无溶剂快速合成S-1和TS-1分子筛

Silicalite-1(S-1)和Titanium Silicalite-1(TS-1)沸石分子筛因其良好的疏水性、热稳定性和择形性等特点,作为环境友好的绿色催化剂在工业应用上极具优势和价值.采用无溶剂法成功合成了TS-1分子筛,并利用X-射线衍射仪、全自动比表面和孔隙分析仪、紫外可见光谱仪和扫描电镜等表征仪器研究了晶化时间和硅钛摩尔比对所制备TS-1分子筛的物化性质的影响.结果表明,合成的TS-1沸石分子筛具有较高的结晶度和纯度、均一的晶粒大小、高的比表面积和在分子筛骨架中四配位和六配位的钛物种.无溶剂合成TS-1沸石具有低成本、环境友好和高效的优点,研究将为工业上沸石的规模合成提供一定的理论借鉴.

TS-1分子筛研究进程及催化应用

TS-1是一类独特的用于液相选择性氧化反应的分子筛催化剂,在高结晶沸石框架中具有四面体配位Ti^(4+)离子。TS-1/H_(2)O_(2)绿色反应体系已经取得了相当大的突破。TS-1分子筛的催化性能与其拓扑结构、晶体形态、四面体Ti的含量和反应微环境有关。当前石油化工和精细化工等行业对大分子氧化催化剂的需求日益增长,开发催化性能显著提高的新型TS-1的研究成为热点。综述TS-1分子筛近年的研究进展及催化应用。

Interleukin-1 receptor antagonist:From synthesis to therapeutic applications

The cytokine channel’s mechanism for self-regulation involves the application of antagonistic cytokines that are synthesized to connect to the receptors and release soluble cytokine receptors.The very first receptor antagonist of cytokine that was naturally present was interleukin-1 receptor antagonist(IL-1Ra).The IL-1Ra protein forms are disinfected from supernatants of cultured monocytes on stacked IgG.The family of IL-1 consists of IL-1α,IL-1βand IL-1Ra.Human monocytes regulate the production of IL-Ra.IL-Ra takes part in normal physiological functions by using specific antibodies,and acts as an anti-inflammatory agent.IL-Ra is synthesized in the tissues during the period of active disease and can be systematically measured and/or estimated.Maintenance of the levels of IL-Ra and IL-1 is the main factor for host resistance in patients during diseased conditions,as IL-Ra acts as an inherent regulator of various inflammatory responses.In this article,we focuse on how IL-Ra is synthesized and performs its functions once the inflammatory responses are activated.

Effects of the Amount of Tetrapropyl Ammonium Hydroxide in Synthesis on TS-1 Properties and Catalytic Performance in Epoxidation of Propylene

Titanium silicalite-1(TS-1) was synthesized by a hydrothermal synthesis method with different amounts of tetrapropyl ammonium hydroxide(TPAOH) as template.The as-prepared TS-1 was characterized by scanning electron microscopy,X-ray powder diffraction,Fourier-transform infrared resonance spectroscopy,ultravioletvisible diffuse reflectance spectroscopy and nitrogen physical adsorption and desorption,and studied in the propylene epoxidation with hydrogen peroxide in a fixed bed reactor.The results showed that the amount of TPAOH had a strong influence on the grain morphology,the amount of framework Ti,and the average particle sizes of TS-1.With the increase of TPAOH amount in the synthesis(the molar ratio of TPAOH/SiO_2 increasing from 0.25 to 0.45),the morphology changed gradually from ellipsoids to cubes,the particle sizes of TS-1 decreased slightly,the amount of the framework Ti increased appreciably,and the catalytic stability in the propylene epoxidation increased markedly.Moreover,all the catalysts had the same selectivity to propylene epoxide.However,when the molar ratio of TPAOH/SiO_2 was further increased to 0.55,the particles became large hexagons with the size distribution in a wide range,and the catalytic stability decreased sharply although the amount of the framework Ti increased further,which can be attributed to the long diffusion paths of the reactants in the zeolite.

Synthesis of Hierarchical TS-1 and Its Recycling Catalytic Property for Oxidative Desulfurization

Because of its unique pore structure,good hydrothermal stability and high specific surface area,hierarchical TS-1 zeolite(HTS-1)has become an important catalyst for the deep oxidative desulfurization of fuel oils.In this work,HTS-1 has been successfully synthesized by a hydrothermal crystallization method using the C-SiO_(2)composite as both silicon source and mesoporous template,tetrapropylammonium hydroxide as microporous template,and tetrabutylorthotitanate as titanium source.The C-SiO_(2)composite is obtained by mild carbonization of the SiO_(2)/T-40(Tween 40)xerogel,which is prepared by the two step sol-gel method.The reaction conditions for the oxidative desulfurization(ODS)of dibenzothiophene(DBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT)over HTS-1 are optimized systematically,and the recycling performances of HTS-1 are investigated in detail.After the 15th run,HTS-1 still maintains high DBT conversion(90.6%)and 4,6-DMDBT conversion(86.0%)without deactivation.The samples before and after recycle tests are characterized by XRD,FT-IR,CHN analysis,UV-Vis and SEM techniques.The results indicate that the crystal structure and morphology of regenerated HTS-1 samples are well kept,which accounts for the good structural stability and reusability of HTS-1.In addition,active intermediates for the ODS of bulky organic sulfides over HTS-1,i.e.,Ti-peroxo(Ti-OOtBu)species,are captured by the UV-Vis technique.Finally,a possible reaction mechanism for the ODS process over HTS-1 is proposed.

Synthesis of TS-1 Films on Porous Supports for Epoxidation ofAllyl Chloride by Hydrogen Peroxide

Titanium silicalite-1(TS-1)films were synthesized on stainless steel plate,glass slide and monolith supports via an in-situ hydrothermal method.Characterization data showed that the formation of TS-1 films was easier on the porous flat support with rough surface such as monolith than on the smooth non-porous supports like glass slide and stainless steel plate.The film on the monolith had the highest uniformity and smallest size of crystals.The catalytic property of monolithsupported film was tested for epoxidation of allyl chloride(ACH)by H2O2in a fixed bed reactor.Under the condition of a methanol(solvent)/ACH(90% )/H2O2(30% )ratio of 12:1:1,a LHSV of 1.35 h-1and a temperature of 318 K,the conversion of allyl chloride and the selectivity to epichlorohydrin reached 79% and 51% ,respectively.

TS-1光催化剂的制备及应用研究进展

钛硅分子筛(TS-1)因具有优异的吸附能力、高选择性的催化活性中心和良好的稳定性而成为一类具有应用潜力的光催化材料。然而,其活性仍受限于电荷分离较低和光吸收不足。在众多光催化剂改性方法中,构建异质光催化体系具有简单可行、形式多样和性能突出等优点,在能源环境方面具有广阔的应用前景。本文总结了TS-1的制备方法、提出了与碳材料偶联、金属/非金属掺杂、贵金属负载和与半导体异质复合4种策略来TS-1光催化活性,分析了TS-1异质光催化剂在水分解制氢、CO 2还原和污染物的降解应用方面的研究现状。

多级孔NiMo负载TS-1分子筛催化剂的制备及其加氢脱硫性能

钛硅(TS-1)分子筛的微孔孔道严重限制了其在复杂分子催化转化中的应用,为了克服这一问题,通过酸洗脱、碱刻蚀及二者相结合的方法制备了多级孔TS-1分子筛,并采用等体积共浸渍法制备了相应的NiMo负载型催化剂;使用X射线衍射(XRD)、N2吸附-脱附、吡啶吸附红外光谱(Py-FTIR)、氢气程序升温还原(H_(2)-TPR)、X射线光电子能谱(XPS)和高分辨透射电子显微镜(HR-TEM)等方法对多级孔TS-1分子筛的理化性质进行了表征;以二苯并噻吩(DBT)为探针对催化剂的加氢脱硫(HDS)性能进行了评价。结果表明,和常规TS-1分子筛相比,多级孔TS-1分子筛保持了MFI拓扑结构,比表面积增大且具有介孔结构,分子筛表面形成了适量的Br?nsted酸中心;相应催化剂上活性金属与载体间相互作用得以改善,MoS_(2)片晶长度和堆垛层数适宜,形成了更多的NiMoS活性相;催化剂活性和选择性均有所提升,尤其是酸洗脱获得的NiMo/AT-TS-1催化剂的活性相较未经处理的NiMo/TS-1催化剂提升了1.2倍,直接脱硫(DDS)路径选择性提升了22%。

金属改性对钛硅分子筛TS-1上油酸甲酯环氧化性能的影响

环氧植物油可广泛用作各种化工材料,为提高植物油环氧化催化剂钛硅分子筛TS-1的活性,采用沉淀沉积法制备了系列金属改性的TS-1催化剂(M/TS-1,M为Mn、Fe、Cu、Mg),对其进行了表征,并以油酸甲酯环氧化为探针反应,考察了金属改性对TS-1上油酸甲酯环氧化性能的影响。结果表明:Fe和Cu的引入提高了TS-1的催化活性,但Mg和Mn改性却抑制了油酸甲酯的环氧化,Cu/TS-1催化剂的催化活性最高;结合多种表征结果发现,Cu/TS-1催化剂的高活性归因于Cu的引入有效地改变了Ti活性中心的电子环境,并增加了新的中强酸性位点;Cu/TS-1催化油酸环氧化的最佳工艺条件为反应温度80℃、H_(2)O_(2)与油酸甲酯物质的量比3∶1、油酸甲酯与催化剂质量比10∶1~20∶1;Cu/TS-1重复使用5次后,油酸甲酯转化率和环氧油酸甲酯收率略有降低。综上,采用Cu改性TS-1可显著提高其催化活性,且Cu/TS-1具有良好的再生性能。

Synthesis and plant-growth regulatory activities of novel imine derivatives containing 1H-1,2,4-triazole and thiazole rings

Eleven new imine derivatives 6 containing 1H-1,2,4-triazole and thiazole rings were synthesized by the condensation of 5-((1H- 1,2,4-triazol-1-yl)methyl)-4-tert-butylthiazol-2-amine with various substituted benzaldehydes.The structures of the title compounds were characterized by ~1H NMR,MS and elemental analysis.The plant-growth regulatory activities of these compounds were evaluated.The primary bioassay results indicated that these target compounds exhibited promising plant-growth regulatory activities.

Synthesis,Crystal Structure and Biological Activity of N-(2,6-Difluorobenzoyl)-N'-[5-(4-trifluoromethyl-phenyl)-1,3,4-thiadiazol-2-yl]ure

The title compound N-（2,6-difluorobenzoyl）-N＇-[5-（4-trifluoromethylphenyl）-1,3,4-thiadiazol-2-yl]urea（C17H9F5N4O2S,Mr = 428.34） has been synthesized by the reaction of 2-amino-5-（4-trifluoromethylphenyl）-1,3,4-thiadiazole with 2,6-difluorobenzoyl isocyanate,and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/n with a = 10.7316（13）,b = 10.5617（13）,c = 16.037（2） ,β = 106.408（2）°,V = 1743.6（4） 3,Z = 4,Dc = 1.632 g/cm3,μ = 0.260 mm-1,F（000） = 864,the final R = 0.0599 and wR = 0.1420 for 3467 observed reflections with I〉 2σ（I）.The urea group,which adopts a planar configuration mediated by the intramolecular N-H...O hydrogen bond,is nearly coplanar with the thiadiazole and 4-trifluoromethylbenzene rings.The title compound was found to exhibit good fungicidal activity against Rhizoctonia solani and Botrytis cinerea.

mi R-192-5p regulates lipid synthesis in non-alcoholic fatty liver disease through SCD-1

AIM To evaluate the levels of mi R-192-5 p in non-alcoholic fatty liver disease(NAFLD) models and demonstrate the role of mi R-192-5 p in lipid accumulation. METHODS Thirty Sprague Dawley rats were randomly divided into three groups, which were given a standard diet, a high-fat diet(HFD), and an HFD with injection of liraglutide. At the end of 16 weeks, hepatic mi R-192-5 p and stearoyl-Co A desaturase 1(SCD-1) levels were measured. Mi R-192-5 p mimic and inhibitor and SCD-1 si RNA were transfected into Huh7 cells exposed to palmitic acid(PA). Lipid accumulation was evaluated by oil red O staining and triglyceride assays. Direct interaction was validated by dual-luciferase reporter gene assays.RESULTS The HFD rats showed a 0.46-fold decrease and a 3.5-fold increase in hepatic mi R-192-5 p and SCD-1 protein levels compared with controls, respectively, which could be reversed after disease remission by liraglutide injection(P < 0.01). The Huh7 cells exposed to PA also showed down-regulation and up-regulation of mi R-192-5 p and SCD-1 protein levels, respectively(P < 0.01). Transfection with mi R-192-5 p mimic and inhibitor in Huh7 cells induced dramatic repression and promotion of SCD-1 protein levels, respectively(P < 0.01). Luciferase activity was suppressed and enhanced by mi R-192-5 p mimic and inhibitor, respectively, in wild-type SCD-1(P < 0.01) but not in mutant SCD-1. Mi R-192-5 p overexpression reduced lipid accumulation significantly in PA-treated Huh7 cells, and SCD-1 si RNA transfection abrogated the lipid deposition aggravated by mi R-192-5 p inhibitor(P < 0.01).CONCLUSION This study demonstrates that mi R-192-5 p has a negative regulatory role in lipid synthesis, which is mediated through its direct regulation of SCD-1.

Synthesis,Crystal Structure and Biological Activity of 2-(Anthracen-9-yl)-5-p-tolyl-1,3,4-oxadiazole

A novel compound,2-（anthracen-9-yl）-5-p-tolyl-1,3,4-oxadiazole（C23H16N2O）,has been synthesized by the condensation of 4-methylbenzohydrazide and anthracene-9-carbaldehyde in an ethanol solution with chloramine-T.The compound was characterized by 1H-NMR,13C-NMR,MS and single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P with a = 7.7817（4）,b = 8.8544（5）,c = 12.4726（8） ,β = 92.8520（10）°,Z = 2,V = 826.58（8） 3,Dc = 1.352 g/cm3,Mr = 336.38,λ（MoKα） = 0.71073 ,μ = 0.084 mm-1,F（000） = 352,R = 0.0381 and wR = 0.1099.The dihedral angle between anthracene skeleton and phenyl ring is 64.19°.A total of 6354 unique reflections were collected,of which 3172 with I 〉 2σ（I） were observed.X-ray analysis indicated an offset face-to-face π-π stacking interaction between anthracene skeletons and an offset face-to-face π-π stacking interaction between phenyl ring planes.The novel compound molecules are connected through the offset face-to-face π-π stacking interactions to generate a three-dimensional network.The preliminary bioassay results showed that the novel compound exhibited significant insect growth inhibitory activity against Spodoptera litura Fabricius larvae.

Synthesis,Crystal Structure,and Biological Activity of Naphthalen-2-yl4-methyl-1,2,3-thiadiazole-5-carboxylate

The title compound naphthalen-2-yl-4-methyl-1,2,3-thiadiazole-5-carboxylate （C 14 H 10 N 2 O 2 S,M r=270.31） was synthesized by the reaction of 4-methyl-1,2,3-thiadiazole-5-carbonyl chloride with 2-naphthol,and its structure was characterized by IR,1 H NMR,high-resolution mass spectrometry and single-crystal X-ray diffraction.The crystal belongs to orthorhombic,space group Pbcn with a=23.475（5）,b=9.6640（19）,c=10.814（2）,β=90.00°,Z=8,V=2453.2（9） 3,M r=270.30,D c=1.464 g/cm 3,μ=0.262 mm-1,F（000）=1120,R=0.0444 and wR=0.1099.X-ray analysis revealed that the thiadiazole and naphthalene rings were non-planar,while the thiadiazole ring and the ester group were essentially planar,and two intermolecular hydrogen bonds C（6） H（6）···O（1） and C（14） H（14）···O（1） were observed.The preliminary biological test showed that the title compound had antifungal and antivirus activities against tobacco mosaic virus.

Synthesis and Structural Characterization of 2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol

2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324（2）,b = 0.6454（3）,c = 0.7062（3） nm,α= 111.550（4）,β= 95.505（4）,γ= 113.395（4）°,V = 0.23595（16） nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F（000） = 126,R = 0.0304 and wR = 0.0907.

Synthesis, Crystal Structure and Antitumor Activity of N-[5-(Benzylthio)-1,3,4-thiadiazol-2-yl]-4-chlorobenzamide

The title compound N-[5-（benzylthio）-1,3,4-thiadiazol-2-yl]-4-chlorobenzamide（C（16）H（12）ClN3OS2, Mr = 361.86） was designed and synthesized as anticancer agent, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1 with a = 5.7417（10）, b = 9.8057（17）, c = 14.330（3） A, a = 91.987（3）, b = 97.154（3）, γ = 93.402（3）°, V = 798.4（2） A3, Z = 2, Dc = 1.505 g/cm^3, μ = 0.507 mm-1） F（000） = 372, the final R = 0.0481 and wR = 0.1290 for 2064 observed reflections with I 〉 2s（I）. In the crystal packing, the molecules form stacks by a three-dimensional framework, which results from intermolecular N（1）-H（1）···N（2） and C（5）-H（5）···N（3） hydrogen bonds together with π-π stacking interactions between the thiadiazole and chlorobenzene rings. The title compound was found to exhibit more potent in vitro antitumor activities against the four tested cancer cell lines than sorafenib.

Synthesis and Crystal Structure of 1-(4-Fluorophenyl)-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H)-one

The crystal structure of the title compound 1-（4-fluorophenyl） -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H） -one（C23H21FN4O2S,Mr = 436.5） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854（3） ,b = 17.2678（4） ,c = 18.1828（5）A,β = 99.364（2） °,V = 4332.58（18） A^3,Z = 4,Dc = 1.338,F（000） =1824,μ = 0.185 mm^-1,MoKa radiation（λ = 0.71073） ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I 〉 2σ（I） . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5（1H） -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.