（S）-噻吗洛尔半水合物的合成及表征

为了开发β受体阻断剂新药（S）-噻吗洛尔半水合物，采用3-吗啉-4-氯-1，2，5-噻二唑为起始原料，经水解反应得到中间体1（3-吗啉-4-羟基-1，2，5-噻二唑）。中间体1与R-环氧氯丙烷发生醚化反应，经后处理及重结晶得到中间体2 {（R）-4-［4-（环氧乙烷-2-基甲氧基）-1，2，5-噻二唑-3-基］吗啉}。中间体2经胺化反应、马来酸成盐及重结晶得到（S）-马来酸噻吗洛尔。（S）-马来酸噻吗洛尔经游离、纯水转晶得到符合药典标准的（S）-噻吗洛尔半水合物，总收率14.05%且e.e.值为99.66%。最终成品经IR、1H-NMR、13C-NMR、MS、TGA、DSC表征，并优化各步反应条件。结果表明:以三乙胺为醚化反应缚酸剂75 ℃反应最佳；以乙醇为胺化反应溶剂46 ℃反应16 h最佳；S-噻吗洛尔的转晶拆分以水作溶剂，比传统不对称合成工艺安全稳定，操作简单，适合工业化生产。     

Characteristics and formation mechanism of porosities in CFRP during laser joining of CFRP and steel

An experimental investigation on the mechanism of porosity formation during the laser joining of carbon fiber reinforced polymer (CFRP) and steel is presented. The porosity morphology and distribution were characterized by optical and scanning electron microscopy, and the thermal pyrolysis behaviors were investigated by thermal analysis and designed back-side cooling experiments. The results show that there are two types of porosities in CFRP. Porosity I only appears when the heat input is more than 77.8 J/mm. It has a smooth inner wall and distributes near the bonding interface between CFRP and steel at the central area of melted zone, which is caused by gaseous products such as CO₂, NH₃, H₂O, and hydrocarbons produced by the pyrolysis of CFRP. Porosity II can be seen under all joining conditions. It has a rough inner wall and distributes far away from the bonding interface, concentrating at the final solidification locations. Porosity II is caused by the shrinkage of melted CFRP during solidification stage.     

内燃机活塞环表面处理技术

活塞环在内燃机中有着支撑、密闭、储油、导热的作用,内燃机活塞环制备材料应该具备优良的加工性能、耐高温、耐腐蚀、导热性好且具有良好的强韧性,较好的与气缸材料表面的磨合性能。球墨铸铁和专用钢材已经成为制备内燃机活塞环的基础材料,目前国内外采用多种表面处理技术比如:镀铬、氮化、PVD与CVD镀膜、喷钼、喷涂陶瓷层等表面处理工艺进行表面改性,提高内燃机活塞环的使用寿命和使用性能。需要不断研究和开发新的内燃机活塞环的表面处理技术来满足实际生产和应用中内燃机越来越高的要求。     

Transparent and flexible films of new segmented polyurethane nanocomposites incorporated by NH2-functionalized TiO2 nanoparticles

In this work, TiO₂ nanoparticles are surface modified by NH₂-terminated organic moieties arised from 4,4′-methylene diphenyl diisocyanate (MDI). These nanoparticles are incorporated into ether-based segmented polyurethane (SPU) matrix. MDI is utilized as monomer together with poly(tetramethylene oxide) (PTMO) comonomer for preparing the final polymer as well. The NH₂-functionalized TiO₂ nanoparticles are covalently linked to the NCO terminals of the resulting SPU macromolecules during film preparation stage. Therefore, in addition to butylene glycol, these surface modified nanoparticles with enhanced organophilicity could play the role of the second chain extender of NCO-capped SPU macromolecules through formation of urea linkages. Optical and thermal behaviors of the transparent and flexible film (SPU/TiO₂–MDI) is compared with those of unmodified TiO₂ (SPU/TiO₂) and TiO₂-unloaded SPU films. Though the particle loading is only 5 wt.%, incorporation of TiO₂ and TiO₂–MDI nanoparticles into the SPU polymer enhances significantly the light absorption in UV region at 300–400 nm. SEM images of the prepared films clearly show a considerable decrease in particle aggregation for TiO₂–MDI into SPU matrix compared to that of unmodified TiO₂. TG analyses indicate a one-step decomposition pattern with onset temperatures of about 360 and 380 °C for neat SPU and SPU/TiO₂–MDI, respectively. Moreover, DTA thermograms of both nanocomposites show obviously two exothermic phase transitions in the thermal range of 330–440 °C.     

Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

The effect of SO₂ gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH₃) over a TiO₂ photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO₂ (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO₂ gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N₂ adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.     

不同晶相结构ZrO2负载铜基催化剂用于二乙醇胺脱氢反应

通过制备不同晶相结构〔单斜相(m-ZrO_2)、四方相(t-ZrO_2)和无定型(a-ZrO_2)〕ZrO_2载体,再通过沉积沉淀法制得Cu/m-ZrO_2、Cu/t-ZrO_2和Cu/a-ZrO_2催化剂,分别用于催化二乙醇胺脱氢合成亚氨基二乙酸反应。采用XRD、氮气物理吸附脱附、XPS、H_2-TPR、CO_2-TPD对催化剂的结构进行了表征。结果表明,Cu/m-ZrO_2催化剂界面更加有利于Cu~+/Cu~0稳定存在,具有更多的碱性位点,且抗氧化性较好。在二乙醇胺脱氢反应中,Cu/m-ZrO_2催化剂性能最好,反应时间为2.5 h,亚氨基二乙酸收率为97.64%。     

Present status and future prospects of plasma sprayed multilayered thermal barrier coating systems

Thermal barrier coatings (TBCs) play a pivotal role in protecting the hot structures of modern turbine engines in aerospace as well as utility applications. To meet the increasing efficiency of gas turbine technology, worldwide research is focused on designing new architecture of TBCs. These TBCs are mainly fabricated by atmospheric plasma spraying (APS) as it is more economical over the electron beam physical vapor deposition (EB-PVD) technology. Notably, bi-layered, multi-layered and functionally graded TBC structures are recognized as favorable designs to obtain adequate coating performance and durability. In this regard, an attempt has been made in this article to highlight the structure, characteristics, limitations and future prospects of bi-layered, multi-layered and functionally graded TBC systems fabricated using plasma spraying and its allied techniques like suspension plasma spray (SPS), solution precursor plasma spray (SPPS) and plasma spray –physical vapor deposition (PS-PVD).     

Direct Injection of CRISPR/Cas9-Related mRNA into Cytoplasm of Parthenogenetically Activated Porcine Oocytes Causes Frequent Mosaicism for Indel Mutations

Some reports demonstrated successful genome editing in pigs by one-step zygote microinjection of mRNA of CRISPR/Cas9-related components. Given the relatively long gestation periods and the high cost of housing, the establishment of a single blastocyst-based assay for rapid optimization of the above system is required. As a proof-of-concept, we attempted to disrupt a gene (GGTA1) encoding the α-1,3-galactosyltransferase that synthesizes the α-Gal epitope using parthenogenetically activated porcine oocytes. The lack of α-Gal epitope expression can be monitored by staining with fluorescently labeled isolectin BS-I-B₄ (IB4), which binds specifically to the α-Gal epitope. When oocytes were injected with guide RNA specific to GGTA1 together with enhanced green fluorescent protein (EGFP) and human Cas9 mRNAs, 65% (24/37) of the developing blastocysts exhibited green fluorescence, although almost all (96%, 23/24) showed a mosaic fluorescent pattern. Staining with IB4 revealed that the green fluorescent area often had a reduced binding activity to IB4. Of the 16 samples tested, six (five fluorescent and one non-fluorescent blastocysts) had indel mutations, suggesting a correlation between EGFP expression and mutation induction. Furthermore, it is suggested that zygote microinjection of mRNAs might lead to the production of piglets with cells harboring various mutation types.     

Glibenclamide for the Treatment of Ischemic and Hemorrhagic Stroke

Ischemic and hemorrhagic strokes are associated with severe functional disability and high mortality. Except for recombinant tissue plasminogen activator, therapies targeting the underlying pathophysiology of central nervous system (CNS) ischemia and hemorrhage are strikingly lacking. Sur1-regulated channels play essential roles in necrotic cell death and cerebral edema following ischemic insults, and in neuroinflammation after hemorrhagic injuries. Inhibiting endothelial, neuronal, astrocytic and oligodendroglial sulfonylurea receptor 1–transient receptor potential melastatin 4 (Sur1–Trpm4) channels and, in some cases, microglial K_ATP (Sur1–Kir6.2) channels, with glibenclamide is protective in a variety of contexts. Robust preclinical studies have shown that glibenclamide and other sulfonylurea agents reduce infarct volumes, edema and hemorrhagic conversion, and improve outcomes in rodent models of ischemic stroke. Retrospective studies suggest that diabetic patients on sulfonylurea drugs at stroke presentation fare better if they continue on drug. Additional laboratory investigations have implicated Sur1 in the pathophysiology of hemorrhagic CNS insults. In clinically relevant models of subarachnoid hemorrhage, glibenclamide reduces adverse neuroinflammatory and behavioral outcomes. Here, we provide an overview of the preclinical studies of glibenclamide therapy for CNS ischemia and hemorrhage, discuss the available data from clinical investigations, and conclude with promising preclinical results that suggest glibenclamide may be an effective therapeutic option for ischemic and hemorrhagic stroke.     

Characterization of a plasma polymer coating from an organophosphorus silane deposited at atmospheric pressure for fire-retardant purposes

Protective coatings from diethylphosphatoethyltriethoxysilane (DEPETS) have been deposited on different polymer substrates in a plasma discharge operated at atmospheric pressure. Plasma polymer chemistry and structure were characterized by means of Fourier transform infrared spectroscopy (FTIR), laser desorption ionization-mass spectrometry (LDI-MS), nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). A chemical structure of the plasma polymer has been proposed based on the coating molecular characterization. Coatings were deposited on polycarbonate (PC) and polyamide 6 (PA6) substrates. The flame retardant properties of coated substrate samples were assessed using cone calorimetry and compared to those of bare substrates. A significant increase in the time to ignition (TTI), up to +143%, was recorded after coating deposition due to the formation of a high-performance barrier layer at the surface of both polymer substrates.