4-氨基安替比林紫外分光光度法测定肉与肉制品中亚硝酸根

亚硝酸根是含氮化合物分解过程中的中间产物,其分解的亚硝基极易与肌红蛋白反应生成具有致癌作用的亚硝基肌红蛋白,从而对人体造成危害,是肉与肉制品中必检测的指标之一.亚硝酸根测定方法,文献报道的方法有国标法[1]、动力学分光光度法[2]、荧光分析法[3]等.本研究发现在盐酸介质中,亚硝酸盐和4-氨基安替比林反应,反应产物溶液在310 nm波长处有特征紫外吸收,据此建立测定亚硝酸根的方法.方法应用于肉与肉制品中亚硝酸根的测定,操作简便,结果满意可靠.     

酪氨酸作试剂荧光光度法测定亚硝酸根

亚硝酸盐广泛存在于土壤、食品及天然水中 ,是水体中氮循环的重要中间物。亚硝酸盐可引起急性中毒 ,还可以与仲胺和酰胺等结合成致癌的亚硝胺化合物 ,是造成环境污染的主要原因之一。因此 ,亚硝酸盐的含量是环境监测和食品分析的重要指标。荧光法测定亚硝酸根常用的试剂是 2 ,3 二氨基萘[1] ,但需用有机溶剂萃取 ,操作繁琐 ,而且由于试剂本身有毒 ,易造成二次污染。近年来有人报道了荧光猝灭法测定亚硝酸根[2 ,3] 。本文以亚硝酸根与酪氨酸反应产物在碱性介质中呈现强的荧光 ,其激发波长和发射波长分别为 31 8.0ｎｍ和 398.4ｎｍ ,建立了水…     

“测定空气中氧气体积分数”实验再改进

“测定空气中氧气体积分数” 的实验是现行各版本5义务教育课程标准实验教科书：化学6 （九年级上册） 中的一个重要实验。笔者针对教材中实验装置的不足[1] ,在前人研究[2~4] 的基础上,设计了一种易于学生理解实验原理的装置。     

药物对福氏志贺氏菌代谢抑制的微量热法研究

药物抑制细菌生长的热化学研究是当今热化学法研究的一个活跃领域．在这项研究中，Boling[1]、Nordmark[2]、屈松生[3]等人已做了不少有意义的工作．在前人工作的基础上，我们用热活性检测系统测定了福氏志贺氏菌属中五株细菌在药物抑制下生长的完整的热谱曲线．按指数生长模型计算出细菌代谢抑制下的生长速车常数，并用计算机拟会出生长速率常数与不同浓度药物之间的关系式，进一步得到生长速率常数为零（临界生长参数[4]）时的用药物浓度．此项研究工作的开展对于深入研究药物对细菌的抑制作用，筛选对某细菌抑制的特效药提供了一种新的…     

溴酸钾氧化酸性铬深蓝动力学光度法测定痕量亚硝酸根

亚硝酸根是环境中重要的污染物之一,是水质、环境、食品等检测的一个重要项目。催化动力学方法测定痕量亚硝酸根已有较多的报道^[1-6],但未见利用酸性铬深蓝指示物质的报道,酸性铬深蓝是一种配位滴定的指示剂。作者发现在稀疏酸介质中,亚硝酸根对溴酸钾氧化酸性铬深蓝褪色反应有灵敏的催化作用,并研究了该指示反应的动力学条件,建立了催化光度法测定亚硝酸根的新方法。该方法灵敏、简便,可用于水、蔬菜中亚硝根的测定。     

分光光度法测定水、土壤和蔬菜中亚硝酸根

2-乙氧-6,9-二氨基吖啶,药名雷佛奴尔(Rivanol))用作亚硝酸根的比色测定,前人虽有报导,但比色条件及试验结果,各作者的报告均不一致;比色测定中的干扰离子的影响仅提及钠、氯根、溴根、硝酸根、硼酸根和乳酸根等六种离子。本文在前人的工作基础上试验了光度测定亚硝酸根的适宜条件和38种离子的干扰影响以及水、土壤和蔬菜中亚硝酸根的光度测定。本法优点在于反应的灵敏度和选择性高(灵敏度为0.016微克/毫升,较     

催化光度法测定痕量亚硝酸根

１引言近年来，有关催化光度法测定亚硝酸根的方法已有若干报道。笔者在前人进行荧光测定的基础上，研究了在稀磷酸介质中，亚硝酸根对溴酸钾氧化中性红的强催化作用，提出了以溴酸钾为氧化剂，中性红为还原剂测定亚硝酸根的催化光度法，结果具有很高的灵敏度和较好的选择性。用于地面水及地下水中ＮＯ－２的测定，结果满意。２实验部分２．１仪器与试剂７５３ＷＢ紫外可见分光光度计（上海光学仪器厂）；电热恒温水浴锅。亚硝酸根标准溶液：由亚硝酸钠配成１．００ｇ／Ｌ亚硝酸根储备液；本溶液贮存于棕色瓶中，每升加入２ｍＬ三氯甲烷和两…     

镧系金属离子的水化能

一、水化能公式 离子水化能是重要的热化学数据,前人曾作过很多研究^[1-4]。     

双自由基CF2与O3的反应机理

主要用作致冷剂和发泡剂的氯氟烃（CFCs）是破坏臭氧层的主要物质之一．对氯氟烃类化合物及其降解产物（包括光解、光氧化、化学反应产物等）在大气中行为问题的研究是大气化学研究的重要内容．前人[1-3]从理论和实验两方面研究了自由基与臭氧的反应机制，但是氯氟烃光解过程中     

CFCl3分子2e和4a1轨道的电子动量谱研究

由于工业的迅速发展,使得空气质量急剧下降,因此对影响大气的分子进行深入研究变得非常必要．本实验室已经对影响环境的甲烷[1]、丙烷[2]、CO2[3]等分子进行了电子动量谱研究,为环保提供了有用的数据．CFCl3作为工业广泛应用的气雾剂和制冷剂原料,它的大量使用导致了大气中臭氧的减少[4]．前人已用光电子谱学的方法[5-8]研究了CFCl3,我们又用电子动量谱的手段对CFCl3分子进行了进一步的研究,即从波函数的层次上详细了解CFCl3的电子结构．     

去氢抗坏血酸分子振动光谱的理论研究

采用RHF, MP2, DFT(B3LYP)方法, 以6-311++G**为基组研究了去氢抗坏血酸分子(DHA)的平衡几何构型和振动光谱. 计算结果表明, 采用RHF, B3LYP以及MP2 方法优化得到的几何结构以及频率值是一致的. 采用B3LYP/6-311++G**计算了DHA分子平衡构型下的谐振动力场﹑振动频率和振动强度. 使用Wilson的GF矩阵方法对DHA分子进行了简正坐标分析, 依据所得的势能分布对DHA分子的振动基频进行了合理的理论归属.     

Potential energy scans and vibrational assignments of cyclopropanecarboxylic acid and cyclopropanecarboxamide

The structural stability and internal rotations in cyclopropanecarboxylic acid and cyclopropanecarboxamide were investigated by the DFT-B3LYP and the ab initio MP2 calculations using 6-311G** and 6-311+G** basis sets. The computations were extended to the MP4//MP2/6-311G** and CCSD(T)//MP2/6-311G** single-point calculations. From the calculations the molecules were predicted to exist predominantly in the cis (C=O group eclipses the cyclopropane ring) with a cis-trans barrier of about 4-6kcal/mol. The OCOH torsional barrier in the acid was estimated to be about 12-13kcal/mol while the corresponding OCNH torsional barrier in the amide was calculated to be about 20kcal/mol. The equilibrium constant k for the cis<-->trans interconversion in cyclopropanecarboxylic acid was calculated to be 0.1729 at 298.15K that corresponds to an equilibrium mixture of about 85% cis and 15% trans. The vibrational frequencies were computed at the DFT-B3LYP level. Normal coordinate calculations were carried out and potential energy distributions were calculated for the low energy cis conformer of the molecules. Complete vibrational assignments were made on the basis of normal coordinate calculations and comparison with experimental data of the molecules.     

Structural, vibrational and quantum chemical investigations on 5-chloro-2-hydroxybenzamide and 5-chloro-2-hydroxybenzoic acid

The Fourier transform infrared (FTIR) and FT-Raman spectra of 5-chloro-2-hydroxybenzamide (5CBA) and 5-chloro-2-hydroxybenzoic acid (5C2HBA) have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. The complete vibrational fundamental modes of the compounds were assigned and analysed using the observed FTIR and FT-Raman data. The vibrational frequencies determined experimentally were compared with the theoretical wavenumbers calculated from ab initio HF and DFT-B3LYP gradient methods employing 6-31G** and 6-311++G** basis sets. The effect of halogen, hydroxyl groups and hydrogen bonding on the characteristic frequencies of the -COOH and -CONH2 group frequencies have been investigated. In 5CBA and 5C2HBA intramolecular hydrogen bond between a hydroxyl group and CO group makes a six membered ring, which causes the O?H interaction onto the resonance of the benzene ring. Comparison of the positions of the ν(OH) bands shows the ν(OH) band of 5CBA is located at considerably higher frequency which confirms a weaker hydrogen bond than in 5C2HBA.     

Structure and vibrational assignment of the enol form of 1,1,1-trifluoro-2,4-pentanedione

Molecular structure of 1,1,1-trifluoro-pentane-2,4-dione, known as trifluoro-acetylacetone (TFAA), has been investigated by means of Density Functional Theory (DFT) calculations and the results were compared with those of acetylacetone (AA) and hexafluoro-acetylacetone (HFAA). The harmonic vibrational frequencies of both stable cis-enol forms were calculated at B3LYP level of theory using 6-31G** and 6-311++G** basis sets. We also calculated the anharmonic frequencies at B3LYP/6-31G** level of theory for both stable cis-enol isomers. The calculated frequencies, Raman and IR intensities, and depolarization ratios were compared with the experimental results. The energy difference between the two stable cis-enol forms, calculated at B3LYP/6-311++G**, is only 5.89 kJ/mol. The observed vibrational frequencies and Raman and IR intensities are in excellent agreement with the corresponding values calculated for the most stable conformation, 2TFAA. According to the theoretical calculations, the hydrogen bond strength for the most stable conformer is 57 kJ/mol, about 9.5kJ/mol less than that of AA and about 14.5 kJ/mol more than that of HFAA. These hydrogen bond strengths are consistent with the frequency shifts for OH/OD stretching and OH/OD out-of-plane bending modes upon substitution of CH(3) groups with CF(3) groups. By comparing the vibrational spectra of both theoretical and experimental data, it was concluded that 2TFAA is the dominant isomer.     

Three rotor potential energy scans, conformational equilibrium constants and vibrational analysis of 3-fluoro-1-propanol CH(2)FCH(2)CH(2)OH

The conformational stability and the three rotor internal rotations in 3-fluoro-1-propanol were investigated by the DFT-B3LYP/6-311+G** and the ab initio MP2/6-311+G** levels of theory. The calculated potential energy curves of the molecule at both levels of theory were consistent with complex conformational equilibria of about 12 minima, all of which were predicted to have real frequencies at both the B3LYP and the MP2 levels. The lowest energy minimum in the potential curves of 3-fluoro-1-propanol was predicted to correspond to the Gauche-gauche-trans (Ggt) conformer in excellent agreement with microwave and electron diffraction results. The equilibrium constants for the conformational interconversion of the molecule were calculated and found to correspond to an equilibrium mixture of about 33% Ggt, 14% Ggg1 and 13% Gg1g and about 43% Ggt, 12% Ggg1 and 10% Gg1g distribution by the B3LYP/6-311+G** and the MP2/6-311+G** calculations, respectively, at 298.15K. The vibrational frequencies of each molecule in its three stable forms were computed at B3LYP level and complete vibrational assignments were made based on normal coordinate calculations and comparison with experimental data of the molecule.     

Density functional theory studies on the structures and vibrational spectra of 3,6-dichlorocarbazole and 3,6-dibromocarbazole

Becke 3-Lee-Yang-Parr density functional theory (DFT) calculations using 6-311G** and 6-311G(2df,p) basis sets were carried out to study molecular structures and vibrational spectra of 3,6-dichlorocarbazole and 3,6-dibromocarbazole. The optimized geometries, vibrational frequencies, IR intensities, and Raman activities have been obtained. On the basis of B3LYP calculations, a normal mode analysis was performed to assign the vibrational fundamental frequencies according to the potential energy distributions. The computational frequencies are in good agreement with the observed results.     

Density functional theory study on fundamental vibrational spectra of disilyl iodide and its isotopomer

Density function theory calculations using B3' exchange functional and LYP' correlation functionals (B3LYP) with the 3-21G** basis set were carried out to study the molecular structure and fundamental vibrational frequencies of Si2H5Br, Si2H5I and their isotopomers. One scale factor used to scale Si-H(D) force constants for Si2H5Br is transferred from Si2H5Br to Si2H5I. Other scale factors of force constants for Si2H5I and Si2D5I are determined by a least-squares fitting to experimental vibrational frequencies. The predictions of fundamental vibrational frequencies for Si2H5I and its isotopomer are given. The scaled DFT force fields using B3LYP/3-21G** reproduced the observed fundamental vibrational frequencies of Si2H5I and its deuterium isotopomer with a mean absolute deviation of 6 cm(-1). Reassignment of some fundamental vibrational modes of Si2H5I and its isotopomer is discussed.     

Structure and vibrational frequencies of 2-butanimine

The conformational behavior and structural stability of 2-butanimine were investigated by utilizing ab initio calculations with 6-311++G** basis set at HF, MP2, B3LYP and BLYP levels. The vibrational frequencies of 2-butanimine were computed. Complete vibrational assignments were made on the basis of normal coordinate calculations for stable conformer of the molecule. HF results without scaled quantum mechanical (SQM) force field procedure considered are in bad agreement with experimental values. Of the two DFT methods, BLYP reproduces the observed fundamental frequencies most satisfactorily with the mean absolute deviation of the non-CH stretching modes less than 21.3 cm(-1). The results indicate that BLYP calculation is a very promising approach for understanding the observed spectral features.     

A study of internal rotations and vibrational spectra of oxiranemethanol (glycidol)

The conformational stability and the C–O and O–H internal rotations in oxiranemethanol were investigated at the DFT-B3LYP/6-311G**, MP2/6-311G** and MP4(SDQ)/6-311G** levels of theory. Three minima were predicted in the CCOH potential energy scans of the molecule to have relative energies of about 2 kcal/mol or less and all were calculated to have real frequencies upon full optimization of structural parameters at the DFT and the MP2 levels of calculations. The Cg1 (H bond inner) conformation was predicted to be the lowest energy conformation for oxiranemethanol in excellent agreement with an earlier microwave study. The equilibrium mixture was calculated from Gibb's free-energy changes to be about 79% Cg1, 17% G1g and 3% Gg1 at the B3LYP/6-311G** level and about 87% Cg1, 11% G1g and 2% Gg1 at the MP2/6-311G** level for oxiranemethanol at 298.15 K. No conclusive evidence was obtained for the presence of high-energy form in the liquid phase of oxiranemethanol. The vibrational frequencies of oxiranemethanol in its three stable forms were computed at the B3LYP level and complete vibrational assignments were made for the lowest energy Cg1 form on basis of calculated and experimental data of the molecule.     

Tricyclo[2.2.0.0]hexane: a new hypothetical molecule which should have only one inverted carbon atom

HF and MP2 calculations with the 6-31G** and 6-311G** basis sets and those at MP2/cc-pVTZ level were carried out for the hypothetical tricyclo[2.2.0.0^1,3]hexane. The results indicate that the molecule under study should have one carbon atom with highly unusual inverted configuration. The analysis of the vibrational frequencies of this molecule as well as the analysis of its plausible decomposition routes performed at the DFT level indicate that this unique molecule could be a plausible synthetic target.