Synthesis and characterization of two new types of oxovanadium complexes with pyrazole as ligand

Coordination chemistry of pyrazole-base ligands has been extensively studied since the poly(pyrazole)borate was invented by Trofimenko in 1966[1―4]. A variety of bidentate or multidentate pyrazole-derived ligands have been employed in coordination chemis…     

Hydrothermal synthesis and characterization of new hybrid open-framework indium phosphate-oxalates

Crystalline open-framework inorganic materials have been widely studied because of the wide variety of the structures as well as their applications in heterogeneous catalysis, adsorption and ion exchange[1,2]. Of many open-framework solids, metal phosphates are an important family of materials, a large number of aluminum phos-phates[3,4], gallium phosphates[5—7], zinc phosphates[8—10], cobalt phosphate[11], beryllium phosphates[12—14] have been prepared and characterized. Recently, open-fra…     

K4Sn3Se8的固相合成、晶体结构和反射光谱研究

采用反应性熔盐法，通过中温固相反应在500℃下合成晶体K₄Sn₃Se₈。该晶体属正交晶系，空间群Ccca，晶胞参数：a=0.82115(6)nm，b=2.7790(2)nm，c=0.81865(6)nm，V=1.8682(2)nm³，Z=4。K₄Sn₃Se₈由[Sn₃Se₈]₄三聚体负离子和K⁺正离子组成。漫反射光谱研究表明该材料能隙(Eg)为2.6eV，属于半导体，对太阳能具有选择吸收的特性。     

Crystal structure, magnetic and photoelectric properties of coordination polymer[ Co2（C3H4N2）4（ C10H2O8） ]n

The coordination polymer is designed and synthe-sized through the choice of organic ligand and coordina-tion geometry of metal ion as well as the control over theinfinite network topology structure, which usually con-tains both the characteristic of the organic molecules andmetal ions. So, it exhibits more singular function and haspotential application in optics, electrics, information, ca-talysis, medicament, metallurgy, novel material and lifesciences fields. And it has been the confluence m…     

Spectrofluorimetric determination of artemisinin with pyronine B as the substrate for horseradish peroxidase

Enzyme-catalytic fluorescence determination of artemisinin （qinghaosu, QHS） was developed using pyronine B （PB） as substrate of horseradish peroxidase （HRP）. The interaction between HRP and QHS was an enzyme-substrate model. The catalytic characteristic of HRP in the oxidation reaction, in which the fluorescence of PB was decreased in the presence of QHS, was studied. The steady-state catalytic rate depended upon enzyme and substrate concentrations, and the Michaelis-Menten parameters Km, Vmax and Kcat were 8.4×10^-5mol·L^-1, 7.4×10^-6mol·L^-1s^-1 and 50.23s^-1. The catalytic activity of enzyme was inhibited in the presence of deactivated agents and at high temperature, respectively. Under optimum conditions, linear relationship between fluorescence intensity change （F0-F） of pyronine B and concen- tration of QHS was in the range of 1.41×10^-7-1.27×10^-6mol·L^-1. The detection limit （3σ） was determined to be 2.7×10^-8mol·L^-1. The proposed method was applied to the concentration determination of QHS in the media of plasma or urine samples.     

Structure and magnetic properties of vacuum annealed FePt/Ag nano-multilayers

The hard disk driver (HDD) technology has been loping quickly for recent years. An aerial density of 2 has been demonstrated by Fujitsu and Seagate espectively. To further improve the recording density, the ic effect will be a serious problem tropy of a- alloy thin films in the ordered 0 phase exhibit a perpendicular magnetic anisotropy Ku of the order of 106 J/m3 at room tempera-[1,2] and is very attractive for future high density mag- In the FePt (L10) phase, Fe and Pt atomic c axis, w…     

正相伴序列的矩完全收敛性

设 Xn;n≥1是一均值为0、方差有限的正相伴平稳序列.记Sn= Xk,Mn= |Sk|,n≥1.证明了在一定条件下,由E|X1|p(|X1|(1/α))∞可推出对任意的ε0,有 npα-2-αh(n)EMn-εn(1/p)+∞,其中h(n)为一在无穷处的缓变函数,x+=maxx,0.       

Special IR properties of palladium nanoparticles and their aggregations in CO molecular probe infrared spectroscopy

Dispersed Pd nanoparticles (Pdn) have been synthesized by reducing H2PdCI4 with ethanol, and stabilized using poly(vinylpyrrolidone) (PVP). The Pdn is applied to the glassy carbon substrate to form a thin film, and then the potential cyclic scanning at 50 mV.s^-1 from -0.25 to 1.25 V was carried out for about 30 min to form the aggregations of Pdn (Pdn^ag). FTIR spectroscopy of both transmission and reflection modes was employed to study CO adsorption on Pdn and Pdn^ag in both solidlliquid and solidlgas interfaces. It has been revealed that CO adsorption on Pdn film yields two IRbands near 1964 and 1906 cm-1, which are assigned to IR absorption of CO bonded on asymmetric and symmetric bridge sites, respectively. In contrast to the IR properties of CO adsorbed on Pdn, only species of CO bonded on asymmetric bridge sites was determined on Pdn^ag, and the direction of the IR band near 1963 cm^-1 is completely inverted. The full width at half-maximum (FWHM) of the COB^as band near 1964 cm^-1 is measured to be 14 cm^-1 on Pdn film, while it is 24 cm^-1 on Pdn^ag film. The results of the present study demonstrated that the inverting of the IR band direction is a general phenomenon that is closely related to the interaction between nanoparticles in aggregation of Pdn.     

盐酸介质中油酸钠在钢表面的吸附及缓蚀作用

 用失重法和动电位极化曲线法研究了阴离子表面活性剂油酸钠(SO)对冷轧钢在1.0mol/LHCl介质中的缓蚀作用.结果表明:油酸钠对冷轧钢具有良好的缓蚀作用,为混合抑制型缓蚀剂,缓蚀率随油酸钠的质量浓度增加而增大;油酸钠在钢表面的吸附符合校正的Langmuir吸附模型.通过吸附理论和动力学Arrhenius公式分别求出了相应的吸附热力学参数(吸附自由能ΔG⁰,吸附热ΔH⁰,吸附熵ΔS⁰)和动力学参数表观活化能E_a,并根据这些参数详细讨论了缓蚀作用机理.     

Dawson结构多金属含氧酸盐热解性质研究(英)

用变温XRD,变温IR以及TG-DTA等方法,系统地研究了具有Dawson结构的Y_mH_nP₂M₁₈O₆₂&;#8226;qH₂O（Y=K⁺, NH⁴⁺, Cu²⁺;M=Mo,W）的热解性质,获得了它们较为精确的热分解温度,对其热分解的判断方法提出了一些新的见解.结果表明,以钼为配位原子的Dawson结构钾盐,铵盐,铜盐分别在250 ℃, 210 ℃, 240 ℃ 发生了热重排,生成了具有Keggin结构的化合物.以钨为配位原子的钾盐在410 ℃也有相似的行为,但铵盐和铜盐却没有观察到类似的热重排现象,分别在400 ℃, 450 ℃直接热分解为WO₃.这些结果显示,热重排现象的发生可能与相应的Keggin结构化合物的热稳定性有关.     

H+2基态近似解析波函数对振动能级影响的研究

具体考察了H^+₂基态近似解析波函数φH^+₂=1/2(1+S)^1/2φH(z,r_a)+φ_H(z,r_b))对振动能级的影响,得到了基于此波函数的波恩-奥本海默近似下的H^+₂势能曲线的解析表达式,并由此计算了振动能.结果发现,当仅考虑H^+₂的基态,z取1.23时,振动能级和平衡位置都与实验值很相符.当考虑较高的振动能级时,波函数中的z取1.13会更合理,因此时的振动能级和实际振动能级值符合得很好.     

Effect of total aluminum concentration on the formation and transformation of nanosized Al13 and Al30 in hydrolytic polymeric aluminum aqueous solutions

Influence of total aluminum concentration （CAIT） on the generation and transformation of nanosized AI13 and AI30 in hydrolytic polyaluminum aqueous solutions was investigated using high field 27AI NMR and time-developed AI-Ferron complex colorimetry. When prepared at the optimal basicity （B） of Al13 generation and 80℃, the All3 species in polyaluminum solution tends to further polymerize and convert to AI30 and higher polymers when CAI; 〉0.2 mol· L^-1, but Al13 does not convert to AI30 quantificationally, as the formation of Alu from Al13 and AI30 is accelerated in the same way. The conversion rate of All3 is accelerated by the increase in CAIT. When CAlT 〉0.75 mol·.L^-1, Al13 content decreases rapidly, and AI30 content increases continuously and becomes the dominant nanometer polynuclear aluminum species. AIm is one of prerequisites of Al13 conversion to AI30. When CAI; increases and B reduces, the polymerization rate between Al13 and Aim increases, and at the same time, the dissociation reaction rate of All3 and AI30 by H^＋ also increases. The latter becomes the dominant reaction in polyaluminum solution with low B value, so AI30 decreases with the increasing CAlT. The hydrolytic polyaluminum solution with Al13 content beyond 80% can only be prepared under the condition of CAlT〈0.5 mol· L^-1 and optimal B value.     

表达胰岛素的毕赤酵母生长动力学及诱导策略

对本实验室构建的一株重组巴斯德毕赤酵母基因工程菌的生长及诱导进行了研究,结果表明生长阶段菌体的生长与限制性基质甘油残留浓度的关系符合Monod关系式,细胞最大生长比速率为0.204h^-1,饱和常数为24.3g/L。经参数推导得理论最大细胞对甘油得率为0.497g/g,以及菌体生长维持系数为0.007g/g·h,后者说明此株工程菌有高密度发酵的潜力。诱导阶段补加酵母提取物、大豆蛋白胨和微量元素能有效提高目的蛋白产量。在发酵罐上罐试验中,目的蛋白产量达256mg/L,蛋白产量是摇瓶发酵蛋白产量的5倍多。     

Synthesis and characterization of organometallic macrocyclic rhodium (Ⅲ) complex with pyrazine ligands

The synthesis and structure research of organometal-lic macrocyclic complexes has been a very active field of modern chemistry [1—3]. In this field, Pd2+, Pt2+ complexes were first used as the building block, connected by het-erocyclic ligands, to construct metal macrocyclic com-pound[4,5]. The fac-Re(CO)5X (X = Cl, Br) fragment, for example, was shown to be a versatile building block for the synthesis of metallamacrocycles[6]. Some of this kind of molecule have been found applications in…     

有限集合上封闭集族的计数

设集合X={a1,a2,a3,…,an},f(n,m)表示X的含m个元素的不同封闭集族的数目。证明了f(n,m)={3n-2n,m=2;4n-2.3n+2n,m=3;5n-25.4n+2.3n-2n-1,m=4;6n-3.5n+3.4n-3n,m=5其中n=1,2,3,…。     

K2CuIn3Se6的固相合成、晶体结构和性能

采用反应性熔盐法以n(K₂Se₃ )∶n(Cu)∶n(In)∶n(Se) =2∶2∶1∶6的摩尔比,在773K下反应5d,得到四元金属硒化物K₂CuIn₃Se₆。该晶体属于单斜晶系,空间群为C2/c ,晶胞参数a =1 .1484(2)nm,b =1.1458(2)nm,c =2.1327(4)nm,β =97.81(3)^o,V=2.7802(1)nm³,Z=8.K₂CuIn₃Se₆具有层状结构,含有二维共价结构的负离子,²∞[CuIn₃Se₆]^2-.²∞ [CuIn₃Se₆]^2-由配位四面体[CuSe₄]和[InSe₄]共顶点连接而成。²∞[CuIn₃Se₆]^2-和K+ 以静电力堆积成晶体。漫反射光谱研究表明,该晶体具有1.6eV的光学能隙,属于半导体,对太阳能有选择吸收的特性。     

Synthesis and crystal structure of the trimetallic erbium tetrahydride complex [Li(THF)4][{(ButCp)2Er(μ-H)} 3-(μ3-H)]

Reaction of [(Bu′tCp)2Er(μ-CI)]2 with Bu′Li in 1:1 molar ratio in THF at -78℃, after work-up, afforded the trimetallic erbium tetrahydride complex [Li(THF)4][{(Bu′Cp)2Er(μ-H)}3(μ3-H)] (1) by β-hydrogen elimination reaction. Crystal structure determination reveals that complex 1 has discrete ion pair structure. The anion is composed of three (Bu′Cp)2Er units to form a triangle array connected by three bridged hydrogen atoms, and the fourth hydrogen atom coordinated to three Er^3 ions. The coordination num-ber for each Er^3 ion is 9.     

Degradation of organic matter in the sediments of Hongfeng Reservoir

In this work, the distribution of organic carbon, DNA and lipids in the sediments of Hongfeng Reservoir were described in addition to SO4^2- profile in pore water. The contents of organic carbon in the sediments range from 23.3 to 76.8 mg·g^-1, with the peak value appearing at the depth of 8 cm bellow the sediments water interface （SWI）, and tend to decrease gradually with sedimentation depth. The concentrations of SO4^2- decreased from 40.50 mg·L^-1 to 12.00 mg·L^-1 at SWI in top 4 cm sediment, and was kept at 12.0 mg·L^-1 bellow that depth. Newly produced organic carbon can be conserved as long as 14 years in the sediments. The contents of DNA were relatively high in top 9 cm surface sediments, as revealed by agarose gel images, close to those of organic carbon and sulphate reduction index （SRI）. This study shows that bacteria played an important role in organic matter degradation; SO4^2- is the primary electron acceptor under anaerobic condition in this reservoir; DNA in the lake sediments can provide important information for the study of cycling of nutrient elements in the lake.     

Permeation of vanadium（Ⅲ, Ⅳ, Ⅴ）-dipicolinate complexes across MDCK cell monolayer and comparison with Caco-2 cells

The permeation and eytotoxicity of three insulin-mimetic vanadium（Ⅲ, Ⅳ, Ⅴ）-dipicolinate complexes were studied using the MDCK cell monolayer in comparison with the Caeo-2 cells. On MDCK cell monolayer, the apparent permeation coefficients （Papp） were estimated to be （7.5±1.0）×10^-6, （1.0±0.2）×10^-6, （1.7±0.4）× 10^-6cm/s for V（Ⅴ）, V（Ⅵ）, and V（Ⅲ）-dipie complexes, respectively. The permeability of V（Ⅴ）-dipie complexes is much better than the others, which is in agreement with its better hypoglycemie effect in animal tests. On Caeo-2 cell monolayer, Papp were found to be in the range of 1-3×10^-6 ends and not to be affected by excessive amounts of dipieolinate ligand. By contrast, the permeability in the AP→BL direction across the MDCK monolayer increased greatly in the presence of free ligands, suggesting existence of active transport mechanism of vanadium complex anions on the MDCK cells. The eytotoxieity of the three complexes was found similar and the IC50 were measured in the range of 0.6-0.9 mmol/L for MDCK cells and 1.6--2 mmol/L for Caco-2 cells. The cytotoxicity of three vanadium complexes was conceivably in consistence with their permeability, suggesting that the toxicity, permeation and cellular metabolism of vanadium complexes are closely related.     

Density functional theory study of proton transfer in carbonic anhydrase

Proton transfer in carbonic anhydrase Ⅱ has been studied at the B3LYP/6-31G（D） level. The active site model consists of the zinc ion, four histidine residues, two threonine residues, and three water molecules. Our calculations showed that the proton of the zinc-bound water molecule could be transferred to the nearest water molecule and an intermediate containing H3O^＋ is then formed. The intermediate is only 1.3 kJ·mol^-1 above the reactant complex, whereas the barrier height for the proton transfer is about 8.1 kJ·mol^-1.