Development of a miniature simultaneous MPT spectrometer

An unique miniature simultaneous microwave plasma torch (MPT) atomic emission spectrometer employing linear UV intensified charge-coupled device (ICCD) array detector has been developed and studied preliminarily. The detection limits and precisions of the spectrometer for Ag, Al, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Sr and V by using different CCD exposure times have been determined. An analysis of a practical sample has been carried out. The preliminary results demonstrate that such simultaneous spectrometer has advantages of saving sample and time, especially suitable for use as detector for chromatography and in combination with flow injection systems. Taking analytical figures of merit and portability into accounts, the miniature simultaneous MPT system will have extended application areas and greater competition potential as compared with commercialized scanning MPT spectrometers.     

Simultaneous spectrophotometric determination of ethinylestradiol and levonorgestrel by partial least squares and principal component regression multivariate calibration

Two spectrophotometric methods for the determination of Ethinylestradiol (ETE) and Levonorgestrel (LEV) by using the multivariate calibration technique of partial least square (PLS) and principal component regression (PCR) are presented. In this study the PLS and PCR are successfully applied to quantify both hormones using the information contained in the absorption spectra of appropriate solutions. In order to do this, a calibration set of standard samples composed of different mixtures of both compounds has been designed. The results found by application of the PLS and PCR methods to the simultaneous determination of mixtures, containing 4–11 μg ml⁻¹ of ETE and 2–23 μg ml⁻¹ of LEV, are reported. Five different oral contraceptives were analyzed and the results were very similar to that obtained by a reference liquid Chromatographic method.     

Microdevices for manipulation and accumulation of micro- and nanoparticles by dielectrophoresis

Microfluidic devices with three-dimensional (3-D) arrays of microelectrodes embedded in microchannels have been developed to study dielectrophoretic forces acting on synthetic micro- and nanoparticles. In particular, so-called deflector structures were used to separate particles according to their size and to enable accumulation of a fraction of interest into a small sample volume for further analysis. Particle velocity within the microchannels was measured by video microscopy and the hydrodynamic friction forces exerted on deflected particles were determined according to Stokes law. These results lead to an absolute measure of the dielectrophoretic forces and allowed for a quantitative test of the underlying theory. In summary, the influence of channel height, particle size, buffer composition, electric field, strength and frequency on the dielectrophoretic force and the effectiveness of dielectrophoretic deflection structures were determined. For this purpose, microfluidic devices have been developed comprising pairs of electrodes extending into fluid channels on both top and bottom side of the microfluidic channels. Electrodes were aligned under angles varying from 0 to 75 degrees with respect to the direction of flow. Devices with channel height varying between 5 and 50 microm were manufactured. Fabrication involved a dedicated bonding technology using a mask aligner and UV-curing adhesive. Particles with radius ranging from 250 nm to 12 microm were injected into the channels using aqueous buffer solutions.     

一种新的滤纸基质固体表面低温荧光(燐光)测定装置

对自行研制的铜制滤纸基质低温荧光（燐光）测定的样品支架，进行了滤纸基质固体表面低温荧光测定的可行性研究。与同类冷冻装置和室温装置比较，本装置用于滤纸基质固体表面低温荧光（燐光）测定具有以下优点；样品的分析周期大大地缩短，由45min缩短为5-6min；装置简单、便宜耐用；操作简便，简化了室温测定时的滤纸干燥程序，应用范围广，方法的重现性好，检样分析结果的相对标准偏差RSD%小于10%，荧光（燐光）分析灵敏度高，检出限低，线性范围宽。     

Determination of benzene, toluene, ethylbenzene and xylenes in air by solid phase micro-extraction/gas chromatography/mass spectrometry

The aim of the study was to analyse BTEX compounds (benzene, toluene, ethylbenzene, xylenes) in air by solid phase micro-extraction/gas chromatography/mass spectrometry (SPME/GC/MS), and this article presents the features of the calibration method proposed. Examples of real-world air analysis are given. Standard gaseous mixtures of BTEX in air were generated by dynamic dilution. SPME sampling was carried out under non-equilibrium conditions using a Carboxen/PDMS fibre exposed for 30 min to standard gas mixtures or to ambient air. The behaviour of the analytical response was studied from 0 to 65 g/m³ by adding increasing amounts of BTEX to the air matrix. Detection limits range from 0.05 to 0.1 g/m³ for benzene, depending on the fibre. Inter-fibre relative standard deviations (reproducibility) are larger than 18%, although the repeatability for an individual fibre is better than 10%. Therefore, each fibre should be considered to be a particular sampling device, and characterised individually depending on the required accuracy. Sampling indoor and outdoor air by SPME appears to be a suitable short-delay diagnostic method for volatile organic compounds, taking advantage of short sampling time and simplicity.     

Multivariate monitoring of soybean oil ethanolysis by FTIR

In this work, an analytical procedure was developed to monitor the ethanolysis of degummed soybean oil (DSO) using Fourier-transformed mid-infrared spectroscopy (FTIR) and methods of multivariate analysis such as principal component analysis (PCA) and partial least squares regression (PLS). The triglycerides (reagents) and ethyl esters (products) involved in ethanolysis were shown to have similar FTIR spectra. However, when the FTIR spectra derived from seven standard mixtures of triolein and ethyl oleate were treated by PCA at the region that represents the CO stretching vibration of ester groups (1700-1800 cm⁻¹), only two principal components (PC) were shown to capture 99.95% of the total spectral variance (92.37% for the former and 7.58% for the latter PC). This observation supported the development of a multivariate calibration model that was based on the PLS regression of the FTIR data. The prevision capability of this model was measured against 40 reaction aliquots whose ester content was previously determined by size exclusion chromatography. Only small discrepancies were observed when the two experimental data sets were treated by linear regression (R²=0.9837) and these deviations were attributed to the occurrence of non-modeled transient species in the reaction mixture (reaction intermediates), particularly at short reaction times. Therefore, the FTIR/PLS model was shown to be a fast and accurate method to predict reaction yields and to follow the in situ kinetics of soybean oil ethanolysis.     

Performance validation of step-isothermal calorimeters

Isothermal calorimetry is becoming indispensable as a tool for the study of a wide variety of systems. As with all scientific instruments it is essential that robust calibration routines be developed in order to validate the data obtained. Chemical test reactions offer many advantages over (the traditionally used) joule effect heating methods, not least because they have the potential to validate instrument performance (i.e. they can be used to assess all aspects of calorimeter operation). In this work the results of a validation exercise, conducted by Thermal Hazard Technology as part of an installation routine, using the base catalysed hydrolysis of methyl paraben are discussed. In the case described, a systematic misreporting of the reported temperature of a calorimeter was identified, caused by an upgrade to the calorimeter's firmware, a discrepancy which may not have been noted using traditional electrical calibration methods and one which highlights the importance of both manufacturers and end-users adopting chemical test reactions into their test and validation routines.     

Simultaneous determination of albumin and immunoglobulin G with fluorescence spectroscopy and multivariate calibration

A method is proposed for the simultaneous determination of albumin and immunoglobulin G (IgG1) with fluorescence spectroscopy and multivariate calibration with partial least squares regression (PLS). The influence of some instrumental parameters were investigated with two experimental designs comprising 19 and 11 experiments, respectively. The investigated parameters were excitation and emission slit, detection voltage and scan rate. When a suitable instrumental setting had been found, a minor calibration and test set were analysed and evaluated. Thereafter, a larger calibration of albumin and IgG1 was made out of 26 samples (0-42 μg ml⁻¹ albumin and 0-12.7 μg ml⁻¹ IgG1). This calibration was validated with a test set consisting of 14 samples in the same concentration range. The precision of the method was estimated by analysing two test set samples for six times each. The scan modes tested were emission scan and synchronous scan Δ60 nm. The results showed that the method could be used for determination of albumin and IgG1 (albumin, root mean square error of prediction (RMSEP) <2, relative standard error of prediction (RSEP) <6% and IgG1, RMSEP <1, RSEP <8%) in spite of the overlapping fluorescence of the two compounds. The estimated precision was relative standard deviation (R.S.D.) <1.7%. The method was finally applied for the analysis of some sample fractions from an albumin standard used in affinity chromatography.     

分子电子学的新进展

分子尺度电子学通过构筑基于微尺度电极和单个分子或者少量分子聚集体的"电极-分子-电极"结，研究跨越分子的电荷输运性质.它将分子本征化学特性与器件构筑相结合，考察分子的理化特性与电荷输运的构效关系，揭示微尺度的量子输运动力学原理，并探索基于分子的功能电子器件.是一个集化学、物理学与微电子学为一体的交叉学科.总结整理了分子电子学近些年在器件制备、输运机理及应用方面部分有代表性的进展.     

Analysis of microgram amounts of particulate material by simultaneous multiwavelength AES

A unique simultaneous emission spectrograph is utilized to perform qualitative and quantitative analysis on trace quantities of solid particulates. The atomic emission spectroscopic system consists of a direct current plasma source and an echelle spectrograph with a charge injection device detector, enabling the system to simultaneously measure the wavelength range from 220 nm to 520 nm with 0.02 nm resolution at 300 nm. Monitoring all wavelengths simultaneously allows the qualitative and quantitative determination of most major and minor constituent in a trace quantity of sample with little prior knowledge about the sample. The ability to perform qualitative and quantitative analysis on particulates is demonstrated by evaluating NBS certified coal fly ash, as well as a sample taken from the respirator air filter at an acute care unit in a hospital.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria