Synthesis and Structural Characterization of new Tri (2-methyl-2- phenylpropyl) tin Carboxylates containing Germanium

Organotincompoundsareextensivelystudiedfortheirbiologicalactivity'.Organogermaniumisanotherkindofelementthathasawiderangeofbiologicalactivity=.Tolinkbiologicalactivepropertiesoforganotinandorganogermaniumcompounds.wehavepreviouslyreportedthebiologicalactivityoftrialkyltingermylpropionates'andanticanceractivityofdibutyltindigermylpropionates'.ItiswellknownthatTorque(his[tri(2-methyl-2-phenylpropyl)tin]oxide)iswidelyusedinagricultureasanacaricide.Inthispaper,asthecontinuationofourpreviouswork"'…     

The Luminescence of The Phosphor Sr_2ZrO_4 with One-dimensional Chains Structure

IntroductionThenumberofzirconateswhichcanbeexcitedbyconventionalUVexcitation(X>240urn)issmall,sothatzirconateemissioniseasilyoverlooked.SomecompoundswhichabsorbcoventionalUVradiation.ig.ZrO,andBaZrO,(240urn)donotluminenceowingtoenergymigration=.Ontheotherhand,althoughseveralzircinatessuchasZrP,O,:.BaZrSi,O,'andSrZrSi=O,'showefficientUVzirconateemission(around300"m),theirexcitationwavelengthsareshorterthanusual(200"m).Moreover.theirluminescenceareatverylowtemperature(4.2K),whichlimits…     

四川地区宫颈癌组织HPV18和HPV45 E6基因突变分析

采用聚合酶链反应技术对四川地区2003~2004年收集的60例宫颈癌患者的癌组织DNA进行人乳头瘤病毒(HPV) E6基因扩增, 获得HPV18和45型E6基因. 序列分析发现, 18型三例E6基因有同样的两处同义突变; 45型两例E6基因发生突变, 一例有两处碱基突变, 另一例发生六处碱基突变, 其中两处涉及氨基酸变化, 均位于E6抗原决定簇区. HPV45型E6基因中134位c→t, 157位c→t, 259位g→t和341位t→c的碱基点突变未见报道. 另外， 该地区HPV18和45型突变株之间存在碱基互变,  它们之间的最小差异比野生型HPV18和HPV45之间的差异小4.05%, 该数值比在非洲发现的突变株的要小很多, 该结果支持HPV18和HPV45可能起源于非洲的观点.     

Detection of paracetamol by capillary electrophoresis with chemiluminescence detection

Indirect detection of paracetamol was accomplished using a capillary electrophoresis-chemiluminescence (CE-CL) detection system, which was based on its inhibitory effect on a luminol-potassium hexacyanoferrate(III) (K₃[Fe(CN)₆]) CL reaction. Paracetamol migrated in the separation capillary, where it mixed with luminol included in the running buffer. The separation capillary outlet was inserted into the reaction capillary to reach the detection window. A four-way plexiglass joint held the separation capillary and the reaction capillary in place. K₃[Fe(CN)₆] solution was siphoned into a tee and flowed down to the detection window. CL was observed at the tip of the separation capillary outlet. The CL reaction of K₃[Fe(CN)₆] oxidized luminol was employed to provide the high and constant background. Since paracetamol inhibits the CL reaction, an inverted paracetamol peak can be detected, and the degree of CL suppression is proportional to the paracetamol concentration. Maximum CL signal was observed with an electrophoretic buffer of 30 mM sodium borate (pH 9.4) containing 0.5 mM luminol and an oxidizer solution of 0.8 mM K₃[Fe(CN)₆] in 100 mM NaOH solution. Under the optimal conditions, a linear range from 6.6 × 10⁻¹⁰ to 6.6 × 10⁻⁸ M (r = 0.9999), and a detection limit of 5.6 × 10⁻¹⁰ M (signal-to-noise ratio = 3) for paracetamol were achieved. The relative standard deviation (R.S.D.) of the peak area for 5.0 × 10⁻⁹ M of paracetamol (n = 11) was 2.9%. The applicability of the method for the analysis of pharmaceutical and biological samples was examined.     

Structural study of gold clusters

Density functional theory (DFT) calculations were carried out to study gold clusters of up to 55 atoms. Between the linear and zigzag monoatomic Au nanowires, the zigzag nanowires were found to be more stable. Furthermore, the linear Au nanowires of up to 2 nm are formed by slightly stretched Au dimers. These suggest that a substantial Peierls distortion exists in those structures. Planar geometries of Au clusters were found to be the global minima till the cluster size of 13. A quantitative correlation is provided between various properties of Au clusters and the structure and size. The relative stability of selected clusters was also estimated by the Sutton-Chen potential, and the result disagrees with that obtained from the DFT calculations. This suggests that a modification of the Sutton-Chen potential has to be made, such as obtaining new parameters, in order to use it to search the global minima for bigger Au clusters.     

Theoretical study of properties of H bonds and intermolecular interactions in linear cis-,trans-cyclotriazane clusters (n = 2-8)

Our calculations based upon Becke's three-parameter functional of density-functional theory (DFT) with the correlation of Lee, Yang, and Parr (B3LYP), natural bond orbital, and atoms in molecule indicate that in drastic contrast to most H-bonded systems, the anticooperative and cooperative effects coexist in the linear H-bonded cis-,trans (c,t)-cyclotriazane clusters (n = 2-8). As cluster size increases, the properties along the H-bonded chains at trans-positions take on the unexpectedly anticooperative changes which are reflected in elongation of the N...H hydrogen bonds, frequency blueshift in the N-H stretching vibrations, decay in the n(N)-->sigma*(N-H) charge transfers, and weakening of strengths of the N...H bonds. And the cooperative changes in the corresponding properties for the cis- H-bonded chains are observed to be concurrent with the anticooperativities. The rise and fall in the n(N)-->sigma*(N-H) interactions cause increment and decrement in capacities of the clusters to concentrate electrons at the bond critical points of the N...H bonds, and thereby leading to the cooperative and the anticooperative changes especially in the N...H lengths and the N-H stretching frequencies. In terms of three-body symmetry-adapted perturbation theory (three-body SAPT), the first exchange nonadditivity plays a more important role in stabilizing trimer than the nonadditive induction. However, the dominance of the first exchange nonadditivity in three-body interaction unexpectedly triggers the anticooperative effect that counteracts the concurrent cooperative effect. According to the SAPT(DFT), which is a combination of SAPT with asymptotically corrected DFT, DFT/B3LYP is able to succeed in describing the electrostatic, exchange, and induction components, but fails to yield satisfactory interaction energies due to the fact that about 40% of short-range dispersion energy is neglected by the DFT, which is different from many H-bonded described well by the DFT. A quantum cluster equilibrium model illustrates that the c,t-cyclotriazane liquid phase exhibits a weak cooperative effect.     

Enthalpy change and mechanism of oxidation of o-phenylenediamine by hydrogen peroxide catalyzed by horseradish peroxidase

The hydrogen peroxide-oxidation of o-phenylenediamine (OPD) catalyzed by horseradish peroxidase (HRP) at 37 °C in 50 mM phosphate buffer (pH 7.0) was studied by calorimetry. The apparent molar reaction enthalpy with respect to OPD and hydrogen peroxide were −447 ± 8 kJ mol⁻¹ and −298 ± 9 kJ mol⁻¹, respectively. Oxidation of OPD by H₂O₂ catalyzed by HRP (1.25 nM) at pH 7.0 and 37 °C follows a ping-pong mechanism. The maximum rate V_max (0.91 ± 0.05 μM s⁻¹), Michaelis constant for OPD K_m,S (51 ± 3 μM), Michaelis constant for hydrogen peroxide Km,H₂O₂ (136 ± 8 μM), the catalytic constant k_cat (364 ± 18 s⁻¹) and the second-order rate constants k₊₁ = (2.7 ± 0.3) × 10⁶ M⁻¹ s⁻¹ and k₊₅ = (7.1 ± 0.8) × 10⁶ M⁻¹ s⁻¹ were obtained by the initial rate method.     

微囊藻毒素-LR免疫亲和层析柱的研制和应用

用CNBr-activated Sepharose4B和微囊藻毒素-LR的单克隆抗体制备了免疫亲和层析柱,测得抗体偶联率在75.7%~94.1%之间。制得的免疫亲和层析柱最大柱容量在76~95ng之间,柱空白为0,回收率在90.8%~105.1%之间。柱子再生重复使用6次后,回收率不低于75%。建立了免疫亲和层析柱-高效液相色谱测定水样中的微囊藻毒素-LR的方法。该法检出限为5ng/L;线性定量范围为10~500ng/L。实验结果显示,免疫亲和层析柱特异性好,一次净化能除去绝大部分干扰物,净化效果明显优于现有的固相萃取柱。     

4-乙酰基-1,3-二氟苯硝化反应机理研究

以4-氨基-1,3-二氟苯、乙酸酐和浓硝酸等为原料,合成了4-乙酰基-5-硝基-1,3-二氟苯,并且采用FTIR和1H NMR对产物进行了表征.采用量子化学方法,探讨了在酸催化条件下4-乙酰基-1,3-二氟苯硝化反应过程中的微观机理,在密度泛函理论的B3LYP/6-311G**水平下搜索得到反应路径,并对各中间体、过渡态和产物进行几何优化、振动频率分析和标准热力学函数计算;反应路径经过IRC验证.在MP2/6-311G**水平上对所有中间体、过渡态和产物进行更精确的能量计算.     

Synthesis of di-μ-oxo-tetra-(α-pentyloxy)tin(Ⅳ)phthalocynine

Axially substituted tin phthalocyanines, namely dichloride-tetra-(pentyloxy) tin (IV) phthalocyanine 3 and its dimmer di-cyanine 4 were synthesized. The catalytic effect of H2O-free CaCl2 in quinoline was used for condensation of dihydroxy tin phthalocyanine 3 to the cofacially array dimmer 4. Their structures were characterized by UV-vis, IR, elemental analysis, MS, as well as 1HNMR spectroscopy.