双核Pt(Ⅳ)配合物与Guanosine-5''''-Monophosphate和Glutathione反应的核磁共振光谱研究

合成了一个新型的双核Pt(Ⅳ)配合物{[cis-Pt(NH3)2Cl(OH)2]2(4,4'-methylenedianiline)}(NO3)2(化合物1)及相应的 15N标记化合物{[cis-Pt(15NH3)2Cl(OH)2]2(4,4'-methylenedianiline)}(NO3)2(化合物15N-1).利用1H NMR和ESMS进行了结构表征,化合物15N-1的2D[1H,15N]HSQC NMR发现,该化合物在水溶液中存在同分异构体.2D[1H,15N]HSQC NMR技术跟踪了化合物15N-1与Guanosine-5'-Monophosphate(5'-GMP)和Glutathione(GSH)的反应.结果显示,5'-GMP能在0.5 h内将化合物1还原,而GSH在6 h以后才能够部分的将化合物1还原.化合物1所表现出来的反应性能将有利于提高其治疗效果和降低毒副作用.     

溶剂对呋喃二羧酸与Mn(Ⅱ)自组装的结构调控

以呋喃二羧酸 (H2FDC) 与 Mn(II) 为研究对象,通过改变溶剂体系分别得到了化合物 Mn(FDC)(H2O)3 (1) 和化合物 [NH4]2?[Mn3(FDC)4]?2DMF?2H2O (2). 呋喃二羧酸与 Mn(II)在DMF与水的混合溶剂中形成了具有一维链状结构的化合物1,而在DMF溶剂中则形成了具有三维开放结构的化合物2,这反应了溶剂对产物结构具有重要的影响. 变温磁化率测试及量子蒙特卡洛方法拟合都表明化合物1和2 都表现为反铁磁性.     

以芳香族多羧酸为配体的Ni(II)配位超分子的研制及光诱导下的表面电子行为

采用水热方法合成了2个Ni(II)配合物[Ni3(btc)2(H2O)14]·4H2O(1)和[Ni2(btec)(bipy)2(H2O)6]·2H2O(2), (H3btc=1,3,5-benzenetricarboxylic acid, H4btec=1,2,4,5-benzenetetracarboxylic acid, bipy=2,2'-bipyridyl). 通过X射线单晶衍射(XRD)、红外光谱(IR)、紫外-可见-近红外吸收光谱(UV-Vis-NIR)对化合物进行了表征. 结果表明, 化合物(1)是由2个均苯三甲酸根桥连的三核Ni(II)离子的化合物, 而化合物(2)是由1个均苯四甲酸根桥连的双核化合物, 分子中bipy分子作为端基配体. 分子中大量的水分子和羧酸根的存在使2个化合物分别被连成具有三维(3D)和二维(2D)结构的配位超分子化合物. 着重研究了化合物的表面光电压光谱(SPS), 并将其与UV-Vis-NIR吸收光谱进行了分析和对比, 发现SPS 中表面光伏响应带与UV-Vis-NIR 吸收光谱的吸收峰在数量和位置上都是一一对应的. 此外, 对比2个化合物的表面光电压光谱可以看出,配合物的结构及中心金属的配位微环境对其表面光伏响应带的强度、位置和形状均有一定影响.     

以芳香族多羧酸为配体的Ni（Ⅱ）配位超分子的研制及光诱导下的表面电子行为

采用水热方法合成了2个Ni(Ⅱ)配合物[Ni3(btc)2(H3O)14]·4H2O(1)和[Ni2(btec)(bipy)2(H2O)6]·2H2O(2),(H2btc=1,3,5-benzenelxicarboxylic acid,H4btec=1,2,4,5-benzenetetracarboxylic acid,bipy=2,2'bipyridyl).通过X射线单晶衍射(XRD)、红外光谱(IR)、紫外-可见-近红外吸收光谱(UV-Vis-NIR)对化合物进行了表征.结果表明,化合物(1)是由2个均苯三甲酸根桥连的三核Ni(Ⅱ)离子的化合物,而化合物(2)是由1个均苯四甲酸根桥连的双核化合物,分子中bipy分子作为端基配体.分子中大量的水分子和羧酸根的存在使2个化合物分别被连成具有三维(3D)和二维(2D)结构的配位超分子化合物.着重研究了化合物的表面光电压光谱(SPS),并将其与UV-Vis-NIR吸收光谱进行了分析和对比,发现SPS中表面光伏响应带与UV-Vis-NIR吸收光谱的吸收峰在数量和位置上都是一一对应的.此外,对比2个化合物的表面光电压光谱可以看出,配合物的结构及中心金属的配位微环境对其表面光伏响应带的强度、位置和形状均有一定影响.     

两个含dmit配体的二核钨簇合物的合成,结构表征和电学性质

通过配体取代反应, 以W2S4(dtp)2 (dtp = S2P(OC2H5)2-)为起始物, 将它和(PhCO)2dmit(dmit = )及R4NBr (R = Et, Bu)反应, 首次获得两个二核钨化合物(Bu4N)2W2S4(dmit)2 (I)和(Et4N)2W2S4(dmit)2 (II). 并对这两个化合物进行了红外光谱表征, 测定了化合物(I)的13C NMR谱和晶体结构. 结构分析表明, 在化合物(I)的晶胞堆积中存在S(((S超分子相互作用. 对化合物(II)的变温电导率测定证实化合物(II)具有半导体导电性. 化合物(I)的结晶学参数为: 正交晶系, 空间群Pbcn, 晶胞参数a = 18.048 (5), b = 15.937 (5), c = 19.191 (6) ?, V = 5520 (5) ?3, Z = 4, R = 0.084, Rw = 0.090     

4-取代苯基-1,5-苯并硫氮杂-2-甲酸的合成及抑菌活性

合成了七元环的杂化合物2a~2k,并发现化合物2a~2k会向其同分异构体六元环内酰胺3a~3k转化.化合物2a~2k的结构通过红外光谱(IR)、核磁共振波谱(NMR)、质谱(MS)和元素分析确证.初步的抑菌活性测试结果表明,化合物2a~2k对白色念珠菌、标准新生隐球菌、临床新生隐球菌、大肠杆菌和枯草牙孢杆菌均有较好的抑菌活性,而六元环内酰胺3a~3k对所测菌种没有活性.实验还测定了部分混合物(2a~2e和3a~3e)的抑菌活性,结果表明化合物2a~2e和3a~3e混合物的抑真菌效果比单一的化合物2a~2e要好,化合物3a~3e的存在增强了化合物2a~2e的抑菌活性.     

[Co（bim）x]配合物修饰的｛P2Mo5O23｝超分子的合成、晶体结构和电化学性质

利用水热技术合成了一种新型[Co(bim)x]配合物修饰的磷钼多金属氧酸盐超分子化合物[Co(bim)3] [Co(Hbim)2( H2 O) P2 Mo5 O23]·5H2O.通过元素分析、红外光谱、热重分析和X射线单晶衍射对化合物进行了表征.化合物属于单斜晶系,P2(1)空间群;晶胞参数:a=11.505 (2) nm,b=19.123 (3) nm,c=13.852(2) nm,α=90.00°,β=100.073(2)°,γ=90.00°,V=3 000.6(8)nm3,F(000)=1 756.0,Z=2.并测试了合成化合物的电化学性质.     

Malfilamentoside A的构型确定与新呋喃糖苷类化合物Malfilamentoside D（英文）

基于高效液相色谱-二级阵列检测器(HPLC-DAD)追踪方法,从高原土壤来源真菌Auxarthronum brinum SCSIO 40432发酵产物中分离获得8个化合物,包括malfilamentoside A (1)、新的芳香呋喃酮糖苷类化合物malfilamentoside D(2)及6个已知化合物(3～8).通过1D、2DNMR确定了化合物的平面结构,首次通过X射线单晶衍射确定了malfilamentoside A (1)的绝对构型,比较化合物1和2的电子圆二色谱(ECD)谱确定了malfilamentoside D (2)的立体构型.化合物1对黄嘌呤氧化酶有弱的抑制活性.     

基于稳定的膦叶立德合成2(5H)-呋喃酮和2(5H)-吡咯酮作为细菌群体感应抑制剂的研究

利用稳定的乙酸乙酯基膦叶立德与含羰基化合物反应,合成了不同的2(5H)-呋喃酮,然后将获得的部分2(5H)-呋喃酮与醋酸铵反应转化为2(5H)-吡咯酮类化合物.所合成化合物均经1H NMR、13C NMR和MS等确认.通过测定所得到的化合物对于绿脓杆菌的最低抑菌浓度(MIC)来检验其抑菌活性;利用细莆生物膜染色实验来检测所得到的化合物对细菌群体感应系统和细菌生物膜的影响.活性实验结果表明,所得到的2(5H)-呋喃酮类化合物和2(5H)-吡咯酮类化合物均具有一定的抑制细菌群体感应的能力.     

含α-氨基酸的新型有机锗化合物的合成与生物活性研究

设计合成了两个系列20个含α-氨基酸的新型有机锗化合物, 对化合物进行了波谱表征, 用X射线衍射测定了化合物Ph3GeCH(Ph)CH2CONHCH(CH2COOC2H5)COOC2H5的晶体结构. 抗肿瘤实验结果表明, 这两个系列的化合物有一定的抗KB, HCT-8和Bel-7402活性.     

Activation of hepatic microsomal Ca2+-adenosine triphosphatase by calcium-binding protein regucalcin

The effect of regucalcin, a calcium-binding protein isolated from rat liver cytosol, on Ca2+-adenosine triphosphatase (ATPase) activity in hepatic microsomes was investigated. Mg2+-ATPase activity was clearly increased by the presence of 50 microM Ca2+. Regucalcin (1.0-4.0 microM) caused a remarkable elevation (about 3-fold) of Ca2+-ATPase activity. Also, Mg2+-ATPase activity was increased (about 1.6-fold) by the presence of regucalcin (2.0 and 4.0 microM). Guanosine-5'-O-(3-thiotriphosphate) (GTPrs; 10(-5) and 10(-4) M) and nicotinamide adenine dinucleotide phosphate oxidized form (NADP+; 10(-5) to 10(-3) M) or reduced form (NADPH; 10(-4) and 10(-3) M) significantly increased Ca2+-ATPase activity. These increases were not enhanced by the presence of regucalcin (2.0 microM). Of various metal ions, a comparatively low concentration of V5+ (10(-5) M) or Cd2+ (10(-6) M) significantly increased Ca2+-ATPase activity, while Hg2+, Zn2+, Cu2+ and Mn2+ did not have such an effect. Regucalcin (2.0 microM) did not enhance the effect of V5+ and Cd2+ on Ca2+-ATPase activity. The present finding, that regucalcin activates hepatic microsomal Ca2+-ATPase, suggests a cell physiological role of regucalcin as an activator in the microsomal Ca2+-pump activity. This action of regucalcin may not be influenced by other regulators.     

Isolation and structural determination of new sphingolipids and pharmacological activity of africanene and other metabolites from Sinularia leptoclados.

Two new sphingolipids, (2S,3S,4R)-1,3,4-trihydroxy-2-[((R)-2'-hydroxytetradecanoyl) amino] tricosane (4) and (2S,3S,4R)-1,3,4-triacetoxy-2-[((R)-2'-acetoxyoctadecanoyl) amino]octadecane (5) along with africanene (1, reasonably good yield), 23-demethylgargosterol (2) and batylalcohol (3) have been isolated from the soft coral Sinularia leptoclados. Preliminary studies for pharmacological activity (blind screening and toxicity studies) of africanene were conducted. Africanene exhibited in vitro and in vivo cytotoxicity, dose dependent hypotensive activity as well as antiinflammatory activity. The pharmacological and toxicity studies on africanene are being reported for the first time and findings strongly encourage further investigation. Compounds 1, 4 and 5 were studied for the antibacterial, antifungal and antiviral activity while compounds 4 and 5 were also studied for the short term in vitro cytotoxic activity.     

Intrinsic peroxidase-like activity and catalase-like activity of Co3O4 nanoparticles

We demonstrate that Co(3)O(4) nanoparticles (NPs) exhibit intrinsic peroxidase-like activity and catalase-like activity. The peroxidase-like activity of the Co(3)O(4) NPs originates from their ability of electron transfer between reducing substrates and H(2)O(2), not from ˙OH radical generated. As peroxidase mimetics, Co(3)O(4) NPs were used for colorimetric determination of H(2)O(2) and glucose.     

N－5－四唑基－N′－芳甲酰基脲的合成及其生物活性

合成了15个新的含四唑的基的芳甲酰基脲类化合物，用IR，^1H NMR和元素分 析证实了它们的结构，并进行了初步的生物活性试验，生测结果证明一些目标化合 物具有优良的植物生长调节活性，其中N－5－四唑基－N′－芳甲酰基脲（2h)和N －5－四唑基－N′－对溴苯基甲酰基脲（2j)具有很好的生长素活性，2h,2j和N－ 5－四唑基－N′－对甲基苯基甲酰基脲（2m）具有优良的细胞分裂素活性。     

二氧化铈-铈掺杂锰氧化物纳米复合物高效紫外-可见-红外光热催化净化乙酸乙酯

乙酸乙酯是一种重要的有机溶剂,广泛应用于涂料、粘合剂和塑料及石化等工业生产,但作为一种主要的挥发性有机污染物(VOCs),其对大气环境造成严重污染.目前工业上主要采用负载型贵金属催化剂催化燃烧的方法进行净化处理,但该方法存在催化剂价格昂贵和能耗高的问题,迫切需要开发活性高、稳定性好、成本低及能耗小的催化新方法和新材料....     

Solution combustion synthesis of Co oxide-based catalysts for phenol degradation in aqueous solution

Solution combustion using urea as a fuel was employed to synthesise Co oxide and Al(2)O(3)-, SiO(2)- and TiO(2)-supported Co oxide catalysts. The catalysts were characterised using several techniques such as N(2) adsorption/desorption, XRD, FTIR, UV-vis diffuse reflectance and SEM-EDX, and their catalytic activity was evaluated in phenol degradation in aqueous solution with sulphate radicals. Solution combustion is a simple and effective method in preparation of supported Co catalysts. Co(3)O(4) was the major Co crystal phase in the samples prepared via the combustion synthesis. Bulk Co(3)O(4) particles were not effective in reaction, but supported Co oxides showed higher activity than unsupported Co oxide. The supports influenced Co dispersion and catalytic activity. Co/TiO(2) exhibited the highest activity, but it deactivated much faster than other two supported catalysts. Co/SiO(2) showed a comparable activity to Co/Al(2)O(3) and the best stability among the three Al(2)O(3)-, SiO(2)- and TiO(2)-supported Co catalysts.     

制备参数对β-Mo2N0.78催化剂加氢脱硫活性影响的研究

以N2与H2的混合气为反应气，和三氧化钼进行多段程序升温反应，制得一种β晶型的氮化钼。以噻吩为模型化合物的常压加氢脱硫反应表明，β-Mo2N0.78具有较强的加氢脱硫活性和强的抗硫化性能。同时考察了预还原、反应温度以及氮化末温、升温速率、反应气中N2-H2比及氮化时间等制备参数对β-Mo2N0.78加氢脱硫活性的影响。研究发现，β-Mo2N0.78的加氢脱硫活性在320 ℃～400 ℃随反应温度的升高增强，而还原预处理会降低催化剂的活性。氮化末温、氮化时间、反应气组成和升温速率等制备参数对催化剂的活性有明显的影响：随着氮化末温的升高，所制备的催化剂催化加氢脱硫活性降低；在氮化末温恒温较长时间，可以引起制备催化剂的加氢脱硫活性下降；存在最佳的反应气组成和各段升温速率。小晶粒的β-Mo2N0.78具有强的加氢脱硫活性。     

Pt/Ce0.75Zr0.25O2的催化性能及其氧移动性的 18O 同位素交换表征

 采用浸渍法制备了Pt/Ce0.75Zr0.25O2催化剂,考察了催化剂对乙醇及CO的氧化活性,并采用 18O 同位素交换、乙醇程序升温表面反应(C2H5OH-TPSR)、一氧化碳程序升温脱附(CO-TPD)和程序升温还原(H2-TPR)等技术对催化剂进行了表征. 结果表明, Pt/Ce0.75Zr0.25O2催化剂表现出较高的乙醇和CO氧化活性,其催化活性随着Pt负载量的增加而提高. 当Pt负载量为3%时,活性最高. 继续增加Pt负载量,催化剂活性下降. C2H5OH-TPSR和CO-TPD结果表明,催化剂对乙醇或CO的氧化活性与从催化剂表面脱附出来的CO2量有对应关系, CO2脱附量越大,催化剂活性越高. 18O 同位素交换结果表明,表面氧交换能力与其氧化活性有一定对应关系,催化剂的表面氧交换能力越高,氧化活性越高.     

Pharmacological evaluation of some new 6-amino/methyl pyridine derivatives

In the present study, a series of 2-substituted-pyridines were synthesized and characterized by IR, (1)H-NMR and Elemental Analysis. The compounds were assayed against seizures induced by maximal electro shock (MES) and pentylenetetrazole (scMet). Neurologic deficit was evaluated by the rotarod test. The decrease in the elevated motor activity by introceptive chemical stimuli (amphetamine antagonistic activity) was studied at the dose level of 25 and 50 mg/kg, antihistaminic and cardiac activity were also studied. All the compounds exhibited significant anticonvulsant activity. Compounds 2-(2-hydroxy-3-piperazinopropylamino)-6-aminopyridine, 2-[2-hydroxy-3-(1-imidazolyl)propylamino]-6-aminopyridine, 2-[2-(1-imidazolyl)ethylamino]-6-methylpyridine and 2-[2-(methylamino)ethylamino]-6-methylpyridine were most active of the series against MES-induced seizures. Compounds 2-[2-(phenylamino)ethylamino]-6-aminopyridine, 2-[2-[bis(2-hydroxyethyl)amino]ethylamino]-6-aminopyridine, 2-[2-(diethylamino)ethylamino]-6-methylpyridine and 2-[2-hydroxy-3-(1-imidazolyl)propylamino]-6-methylpyridine exhibited significant decrease in the elevated motor activity at the dose of 50 mg/kg. Remarkable sympathetic blocking activity was observed with 2-(2-hydroxy-3-piperazinopropylamino)-6-aminopyridine, 2-(2-hydroxy-3-morpholinopropylamino)-6-methylpyridine and 2-(2-hydroxy-3-piperazinopropylamino)-6-methylpyridine only. Compounds 2-[2-(diethylamino)ethylamino]-6-aminopyridine, 2-[2-[bis(2-hydroxyethyl)amino]ethylamino]-6-aminopyridine, and 2-[2-(diethylamino)ethylamino]-6-methylpyridine exhibited significant blocking of histamine induced contraction on guinea pig ileum.     

Study on catalytic oxidation of planar binuclear copper phthalocyanine on 2-mercaptoethanol

Mononuclear copper phthalocyanine (CuPc) and binuclear copper phthalocyanine (Cu2Pc2) were synthesized by the phenylanhydride-urea route, and their catalytic oxidation activity on 2-mercaptoethanol was studied. Based on the experimental results, a catalytic mechanism of Cu2Pc2 on 2-mercaptoethanol has been proposed. Furthermore, the effects of pH, Cu2Pc2 concentration, and temperature on the catalytic oxidation activity were evaluated. The results showed that CuPc has no catalytic activity, while Cu2Pc2 has high catalytic oxidation activity towards 2-mercaptoethanol with the optimal activity at pH 11. The reaction can further be enhanced by increasing Cu2Pc2 concentration and temperature, due to its endothermic characteristics.