Synthesis of Silsesquioxane Cages from Phenyl-cis-tetrol, 1,3-Divinyltetraethoxydisiloxane and Cyclopentyl Resins

The synthesis of T_8, T_ 10 and T_ 12 silsesquioxane cages from a range of starting materials: phenyl-cis-tetrol, 1,3-divinyltetraethoxydisiloxane and cyclopentyl T resins by using tetra n-butylammonium fluoride(TBAF) as the catalyst is described in this paper. The reaction yields obtained viathe current route are better compared to those viathe literature routes. Some of the cage compounds have been characterized by X-ray crystallography.

Studies on the Preparation and Catalyticproperties of Fe-C-Mn Ultrafine particle Catalyst in F-T synthesis

Based on the Fe/C ultrafine particle obtained by means of laser pyrolysis method, a series of Fe-C-Mn ultrafine particle catalysts for F-T synthesis were prepared by adding certain amounts of Mn organic compounds to the Fe/C UFP. XRD and TEM tests for the obtained catalysts showed that the active phases, α-Fe, Fe3Cand (Fe,Mn)O. were directly obtained. and that the particle size was in the range of 2-4 nm. The catalysts so obtained have stable structure, long life, high activity and selectivity for light olefins, especially for propylene. Testing of the crystal structure in the process of the reaction demonstrated the carbonide mechanism of FT synthesis and the presence of α-Fe, FexCy and (Fe, Mn)O, thus supporting the belief that these are the active phases.

Mannogalactoglucan from mushrooms protects pancreatic islets via restoring UPR and promotes insulin secretion in TIDM mice

Type 1 diabetes mellitus(T1DM) lacks insulin secretion due to autoimmune deficiency of pancreaticβ-cells.Protecting pancreatic islets and enhancing insulin secretion has been therapeutic approaches.Mannogalactoglucan is the main type of polysaccharide from natural mushroom,which has potential medicinal prospects.Nevertheless,the antidiabetic property of mannogalactoglucan in T1DM has not been fully elucidated.In this study,we obtained the neutral fraction of alkali-soluble Armillaria mellea polysaccharide(AAMP-N) with the structure of mannogalactoglucan from the fruiting body of A.mellea and investigated the potential therapeutic value of AAMP-N in T1DM.We demonstrated that AAMP-N lowered blood glucose and improved diabetes symptoms in T1DM mice.AAMP-N activated unfolded protein response(UPR) signaling pathway to maintain ER protein folding homeostasis and promote insulin secretion in vivo.Besides that,AAMP-N promoted insulin synthesis via upregulating the expression of transcription factors,increased Ca^(2+) signals to stimulate intracellular insulin secretory vesicle transport via activating calcium/calmodulin-dependent kinase Ⅱ(CamkⅡ) and cAMP/PKA signals,and enhanced insulin secretory vesicle fusion with the plasma membrane via vesicle-associated membrane protein 2(VAMP2).Collectively,these studies demonstrated that the therapeutic potential of AAMP-N on pancreatic islets function,indicating that mannogalactoglucan could be natural nutraceutical used for the treatment of T1DM.

SYNTHESIS AND PURIFICATION OF N,N'-E1S(P-CARBOMETHOXYBENZOYL)BUTANEDIAMINE(T4T-DIMETHYL)

T4T-dimethyl is commonly employed as hard segment when polyesteramide is produced. Polyesteramide is one of thermoplastic elastomers, like polyurethane which is composed of two different types of segments, usually referred to as soft and hard segments. The characters of hard segment have much influence on the properties of the polymer. To get the polyesteramide with high order, it is desirable to make T4T-dimethyl pure. In this paper, how to synthesize, to purify as well as to detect the purity of T4T-dimethyl are described in detail.

Effect of Several Anions on Fe-Based Catalyst for Fischer-Tropsch Synthesis

The influence of several anions on Fe-based Fischer-Tropsch catalyst, used in the synthesis of light olefins from synthesis gas, was studied. The results indicated that the addition of anions resulted in the reduction of catalytic activity. When the anion content in the catalyst was 500 ppm, the influence of different anions on the catalysis activity was as follows： S^2- 〉Cl^-〉SO4^2-〉NO3. The addition of S^2- improved the selectivity of total hydrocarbons in the products, and Cl^- reduced this selectivity but increased the olefin content in the total hydrocarbons at the same time. When the contents of S^2- and Clin the catalyst were less than 50 ppm, their influence could be ignored. The XRD results indicated that the addition of anions reduced the contents of α-Fe and FeaC, which were the active components in the catalyst.

Synthesis of N1-Substituted-3-aryl-4-alkyl-4, 5-dihydro-1H-1-pyra-zolethiocarboxamide as Novel Small Molecule Inhibitors of Cysteine Protease of T.cruzi

A series of N1-substituted-3-aryl-4-alkyl-4, 5-dihydro-1H-1-pyrazolethiocarboxamide were prepared from the Mannich bases of aryl ketones in good yields. Some derivatives were found to be active against the cysteine protease of T.cruzi..

SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTAL POLYMERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNITS (Ⅱ)

A series of liquid crystalline polymers with T-shaped two-dimensional mesogenic unitswere synthesized via low temperature solution polycondensation of 2-(4'-alkoxy-phenyl)hydroquinone with various diacyl dichlorides. The polymers were found to be nematic andshown thermotropic liquid crystalline behaviors through observations using DSC, polarizedmicroscopy and X-ray diffraction. The melting temperature T_m and the isotropizationtemperature T_i of the polymers change regularly with varying of the monomer structures.

SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTAL POLYESTERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNITS(Ⅲ)

A new series of liquid crystal polyesters with T-shaped two-dimensional mesogenic units weresynthesized by melt polycondensation of the diacetates of 2-(4'-alkoxy -phenyl)-hydroquinones with 4,4'-alkylenedioxydibenzoic acid. The polymers were characterized by using polarized microscopy, DSC and X-ray diffraction. It was realized that all the polymers have nematic thermotropic liquid crystallinecharacteristics. The melting temperature (T_m) and isotropization temperature (T_i) of the polymers changeregularly with varying lengths of the alkoxy side group and the length of the alkylene group in the main chainin company with an even-odd effect. The mesophase temperature range also varies regularly with the polymerstructure. It is shown that the mesophase range has been widened.

SYNTHESIS OF LIQUID CRYSTALLINE COPOLYESTERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNIT AND CROWN ETHER CYCLE

A novel series of liquid crystalline copolyesters with T-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4′-bis(4-hydroxyphenylazo)dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4′-(α,ω-hexanedioyloxy)dibenzoyl dichloride(M_1),2-(4′-ethoxyphenyl)hydroquinone(M_2)and cis-4,4′-bis(4- hydroxyphenylazo)dibenzo-18-crown-6(M_3).The molecular weights of copolyesters are not high,and the intrinsic viscosity [η]of copolyesters ranges from 0.29-0.43.The monomers ...

A Convenient Method for Synthesis of Novel Cyclic Ethers (1R,2R,3R,5S,7S,9R,12R)-3-(t-Butyldimethylsilyl)oxy-7-methoxymethyl-oxy-2,10-dimethyl-12-oxatricyclo [7.2.1.0^(5,12)] dodecane

Novel cyclic esters (1R, 2R, 3R, 5S, 7S, 9R, 12R)-3-(t-butyldimethylsilyl)oxy-7- methoxymethyloxy-2, 10-dimethyl-12-oxatricyclo [7.2.1.05,12] dodecane were prepared when their precursor 1 was treated with SOCl2/pyridine. A plausible mechanism was hypothesized.

Synthesis and Crystal Structure of[Li(dme)3][(t-BuC_5H_4)_2Gd(NPh_2)_2]·1/2dme

The crystal structure of the title complex[Li (dme)3] [(t-BuC_5H_4)_2Gd (NPh_2)_2]·1/2dme,C56H81O7N2LiGd(M,r=1058. 63), has been determined by single-crystal X-ray diffraction. The crystal is triclinic with space group P1, a=12. 741 (3),b =13. 353(3), c=16. 843(4) A, a=94. 70(2), β=91. 57(2)', r=92. 03(2), V=2852. 7(1) A3, Dc= 1.23g/cm3, F(000)=1038, u=12. 5 cm-1, Z=2, and finalR=0. 050 and Rw=0. 045 for 5829 reflections (I≥3d(I)). The structure analysis re-vealed that the complex consists of disconnected ion pairs of (Li (dine)3 ]+ and [(t-BuC5H4),Gd (NPh2)2]-. The Gd atom is connected to two n5-bonded t-butylcy-clopentadienyl groups and two a bonded diphenylamidos in a distorted tetrahedral ar-rangement. The Li atom is coordinated by six O atoms from three dimethoxyethane lig-ands forming an octahedron structure.

(+)/(-)-Gerbeloid A,a pair of unprecedented coumarin-based polycyclic meroterpenoid enantiomers from Gerbera piloselloides:Structural elucidation,semi-synthesis,and lipid-lowering activity

A pair of coumarin-based polycyclic meroterpenoid enantiomers(+)/(-)-gerbeloid A[(+)-1a and(-)-1b]were isolated from the medicinal plant Gerbera piloselloides,which have a unique caged oxatricyclo[4.2.2.0^(3,8)]decene scaffold.Their planar and three-dimensional structures were exhaustively characterized by comprehensive spectroscopic data and X-ray diffraction analysis.Guided by the hypothetical biosynthetic pathway,the biomimetic synthesis of racemic 1 was achieved using 4-hydroxy-5-methylcoumarin and citral as the starting material via oxa-6πelectrocyclization and intramolecular[2+2]photocycloaddition.Subsequently,the results of the biological activity assay demonstrated that both(+)-1a and(-)-1b exhibited potent lipid-lowering effects in 3T3-L1 adipocytes and the high-fat diet zebrafish model.Notably,the lipid-lowering activity of(+)-1a is better than that of(-)-1b at the same concentration,and molecular mechanism study has shown that(+)-1a and(-)-1b impairs adipocyte differentiation and stimulate lipolysis by regulating C/EBPα/PPARγsignaling and Perilipin signaling in vitro and in vivo.Our findings provide a promising drug model molecule for the treatment of obesity.

煤间接液化F-T合成装置危险性分析及安全管控措施

煤间接液化F-T合成装置的工艺反应速度快、放热量大、反应中间产物不稳定,大部分原料、产品属于易燃易爆物料,具有较高的危险性,发生事故后危害性大。减少安全事故,降低事故危害程度,保证装置“安全、稳定、长周期、满负荷、优质”的运行,保障员工生命和财产安全,已成为企业工作的重点。以国内某企业一套煤间接液化F-T合成装置为例,对其生产过程中可能存在的危险有害因素、危险性进行分析,并从4个安全管理方面提出预防和控制危险性的措施及建议,以保障装置安全稳定运行。

微波合成a＆b取向的T型分子筛膜及其在渗透汽化耦合酯化反应中的应用

利用微波辅助水热合成法制备了高性能的a&b取向的T型分子筛膜.并用于乙酸与正丁醇的渗透汽化耦合反应,结果表明,T型分子筛膜可以有效地从反应混合物中脱出产物水,其它反应物与产物仍留在反应体系中,反应转化率可以达到100%.

F-T合成催化剂H_2S中毒热力学和抗硫可行性预测

利用热力学基础数据对F-T合成催化剂硫化氢中毒的热力学进行了计算。在热力学上,Ru、Fe、Co的毒化在F-T合成反应可以发生的条件下均是自发过程。F-T合成反应体系中10-8级浓度的H2S即可使Ru基催化剂中的金属Ru生成RuS2而中毒。Fe和Co毒化后生成的硫化物种类多,对这些反应的热力学计算表明,对于不同的反应,其平衡常数的差异很大,对应中毒反应发生时,所需的硫化氢的浓度也不同,并得出了不同毒化反应的硫化氢浓度范围。计算结果可为抗硫性F-T合成催化剂的开发提供数据依据和理论指导。

锰助剂对F-T合成Co/Al_2O_3催化剂反应性能的影响

采用程序升温和原位红外技术对锰改性Co/Al2O3催化剂进行了表征,并与CO加氢反应活性和选择性进行关联.结果表明,添加适量锰能够增加反应活性,提高C5+烃选择性,抑制甲烷及低碳烃的生成.XRD和FT-IR结果表明锰助剂的添加能够促进活性相的分散,促进桥式CO吸附位数的增加.H2-TPD表明锰的加入可增加低温吸附氢量,但吸附氢量随锰含量的增加而减少.钴基催化剂的费托合成反应性能可以用锰添加导致的CO吸附态物种的变化来解释.

Zn对沉淀铁催化剂结构及其F-T合成性能的影响

采用低温N2吸附、XRD、MES、CO-TPR和H2-DTG研究了Zn(100 gFe/x gZn,x=7～100)助剂对Fischer-Tropsch(F-T)合成Fe基催化剂的织构性质、还原行为以及相变结构的影响;在H2/CO=2.0、260℃、1.5 MPa和4 000 mL/(g.h)条件下在固定床反应器上考察了Zn助剂含量对Fe基催化剂F-T合成反应活性、烃产物选择性和运行稳定性的影响。研究结果表明,随着Zn含量的增加,氧化态催化剂的物相由α-Fe2O3和ZnFe2O4逐渐向ZnFe2O4和ZnO转变,ZnFe2O4在催化剂中优先生成,只有在超出其计量比1∶2之后才有ZnO出现。由于ZnFe2O4较为稳定,能够促进催化剂中Fe物相的分散,导致比表面积增加。在还原和反应态催化剂中,ZnFe2O4一方面抑制催化剂的过度还原和碳化;另一方面表现为稳定活性相铁碳化物。催化剂的F-T反应性能评价结果表明,纯铁催化剂由于铁碳化物氧化而迅速失活,而Zn助剂催化剂却由于ZnFe2O4的稳定作用,活性较为稳定。同时,由于催化剂在反应初相变的影响,导致Zn助剂催化剂的初始烯烃选择性随着Zn含量的增加而增加,在相态稳定之后选择性趋于一致。

光伏T接高压配电网电流差动保护研究

分析了光伏电站故障电流的特性,研究了两个目前常用电流差动保护判据应用在光伏T接线路上存在的问题。研究结果表明,传统T接线路差动保护判据不能同时满足内部故障的灵敏性和外部故障的可靠性。结合光伏电源故障电流特点,提出了适合于光伏T接线路电流差动保护的综合判据。对改进后的判据进行了大量的仿真试验,仿真结果表明,该判据能满足区内故障时的灵敏性和区外故障时的可靠性,并且具有很强的抗过渡电阻的能力。

F-T合成粗油品的加工

介绍了国内外低温F-T合成粗油品组成.同石油原油相比,F-T合成粗油品主要由链烷烃和链烯烃组成,环烷烃和芳烃含量很少,且具有硫、氮等含量少的优点.根据合成粗油品特点,结合相关产品市场行情及国家需要,考虑到规模对经济效益的影响,来研究加工改质工艺方案的设计思路,从而提高煤基合成油经济效益,推进其工业化进程.

F-T合成催化剂羰基硫中毒热力学分析

利用热力学基础数据和相关软件对F-T合成催化剂COS中毒的热力学进行了计算。在热力学上,Ru、Fe、Co的COS中毒在F-T合成反应可以发生的条件下均是自发过程。F-T合成反应体系中10-9级的COS即可使Ru基催化剂中的金属Ru生成RuS2而中毒。Fe和Co毒化后生成的硫化物种类较多,对反应的热力学计算结果表明,对于不同的反应,其平衡常数的差异很大,对应中毒反应发生时,所需COS的浓度也不同。由于Fe基F-T合成催化剂活性相的复杂性,利用对催化剂相关性质的修饰开发具有一定抗硫性的铁基F-T合成催化剂是可行的;对于Co催化剂,利用F-T合成的反应特点和催化剂改性开发具有一定抗硫性催化剂也是可能的。