Mercury-free sono-electroanalytical detection of lead in human blood by use of bismuth-film-modified boron-doped diamond electrodes

We report the electroanalytical determination of lead by anodic stripping voltammetry at in-situ-formed, bismuth-film-modified, boron-doped diamond electrodes. Detection limits in 0.1 mol L^–1 nitric acid solution of 9.6x10^–8 mol L^–1 (0.2 ppb) and 1.1x10^–8 mol L^–1 (2.3 ppb) were obtained after 60 and 300 s deposition times, respectively. An acoustically assisted deposition procedure was also investigated and found to result in improved limits of detection of 2.6×10^–8 mol L^–1 (5.4 ppb) and 8.5×10^–10 mol L^–1 (0.18 ppb) for 60 and 300 s accumulation times, respectively. Furthermore, the sensitivity obtained under quiescent and insonated conditions increased from 5.5 (quiescent) to 76.7 A mol^–1 L (insonated) for 60 s accumulation and from 25.8 (quiescent) to 317.6 A mol^–1 L (insonated) for 300 s accumulation. Investigation of the use of ultrasound with diluted blood revealed detection limits of the order of 10^–8 mol L^–1 were achievable with excellent inter- and intra-reproducibility and sensitivity of 411.9 A mol^–1 L . For the first time, electroanalytical detection of lead in diluted blood is shown to be possible by use of insonated in-situ-formed bismuth-film-modified boron-doped diamond electrodes. This method is a rapid, sensitive, and non-toxic means of clinical sensing of lead in whole human blood.     

Term crossing in the auxiliary Hamiltonian in calculations of energy-level lower bounds in quantum mechanical systems

We study a method for calculating lower bounds on energy levels that uses an auxiliary Hamiltonian with projection operators. We show that a change in the physical parameters of the problem can lead to the crossing of terms of the auxiliary Hamiltonian with the same symmetry. Such crossings, if not accounted for, will lead to incorrect estimates of the energy levels of quantum systems. As an illustration we consider the lower bound for the ground-state energy of the ion H^–.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 5, pp. 513–519, September–October, 1988.     

Spin-spin coupling of77Se and31P nuclei in cyclic organophosphorous compounds

We have established that direct phosphorus-selenium spin-spin coupling constants in cyclic compounds with P=Se exocyclic and P-C endocyclic bonds are found in the range¹J_PSe=–708 to –859 Hz; in this case, it is greater for the axial orientation of P=Se than for the equatorial orientation.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 776–780, April, 1990.     

Trace elements analysis in rice

Various rice species, marketed in Austria, were analyzed for their Se, Cr, Ni, Rb, Fe, Co, Cs, Ag and Hg contents by neutron activation analysis. The concentration values found for Se ranged between 0.023 and 0.265 ppm, for Cr 0.540–1.875 ppm, for Ni 0.359–0.965 ppm, for Rb 1.604–6.400 ppm, for Fe 24.3–139.8 ppm, for Co 0.026–0.055 ppm, for Cs 0.016–0.032 ppm, for Ag 0.0006–0.0034 ppm, for Hg 0.003–0.023 ppm. Statistical analysis showed in the majority of cases that there is a significant difference in Se, Cr, Ni, Rb, Fe, Co, Hg contents but not in Cs. Highest values of Se and Fe were found in rice from Belgium /long seed, super patna/, whereas the Cr concentration was the highest in rice from Thailand /siam patna/. Ni was highest in rice from Uncle Ben's, Rb in Kresto from USA.     

Induced free-radical chain decomposition of dimethylacetamide hydroper oxide in dimethylacetamide as the medium

Conclusions The thermal gross decomposition of dimethylacetamide hydroperoxide (ROOH) in dimethylacetamide (RH) as the medium proceeds in harmony with the equation: W_p=k_ind [ROOH]₀ ^m/[RH]₀ ⁿ, where m=1.5–2; n=2–0.5. Alkyl radicals with a chain length of 195–3 units are mainly responsible for the induced decomposition. We determined the ratio between the molecular and radical directions of the decomposition and k_ind in the range 80–132°.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 967–970, April, 1978.     

Multielement measurements in Mexican cigarette tobacco

The concentration of 21 elements in cigarette tobacco in nine different brands manufactured and commercially available in Mexico has been determined using neutron activation analysis. The concentration range of the measured elements (in g g^–1) were: As, (four brands) <0.55–3.24; Ba, 64–251; Br, (four brands) 49–136; Ce, <0.3–1.7; Co, 0.29–0.55; Cr, <0.8–2.4; Cs, 0.091–0.40; Eu, <0.03; Fe, 420–680; Hf, <0.03–0.13; K, (four brands) 18300–40300; La, (four brands) <0.2–0.66; Na, (four brands) 309–566; Rb, 19–50; Sb, <0.7; Sc, 0.13–0.22; Se, <0.7; Sm, (four brands) 0.07–0.14; Sr, 227–472; Th, <0.1–0.17 and Zn, 14–56. The results are compared with the literature values for the concentration of the above elements in cigarette tobacco from other countries.     

Simple types of kinetic oscillators in heterogeneous catalysis

We consider kinetic oscillators in heterogeneous catalysis with the most common types of feedback. We determine simple abstract schemes for the mechanisms of reactions which can occur in the isothermal selfexcited oscillation regime. These schemes are a component of the mechanisms for specific heterogeneous catalytic reactions which are characterized by self-excited oscillations.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 29, No. 4, pp. 306–318, July–August, 1993.     

Negative ion formation in compounds relevant to SF6 decomposition in electrical discharges

Dissociative and nondissociative electron attachment in the electron impact energy range 0–14 eV are reported for SOF₂ SOF₄, SO₂F₂, SF₄, SO₂, and SiF₄ compounds which can be formed by electrical discharges in SF₆. The electron energy dependences of the mass-identified negative ions were determined in a time-of-flight mass spectrometer. The ions studied include F^– and SOF ₂ ^–* from SOF₂; SOF ₃ ^– and F^– from SOF₄; SO₂F ₂ ^–* , SO₂F^–, F ₂ ^– , and F^– from SO₂F₂; SF ₄ ^–* and F^– from SF₄; O^–, SO^–, and S^– from SO₂; and SiF ₃ ^– and F^– from SiF₄. Thermochemical data have been determined from the threshold energies of some of the fragment negative ions. Lifetimes of the anions SOF ₂ ^–* , SO₂F ₂ ^–* , and SF ₄ ^–* are also reported.     

Radiation dose assessment for137Cs from fish in the Aegean Sea before and after the Chernobyl accident

The effective doses from fish in the Aegean Sea have been calculated for the nuclide¹³⁷Cs covering the period 1975–1982. The effective dose varies between 3×10^–5 and 10×10^–5 mSv y^–1 for adults and 14×10^–5 to 56×10^–5 mSv y^–1 for children, while the cumulative effective dose for the period 1975–1982 equals to 40.86×10^–5 and 229.57×10^–5 for both adults and children of 10 y old, respectively. When compared to doses derived from the Chernobyl accident /May 1986/ it was found that the additional dose incurred by Greek individuals in May 1986 was approximately equal to the cumulative dose of 8 y contribution period /1975–1982/ for adults and to a year's contribution for children of 10 y old.     

Modulation effects in A 2+1 electron spin echo pulse sequence

Conclusions Theoretical and experimental studies have been made on the ME trends in 2+1 sequences. The method has advantages over previous ones in having less dead time (not more than 50–100 nsec, as against not less than 300–400 nsec in the two-pulse case) and the absence of relaxation decay and combination frequencies.On the other hand, the method requires more exact information on the pulse lengths and amplitudes and exact shape data.We consider the method most promising for systems showing rapid fall in modulation amplitude, i.e., with nuclei close to the electron spin's.We are indebted to A. Yu. Pusep, S. A. Dikanov, and Yu. D. Tsvetkov for an extremely useful discussion.Institute of Chemical Kinetics and Combustion, Siberian Branch, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 29, No. 1, pp. 73–80, January–February, 1988.     

Occurrence and distribution of metals and porphyrins in Nigerian coal minerals

The metal contents of Nigerian coal minerals were analyzed using an atomic absorption spectrophotometer. Calcium, Na, and Fe occurred as the major elements with concentrations ranging from 9 782 μg/g for Ca to 432 μg/g for Na whereas K, Mg, Mn, Ni, Cr, Zn, Pb, and Cu, which occurred at trace levels ranged from 673.73 μg/g for Mg to 2.97 μg/g for Mn. The results of the quantitative analysis of porphyrins extracted from the coal minerals showed that Onyeama coal has the highest amount of porphyrins (ca～0.96 μg/g) while Okpara has the lowest (ca～0.30 μg/g). The porphyrins were qualitatively characterized by a combination of thin layer chromatography (TLC), infrared, and ultraviolet-visible spectrophotometers. The results of the mid infrared analysis (MIR) showed the presence of absorption bands at 3 440 cm～1～3 450 cm-1 and 1 640 cm-1～1 680 cm-1 , which are owing to the stretching vibrations of N - H and C = C of aromatics, with C- H out of plane (oop) bending vibrations at wavenumbers less than 900 cm-1, all of which are characteristic absorptions of porphyrin free base. The ultraviolet-visible data showed prominent peaks at ～400 nm(Soret band) and at wavelength ranges of 535 nm～550 nm(β-band) and 565 nm～ 600 nm (α-band) for the coal porphyrins analyzed. The geochemical significance of the metals and porphyrins in coal minerals are discussed.     

Critical micelle concentrations for alkyltrimethylammonium bromides in water from 25 to 160°C

Critical micelle concentrations were determined by conductance measurements for decyl-, dodecyl-, tetradecyl- and hexadecyltrimethylammonium bromide in water at 25, 60, 95, 130, and 160°C. The results are discussed in terms of the equilibrium model and the nonlinear Poisson-Boltzmann model for micelle formation. The free energies of transferring a methylene group from water to the oil-like interior of the micelle are found to be –781 at 25°C, –796 at 60°C, –819 at 95°C, –815 at 130°C, and –787 at 160°C cal-mol^–1.     

Trace element determination in seawater by ICP-SFMS coupled with a microflow nebulization/desolvation system

Direct and simultaneous determination of Al, Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Sb, U, V and Zn in diluted (1:10 v:v) seawater from the Antarctic Ocean and the Venice Lagoon at the ng mL^–1 and pg mL^–1 level has been performed by using an inductively coupled plasma sector field mass spectrometer (ICP-SFMS). Samples were analysed by using a PFA microflow nebulizer coupled with a desolvation system or a PFA microflow nebulizer coupled with a Teflon spray chamber, respectively. Measurements were carried out at low (LR, m/m=300), medium (MR, m/m=3,000) and high (HR, m/m=7,500) resolutions depending on the studied isotope. To avoid contamination, sample pre-treatment was carried out in a clean laboratory equipped with a Class 100 vertical laminar flow hood. Concentration ranges (minimum–maximum in ng mL^–1) found in the Antarctic seawater samples (in depth profiles) were: Ag 0.0004–0.0018, As 0.69–1.32, Cd 0.031–0.096, Co 0.018–0.065, Cr 0.18–0.46, Cu 0.04–1.58, Fe 0.13–1.63, Mn 0.02–0.12, Mo 5.97–12.46, Pb 0.007–0.074, Sb 0.033–0.088, U 0.5–1.9, V 0.6–2.5 and Zn 0.16–0.80. Concentration ranges (min–max in ng mL^–1) found in the Venice Lagoon water samples (temporal profile from a benthic chamber experiment) were: Al 0.24–0.61, Ag 0.007–0.031, As 1.42–2.27, Cd 0.050–0.182, Co 0.440–1.461, Cr 0.15–0.34, Cu 0.81–2.46, Fe 0.25–1.66, Mn 11.6–31.7, Mo 6.50–10.6, Pb 0.047–0.225, Sb 0.240–0.492, U 1.7–3.3, V 1.3–2.8 and Zn 5.20–21.5. The detection limits range between 0.06 pg mL^–1 for Ag and U to 15 pg mL^–1 for Fe. In order to check the accuracy of the analytical procedure, measurements of the trace elements in a certified reference material (coastal Atlantic seawater, CASS-4-NRCC) were compared with the certified values. In addition, the results from the Antarctic and Venice Lagoon samples were compared with those obtained by using different analytical techniques.     

Quantum chemical study of the mechanism of the reaction of tetraphosphorus with alcohol in the coordination sphere of copper(II)

We have used the CNDO Method to study ^–1-tetraphosphorus complexes of copper (II) containing MeOH, MeO^–, H₂O, HO^–, Cl^–, Br^–, I^–, formed during the new reaction of oxidative alkoxylation of P₄ to trialkylphosphates in alcohol-benzene solutions of Cu(II). We studied the nature of the activation of the coordinated molecules and ions by comparing the charges on al the atoms and the values of the total, vocalent, and ionic energies of the intramolecular and intermolecular bonds. We observed the effect of conversion of the tetraphosphorus (which does not display acid-base properties) to a strong electron acceptor, tending toward electrophilic addition of coordinated nucleophiles. The calculated quantum chemical characteristics of the tetraphosphorus complexes correlate well with experiment.D. V. Sokol'skii Institute of Organic Catalysis and Electrochemistry, Kazakh Academy of Sciences, Alma-Ata. Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 27, No. 6, pp. 659–672, November–December, 1991. Original article submitted April 19, 1990.     

Determination of the rate constants for reactions of gaseous substrates with adsorbed O− radical anions

We consider the possibility of determining the rate constants for reactions of gaseous substrates with O^– radical anions adsorbed on catalysts from the loss of the substrate from the gas phase. We consider two reaction pathways, including attack on O^– by the substrate from the gas phase and from the surface of the contact catalyst, under conditions of equilibrium distribution of the substrate between the phases.L. M. Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry, National Academy of Sciences of Ukraine, 70 ul. R. Lyuksemburg, Donetsk 340114, Ukraine. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 32, No. 2, pp. 80–82, March–April 1996. Original article submitted June 6, 1995.     

Dehydrogenation of 1-methylcyclopentene in the presence of oxide catalysts

Summary We studied the dehydrogenation of 1-methylcyclopentene in the presence of an alumina-molybdenum catalyst at 600°, a flow rate of 1.0 h^–1 and residual pressures of 20 and 100 mm of Hg. In both cases the yield of methylcyclopentadiene amounted to 30% based on the starting hydrocarbon.We express our deep appreciation to É. G. Ostapenko and E. D. Tulupova for assistance in performing the Chromatographic analyses.Translated from Izvestiya Akademii Nauk SSR, Seriya Khimicheskaya, No. 5, pp. 912–914, May, 1964     

Full configuration interaction calculation for π-electron spectra of polycyclic hydrocarbons

We discuss some characteristics of full configuration interaction calculations for the -electron spectra of polycyclic hydrocarbons.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, Nos. 5–6, pp. 479–482, September–December, 1992.     

Quantitative investigation of spatiotemporal chaos in the ferroin-catalyzed Belousov-Zhabotinskii reaction in a batch reactor

We have analyzed experimental data on the time dependence of the potentials of 16 platinum point-contact electrodes for spatiotemporal chaos in the Belousov-Zhabotinskii reaction. We show that the largest Lyapunov exponent is a convenient characteristic for spatiotemporal chaos. We found that in going from temporal to spatiotemporal chaos, the embedding dimension of the system increases by a factor of three. We have observed that as the largest Lyapunov exponent increases, we observe a decrease in the degree of spatial correlation of the process.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 31, No. 1, pp. 34–39, January–February, 1995.We would like to thank the Foundation for Basic Research of the State Science and Technology Committee of Ukraine for financial support of this work (Project 3.3/87).     

Ab initio quantum chemical calculation of the mechanism for molecular addition of chlorine to acetylene in the gas phase

We have investigated the mechanism of gas-phase chlorination of acetylene using anab initio quantum chemical method in a 3–21G° basis. We show that formation ofcis andtrans addition products may be connected with the appearance of carbene in the reaction medium, formed upon addition of a chlorine molecule to one of the acetylene carbon atoms. We have found that intermediate carbene may also be a source for the appearance of radicals in the reaction medium.Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 5 ul. Murmanskaya, Kiev 253094, Ukraine. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 32, No. 1, pp. 17–19, January–February, 1996. Original article submitted April 6, 1995.     

Features of a theoretical description of ionization potentials of the LiF molecule and electron affinity of the F atom

We have performed calculations of the ionization potentials of the LiF molecule and the electron affinity of the F atom (as the ionization potential of F^–) by the Green's function method in the approximation adapted for calculation of the ionization potentials for ionization from upper MO's and the ADC(3) approximation. We have shown that quantitative agreement with experimental values can be obtained only as a result of infinite partial summation of diagrams in the ADC(3) scheme.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 6, pp. 723–726, November–December, 1990.