When It's Heavier: Interfacial and Solvation Chemistry of Isotopes in Aqueous Electrolytes for Zn-ion Batteries

The electrochemical effect of isotope (EEI) of water is introduced in the Zn-ion batteries (ZIBs) electrolyte to deal with the challenge of severe side reactions and massive gas production. Due to the low diffusion and strong coordination of ions in D₂O, the possibility of side reactions is decreased, resulting in a broader electrochemically stable potential window, less pH change, and less zinc hydroxide sulfate (ZHS) generation during cycling. Moreover, we demonstrate that D₂O eliminates the different ZHS phases generated by the change of bound water during cycling because of the consistently low local ion and molecule concentration, resulting in a stable interface between the electrode and electrolyte. The full cells with D₂O-based electrolyte demonstrated more stable cycling performance which displayed ∼100 % reversible efficiencies after 1,000 cycles with a wide voltage window of 0.8–2.0 V and 3,000 cycles with a normal voltage window of 0.8–1.9 V at a current density of 2 A g⁻¹.     

Versatile Biocatalytic C(sp3)−H Oxyfunctionalization for the Site- Selective and Stereodivergent Synthesis of α- and β-Hydroxy Acids

C(sp³)−H oxyfunctionalization, the insertion of an O-atom into C(sp³)−H bonds, streamlines the synthesis of complex molecules from easily accessible precursors and represents one of the most challenging tasks in organic chemistry with regard to site and stereoselectivity. Biocatalytic C(sp³)−H oxyfunctionalization has the potential to overcome limitations inherent to small-molecule-mediated approaches by delivering catalyst-controlled selectivity. Through enzyme repurposing and activity profiling of natural variants, we have developed a subfamily of α-ketoglutarate-dependent iron dioxygenases that catalyze the site- and stereodivergent oxyfunctionalization of secondary and tertiary C(sp³)−H bonds, providing concise synthetic routes towards four types of 92 α- and β-hydroxy acids with high efficiency and selectivity. This method provides a biocatalytic approach for the production of valuable but synthetically challenging chiral hydroxy acid building blocks.     

Silica Nanoparticles Induced Embryonic Dysplasia and Apoptosis Via Endoplasmic Reticulum Stress in Zebrafish(Danio Rerio)

The possible detrimental effects of nanomaterials on organisms have become a public concern because of the wide applications of nanomaterials in modern society. This study investigates the effects of silica nanoparticles (nano-SiO₂) on zebrafish development. Fluorescent nano-SiO₂ (FITC-nano-SiO₂) is synthesized with an emission wavelength of 517 nm. Due to similar hydrodynamic size, FITC-nano-SiO₂ is used to simulate the distribution of nano-SiO₂ in zebrafish. Nano-SiO₂ regulated col2a1a, col9a2, lect1, and her12 to delay liver development and regulated prox, wnt2bb, mypt1, and hhex caused spinal curvature. The hand2, mef2a, nkx2.5, and atp1a2a are significantly down-regulated. The whole embryo in situ hybridization revealed amhc and flk1 are also down-regulated. This suggests that nano-SiO₂ affected heart and blood vessels development of zebrafish. Furthermore, it is found that cell apoptosis occurred in the heart. The proapoptotic genes (bax, bid) are upregulated, and the antiapoptotic genes (bcl-2, mcl-1b) are down-regulated. Nano-SiO₂ increases the endoplasmic reticulum (ER) stress-related genes (chop, bip, perk, elF2α), indicating that the ER stress is involved in cell apoptosis. This study provides a toxicological basis for evaluating the possible hazards of nano-SiO₂ to aquatic organisms.     

Insights into the Diffusion Behaviors of Water over Hydrophilic/Hydrophobic Catalysts During the Conversion of Syngas to High-Quality Gasoline

Although considerable efforts towards directly converting syngas to liquid fuels through Fischer–Tropsch synthesis have been made, developing catalysts with low CO₂ selectivity for the synthesis of high-quality gasoline remains a big challenge. Herein, we designed a bifunctional catalyst composed of hydrophobic FeNa@Si-c and HZSM-5 zeolite, which exhibited a low CO₂ selectivity of 14.3 % at 49.8 % CO conversion, with a high selectivity of 62.5 % for gasoline in total products. Molecular dynamic simulations and model experiments revealed that the diffusion of water molecules through hydrophilic catalyst was bidirectional, while the diffusion through hydrophobic catalyst was unidirectional, which were crucial to tune the water-gas shift reaction and control CO₂ formation. This work provides a new fundamental understanding about the function of hydrophobic modification of catalysts in syngas conversion.     

Asymmetric C1 Extension of Aldehydes through Biocatalytic Cascades for Stereodivergent Synthesis of Mandelic Acids

The development of mild, efficient, and enantioselective methods for preparing chiral building blocks from simple, renewable carbon units has been a long-term goal of the sustainable chemical industry. Mandelate derivatives are valuable pharmaceutical intermediates and chiral resolving agents, but their manufacture relies heavily on highly toxic cyanide. Herein, we report (S)-4-hydroxymandelate synthase (HmaS)-centered biocatalytic cascades for the synthesis of mandelates from benzaldehydes and glycine. We show that HmaS can be engineered to perform R-selective hydroxylation by single-point mutation, empowering the stereodivergent synthesis of both (S)- and (R)-mandelate derivatives. These biocatalytic cascades enabled the production of various mandelate derivatives with high atom economy as well as excellent yields (up to 98 %) and ee values (up to >99 %). This methodology offers an effective cyanide-free technology for greener and sustainable production of mandelate derivatives.