Oxorhenium(V) dithiolates catalyze the oxidation by tert-butyl hydroperoxide of sulfoxides and sulfides, including 4,6-dimethyldibenzothiophene

tert-Butyl hydroperoxide (TBHP) efficiently converts a wide variety of sulfides to sulfoxides and sulfones. The method offers the advantage that one product or the other can be obtained in high purity by a modest variation of conditions. The reactions occur smoothly at 25minus sign50 C in chloroform and, to the extent studied, in toluene and methylene chloride. A catalyst is required; the most extensively studied was MeReO(mtp)PPh(3), 1, where mtpH(2) is 2-(mercaptomethyl)thiophenol. Other chelating dithiolate ligands can be used with comparable results. These oxidations were tested for dialkyl, alkylminus signaryl, and diaryl sulfides; thiophenes; and thianthrene. Even the "hard" sulfide, 4,6-dimethyldibenzothiophene (DMDBT) was quantitatively oxidized to the dioxide with TBHP:DMDBT 3.0-3.5 and 0.05-3.8 mol % 1. The mechanism was explored in kinetics studies carried out only for methyl tolyl sulfide. The product buildup curve was complex, with an induction period followed by a rapid growth phase. The kinetic data could be modeled adequately but not perfectly by allowing five rate constants to refine. Their values are consistent with the chemical sense of the mechanism.     

Harnack Inequalities for Functional SDEs Driven by Subordinate Brownian Motions

Potential Analysis - Using coupling by change of measure and an approximation technique, Wang’s Harnack inequalities are established for a class of functional SDEs driven by subordinate...     

扭曲的涡旋光束在海洋湍流中的传输因子

基于扩展惠更斯-菲涅尔原理和维格纳分布函数(Wigner distribution function,WDF)二阶矩,推导了部分相干扭曲涡旋光束(partially coherent twisted vortex beam,PCTVB)在海洋湍流中传输时的M2因子和角扩展θ(z)。通过数值模拟方法详细研究了海洋湍流对光束M2因子和角扩展θ(z)的影响,结果表明温度方差耗散率ΧT和温度盐度贡献比w越大、动能耗散率ε和各向异性因子ξ越小时对PCTVB的M2因子和角扩展θ(z)的影响越大。此外研究发现,相较于非扭曲涡旋光束(PCVB),PCTVB有更好的抗海洋湍流的能力,且增大拓扑荷数m以及扭曲因子绝对值｜μ｜后,PCTVB的M2因子和角扩展θ(z)显著减小,光束的抗海洋湍流能力增强。并且增大束腰宽度w0和波长λ,以及减小初始相干长度δηη(η=x,y)同样可以增加光束抗海洋湍流的能力。本文的数值研究结果对海洋光通信具有重要意义。     

Electrochemically Induced Crystalline-to-Amorphous Transition of Dinuclear Polyoxovanadate for High-Rate Lithium-Ion Batteries

Polyoxometalates are intriguing high-capacity anode materials for alkali-metal-ion storage due to their multi-electron redox capabilities and flexible structure. However, their poor electrical conductivity and high working voltage severely restrict their practical application. Herein, the dinuclear polyoxovanadate Sr₂V₂O₇·H₂O with unusually high electrical conductivity is reported as a promising anode material for lithium-ion batteries. During the initial lithiation process, the Sr₂V₂O₇·H₂O anode experiences an electrochemically induced crystalline-to-amorphous transition. The resulting amorphous structure provides high redox activity and fast reaction kinetics via reversible V^4.9+/V^2.8+ redox couple through the intercalation mechanism. Furthermore, when coupled with the LiFePO₄ cathode, the strong V O bonds of the amorphous anode provide excellent structural stability, with the full-cell capable of performing >12 000 cycles with a capacity retention of 72%. Another advantage of Sr_2xV₂O_7-δ·yH₂O (0.5 ≤ x ≤ 1.0) is its composition adjustability, which enables delicately regulating the Sr vacancy content without destroying the structure. The defect Sr_2xV₂O_7-δ·yH₂O (x = 0.5) electrodes show significantly improved specific capacity and rate capability without sacrificing other key properties, delivering a high specific capacity of 479 mAh g^-1 at 0.1 mA cm^-2 and 41.9% of its capacity in 2 min. Overall, the preliminary study points the way forward for the facile preparation of high-quality polyoxometalates for advanced energy storage applications and beyond.     

Versatile Hypoxic Extracellular Vesicles Laden in an Injectable and Bioactive Hydrogel for Accelerated Bone Regeneration

Extracellular vesicles (EVs) derived from mesenchymal stem cells (MSCs) have emerged as an appealing alternative to cell therapy in regenerative medicine. Unlike bone marrow MSCs (BMSCs) cultured in vitro with normoxia, bone marrow in vivo is exposed to a hypoxic environment. To date, it remains unclear whether hypoxia preconditioning can improve the function of BMSC-derived EVs and be more conducive to bone repair. Herein, it is found that hypoxia preconditioned BMSCs secrete more biglycan (Bgn)-rich EVs via proteomics analysis, and these hypoxic EVs (Hypo-EVs) significantly promote osteoblast proliferation, migration, differentiation, and mineralization by activating the phosphatidylinositide 3-kinase/protein kinase B pathway. Subsequently, an injectable bioactive hydrogel composed of poly(ethylene glycol)/polypeptide copolymers is developed to improve the stability and retention of Hypo-EVs in vivo. The Hypo-EVs-laden hydrogel shows continuous liberation of Hypo-EVs for 3 weeks and substantially accelerates bone regeneration in 5-mm rat cranial defects. Finally, it is confirmed that Bgn in EVs is a pivotal protein regulating osteoblast differentiation and mineralization and exerts its effects through paracrine mechanisms. Therefore, this study shows that hypoxia stimulation is an effective approach to optimize the therapeutic effects of BMSC-derived EVs and that injectable hydrogel-based EVs delivery is a promising strategy for tissue regeneration.     

Interfacial Proton Supply/Filtration Regulates the Dynamics of Electrocatalytic Nitrogen Reduction Reaction: A Perspective

As a promising energy carrier, ammonia synthesis by electrocatalytic nitrogen reduction reaction (eNRR) is a promising green and low-carbon ammonia synthesis strategy that can replace the traditional Haber–Bosch process. However, the development of eNRR processes is mainly severely constrained by competitive hydrogen evolution reaction (HER), and the corresponding strategies to inhibit this adverse side reaction to obtain high eNRR selectivity are still limited. In addition, for this complex reaction involving gas–liquid–solid three-phase interface and proton/electron transfer, it is great significance to analyze and summarize the existing inhibition HER strategies from the viewpoint of dynamics. In view of this, this work reviews proton supply/filtration regulation strategy in catalytic system, allowing a systematic survey of the literature focusing on interface membrane regulation (inorganic membrane and organic membrane), electrolyte regulation (metal-mediated strategy and electrolyte ion regulation strategy) and system device design (electrode structure design and electrolytic cell device design). Constructive catalytic system design guidance is also suggested to inhibit hydrogen evolution and improve NH₃ selectivity, aiming for scalable and economically feasible applications.     

Ultrafast Switchable Passive Radiative Cooling Smart Windows with Synergistic Optical Modulation

Switchable passive radiative cooling (PRC) smart windows can modulate sunlight transmission and spontaneously emit heat to outer space through atmospheric transparent window, presenting great potential in building energy conservation. However, realizing stable and on-demand control of the cooling efficiency for PRC materials is still challenging. Herein, an electro-controlled polymer-dispersed liquid crystal (PDLC) smart window showing PRC property is designed and prepared by adding mid-infrared emitting reactive monomers into the conventional PDLC matrix. It is found that not only the electro-optical properties but also the PRC efficiency of PRC PDLC film are tunable by regulating the content of the mid-infrared emitting components, film thickness, and micromorphology. This advanced PRC PDLC material achieves a near/sub-ambient temperature when the solar irradiance is below 400 W m⁻² and can dynamically manage daytime cooling efficiency. Importantly, its PRC efficiency is capable of being tuned in an on-demand and ultrafast millisecond-scale way, whose controllable transparency enables multistage heat regulation. This study is hoped to provide new inspiration in the preparation of advanced optical devices and energy-efficient equipment.