Abstract: An improved alkaline pretreatment of biomass is provided that is a single-stage, two oxidant alkaline oxidative pretreatment process. The process uses a homogenous catalyst with at least two oxidants (Hydrogen peroxide and enhanced levels of oxygen) in an alkaline environment to catalytically pretreat lignocellulosic biomass in a single-stage oxidation reaction. The provided single-stage alkaline-oxidative pretreatment improves biomass pretreatment and increase enzymatic digestibility to improve the economic feasibility of production of lignocellulose derived sugars.

Abstract: Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on ?-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric ?-hydroxy acid. The polymeric ?-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The ?-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

Abstract: Substituted hydroquinones and quinones and methods of synthesizing such compounds are disclosed herein. The substituted hydroquinones have the formula: while the substituted quinones have the corresponding oxidized structure (1,4-benzoquinones). One, two, three, or all four of R1, R2, R3 and R4 comprise a thioether moiety and a sulfonate moiety, and wherein each R1, R2, R3 and R4 that does not comprise a thioether and a sulfonate moiety sulfonate moiety is independently a hydrogen, an alkyl or an electron withdrawing group. The substituted hydroquinones and quinones are soluble in water, stable in aqueous acid solutions, and have a high reduction potential in the oxidized form. Accordingly, they can be used as redox mediators in emerging technologies, such as in mediated fuel cells or organic-mediator flow batteries.

Abstract: An improved alkaline pretreatment of biomass is provided that uses a homogenous catalyst with one or more metals and metal coordinating ligands, wherein the homogeneous catalyst is used with at least two oxidants in an oxidation reaction to catalytically pretreat lignocellulosic biomass. In one embodiment, hydrogen peroxide and oxygen are utilized as co-oxidants during alkaline-oxidative pretreatment to improve biomass pretreatment and increase enzymatic digestibility. In one embodiment, the homogenous catalyst is copper (II) 2,2?-bipyridine (Cu(bpy)). Related methods are also disclosed to improve the economic feasibility of production of lignocellulose derived sugars.

Abstract: Non-natural oligomers have recently shown promise as functional analogues of lung surfactant proteins B and C (SP-B and SP-C), two helical and amphiphilic proteins that are critical for normal respiration. The generation of non-natural mimics of SP-B and SP-C has previously been restricted to step-by-step, sequence-specific synthesis, which results in discrete oligomers that are intended to manifest specific structural attributes. Presented herein an alternative approach to SP-B mimicry that is based on sequence-random copolymers containing cationic and lipophilic subunits. These materials, members of the nylon-3 family, are prepared by ring-opening polymerization of ?-lactams. The best of the nylon-3 polymers display promising in vitro surfactant activities in a mixed lipid film. Pulsating bubble surfactometry data indicate that films containing the most surface-active polymers attain adsorptive and dynamic-cycling properties that surpass those of discrete peptides intended to mimic SP-B.

Abstract: Anode half-cells for the electrocatalytic oxidation of a liquid or gaseous fuel or other reductant are disclosed, along with electrochemical cells that include such half-cells. The anode half-cells include redox mediator/heterogeneous redox catalyst pairs within an electrolyte solution that is also in contact with an electrode. The electrode is not in direct contact with the heterogeneous catalyst. The redox mediator must include at least one carbon atom and be capable of transferring or accepting electrons and protons while undergoing reduction or oxidation. In operation, the fuel or other reductant is oxidized and the redox mediator is reduced at the heterogeneous catalyst. The reduced form of the redox mediator can then migrate to the electrode, where it is converted back to its oxidized form, which can then migrate back to the heterogeneous catalyst, where the cycle is repeated.

Abstract: Substituted hydroquinones and quinones and methods of synthesizing such compounds are disclosed herein. The substituted hydroquinones have the formula: while the substituted quinones have the corresponding oxidized structure (1,4-benzoquinones). One, two, three, or all four of R1, R2, R3 and R4 comprise a thioether moiety and a sulfonate moiety, and wherein each R1, R2, R3 and R4 that does not comprise a thioether and a sulfonate moiety sulfonate moiety is independently a hydrogen, an alkyl or an electron withdrawing group. The substituted hydroquinones and quinones are soluble in water, stable in aqueous acid solutions, and have a high reduction potential in the oxidized form. Accordingly, they can be used as redox mediators in emerging technologies, such as in mediated fuel cells or organic-mediator flow batteries.

Abstract: Substituted hydroquinones and quinones and methods of synthesizing such compounds are disclosed herein. The substituted hydroquinones have the formula: while the substituted quinones have the corresponding oxidized structure (1,4-benzoquinones). One, two, three, or all four of R1, R2, R3 and R4 comprise a thioether moiety and a sulfonate moiety, and wherein each R1, R2, R3 and R4 that does not comprise a thioether and a sulfonate moiety sulfonate moiety is independently a hydrogen, an alkyl or an electron withdrawing group. The substituted hydroquinones and quinones are soluble in water, stable in aqueous acid solutions, and have a high reduction potential in the oxidized form. Accordingly, they can be used as redox mediators in emerging technologies, such as in mediated fuel cells or organic-mediator flow batteries.

Abstract: Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on ?-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric ?-hydroxy acid. The polymeric ?-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The ?-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

Abstract: Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on ?-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric ?-hydroxy acid. The polymeric ?-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The ?-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

Abstract: Disclosed is a method of making ?-polypeptides. The method includes polymerizing ?-lactam-containing monomers in the presence of a base initiator and a co-initiator which is not a metal-containing molecule to yield the product ?-polypeptides. Specifically disclosed are methods wherein the base initiator is potassium t-butoxide, lithium bis(trimethylsilyl)amide (LiN(TMS)2), potassium bis(trimethyl-silyl)amide, and sodium ethoxide, and the reaction is carried out in a solvent such as chloroform, dichloromethane, dimethylsulfoxide, or tetrahydrofuran.

Abstract: Cathodic half-cells for the electrocatalytic reduction of oxygen are disclosed. Within the half-cell, a redox catalyst containing one or more non-Pt transition metals attached to a solid support (i.e., a “heterogenized” non-Pt transition metal-containing catalyst) is separate from and not in direct contact with the cathode electrode. In use, both the cathode electrode and the redox catalyst are in contact with an electrolyte solution that also contains a redox mediator. The oxidized form of the redox mediator is reduced at the cathode electrode, and the resulting reduced form migrates to the redox catalyst, where the mediator is oxidized back to its oxidized form, while oxygen is simultaneously reduced. The oxidized form of the redox mediator then migrates back to the cathode electrode, where the process is repeated. The disclosed cathodic half-cells can be used in combination with an anode half-cell in a variety of different electrochemical cells, such as in fuel cells or in electrosynthetic cells.

Abstract: Substituted hydroquinones and quinones and methods of synthesizing such compounds are disclosed herein. The substituted hydrroquinones have the formula: while the substituted quinones have the corresponding oxidized structure (1,4-benzoquinones). One, two, three, or all four of R1, R2, R3 and R4 comprise a thioether moiety and a sulfonate moiety, and wherein each R1, R2, R3 and R4 that does not comprise a thioether and a sulfonate moiety sulfonate moiety is independently a hydrogen, an alkyl or an electron withdrawing group. The substituted hydroquinones and quinones are soluble in water, stable in aqueous acid solutions, and have a high reduction potential in the oxidized form. Accordingly, they can be used as redox mediators in emerging technologies, such as in mediated fuel cells or organic-mediator flow batteries.

Abstract: Anode half-cells for the electrocatalytic oxidation of a liquid or gaseous fuel or other reductant are disclosed, along with electrochemical cells that include such half-cells. The anode half-cells include redox mediator/heterogeneous redox catalyst pairs within an electrolyte solution that is also in contact with an electrode. The electrode is not in direct contact with the heterogeneous catalyst. The redox mediator must include at least one carbon atom and be capable of transferring or accepting electrons and protons while undergoing reduction or oxidation. In operation, the fuel or other reductant is oxidized and the redox mediator is reduced at the heterogeneous catalyst. The reduced form of the redox mediator can then migrate to the electrode, where it is converted back to its oxidized form, which can then migrate back to the heterogeneous catalyst, where the cycle is repeated.

Abstract: Non-natural oligomers have recently shown promise as functional analogues of lung surfactant proteins B and C (SP-B and SP-C), two helical and amphiphilic proteins that are critical for normal respiration. The generation of non-natural mimics of SP-B and SP-C has previously been restricted to step-by-step, sequence-specific synthesis, which results in discrete oligomers that are intended to manifest specific structural attributes. Presented herein an alternative approach to SP-B mimicry that is based on sequence-random copolymers containing cationic and lipophilic subunits. These materials, members of the nylon-3 family, are prepared by ring-opening polymerization of ?-lactams. The best of the nylon-3 polymers display promising in vitro surfactant activities in a mixed lipid film. Pulsating bubble surfactometry data indicate that films containing the most surface-active polymers attain adsorptive and dynamic-cycling properties that surpass those of discrete peptides intended to mimic SP-B.

Abstract: Disclosed are methods for synthesizing an ester or a carboxylic acid from an organic alcohol. To form the ester one reacts, in the presence of oxygen gas, the alcohol with methanol or ethanol. This reaction occurs in the presence of a catalyst comprising palladium and a co-catalyst comprising bismuth, tellurium, lead, cerium, titanium, zinc and/or niobium (most preferably at least bismuth and tellurium). Alternatively that catalyst can be used to generate an acid from that alcohol, when water is also added to the reaction mix.

Abstract: Non-natural oligomers have recently shown promise as functional analogs of lung surfactant proteins B and C (SP-B and SP-C), two helical and amphiphilic proteins that are critical for normal respiration. The generation of non-natural mimics of SP-B and SP-C has previously been restricted to step-by-step, sequence-specific synthesis, which results in discrete oligomers that are intended to manifest specific structural attributes. Presented herein an alternative approach to SP-B mimicry that is based on sequence-random copolymers containing cationic and lipophilic subunits. These materials, members of the nylon-3 family, are prepared by ring-opening polymerization of ?-lactams. The best of the nylon-3 polymers display promising in vitro surfactant activities in a mixed lipid film. Pulsating bubble surfactometry data indicate that films containing the most surface-active polymers attain adsorptive and dynamic-cycling properties that surpass those of discrete peptides intended to mimic SP-B.

Abstract: Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on ?-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric ?-hydroxy acid. The polymeric ?-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The ?-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

Abstract: Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on ?-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric ?-hydroxy acid. The polymeric ?-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The ?-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

Abstract: Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on ?-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric ?-hydroxy acid. The polymeric ?-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The ?-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.