Covalent immobilization of heparin on a collagen film

Four procedures for the covalent immobilization of heparin (Hp) on a collagen film (CF) have been investigated. In three of them (methods (I–A, B, C), the CF was first treated with epichlorohydrin and ammonia and the Hp was added with the aid of CMBC (method I–A), by reductive amination in the presence of NaCH CN (method I–B), and with the aid of CMEC after succinylation (method I–C). In the fourth procedure (method II), the CF was activated by treatment with alkali and the Hp was added with the aid of CMEC. It was shown that the maximum amount of Hp was immobilized by method II.M. V. Lomonosov Moscow State University. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 700–704, September–October, 1987.     

Construction of Trigonometrically and Exponentially Fitted Runge–Kutta–Nyström Methods for the Numerical Solution of the Schrödinger Equation and Related Problems – a Method of 8th Algebraic Order

General conditions are presented for an m-stage Runge–Kutta–Nyström fitting to exponential and trigonometric functions. As an example an 8th order Runge–Kutta–Nyström method is constructed. Numerical results on the numerical solution of the Schrödinger equation and related problems indicate that the new method is more accurate than the classical one (we call classical Runge–Kutta–Nyström method the corresponding method with constant coefficients).     

Study and prediction of alkylbenzenes’ vapour pressures

Vapour pressures of 1,4-di-tert-butylbenzene (379–1647 Pa), 1,3,5-tri-tert-butylbenzene (203.9–241 Pa), 1-methyl-3,5-di-tert-butylbenzene (16.7–435.8 and 1318–103,880 Pa), and 1,2,2-trimethylpropybenzene (36.3–287.4 Pa) have been measured using a transpiration method and an ebuliometric method. Based on the literature and obtained by the authors experimental data a comparative study of prediction capabilities of the following methods has been carried out: Ambrose–Walton's, Lee–Kesler's, Riedel's and the modification of Riedel's method made by Vetere.     

Synthesis and characterization of platinum monolayer oxygen-reduction electrocatalysts with Co–Pd core–shell nanoparticle supports

We synthesized Pt monolayer electrocatalysts for oxygen-reduction using a new method to obtain the supporting core–shell nanoparticles. They consist of a Pt monolayer deposited on carbon-supported Co–Pd core–shell nanoparticles with the diameter of 3–4 nm. The nanoparticles were made using a redox-transmetalation (electroless deposition) method involving the oxidation of Co by Pd cations, yielding a Pd shell around the Co core. The quality of the thus-formed core–shell structure was verified using transmission electron microscopy and X-ray absorption spectroscopy, while cyclic voltammetry was employed to confirm the lack of Co oxidation (dissolution). A Pt monolayer was deposited on the Co–Pd core–shell nanoparticles by the galvanic displacement of a Cu monolayer obtained by underpotential deposition. The total noble metal mass-specific activity of this Pt monolayer electrocatalyst was ca. 3-fold higher than that of commercial Pt/C electrocatalysts.     

Square-wave voltametric method for determination of molinate concentration in a biological process using a hanging mercury drop electrode

A square-wave voltammetric (SWV) method using a hanging mercury drop electrode (HMDE) has been developed for determination of the herbicide molinate in a biodegradation process. The method is based on controlled adsorptive accumulation of molinate for 10 s at a potential of –0.8 V versus AgCl/Ag. An anodic peak, due to oxidation of the adsorbed pesticide, was observed in the cyclic voltammogram at ca. –0.320 V versus AgCl/Ag; a very small cathodic peak was also detected. The SWV calibration plot was established to be linear in the range 5.0×10^–6 to 9.0×10^–6 mol L^–1; this corresponded to a detection limit of 3.5×10^–8 mol L^–1. This electroanalytical method was used to monitor the decrease of molinate concentration in river waters along a biodegradation process using a bacterial mixed culture. The results achieved with this voltammetric method were compared with those obtained by use of a chromatographic method (HPLC–UV) and no significant statistical differences were observed.     

Determination of methylmercury fluxes across the air–water and air–soil interfaces by gas chromatography with electron capture detection

A method for the determination of methylmercury (MeHg) fluxes across the air–water and air–soil interfaces was developed using an in situ chamber. The MeHg in the air coming out of the chamber was captured by a column containing sulfhydryl cotton fiber adsorbent. MeHg was then desorbed from the column by using 2 mol L^–1 HCl. The MeHg in the effluent was extracted with benzene, and determined by gas chromatography with electron capture detection. Finally, the MeHg flux was calculated using the chamber. The method was applied to simulated experiments, and the results showed that the MeHg fluxes in the air–water system were higher than those in the air–soil–water system. The method was also successfully applied to the field measurements of an environment polluted by a chemical factory, and the results showed that the MeHg fluxes across the air–soil and air–water interfaces were 0.21–3.09 and 0.14–0.79 ng m^–2 h^–1, respectively. The method will be a useful tool in the environmental study of MeHg.     

Microdetermination of Proteins with the 1,10-Phenanthroline–H2O2–Cetyltrimethylammonium Bromide–Cu(II) Chemiluminescence System

Proteins can enhance the chemiluminescence (CL) intensity of the 1,10-phenanthroline–H₂O₂–cetyltrimethylammonium bromide (CTMAB)–Cu(II) system because unsaturated complexes of Cu(II) with protein have a much stronger catalytic effect on the CL reaction than does Cu(II). On this basis, a new flow injection analysis method for detection of some proteins was established. The method gives linear responses over two orders of magnitude and detection limits at the 0.02–0.05 μg ml⁻¹level for bovine serum albumin, human serum albumin, γ-globulin, and egg albumin. The method was used for determination of proteins in human serum with satisfactory results.     

Redox-iodometry: a new potentiometric method

A new iodometric method for quantifying aqueous solutions of iodide-oxidizing and iodine-reducing substances, as well as plain iodine/iodide solutions, is presented. It is based on the redox potential of said solutions after reaction with iodide (or iodine) of known initial concentration. Calibration of the system and calculations of unknown concentrations was performed on the basis of developed algorithms and simple GWBASIC-programs. The method is distinguished by a short analysis time (2–3 min) and a simple instrumentation consisting of pH/mV meter, platinum and reference electrodes. In general the feasible concentration range encompasses 0.1 to 10^–6 mol/L, although it goes down to 10^–8 mol/L (0.001 mg Cl₂/L) for oxidants like active chlorine compounds. The calculated imprecision and inaccuracy of the method were found to be 0.4–0.9% and 0.3–0.8%, respectively, resulting in a total error of 0.5–1.2%. Based on the experiments, average imprecisions of 1.0–1.5% at c(Ox)>10^–5 M, 1.5–3% at 10^–5 to 10^–7 M, and 4–7% at <10^–7 M were found. Redox-iodometry is a simple, precise, and time-saving substitute for the more laborious and expensive iodometric titration method, which, like other well-established colorimetric procedures, is clearly outbalanced at low concentrations; this underlines the practical importance of redox-iodometry.

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An erratum to this article is available at .     

Spectrophotometric determination of cationic and anionic surfactants with anionic dyes in the presence of nonionic surfactants,part II: Development of batch and flow injection methods

On the basis of the changes in absorption spectra of azo dyes on the addition of an organic onium ion, spectrophotometric methods for the determination of organic onium salts and anionic surfactants were developed, and applied to flow injection method. Propyl orange (PO^–) was used for the determination of organic onium ions. Pairs of PO^– and Zeph⁺ (tetradecyldimethyl-benzylammonium ion) or PO^– and nC₁₈TMA⁺ (n-octadecyltrimethylammonium ion) were used for the determination of anionic surfactants. The determination range of organic onium ions were (0–3) × 10^–5 M by a batch method and were (0–2) × 10^–5 M by a flow injection method. The determination ranges of anionic surfactants were (0–2) × 10^–5 M by the batch method, and were (0–5) × 10^–5 M by the flow injection method, and the detection limit corresponding toS/N = 3 was 3 × 10^–7 M by the flow injection method. By the proposed flow injection method, anionic surfactants in water samples were determined.     

Pre-column derivatization of rofecoxib for determination in serum by HPLC

An HPLC method for determination of rofecoxib in human serum is presented. The method is based on pre-column derivatization of analyte to a phenanthrene derivative of the drug. Rofecoxib and the internal standard were extracted from serum using liquid–liquid extraction. Upon exposure to UV light, the drug was found to undergo a photocyclization reaction, giving a species with high absorbance. Validation of the method has been studied in the concentration range 10–500 ng ml^–1.     

Isolation of phosphatidylinositol from soybean phosphatides

A method is described for isolating phosphatidylinositol (PI) from a lipid extract of soybean phosphatides. The method includes the separation of the extract with the aid of a Büchner funnel and alumina into two fractions — choline-containing phospholipids and a PI fraction — and the purification of the latter on a column of DEAE-cellulose. As a by-product, phosphatidylethanolamine with a chromatographic purity of 95–96% is obtained from the PI fraction.Institute of Marine Biology, Far Eastern Scientific Center, Academy of the Sciences of the USSR, Vladivostok. Far Eastern State University, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 35–38, January–February, 1984.     

Kinetic-Spectrophotometric Determination of Trace Quantities of Thiocyanate Based on Its Landolt Effect on the Reaction of Bromate with Hydrochloric Acid1

A new method for the rapid and sensitive determination of trace quantities of thiocyanate based on its Landolt effect on the bromate-hydrochloric acid reaction was developed. The induction period of the reaction is proportional to the SCN^– concentration. The decolorization of methyl orange by the reaction products was used to monitor the reaction spectrophotometrically at 525 nm. We were able to determine thiocyanate in the range 2 × 10^–7–4 × 10^–5 M by this method. The relative standard deviation for 10 determinations of 1.5 × 10^–6 M thiocyanate ion is 0.19% and the detection limit of the method was 7.00 × 10^–8 M. The method was applied to the determination of thiocyanate in human blood serum and of saliva samples with satisfactory results.     

Determination of serum cortisol using isotope dilution–liquid chromatography–mass spectrometry as a candidate reference method

We propose isotope-dilution mass spectrometry as a candidate reference method for determination of serum cortisol. The method uses liquid chromatography–mass spectrometry (LC–MS), interfaced with electrospray ionization, and selective monitoring of the [M+H]⁺ ions of cortisol and isotopically labeled cortisol. The isotope-dilution–liquid chromatography–mass spectrometry (ID–LC–MS) method simplifies sample-preparation, because samples are processed by simple solvent extraction without further clean-up and derivatization. We studied the time required for complete equilibration of endogenous cortisol and labeled cortisol spiked into serum and found it to be less than 1 h. The repeatability and the reproducibility of the method were evaluated and found to be 0.55% of the measurement value. CRM 192 and 193 from the Bureau Communautaire de Reference were analyzed for verification of the method. The results obtained from the ID–LC–MS method agreed with the certified values. The relative uncertainty of measurement results for samples in the range of a few tens of micrograms per kilogram to several hundred micrograms per kilogram was evaluated and found to be 0.56%. Immunoassay carried out by three independent clinical laboratories produced results more than 15% higher than this ID–LC–MS method, suggesting the presence of bias in the immunoassay methods.     

Spectrophotometric Determination of Certain Vicinal Dihydroxybenzene Derivatives with Sodium Bismuthate

A simple and accurate spectrophotometric method is developed for the determination of certain vicinal dihydroxybenzene derivatives, namely, dopamine (DPH), levodopa (LD), methyldopa (MD) and pyrocatechol (PC) using sodium bismuthate in an acid medium. The method is based on the formation of a yellow colored product by the oxidation of vicinal dihydroxybenzene derivatives using sodium bismuthate. Beer's law was obeyed over the concentration range of 8–130 g/mL with the maximum absorption at 422–429 nm. The molar absorptivity and Sandell's sensitivity as evaluated from Beer's law data were found to be in the range of 1.02–1.34 × 10^–3L mol^–1cm^–2and 108–185 ng/cm²respectively. The proposed method has been successfully applied for the determination of DPH, LD and MD in injections and tablets of pharmaceutical preparations. The reliability of the methods was established by replicate determinations with the reported and official method.     

Direct determination of iron in ferritin using the polarographic catalytic current

A new method for the determination of iron in ferritin using the polarographic catalytic current has been developed. Iron is released in NaOH and triethanolamine (TEA) solution and subsequently determined based on the polarographic catalytic wave in the presence of bromate with the peak potential of –1.0 V (vs.SCE). The 2.5-derivative peak height of iron is linearly proportional to its concentration in the range of 8.0 × 10^–8–1.0 × 10^–6 g/ml with a correlation coefficient of 0.9991. The method has been applied to the determination of iron in human fetal liver and horse-spleen ferritin and the recovery is 95–112%.     

Determination of pipemidic acid based on flow-injection chemiluminescence due to energy transfer from peroxynitrous acid synthesized on-line

A flow-injection chemiluminescence (CL) method for the determination of pipemidic acid is described. It is based on energy transfer from excited state peroxynitrous acid to pipemidic acid, in which the excited state peroxynitrous acid is synthesized on-line by the mixing of acid hydrogen peroxide with nitrite in a flow system and the CL is from two excited states of pipemidic acid. The proposed method allows the measurement of pipemidic acid over the range of 2.0×10^–7–2.0×10^–5 mol l^–1 . The detection limit is 6.3×10^–8 mol l^–1, and the relative standard deviation for 2.0×10^–6 mol l^–1 pipemidic acid (n= 9) is 0.9%. This method was evaluated by the analysis of pipemidic acid in pharmaceutical preparations.     

Microdetermination of sulfite with a piezoelectric crystal detector

A piezoelectric method is proposed for the determination of sulfite in concentration range 1 × 10^–7–1 × 10^–5 mol/1. The method is based on the redox reaction of sulfite with iodine followed by measuring frequency change of the piezoelectric crystal caused by the unreacted iodine. The method is applied to the determination of sulfite in liquor.     

Spectrophotometric determination of manganese with derivatives of 1,3,3-trimethyl-2-[3-(1,3,3-trimethyl-1,3- H-indol-2-ylidene)propenyl]-3 H-indolium

A new, simple, rapid, and sensitive spectrophotometric method has been developed for the determination of manganese in sewage. The method is based on the reaction of manganese with derivatives of 1,3,3-trimethyl-2-[3-(1,3,3-trimethyl-1,3-H-indol-2-ylidene)propenyl]-3H-indolium to form a colored ion associate with a sensitive absorption maximum at 560 nm. The appropriate reaction conditions have been established: pH 8.5–10.0, 1.25–2.3×10^–3 mol L^–1 1-nitroso-2-naphthol, and 1.6–2.4×10^–4 mol L^–1 dye reagent. Beer's law is obeyed for manganese concentrations up to 4.2 mg L^–1. The limit of detection is 0.01 mg L^–1 Mn²⁺; the molar absorptivity of the ion associate was 7.5×10⁴ L mol^–1 cm^–1. The effect of various foreign ions was examined. A reaction mechanism is suggested. The developed procedure was tested for determination of manganese in sewage with satisfactory precision and accuracy.     

Determination of carbendazim,thiabendazole, and<Emphasis Type="Italic"> o-</Emphasis>phenylphenol residues in lemons by HPLC following sample clean-up by ion-pairing

An efficient analytical method is presented involving effective sample clean-up with solid-phase extraction and HPLC-UV analysis for the simultaneous determination of carbendazim, thiabendazole, and o-phenylphenol residues in lemons. Sample preparation involves extraction with acetonitrile acidified with trifluoroacetic acid and an ethyl acetate/petroleum ether mixture. Purification of the crude extract was carried out with liquid–liquid partitioning after addition of an aqueous ammonia solution. Final clean-up was performed on polymeric reversed-phase cartridges pretreated with sodium dodecyl sulfate. Chromatographic analysis was performed on a reversed-phase HPLC column isocratically eluted with an acetonitrile/water/ammonia mixture and UV detection at 254 nm. The chromatographic method is repeatable, reproducible, and sensitive. Fungicide recoveries from lemon samples fortified at levels of 5 and 1 mg kg^–1 were 81–85% for carbendazim, 96–98% for thiabendazole, and 81–106% for o-phenylphenol with coefficients of variation of 2.5–7.4%. Detection limits for carbendazim, thiabendazole, and o-phenylphenol in lemons were 0.21, 0.27, and 0.51 mg kg^–1, respectively.     

Neutron Activation Analysis of Bottom and Fly Oil Ash Leachates

Seven samples of oil fly and bottom ashes were leached with water using a Canadian standard test method for shake extraction of solid waste. The concentrations of 20 elements in the leachates were determined by the computerized systematic instrumental absolute neutron activation analysis. The ranges of concentrations (in ppm) found for the elements in the leachates were: Al (3–526), Ba (0.5–6), Ca (100–695), Cl (13–59), Co (1–6.3), Cr (0.2–6.6), Cs (0.03–0.4), Eu (0.003–0.01), Fe (28–690), K (42–464), La (0.3–49), Mg (214–3150), Mn (1.2–20), Na (88–4050), Sb (0.04–0.4), Sc (0.003–0.07), Sr (1.2–23), U (0.07–1), V (1.2–4540) and Zn (2.3–200). These findings were compared with the maximum concentrations allowed for these elements by Canadian regulations. The concentrations of Cr and U were found to be higher than their permissible limits on 7 occasions. The purpose of this study was to determine the background levels of different elements in oil ash leachates, in order to evaluate their potential impact on underground water.