% by weight of polypeptide in relation to synthetic polymeric materials, respectively. Examples 33-38 Useful solutions were prepared to produce a biocompatible membrane according to the present invention, generally as described in Examples 1-5 respectively, however, the synthetic polymeric material used was a mixture of two block copolymers, both of which were poly (2-methyloxazolyl) - ~ polydimethylsiloxane-poly (2-methyloxazoline), (total 7% w / v) one of which has an average molecular weight of 2 kD-5 kD-2 kD and the other of 1 kD-2 kD-1 kD and the ratio of the first block copolymer to the second was from about 67% to 33% by weight of the total polymer used. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example No. 1, a final solution is produced which includes 0.06, 0.015, 0.030, 0.045 and 0.0075% by weight ^ volume of dodecyl maltoside and 0.75, 1.5 , 3.0, 4.5 and 6. 0% by weight of polypeptide in relation to synthetic polymeric materials, respectively. Examples Nos. 39-43 Useful solutions for producing a biocompatible membrane can be prepared according to the present invention, generally as described in Examples Nos. 11-15 respectively, however, the synthetic polymeric material used was a mixture of two copolymers in block, both of which were poly (2-methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline), (10% w / v) one of which has an average molecular weight of 1 kD-2 kD-1 kD and the other of 3 kD-7 kD-3 kD and the ratio of the first block copolymer to the second is from about 33% to 67% by weight of the total polymer used. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example No. 1, a final solution is produced which includes 0.075, 0.15, 0.30, 0.45 and 0.60% weight / volume of dodecyl maltoside and 0.75, 1.5 , 3.0, 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 44-48 Useful solutions were prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 6-10 respectively, however, the synthetic polymeric material used was a mixture of two copolymers in block, both of which were poly (2-methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline), (5% w / v) one of which has an average molecular weight of 2 kD- 5 kD-2 kD and the other of 3 kD-7 kD-3 kD and the ratio of the first block copolymer to the second was from about 33% to 67% by weight of the total polymer used. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.060% w / v dodecyl maltoside and 0.75, 1.5, 3.0 , 4.5 and 6.0% by weight of the polypeptide relative to the synthetic polymeric materials respectively Examples 49-53 Useful solutions were prepared to produce a biocompatible membrane in accordance with the present invention, generally as described in Examples 1-5 respectively, however, the synthetic polymeric material used may be a mixture of two block copolymers, both of which were poly (2-methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline), (7% w / v) one of which it has an average molecular weight of 2 kD-5 kD-2 kD and the other of 3 kD-7 kD-3 kD and the ratio of the first block copolymer to the second is from about 67% to 33% in pe of the total polymer used. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.06, 0.015, 0.030, 0.045 and 0.0075% w / v of dodecyl maltoside and 6.0, 1.5, 3.0 , 4.5 and 0.025% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples 54-58 Useful solutions were prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 1-5 respectively, however, the synthetic polymer used can be a mixture of poly (2-) methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline), (7% w / v) having an average molecular weight of 2 kD-5 kD-2 kD in a solvent of 95% ethanol, 5% water mixed with a 23.5% w / v solution of polyethylene glycol with an average molecular weight of about 3,300 Daltons in water in the proportion of 85% triblock copolymer solution, 15% by volume solution of polyethylene glycol. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1, a final solution including 0.06 is produced., 0.015, 0.030, 0.045 and 0.0075% by weight / volume of dodecyl maltoside and 6.0, 1.5, 3.0, 4.5 and 0.75% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 59-63 A solution useful for producing a biocompatible membrane was prepared in accordance with the present invention, generally as described in Example No. 12, however, the synthetic polymer used was a mixture of 10% by weight / volume of poly (2-ethyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline), having an average molecular weight of 2 kD-5 kD-2 kD in a solvent of 95% ethanol, 5% water mixed with a solution of 23.5% w / v of polyethylene glycol with an average molecular weight of about 8,000 Daltons in water in the proportion of 85% triblock copolymer solution, 15% by volume solution of polyethylene glycol. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.15% w / v of dodecyl maltoside and 1.5% by weight of polypeptide relative to the synthetic polymeric materials . Similar solutions can be made using the procedures of Examples 11 and 13-15. Examples Nos. 64-68 Useful solutions were prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples 28-32 respectively, however, the synthetic polymer used may be a mixture of 5% by weight / volume of poly (2-methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline), having an average molecular weight of 3 kD-7 kD-3 kD in a solvent of 95% ethanol, 5% water mixed with a 23.5% w / v solution of polyethylene glycol with an average molecular weight of about 3,300 Daltons in water in the proportion of 85% triblock copolymer solution, 15% by volume solution of polyethylene glycol. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.060% w / v dodecyl maltoside and 0.75, 1.5, 3.0 , 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples 69-73 Useful solutions were prepared for producing a biocompatible membrane according to the present invention, generally as described in Examples Nos. 1-5 respectively, however, the synthetic polymer used can be a mixture of 7% by weight / volume of poly (2-methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline), having an average molecular weight of 3 kD-7 kD-3 kD in a solvent of 95% ethanol, 5% water mixed with a 23.5% w / v solution of polyethylene glycol with an average molecular weight of about 8,000 Daltons in water in the proportion of 85% triblock copolymer solution, 15% by volume solution of polyethylene glycol. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.060, 0.015, 0.030, 0.045 and 0.075% w / v of dodecyl maltoside and 6.0, 1.5, 3.0 , 4.5 and 0.75% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 74-78 Useful solutions were prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 6-10 respectively, however, the synthetic polymer used may be a mixture of 5% in weight / volume of poly (2-methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline), having an average molecular weight of 2 kD-5 kD-2 kD in a solvent of 50% by volume of acetone, 50% by weight volume of heptane mixed with a 5% w / v solution of polystyrene of approximately 250, 000 of molecular weight in 50% by volume of acetone, 50% by volume of octane in the proportion of 80% by volume of block copolymer solution, 20% by volume of polystyrene. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.060% w / v dodecyl maltoside and 0.75, 1.5, 3.0 , 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 79-83 Useful solutions can be prepared to produce a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 1-5 respectively, however, the synthetic polymer used can be a mixture of 7 ¾ in weight / volume of poly (2-methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline), having an average molecular weight of 2 kD-5 kD-2 kD in a solvent of 95% ethanol, 5% mixed water with a 5% w / v solution of polymethyl methacrylate polydimethylsiloxane-polymethyl methacrylate having a molecular weight of 4 kD-8 kD-4 kD in a solvent of 50% by volume of THF, 50% by volume of dichloromethane in the proportion of 66% in volume to 33% in volume, respectively. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.06, 0.015, 0.030, 0.045 and 0.075% w / v of dodecyl maltoside and 6.0, 1.5, 3.0 , 4.5 and 0.075% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 84-88 Useful solutions for producing a biocompatible membrane were prepared in accordance with the present invention, generally as described in Examples Nos. 11-15 respectively, however, the synthetic polymeric material used was 10% by weight / sulfonated styrene / ethylene-butylene / sulfonated styrene volume, supplied as Protolyte® A700, lot number LC-29 / 60-011 by Dais Analytic, Odessa, FL in solvent as supplied, diluted to 50% by volume with ethanol containing 5% by volume of water. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.060% w / v dodecyl maltoside and 0.75, 1.5, 3.0 , 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Example No. 89 A useful solution can be prepared to produce a biocompatible membrane in accordance with the present invention, generally as described in Example No. 84, however, the solvent used to dilute the synthetic polymeric material can include 50% by volume of tetrahydrofuran ("THF"), 50% by volume of dichloromethane. Examples Nos. 90-94 Useful solutions were prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 84-88 above, however, the final concentration of dodecyl maltoside was 0.15% in weight volume. Example No. 95 Useful solutions for producing a biocompatible membrane can be prepared in accordance with the present invention, generally as described in Example No. 85 above, however, the surfactant used in the polypeptide solution can include a mixture of dodecyl β -D-glucopyranoside and dodecyl maltoside and the final concentration of surfactant is 0.15% w / v. Example No. 96 A solution useful for producing a biocompatible membrane was prepared in accordance with the present invention, generally as described in Example No. 87 above, however, the surfactant used in the polypeptide solution included a mixture of a surfactant polymer sold under the trademark PLURONIC L101, lot WPDX-522B from BASF, Ludwigshafen Germany and the same concentration of dodecyl maltoside specified in Example No. 87. The polymeric surfactant was diluted to 0.1% by volume of its concentration supplied in the final solution. Example O; A useful solution for producing a biocompatible membrane was prepared in accordance with the present invention, generally as described in Example No. 88 above, however, the surfactant used in the polypeptide solution included a mixture of a commercially available polymeric surfactant. the trademark DISPERPLAST, lot No. 31 J022 of BYK Chemie, Wallingford CT and the same concentration of dodecyl maltoside specified in Example No. 88. The final concentration of the polymeric surfactant was diluted to 0.135% by volume of its concentration supplied in the final solution. Examples 98-102 Useful solutions were prepared to produce a biocompatible membrane according to the present invention, generally as described in Examples Nos. 84-88 respectively, however, the synthetic polymeric material used was a mixture of two block copolymers , one of which was 10% w / v of sulfonated styrene / ethylene-butylene / sulfonated styrene, supplied as Protolyte® A700, batch number LC-Z3750 ~ -11 ll by Dais Analytic, Odessa, FL in solvent as supplied , diluted to 50% by volume with ethanol containing 5% by volume of water, the other of which was? 5% ñ weightT volume of poly (2-methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline) having an average molecular weight of 2 kD- 5 kD-2 kD and the ratio of the first block copolymer to the second was about 67 % to 33% by weight of the total polymer used. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.060% w / v dodecyl maltoside and 0.75, 1.5, 3.0 , 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 103-107 Useful solutions were prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 84-88 respectively, however, the synthetic polymeric material used was a mixture of two copolymers in bulk, one of which was 10% w / v of sulfonated styrene / ethylene-butylene / sulfonated styrene, supplied as Protolyte® A700, batch number LC-29 / 60-011 by Dais Analytic, Odessa, FL ~~~~ solvent as supplied, diluted to 50% by volume with ethanol containing 5% by volume of water, the other of which was 5% w / v of poly (2-methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline) having an average molecular weight of 2 kD-5 kD-2 kD and the ratio of the first block copolymer to the second was from about 33% to 67% by weight of the total polymer used. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.060% w / v dodecyl maltoside and 0.75, 1.5, 3.0 , 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 108-112 Useful solutions for producing a biocompatible membrane can be prepared in accordance with the present invention, generally as described in Examples Nos. 103-107 respectively, however, the synthetic polymeric material used was a mixture of two copolymers in block, one of which was 10% w / v of sulfonated styrene / ethylene-butylene / sulfonated styrene, supplied as Protolyte® A700, batch number LC-29 / eO-011 by Dais Analytic, Odessa, FL in solvent as was supplied, diluted to 50% by volume with ethanol containing 5% by volume of water, the other of which was 5% by weight / volume of polymethylmethacrylate-polydimethylsiloxane-polymethylmethacrylate having an average molecular weight of 4 kD-8 kD - 4 kD in a solvent mixture of 50% by volume of THF, 50% by volume of dichloromethane, the ratio of the first block copolymer to the second was from about 67% to 33% by weight of the total polymer used. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.060% w / v dodecyl maltoside and 0.75, 1.5, 3.0 , 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 113-117 Useful solutions for producing a biocompatible membrane can be prepared in accordance with the present invention, generally as described in Examples Nos. 103-107 respectively, however, the synthetic polymeric material used can be a mixture of two. block copolymers, one of which was 10% w / v sulfonated styrene / ethylene-butylene / sulfonated styrene, supplied as Protolyte® A700, batch number LC-29 / 60-011 by Dais Analytic, Odessa, FL in solvent as supplied, diluted to 50% by volume with ethanol containing 5% by volume of water, the other of which is 5% by weight / volume of polymethylmethacrylate-polydimethylsiloxane-polymethylmethacrylate having an average molecular weight of 4 kD-8 kD- 4 kD in a solvent mixture of 50% by volume of THF, 50% by volume of dichloromethane, the ratio of the first block copolymer to the second was from about 33% to 67% by weight of the polymer total used. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.060% w / v of dodecyl maltoside and 0.75, 1.5, 3.0, 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Example 118-122 Useful solutions were prepared to produce a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 84-88 respectively, however, the synthetic polymeric material used was a mixture of 10% by weight / volume of sulphonated styrene / ethylene-butylene / sulfonated styrene, supplied as Protolyte® A700, batch number LC-29 / 60-011 by Dais Analytic, Odessa, FL in solvent as supplied, diluted to 50% by volume with ethanol contained 5% by volume of water mixed with a 23.5% w / v solution of polyethylene glycol with average molecular weight of approximately 3,300 Daltons in water in a 85% ratio of triblock copolymer solution, 15% by volume of solution of polyethylene glycol. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.060% w / v dodecyl maltoside and 0.75, 1.5, 3.0 , 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 123-127 Useful solutions for producing a biocompatible membrane were prepared in accordance with the present invention, generally as described in Examples Nos. 84-88 respectively, however, the synthetic polymeric material used was a mixture of 10% in weight / volume of sulfonated styrene / ethylene-butylene / sulfonated styrene, supplied as Protolyte® A700, batch number LC-29 / 60-011 by Dais Analytic, Odessa, FL in solvent as supplied, diluted to 50% by volume with ethanol containing 5% by volume of water mixed with a 23.5% w / v solution of polyethylene glycol with average molecular weight of approximately 8,000 Daltons in water in the proportion of 85% triblock copolymer solution, polyethylene glycol solution to 15% in volume. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution including 0.0075 was produced., 0.015, 0.030, 0.045 and 0.060% by weight / volume of dodecyl maltoside and 0.75, 1.5, 3.0, 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 128-132 Useful solutions for producing a biocompatible membrane can be prepared in accordance with the present invention, generally as described in Examples Nos. 6-10 respectively, however, the synthetic polymeric material used can be 5% by weight. weight / volume of polymethylmethacrylate-polydimethylsiloxane-polymethylmethacrylate having an average molecular weight of 4 kD-8 kD-4 kD in a solvent mixture of 50% by volume THF, 50% by volume dichloromethane. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015, 0.030, 0.045 and 0.060% w / v dodecyl maltoside and 0.75, 1.5, 3.0 , 4.5 and 6.0% by weight of polypeptide in relation to the synthetic polymeric materials respectively. Examples 133-134 Useful solutions were prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 6 and 7 respectively, however, the synthetic polymeric material used was 3.2% w / v. polystyrene-polybutadiene-polystyrene, supplied as Stryolux® 3G55, batch 7453064P from BASF, Ludwigshafen Germany in a 50% / 50% by volume mixture of acetone and hexane. When 6 microliters of the solution are mixed with enough polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015% w / v dodecyl maltoside and 0.75, 1.5 wt% polypeptide relative to the synthetic polymeric materials respectively. Examples Nos. 135-136 Useful solutions were prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 6 and 7 respectively, however, the synthetic polymeric material used was 3.2% by weight / volume of polystyrene-polybutadiene-polystyrene, supplied as Stryolux® 3G55, batch 7453064P of BASF, Ludwigshafen Germany in a 50/50% by volume mixture of acetone and heptane. When 6 microliters of the solution are mixed with enough polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015% w / v dodecyl maltoside and 0.75, 1.5 wt% polypeptide relative to the synthetic polymeric materials respectively. Examples Nos. 137-138 Useful solutions were prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 135 and 136 respectively, however, the synthetic polymeric material used was 5% by weight / volume of polystyrene-polybutadiene-polystyrene, supplied as Stryolux® 3G55, batch 7453064P of BASF, Ludwigshafen Germany in a 50% / 50% by volume mixture of acetone and heptane. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example No. 1 a final solution is produced which includes 0.0075, 0.015% w / v dodecyl maltoside and 0.75, 1.5 wt% polypeptide in relationship with the synthetic polymeric materials respectively. Examples 139-141 Useful solutions can be prepared to produce a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 6 and 8 respectively, however, the synthetic polymeric material used was 5% w / v. polystyrene-polybutadiene-polystyrene, supplied as Stryolux® 3G55, batch 7453064P from BASF, Ludwigshafen Germany in a 50% / 50 by volume mixture of acetone and hexane and 5% by weight volume of poly (2-methyloxazoline) -polydimethylsiloxane-poly ( 2-methyloxazoline) having an average molecular weight of 2 kD-5 kD-2 kD in the same solvent in the proportion of about 80% by volume to 20% by volume, respectively. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015 and 0.030% w / v of dodecyl maltoside and 0.75, 1.5 and 3.0 wt% of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 142-145 Useful solutions can be prepared for producing a biocompatible membrane in accordance with the present invention, generally as described in Examples Nos. 139 and 141 respectively, however, the synthetic polymeric material used was a mixture of 5% in weight / volume of polystyrene-polybutadiene-polystyrene, supplied as Stryolux® 3G55, batch 7453064P of BASF, Ludwigshafen Germany in a 50% / 50% by volume mixture of acetone and hexane and 5% by weight / volume of poly (2-) methyloxazoline) -polydimethylsiloxane-poly (2-methyloxazoline) having an average molecular weight of 3 kD- 7 kD-3 kD in the same solvent in the proportion of about 80% by volume to 20% by volume, respectively. When 6 microliters of the solution are mixed with sufficient polypeptide solution of the type described in Example 1 a final solution is produced which includes 0.0075, 0.015 and 0.030% w / v of dodecyl maltoside and 0.75, 1.5 and 3.0 wt% of polypeptide in relation to the synthetic polymeric materials respectively. Examples Nos. 146-290 Useful solutions can be prepared to produce a biocompatible membrane in accordance with the present invention, generally as described in the Examples Nos. 1-145, respectively, however the polypeptide solution mixed with the synthetic polymer may be a 10 mg / ml solution of Succinate: ubiquinone oxidoreductase (Complex II) in water which may also include 0.15% Thesit (polyoxyethylene) (9) dodecyl ether, Ci2E9) available from Roche, Indianapolis, IN. This surfactant replaces, in general, dodecyl maltoside in Examples 1-145 in similar concentration. Examples Nos. 291-435 Useful solutions for producing a biocompatible membrane according to the present invention can be prepared, generally as described in Examples Nos. 1-145, respectively, however the polypeptide solution used to dilute the synthetic polymer can be a 10 mg / ml solution of the Nucleotide Nicotinamide Transhydrogenase in water which may also include 0.15% Triton X-100. This surfactant replaces, in general, dodecyl maltoside in Examples 1-145 in similar concentration. In addition, in Examples 1-145 which include dodecyl-D-glucopyranoside, this detergent can be substituted with Nonidet P-40 at similar concentration. Example 436 Membranes were formed with a perforated dielectric support. The support is made of KAPTON, available from DuPont (1 thousand thick) and is perforated by means of laser beams with openings of 100 micrometers in diameter and 1 thousand in depth. This distribution of the openings can have a density as high as 1,700 openings / cm2. A biocompatible membrane is formed through the openings using the PEG 8000 / PROTOLYTE A700 membrane described in detail previously. The resulting final solution containing the block copolymer, stabilizer polymer and polypeptide were then deposited on the substrate in a manner that completely covered the openings, drop by drop, by pipette, 4 microliters at a time. The solvent was allowed to evaporate at room temperature under a hood. The membrane-holder assembly was stored in a vacuum chamber before use. A test device was built from DELRAN plastic, in this case a fuel cell. The membrane support assembly produced as described above was sealed in place in the fuel cell with rubber gaskets to form two chambers, an anode compartment and a cathode compartment. The anodic and cathodic compartments were filled (20 ml in each) then with an aqueous electrolyte (TMA 1M-formate, pH of 10 in the anodic compartment and 100 mM of TMA-sulfate, pH 2.0, containing hydrogen peroxide 1% in the cathode compartment). An anode of titanium foil was connected in parallel to an electronically varied load. A computer with an analog / digital board was used to measure the current and output voltage. The circuit was completed by wiring these elements to a graphite cathode electrode in the cathode compartment. The titanium plate anode was immersed in the anolyte. Also contained in the anodic compartment was 5% by volume methanol as fuel, 12.5 mM of NAD + was used as an electron carrier, 1M hydroxyquinone was used as an electron transfer mediator, yeast dehydrogenase alcohol (5,000 units), aldehyde dehydrogenase ( 10 units) and formate dehydrogenase (100 units) were used as soluble enzymes. The current and voltage consistent with the function of Complex I impregnated in the biocompatible membrane were produced in translocating protons from the anodic compartment to the cathodic compartment, even against the proton concentration gradient. The peak current density was 158 mA / cm2. The membrane was stable for approximately 3 days. In comparison, another cell was formed using the same components and previous concentrations, with the exception that the membrane-forming solution did not include PEG 8000, the peak current density was similar. However, the integrity of the membrane was limited to 10-12 hours. The membrane failure was evaluated via visible mediator flow in the cathode compartment. In the absence of Complex I in the membrane, the Protolyte block copolymer however forms membranes that are modestly permeable to protons. The use of such membranes formed without Complex I in a fuel cell, constructed in a manner similar to the previous one, with the exception that 300 mM of PMS was present at the anode as the electron transfer mediator instead of hydroxyquinone, produced at most 4 mA / cm2 for only about 5 minutes before rapidly decreasing in output. POSSIBILITY OF INDUSTRIAL APPLICATION The invention concerns the industries that produce and use membranes including, without limitation, the fuel cell industries. The invention is also applicable to industries that use fuel cells such as automotive and electronic industries. Although the present invention has been described with reference to particular embodiments, it is understood that these embodiments are merely illustrative of the principles and applications of the present invention. Accordingly, it is understood that numerous modifications can be made to the illustrative embodiments and that other distributions may be contemplated without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims (36)

1. NOVELTY OF THE INVENTION Having described the present invention, it is considered as novelty, and therefore the content of the following claims is claimed as property: 1. A stabilized biocompatible membrane characterized in that it comprises: at least one layer of a synthetic polymer material having a first side and a second side and at least one polypeptide associated therewith, the polypeptide capable of participating in a chemical reaction, of participating in transport of molecules, atoms, protons or electrons of the first side of the at least one layer on the second side of the at least one layer, or of participating in the formation of molecular structures that facilitate reactions or transport, and because the synthetic polymeric material includes at least one stabilizing polymer. 2. The biocompatible membrane according to claim 1, characterized in that the at least one polypeptide can participate in proton transport from the first side of the at least one layer to the second side of the at least one layer. The biocompatible membrane according to claim 2, characterized in that the at least one polypeptide can participate in proton transport of the first side of the at least one layer to the second side of the at least one layer and can facilitate the passage of the current through the layer to a degree at least greater than would be using an identical biocompatible membrane without the polypeptide. 4. The biocompatible membrane according to claim 3, characterized in that the at least one polypeptide can participate in the transport of protons from the first side of the at least one layer to the second side of the at least one layer in order to be able to provide at least about 10 picoamperes / cm2 of current density. 5. The biocompatible membrane according to claim 4, characterized in that the at least one polypeptide can participate in proton transport from the first side of the at least one layer to the second side of the at least one layer in order to be able to provide at least about 10 milliamperes / cm2 of current density. 6. The biocompatible membrane according to claim 1, characterized in that the at least one polypeptide is impregnated in the at least one layer. 7. The biocompatible membrane according to claim 1, characterized in that the at least one polypeptide is present in an amount of at least about OTÓ1% by weight of the biocompatible membrane. The biocompatible membrane according to claim 7, characterized in that the at least one polypeptide is present in an amount of at least about 5% by weight of the biocompatible membrane. 9. The biocompatible membrane according to claim 8, characterized in that the at least one polypeptide is present in an amount of at least about 10% by weight of the biocompatible membrane. 10. The biocompatible membrane according to claim 1, characterized in that the synthetic polymeric material includes at least one block copolymer. 11. The biocompatible membrane according to claim 10, characterized in that the at least one block copolymer has a hydrophobic content that exceeds its hydrophilic content. 12. The biocompatible membrane according to claim 10, characterized in that the at least one block copolymer has at least one block having an average molecular weight of between about 1,000 and 157,000 daltons. ~ 13. The biocompatible membrane according to claim 12, characterized in that the at least one block copolymer ~ has at least one T5-safe having an average molecular weight of between about 1,000 and 20,000 daltons. The biocompatible membrane according to claim 1, characterized in that the synthetic polymeric material is provided in an amount of at least about 50% by weight based on the weight of the biocompatible membrane. 15. The biocompatible membrane according to claim 14, characterized in that the synthetic polymeric material is provided in an amount of at least about 50% to about 99% by weight based on the weight of the biocompatible membrane. 16. The biocompatible membrane according to claim 1, characterized in that the synthetic polymeric material includes a mixture of a plurality of block copolymers. 17. The biocompatible membrane according to claim 1, characterized in that the at least one polypeptide can participate in a redox reaction. 18. The biocompatible membrane according to claim 1, characterized in that the at least one poptide has the ability to participate in a redox reaction or in the transport of molecules, atoms, protons or electrons from the first side of the at least one layer on the second side of the at least one layer. 19. The biocompatible membrane according to claim 18, characterized in that the at least one polypeptide has both the ability to participate in a redox reaction and for the transport of molecules, atoms, protons or electrons from the first side of the at least one layer on the second side of the at least one layer. 20. The biocompatible membrane according to claim 1, characterized in that the at least one stabilizing polymer is a polymer capable of forming a plurality of hydrogen bonds. 21. The biocompatible membrane according to claim 1, characterized in that the at least one stabilizing polymer is provided in an amount of up to about 30% based on the weight of the synthetic polymeric material. 22. The biocompatible membrane according to claim 21, characterized in that the at least one stabilizing polymer is provided in an amount of between about 5 and about 20% based on the weight of the synthetic polymeric material. 23. The biocompatible membrane according to claim 1, characterized in that the at least one stabilizing polymer is hydrophilic. 24. A biocompatible membrane characterized in that it comprises: at least one layer of a synthetic polymeric material having a first side and a second side, the synthetic polymeric material is present in an amount of at least about 5% by weight based on the weight of the finished membrane and at least one polypeptide impregnated therein and present in an amount of at least about 10% by weight of the biocompatible membrane, the polypeptide has the ability to participate in a redox reaction or proton transport from the first side of the at least one layer on the second side of the at least one layer and is capable of providing at least about 10 milliamperes / cm2 of current density, and in that the synthetic polymeric material includes at least one stabilizing polymer. 25. A fuel cell characterized in that it comprises: an anode compartment including an anode; a cathode compartment that includes a cathode; and disposed in the anodic compartment, in the cathode compartment, or between the anodic compartment and the cathode compartment, at least one stabilized biocompatible membrane having at least one layer of a synthetic polymeric material including an anodic side and a cathode side and at least one polypeptide associated therewith, the polypeptide capable of participating in a chemical reaction, of participating in proton transport of the anodic side "of the at least one layer to the cathodic side of the at least one layer or of participating in the formation of molecular structures that facilitate reactions or transports, and because the synthetic polymeric material includes at least one stabilizing polymer 26. The fuel cell according to claim 25, characterized in that, when the anode and the cathode are placed in electrical contact. in a circuit, 10 milliwatts / cm2 are generated 27. The fuel cell according to the claim ation 26 characterized in that, when the anode and the cathode are placed in electrical contact in a circuit, 50 milliwatts / cm2 are generated. 28. The fuel cell according to claim 27, characterized in that, when the anode and the cathode are placed in electrical contact in a circuit, 100 milliwatts / cm2 are generated. 29. The fuel cell according to claim 25, characterized in that it additionally comprises: at least one electron carrier in the anodic compartment. 30. The fuel cell according to claim 25, characterized in that it additionally comprises: at least one second polypeptide in the anodic compartment capable of releasing protons or electrons from an electron carrier. 31. The fuel cell according to claim 25, characterized in that it additionally comprises: at least one transfer mediator in the anodic compartment capable of transferring electrons to the anode. 32. The fuel cell according to claim 25, characterized in that the at least one biocompatible membrane is disposed between the anode and the cathode. 33. The fuel cell according to claim 25, characterized in that it additionally comprises: a dielectric material disposed between the anode and the cathode that will allow the flow of protons from the anodic compartment to the cathodic compartment. 34. The fuel cell according to claim 25, characterized in that it additionally comprises a first electron transfer mediator arranged in the anodic compartment is capable of receiving at least one electron from an electron carrier arranged in the anodic compartment and transferring the at least one electron to a second electron carrier, to a second electron transfer mediator or to the anode. 35. The fuel cell according to claim 25, characterized in that it comprises "additionally at least one fuel arranged in the anodic compartment 36. The fuel cell assembly according to claim 35, characterized in that the fuel is an organic compound. 3. The fuel cell according to claim 25, characterized in that the polypeptide has the ability to participate in a redox reaction or in proton transport from the anodic side of the at least one layer to the cathodic side of the at least one layer 38. The fuel cell according to claim 37, characterized in that the polypeptide has the ability to participate in a redox reaction and in the transport of protons from the anodic side of the at least one layer to the cathodic side of the at least one One layer 39. A useful solution for producing a biocompatible membrane characterized in that it comprises: at least u n synthetic polymeric material, the synthetic polymeric material is present in an amount of between about 1 and about 30% w / v, at least one stabilizing polymer present in an amount of up to about 30% by weight of the weight of the synthetic polymeric material, at least one polypeptide, in an amount of between at least about 0.001 and about 10.0% weight / volume, the polypeptide capable of participating in a chemical reaction, of participating in the transport of molecules, atoms, protons or electrons or of participating in the formation of molecular structures that facilitate reactions or transport, in a solvent system that includes both organic solvents and water. 40. The solution in accordance with the claim 39, characterized in that it additionally comprises: at least one detergent in an amount between about 0.01 and about 1.0% by volume. 41. The solution according to claim 39, characterized in that the at least one polypeptide has both the ability to participate in a redox reaction or proton transport. 42. The solution according to claim 41, characterized in that the at least one polypeptide has both the ability to participate in a redox reaction and in proton transport. 43. The solution according to claim 41, characterized in that the at least one polypeptide has the ability to participate in proton transport. 44. The solution according to claim 9, characterized in that the synthetic polymeric material includes at least one block copolymer.