One Novel 2D Co(Ⅱ) Polymer with 1,2,3-Triazole Derivative: Crystal Structure, Fluorescence and Hirshfeld Surface Analysis

One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,2,3-triazole-4-carboxylic acid）. The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η-2：η-1η-1：η-1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.

Synthesis and Crystal Structure of Methyl 2-(Diphenylamino)-4-phenyl-1,3-thiazole-5-carboxylate

The title compound, methyl 2-（diphenylamino）-4-phenyl-1,3-thiazole-5-carboxylate, was synthesized and studied by single-crystal X-ray diffraction method. The structure of the product was confirmed by IR, 1H- and 13C-NMR spectroscopy and elemental analysis. These experimental studies were supported by quantum mechanical calculations. The structure was solved in monoclinic, space group P21/c with a = 9.573（3）, b = 19.533（7）, c = 9.876（3）, β = 92.35（4）°, V = 1845.2（10）3, T = 85（2） K, Z = 4, R = 0.040 and wR = 0.089 for 6424 observed reflections with I2σ（I）.

The Synthesis of 2,4,6-Triisopropyl-1, 3,5-trioxane Catalyzed by Ionic Liquids

The synthesis of 2, 4, 6-triisopropyl-1, 3, 5-trioxane with high yield and desirable selec- tivity from solvent-free cyclotrimerization of isobutyraldehyde catalyzed by ionic liquids was reported in this work.

An efficient synthesis of 2,2′-arylmethylene bis-(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) and 1,8-dioxooctahydroxanthenes using ZnO and ZnO-acetyl chloride

2,2'-Arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) 4l-s produced from reaction between dimedone with various aldehydes in acetonitrile using ZnO as a catalyst;whereas in the presence of ZnO-acetyl chloride catalysts the reaction is limited to give only 1,8-dioxo-octahydroxanthenes 3a-k in very good yields.

Dissolution Properties of 2-(Dinitromethylene)-5-methyl-1,3-diazacyclopentane in Dimethyl Sulfoxide and N-Methyl Pyrrolidone

The molar enthalpies of dissolution for 2-（dinitromethylene）-5-methyl-1,3-diazacyclopentane（DNMDZ） in dimethyl sulfoxide（DMSO） and N-methyl pyrrolidone（NMP） were measured using an RD496-2000 Calvet microcalorimeter at 298.15 K under atmospheric pressure.Empirical formulae for the calculation of the molar enthalpies of dissolution（Δ diss H） were obtained from the experimental data of the dissolution processes of DNMDZ in DMSO or NMP.The relationships between the rate constant（k） and the molality（b） and between the reaction order（n） and the molality（b） were determined.The corresponding kinetic equations describing the two dissolution processes were dα/dt=10^-2.16（1-α） ^1.01 for the dissolution of DNMDZ in DMSO,and dα/dt=10^-2.02（1-α）^ 0.85 for the dissolution of DNMDZ in NMP,respectively.

Synthesis of 2-(N-formyl)-5-aryl/aryloxymethyl-1,3,4-thiadiazoles with potential bioactivity in PEG-400

An environmental benign procedure for synthesis of 2-(N-formyl)-5-aryl/aryloxymethyl-1,3,4-thiadiazoles has been developed by reaction of 2-amino-5-aryl/aryloxymethyl-1,3,4-thiadiazoles with formic acid in PEG-400.The key advantages of this protocol are the shorter reaction time,higher yields,lower cost,simple workup,and environment-friendly compared to conventional organic solvent reaction.The present method does not involve any hazardous organic solvent or catalyst.

Improved Studies on the Synthesis,Characterization and Crystal Structure of 2,2-Dimethyl-5-nitro-5-nitroso-1,3-dioxane

The synthetic process for 2,2-dimethyl-5-nitro-5-nitroso-1,3-dioxane（DMNNDO） was improved by using tri（hydroxymethyl）nitromethane and acetone as starting materials through a ＂one-pot＂ method combined with alkaline hydrolysis and nitrosation reactions. The yield of DMNNDO was increased from 37% to 45%. The structure of DMNNDO was characterized by IR,^1H NMR,^13 C NMR,and elemental analysis. Also the thermal decomposition of DMNNDO was studied by using DSC and TG-DTG to find that there are primarily two exothermic decomposition processes between 90 and 300 oC. The crystal structure of DMNNDO was studied by X-ray single-crystal diffraction for the first time. The molecular structure exists as a dimeric form due to the presence of nitroso group. The crystal belongs to monoclinic system,space group C2/c with a = 14.515（3）,b = 9.955（2）,c = 11.897（2） °,β = 98.500（3）°,V = 1.6998（2） nm^3,Z = 8,D_c = 1.486 g×cm^-3,μ = 0.128 mm^-1,F（000） = 800,S = 1.055,R = 0.0358 and wR = 0.0917. In particular,DMNNDO could be easily hydrolyzed in hydrous systems and the hydrolysis mechanism in CDCl_3 was revealed by means of NMR monitoring.

Synthesis,Crystal Structure,and Magnetic Property of One 3D Nickel Coordination Polymer Based on 2-Hydroxy-5-(3',5'-terephthalic acid)Pyridine and 1,4-Bis(1-imdazoly)benzene

One novel nickel coordination polymer, {[Ni（OTP）（bib）1.5（H2O）]·2H2O}n（1, H2 OTP = 2-hydroxy-5-（3＇,5＇-terephthalic acid） pyridine, bib = 1,4-bis（1-imdazoly）benzene）, has been synthesized and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860（5）, b = 13.8246（6）, c = 19.0140（8） A, β = 104.3870（1）°, V = 3128.2（2） A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F（000） = 1444 and μ（Mo Kα） = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ（I） and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni（OTP）]n chain and the 2D [Ni2（bib）3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.

Synthesis,structural characterization and solubility of 2-(1-substituted-1,11-undecylidene)-5-arylimino-△~3 -1,3,4-thiadiazolines

A series of novel 2-（1-substituted-1,11-undecylidene）-5-arylimino-△^3-1,3,4-thiadiazolines （4） were synthesized and their structure was characterized by ^1H NMR, ^13C NMR and elemental analysis. Their solubility in both polar and non-polar solvents is significantly improved owing to the introduction of ethyl or methylthio group at cyclododecyl ring as compared with parent compounds [1, 2-（1,11-undecylidene）-5-arylimino-△^3-1,3,4-thiadiazolines]. However, their fungicidal activity against Rhizoctonia solani is less than that of parent compounds. X-ray diffraction analysis of a representative compound （4d） showed that the conformation of 12-membered ring is still [3333], in which the ethyl group present at the side-exo position and the thiadiazoline ring at the comer carbon. The thiadiazoline plane is perpendicular to the cyclododecyl one.

Formation of Hybrid Ring Structure of Cyanurate/Isocyanurate in the Reaction be-tween 2,4,6-Tris(4-Phenyl-Phenoxy)-1, 3,5-Triazine and Phenyl Glycidyl Ether

Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound which were well known as reaction products of cyanate esters and epoxy resins, compounds with hybrid ring structure of cyanurate/isocyanurate were determined. Gibbs free energies of the compound having hybrid ring structure of cyanurate/isocyanurate with two isocyanurate moiety were found to be lower than that of the compound with cyanurate ring structure through calculations. Calculation data supported the existence of hybrid ring structure of cy-anurate/isocyanurate. It was revealed that isomerization from cyanurate to isocyanurate occurs via hybrid ring structure of cyanurate/isocyanurate in the reaction of aryl cyanurate and epoxy.

A New Approach to 2,3-Dihydro-1H-1,5-Benzodiazepines from the Reaction of o-Nitrophenylazide with α,β-Unsaturated Ketones Promoted by Samarium Diiodide

o-Nitrophenylazide was reduced by SmI2 in anhydrous THF at room temperature to produce active intermediate 2 (samarium amide), "living" double-anion in situ which reacted smoothly with α，β-unsaturated ketones to afford 2,3-dihydro-1H-1,5-benzodiazepines in good yields under mild and neutral conditions.

Synthesis and biological evaluation of novel 2,4,5-triaryl-1 H-pyrazol-3(2H)-ones as inhibitors of ALK5

A series of 2,4,5-triaryl substituted 1H-pyrazol-3（2H）-ones,as ALK5 inhibitors,were desigened,synthesized and evaluated in vitro.Most compounds exhibited noticeable ALK5 inhibition activities at 1μmol/L and displayed no significant cytotoxicities at 30μmol/L.

Use of Solid-Supported Reagents towards Synthesis of 2-Arylbenzoxazole, 3, 5-Diarylisoxazole and 1, 3, 5-Triarylpyrazole

Herein we report a convenient and efficient synthesis of 2-Arylbenzoxazole from the Schiff’s bases of 2-Aminophenol, 3, 5-Diarylisoxazole from α, β-unsaturated ketoxime and 1,3,5-Triarylpyrazole from 2-pyrazoline and N-Arylhydrazone by using milder, less toxic and less expensive-NBS-SiO2, KMnO4-Al2O3, PCC-SiO2 and ACC-Al2O3 as solid-supported oxidizing agents at room temperature. Within the framework of Green Chemistry, the use of solid supported reagents has many advantages such as 1) they are easy to remove from reactions by filtration 2) excess reagents can be used to drive the reaction without introducing any difficulties in purification 3) such solid-supported reagents react differently, mostly more selectively, than their unbound counterparts and 4) toxic, noxious and explosive chemicals are handled more safely when contained on solid support.

Combining Experimental and Quantum Chemical Study of 2-(5-Nitro-1,3-Dihydro Benzimidazol-2-Ylidene)-3-Oxo-3-(2-Oxo-2H-Chromen-3-yl) Propanenitrile as Copper Corrosion Inhibitor in Nitric Acid Solution

Due to acidic solutions aggressiveness, corrosion inhibitors use is considered to be one the most practical methods to delay metals dissolution in the said solutions. In this study benzimidazolyl derivative namely 2-cyanochalcones 2-(5-nitro-1,3-dihydrobenzimidazol-2-ylidene)-3-oxo-3-(2-oxo-2H-chromen-3-yl) propanenitrile which was synthesized was then applied as a corrosion inhibitor for copper in 1 M HNO3 solution. The inhibition action of this molecule was evaluated by gravimetric and density functional theory (DFT) methods. It was found experimentally that this compound has a better inhibition performance and its adsorption on copper surface follows Langmuir adsorption isotherm. This adsorption evolves with temperature and inhibitor concentration, it is endothermic and occurs spontaneously with an increase in disorder. Corrosion kinetic parameters analysis supported by Adejo-Ekwenchi model revealed the existence of both physisorption and chemisorption. DFT calculations related that compound adsorption on copper surface is due to its electron donating and accepting capacity. The reactive regions specifying the electrophilic and nucleophilic attack sites were analyzed using Fukui and dual descriptor functions. Experimental results obtained were compared with the theoretical findings.

Crystal Structure of 1, 1-Dichloro-la, 3-diphenyl-1, la, 2, 3-tetrahydro-azirino [2, 1-d ] [1, 5]benzothiazepine(C_(22),H_(17)Cl_2NS )

The crystal structure of 1, l-dichloro-la, 3-diphenyl-l, la, 2, 3-te-trahydro-azirino[2, l-d ] [l, 5]benzothizeapine (C22H17Cl2NS, Mr= 398. 35) has beendetermined. The title compound crystallizes in orthorhombic space group Pbca with celldimensions a= 11. 579(3), b= 15. 14O(4), c=2l. 534(5) A, V= 3775. 04(5) A 3, Z= 8, D. = 1' 402g. cm-3, MoKa(λ= 0. 7l073 A ), F (000) = lO64, μ= O. 245mm-1. The structure was solved by using direct methods and refined by full-matrixleast-Squares method, and the final crystallographic discrepancy factor is 0. 046 for4l94 observed rcflections. The molecular backbone is a tricyclic system with the centralseven-membered l, 5-thiazepine ring in twisted boat-like conformation and cis-fused toboth azirine ring and benzene ring.

普罗布考通过TGF-β1/Smad 2/3通路减轻大鼠脑缺血再灌注损伤

目的:探讨普罗布考对大鼠脑缺血再灌注(I/R)的影响及其可能机制。方法:线栓法建立大鼠大脑中动脉栓塞(MCAO)模型,用1.5、3 mg/kg普罗布考进行干预,将200只大鼠分为假手术组、I/R组、溶剂组、小剂量组(1.5 mg/kg)及大剂量组(3mg/kg)。术后15 min腹腔注射药物,于1、3、5 d和7 d取材。观察普罗布考对脑缺血再灌注炎性损伤急性期及恢复早期神经功能评分、梗死灶体积、脑组织水含量的影响,并用ELISA检测脑组织匀浆环氧酶(COX-2)和5脂氧酶(5-LOX)活性变化,免疫印迹检测各组TGF-β1和p-Smad2/3蛋白表达量的变化。结果:与假手术组比较,MCAO术后小鼠出现严重的神经功能障碍、脑水肿和脑梗死,COX-2和5-LOX蛋白表达显著升高,而TGF-β1和p-Smad2/3蛋白表达明显降低;与手术组比较,经普罗布考干预后,小鼠神经功能评分、脑水肿和脑梗死情况明显改善,COX-2和5-LOX蛋白表达明显降低,而TGF-β1和p-Smad2/3蛋白表达明显升高,且大剂量组优于小剂量组。结论:普罗布考能缓解大鼠脑缺血再灌注炎性损伤,其机制可能与激活TGF-β1/Smad2/3信号通路,抑制脑内COX-2与5-LOX的活性有关。

热处理对Mg-3Sn-2Al-1Zn-5Li合金耐蚀性能的影响

对Mg-3Sn-2Al-1Zn-5Li合金进行了不同方式的热处理。利用电化学测试研究了不同热处理状态合金在3.5%NaCl溶液中的腐蚀电化学行为,并通过扫描电镜、能谱以及X射线衍射分析了合金腐蚀形貌及腐蚀产物的成分。结果表明:经固溶处理和时效处理后,合金的耐蚀性能有所提高,并且固溶态的Mg-3Sn-2Al-1Zn-5Li合金有着最佳的耐蚀性能;合金的腐蚀特征为丝状腐蚀,腐蚀产物主要为Mg(OH)_(2)。

缩合试剂2-氯-4,6-二甲氧基-1,3,5-三嗪的合成与应用

2-氯-4,6-二甲氧基-1,3,5-三嗪(CDMT)是商品化的常用于羧酸的活化和酰胺合成的缩合试剂。CDMT制备简单,成本低廉,活性高,适合工业化生产使用。CDMT与羧酸在有机碱N-甲基吗啉(NMM)作用下生成活性脂。本文对2-氯-4,6-二甲氧基-1,3,5-三嗪的合成方法,和其在酰胺,肽,脂,酸酐,醛,酮,芳香酮,炔酮,芳基偶联物,3,5-二取代1,2,4-恶二唑合成中的应用进行了综述。

4-氨基-3,7-双(1H-四唑-5-基)-[1,2,4]三唑并[5,1-c][1,2,4]三嗪(DTTA)的晶体结构和热稳定性

为深入研究新型含能材料4-氨基-3,7-双(1H-四唑-5-基)-[1,2,4]三唑并[5,1-c][1,2,4]三嗪(DTTA)的相关性能。采用核磁共振谱(1H NMR、13C NMR)、红外光谱(IR)、高分辨质谱(HRMS)和X-射线单晶衍射仪等分析仪器对化合物的结构进行了表征。通过溶剂挥发的方式,在DMSO溶液中得到了DTTA的溶剂化物DTTA·2DMSO的晶体结构。结果表明:DTTA·2DMSO属于单斜晶系,空间群为P 21/n,a=4.630 2(5)?,b=23.278(3)?,c=17.069(2)?,140 K时晶体密度ρ=1.561 g·cm-3。测得其25℃下的粉末密度ρ=1.811 g·cm-3。采用Hirshfeld表面对晶体中各种近相互作用进行了分析,晶体内占主导地位的是N…H&H…N作用,占比高达52.4%。采用热重及差示扫描量热仪联用(TG-DSC)研究了DTTA的热分解性能,分解峰温为287℃。对DTTA的理论爆轰性能进行了研究,计算爆速为8 419 m·s-1,计算爆压为24.8 GPa。采用BAM感度测试仪测试了其冲击感度为24 J,摩擦感度大于360 N。用Kissinger法与Ozawa法分别计算了其活化能EK为200.25 kJ·mol-1,r为0.99,EO为199.38 kJ·mol-1,r为0.99。DTTA的综合性能较优异,可以作为一种有潜力的高能量密度炸药使用。

重组糖蛋白激素β5/α2调控cAMP/PKA/CREB通路促进3T3-L1细胞脂肪分解的作用及机制研究

目的研究重组糖蛋白激素β5/α2(rCGH)对3T3-L1脂肪细胞脂解的影响,并探究其潜在机制。方法体外培养3T3-L1前脂肪细胞,并诱导分化为成熟脂肪细胞,给予不同浓度rCGH干预24 h。以CCK-8法检测3T3-L1脂肪细胞的细胞活力,酶学方法测定细胞内甘油三酯(TG)及培养上清中甘油的水平,油红O染色观察脂滴变化。Western blot检测各组脂肪细胞中HSL和ATGL脂解蛋白的表达水平。不同浓度rCGH加或不加PKA抑制剂H89对已分化成熟的3T3-L1脂肪细胞进行联合干预实验,将培养细胞分为对照组、H89预处理组、1μmol·L^(-1)rCGH组和(1μmol·L^(-1)rCGH+H89)联合干预组。酶法测定胞内TG及游离甘油的含量,Western blot检测CREB及脂解相关蛋白的表达。结果不同浓度rCGH(0.25、0.5、1、2μmol·L^(-1))对脂肪细胞细胞活力无显著影响(P>0.05);与对照组相比,rCGH处理显著降低了脂滴大小和细胞内TG含量,同时显著升高了细胞上清液中的甘油浓度。rCGH处理还刺激了p-HSL、ATGL和p-PKA的蛋白表达。此外,加入PKA抑制剂H89,减弱了rCGH对游离甘油水平、细胞内TG含量以及p-HSL、p-PLIN1和p-CREB表达的影响。结论rCGH通过上调HSL、ATGL和PKA活性促进3T3-L1脂肪细胞的脂质分解,促进甘油释放,抑制TG合成和脂质积累,其作用机制与cAMP/PKA/CREB信号通路激活有关。