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At least 73 records · Page 4

Poly(9,9-dioctylfluorene-co-fluorenone-co-methylbenzoic ester), carbon nanotubes, and sulfur nanocomposite, electrode and lithium-fulfur battery including the same

The present invention provides for a composition of matter comprising: poly(9,9-dioctylfluorene-co-fluorenone-co-methylbenzoic ester)(PFM), carbon nanotubes (CNT), and sulfur particles nanocomposite, wherein the nanocomposite is porous. The present invention also provides for an electrode comprising: poly(9,9-dioctylfluorene-co-fluorenone-co-methylbenzoic ester)(PFM), carbon nanotubes (CNT), and sulfur particles nanocomposite, wherein the nanocomposite is porous. The present invention also provides for a lithium sulfur (Li—S) battery comprising: an electrode comprising poly(9,9-dioctylfluorene-co-fluorenone-co-methylbenzoic ester)(PFM), carbon nanotubes (CNT), and sulfur particles nanocomposite, wherein the nanocomposite is porous.

Liu, Gao↗

A Chemoselective and Stereodivergent Platform of Heme‐Nitrene Transferases to Access Chiral Aryl‐β‐Amino Esters and An Investigation of the Sequence‐Activity Landscape

Engineered biocatalysts can utilize nitrene precursors to access enantioenriched amination products, yet they have not been applied to produce valuable, enantiomerically enriched noncanonical β-amino esters. Current approaches to synthesizing β-amino acids rely on pre-oxidized precursors and multistep synthetic approaches involving various protecting groups. We engineered a platform of heme enzymes for stereoselective C–H bond amination of readily available carboxylic ester derivatives to install primary amines. A directed evolution campaign coupled with sequencing of over 1000 variants enabled us to develop engineered variants that use either O-pivaloylhydroxylamine triflic acid (PONT) or hydroxylamine hydrochloride (H 2 NOH∙HCl) as aminating reagents. An analysis of the resulting sequence–activity dataset revealed additional improvements that could be made to the final variant, highlighting the utility of sequencing data to guide future steps in directed evolution campaigns. Furthermore, the evolved nitrene transferases expand the scope of accessible chiral β-amino acid building blocks for peptidomimetic applications and provide new starting points for the design and synthesis of enantioenriched β-amino acid motifs.

amino ester building blocks↗

Structure-based mechanism and inhibition of cholesteryl ester transfer protein

Purpose of Review: Cholesteryl ester transfer proteins (CETP) regulate plasma cholesterol levels by transferring cholesteryl esters (CEs) among lipoproteins. Lipoprotein cholesterol levels correlate with the risk factors for atherosclerotic cardiovascular disease (ASCVD). This article reviews recent research on CETP structure, lipid transfer mechanism, and its inhibition. Recent Findings: Genetic deficiency in CETP is associated with a low plasma level of low-density lipoprotein cholesterol (LDL-C) and a profoundly elevated plasma level of high-density lipoprotein cholesterol (HDL-C), which correlates with a lower risk of atherosclerotic cardiovascular disease (ASCVD). However, a very high concentration of HDL-C also correlates with increased ASCVD mortality. Considering that the elevated CETP activity is a major determinant of the atherogenic dyslipidemia, i.e., pro-atherogenic reductions in HDL and LDL particle size, inhibition of CETP emerged as a promising pharmacological target during the past two decades. CETP inhibitors, including torcetrapib, dalcetrapib, evacetrapib, anacetrapib and obicetrapib, were designed and evaluated in phase III clinical trials for the treatment of ASCVD or dyslipidemia. Although these inhibitors increase in plasma HDL-C levels and/or reduce LDL-C levels, the poor efficacy against ASCVD ended interest in CETP as an anti-ASCVD target. Nevertheless, interest in CETP and the molecular mechanism by which it inhibits CE transfer among lipoproteins persisted. Insights into the structural-based CETP-lipoprotein interactions can unravel CETP inhibition machinery, which can hopefully guide the design of more effective CETP inhibitors that combat ASCVD. Summary: Individual-molecule 3D structures of CETP bound to lipoproteins provide a model for understanding the mechanism by which CETP mediates lipid transfer and which in turn, guide the rational design of new anti-ASCVD therapeutics.

59 BASIC BIOLOGICAL SCIENCES↗

High-Temperature-Performance Cyanate Ester Composites with Carboranes

Cyanate ester (CE) is an important class of materials among high-temperature performance thermosets. It is used in aerospace launch vehicles, heat sinks, booms, and trusses of satellites etc. due to its high glass transition temperatures (>220°C), excellent thermal stability, and low flammability. Current approaches to improve the thermal stability of CE include incorporation of siloxanes or phosphorus- based flame retardants (PFRs). In this work, we have explored boron-based hydroxy (PD) and epoxy (EP) functionalized carborane additives to improve the thermal properties of CE. Carborane fillers were solvent blended at various mass loadings in the resin and cured to study their effect on thermal properties. PD and EP carboranes react with CE to form iminocarbonate and oxazolidinone linkages respectively. Cure kinetics studies at different wt% loadings explained that carboranes catalyze the curing reaction by reducing curing activation energy by about 54% and 26% for 10 wt% loadings of PD and EP carboranes respectively. In addition, carborane-filled cyanate ester (CE) nanocomposites demonstrate an exceptionally high thermal stability as compared to the pristine resin in air and inert environment. Our thermogravimetric analysis (TGA) experiments show that the ultimate char yield of the resin can be increased from 0% to as high as 76% and 82% with 30 wt% PD and EP carborane loading respectively at 1000 °C in air. The initial degradation temperature T d;5 of the composites decreased with increasing carborane loadings in both air and argon. For instance, T d;5 for CE was 465 and 471.6 °C in argon and air while that for P20 was 437.4 and 452.1 °C. Modulated TGA studies gave evidence of the effect of carboranes on degradation kinetics and the mechanism of the resin in air and inert environment. The effect of bonding between carboranes and CE at various loadings on the thermal expansion of the matrix was also studied using Thermomechanical Analyzer (TMA). PD carborane reduced the T g for P20 to about 225 °C while CE had T g >350 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering Catalysts for Selective Ester Hydrogenation

The development of efficient catalysts and processes for synthesizing functionalized (olefinic and/or chiral) primary alcohols and fluoral hemiacetals is currently needed. These are valuable building blocks for pharmaceuticals, agrochemicals, perfumes, and so forth. From an economic standpoint, bench-stable Takasago Int. Corp.’s Ru-PNP, more commonly known as Ru-MACHO, and Gusev’s Ru-SNS complexes are arguably the most appealing molecular catalysts to access primary alcohols from esters and H 2 . This work introduces economically competitive Ru-SNP(O) z complexes ( z = 0, 1), which combine key structural elements of both of these catalysts. In particular, the incorporation of SNP heteroatoms into the ligand skeleton was found to be crucial for the design of a more product-selective catalyst in the synthesis of fluoral hemiacetals under kinetically controlled conditions. Based on experimental observations and computational analysis, this paper further extends the current state-of-the-art understanding of the accelerative role of KO- t -C 4 H 9 in ester hydrogenation. Finally, it attempts to explain why a maximum turnover is seen to occur starting at ~25 mol % base, in contrast to only ~10 mol % with ketones as substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Copper-Based Catalysts Confined in Carbon Nanocage Reactors for Condensed Ester Hydrogenation: Tuning Copper Species by Confined SiO 2 and Methanol Resistance

Hydrogenation of aliphatic esters to natural alcohols is an important strategy for the efficient utilization of biomass-derived oils. The synthesis of highly active copper (Cu)-based catalysts is a challenge for condensed-phase ester hydrogenation due to the difficulties in controlling active sites and catalyst deactivation. In this work, a copper-based catalyst confined in a carbon nanocage reactor was successfully designed and prepared. The copper catalyst with 56 wt % SiO 2 exhibited the best performance because of the optimum proportion of Cu + and Cu 0 sites and high dispersion. The interaction between SiO 2 and Cu particles contributes to the formation of Cu + species, which is the key site for the adsorption of carbonyl groups. Meanwhile, the confinement effect of the carbon nanocages effectively inhibited the agglomeration of the copper particles. The catalysts exhibited not only excellent thermal stability but also superior methanol resistance in comparison with the Cu/SiO 2 catalyst. On the basis of the density functional theory (DFT) calculations results, methanol resistance should be attributed to the fewer hydroxyl groups on the catalyst surface, which increase the activation barrier for the dissociation of silica, allowing the stable holding of the copper species in the methanol solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering Yeast for the Production of Acids and Esters (CRADA Final Report)

NREL and Lygos have a mutual interest in engineering yeast for the production of acids and esters as intermediates towards fuels or bioproducts. In particular, the yeast Pichia kudriavzevii is a fantastic candidate for the production of acid and ester based products including butyric acid and ethyl butyrate. However, the strain is relatively uncommon in the biotechnological space and as such there are not an abundant amount of genetic tools that are publically available. However, Lygos has been working with this species in particular for several years and has developed genetic tools and physiological characteristics and are well versed in engineering this strain for acid based products. While currently focusing on malonic acid-derived products, Lygos is not currently targeting butyric acid and ethyl butyrate but have a long term interest in these molecules and derivatives therein. This CRADA proposal seeks to leverage NREL’s immediate focus on butyric acid and ethyl butyrate, and general bioprocess expertise with Lygos’ specific knowledge on engineering P. kudriavzevii for the production of acid-based products.

09 BIOMASS FUELS↗

Room‐Temperature Formate Ester Transfer Hydrogenation Enables an Electrochemical/Thermal Organometallic Cascade for Methanol Synthesis from CO 2

Abstract The reduction of CO 2 to synthetic fuels is a valuable strategy for energy storage. However, the formation of energy‐dense liquid fuels such as methanol remains rare, particularly under low‐temperature and low‐pressure conditions that can be coupled to renewable electricity sources via electrochemistry. Here, a multicatalyst system pairing an electrocatalyst with a thermal organometallic catalyst is introduced, which enables the reduction of CO 2 to methanol at ambient temperature and pressure. The cascade methanol synthesis proceeds via CO 2 reduction to formate by electrocatalyst [Cp*Ir(bpy)Cl] + (Cp*=pentamethylcyclopentadienyl, bpy=2,2′‐bipyridine), Fischer esterification of formate to isopropyl formate catalyzed by trifluoromethanesulfonic acid (HOTf), and thermal transfer hydrogenation of isopropyl formate to methanol facilitated by the organometallic catalyst (H‐PNP)Ir(H) 3 (H‐PNP=HN(C 2 H 4 P i Pr 2 ) 2 ). The isopropanol solvent plays several crucial roles: activating formate ion as isopropyl formate, donating hydrogen for the reduction of formate ester to methanol via transfer hydrogenation, and lowering the barrier for transfer hydrogenation through hydrogen bonding interactions. In addition to reporting a method for room‐temperature reduction of challenging ester substrates, this work provides a prototype for pairing electrochemical and thermal organometallic reactions that will guide the design and development of multicatalyst cascades.

Fernández, Sergio [Department of Chemistry Univers↗

Room-Temperature Formate Ester Transfer Hydrogenation Enables an Electrochemical/Thermal Organometallic Cascade for Methanol Synthesis from CO 2

The reduction of CO 2 to synthetic fuels is a valuable strategy for energy storage. However, the formation of energy-dense liquid fuels such as methanol remains rare, particularly under low-temperature and low-pressure conditions that can be coupled to renewable electricity sources via electrochemistry. Here, in this study, a multicatalyst system pairing an electrocatalyst with a thermal organometallic catalyst is introduced, which enables the reduction of CO 2 to methanol at ambient temperature and pressure. The cascade methanol synthesis proceeds via CO 2 reduction to formate by electrocatalyst [Cp*Ir(bpy)Cl] + (Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine), Fischer esterification of formate to isopropyl formate catalyzed by trifluoromethanesulfonic acid (HOTf), and thermal transfer hydrogenation of isopropyl formate to methanol facilitated by the organometallic catalyst (H-PNP)Ir(H) 3 (H-PNP=HN(C 2 H 4 P i Pr 2 ) 2 ). The isopropanol solvent plays several crucial roles: activating formate ion as isopropyl formate, donating hydrogen for the reduction of formate ester to methanol via transfer hydrogenation, and lowering the barrier for transfer hydrogenation through hydrogen bonding interactions. In addition to reporting a method for room-temperature reduction of challenging ester substrates, this work provides a prototype for pairing electrochemical and thermal organometallic reactions that will guide the design and development of multicatalyst cascades.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Synthesized Homochiral Spiroborate Ester Metal–Organic Framework with Mono–, Di–, and Trivalent Cations

Here we report here a one–step method for synthesizing multi–component and in–situ–formed homochiral spiroborate–ester–based metal–organic framework CPM–B1. This unique material successfully integrates COF fragment spiroborate ester within the MOF and simultaneously incorporate homochirality and helicity. In addition, CPM–B1 is a rare example of framework materials that results from the cooperative assembly of three charge–complementary cations: +1 (lithium), +2 (cobalt), and +3 (boron). The sophistication of the co–assembly is further highlighted by the three structural roles of lithium ions. This unique structure contributes to its multi–functional properties such as ionic conductivity and catalytic activity for oxygen reduction reaction (by CPM–B1 carbonized material) and provides a new path to develop MOF materials with complex secondary building units and multi–functional applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electricity-driven recycling of ester plastics using one-electron electro-organocatalysis

Here, we report the catalytic use of electrochemically generated one-electron reducing agents to produce ester anion radicals that can decompose to acids and alcohols in the presence of oxygen. Through this approach, we demonstrate that molecular analogs of polyethylene terephthalate (PET) can be deconstructed into their molecular components. We additionally show efficient reductive scission of ester bonds in PET plastic using catalytically regenerated reducing agents based on benzimidazolium cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On electron beam-induced degradation of vinyl ester thermosets

We have demonstrated that electron beam radiolysis induces scissions of the C-O-C bonds along the backbone of the chains of unsaturated polyester thermosets of different compositions based on dicyclopentadiene, isophthalic acid, epoxy vinyl ester, and terephthalic acid. The radiolysis is imminent irrespective of the degree of crosslinking in the thermosets both in neat resins and in the presence of solvents. Electron Paramagnetic Resonance (EPR) results show the formation of the alkoxyl radicals and C-centered radicals as the primary intermediate products of the C-O-C scissions. While the alkoxyl radicals of these resins exhibit very good stability even six months after the irradiation, the C-centered radicals decay very rapidly via their reactions with oxygen that is available either as adsorbed in the resins, dissolved in solvents or from the environment. The radiolytically produced •OH radicals in the unsaturated-ester aqueous solutions play a major role in inducing scissions on the backbone of the polymer chains. The solvated electrons (e s ) from organic solvents, such as dimethyl sulfoxide and isopropyl alcohol, also induce direct scission of the C-O-C bonds, giving rise to the formation of alkoxyl radicals and C-centered radicals. However, a considerable fraction of es is scavenged by the dissolved O 2 to produce O 2 - . Despite the radiation-induced scissions, irradiation of the resins at a dose level of 1000 kGy results in an increase of the glass transition temperature, Tg. This is due to the simultaneous radiation-induced polymerization of the vinyl monomers, toluene, and styrene that are present in the resins. The increase in Tg is observed in all the resins except for the terephthalic polyester resin in aqueous solution, in which the absence of these monomers results in Tg decreasing sharply with irradiation. This work demonstrates that ionizing radiation triggers continuous free radical-chain reactions that lead to the formation of recyclable oligomers.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Catalytic conversion of cellulose and its derived sugars to 5-Hydroxymethylfurfural, levulinate esters, and sorbitol: a comprehensive review

Cellulose, an abundant, renewable, and sustainable non-edible carbon source from agriculture and forestry, has attracted great attention for producing diverse value-added chemicals and fuels. However, the rigid 3D structure of cellulose, maintained by an extensive hydrogen bonding network, hinders chemical conversion, requiring effective pretreatment to break down the crystalline structure. High-value cellulose-derived compounds such as 5-hydroxymethylfurfural (5-HMF), levulinate esters, and sorbitol, recognized as critical platform chemicals by the U.S. Department of Energy, are particularly attractive for versatile applications. This review provides a comprehensive overview of methodologies for the chemical synthesis of 5-HMF, levulinate esters, and sorbitol, focusing on direct catalytic conversion of cellulose. It delves into recent advancements in reaction systems and catalysts, highlighting catalytic pathways, selectivity, strategies for process optimization, and computational approaches, while discussing the challenges associated with the catalytic conversion of cellulose into these high-value products and offering potential strategies for enhancing future catalytic processes.

Huang, Kaixuan [Yancheng Teachers Univ. (China); N↗

The importance of ester cleavage in the butylamine pretreatment of hybrid poplar

Butylamine is an effective in-and-out pretreatment solvent for hybrid poplar. It penetrates the cell walls and breaks ester cross-linkages, facilitating lignin release and improving enzymatic digestion. This work explores the “in-and-out” pretreatment of hybrid poplar with butylamine as a distillable protic solvent and reagent. The butylamine solvent can be removed by vacuum distillation with >95% solvent removal in all cases, providing a valuable scheme for efficient solvent recovery and recycling. Running the reaction with neat butylamine at 140 °C for 3 hours results in high yields of monosaccharides (90% glucose and 71% xylose) after enzymatic digestion, and a good tolerance to water content with no significant reduction in glucose yield up to an 8 : 1 water : butylamine ratio. We investigate the mechanisms of this pretreatment using powder X-ray diffraction, thermogravimetric analysis, fluorescence microscopy, elemental analysis, solid state and solution state nuclear magnetic spectroscopy to observe chemical and material markers of the pretreatment chemistry. The results suggest that the butylamine leaves the macro and microstructural properties of the lignocellulose relatively unaltered, but conducts targeted ester cleavage chemistry to remove cross-links between the various biopolymers and partially solubilize the lignin component of the biomass. These findings should act to guide future development of pretreatment chemistry for the development of biorefinery processes, and assist in the utilization of biomass as a starting point for chemical syntheses.

Palasz, Joseph M↗

Investigation of the Electrode-Electrolyte Interphase in Ester-Based Electrolytes in NCM523/Graphite Cells

The use of methyl acetate (MA) and methyl propionate (MP) as co-solvents in carbonate/LiPF 6 electrolytes have been investigated in LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523)/graphite cells to improve electrochemical performance at low temperature (−20 °C). Consistent with previous investigations, improved low temperature performance was observed with all electrolyte formulations containing esters. Detailed ex situ surface analysis of the surface films generated with the ester-based electrolytes containing electrolyte additives reveal significant changes to the SEI on graphite upon cycling at moderately elevated temperature (45 °C). In the presence of vinylene carbonate (VC) lithium plating is observed upon cycling at low temperature (−20 °C) which leads to a thicker solid electrolyte interface (SEI) upon cycling at 45 °C. Incorporation of fluoroethylene carbonate (FEC) as an electrolyte additive results in the generation of a thin SEI and alters the structure of the surface film on the NCM523 cathode resulting in stable cycling over a wide temperature range.

Rodrigo, Nuwanthi D. (ORCID:0000000343129536)↗

Use of Ethylene Carbonate Free Ester Solvent Systems with Alternative Lithium Salts for Improved Low-Temperature Performance in NCM622∣∣ Graphite Li-ion Batteries

An investigation of alternative lithium salts, lithium tetrafluoroborate (LiBF 4 ), lithium difluoro(oxalato)borate (LiDFOB) and lithium hexafluorophosphate (LiPF 6 ), in novel ester-based (methyl acetate/fluoroethylene carbonate- MA/FEC or methyl propionate/fluoroethylene carbonate- MP/FEC) electrolyte formulations has been conducted in LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)/graphite cells to improve low temperature cycling performance of lithium ion batteries at −20 °C. Improved low temperature performance was observed with all the lithium salts in MA/FEC electrolyte while comparable room temperature (25 °C) capacities were observed with LiPF 6 salt only. Detailed ex-situ analysis of surface films generated with LiBF 4 , LiDFOB and LiPF 6 in ester-based electrolytes reveals that the solid electrolyte interphase (SEI) is predominately composed of lithium salt decompaction products and addition of 10% FEC (by volume%) may not be sufficient at forming a protective SEI.

25 ENERGY STORAGE↗

High wax ester and triacylglycerol biosynthesis potential in coastal sediments of Antarctic and Subantarctic environments

The wax ester (WE) and triacylglycerol (TAG) biosynthetic potential of marine microorganisms is poorly understood at the microbial community level. The goal of this work was to uncover the prevalence and diversity of bacteria with the potential to synthesize these neutral lipids in coastal sediments of two high latitude environments, and to characterize the gene clusters related to this process. Homolog sequences of the key enzyme, the wax ester synthase/acyl-CoA:diacylglycerol acyltransferase (WS/DGAT) were retrieved from 13 metagenomes, including subtidal and intertidal sediments of a Subantarctic environment (Ushuaia Bay, Argentina), and subtidal sediments of an Antarctic environment (Potter Cove, Antarctica). The abundance of WS/DGAT homolog sequences in the sediment metagenomes was 1.23 ± 0.42 times the abundance of 12 single-copy genes encoding ribosomal proteins, higher than in seawater (0.13 ± 0.31 times in 338 metagenomes). Homolog sequences were highly diverse, and were assigned to the Pseudomonadota, Actinomycetota, Bacteroidota and Acidobacteriota phyla. The genomic context of WS/DGAT homologs included sequences related to WE and TAG biosynthesis pathways, as well as to other related pathways such as fatty-acid metabolism, suggesting carbon recycling might drive the flux to neutral lipid synthesis. These results indicate the presence of abundant and taxonomically diverse bacterial populations with the potential to synthesize lipid storage compounds in marine sediments, relating this metabolic process to bacterial survival.

59 BASIC BIOLOGICAL SCIENCES↗

Characterization of Kariya ( Hildegardia barteri (Mast.) Kosterm) Seed Oil Fatty Acid Methyl Ester Prepared from Basic Catalytic Transesterification

The rising global energy demand, alongside concerns regarding environmental deterioration due to the use of fossil fuels, has spurred extensive investigation into renewable energy alternatives. Biomass-derived biodiesel, especially from lesser-known oil sources, emerges as a promising option. This research focuses on analyzing the fatty acid methyl esters (FAMEs) derived from Kariya (Hildegardia barteri (Mast.) Kosterm) seed oil through basic catalytic transesterification using gas chromatography–flame ionization detector (GC–FID) analysis, assessing its potential as a biodiesel feedstock. Oil extraction from Kariya seeds was carried out using three solvents (n-hexane, ethanol, and a 1:1 blend of hexane and ethanol), followed by transesterification with methanol. Gas chromatography–mass spectrometry (GC–MS) and GC–FID analyses were utilized to identify and quantify FAMEs in the resulting biodiesel. The results revealed various FAMEs, including methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, and methyl linolenate. Significant differences in FAME composition were observed among the samples, with hexane–ethanol Kariya oil biodiesel (HE-KOB) showing the highest FAME content (76.1%). This combination of solvents exhibited synergistic effects on the composition of HE-KOB, suggesting potential optimization strategies for biodiesel production. Fourier transform infrared spectroscopy (FTIR) provided additional insights into the molecular composition of the biodiesel samples, confirming their biodiesel nature through the identified functional groups such as methyl, methylene, hydrocarbon, ester, aldehyde, and alkene. Thermogravimetric analysis (TGA) for thermal decomposition also gave an insight into FAME composition and its contribution to the degree of conversion of biodiesel to energy. These findings highlight the feasibility of utilizing Kariya seed oil as a biodiesel feedstock, emphasizing the importance of solvent selection and transesterification conditions in optimizing FAME yield and composition. This research contributes to the exploration of underutilized oil sources for sustainable biodiesel production, aligning with the global shift towards cleaner and renewable energy sources.

09 BIOMASS FUELS↗