Wisconsin Alumni Research Foundation

Northwestern University

Michigan State University

Montana State University

Shannon S Stahl

Samuel Helmer Gellman

James B Gerken

Denis Kissounko

Bernard Weisblum

Sarah Elizabeth Lee

Mehmet F Ilker

Annelise E Barron

Thatcher W Root

Michelle Dohm

Mohammad Rafiee

Colin W Anson

Brendan P Mowery

Adam Bradley Powell

Alireza Rahimi

Christopher C Scarborough

Stephen Tereniak

David S Mannel

Maaz S Ahmed

Joshua J Coon

Eric Linke Hegg

David B Hodge

Bryan Bals

Arne Ulbrich

Christen Bell Smith

Yuliya Preger

Sarah E Eldred

Zhaoyang Yuan

Hao Luo

Firat Ilker

Methods of depolymerizing lignin and products obtained therefrom. The methods include reacting lignin in a liquid solvent comprising an oxidation catalyst with the solvent being in contact with Ogas. The solvent can include aprotic polar solvents. The oxidation catalyst can include heterogeneous catalysts. The methods can be used in the oxidative catalytic fractionation of raw biomass to generate soluble aromatic monomers and a solid carbohydrate residue. Depolymerized lignin products include phenolic and benzoquinone monomers, such as p-hydroxybenzoic acid, vanillin, syringaldehyde, vanillic acid, and/or syringic acid.

Methods of depolymerizing lignin

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.

Economical methods for performing oxidative catalytic pretreatment of plant biomass using a single-stage two oxidant process

An oxidative homocoupling method of synthesizing certain 2,2'-bithiophenes from thiophenes using oxygen as the terminal oxidant is disclosed. In non-limiting examples, the method uses oxygen along with a catalytic system that includes palladium, an assistive ligand, and a non-palladium metal additive to catalyze one of the following reactions: Associated catalytic systems and compositions are also disclosed.

Method for aerobic oxidative coupling of thiophenes with a ligand-supported palladium catalyst

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 &#x3b2;-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 &#x3b2;-hydroxy acid. The polymeric &#x3b2;-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The &#x3b2;-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.

Polycarboxylated compounds and compositions containing same

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 R, R, Rand Rcomprise a thioether moiety and a sulfonate moiety, and wherein each R, R, Rand Rthat 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.

High solubility thioether quinones

An oxidative homocoupling method of synthesizing certain 2,2'-bithiophenes from thiophenes using oxygen as the terminal oxidant is disclosed. In non-limiting examples, the method uses oxygen along with a catalytic system that includes palladium, an assistive ligand, and a non-palladium metal additive to catalyze one of the following reactions:  Associated catalytic systems and compositions are also disclosed.

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 &#x3b2;-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. Attachment of an N-terminal octadecanoyl unit to the nylon-3 copolymers affords further improvements by reducing the percent surface area compression to reach low minimum surface tension.

Nylon-3 co-polymers and synthetic lung surfactant compositions containing same

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. The disclosed anode half-cells can be used in electrochemical cells, such as in fuel cells that produce electricity, or in electrosynthetic cells that produce one or more desired chemical products.

Flow-based anode for the electrocatalytic oxidation of a fuel or other reductant

High-solubility thioether quinones

Disclosed is a method of making &#x3b2;-polypeptides. The method includes polymerizing &#x3b2;-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 &#x3b2;-polypeptides. Specifically disclosed are methods wherein the base initiator is potassium t-butoxide, lithium bis(trimethylsilyl)amide (LiN(TMS)), potassium bis(trimethyl-silyl)amide, and sodium ethoxide, and the reaction is carried out in a solvent such as chloroform, dichloromethane, dimethylsulfoxide, or tetrahydrofuran.

Poly-&#x3b2;-peptides from functionalized &#x3b2;-lactam monomers and antibacterial compositions containing same

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.

Conversion of alcohols to carboxylic acids using heterogeneous palladium-based catalysts

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 &#x3b2;-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. Attachment of an N-terminal octadecanoyl unit to the nylon-3 copolymers affords further improvements by reducing the percent surface area compression to reach low minimum surface tension.

Nitroxyl-mediated oxidation of lignin and polycarboxylated products

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Growing community of inventors

Madison, WI, United States of America

Shannon S Stahl