Oxidation of aqueous sulfur dioxide catalyzed by poly-4-vinylpyridine-Cu(II) complex. Part 1: Homogeneous phase oxidation

The oxidation of aqueous sulfur dioxide in the presence of polymer-supported copper(II) catalyst is also accompanied by homogeneous oxidation of aqueous sulfur dioxide catalyzed by leached copper(II) ions. Aqueous phase oxidation of sulfur dioxide of low concentrations by oxygen in the presence of dissolved copper(II) has therefore been studied. The solubility of SO2 in aqueous solutions is not affected by the concentration of copper(II) in the solution. In the oxidation reaction, only HSO3- is the reactive S(IV) species. Based on this observation a rate model which also incorporates the effect of sulfuric acid on the solubility of SO2 is developed. The rate model includes a power-law type term for the rate of homogeneous phase reaction obtained from a proposed free-radical chain mechanism for the oxidation. Experiments are conducted at various levels of concentrations of SO2 and O-2 in the gas phase and Cu(II) in the liquid phase. The observed orders are one in each of O-2, Cu(II) and HSO3-. This suggests a first-order termination of the free radicals of bisulfite ions.

An Iron Complex of Dipyridophenazine as a Potent Photocytotoxic Agent in Visible Light

Ternary iron(III) complexes (FeL(B)] (1-3) of a trianionic tetradentate phenolate-based ligand (L) and henanthroline base (B), namely, 1,10-phenanthroline (phen, 1), dipyridoquinoxaline (dpq, 2), and dipyridophenazine (dppz, 3), have been prepared and structurally characterized and their DNA binding, cleavage, and photocytotoxic properties studied. The complexes with a FeN3O3 core show the Fe(III)/Fe(II) redox couple near -0.6 V in DMF, a magnetic moment value of similar to 5.9 mu(B), and a binding propensity to both calf thymus DNA and bovine serum albumin (BSA) protein. They exhibit red-light-induced DNA cleavage activity following a metal-assisted photoredox pathway forming HO center dot radicals but do not show any photocleavage of BSA in UV-A light. Complex 3 displays photocytotoxicity in the human cervical cancer cell line (HeLa) and human keratinocyte cell line (HaCaT) with respective IC50 values of 3.59 mu M and 6.07 mu M in visible light and 251 nM and 751 nM in UV-A light of 365 nm. No significant cytotoxicity is observed in the dark. The photoexposed HeLa cells, treated prior with complex 3, have shown marked changes in nuclear morphology as demonstrated by Hoechst 33258 nuclear stain. Generation of reactive oxygen species has been evidenced from the fluorescence enhancement of dichlorofluorescein upon treatment with 3 followed by photoexposure. Nuclear chromatin cleavage has been observed in acridine orange/ethidium bromide dual staining of treated HeLa cells and from alkaline single-cell gel electrophoresis. Caspase 3/7 activity in HeLa cells has been found to be upregulated by only 4 fold after photoirradiation, signifying the fact that cell death through a caspase 3/7 dependent pathway may not be solely operative.

Structure of tri-1-naphthylborane-benzene (1/1) complex, c30h21b.c6h6

M r= 470.46, rhombohedral, R3, a =8.710(4)A, a=91.10(3) o, V= 660.4 (9) A 3, Z= 1,D m= 1.170 (flotation in KI solution), D x=1.183 Mg m -a, Mo Kct, 2 = 0.7107/~,, /t =0.033 mm -1, F(000) - 248.0, T= 293 K, R -- 4.6%(481 unique reflections). The molecule has C a symmetry and is propeller shaped, the angle of twist about the B-C bond being 41.5 (7) °. The space group being chiral, this is yet another example of spontaneous resolution. The results of a thermal-motion analysis are discussed.

XANES and EXAFS of copper compounds: Studies of copper carboxylates with metal-metal bonds and of the complex formed byPseudomonas aeruginosa

X-ray absorpion near edge structure (xanes) of copper compounds with copper in 1+, 2+ and 3+ states has been studied. Extended x-ray absorption fine structure (exafs) has been employed to determine bond distances and coordination numbers in several model copper compounds. Employing bothxanes andexafs, the structure of the copper complex formed by the micro-organismPseudomonas aeruginosa has been shown to be square-planar with the Cu-O distance close to that in cupric glucuronates and cupric acetylacetonate.exafs has been shown to be useful for studying metal-metal bonds in copper carboxylates.

NMR (1H, 13C) and MO (ab initio, CNDO/2, EHT) studies on basic and N-protonated hydrazinecarbothioamide

The conformational preferences of hydrazinecarbothioamide (HCTA, H2NNHCSNH2) in its basic and N-protonated (PHCTA, H3NNNHCSNH2) forms have been studied by 1H and 13C NMR spectroscopy and by theoretical LCAO-MO methods (ab initio, CNDO/2 and EHT). The hindered rotation around the C---N bond has been investigated by a total line shape analysis for the thioamide protons and by the three MO methods. Changes in the molecular conformation and electronic structure on protonation are briefly discussed.

Basic Needs and Much More With One Kilowatt Per Capita

Conventional thinkin g holds that increased energy consumption is a prerequisite for economic and social development. This belief, together With the prospect of dwindling global petroleum supplies and the high costs of expanding energy supply generally, lead many to believe that it is not feasible to improve living standards substantially in the developing countries. But by shifting to high-quality energy carriers and by exploiting cost-effective opportunities for more efficient energy use, it would be possible to satisfy basic human needs and to provide considerable further improvements in living standards without significantly increasing per-capita energy use above the present level.

Structural studies of analgesics and their interactions .10. A hydrated 1-1 complex between niflumic acid and ethanolamine, c13h8f3n2o-2.c2h8no+.h2o.

Mr= 361.3, triclinic, P1, a = 6-239 (2), b=11.280(2), c=12-451(2)A, a=101.2 (1), B= 92.3 (1), 7=99.9(1)°, V=844.123 A3, Z=2, Dx= 1.42, D m = 1.42 (1) Mg m -3, n(Cu Ka) = 1.5418 ,A., g = 1-102 mm -1, F(000) = 376, T= 293 K. Final R = 0.064 for 2150 observed reflections. The niflumic acid anions consist essentially of three planar groupings, namely, two six-membered rings and a carboxylate group attached to one of them. The invariant common structural features observed in the crystal structures of fenamates, namely, the coplanarity of the carboxyl group and the six-membered ring bearing it, and the internal hydrogen bond between the carboxyl group and the imino N atom that bridges the two sixmembered rings, are retained in the complex. The amino N atom is gauche with respect to the terminal hydroxyl group in the ethanolamine cation. The complexation between the two molecules is achieved through ionic and hydrogen-bonded interactions involving the carboxylate group in niflumic acid.

Cytochrome c oxidase is preferentially synthesized in the rough endoplasmic reticulum--mitochondrion complex in rat liver

The specific activity and content of cytochrome oxidase in the rough endoplasmic reticulum--mitochondrion complex are higher than in the mitochondrial fraction. Radiolabelling studies with the use of hepatocytes and isolated microsomal and rough endoplasmic reticulum--mitochondrion fractions, followed by immunoprecipitation with anti-(cytochrome oxidase) antibody, reveal that the nuclear-coded cytoplasmic subunits of cytochrome oxidase are preferentially synthesized in the latter fraction. The results have a bearing on the mechanism of transport of these subunits into mitochondria.

A comparison of the molecular orbital (ab initio, CNDO and EHT) methods applied to the conformational study of thiocarbonohydrazide in its basic and diprotonated forms

Conformational preferences of thiocarbonohydrazide (H2NNHCSNHNH2) in its basic and N,N′-diprotonated forms are examined by calculating the barrier to internal rotation around the C---N bonds, using the theoretical LCAO—MO (ab initio and semiempirical CNDO and EHT) methods. The calculated and experimental results are compared with each other and also with values for N,N′-dimethylthiourea which is isoelectronic with thiocarbonohydrazide. The suitability of these methods for studying rotational isomerism seems suspect when lone pair interactions are present.

Dinitrogen complex of magnesium

No abstract is available.

Distribution of phosphorus and oxygen between liquid steel and basic oxygen steelmaking slag

The efficiency of dephosphorisation is governed by the thermodynamic behaviour of phosphorus and oxygen in molten metal, and P2O5 and FeO in slag. The equilibrium distribution of phosphorus and oxygen, for a wide range of chemical compositions simulating the evolution of slag composition during a typical BOF blow, has been experimentally determined. A mathematical model for estimation of the activity coefficients, as a function of the chemical composition, was also attempted.

Low PAPR Square STBCs from Complex Partial-Orthogonal Designs (CPODs)

Space-time codes from complex orthogonal designs (CODs) with no zero entries offer low Peak to Average Power Ratio (PAPR) and avoid the problem of switching off antennas. But square CODs for 2(a) antennas with a + 1. complex variables, with no zero entries were discovered only for a <= 3 and if a + 1 = 2(k), for k >= 4. In this paper, a method of obtaining no zero entry (NZE) square designs, called Complex Partial-Orthogonal Designs (CPODs), for 2(a+1) antennas whenever a certain type of NZE code exists for 2(a) antennas is presented. Then, starting from a so constructed NZE CPOD for n = 2(a+1) antennas, a construction procedure is given to obtain NZE CPODs for 2n antennas, successively. Compared to the CODs, CPODs have slightly more ML decoding complexity for rectangular QAM constellations and the same ML decoding complexity for other complex constellations. Using the recently constructed NZE CODs for 8 antennas our method leads to NZE CPODs for 16 antennas. The class of CPODs do not offer full-diversity for all complex constellations. For the NZE CPODs presented in the paper, conditions on the signal sets which will guarantee full-diversity are identified. Simulation results show that bit error performance of our codes is same as that of the CODs under average power constraint and superior to CODs under peak power constraint.

Effect of chelating anions on metal-crown interaction. Part III. X-ray structure of potassium picrate complex of benzo-15-crown-5

The cr~¢stal structure of [potassium(benzo-15-crown-5)](picrate) shows that in the complex the metal is sandwiched between two crowns andhas no interaction with plcrate.