Structure analytical methods for quantitative reference applications

The analytical methods mass spectrometry, UV/Vis, IR, Raman, Fluorometry, XRD, Mössbauer, and NMR used to elucidate chemical structure are evaluated regarding their capabilities to be used as primary analytical techniques in quantitative measurements, considering the criteria in the CCQM definition of primary methods. This includes a review of the respective measurement equations, the evaluation of the measurement uncertainty, and a discussion of evidence for the “highest metrological level”, as obtained from intercomparisons in contest with other methods. It is shown that only few methods fulfill the CCQM criteria. Quantitative NMR spectroscopy is one of them and may be considered as a potential primary method as recommended by CCQM because of being free of empirical factors in the uncertainty budget.     

Gas chromatographic system equipped with a mass detector and a selective nitrogen-phosphorous detector operating simulataneously in the analysis of pesticide residues

The possibility to perform gas chromatographic analysis using both a mass detector and a selective nitrogen-phosphorous detector will enable highly sensitive analytical results and an optimal identification reliability. In this work we describe an easily workable technical solution, which has been accomplished in our laboratory and the application of the above system to analytical procedures for the detection and determination of nitrogenous herbicides in drinking water and phosphorylated pesticides in agricultural products is discussed.     

Flow injection-spectrophotometric determination of cresol compounds in water by reaction withp-aminophenol

A spectrophotometric method has been developed for the simultaneous determination ofo-cresol andm-cresol in water by reaction withp-aminophenol (PAP). Three different methodologies have been assayed; (i) batch analysis, after reaction in an alkaline medium in the presence of dissolved molecular oxygen as oxidizing agent, (ii) a stopped-flow procedure, carried out in the presence of KIO₄ and (iii) a flow injection method based on the same approach. The batch procedure requires 22 min for the full development of colour witho-cresol and 12 min form-cresol. In the stopped-flow mode, using KIO₄ and a reaction time of 12 min, better sensitivity can be obtained for both compounds and limits of detection of 10 g 1^–1 foro-cresol and 30 g 1^–1 form-cresol were found. The flow injection method has a lower sensitivity but permits more than 80 injections per hour. Based on the different maximum absorbance wavelengths obtained for the reaction products of PAP witho-cresol (614 nm) andm-cresol (632 nm), both compounds can be simultaneously determined in water samples and recoveries of 90 to 115% were found in spiked water samples of different types.     

Synthesis and structure of complex compound Rh(III) of (NH4)2[Rh(NO2)3(NH3)(µ-OH)]2 composition

The crystalline structure of a new compound Rh(III) of (NH₄)₂[Rh(NO₂)₃(NH₃)(μ-OH)]₂ composition has been determined. The crystallographic characteristics are H₁₆N₁₀O₁₄Rh₂: a = 6.3963(2) Å, b = 9.3701(4) Å, c = 13.6646(5) Å, β = 102.266(1)°, V = 800.28(5) ų, Z = 2, d _calc = 2.432 g/cm³. The distance Rh...Rh in the dimer is 3.200 Å. Original Russian Text Copyright ? 2006 by S. P. Khranenko, I. A. Baidina, and S. A. Gromilov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 2, pp. 380–384, March–April, 2006.     

Trace anion determination in concentrated hydrofluoric acid solutions by two-dimensional ion chromatography II. Method performance study with a hydroxide eluent and a low noise suppressor

The two-dimensional ion exclusion chromatography/ion chromatography (ICE-IC) approach is considered to be the method of choice for the determination of trace anions in concentrated hydrofluoric acid (48-50%, w/w). In order to achieve lower detection limits, this method was for the first time used with electrolytically generated and purified hydroxide eluents in combination with a low noise electrochemical suppressor. Compared to carbonate based eluents, the achieved gain in peak height sensitivity for chloride, sulfate, nitrate and phosphate is a factor of 6, 7, 16 and 13, respectively. The instrumental detection limits, based on the background noise, are 2, 0.2, 0.4 and 1.4 microg/kg HF 50% (w/w) for the same anions. Their method detection limits, calculated according to SEMI, are all within the 6-10microg/kg HF 50% (w/w) range and thus at least 10 times lower than the current Tier C grade requirements. The chromatographic run time could be shortened with some 10 min by the use of a relatively fast high-capacity hydroxide selective anion exchange column.     

Creatinine biosensor based on ammonium ion selective electrode and its application in flow-injection analysis

A new, highly sensitive, fast responding and stable potentiometric biosensor for creatinine determination is developed. The biosensor is based on an ammonium ion-selective electrode. Creatinine deiminase (EC 3.5.4.21) is chemically immobilized on the surface of the polymeric ion-sensitive membrane in the form of monomolecular layer using a simple, one-step carbodiimide covalent attachment method. The resulting enzyme electrodes are useful for measurement under flow injection analysis (FIA) conditions. The biosensors exhibit excellent operational and storage stability. The enzyme electrodes retain over 70% of initial sensitivity after ten weeks of work under FIA conditions. The storage stability at 4 °C is longer than half a year without loss of sensitivity. Under optimized conditions near 30 samples per hour can be analyzed and the determination range (0.02-20.0 mmol l⁻¹) fully covers creatinine concentrations important from clinical and biomedical point of view. The simple biosensor/FIA system has been successfully used for determination of creatinine in urine, serum and posthemodialysate samples.     

Synthesis,spectroscopic studies,and x-ray crystallographic analysis of the organotin carbohydrate: 1,2∶3,4-di-O-isopropylidene-6-O-triphenylstannylmethyl-α-D-galactopyranose

The title organotin carbohydrate, C₃₁H₃₆O₆Sn, has been synthesized and its molecular structure has been determined in solution and in the solid state. NMR, infrared, mass and X-ray crystallographic techniques were used. The chiral molecules crystallize in the monoclinic space group P2₁ withZ=2. The triphenyltin and carbohydrate moieties are linked by a trans methylene-oxygen-methylene arrangement. The pyranosyl ring adopts a twist-boat conformation and the isopropylidene rings adopt different (half-chair and envelope) forms. Solution and solid-state conformations are similar as only three ¹³C shift values are greater than 2ppm; the ¹¹⁹Sn value is 12 ppm.     

Electrospray tandem mass spectrometric analysis of zeaxanthin and its oxidation products

Carotenoids have been implicated in protection of the eye from light-mediated photo-toxicity caused by free radicals. Under conditions of normal oxidative stress the carotenoids serve as protective antioxidants; however, when the oxidative stress exceeds the antioxidant capacity, carotenoids can be oxidized into numerous cleavage products. The determination and identification of oxidized carotenoids in biological samples remains a major challenge due to the small sample size and low stability of these compounds. We investigated the reaction of various zeaxanthin cleavage products with O-ethyl hydroxylamine to evaluate their levels in a biological sample. For this, a sensitive and specific electrospray tandem mass spectrometry (ESI-MS/MS) was developed, avoiding the classical lower sensitive and specific HPLC-UV and fluorescence absorption methods. Protonated molecules [M + H](+) of carotenoids upon collision-induced dissociation produced a number of structurally characteristic product ions. A series of complicated clusters of product ions differing in 14 (CH(2))and 26 (C(2)H(2))Da was characteristic of the polyene chain of intact carotenoids. All carotenoid ethyl oximes of zeaxanthin cleavage products were characterized by the losses of 60 and 61 Da in their MS/MS spectra. Through the application of the LC/MS/MS method, we identified two oxime derivatives of 3-hydroxy-beta-ionone and 3-hydroxy-14'-apocarotenal with protonated molecules at m/z 252 and m/z 370 respectively, in a human eye sample.     

Modern Analysis

The important advances being made in modern analytical methods are indicative of the fundamental changes that are occuring in the theory and practice of “analytical chemistry”. “Information optimization” demands a new approach in teaching and research, and calls for the intergration of chemistry with other scientific and technical disciplines.     

Chemical and thermal analysis of the biopolymers in thyme (Thymus vulgaris)

Thyme (Thymus vulgaris) has been known, long time ago, for its aromatic properties. It contains essential oils and polymers such as cellulose (mixture of hemicellulose and cellulose) and lignin. The thyme, studied in this work, was gathered from the same place, in the period from November 1999 to October 2000. The chemical analysis (water, total ash, essential oils, extractive substances, cellulose, holocellulose and lignin) can be used roughly in the characterisation of the four periods that correspond to the four seasons of the year. The cellulose level was found to be more than lignin level in the wet periods (growth of the plant). The opposite was found in the dry periods. The total ash and essential oil levels were found to be high during the period of high pluviometry. The thermal decomposition of cellulose and holocellulose was found to fit well with the first-order kinetics. The activation energy, under air flow, was 185 and 196 kJ mol⁻¹ for cellulose and holocellulose, respectively. The maximum decomposition rate and thermal analysis heating rate of lignin were found to have a direct linear relationship.