芳香杂环并吡咯的合成和在天然产物全合成中的应用

叠氮基-丙二酸烷叉酯的分子内1,3-二极环加成和环翻转反应被用于制备异缩合杂环芳香吡咯的新方法, 报导了这一方法用于合成2,4-二氢吡咯[3,4-b]吲哚环系, 同样这一环系被用于椭园玫瑰树碱的全合成。     

The use of radionuclides for the determination of adsoroption isotherms of volatile chlorides

It is demonstrated that gas-solid chromatography is a useful method for the investigation of the adsorption, properties of inorganic compounds at temperatures up to 1100 K. The use of radioisotopes enables the application of this method to extreme small concentrations and surface areas. Adsorption entropies and enthalpies for various chlorides on a quartz glass surface are presented, as well as several other adsorption data of inorganic chlorides. The possibility to use data obtained by this method for the optimization of separations is shown.     

Evaluation of the possibility of detecting benzenic pollutants by direct spectrophotometry on PDMS solid sorbent

Solid-phase extraction has become one of the most commonly used techniques for preconcentration of analytes from environmental samples. In the standard use of solid sorbent phases the extracted pollutants are subsequently eluted with a suitable organic solvent before chromatographic analysis. An alternative to this procedure is analysis of the adsorbed and concentrated pollutants by direct application of a spectroscopic method (fluorimetry or absorptiometry) to the phase. Although this method cannot be expected to give results as precise as those given by chromatographic methods, it might have valuable applications, particularly for "on site" pollution monitoring. This paper reports an evaluation of the capability of the method for the spectrophotometric detection of BTX (benzene, toluene, xylenes) in aqueous media and in contaminated atmospheres, with polydimethylsiloxane (PDMS) as sorbent. The tests performed, with the estimated detection limits, indicate that the method is relatively simple and easy to operate and sensitive enough for application to the monitoring of pollution both in water and in air in an industrial ambient atmosphere.     

Influence of the sample toxic profile on the suitability of a high performance liquid chromatography method for official paralytic shellfish toxins control

An HPLC-FLD method, involving pre-chromatographic oxidation of the PSP toxins with hydrogen peroxide and periodate, has been AOAC validated through a collaborative trial and adopted as AOAC Official Method. This method could be a candidate for replacing the mouse bioassay (MBA) for the Official Control of PSP toxins at European level, once accepted by the legislation. An interlaboratory exercise has been organized by the CRLMB to evaluate its "fitness for purpose" for the Official Control of PSP toxins in the EU laboratories. Eighteen EU laboratories took part in the study and had to analyze six bivalve mollusc samples with several PSP toxic profiles. The performance of the participant laboratories in the application of this method was compared with that obtained at the collaborative trial. Information on problems/drawbacks encountered by participants in the application of this method was also sought. The HPLC validated method is only applicable for Official PSP Control for certain samples. This depends on sample PSP toxic profile. Results obtained for samples where only GTX2,3 and STX were present were satisfactory and in agreement with MBA results. Results obtained for a sample with a toxic profile dominated by GTX6 and suspected to contain also C1,2 and C3,4 were not satisfactory. GTX5 and dc-STX could be quantified, although the results achieved (total toxicity) were lower than those obtained by MBA. It can be also useful as a screening method, complementary to MBA, helping in the reduction of the animals used. However, the lack of several PSP standards, the fact that the method is not validated for all the PSP toxins, and several drawbacks found in its application are a handicap to fully implement it for Official PSP Control as a viable replacement for bioassay.     

维生素E母核合成研究进展

综述了2,3,5-三甲基氢醌的合成工艺进展,主要包括2,3,6-三甲基苯酚(TMP)氧化还原法、TMP羟基化法与异佛尔酮法,详细阐述了其中关键反应步骤的机理,并指出新型催化剂的开发与应用将是此领域的重点研究方向。     

固相微萃取技术在法庭科学领域中的应用

综述国内外固相微萃取技术在法庭科学领域中毒物、毒品和微量物证(炸药残留物、助燃剂残留物、人体气味)样品前处理及分析中的应用,以及在火场助燃剂残留物及人体气味鉴别方面的应用;对固相微萃取技术在法庭科学领域中的发展方向进行了展望。可以对法庭科学领域毒物毒品、微量物的相关研究和侦查办案提供参考。     

Improving the selectivity of non-polar alkanes, alkenes, and aromatic hydrocarbon compounds by the application of acetonitrile as a Cl reagent

The selective enhancement of membrane introduction mass spectrometry for non-polar alkanes, alkenes, and aromatic hydrocarbon compounds by the application of acetonitrile as a chemical ionization reagent was investigated. Acetonitrile Cl is able to produce specific fragment ions for many of the compounds test and this can be used to identify and quantify the parent neutrals. This method provided relatively high detection limits of the test compounds. This method could potentially be useful for analytical applications such as the detection of non-polar hydrocarbons for environmental studies if CH₃CN Cl/MIMS is coupled with a preconcentration method.     

Semi-theoretical approach to the applications of the sum peak method

Although application of the sum peak method to determine the PAC parameter was limited to point source like specimens, a theoretical consideration has been made to examine the possibility of application of the sum peak method to specimens with finite dimension in this work. It has been revealed that the sum peak method can be applied to those specimens in the same manner as to point source like ones. Furthermore, the possibility of application of the sum peak method to determinations of the time differential attenuation factor G₂₂/t/ has been discussed, and its procedure has been proposed.     

四硫化三铁纳米粒子的制备及应用

近些年来磁性Fe3S4纳米粒子由于其独特的物理化学性质,如量子尺寸效应、电磁学特性,在环境治理、能源储存、催化剂、生物医学应用等方面展示出了其巨大的潜力。本文总结了近10年来国内外Fe3S4纳米粒子的制备方法及对比了不同合成方法的优缺点,主要包括：共沉淀法、水热法(溶剂热法)、热分解法和模板法。并且综述了Fe3S4纳米材料在环境治理、能源储存、生物医学等方面的应用。最后,分析了Fe3S4纳米材料在制备中存在的一些问题,并对其的发展方向进行了展望。     

Prediction of the Raman spectrum of the aqueous formate anion by a combined density functional theory and self-consistent-reaction-field study

Formate, HCOO⁻, is a small ion that can be used as a convenient model to represent general carboxylic acids as well as the terminal side chains of glutamic and aspartic amino acids in biological systems. Several ab initio techniques (Hartree–Fock and density functional theory methods) were used to study the formate anion in aqueous solution, where the solvent was treated as an electrostatic influence by means of a self-consistent-reaction-field (SCRF) method. The comparison of calculated frequencies with Raman experimental data constitutes a good test for the solvation model employed in this work. The results showed that the application of a SCRF method not only produced smaller errors but also improved the linear correlation between predicted and experimental values. This latter characteristic enables a more efficient application of a linear scaling factor, λ, which corrects the calculated frequencies. In fact, the application of λ to the values calculated for the continuum, when compared to those obtained for a vacuum, resulted in smaller root-mean-square errors of the deviations from the experimental data. Received: 15 May 2000 / Accepted: 19 June 2000 / Published online: 11 September 2000     

Simple and rapid characterization of soybean cultivars by perfusion reversed-phase HPLC: application to the estimation of the 11S and 7S globulin contents

A perfusion RP HPLC method enabling the separation of soybean proteins in an analysis time lower than 3 min has been used to obtain the chromatographic profiles of different soybean cultivars. The chromatograms obtained for each soybean variety presented clear differences that justified the potential use of this method for cultivar characterization. The area percentages obtained were employed as variables for cluster and principal components analysis of these soybeans. The application of these multivariate methods enabled the grouping of the soybeans in different categories. The protein fractions obtained from these soybeans by the application of a fractionation method were also analyzed. The chromatographic profiles obtained enabled the assignment of peaks to the main soybean proteins (7S and 11S globulins). These data were used for the estimation, for the first time, of the 7S and 11S globulin contents in soybean cultivars.     

The synthetic construction of spin eigenfunctions in second quantization representation

The second quantization method is used to derive a recursion formula for the construction of spin eigenfunctions in the branching diagram method which simplifies the application of this method considerably. By application of this recursion formula the branching diagram functions are expressed as linear combinations of spin-paired functions. A one-to-one correspondence is established between the set of branching diagram paths and the set of spin-paired functions used to construct the branching diagram functions. This leads to a simple method for the construction of independent sets of spinpaired functions for arbitrary multiplicities.     

Quick estimation of the Dpb for predicting the strength of chemical bond in situ

An approximate method has been established to calculate the depth of the potential acting on an electron in a molecule at the saddle point along a chemical bond, denoted by Dpb. It is a new indicator which can be used for predicting the strength of a chemical bond. In this work, as a practical application for demonstrating thismethod, we calculated the Dpb of deoxyribonucleosides and ribonucleosides along all C-H and N-H chemical bonds using the method. The results are in fair agreement with those results of previously reported experimental and theoretical observations.     

Description of interelectronic correlation with the Pluvinage method

A correlated wave function method, already used for two-electron molecular systems is extended here to the case of two-electron atomic systems. A careful investigation of some exact properties of the wave function is performed (Kato's conditions, Fock's development, fulfilment of the virial theorem), showing its good behaviour at small interelectronic distances or in strongly correlated states. The application to Helium and H^? doubly-excited states is developed as a preliminary case of a more general study concerned with alkali-negative ions featuring in the second paper of this series. Energies and some autoionizing widths of He and H^? are calculated. Given the simplicity of our model, close agreement is found in all cases with experimental and other theoretical works. This provides a confirmation of the large application field of this method to general correlated two-electron systems.     

Comparison of sulphur-mode and tin-mode flame photometric detectors for the gas chromatographic determination of organotin compounds

A comparison of sulphur-mode (393 nm) and tin-mode (610 nm) flame photometric detectors for the gas chromatographic determination of butyl- and phenyltin compounds is described. The chromatographic peaks of the butyl- and phenyltin compounds were well separated, and high sensitivity was achieved in both modes; however, the tin-mode was more specific for tin compounds than the sulphur-mode. The absolute detection limits with the sulphur-mode and the tin-mode were 3.9-7.6 pg and 2.6-5.1 pg as tin, respectively. The application of the tin-mode gas chromatographic method to the determination of organotin compounds in fish is presented. For this application, organotins are extracted (as chloride) with hydrochloric acid and n-hexane-benzene (3:2, containing 0.05% tropolone) and the extracts are pentylated by a Grignard reagent prior to gas chromatography. The absolute recoveries of butyl- and phenyltin compounds added to fish samples ranged from 68.5 to 84.4% (the coefficients of variation were less than 6.6% for all substances, n = 8). Significant amounts of three organotin compounds (di- and tributyltin and triphenyltin) in fish samples were detected by this method. This technique may have application for other organotin compounds and the monitoring of butyl- and phenyltin compounds in the environment.     

Newton–Raphson optimization of the explicitly correlated Gaussian functions for calculations of the ground state of the helium atom

Explicitly correlated Gaussian functions have been used in variational calculations on the ground state of the helium atom. The major problem of this application, as well as in other applications of the explicitly correlated Gaussian functions to compute electronic energies of atoms and molecules, is the optimization of the nonlinear parameters involved in the variational wave function. An effective Newton–Raphson optimization procedure is proposed based on analytic first and second derivatives of the variational functional with respect to the Gaussian exponents. The algorithm of the method and its computational implementation is described. The application of the method to the helium atom shows that the Newton–Raphson procedure leads to a good convergence of the optimization process. © 1994 by John Wiley & Sons, Inc.     

Capillary GC-MS — Stable isotope dilution analysis of methylmalonic acid in plasma: A candidate reference method for the diagnosis and the follow-up of methylmalonic acidaemias

Summary Because methylmalonic acid (MMA) accumulates in the body fluids of patients suffering from inherited metabolic disorders involving its pathway, the quantitation of this metabolite is not only fundamental to diagnosis but is also important in the follow-up of affected patients under treatment.We describe the method set up and used in our laboratory for the measurement of MMA in body fluids and propose its application to plasma as the reference method for the biochemical diagnosis and follow-up of methylmalonic acidaemias.     

DNA银纳米簇在功能核酸荧光生物传感器中的应用

DNA银纳米簇(DNA-AgNCs)是以DNA为模板, 通过碱基杂环上的N原子与Ag⁺结合, 用NaBH₄将Ag⁺还原得到的具有荧光性质的新兴纳米探针. 由于DNA-AgNCs具有合成方法简单、 生物相容性好和荧光发射波长可调等优点, 使其在分析检测等领域具有广泛的应用. 本文对DNA-AgNCs的合成和荧光性质两个方面进行了综述, 分类总结了以DNA-AgNCs为无标记荧光探针在功能核酸荧光生物传感器方面的应用, 对其不足与应用潜力进行展望, 以期为未来的研究与应用提供借鉴.     

Experiences with the development and operation of a large-scale preparative gas chroamtograph

Summary A large-scale preparative gas chromatograph containing a 3 m long 100 mm l. D. column was built to investigate the application of preparative gas chromatography for the separation and production of various organic compounds. In this paper some experiences are reported concerning the operation of this large-scale preparative unit. In particular the efficiency of the receivers, the method of sample introduction as well as the stability of column packing were investigated.     

On the determination of the point of fracture initiation by the load separation criterion in J-testing of ductile polymers

The application of an experimental approach based on the load separation criterion for the determination of the point of fracture initiation in a fracture test on a ductile polymer was critically examined. To this aim, the fracture process outlined by the application of this method was related to that described by the visual analysis of the fracture surfaces obtained in fracture tests on nominally identical specimens, in which different levels of crack extension were produced. The material examined was an acrylonitrile-butadiene-styrene (ABS) resin, and the fracture tests were performed at low loading rate on single-edge notched in bending specimens.The results demonstrated that this load separation criterion based methodology is a promising approach for the determination of the point of fracture initiation, and for material fracture resistance, J_Ic, evaluation. The method also has experimental simplicity and a high degree of repeatability.