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.     

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.     

The 4700 aB.P. volcanic signal detected in Vostok BH8 ice core, Antarctica

The detailed electrical conductivity measuremerit （ECM）, trace chemical compositions and microparticles concentration analysis are performed for BH8 ice core from the depth of 126.0m to 130.0m at Vostok Station. At depth 128.7m, a volcanic signal 4726 a B.P. is detected. The volcanic sulphate flux is 95.8 kg·km^-2, sulphate peak concentration 1352.8 ng·g^-1, duration time about 10.1 years, comparable with some well-known volcanic events. The results indicate that it seems to be a relatively large scale, long lasting volcanic signal with farther volcanic origin.     

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.     

α-硫辛酸和二氢硫辛酸的抗氧化作用

采用多种化学发光体系和比色体系研究了氧化型硫辛酸——α-硫辛酸（α-lipoic acid, LA）和还原型硫辛酸——二氢硫辛酸（dihydrolipoic acid, DHLA）直接清除活性氧、抗脂质过氧化以及对&;#8226;OH引起的DNA氧化损伤的保护作用.实验发现，LA和DHLA能有效清除相应体系中的活性氧过氧化氢（H₂O₂）、羟自由基（&;#8226;OH）、过氧亚硝基阴离子（ONOO^-）和二苯代苦味肼基自由基（DPPH&;#8226; ），能显著抑制脂质过氧化，并对&;#8226;OH引起的DNA氧化损伤有良好的保护作用，而DHLA还可以有效清除超氧阴离子自由基（O&;#8226;₂^-）.这些结果提示，LA和DHLA都是良好的抗氧化剂，但相比之下DHLA的抗氧化能力要显著强于LA.本研究为LA和DHLA保健和药用价值的进一步开发，提供了自由基生物学方面的依据.     

农田氮素非点源污染模型及年负荷估算研究

研究了农田中氮素随径流动力输出的过程，并依据径流特征和农田氮肥施用情况，将全年区分为水田施肥期、水田生长期和非水田期.按试验时的天气条件，分别采用人工模拟降雨或农田实测降雨的资料，分析农田非点源污染回归模型.水田施肥期采用人工模拟集中降雨情形，降雨强度为2 mm&;#8226;min^-1，模型氮素浓度范围为28~45 mg&;#8226;L^-1；水田生长期和非水田期采用天然降雨，降雨强度为0.037 6~0.075 1 mm&;#8226;min^-1，模型氮素浓度为0.2~4.0 mg&;#8226;L^-1.在分析长系列降雨资料的基础上，综合运用修正SCS（Soil Conservation Service）法、单位线法和相关分析法，估算得到农田径流过程排放的氮素量，再加上地下水渗漏流失的氮素量，取得上海地区一般降水年份农田的氮素非点源污染年负荷量为26.5 kg&;#8226;ha^-1.     

Synthesis of layered LiMnO2 by in situ oxidationintercalation and a study of the reaction mechanism and electrochemical performance

Lithium-ion batteries have become the main candi-date for rechargeable power sources in current electronicproducts because of their high open circuit voltage, highenergy density, longevity and absence of memory effect.Layered LiCoO2 has been used commerci…     

缺位磷钨杂多阴离子PW11O7-39电催化降解邻苯二甲酸二甲酯

 以Keggin型缺位磷钨杂多阴离子PW₁₁O^7-₃₉(PW₁₁)为电催化剂,邻苯二甲酸二甲酯(DMP)为模型污染物,详细研究了PW₁₁对DMP降解的电催化作用。实验结果表明,在pH=2.5,E=-0.6 V和60 mL·min^-1O₂流速下,0.05 mmol·L^-1DMP反应120 min的降解率达96%,总有机碳(TOC)去除约34%。DMP的电催化降解服从准一级反应动力学模型,准一级表观速率常数(k obs)与DMP的初始浓度有关, 当DMP的初始浓度为0.05, 0.2 和0.3 mmol·L^-1时,kobs分别为2.9×10^-2, 7.5×10^-3和4.9×10^-3min^-1。     

Fluorescence study on the interaction between apoCopC and cupric

The interaction between apoCopC and cupric was investigated by fluorescence spectra, in phosphate （20 mmol/L） buffer at pH 6.0. Results suggest that the environment is measured to be hydrophobic completely around tryptophan （83）. At the same time, apoCopC fluorescence at 320 nm was significantly quenched with the addition of cupric and the 1：1 stoichiometric ratio of apoCopC to cupric was confirmed by fluorescence. In addition, the conditional binding constants were calculated to be Kcu-copc=（1.8±0.58）×10^13 mol^-1 L on the basis of the results of fluorescence titration curves. The apoCopC has the ability to bind specifically cupric ion.     

时标上三阶非线性p-Laplacian三点边值问题的正解

 研究了时标上三阶非线性p-Laplacian三点边值问题［Φ_p(p(t)u ^Δ∆ (t))］^Δ+a(t)f(t,u(t))=0,t∈［0,T］,βu(0)－γu^Δ(0)=0,u^Δ(T)=αu(η),u ^Δ∆(0)=0借助于锥上的五泛函不动点定理,得到了边值问题至少有三个正解的一些新的结果,同时给出了例子验证了主要结果。     

谷氨酰胺转胺酶发酵培养基的响应面分析优化

利用SAS（Statistical Analysis System）软件中二水平设计的Plackett-Burman设计和响应面分析法（Response Surface Analysis，简称RSA），研究了链霉菌（Streptomyces sp.）HS-1摇瓶发酵生产谷氨酰胺转胺酶的发酵培养基.通过二水平设计实验考察了八种因素对发酵生产谷氨酰胺转胺酶的影响，利用极差分析确定其中以豆饼粉水解物、甘油以及硫酸铵为影响链霉菌发酵生产谷氨酰胺转胺酶的重要因素.通过响应面分析法建立了这三个重要因素的二次回归模型，应用规范分析找到最优点，分别为豆饼粉水解物24.0 g &;#8226; L^-1，甘油24.4 g &;#8226; L^-1，硫酸铵5.40g &;#8226; L^-1.摇瓶实验表明，应用优化培养基谷氨酰胺转胺酶酶活由6.27 μ &;#8226; mL^-1提高到7.30μ &;#8226;mL^-1，提高了16.4%.     

[Zn(bim)2]·(H2O)1.67: A metal-organic open-framework with sodalite topology

Considerable efforts have been focused on the crystal engineering of the supramolecular architectures with desired properties such as zeolitic, magnetic and electric conducting materials[1—3]. But crystal engineering is still a great challenge to the chemists since lack of control over the coordination modes of metal centers and ligands during assembly of extended structures[4]. Some successful synthetic strategies based on topologic control of building blocks have been developed especially i…     

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.     

盐酸环丙沙星在不同模拟水体中的降解与残留

 通过反相高效液相色谱法研究在不同模拟水体中,溶液质量浓度、pH对盐酸环丙沙星（CPFX）在水和底泥中含量变化的影响,分析其在模拟水体中降解和残留规律。研究结果表明：在1、5、10 mg·L^-1三个CPFX溶液质量浓度中,光降解度最高的溶液质量浓度为1 mg·L^-1,自然光照下,72 h后盐酸环丙沙星在有底泥和无底泥的水体中残留率分别为19 %和20 %,光降解率与初始质量浓度成反比。在pH分别为3、5、9、11条件下,pH=9的微碱性环境下最易光降解,而当pH=3时其光稳定性最佳,48 h后水体残留率分别为22.6 %和95.7 %。盐酸环丙沙星进入模拟水生态系统后,水体中CPFX质量浓度迅速下降,45 d后检测不到它的存在;底泥中CPFX质量分数迅速上升,之后缓慢下降,45 d后底泥中仍有一定残留量,达到93.86 μg·kg^-1。     

Theoretical study on magneto-structural correlation of trinuclear copper （II） complex with the hydroxo bridge and bidentate syn-syn carboxylate group

During the past decade, molecular magnetism has received much attention both experimentally and theo- retically. Especially, the study of magneto-structure correlation attracts a continuous interest due to its fun-damental role in the design of molecular-…     

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…     

产环己酰亚胺新菌株YIM41004种子培养基优化研究初报

 对产环己酰亚胺新菌株Streptomyces yunnanensis YIM41004的摇瓶种子培养基进行了优化,获得最佳配方为葡萄糖25 g,蛋白胨7.5 g,酵母膏7.5 g,CaCO₃3 g,MgSO₄.7H₂O 1 g,MnSO₄.4H₂O 0.1 g,KH₂PO₄0.2 g,水1 000 mL;最佳培养条件为起始pH7.8,500mL种子瓶装量100mL,最佳种龄32~36 h.用优化后的种子培养基培养种子用于摇瓶发酵,结果表明在接种量为10%体积分数时,环己酰亚胺产量达到最高,为498.9 mg.L^-1,比用原始种子培养基时的产量450 mg.L^-1高出10.7%.     

Novel photocatalysis oxidation system UV/Fe^2＋/air to degrade 4-CP wastewater

This paper reported the degradation of 4-CP wastewater by a novel photocatalysis oxidation system-- UV/Fe^2＋/air system, in which air was used as a cheap oxidant that reacted with the excitation state of organics to form H2O2 under the UV light. The formed H2O2 reacted with the added ferrous ion to form Fenton reaction and led to the quick degradation of organic pollutants. It was found that 4-CP could be completely removed within 40 min. The degradation of 4-CP in the UV/Fe^2＋/air system was superior to the conventional UV/Fenton system （the initial concentration of H2O2 was 22 mg·L^-1）. UV/Fe^2＋/air is an effective and cheap method for treatment of the organics that can be excited by UV light.     

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…     

高氯酸银-苯配合物结构的重新测定和从头计算

在低温下对高氯酸银-苯配合物AgClO₄&;#8226;C₆H₆的晶体结构进行了重新测定，晶体属斜方晶系，空间群Cmcm（#63）.晶胞参数：a=8.154 0(6)×10^-10 m， b=7.918(4)×10^-10 m， c=11.717(1)×10^-10 m，V=756.4(4)×10-³⁰m³, Z = 4, 精度偏离因子R=0.023, Rw =0.050.根据该配合物晶体结构特征和从头计算的研究结果, 与前人报道的结构数据进行了对比, 指出两次测定在结构上的差异.据此, 提出了目前在中外教科书中有关苯在与银离子配位时发生严重变形的描述有待更正的必要性.