Integrated Capture and Electroreduction of Flue Gas CO₂ to Formate Using Amine Functionalized SnO_<i>x</i> Nanoparticles

Flue gas from fossil fuel combustion contributes significantly to CO2 emissions. Due to the low CO2 concentration and the existence of reactive O2 in the flue gas, direct flue gas CO2 electrochemical conversion is a challenging task. Here we integrated both CO2 capture and electrochemical conversion into CO2 enriching catalysts by grafting alkanolamines on a tin oxide surface, which can electrochemically reduce simulated flue gas (SFG, 15% CO2, 8% O2, 77% N2) to formate. Maximum formate Faradaic efficiency of 84.2% has been reached by diethanolamine modified tin oxide (DEA–SnOx/C) at −0.75 V vs RHE with partial current density of 6.7 mA·cm–2 in 0.5 M KHCO3 under simulated flue gas atmosphere. Surface amino groups not only enrich CO2 locally but also inhibit O2 reduction, and in situ infrared (in situ IR) spectroscopy confirmed that amino groups accelerate CO2 reduction by promoting the formation of key intermediates (OCHO–*)

DataSheet_1_An extracellular protease containing a novel C-terminal extension produced by a marine-originated haloarchaeon.pdf

Marine microorganisms have long been acknowledged as a significant reservoir of enzymes required for industrial use. In this study, a novel extracellular protease HslHlyB derived from marine-originated haloarchaeon Halostella pelagica DL-M4T was identified. HslHlyB contained polycystic kidney disease (PKD) domain and pre-peptidase C-terminal (PPC) domain at the C-terminus. Truncation and replacement of the C-terminal extension (CTE) of HslHlyB demonstrated the importance of the CTE in maintaining the protease activity secreted by haloarchaeon. HslHlyB and HslHlyBΔCTE were expressed in Escherichia coli BL21(DE3), and purified by high-affinity column refolding and gel filtration chromatography. The molecular masses of HslHlyB and HslHlyBΔCTE were 42 kDa and 20 kDa, respectively. The optimum catalytic reaction conditions were 50°C, pH 8.5, NaCl 3.5 M and 50°C, pH 7.5, NaCl 3 M, respectively. They showed good stability and hydrolysis capabilities towards a wide range of protein substrates. HslHlyBΔCTE showed higher catalytic reaction rate and better thermal stability than the wild type against azocasein and tetrapeptide substrate. The hydrolysates of soybean protein hydrolyzed by HslHlyBΔCTE had smaller average molecular masses and shorter average peptide chain lengths than those by HslHlyB. These results indicated the diversity of halolysins from marine-originated haloarchaea to harness organic nitrogen in the marine environment and provided promising candidates for application in various industries.</p

Tailored Bimetallic Ni–Sn Catalyst for Electrochemical Ammonia Oxidation to Dinitrogen with High Selectivity

Direct electrochemical ammonia oxidation reaction (eAOR) is an efficient and sustainable strategy to process wastewater containing ammonia, and it endures overoxidation and severely competitive oxygen evolution reaction (OER). Herein, we synthesized a Ni(OH)2/SnO2 composite catalyst by a multistep strategy and applied it to the eAOR process. Ni(OH)2/SnO2 exhibited a N2–N Faradaic efficiency (FEN2–N) of 84.2%, with a N2 partial current density (jN2–N) of 2.7 mA cm–2 at 1.55 V vs reversible hydrogen electrode (RHE) in 0.5 M K2SO4 with 10 mM NH3–N (pH 11). The oxophilic Sn promoted NH3 absorption on Ni sites while suppressing the OER. As the active species, NiOOH accelerated the dimerization of intermediates (*NH2 or *NH) to form N2

Temperature-Dependent Electrosynthesis of C₂ Oxygenates from Oxalic Acid Using Gallium Tin Oxides

The electrosynthesis of multi-carbon chemicals such as glyoxylic acid (GX) and glycolic acid (GC) from oxalic acid (OA) offers a feasible pathway to achieve sustainable chemical production, especially when coupled with the electroreduction of CO2 to form OA. Here, we demonstrate a series of gallium tin oxide catalysts for selective, controlled OA electroreduction to GX and GC in acidic media. The product distribution can be tuned by changing the reaction temperatures. At room temperature using the GaSnOx/C catalyst, GX can be obtained with a GX Faradaic efficiency (FEGX) of 92.7% at −0.7 V vs RHE and a GX current density (jGX) of −100.2 mA cm–2. At a raised temperature of 80 °C using the GaSnOx/C catalyst, a GC Faradaic efficiency (FEGC) of 91.7% at −0.8 V vs RHE can be obtained. The accelerated OA electroreduction results from the Ga/Sn synergy in the catalysts. A proper Ga/Sn ratio not only enriches OA adsorption and enhances surface binding of intermediates, but also ensures catalyst stability in acidic media

Swelling/Deswelling-Induced Reversible Surface Wrinkling on Layer-by-Layer Multilayers

Layer-by-layer (LbL) multilayer film is incorporated in the fabrication of a film/substrate system for the investigation of swelling/deswelling-induced wrinkle evolution for the first time. As one typical example, hydrogen-bonded (PAA/PEG)_<i>n</i> (PAA, poly­(acrylic acid); PEG, poly­(ethylene glycol)) is deposited on a poly­(dimethylsiloxane) (PDMS) substrate via the LbL technique. Heating treatment causes the covalent cross-linking reaction to occur in the H-bonded multilayers with simultaneously spontaneous formation of labyrinth wrinkles. Subsequent water immersion leads to the evolution of a series of the swelling-sensitive wrinkles in the thermally cross-linked (PAA/PEG)_<i>n</i>/PDMS bilayer, ranging from initial labyrinth wrinkles (a) to an intermediate smooth wrinkle-free state (b), hexagonally arranged dimples (c), and the later-segmented labyrinth patterns (d). Upon deswelling by reheating of the swollen bilayer, the reverse wrinkle evolution happens via the process of d → b, or d → b → a, or c → b, or c → b → a, which is dependent on the reheating temperature and the swelling-induced pattern. We investigate the influences of experimental conditions on the swelling kinetics and the resulting wrinkle evolution, which include the thickness of (PAA/PEG)_<i>n</i>, the additionally deposited outermost layer (e.g., Pt and polystyrene), and the swelling solution pH. The involved mechanism has been discussed from the viewpoint of the relation between the wrinkling behavior and the swelling/deswelling-induced stress state. The results indicate that the combined strategy of LbL assembly with the introduction of additional layers endows us with considerable freedom to fabricate multifunctional film/substrate systems and to tune the instability-driven patterns for advanced properties and extended applications

Biosynthesis, Characterization, and Hemostasis Potential of Tailor-Made Poly(3-hydroxybutyrate-<i>co</i>-3-hydroxyvalerate) Produced by Haloferax mediterranei

We report the biosynthesis of poly­(3-hydroxybutyrate-<i>co</i>-3-hydroxyvalerate) random copolymers (R-PHBV) or higher-order copolymers (O-PHBV) in Haloferax mediterranei, with adjustable 3-hydroxyvalerate (3HV) incorporation by cofeeding valerate with glucose. Their microchemical structure, molecular weight and its distribution, and thermal and mechanical properties were characterized by NMR, GPC, DSC, TGA, and universal testing machine, respectively. ¹³C NMR studies showed that O-PHBV copolymers consisted of short segments of PHB and PHV covalently linked together with random PHBV segments. Consistently, two <i>T</i>_g were observed in the DSC curves of O-PHBV. The “blocky” feature of O-PHBV enhanced crystallinity percentages and improved Young’s modulus. Notably, the film of one O-PHBV copolymer, O-PHBV-1, showed unique foveolar cluster-like surface morphology with high hydrophobicity and roughness, as characterized using static contact angle and SEM and AFM analyses. It also exhibited increased platelet adhesion and accelerated blood clotting. The excellent hemostatic properties endow this copolymer with great potential in wound healing

Swelling/Deswelling-Induced Reversible Surface Wrinkling on Layer-by-Layer Multilayers

Layer-by-layer (LbL) multilayer film is incorporated in the fabrication of a film/substrate system for the investigation of swelling/deswelling-induced wrinkle evolution for the first time. As one typical example, hydrogen-bonded (PAA/PEG)_<i>n</i> (PAA, poly­(acrylic acid); PEG, poly­(ethylene glycol)) is deposited on a poly­(dimethylsiloxane) (PDMS) substrate via the LbL technique. Heating treatment causes the covalent cross-linking reaction to occur in the H-bonded multilayers with simultaneously spontaneous formation of labyrinth wrinkles. Subsequent water immersion leads to the evolution of a series of the swelling-sensitive wrinkles in the thermally cross-linked (PAA/PEG)_<i>n</i>/PDMS bilayer, ranging from initial labyrinth wrinkles (a) to an intermediate smooth wrinkle-free state (b), hexagonally arranged dimples (c), and the later-segmented labyrinth patterns (d). Upon deswelling by reheating of the swollen bilayer, the reverse wrinkle evolution happens via the process of d → b, or d → b → a, or c → b, or c → b → a, which is dependent on the reheating temperature and the swelling-induced pattern. We investigate the influences of experimental conditions on the swelling kinetics and the resulting wrinkle evolution, which include the thickness of (PAA/PEG)_<i>n</i>, the additionally deposited outermost layer (e.g., Pt and polystyrene), and the swelling solution pH. The involved mechanism has been discussed from the viewpoint of the relation between the wrinkling behavior and the swelling/deswelling-induced stress state. The results indicate that the combined strategy of LbL assembly with the introduction of additional layers endows us with considerable freedom to fabricate multifunctional film/substrate systems and to tune the instability-driven patterns for advanced properties and extended applications

Data_Sheet_5_Impact and Molecular Mechanism of Microplastics on Zebrafish in the Presence and Absence of Copper Nanoparticles.docx

The adverse effects of microplastics (MPs) in aquatic environments have attracted increasing attention and posed health risks along with nanomaterials. Therefore, the toxic effects of polystyrene microplastics (PS-MPs) with different particle sizes (0.07, 0.7 and 7 μm) on zebrafish in the presence and absence of copper nanoparticles (Cu-NPs) were evaluated. The acute toxicity of MPs on zebrafish was 7 μm > 0.07 μm > 0.7 μm. Both 0.07 and 7 μm MPs acted on chromosomes and significantly affected cell cycle process by affecting palmitoyl hydrolase activity; while 0.7 μm MPs acted on extracellular space and significantly affected the activity of endopeptidase inhibitor to affect the cholesterol transport. And 0.07 and 7 μm MPs dominantly affected “cell cycle” pathway by inhibiting DNA replication, delaying the progression of S phase and G2/M phase, and affecting the accurate arrangement and separation of chromosomes; while the 0.7 μm MPs activated numerous platelets to aggregate and adhere in damaged parts, enhanced the coagulation function of platelets, and promoted the formation of fibrin clots, thus abnormally activating the “hemostasis” pathway. The presence of Cu-NPs significantly changed the toxicity-related pathways induced by 7 μm MPs from “cell cycle” into “hemostasis,” but not for the smaller-sized MPs (0.07 and 0.7 μm). The combined exposure of Cu-NPs and 7 μm MPs acted on the extracellular region and significantly affected cholesterol transport by affecting the activity of cholesterol transporters. This study provides theoretical insights for the health risks of MPs to aquatic species and even humans in the actual ecosystem.</p

Genetic Map Construction and Detection of Genetic Loci Underlying Segregation Distortion in an Intraspecific Cross of <i>Populus deltoides</i>

<div><p>Based on a two-way pseudo-testcross strategy, high density and complete coverage linkage maps were constructed for the maternal and paternal parents of an intraspecific F2 pedigree of <i>Populus deltoides</i>. A total of 1,107 testcross markers were obtained, and the mapping population consisted of 376 progeny. Among these markers, 597 were from the mother, and were assigned into 19 linkage groups, spanning a total genetic distance of 1,940.3 cM. The remaining 519 markers were from the father, and were also were mapped into 19 linkage groups, covering 2,496.3 cM. The genome coverage of both maps was estimated as greater than 99.9% at 20 cM per marker, and the numbers of linkage groups of both maps were in accordance with the 19 haploid chromosomes in <i>Populus</i>. Marker segregation distortion was observed in large contiguous blocks on some of the linkage groups. Subsequently, we mapped the segregation distortion loci in this mapping pedigree. Altogether, eight segregation distortion loci with significant logarithm of odds supports were detected. Segregation distortion indicated the uneven transmission of the alternate alleles from the mapping parents. The corresponding genome regions might contain deleterious genes or be associated with hybridization incompatibility. In addition to the detection of segregation distortion loci, the established genetic maps will serve as a basic resource for mapping genetic loci controlling traits of interest in future studies.</p></div

Data_Sheet_1_Impact and Molecular Mechanism of Microplastics on Zebrafish in the Presence and Absence of Copper Nanoparticles.xlsx

The adverse effects of microplastics (MPs) in aquatic environments have attracted increasing attention and posed health risks along with nanomaterials. Therefore, the toxic effects of polystyrene microplastics (PS-MPs) with different particle sizes (0.07, 0.7 and 7 μm) on zebrafish in the presence and absence of copper nanoparticles (Cu-NPs) were evaluated. The acute toxicity of MPs on zebrafish was 7 μm > 0.07 μm > 0.7 μm. Both 0.07 and 7 μm MPs acted on chromosomes and significantly affected cell cycle process by affecting palmitoyl hydrolase activity; while 0.7 μm MPs acted on extracellular space and significantly affected the activity of endopeptidase inhibitor to affect the cholesterol transport. And 0.07 and 7 μm MPs dominantly affected “cell cycle” pathway by inhibiting DNA replication, delaying the progression of S phase and G2/M phase, and affecting the accurate arrangement and separation of chromosomes; while the 0.7 μm MPs activated numerous platelets to aggregate and adhere in damaged parts, enhanced the coagulation function of platelets, and promoted the formation of fibrin clots, thus abnormally activating the “hemostasis” pathway. The presence of Cu-NPs significantly changed the toxicity-related pathways induced by 7 μm MPs from “cell cycle” into “hemostasis,” but not for the smaller-sized MPs (0.07 and 0.7 μm). The combined exposure of Cu-NPs and 7 μm MPs acted on the extracellular region and significantly affected cholesterol transport by affecting the activity of cholesterol transporters. This study provides theoretical insights for the health risks of MPs to aquatic species and even humans in the actual ecosystem.</p