Simulation by Molecular Dynamics of Erbium-Activated Silica-Titania Glasses

Rare-earth doped silicate-based glasses are widely used in telecommunication technology. A limitation in the performance of active optical devices such as amplifier comes from the rare-earth clustering. Simulation methods give complementary informations to the spectroscopic usual investigations. We present a molecular dynamics simulation of a SiO₂-TiO₂:Er³⁺ system in varying its composition. Different distribution functions have been analyzed in order to have information about the clustering of erbium. To this purpose, the titanium distribution has been studied for concentration 7.8 and 15.7% Ti/(Ti + Si). We have simulated the structure of the system doped with 1 and 2.3 mol%. A calculation of the crystal field strength for the different kinds of erbium site has been interpreted in the light of the local structure. The important trend of erbium for clustering in our modeled system has been explained by the energetic requirements of the rare-earth.     

Catalytic cycloisomerization of enynes by using a nickel-zinc-acid system

Catalytic cycloisomerization of enynes has been accomplished in the presence of an Ni0-PPh3-Zn-carboxylic acid or -ZnCl2 system. A nickel(I)-hydride complex, thought to be generated by reduction of the protonated nickel(II) complex with Zn, is proposed as the catalytic species. This cycloisomerization shows reactivity behavior that is different from that of a conventional metal-catalyzed reaction. In particular, in the reaction with (E)-enynes, the catalytic system has a selectivity that favors the formation of the 1,3-diene over the 1,4-diene. In addition, this catalytic system has been applied to the domino cyclization of dienynes for the construction of tricyclic compounds.     

Catalysis of novolacs by p-phenolsulfonic acid

The reaction rate of phenol and aqueous formaldehyde in the presence of p-phenolsulfonic acid has been studied. The increase in pH during the reaction, which decreases the reaction rate, can be correlated with the disappearance of polyoxymethylene (formaldehyde), but not as previously supposed solely with the dilution effect of the water formed from the reaction. Gel-permeation chromatography was used to monitor the consumption of phenol and the growth of polymeric species. It has been demonstrated that the formation of a second liquid phase during the novolac process is independent of the amount of catalyst. The liquid two-phase system and its relation to the reaction rate have been examined. The final molecular weight distribution of novolacs is dependent not only on the initial pH of the system, but also on the pH at the onset of devolatilization.     

Internal Standard Correction of Results Obtained by Atmospheric Pressure Chemical Ionization Mass Spectrometry

An internal standard system has been developed for a mass spectrometer equipped with an atmospheric pressure chemical ionization source. The system has been used to overcome sensitivity drift problems that are commonly encountered when the spectrometer is used for long-term environmental monitoring. Additionally, the internal standard has been used to correct sensitivity changes induced by the matrix being analyzed. Principal components of the system are a low concentration internal standard source and a flow-delivery system for introducing the standard to the reagent gas delivery stream of the spectrometer. Following an experiment, real-time data are downloaded to a personal computer where internal standard correction and data analysis are performed. Application of the internal standard to the measurement of nicotine and pyridine is demonstrated.     

毛细管电泳测定物质三元相互作用体系的结合系数

毛细管电泳一般只能对二元结合体系的结合常数进行测定。研究了三元相互竞争体系的毛细管电泳测定方法,测定了金属锌离子与酒石酸和半胱氨酸以及锌离子与乳酸和半胱氨酸两个三元结合体系的结合常数,并以此比较了两种锌形态与半胱氨酸结合能力的大小。本法可用于测定两配体相互竞争结合体系的结合常数。     

Analysis of Plasma Angiotensins by Reversed Phase HPLC and Radioimmunoassay

Abstract

The analysis of biologically active angiotensin peptides in blood plasma by high performance liquid chromatography in a weakly non-polar reversed phase (C₂) chromatographic system combined with quantification of chromatographically isolated peptides by radioimmunoassay has been developed. This system is able to resolve each of seven closely-related peptides of the angiotensin group. The chromatographic system was applied to plasma samples which have been prepared for chromatographic analysis by C₁₈ cartridge extraction. Samples were reconstituted in HPLC solvent prior to injection into the HPLC system. Separated angiotensin were collected by fraction collector and the volatile components of the solvent system were blown off under an air stream. The content of several of the various angiotensin peptides in the fractions was then determined by radioimmunoassay using an appropriate antiserum. Antiserum to angiotensin II (octapeptide) was used to quantify the biologically active components angiotensin II, angiotensin III (hepta-peptide) and C-terminal hexapeptide. Recovery of angiotensin II in the C₁₈ cartridge extraction has been assessed at 85.0 ± 0.9% (mean ± SEM) using I¹²⁵-labelled angiotensin II, and 82.2 ± 4.45% using synthetic unlabelled angiotensin II. Recovery of standard preparations of angiotensin II in the HPLC system have been estimated at 67.5 ± 6.08%. The application of this technique to evaluating some components of the angiotensin in normal plasma is presented.     

Improved method for determining binary adsorption isotherms by using concentration pulse chromatography: adsorption of CO2 and N2 by silicalite at different pressures

Adsorption separation of carbon dioxide from nitrogen at different system total pressures with silicalite as the adsorbent was studied by using concentration pulse chromatography. Improving the methodology for determining binary adsorption isotherms by concentration pulse method (CPM) was also the goal of this study. Binary adsorption isotherms, x–y phase diagrams and separation factor plots have been determined at 26 °C to look at the influence of pressure on the separation using concentration pulse chromatography. Available methods for determining binary adsorption isotherms using CPM have been reviewed and shown to be incapable of interpreting this particular binary system. An improved novel model has been proposed to interpret the data in this study. It has been referred to as the Kennedy-Tezel concentration pulse method (KT-CPM) and has been shown to be superior to other methods used in the literature. Results using this data were found to be consistent with the previous results in the literature. The binary isotherms for the CO₂–N₂ system show a decrease in CO₂ selectivity as total system pressure increases. The optimal separation factor for silicalite was found to increase with decreasing system pressure and decreasing mole fraction of CO₂ in the feed mixture.     

On-Line Monitoring of MWD in a Batch Polymerization Reactor by Size Exclusion Chromatography

Abstract

A novel highly automated SEC system has been developed for online measurement of MWD in a batch solution polymerization reactor. The system includes a liquid exclusion chromatograph, an automatic sampling system, a programmable microprocessor based sequence timer and a process computer. Two main real-time computer programs have been developed to supervise the automatic collection (SEC-Data Acquisition Program) and interprepation (SEC-Data Interprepation Program) of SEC data. Experimental results show that the new system can provide reliable on-line measurements of number average and weight average molecular weights of a sample during the course of polymerization.     

Crystallization kinetics of thermosensitive colloids probed by transmission spectroscopy

The kinetics of crystallization of poly-N-isopropylacrylamide (PNIPAM) particles has been investigated using the UV-visible transmission spectroscopy. Since the particle size decreases with the increase in temperature, microgel dispersions of different volume fractions have been obtained by varying the temperature of a single sample. It is found that the rates of the change in crystallinity, the average crystallite size, and the number density of crystallites at the most rapid stage over a certain time interval at various temperatures can be described by the power-law relations. At 19 degrees C, the PNIPAM system behaves as a hard sphere system under microgravity. The hard sphere theory based on Monte Carlo simulation has been used as a reference point to compare with conventional hard spheres, soft spheres, and PNIPAM spheres.     

等离子体引发丙烯酰胺的反相悬浮聚合

通过等离子体引发技术进行了丙烯酰胺的反相悬浮聚合研究,考察了后聚合时间,放电时间,放电功率,单体浓度,分散剂浓度及溶剂极性对聚合物分子量和转化率的影响。结果发现：延长后聚合时间有利于反应的进行,而在聚合反应中存在着一个最佳的单体浓度值,增加溶剂的极性有利于反应进行,降低体系中空气残留量也有利于反应进行。     

Conductometric determination of ammonium by a multisyringe flow injection system applying gas diffusion

A multisyringe flow injection system (MSFIA) coupled to a gas-diffusion cell has been developed for the conductometric determination of ammonium in different water samples. Operation strategies, membrane, reagent concentrations, and flow rates have been studied to optimize the sensitivity of detection and to fit the required working range. The proposed MSFIA system has been compared with former FIA and SIA systems using gas diffusion. The system was applied to the determination of ammonium in water samples of different matrices in order to evaluate its performance. These samples were coastal waters, pond waters, and compost aqueous extracts. Good recoveries of 102?±?13% were obtained and no significant differences with the reference methods were found. The system can be used for a wide concentration range of ammonia, from 0.075 to 360?mg?L^?1, without sample dilution and with a precision better than 2% of RSD. The throughput of the method was 32 injections per hour.     

Efficient oxidation of secondary alcohols to Ketones by NaOCl catalyzed by Salen-Mn(III)/NBS

An efficient catalytic system salen-Mn(III)/NBS for oxidation of secondary alcohols to ketones by inexpensive and readily available oxidizing agent NaOCl has been developed. The process resulted in good to excellent yields under the action of 2 mol % of salen-Mn(III) and 13 mol % of NBS at room temperature. However, such system was not efficient in oxidation of secondary benzyl alcohols with a strong electronicdonating substituent attached to the benzene ring due to bromination of the alcohols.     

Control of voltammetric experiments by means of the Commodore 64 microcomputer

An electronic interface for the Commodore 64 microcomputer suitable for generation of voltammetric waveforms and for data acquisition has been built. Used together with analogue voltammetric instruments the interface makes updating of the measurement techniques possible. Also, fast A/D-conversion and a floppy disk drive make the system useful as a universal data-acquisition unit in the laboratory. The system has been tested together with an amperometric detector in the square-wave voltammetric determination of paracetamol and iodide.     

Determination of polar analytes in aqueous matrices by purge and trap

(not readable) fully autimated purge and trap system has been developed for (not readable) detemination of volatile wine components. The proposed system consists of sampler, a purge and trap instrument, and a GC, (not readable) steps, from the uptake of the infiltrated wine from the sampler (not readable) to the printout of the intergrated chromatograms, proceed(not readable), Typical problems occurring when analyzing polar analytes by the classical purse and trap approach have been specifically addressed. The system has been desiggned to handle such difficult (not readable) analytes. Efforts have been made to improve the reproducibility and the carry-over of these analytes. The measures adopted include: thorough rinsing and subsequent conditioning of the P + T parger; elimination of matrix effects by dilution and high salt (not readable); tight specification of purge relevant parameters; split-inter-(not readable) to improve GC retention time reproducibility.     

A new accessory for the detection of trace components by FT-IR spectroscopy

We have developed a specific compartment to increase the sensitivity of a routine FT-IR spectrometer. A high performance MCT detector has been included in the system. The SNR of the spectrometer has been improved by a factor of 10.     

Determination of aminocresol isomers by high-speed liquid chromatography

Aminocresol isomers (4-hydroxy-m-toluidine [II], 3-hydroxy-p-toluidine [II], 2-hydroxy-p-toluidine [III]) and p-aminophenol have been separated and determined by a high-speed liquid Chromatographie method. Since this method is applicable in aqueous media, it was used to investigate the suitability of a haemin-cysteine system as a model for the cytochrome P-450 mono-oxygenase system, by determination of the [I], [II], [III] and p-aminophenol formed.     

Control of the excitability of neuronal tissue by weak external forces

The spreading depression (SD) is a pronounced example of excitation-depression waves in excitable media, to which neuronal tissue according to its structure and functions belongs. SD waves can especially easily be observed in the vertebrate retina which is neuronal tissue and a true part of the central nervous system (CNS). According to the high intrinsic optical signal (IOS) concomitant with the retinal spreading depression (rSD), it can be monitored with standard video imaging techniques, thus the retina has been used in our studies as a suitable model system for neuronal tissue in general. In particular, the control of wave set-up and propagation in excitable media by weak external forces is of high interest. Accordingly, the interaction of rSD waves with DC and AC electromagnetic fields of low amplitude and frequency and with gravity has been investigated in this study. The dependence of rSD-wave propagation velocity on the given parameters as one important indication of excitability control has been investigated in detail. Our results with rSD waves are partially compared to another well known excitable medium, the Belousov-Zhabotinsky reaction, where some data about the effects of electrical fields and gravity have already been published.     

Efficient allylation of aldehydes with allyltributylstannane catalyzed by CuI

Cuprous iodide has been found to be a very effective catalyst for allylation of aldehydes with allyltributylstannane. The catalytic system efficiently promotes the allylation reaction in DMF to produce homoallylic alcohols in high yield.     

Fast choice of separation conditions for analyses by capillary zone electrophoresis using an information system Xemic

An information system Xemic applicable in analytical chemistry is described and its use in capillary electrophoresis for searching suitable separation conditions is demonstrated. This system is capable to provide suitable separation conditions even for analytes for which no electrophoretic experiments have been published so far. The system works with a database of components of anionic character the analyses of which have been performed, published in reviewed scientific journals, and included into a database created by an expert. Moreover, the system learned to search also in abstracts or complete scientific articles to find articles dealing with the determination of a substance in a given sample matrix. When no experiments have been published so far for a defined substance in a specific matrix, Xemic shows the separation conditions for determination of the substance regardless of the matrix. When no response can be found for the analyte of interest at all, the system Xemic works like an expert in the field and searches chemically similar substances and offers a series of substances the physicochemical properties of which are close to the followed analyte with respect to the behavior in the electric field, and shows working conditions for their analysis. Thus, the analyst puts only the order in the form of a given analyte in a given matrix and obtains a recommendation of a separation system that should enable to perform a successful separation. The system is not rigid and enables the operator to change the importance of individual attributes used in similarity search so as to obtain a broader or narrower group of similar components. With a certain probability the analyte of interest can be successfully analyzed under separation conditions that suited for the analysis of the most similar substances in the given matrix.     

液膜分离富集、测定痕量钼

用乳状液膜体系对钼进行富集。该体系包括载体 ( 5,8-二乙基 - 7-羟基十二烷 - 6-单肟 ,简称LIX63)、表面活性剂 (N1 1 3C)、溶剂(煤油 )以及内相 ( 0 .1 5mol/LNaOH溶液 )。研究了乳状液膜的稳定性、温度、钼的浓度、外相的HNO3溶液浓度及乳水比等因素对分离富集钼的影响。实验表明 ,在适宜的条件下 ,钼的迁移率可达 99.5%～1 0 0 .2 %。该法已应用于富集、测定纯钨和钢铁中的痕量钼 ,结果相当满意