Unbridged bidentate aluminum complexes supported by diaroylhydrazone ligands: Synthesis,structure and catalysis in polymerization of ε-caprolactone and lactides

A series of novel diaroylhydrazone aluminum complexes have been synthesized and well-defined structurally, and their catalytic performance in the polymerization of ε-caprolactone and lactides have also been evaluated. Complexes [(L^1–4)₂AlMe] ( 1 – 4 ) {[L¹ = (3,5-^tBu₂–2-OMe-C₆H₂)CH=NNCOC₆H₅], [L² = (3,5-^tBu₂–2-OMe-C₆H₂)CH=NNCO(C₆H₄–4-OCH₃)], [L³ = (3,5-^tBu₂–2-OMe-C₆H₂)CH=NNCO(C₆H₄–4-Br)] and [L⁴ = (2-OMe-C₆H₄)CH=NNCO(C₆H₄–4-^tBu)]} were prepared through treatment of AlMe₃ with the corresponding proligands L^1–4H in molar ratios of 1: 1 or 1: 2. Chemical structures of all the complexes were well-defined by elemental analysis, NMR spectra as well as single-crystal X-ray study. Complexes [(L^1–4)₂AlMe] ( 1 – 4 ) in this work represent the first examples of aluminum complexes of aroylhydrazone ligands with crystallographic characterization. Specifically, they are all in monomeric form with a penta-coordinated aluminum center, including two approximately co-planar five-membered metallacycles with aluminum. Introduced bulky tert-butyl substituents in aroylhydrazone ligands could affect the geometry around the central metal which is a distorted square-based pyramid in complexes 1 – 3 while being a trigonal bipyramidal in complex 4 , thus affecting their catalytic behaviors. The complexes can successfully catalyze the ring-opening polymerization of ε-caprolactone and _L-lactide under mild conditions without any activator. In addition, complexes 1 – 4 could also polymerize rac-lactide, affording atactic polylactides with high conversions and good controllability in relatively short reaction time.     

Global optical model potential describing 12C-nucleus elastic scattering

We construct a new global optical model potential to describe the elastic scattering of ¹²C. The experimental data of elastic-scattering angular distributions and total reaction cross sections for targets from ²⁴Mg to ²⁰⁹Bi are considered below 200 MeV within the framework of the optical model. The results calculated using the derived global optical potential are then compared with the existing experimental data. The reliability of the global optical potential is further tested by predicting the elastic scattering data out of the mass and energy ranges, within which the global potential parameters are determined, and reasonable results are also obtained.     

Calculation of Relative Solubility of Semipolar Solvents by Abraham Solvation Parameter Model for Extractables and Leachables Analysis in Chemical Characterization of Medical Devices

Journal of Solution Chemistry - Organic solvents of different polarities (polar, semipolar, and nonpolar) are typically used in extraction studies on medical devices for chemical characterization...     

Carbon-Based Materials as Lithium Hosts for Lithium Batteries

Lithium (Li) metal has attracted significant attention in areas that range from basic research to various commercial applications due to its high theoretical specific capacity (3860 mA h g⁻¹) and low electrochemical potential (−3.04 vs. standard hydrogen electrode). However, dendrites often form on the surfaces of Li metal anodes during cycling and thus lead to battery failure and, in some cases, raise safety concerns. To overcome this problem, a variety of approaches that vary the electrolyte, membrane, and/or anode have been proposed. Among these efforts, the use of three-dimensional frameworks as Li hosts, which can homogenize and minimize the current density at the anode surface, is an effective approach to suppress the formation of Li dendrites. Herein, we describe the development of using carbon-based materials as Li hosts. While these materials can be fabricated into a variety of porous structures, they have a number of intrinsic advantages including low costs, high specific surface areas, high electrical conductivities, and wide electrochemical stabilities. After briefly summarizing the formation mechanisms of Li dendrites, various methods for controlling structural and surface chemistry will be described for different types of carbon-based materials from the viewpoint of improving their performance as Li hosts. Finally, we provide perspective on the future development of Li host materials needed to meet the requirements for their use in flexible and wearable devices and other contemporary energy storage techniques.     

Biohybrid Organic Heterostructure Based on Chlorophyll-Bacteriochlorophyll Aggregates for Ecofriendly Hydrogen Production

Hydrogen energy is an abundant, clean, sustainable and environmentally friendly renewable energy source. Therefore, the production of hydrogen by photocatalytically splitting water on semiconductors has been considered in recent years as a promising and sustainable strategy for converting solar energy into chemical energy to replace conventional energy sources and to solve the growing problem of environmental pollution and the global energy crisis. However, highly efficient solar-driven photocatalytic hydrogen production remains a huge challenge due to the poor visible light response of available photocatalytic materials and the low efficiency of separation and transfer of photogenerated electron-hole pairs. In the present work, organic heterojunction structures based on bacteriochlorophyll (BChl) and chlorophyll (Chl) molecules were introduced and used for solar-driven photocatalytic hydrogen production from water under visible light. Also, noble metal-free photocatalyst was successfully constructed on Ti₃C₂T_x nanosheets by simple successive deposition of Chl and BChl, which was used for the photocatalytic splitting water to hydrogen evolution reaction (HER). The results show that the optimal BChl@Chl@Ti₃C₂T_x composite has a high HER performance with 114 μmol/h/g_cat, which is much higher than the BChl@Ti₃C₂T_x and Chl@Ti₃C₂T_x composites.     

利用空间位阻和氢溢流协同作用促进5-羟甲基糠醛选择性加氢制备5-甲基糠醛

化学工业生产中，用氢气为还原剂，通过选择性加氢可以制备多种重要化学品。5-羟甲基糠醛是重要的生物质基平台化合物，而5-甲基糠醛是用途广泛的化学品。由5-羟甲基糠醛加氢得到5-甲基糠醛是一条非常理想的路径，但是选择性活化C-OH非常困难。本文设计并制备了Pt@PVP/Nb₂O₅(PVP: 聚乙烯吡咯烷酮)催化剂，该催化体系巧妙地结合了位阻效应、氢溢流和催化剂界面的电子效应，系统研究了该催化剂对5-羟甲基糠醛选择性加氢制备5-甲基糠醛催化性能，在最优条件下，5-甲基糠醛的选择性可达92%。利用密度泛函理论计算研究了5-羟甲基糠醛选择性加氢制备5-甲基糠醛反应路径。     

High Uptake of ReO4− and CO2 Conversion by a Radiation‐Resistant Thorium–Nickle [Th48Ni6] Nanocage‐Based Metal–Organic Framework

Assembled from [Th₄₈Ni₆] nanocages, the first transition‐metal (TM)‐thorium metal–organic framework (MOF, 1 ) has been synthesized and structurally characterized. 1 exhibits high solvent and acid/base stability, and resistance to 400 kGy β irradiation. Notably, 1 captures ReO₄^? (an analogue of radioactive ⁹⁹TcO₄^?, a key species in nuclear wastes) with a maximum capacity of 807 mg g^?1, falling among the largest values known to date. Furthermore, 1 can enrich methylene blue (MB) and can also serve as an effective and recyclable catalyst for CO₂ fixation with epoxides; there is no significant loss of catalytic activity after 10 cycles. Theoretical studies with nucleus‐independent chemical shifts and natural bond orbital analysis reveal that the [Th₆O₈] clusters in 1 have a unique stable electronic structure with (d–p)π aromaticity, partially rationalising 1 ′s stability.     

正负双向脉冲式爆炸及其诱导的簇发振荡

簇发振荡普遍存在.探索通向簇发振荡的可能路径是簇发研究的热点问题之一."脉冲式爆炸(pulsed-shaped explosion,PSE)"是一种最近被报道的可以诱发簇发振荡的新机制,其特征为平衡点和极限环表现出了与参数变化相关的脉冲式急剧量变.PSE会导致系统轨线急剧跃迁,从而诱发典型的簇发振荡.然而,目前报道的PSE中仅含有"单向的尖峰",未发现"双向的尖峰",且由其诱发的簇发振荡仅含单向的振荡簇.本文以多频激励Rayleigh系统为例,旨在揭示PSE的不同表现形式以及与此相关的簇发动力学.利用频率转换快慢分析法得到了Rayleigh系统的快子系统和慢变量.针对快子系统的分析表明,PSE表现出了较为复杂的动力学特性,其特征是PSE包含了正负双向两个不同的尖峰,此即所谓的正负双向PSE.其急剧量变行为,导致了系统轨线在单个振荡周期内出现正向和负向的多次跃迁,由此得到了由正负双向PSE所诱发的簇发振荡.根据吸引子类型分别揭示了点--点型和环--环型两类簇发振荡模式的产生机制.本文的研究给出了PSE的不同表现形式,丰富了多时间尺度下的簇发振荡的诱发机制.      

Screening potential antagonists of epidermal growth factor receptor from Marsdenia tenacissima via cell membrane chromatography model assisted by HPLC–ESI–IT–TOF–MS

Marsdenia tenacissima, or Tongguanteng in Chinese, is a traditional Chinese herb and has a broad application in clinical practice for its pharmacological effects of treating asthma, pneumonia, tonsillitis, pharyngitis tumors, etc. However, few studies have reported the screening of the active components of this medicine for tumor therapy. In this work, a two‐dimensional analytical system was developed to screen antagonists of epidermal growth factor receptor (EGFR) from M. tenacissima. A fraction was retained on the EGFR cell membrane chromatography (CMC) column, separated and identified as tenacissoside G (TG), tenacissoside H (TH) and tenacissoside I (TI) by two‐dimensional HPLC–IT–TOF–MS. Molecular docking and 3‐(4,5‐dimethyl‐2‐thiazolyl)‐2,5‐diphenyl‐2‐H‐tetrazolium bromide (MTT) assay were carried out to assess the activity of TS (including TG, TH and TI). Molecular docking results showed that the binding mode of TS on EGFR is similar to that of gefitinib. The MTT assay demonstrated that gefitinib and TS (especially TI) could inhibit the growth of EGFR highly expressed cell lines in a dose‐dependent manner in the range of 5–50 μmol/L. In conclusion, the two‐dimensional EGFR/CMC–HPLC–IT–TOF–MS system could be a useful approach in drug discovery from traditional Chinese medicines for searching for potential antitumor candidates.