Cu(Ⅱ)、Zn(Ⅱ)Schiff碱配合物的合成及其光热性质

用5-硝基水杨醛与色氨酸缩合制备了一种Schiff碱配体,将其与过渡金属Cu(Ⅱ)、Zn(Ⅱ)进行作用合成出两种新型的配合物.采用元素分析、差热-热重、IR、UV、摩尔电导率等对配体和配合物进行了表征,并测定了化合物的荧光性质和对超氧离子的催化歧化作用.     

DFT Study on Some Properties of Polybrominated Phenoxathiin 10-Oxides

With the B3LYP calculation method of density functional theory(DFT)and the 6-31G* basis set,full optimization calculation was made for phenoxathiin10-oxide(PTO)and 135 polybromine phenoxathiin 10-oxides(PBPTOs)with the Gaussian 03 program and molar heat capacity in constant volume(CVθ)value of each molecule in the standard state was obtained.The relation between CVθ and the substitution position and number of bromine atom(NPBS)was studied,and the results indicated good correlation(R2 = 1.000)between CVθ and NPBS of PBPTO compounds.Based on the output file of Gaussian 03 program,molar heat capacity at constant pressure(Cp,m)of PBPTO compounds from 200 to 1,000 K was calculated with the statistical thermodynamics program,and the correlation equation between Cp,m and temperature(T,T-1 and T-2)was obtained with the least-squares method,and the correlation coefficient of the correlation equation(R2)was 1.000.In addition,based on the partition function of each molecule calculated by vibration analysis,the relative rate constant of formation of each molecule was calculated.     

How Many Methanol Molecules Can Solvate a Glycine: a PBE1PBE Approach

Microsolvation of glycine in methanol clusters is explored by the use of DFT calculation method. The lowest energy conformations within 16.72 kJ·mol-1 of the glycine clustering with one to six methanol molecules, which are obtained at the B3LYP/6-31+G(d) level of theory, are reoptimized at PBE1PBE/6-311+G(d,p). The calculated results agree with our previous results with B3LYP (Chin. J. Chem. Phys. 22 (2009) 577) that the clusters of two forms (Z-and N-form) tend to be isoenergetic when the number of the solvate molecules reaches six. Furthermore, this result is in good agreement with the experiment of the tryptophan-methanol clusters, implying that the present treatments are reasonable and reliable. The results also indicate that nine methanol molecules are not enough to fully solvate a glycine molecule, and a tentative estimation is obtained that ten methanol molecules may fully solvate a glycine molecule, which consists with the experiment results.     

Synthesis and Crystal Structure of 2-Oxo-3-phenyl-1-oxaspiro[4.5]dec-3-en-4-yl 4-chlorobenzoate

The title compound 2-oxo-3-phenyl-1-oxaspiro[4.5]dec-3-en-4-yl 4-chloro-benzoate 6 (C22H19ClO4, Mr = 382.82) has been synthesized by the condensation reaction of 4-hydroxy-3-phenyl-1-oxaspiro[4.5]dec-3-en-2-one 5 with 4-chlorobenzoyl chloride, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/n with a = 10.6749(11), b = 6.0573(7), c = 29.680(2) , β = 94.073(3)o, V = 1914.3(3) 3, Z = 4, Dc = 1.328 g/cm3, F(000) = 800, μ = 0.224 mm–1, S = 1.003, the final R = 0.0605 and wR = 0.1500 for 1828 observed reflections with I > 2σ(I) and 244 variable parameters. The crystal analysis shows that the molecular structure of the title compound has one planar furan ring, one chair conformation cyclohexane ring and two benzene rings. The furan and cyclohexane rings adopt whorl conformations.     

双功能交联分子对生物大分子DNA磷酸骨架的修饰

利用DNA分子在水溶液中解离出的阴离子通过亲核取代反应亲核进攻重氮基乙酸叔丁酯的易离去基团重氮基来完成对DNA磷酸骨架的修饰。我们用NMR(31P)与琼脂糖凝胶电泳对结果进行表征,结果表明,DNA磷酸骨架上部分磷原子的羟基被重氮基乙酸叔丁酯修饰。     

冷原子荧光光谱法测定南宁市邕江支流水域中无机汞和总汞

采用氢化物发生-冷原子荧光光谱法,测定了南宁邕江支流水域中无机汞和总汞.实验结果表明,南宁邕江支流水域中汞含量均小于国家规定的地表水Ⅰ类水域的标准,水质良好.同时对样品的测量检出限及方法回收率进行实验,结果表明在优化的实验条件下检出限为0.021 ng/L,相对标准偏差为2.24％,无机汞和总汞的加标回收率分别为90....     

ABTT浊点萃取分光光度法测定水样中镉

利用非离子表面活性剂Triton X-114在温度高于其浊点时形成相分离行为,建立了浊点萃取-分光光度法测定水样中痕量镉的新方法,优化了以1-偶氮苯-3-噻唑-三氮烯(ABTT)为显色剂,Triton X-114浊点萃取富集痕量镉的实验条件.在最大吸收波长λ=520 nm,其表观摩尔吸光系数为6.84×105L·mol...     

固相萃取-高效液相色谱/串联质谱检测谷物中黄曲霉毒素B1、B2、G1、G2和M1

建立了高效液相色谱/串联质谱(LC-MS/MS)同时检测谷物中的黄曲霉毒素B1、B2、G1、G2和M1的方法.并优化了液相色谱条件和质谱的相关参数.谷物样品经研磨成粉末后,直接经甲醇-水( V∶V=10∶90)提取,Oasis HLB固相萃取净化,乙腈-水(0.2％甲酸)梯度洗脱,选择电喷雾离子源(ESI),正离子扫描...     

表面分子印迹磁性固相萃取-液相色谱-荧光光谱法测定河水中双酚A

通过原子转移自由基聚合(Atom Transfer Radical Polymerization-ATRP)法制备核壳结构单分散性磁性亚微米粒子( Fe304@ MIPs),并建立了磁性固相萃取-高效液相色谱荧光光谱(MSPE- HPLC - FLD)测定河水中环境类雌激素 双酚A (BPA)的方法.利用透射...     

气相色谱法同时测定合成ABL反应液中原料、中间体及产品

建立了以己酸乙酯为内标物,同时测定α-乙酰基-γ-丁内酯(ABL)、γ-丁内酯(GBL)和α-(2-四氢呋喃亚基)-γ-丁内酯(AGBL)含量的气相色谱分析方法.并在GBL和乙酸乙酯为原料生产ABL的过程中得到应用.结果表明:ABL、GBL和AGBL浓度分别在0～ 30.13g/L、0～ 15.08g/L和0～9.06...