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271.
Selective flow-injection determination of methanol in the presence of ethanol based on a multi-enzyme system with chemiluminescence detection 总被引:2,自引:0,他引:2
Yoshiie Sekine
Masayasu Suzuki
Toshifumi Takeuchi Eiichi Tamiya Isao Karube 《Analytica chimica acta》1993,280(2):179-184A highly selective flow-injection system was developed for the determination of methanol. The system consisted of three immobilized enzymes with luminol chemiluminescence detection. First, methanol was oxidized in the presence of alcohol oxidase to yield formaldehyde and hydrogen peroxide. The hydrogen peroxide produced was then destroyed by catalase. The formaldehyde formed in the first stage was further oxidized by NAD+-formaldehyde dehydrogenase. The NADH formed was oxidized by 1-methoxy-5-methylphenazinium methylsulphate (1-MPMS), and finally the reduced 1-MPMS was spontaneously oxidized and hydrogen peroxide was produced. The concentration of the hydrogen peroxide produced, which was proportional to the initial concentration of methanol, was determined by luminol chemiluminescence. The determination range was from 0.1 to 100 mg l−1 and the response time was less than 2 min per sample with a relative standard deviation of less than 3%. The system showed good selectivity for methanol; the response was ca. 50 times higher than for ethanol. 相似文献
272.
Petra Spitzer Bruno Rossi Yves Gaignet Stéphane Mabic Uwe Sudmeier 《Accreditation and quality assurance》2005,10(3):78-81
There is currently a major issue with the calibration of conductivity meters used for high purity water: the lack of availability of a reference material or reference methods for low conductivity ranges (conductivity below 1 S cm–1 at 25.0 °C, resistivity >1 M cm at 25.0 °C). This paper describes the current status of conductivity measurements in high purity water. A new and improved approach, currently being investigated, should allow us to make the calibration of conductivity meters used for low conductivity ranges traceable to the SI.Milipore, Milli-Q and Elix are registered trademarks of Millipore Corporation. 相似文献
273.
Summary The thermal behavior of KH2PO4, NaH2PO4 and Na2HPO4 under non-isothermal conditions using TG method with different heating rates was studied. The values of the reaction rate were processed by means of Friedmans differential-isoconversional method. A dependence of the activation energy vs. conversion was observed. Therefore a procedure based on the compensation effect (suggested by Budrugeac and Segal) was applied. A less speculative data processing protocol was offered by the non-parametric kinetics method suggested by Serra, Nomen and Sempere. Three steps were observed by non-isothermal heating: a dehydration, a dimerization and a polycondensation. The differences in the intimate reaction mechanism are determined by the initial number of water molecules. 相似文献
274.
Summary An extension of the multiconfigurational SCF approach for the resolution of the vibrational problem is presented; it follows the philosophy of the CASSCF method developed in Quantum Chemistry. The new method allows a more complete treatment of anharmonic mode couplings, converges much faster and gives a clearer physical insight of vibrational interactions. This is exemplified by the calculation of infrared transition moments in the H2O and D2O isotopomers of the water molecule. It is shown how this property varies with the quality of the wave function when vibrational resonances occur. A detailed analysis by means of this new VCASSCF method demonstrates the crucial importance of excited bending oscillators in the intensity of some pure stretching transitions.Boursier F.R.I.A. 相似文献
275.
Martí S Andrés J Moliner V Silla E Tuñón I Bertrán J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(4):984-991
In this paper a deeper insight into the chorismate-to prephenate-rearrangement, catalyzed by Bacillus subtilis chorismate mutase, is provided by means of a combination of statistical quantum mechanics/molecular mechanics simulation methods and hybrid potential energy surface exploration techniques. The main aim of this work is to present an estimation of the preorganization and reorganization terms of the enzyme catalytic rate enhancement. To analyze the first of these, we have studied different conformational equilibria of chorismate in aqueous solution and in the enzyme active site. Our conclusion is that chorismate mutase preferentially binds the reactive conformer of the substrate--that presenting a structure similar to the transition state of the reaction to be catalyzed--with shorter distances between the carbon atoms to be bonded and more diaxial character. With respect to the reorganization effect, an energy decomposition analysis of the potential energies of the reactive reactant and of the reaction transition state in aqueous solution and in the enzyme shows that the enzyme structure is better adapted to the transition structure. This means not only a more negative electrostatic interaction energy with the transition state but also a low enzyme deformation contribution to the energy barrier. Our calculations reveal that the structure of the enzyme is responsible for stabilizing the transition state structure of the reaction, with concomitant selection of the reactive form of the reactants. This is, the same enzymatic pattern that stabilizes the transition structure also promotes those reactant structures closer to the transition structure (i.e., the reactive reactants). In fact, both reorganization and preorganization effects have to be considered as the two faces of the same coin, having a common origin in the effect of the enzyme structure on the energy surface of the substrate. 相似文献
276.
A family of multiderivative methods with minimal phase-lag are introduced in this paper, for the numerical solution of the Schrödinger equation. The methods are called multiderivative since uses derivatives of order two, four or six. Numerical application of the new obtained methods to the Schrödinger equation shows their efficiency compared with other similar well known methods of the literature.Active Member of the European Academy of Sciences and Arts 相似文献
277.
Waldemar Adam 《Angewandte Chemie (International ed. in English)》1974,13(10):619-627
The photodecarboxylation of malonyl peroxides into α-lactones[1] and the thermal conversion of the 1,4-endo-peroxide 4,5-epoxy-3,6-epidioxy-1-cyclohexene into the novel benzene trioxide[2] are two recent examples of the potential of cyclic peroxides in the synthesis of unusual organic molecules. The former transformation entails a fragmentation, the latter a rearrangement process. Most reported examples fall into one of these two gross reaction types. Of the numerous examples that have been reported in the literature during the last two decades, only those shall be focused on that lead to unusual compounds or constitute efficient syntheses of known compounds, in order to stress the convenience of cyclic peroxides in the synthesis of organic compounds. 相似文献
278.
Fabio E. Penotti 《International journal of quantum chemistry》2006,106(5):1153-1159
Nonorthogonal single‐configuration and multiconfiguration ab initio calculations are carried out on the BeH2 molecule in its equilibrium (D∞h) geometry, using a highly optimized even‐tempered Slater‐type orbital (STO) basis set. The results are used as a basis for a discussion of the electronic structure of the molecule in modern‐VB terms. A value of Re = 1.329 Å is obtained. Values are also obtained for the symmetric‐stretch harmonic frequency (2053 cm?1), electric quadrupole moment (?5.60 Buckingham), and nuclear quadrupole coupling constants (?3.59 MHz for 9Be and 0.0915 MHz for 2H). © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献
279.
Wolfgang Oppolzer 《Angewandte Chemie (International ed. in English)》1989,28(1):38-52
Metallo-ene reactions, hardly recognized until very recently, have experienced a breathtaking development when applied in an intramolecular sense. Efficient regio- and stereoselective magnesium-ene cyclizations have served as a cornerstone for numerous syntheses of structurally diverse natural products (e.g., sesquiterpenes of marine or plant origin, alkaloids, fragrances, insect defense compounds, and a fungitoxin). A brilliant example is the synthesis of the elusive odorant (+)-khusimone which outshines 20 years of work in the field of tricyclovetivane synthesis. Palladium-, platinum-, and nickel-catalyzed versions of the metallo-ene reaction are in a comparatively early stage of exploration, but, nevertheless, reveal intriguing potential. Hence an almost 100% stereospecific C? O→C? ;Pd-→ C? C chirality transfer permits simple and selective, cis- or trans-annelation processes. The mild cyclization conditions are compatible with various functional groups, such as nitrogen moieties, which offer interesting perspectives for the preparation of heterocycles (e.g., alkaloids) difficult to obtain by other methods. Carbon monoxide insertion reactions of the cyclized σ-metal intermediates were shown to afford annelated cyclopentanones and cyclopentenones with concomitant stereocontrolled formation of four carbon–carbon bonds. These and other observations, highlighted in this article, provide a platform for further extensions and applications of this powerful method in organic synthesis. 相似文献
280.
Hanns Malissa 《Angewandte Chemie (International ed. in English)》1976,15(3):141-149
Environmental analyses show that the air which we breathe, and which is so essential to life, is in general a mixture of gaseous, liquid, and solid components. The solid airborne particles, whose concentration, homogeneity, chemical composition, size, and shape can vary over wide ranges, and whose origin may be “natural” or “artificial” are referred to as “dust”. Dust particles can act, inter alia, as condensation nuclei, catalysts, and directly as hazardous materials. Unfortunately, we still know far too little about dust. Dust analysis is extremely difficult and challenging, even for modern analytical chemistry; it is still far from being fully automated. The simultaneous determination of as many “dust parameters” as possible, and particularly the synoptic consideration of all available data against a background of physicochemical and technological knowledge on the development, transformation, and effects of dust, are summarized as “integrated dust analysis”. 相似文献