Abstract: Catalyst systems employing inexpensive and readily-available protic co-catalysts to increase a proton reduction rate in a hydrogen evolution reaction (HER) are described herein. The protic co-catalysts function to increase the rate without being consumed in the process of water splitting to hydrogen and oxygen. They may simultaneously serve to stabilize the pH of the water and be the electrolyte to carry the current for the electrolytic splitting of water. The protic co-catalysts also decrease the overpotential energy requirement for the process of water splitting. These protic co-catalysts can be used with both heterogeneous and homogenous catalysts, as well as assist photocatalysis and other processes for the reduction of protons.

Abstract: Metallopolymers composed of polymers and catalytically active diiron-disulfide ([2Fe-2S]) complexes. [FeFe]-hydrogenase mimics have been synthesized and used to initiate polymerization of various monomers to generate metallopolymers containing active [2Fe-2S] sites which serve as catalysts for a hydrogen evolution reaction (HER). Vinylic monomers with polar groups provided water solubility relevant for large scale hydrogen production, leveraging the supramolecular architecture to improve catalysis. Metallopolymeric electrocatalysts displayed high turnover frequency and low overpotential in aqueous media as well as aerobic stability. Metallopolymeric photocatalysts incorporated P3HT ligands to serve as a photosensitizer to promote photoinduced electron transfer to the active complex.

Abstract: Methods of vulcanization using a high content sulfur polymer, instead of elemental sulfur, have been developed. These high sulfur content polymers are referred to as Chalcogenide Hybrid Inorganic/Organic Polymers (CHIP) materials and have good polymer compatibility in that they are soluble in a number of polymers. Furthermore, CHIP materials may have weaker bonds than the S—S bonds of elemental sulfur and thus provide for a higher crosslinking efficiency vulcanization.

Abstract: Methods of vulcanization using a high content sulfur polymer, instead of elemental sulfur, have been developed. These high sulfur content polymers are referred to as Chalcogenide Hybrid Inorganic/Organic Polymers (CHIP) materials and have good polymer compatibility in that they are soluble in a number of polymers. Furthermore, CHIP materials may have weaker bonds than the S—S bonds of elemental sulfur and thus provide for a higher crosslinking efficiency vulcanization.

Abstract: Metallopolymers composed of polymers and catalytically active diiron-disulfide ([2Fe-2S]) complexes are described herein. [FeFe]-hydrogenase mimics have been synthesized and used to initiate polymerization of various monomers to generate metallopolymers containing active [2Fe-2S] sites which serve as catalysts for a hydrogen evolution reaction (HER). Vinylic monomers with polar groups provided water solubility relevant for large scale hydrogen production, leveraging the supramolecular architecture to improve catalysis. Metallopolymeric electrocatalysts displayed high turnover frequency and low overpotential in aqueous media as well as aerobic stability. Metallopolymeric photocatalysts incorporated P3HT ligands to serve as a photosensitizer to promote photoinduced electron transfer to the active complex.

Abstract: The present invention provides chalcogenide hybrid organic/inorganic polymers (“CHIPs” or organic chalcogenide polymers) and methods for producing and using the same. In particular, the chalcogenide hybrid organic/inorganic polymers of the invention comprise a hydrocarbon cyclic ring structure and one or more chalcogenide selected from the group consisting of sulfur, selenium, cyclic selenium sulfide, and a combination thereof.

Abstract: Copolymerization of elemental sulfur with functional comonomers afford sulfur copolymers having a high molecular weight and high sulfur content. Nucleophilic activators initiate sulfur polymerizations at relative lower temperatures and in solutions, which enable the use of a wider range of comonomers, such as vinylics, styrenics, and non-homopolymerizing comonomers. Nucleophilic activators promote ring-opening reactions to generate linear polysulfide intermediates that copolymerize with comonomers. Dynamic sulfur-sulfur bonds enable re-processing or melt processing of the sulfur polymer. Chalcogenide-based copolymers have a refractive index of about 1.7-2.6 at a wavelength in a range of about 5000 nm-8????. The sulfur copolymer can be a thermoplastic or a thermoset for use in elastomers, resins, lubricants, coatings, antioxidants, cathode materials for electrochemical cells, dental adhesives/restorations, and polymeric articles such as polymeric films and free-standing substrates.

Abstract: Catalyst systems employing inexpensive and readily-available protic co-catalysts to increase a proton reduction rate in a hydrogen evolution reaction (HER) are described herein. The protic co-catalysts function to increase the rate without being consumed in the process of water splitting to hydrogen and oxygen. They may simultaneously serve to stabilize the pH of the water and be the electrolyte to carry the current for the electrolytic splitting of water. The protic co-catalysts also decrease the overpotential energy requirement for the process of water splitting. These protic co-catalysts can be used with both heterogeneous and homogenous catalysts, as well as assist photocatalysis and other processes for the reduction of protons.

Abstract: Methods of vulcanization using a high content sulfur polymer, instead of elemental sulfur, have been developed. These high sulfur content polymers are referred to as Chalcogenide Hybrid Inorganic/Organic Polymers (CHIP) materials and have good polymer compatibility in that they are soluble in a number of polymers. Furthermore, CHIP materials may have weaker bonds than the S—S bonds of elemental sulfur and thus provide for a higher crosslinking efficiency vulcanization.

Abstract: Metallopolymers composed of polymers and catalytically active diiron-disulfide ([2Fe-2S]) complexes are described herein. [FeFe]-hydrogenase mimics have been synthesized and used to initiate polymerization of various monomers to generate metallopolymers containing active [2Fe-2S] sites which serve as catalysts for a hydrogen evolution reaction (HER). Vinylic monomers with polar groups provided water solubility relevant for large scale hydrogen production, leveraging the supramolecular architecture to improve catalysis. Metallopolymeric electrocatalysts displayed high turnover frequency and low overpotential in aqueous media as well as aerobic stability. Metallopolymeric photocatalysts incorporated P3HT ligands to serve as a photosensitizer to promote photoinduced electron transfer to the active complex.

Abstract: Copolymerization of elemental sulfur with functional comonomers afford sulfur copolymers having a high molecular weight and high sulfur content. Nucleophilic activators initiate sulfur polymerizations at relative lower temperatures and in solutions, which enable the use of a wider range of comonomers, such as vinylics, styrenics, and non-homopolymerizing comonomers. Nucleophilic activators promote ring-opening reactions to generate linear polysulfide intermediates that copolymerize with comonomers. Dynamic sulfur-sulfur bonds enable re-processing or melt processing of the sulfur polymer. Chalcogenide-based copolymers have a refractive index of about 1.7-2.6 at a wavelength in a range of about 5000 nm-8????. The sulfur copolymer can be a thermoplastic or a thermoset for use in elastomers, resins, lubricants, coatings, antioxidants, cathode materials for electrochemical cells, dental adhesives/restorations, and polymeric articles such as polymeric films and free-standing substrates.

Abstract: Sulfur composites and polymeric materials having a high sulfur content and prepared from elemental sulfur as the primary chemical feedstock. The sulfur copolymers are prepared by the polymerization of elemental sulfur with one or more monomers of amines, thiols, sulfides, alkynylly unsaturated monomers, nitrones, aldehydes, ketones, thiiranes, ethylenically unsaturated monomers, or epoxides. The sulfur copolymers may be further dispersed with metal or ceramic composites or copolymerized with elemental carbon, photoactive organic chromophores, or reactive and solubilizing/biocompatible moieties. The sulfur composites and polymeric materials feature the ability self-healing through thermal reformation. Applications utilizing the sulfur composites and polymeric materials may include electrochemical cells, optics, H2S donors and antimicrobial materials.

Abstract: Electrochemical oxidation of organic disulfides is conducted in an electrolytic solution containing an arene (e.g., anthracene, acenaphthylene, phenanthrene), and depending on the arene used and/or the product desired, an organic base (e.g., pyridine) to effect the synthesis of organothiated products in good yields.

Abstract: Electrolysis of organic disulfides in liquid sulfur dioxide is used to obtain organothiating agents, which can then be reacted with appropriate substrates to effect the synthesis of organothioaromatic compounds efficiently and in high yields. With appropriate phenolic compounds, regioselective substitution occurs in which para substitution greatly exceeds ortho substitution.

Abstract: A method for stuffing a tubular food casing to reduce trapped air in the finished product. The method comprises placing a shirred stick of food casing on a stuffing horn having an exit end through which food product flows into the casing, withdrawing a leading end portion of the casing over the exit end of the horn, closing the leading end portion, sealing the casing against the horn, drawing a vacuum within the tubular food casing, conducting food product through the exit end of the stuffing horn into said tubular food casing while maintaining the vacuum to stuff a portion of the food casing while withdrawing more casing over the exit end of the stuffing horn, and closing the food casing behind the stuffed portion of the food casing.

Abstract: A photoactivatible nucleoside analogue is disclosed, comprising a coumarin moiety linked through its phenyl ring to the 1-position of a ribose or deoxyribose sugar moiety. The resulting nucleoside analogue is typically used as a photocrosslinking group when inserted into a polynucleotide as a replacement for one or more of the complementary nucleoside bases present in a probe used in a hybridization assay.

Abstract: A method for the stereoselective snythesis of a cis-syn, furan-side mono-adducted linear furocoumarin:nucleoside adduct, which comprises reacting a linear furocoumarin with a nucleophilic acid to form a 3,4-dihydro-4-substituted linear furocoumarin intermediate, and contacting the intermediate with a nucleoside under photoactivating conditions. The reaction produces a cis-syn, furan-side, mono-adducted 3,4-dihydro-4-substituted linear furocoumarin:nucleoside adduct which can then be deblocked to give the final product under mild conditions.