Arylferrocenylmethanols: a new family of ferrocenes to be used as mediators in biosensors

Arylferrocenylphenylmethanols, ArFcPhCOH, were prepared from the corresponding aryl ferrocenyl ketones, ArCOFc, prepared by Friedel–Crafts acylation. pK_a values of ArCOFc were determined in sulfuric acid. The electrochemical properties of ArFcPhCOH were investigated. Copyright © 2003 John Wiley & Sons, Ltd.     

Fast Analysis of Statins in Pharmaceuticals by MEKC

A universal micellar electrokinetic capillary chromatographic (MEKC) method with diode-array detection for the simultaneous and short-time analysis of lovastatin, simvastatin, pravastatin, fluvastatin, atorvastatin and rosuvastatin was introduced. Base hydrolysis was used to open lactone ring of lovastatin and simvastatin, administered as lactone prodrugs, in order to transform these compounds to the corresponding β-hydroxyl acid forms before MEKC analysis. This approach offered shorter analysis time due to a decrease of the migration times of negatively charged statin drugs in comparison to neutral lactone forms. Optimized conditions were found to be a 25 mM borate buffer pH 9.5 with 25 mM sodium dodecyl sulphate and 10% methanol added as an organic modifier, an applied voltage of 23 kV and a separation temperature of 30 °C. Ketoprofen was used as an internal standard. The linearity of the detector response for each statin was within the concentration range from 10 to 100 μg mL^?1 with a correlation coefficient greater than 0.9994. Analyses of six statin drugs in pharmaceutical samples were carried out in only 5 min. The interference of the tablet sample matrix was not observed. The recovery values were in the range of 98.04–100.80%.     

Investigation of novel composites to be used as backfill materials in radioactive waste disposal facilities

Journal of Radioanalytical and Nuclear Chemistry - The current work aims at the preparation and characterization of novel composite materials of acrylic acid/charcoal/montmorillonite (MMT) (PAACM...     

Application of Hadamard transformation to MEKC

The Hadamard transform (HT) technique, which permits the S/N in CE to be improved, was applied to MEKC. Multiple sample injection of fluorescent analytes according to a Hadamard code sequence was performed using an optically gated sample injection technique, in which a sample plug was produced based on photodegradation by irradiation with an intense laser beam. The capillary and reservoirs were filled with a sample solution containing buffer components and SDS as a pseudostationary phase. A preliminary study confirmed that fluorescein ion could be photobleached in the presence of SDS. The optically gated sample injection technique was then applied to multiple sample injection, based on a Hadamard matrix. The S/N in the electropherogram obtained by HT-MEKC was improved substantially compared to that obtained by a single injection method. When the technique was applied to the separation of several amino acids labeled with FITC, the S/N ratio for each amino acid was enhanced, without any evidence of degradation in separation resolution. Moreover, HT-MEKC was applied to the analysis of amino acids contained in a Japanese beverage, resulting in improved S/Ns for the amino acids.     

The use of internal standards in ICP-MS

Careful study of the matrix effect in ICP-MS showed that, in all cases studied, the magnitude of the signal suppression or enhancement depends in a regular way on the mass number. Hence, accurate correction for non-spectral interferences is only possible using an internal standard with mass number close to that of the analyte element(s). It is also shown that using an internal standard with mass number close to that of the analyte improves the precision. For both cases, the ionization energy of the internal standard seems to be of no or only secondary importance. To obtain optimal precision and accuracy, the internal standard should be selected as close in mass number as possible to that of the analyte element(s). When a number of elements over a considerable mass range are to be determined, several internal standards have to be used.     

Formamide as an organic modifier in MEKC with SDS

The effect of formamide (FA) as a modifier on the retention in MEKC with SDS as the detergent was investigated. The mobility of a series of alkylphenones and of a zwitterionic fluorescent compound as a function of the FA and the SDS concentration was determined for this purpose. Buffering electrolyte was borate, pH 9.23, with total ionic strength of 50 mM. The dependence of the mobility on the FA content – up to 63% w/w – of the BGE (at 10 mM SDS) allows the conclusion that the micelles are destabilized, and the CMC is shifted to higher values. In the system containing 33% FA or more no micelles are present anymore, and the retention factors of all compounds tend to zero. In an MEKC system with 27% v/v FA the CMC of SDS is increased from 2.4 mM in the aqueous BGE with the same buffer composition to 9.7 mM, a behavior that is in contrast to electrolyte‐free FA–water systems. The partition constants of free analytes and the formation constants of the adduct between analyte and detergent monomer (assuming 1:1 stoichiometry) were derived from the dependence of the mobility on the SDS concentration. In addition, the involved equilibria were extended by that from the distribution of the analyte–monomer adduct between aqueous and micellar phase, and the according partition constants were derived as well. A selective change in the extent of partitioning was observed for the zwitterionic compound. In general, all binding constants were decreased upon addition of FA, though to a different extent. Although the binding constants of the analyte–monomer associate were only slightly influenced, the most pronounced decrease is found for their partitioning into the micelles.     

Application of polyelectrolyte complexes as novel pseudo-stationary phases in MEKC

Polyacrylic acid (PAA) and polymethacrylic acid (PMAA) with carboxyl groups partially blocked by dodecyltrimethylammonium bromide (DTAB) and tetrabutylammonium bromide (TBAB) were tested as new pseudo-stationary phases in micellar electrokinetic chromatography (MEKC). The separation of was examined using PAA and PMAA. Excellent resolution of the substituted phenols and derivatized amino acids was demonstrated using additives of PAA-DTAB polyelectrolyte complex in the running phosphate buffer. It was found that the capacity factors were proportional to the concentration of the complex PAA/DTAB. Critical micelle concentration was effectively zero. It was found that the migration times and efficiency of separation of phenols and derivatives of amino acids depended on the type of polymers and alkyltrimethylammonium salts used.     

Use of CRM's as mutual calibrating materials and control of syntheti multielement standards as used in INAA

The comparability of analytical results from different laboratories requires accurately known concentrations in the applied standards. Dilution effects of different multielement synthetic standard solutions have been studied by measuring 10–12 different concentrations of the same solution. Peak area comparison of four Certified Reference Materials (CRM's) using one value for the evaluation of the other three repetitively led to the intercomparison (degree of compatibility) of the certified values. The idea of the preparation of each laboratory's secondary reference standard by comparison of synthetic multielement standards with as many CRM's as practically feasible is advocated to improve the reliability of analytical results.     

可作为聚合单体的含硫杂杯[4]芳烃的合成

以对叔丁基苯酚为起始原料,经过六步反应,在杯芳烃母体的下沿引入含硫类冠醚结构,上沿引入两个氨基,得到一个未见报道的硫杂杯芳烃,并通过1HNMR、MS、IR、元素分析和熔点测定确定了产物结构。本实验所得产物使硫杂杯芳烃独特的性能应用于功能高分子材料中成为可能。     

Monofluorinated analogues of polycyclic aromatic hydrocarbons as internal standards for GC-MS in environmental analysis

Summary In the gas chromatographic determination of polycyclic aromatic hydrocarbons (PAHs), internal standards (ISs) are frequently used in order to correct for losses and fluctuating experimental parameters. In this study eight monofluorinated PAHs (F-PAHs) are used to this end. Analysis was by means of large-volume injection-gas chromatography with mass spectrometric detection (LVI-GC-MS). Relevant experimental results and performance data are presented, and it is demonstrated that the use of at least one F-PAH as IS improves the repeatability dramatically. As a brief application, F-PAHs were used as ISs for the trace-level determination of PAHs in soil, after extraction by means of pressurized liquid extraction (PLE) and liquid partitioning (LP). The suitability of the approach was demonstrated with naphthalene and pyrene as test compounds.     

Analysis of Atorvastatin and Related Substances by MEKC

A new micellar electrokinetic capillary chromatographic (MEKC) method has been developed for simultaneous quantitation of atorvastatin (AT) and its related substances. The separation was carried out in an extended light path capillary at applied voltage of 30 kV using a background electrolyte consisting of 10 mM sodium tetraborate buffer pH 9.5, 50 mM sodium dodecyl sulphate and 20% (v/v) methanol. The addition of methanol to the running buffer resulted in a very effective choice to achieve resolution between the peaks of charged substances adjacent to AT as well as the peaks of neutral drug-related substances. Linear calibration curves were established over the concentration range 100–1,200 μg mL^?1 for AT and 1.0–12.5 μg mL^?1 for related substances. The proposed MEKC procedure has been validated with respect to selectivity, precision, linearity, limits of detection, and quantitation, accuracy and robustness. The method has been successfully applied to the determination of AT and purity evaluation of bulk drug and formulated products.     

Synthetic multielement standards used for instrumental neutron activation analysis as rock imitations

Complex (multielemental) standards representing microelement composition of standard rocks such as trap ST-1 (USSR), gabbrodiorite SGD-1 (USSR), albitized granite SG-1 (USSR), basalt BCR-1 (USA) and granodiorite GSP-1 (USA) have been synthesized. It has been shown that the concentration of each microelement in the synthetic standards can be given with a high precision. Comparative investigation has been carried out of the synthetic imitations and the above natural standard rocks. It has been found that the result of the instrumental neutron activation analysis using the synthetic standards is as good as in the case when natural standard rocks are used. The results obtained have been also used for substantiation of the versatility of the method used for standard preparation, i.e. a generalization has been made of a possibility of using this method for the preparation of synthetic standards representing the microelement composition of any natural rocks with various compositions and concentrations of microelements.     

Synthesis of Amino Acid Derivatives of Neamine and 2-Deoxystreptamine to be used as Mutasynthons

ABSTRACT

6′-N derivatives of neamine with alanine, phenylalanine and lysine were synthesized either using an active esters method in one step under controlled conditions, or using a mixed anhydride method after blocking every functional group of neamine and leaving the 6′-amino group free to react. Similarly N,N′-diamino acid and monoamino acid derivatives of 2-deoxystreptamine were synthesized.     

Radiation effects on agar, alginates and carrageenan to be used as food additives

Agar, alginates and carrageenan are hydrocolloids that induce stabilization of physical properties of the food product during shelf life and prevention of undesirable changes such as moisture migration, gas cell coalescence or textural profile changes. In this work, agar, alginates and carrageenan was irradiated as powder with different doses (0–10 kGy) of Co-60 and the rheological functional performance of water solutions of these irradiated additives was studied. The results are analyzed taking in account the future applications of those additives in irradiated foods.     

Synthesis and functionalization of carbon xerogels to be used as supports for fuel cell catalysts

The synthesis and properties of carbon xerogels are briefly described in this mini-review, emphasizing the methods used for tuning their surface chemistry and textural properties in order to design efficient electrocatalysts for fuel cells. In particular, the role played by the surface functional groups in determining the loading, dispersion, oxidation state and stability of the metal phases is addressed.     

Fluorescein thiocarbamyl amino acids as internal standards for migration time correction in capillary sieving electrophoresis

A number of algorithms have been developed to correct for migration time drift in capillary electrophoresis. Those algorithms require identification of common components in each run. However, not all components may be present or resolved in separations of complex samples, which can confound attempts for alignment. This paper reports the use of fluorescein thiocarbamyl derivatives of amino acids as internal standards for alignment of 3-(2-furoyl)quinoline-2-carboxaldehyde (FQ)-labeled proteins in capillary sieving electrophoresis. The fluorescein thiocarbamyl derivative of aspartic acid migrates before FQ-labeled proteins and the fluorescein thiocarbamyl derivative of arginine migrates after the FQ-labeled proteins. These compounds were used as internal standards to correct for variations in migration time over a two-week period in the separation of a cellular homogenate. The experimental conditions were deliberately manipulated by varying electric field and sample preparation conditions. Three components of the homogenate were used to evaluate the alignment efficiency. Before alignment, the average relative standard deviation in migration time for these components was 13.3%. After alignment, the average relative standard deviation in migration time for these components was reduced to 0.5%.     

Monofluorinated polycyclic aromatic hydrocarbons as internal standards in Shpol’skii spectroscopy: 1-fluoropyrene as an example

As a sequel to an earlier paper, we have studied the behaviour of 1-fluoropyrene and pyrene in lamp-excited Shpol’skii spectrofluorimetry at 11 K in two different matrices, n-octane and n-hexane, using two different solidification processes. Particular attention is paid to the suitability of 1-fluoropyrene as an internal standard (IS) to correct for different sources of variability. As a demonstration of the applicability of this approach, four polycyclic aromatic hydrocarbons (PAHs; pyrene, chrysene, benzo[a]pyrene and benzo[k]fluoranthene) were determined in a river sediment extract. The results agreed well with those obtained by HPLC with fluorescence detection.