Insertion Chemistry of Lutetacyclopropene toward Unsaturated C−O/C−N Bonds

Although the reaction chemistry of transition metallacyclopropenes has been well-established in the last decades, the reactivity of rare-earth metallacyclopropenes remains elusive. Herein, we report the reaction of lutetacyclopropene 1 toward a series of unsaturated molecules. The reaction of 1 with one equiv. of PhCOMe, Ar¹CHO (Ar¹=2,6-Me₂C₆H₃), W(CO)₆, and PhCH=NPh provided oxalutetacyclopentenes, metallacyclic lutetoxycarbene, and azalutetacyclopentene via 1,2-insertion of C=O, C≡O, or C=N bonds into Lu−C_sp2 bond, respectively. However, the reaction between 1 and Ar²N=C=NAr² (Ar²=4-MeC₆H₄) gave an acyclic lutetium complex with a diamidinate ligand by the coupling of one molecule of 1 with two carbodiimides, irrespective of the amount of carbodiimide employed. More interestingly, when 1 was treated with two equiv. of Ar¹CHO, the reductive coupling of two C=O bonds was discovered to give a lutetium pinacolate complex along with the release of tolan. Remarkably, the reactivity of 1 is significantly different from that of scandacyclopropenes; these metallacycles derived from 1 all represent the first cases in rare-earth organometallic chemistry.     

原子荧光法测定茶叶中的硒含量

采用原子荧光法测定茶叶中的硒含量,对样品消解温度及仪器条件进行了优化。还原剂为1.0%硼氢化钾–0.5%氢氧化钾溶液,载流液为3%盐酸溶液。在优化条件下,硒的质量浓度在0~20 ng/mL范围内与荧光强度呈良好的线性关系,相关系数r=0.999,检出限为0.8 ng/mL。该法的加标回收率为88.08%~101.39%,测定结果的相对标准偏差为2.03%~4.84%(n=6)。该方法实际操作性强,准确度高,适用于日常检验工作中对批量茶叶中硒含量的测定。     

RESEARCH ON IMPROVEMENTS OF LRN TURBULENCE MODEL BASED ON FLOW AROUND AUTOMOBILE BODY 1)

本文将汽车绕流模块化为各典型局部流动,通过常用湍流模型对各典型局部流动进行数值模拟,结果验证了湍流模型对转捩的捕捉能力是准确模拟汽车绕流的关键. 在分析汽车绕流分离及转捩机理的基础上,优化了稳态和瞬态求解方法,改进了湍流模型对转捩的预测能力,进而提高了湍流模型在汽车流场模拟上的精度. 针对汽车绕流的稳态问题,将流线曲率因子及 响应阈值引入 LRN $k$-$\varepsilon $ (low Reynolds number $k$-$\varepsilon $) 模型,获得了一种能够更准确预 测转捩的改进低雷诺数湍流模型 (modified LRN $k$-$\varepsilon $),改善了原模型对湍流耗散率的过强依赖性及全应力发展预测不足等问题;针对汽车绕流瞬态求解,通过分析 RANS/LES 混合湍流模型的构造思想及特点,引入约束大涡模拟方法,结合本文提出的改进的 LRN $k$-$\varepsilon $ 湍流模型,提出了一种能准确捕捉转捩现象 的转捩 LRN CLES 模型. 分别将改进的模型用于某实车外流场和风振噪声仿真中,通过 Ansys Fluent 求解器计算,并将计算结果与常用湍流模型的仿真结果、HD-2 风洞试验结果和实车道路实验结果进行对比,表明改进后的湍流模型能够更准确模拟复杂实车的稳态和瞬态特性,为汽车气动特性的研究提供了可靠理论依据及有效数值解决方法.     

Evoking Ferroptosis by Synergistic Enhancement of a Cyclopentadienyl Iridium-Betulin Immune Agonist

Ferroptosis is a form of programmed cell death driven by iron-dependent lipid peroxidation (LPO) with the potential for antitumor immunity activation. In this study, a nonferrous cyclopentadienyl metal-based ferroptosis inducer [Ir(Cp*)(Bet)Cl]Cl ( Ir-Bet ) was developed by a metal-ligand synergistic enhancement (MLSE) strategy involving the reaction of [Ir(Cp*)Cl]₂Cl₂ with the natural product Betulin. The fusion of Betulin with iridium cyclopentadienyl (Ir-Cp*) species as Ir-Bet not only tremendously enhanced the antiproliferative activity toward cancer cells, but also activated ferritinophagy for iron homeostasis regulation by PI3K/Akt/mTOR cascade inhibition with a lower dosage of Betulin, and then evoked an immune response by nuclear factor kappa-B (NF-κB) activation of Ir-Cp* species. Further immunogenic cell death (ICD) occurred by remarkable ferroptosis through glutathione (GSH) depletion, glutathione peroxidase 4 (GPX4) deactivation and ferritinophagy. An in vivo vaccination experiment demonstrated desirable antitumor and immunogenic effects of Ir-Bet by increasing the ratio of cytotoxic T cells (CTLs)/regulatory T cells (Tregs).     

Analysis of Protein Moiety of Polysaccharide Conjugates Water-extracted from Low Grade Green Tea

Tea polysaccharide conjugates(TPCs) were water-extracted and purified from low-grade green tea. Although TPC contains 1.97% covalent binding proteins, Coomassie brilliant blue G250 and R250 could not detect this protein. The "should-shape" absorption peak observed at 250-280 nm in the UV-Vis spectrum was caused by quinone compounds derived from polyphenol oxidation during TPC extraction. The UV-Vis spectrum could be used to detect the decolorizing degree of TPC. TPC aqueous solution merely presented the negative charge properties of its polysaccharides instead of the acid-base property of its protein section, and exhibited higher stability at pH greater than 5.0. No precipitation or haze occurred in three TPC/epigallocatechin gallate(EGCG) aqueous mixtures during 12 h storage. TPC had emulsifying activity, which indicated that its protein moiety formed hydrophobic groups. It is proposed that some of the physicochemical properties of the TPC protein moiety are shielded by its polysaccharide chain.     

A Supersonic Aerodynamic Energy Harvester:A Functionally Graded Material Beam with a Giant Magnetostrictive Thin Film

In this study,a simply supported functionally graded material beam with a giant magnetostrictive thin film(GMF)was selected as an energy harvester.Based on the ...     

Optimization of Naringenin Nanoparticles to Improve the Antitussive Effects on Post-Infectious Cough

Naringenin (NRG) is a natural compound with several biological activities; however, its bioavailability is limited owing to poor aqueous solubility. In this study, NRG nanoparticles (NPs) were prepared using the wet media milling method. To obtain NRG NPs with a small particle size and high drug-loading content, the preparation conditions, including stirring time, temperature, stirring speed, and milling media amount, were optimized. The NRG (30 mg) and D-α-tocopherol polyethylene glycol succinate (10 mg) were wet-milled in deionized water (2 mL) with 10 g of zirconia beads via stirring at 50 °C for 2 h at a stirring speed of 300 rpm. As a result, the NRG NPs, with sheet-like morphology and a diameter of approximately 182.2 nm, were successfully prepared. The NRG NPs were stable in the gastrointestinal system and were released effectively after entering the blood circulation. In vivo experiments indicated that the NRG NPs have good antitussive effects. The cough inhibition rate after the administration of the NRG NPs was 66.7%, cough frequency was three times lower, and the potential period was 1.8 times longer than that in the blank model group. In addition, the enzyme biomarkers and histological analysis results revealed that the NRG NPs can effectively regulate the inflammatory and oxidative stress response. In conclusion, the NRG NPs exhibited good oral bioavailability and promoted antitussive and anti-inflammatory effects.     

Fiber-shaped organic electrochemical transistors for biochemical detections with high sensitivity and stability

Precise and continuous monitoring of biochemicals by biosensors assists to understand physiological functions for various diagnostics and therapeutic applications. For implanted biosensors, small size and flexibility are essential for minimizing tissue damage and achieving accurate detection. However, the active surface area of sensor decreases as the sensor becomes smaller,which will increase the impedance and decrease the signal to noise ratio, resulting in a poor detection limit. Taking advantages of local amplification effect, organic electrochemical transistors(OECTs) constitute promising candidates for high-sensitive monitoring. However, their detections in deep tissues are rarely reported. Herein, we report a family of implantable, fiber-shaped all-in-one OECTs based on carbon nanotube fibers for versatile biochemical detection including H_2O_2, glucose, dopamine and glutamate. These fiber-shaped OECTs demonstrated high sensitivity, dynamical stability in physiological environment and antiinterference capability. After implantation in mouse brain, 7-day dopamine monitoring in vivo was realized for the first time.These fiber-shaped OECTs could be great additions to the "life science" tool box and represent promising avenue for biomedical monitoring.     

丁苯橡胶合成用活化剂乙二胺四乙酸盐溶液比热容的测定

丁苯橡胶合成用活化剂乙二胺四乙酸盐溶液比热容的测定赵小明，刘志刚，陈钟颀（西安交通大学热工教研室西安７１００４９）关键词ＥＤＴＡ溶液，比热容，绝热量热法比热容是物质重要参数，与物质结构密切相关。它对物理学和化学的理论研究及许多与化工、能源和材料有关的...     

用2-QADN2,7-金属络合物示波极谱法同时测定铜镍钴镉

本文研究了2-QADN2,7-金属络合物的极谱特性。在pH9.60的缓冲溶液中,Cu(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)和Cd(Ⅱ)与2-QADN2,7的络合物在-0.37、-0.69、-0.77和-0.82V产生灵敏的极谱波,利用这些波可测定痕量的铜、镍、钴和镉。铜的检测下限为2.0×10~(-8)mol/L,镍、钴及镉的检测下限为5.0×10~(-8)mol/L。提出的方法用于同时测定头发和茶叶中的痕量铜、镍和钴,结果满意。