用微芯片化学反应器实现酶催化化学发光测定葡萄糖的研究

葡萄糖是临床化学诊断以及食品分析中重要的检测项目 ,最常用的测定方法是采用葡萄糖氧化酶(GOD)催化葡萄糖与氧分子间反应 ,生成葡萄糖酸和过氧化氢 [1] ,而对过氧化氢的检测则可采用过氧化酶 (POD)催化鲁米诺的化学发光反应进行 [2 ] .FIA对整个过程的实现是十分有效的方式 ,但由于多采用固定化酶反应器 [3～ 5] 使其在制备及分析上较复杂且费用高 .由 Manz等[6] 提出的微型全分析系统(μ- TAS)在针对不同体系的微量分析及在线监测上均具有突出的优越性 .本文使用的含微混合器的微芯片化学反应器采用μ- TAS设计思想 ,建立了化学发…     

Molecular-beam mass spectrometry of van der Waals clusters. Mass spectrum of hydrogen sulfide dimer

Hydrogen sulfide clusters generated by ultrasonic expansion of an H₂S-Ar mixture into a vacuum were detected by electron impact mass spectrometry. The mass spectrum of the dimer, (H₂S)₂, was obtained under conditions of predominant dimerization. A mechanism of the formation of ions that involves intracluster reactions between the fragment ions of the monomer and the monomer molecule has been suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 839–844, May, 1995.The work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 93-03-4933). The authors are also grateful to the European Environmental Research Organisation (EERO) for support.     

Synthesis and Electrochemical Studies of Spinel LiNi1−xMnxVO4

Spinel compound LiNi_1−xMn_xVO₄ (0≤x≤0.4) had been prepared by using the moist chemical method. X-ray diffraction spectra showed that the lattice constant increased with x in the LiNi_1−xMn_xVO₄, XPS spectra indicating that Li1s had a chemical shift towards lesser binding energy, and manganese in LiNi_1−xMn_xVO₄ existing as the mixed valence of Mn²⁺ and Mn³⁺. The electrochemical charge and discharge testing at a current density of 0.1 mA/cm² between the potentials of 4.0 and 3.0 V vs Li/Li⁺ in 1 mol/dm³ LiPF₆/EC+DEC (1:1 by volume) at 25°C showed that LiNi_1−xMn_xVO₄ cell has a better rechargeability, but a lower cell voltage of 4.0 V vs Li/Li⁺ than that without the doping sample, and the capacity and the cycle efficiency of the Li/LiNi_1−xMn_xVO₄ cells increased with x in the LiNi_1−xMn_xVO₄.     

A fluorescent chemical sensor for Fe based on blocking of intramolecular proton transfer of a quinazolinone derivative

In this paper, 2-(2′-hydroxy-phenyl)-4(3H)-quinazolinone (HPQ), a typical compound that exhibits excited state intramolecular proton transfer (ESIPT) reaction and possesses good photophysical properties, is synthesized and used as fluoroionophore for Fe³⁺ sensitive optochemical sensor. The decrease of fluorescence intensity of HPQ membrane upon the addition of Fe³⁺ was attributed to the blocking of ESIPT reactions of HPQ and quenching its fluorescence. The effect of the composition of the sensing membrane was studied, and experimental conditions were optimized. The sensor shows a linear response toward Fe³⁺ in the concentration range of 7.1 × 10⁻⁷ M to 1.4 × 10⁻⁴ M with a limit of detection of 8.0 × 10⁻⁸ M, and a working pH range from 2.5 to 4.5. It shows excellent selectivity for Fe³⁺ over a large number of cations such as alkali, alkaline earth and transitional metal ions. The proposed sensor is applied to the determination of the content of iron ions in pharmaceutical preparations samples with satisfactory results.     

Ab initio molecular modeling of 13C NMR chemical shifts of polymers. 1. Ethylene–norbornene copolymers

Cycloolefin copolymers (COC) have recently raised much interest because of their excellent thermal and optical properties, largely determined by the chain composition and stereochemistry. Previous force‐field computations allowed us to define the main conformational characteristics of ethylene–norbornene (E–N) copolymers and to contribute to the elucidation of their microstructure on the basis of empirical relationships between conformation and ¹³C nuclear magnetic resonance (NMR) chemical shifts. A thorough test of ab initio ¹³C chemical shifts computations [gauge‐invariant atomic orbitals (GIAO)] on known cases shows that the agreement with experimental data is quite good, especially with the MPW1PW91 density functional theory (DFT), using the 6‐311+G(2d,p) basis set on properly energy‐minimized structures. We applied this method on proper model compounds to confirm the signal assignment of the spectra of E–N copolymers in the presence of norbornene microblocks, where strong effects arising from ring distortions are expected to occur. The results nicely confirm the latest assignment of norbornene signals belonging to ENNE sequences. This shows the great potentialities of GIAO/DFT computations with regard to complex spectra interpretation and polymer microstructural investigations. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Calculation of circular dichroism spectra of michellamines A and C, based on a complete conformational analysis

The first quantum chemical calculation of the circular dichroism (CD) spectra of michellamines has been achieved, based on a complete quantum chemical conformational analysis. Michellamines are dimeric naphthylisoquinoline alkaloids and thus naturally occurring quateraryls, with a large molecular size and flexibility and equipped with stereogenic centers and axes.     

~(13)C化学位移在达玛烷型皂甙结构研究中的应用

本文将迄今为止国内外文献报道的200余种达玛烷型皂甙类化合物的~(13)C化学位移按其结构特征分类整理,以原人参二(三)醇等为模型化合物,讨论了皂甙元结构变化引起的位移变化(Δδ_C)规律。     

Characterization of the Converging Jet Region in a Triple Torch Plasma Reactor

Enthalpy probe measurements were taken of the converging plasma plume in a triple torch plasma reactor and related to substrate heat flux measurements. Results show excellent entrainment of process gases injected into the converging plasma plume by way of the central injection probe. At lower pressures (40 kPa), the plasma volume is equivalent to at least a 3 cm diameter, 4 cm long cylinder, with relatively uniform temperature, velocity, and substrate heat flux profiles when compared to a typical dc arc jet. Converging plasma plume size, substrate heat flux, and enthalpy profiles are also shown to be a strong function of applied system power. Substrate heat flux measurements show smaller radial gradients than enthalpy probe measurements, because of the high radial velocity component of gases above the substrate boundary layer. Enthalpy probe measurements were also conducted for diamond deposition conditions and approximate temperature and velocity profiles obtained. Problems with the uniform gas mixture assumption prohibited more accurate measurements. Reproducibility of enthalpy measurement results was shown with an average standard deviation of 11.8% for the velocity and 7.6% for the temperature measurements.     

Chemical reaction dynamics of PeCB and TCDD decomposition: A tight‐binding quantum chemical molecular dynamics study with first‐principles parameterization

The decomposition reaction dynamics of 2,3,4,4′,5‐penta‐chlorinated biphenyl (2,3,4,4′,5‐PeCB), 3,3′,4,4′,5‐penta‐chlorinated biphenyl (3,3′,4,4′,5‐PeCB), and 2,3,7,8‐tetra‐chlorinated dibenzo‐p‐dioxin (2,3,7,8‐TCDD) was clarified for the first time at atomic and electronic levels, using our novel tight‐binding quantum chemical molecular dynamics method with first‐principles parameterization. The calculation speed of our new method is over 5000 times faster than that of the conventional first‐principles molecular dynamics method. We confirmed that the structure, energy, and electronic states of the above molecules calculated by our new method are quantitatively consistent with those by first‐principles calculations. After the confirmation of our methodology, we investigated the decomposition reaction dynamics of the above molecules and the calculated dynamic behaviors indicate that the oxidation of the 2,3,4,4′,5‐PeCB, 3,3′,4,4′,5‐PeCB, and 2,3,7,8‐TCDD proceeds through an epoxide intermediate, which is in good agreement with the previous experimental reports and consistent with our static density functional theory calculations. These results proved that our new tight‐binding quantum chemical molecular dynamics method with first‐principles parameterization is an effective tool to clarify the chemical reaction dynamics at reaction temperatures. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Chemical Sensors for Electronic Nose Systems

Chemical sensors have been widely used for the analysis of volatile organic compounds. Employing chemical sensors in an array format with pattern recognition provides a higher degree of selectivity and reversibility leading to an extensive range of applications. When such systems are used for odour analysis they are termed electronic noses. Application of electronic noses ranges from the food industry, medical industry to environmental monitoring and process control. Many types of different gas sensors have been employed in the array. These include conducting polymers, metal oxide semiconductors, piezoelectric, optical fluorescence and amperometric gas sensors The transducer principle of these sensors is varied and is discussed in detail within this review. Examples of the current trends in sensor array technology as well as the applications to which the sensor-based noses have been applied are also discussed.