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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3

Conversion of lignin into value-added materials and chemicals via laccase-assisted copolymerization

With today’s environmental concerns and the diminishing supply of the world’s petroleum-based chemicals and materials, much focus has been directed toward alternative sources. Woody biomass presents a promising option due to its sheer abundance, renewability, and biodegradability. Lignin, a highly irregular polyphenolic compound, is one of the major chemical constituents of woody biomass and is the second most abundant biopolymer on Earth, surpassed only by cellulose. The pulp and paper and cellulosic ethanol industries produce lignin on the scale of millions of tons each year as a by-product. Traditionally, lignin has been viewed as a waste material and burned as an inefficient fuel. However, in recent decades, research has focused on more economical ways to convert lignin into value-added commodities, such as biofuels, biomaterials, and biochemicals, thus developing and strengthening the concept of fully integrated biorefineries. Owing to the phenolic structure of lignin, it is possible to enzymatically graft molecules onto its surface using laccases (benzenediol:oxygen oxidoreductases, EC 1.10.3.2) to create exciting novel biomaterials. These environmentally friendly enzymes use oxygen as their only co-substrate and produce water as their sole by-product, and have thus found great industrial application. Furthermore, this mini-review highlights recent advances in the field of laccase-facilitated functionalization of lignin as well as promising future directions for lignin-based polymers.

09 BIOMASS FUELS↗

Conferring Antibacterial Properties on Sesbania Gum via Microwave-Assisted Graft Copolymerization of DADMAC

Microbial contamination, the consequences of both anthropogenic and geogenic activity, includes high health and environmental threats and may adversely affects the ecological niche. The present work is a successful attempt towards the fabrication of anti-bacterial agent by incorporation of cationic monomer, diallyldimethylammonium chloride (DADMAC) on sesbania gum through microwave assisted method. The grafted chains of poly (DADMAC) provide positive charge to sesbania gum which in turn confers antibacterial activity. The synthesized product was characterized through FTIR, SEM, TGA, DSC elemental and viscometric analysis. The inhibitory activity of the synthesized product has been evaluated in vitro against both Gram-positive (Staphylococcus aureus NCIM 2122 and Bacillus anthracis) as well as Gram-negative (Salmonella typhi NCIM 2501 and Escherichia coli NCIM 2832) bacteria through standard agar cup method. Optimum minimum inhibitory concentration for each grade of graft copolymer measured by calculating the zone of inhibition has been found at 750 µg/ml. Graphical Abstract: .

36 MATERIALS SCIENCE↗

Structural Modification of Starch Nanoparticles Via Graft Copolymerization Using KMnO{sub 4}, HClO{sub 4} and HNO{sub 3} Redox Pair

The novelty addressed here is commenced with a view to use our formerly prepared starch nanoparticles (SNPs) of size around 80–100 nm as a starting substrate for grafting meth acrylic acid (MAA) using KMnO{sub 4}, HClO{sub 4} in presence of HNO{sub 3} as innovative redox pair in aqueous medium. This was done to see the effect of SNPs with respect to well-dispersed nanosized particles, large surface areas, biodegradability and reactivity on the rate and extent of grafting. Besides; maximize the graft yield and graft reaction efficiency and reduce the homopolymer formation to lower extent. This could be accomplished via an in-depth assessment into the chief factors affecting the polymerization reaction such as initiator, monomer, SNPs and acid concentrations, time and temperature of polymerization, and liquor ratio. The results obtained indicate that the magnitude of the polymer yield including graft yield, graft reaction efficiency and homopolymer formation are determined by these factors. The structure of the resultant copolymers was confirmed instrumentally by Fourier transforms infrared spectroscopy; while both the surface morphology, crystalline structure and thermal properties were characterized by scanning electron microscopy, X-ray diffraction and thermal gravimetric analysis. Furthermore, the resultant copolymers were evaluated as environmental remediation materials via cadmium ions and cationic dyes removal from their solutions with different extent; in addition to higher swelling and chemical resistance in water as polar solvent and hydrochloric acid as acidic solution. The anticipated mechanisms involved in the synthesis are reported.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Copolymerization of CO and N 2 to Extended CON 2 Framework Solid at High Pressures

Synthesis of novel extended forms of nitrogen and nitrogen-rich materials has been a topic of interest in development of high-energy-density materials. Here, we present the formation of high-density (3.983 g/cm 3 ) copolymer CON 2 , formed in crystalline form by laser heating of CO–N 2 mixtures above 1700 K and 45 GPa—a substantially lower pressure–temperature condition than those required for converting pure nitrogen (above 110 GPa and 2000 K). It can be made even at lower pressures ~20 GPa at ambient temperature for amorphous solid. According to the refined structure, the crystalline polymer is made of nitrogen-hybridized, eight-membered rings of singly bonded CON 2 in a three-dimensional framework structure in the space group of P4 3 , as one of the previously predicted structures. Furthermore, unlike the predicted structures, the present P4 3 solid converts back to ε-N 2 -like and δ-N 2 -like molecular phases as pressure unloads to 20 and 10 GPa, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Multiscale Simulation Study of Influence of Morphology on Ion Transport in Block Copolymeric Ionic Liquids

In this work, we present results of a multiscale simulation study involving coarse-graining and reverse-mapping steps probing at an atomistic resolution the influence of morphology on ion transport in block copolymer polymeric ionic liquids. We provide a detailed description of the multiscale simulation methodology and then describe the results in the context of four microphase-separated morphologies: two lamella systems, a cylinder, and a gyroid morphology. For the framework adopted in this study (in which the total number of ions was maintained fixed), morphology had little influence on the fraction of ions segregating to the interface and the coordination and hopping characteristics of such interfacially present ions. Such results manifested in anion mobilities being insensitive to the morphology once the dimensionality of the morphology was accounted for. Overall, our results are consistent with the hypothesis that the mobility of ions in such microphase-separated morphologies, after accounting for the dimensionality effects, can be roughly correlated to a linear superposition based on the fraction of bulk anions, which possess mobilities unperturbed from their values in the conducting homopolymers, and the interfacial anions, which exhibit much lower mobilities.

36 MATERIALS SCIENCE↗

Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties

Living anionic polymerization of acrylates is challenging due to intrinsic side reactions including backbiting reactions of propagating enolate anions and aggregation of active chain ends. In this study, the controlled synthesis of poly(1-adamatyl acrylate) (PAdA) was performed successfully for the first time via living anionic polymerization through investigation of the initiation systems of sec-butyllithium/diphenylethylene/lithium chloride (sec-BuLi/DPE/LiCl), diphenylmethylpotassium/diethylzinc (DPMK/Et 2 Zn), and sodium naphthalenide/dipenylethylene/diethylzinc (Na-Naph/DPE/Et2Zn) in tetrahydrofuran at -78 °C using custom glass-blowing and high-vacuum techniques. PAdA synthesized via anionic polymerization using DPMK with a large excess (more than 40-fold to DPMK) of Et 2 Zn as the ligand exhibited predicted molecular weights from 4.3 to 71.8 kg/mol and polydispersity indices of around 1.10. In addition, the produced PAdAs exhibit a low level of isotactic content (mm triads of 2.1%). The block copolymers of AdA and methyl methacrylate (MMA) were obtained by sequential anionic polymerization, and the distinct living property of PAdA over other acrylates was demonstrated based on the observation that the resulting PAdA-b-PMMA block copolymers were formed with no residual PAdA homopolymer. The PAdA homopolymers exhibit a very high glass transition temperature (133 °C) and outstanding thermal stability (T d : 376 °C) as compared to other acrylic polymers such as poly(tert-butyl acrylate) and poly(methyl acrylate). These merits make PAdA a promising candidate for acrylic-based thermoplastic elastomers with high upper service temperature and enhanced mechanical strength.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Random Copolymerization of Substituted Dioxolanes: Rational Design of High-Performance Polymer Electrolytes

Polymer electrolytes enhance the safety of lithium-ion battery systems, but current state-of-the-art poly­(ethylene oxide)-based polymer electrolytes fail to achieve the electrochemical properties necessary for practical applications. We probed the impact of substituent density on the electrolyte performance by introducing methyl substituents into the backbone of a series of poly­(1,3-dioxolane) (PDXL)-based copolymers. The polymerization of 1,3-dioxolane (DXL) and 4-methyl-1,3-dioxolane (MeDXL) yielded a series of random copolymers that were amorphous above 10% MeDXL incorporation. The copolymers with 10 and 20% MeDXL incorporation exhibited higher efficacies than those of either PDXL or poly­(ethylene oxide) (PEO), highlighting the use of methyl substituents to control the electrochemical properties of polymer electrolytes.

Rugh, Haley J↗