Immobilization and direct electrochemistry of cytochrome <Emphasis Type="BoldItalic">c</Emphasis> at a single-walled carbon nanotube-modified electrode

A single-walled carbon nanotube (SWNT)-modified electrode was fabricated and characterized by SEM and ac impedance techniques. The direct electrochemistry of cytochrome c (Cyt c), which was adsorbed on the surface of the SWNT, was studied by cyclic voltammetry. The results from cyclic voltammetry and infrared spectroscopy indicated that Cyt c remained in its original structure and did not undergo structural change after its immobilization on the SWNT. Further results demonstrated that the SWNT had promotional effects on the direct electron transfer of Cyt c and also indicated that the immobilized Cyt c retained its electrocatalytic activity to the reduction of H₂O₂. This modified electrode might be used in development of new biosensors and the biofuel cells.     

Emission,Emissionslebensdauer und Absorption von [Cr urea6]X3-Einkristallen

Emission and absorption polarization spectra as well as emission lifetimes between room temperature and 5 °K have been measured of [Cr urea₆]X₃ single crystals, where X stands for ClO ₄ ^– , J^–, NO ₃ ^– , Br^–, Cl^–, F^–, and X₃ for JSO ₄ ^3– . The strong temperature dependence of the fluorescence/phosphorescence-ratios, and of the emission lifetimes is discussed. The differences between the spectra as well as the emission lifetimes of the various salts can be attributed to an anion dependent trigonal perturbation.

Die Autoren danken dem Verband der Chemischen Industrie für finanzielle Unterstützung dieser Arbeit.     

Synthesis,molecular structure and stereoisomerization of 2-phosphinyl and 2-phosphonylethyl diorganotin halides

Functionally substituted triorganotin halides V–IX of type R₂Sn(X)(CH₂)₂P(O)PhR′ (R = Me, t-Bu; Rt? = OEt, t-Bu; X = Cl, Br) have been synthesized by halogen cleavage of the corresponding tetraorganotin compounds R₂R²Sn(CH₂)₂P(O)PhR′ (R² = Me or Ph), I–IV. The solid state structure of Me₂Sn (Br) (CH₂)₂P(O)PhBu-t (IX), determined by X-ray diffraction, shows a distorted trigonal-bipyramidal structure at the tin atom, with intramolecular coordination of the PO group. Spectroscopic data are in agreement with such a structure in solution for compounds V–IX. Upon varying the temperature, concentration or solvent in solutions of compounds V–IX a stereoisomerization is observed. On the basis of NMR ¹H, ¹³C, ³¹P, ¹¹⁹Sn), IR and conductivity studies, it is suggested that this stereoisomerization involves a hexacoordinated transition state at the tin atom.     

Extension of the self-consistent spectrophotometric basicity scale in acetonitrile to a full span of 28 pKa units: unification of different basicity scales

The earlier compiled self-consistent spectrophotometric basicity scale in acetonitrile (AN) was expanded to range from 3.8 to 32.0 pK(a) units, that is 28 orders of magnitude. Altogether 54 new relative basicity measurements (DeltapK(a) measurements) were carried out and 37 new compounds were introduced to the scale (it now includes altogether 89 bases). The relative basicity of any two bases in the scale can be obtained by combining at least two independent sets of measurements. Multiple overlapping measurements make the results more reliable. The overall consistency (as defined earlier) of the measurements is s = 0.03 pK(a) units. Thorough analysis of all of our experimental data (DeltapK(a) values of this and earlier works) and experimental pK(a) data in AN available in the literature (works from the groups of Coetzee and Padmanabhan, Kolthoff and Chantooni, Jr., the Schwesinger group, Bren' et al. and some others, altogether 19 papers) was carried out. On the basis of this analysis the anchor point of the scale-pyridine-was shifted upward by 0.20 pK(a) units thereby also revising the absolute pK(a) values of all the bases on the scale. This way very good agreement between our relative data and the absolute pK(a) values of the abovementioned authors was obtained. The revised basicity scale was interconnected with the earlier published self-consistent acidity scale by DeltapK(a) measurements between acids and bases. The rms deviation between the directly measured DeltapK(a) values and the absolute pK(a) values of the compounds was 0.10 pK(a) units.     

Synthesis and characterization of trifluoromethyl fluoroformyl peroxycarbonate,CF3OC(O)OOC(O)F

The synthesis of CF(3)OC(O)OOC(O)F is accomplished by the photolysis of a mixture of (CF(3)CO)(2)O, FC(O)C(O)F, CO, and O(2) at -15 degrees C using a low-pressure mercury lamp. The new peroxide is obtained in pure form in low yield after repeated trap-to-trap condensation and is characterized by NMR, IR, Raman, and UV spectroscopy. Geometrical parameters were studied by ab initio methods [B3LYP/6-311+G(d)]. At room temperature, CF(3)OC(O)OOC(O)F is stable for many days in the liquid or gaseous state. The melting point is -87 degrees C, and the boiling point is extrapolated to 45 degrees C from the vapor pressure curve log p = 8.384 - 1715/T (p/mbar, T/K). A possible mechanism for the formation of CF(3)OC(O)OOC(O)F is discussed, and its properties are compared with those of related compounds.     

New 6-(4-Bromophenyl)-imidazo[2,1-b]thiazole Derivatives: Synthesis and Antimicrobial Activity

Summary.  New 4-alkyl/aryl-1-((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-3-thiosemicarbazides and 3-alkyl/aryl-2-(((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-hydrazono)-4-thiazolidinones were synthesized from 6-(4-bromophenyl)-imidazo[2,1-b]thiazole-3-acetic acid hydrazide. Their structures were elucidated by elemental analyses and spectroscopic data. All compounds were tested for antibacterial and antifungal activities. The antimicrobial activities of the compounds were assessed by the microbroth dilution technique. The compounds were also evaluated for antituberculosis activity against Mycobacterium tuberculosis H₃₇Rv (ATCC 27294); they exhibited varying degrees of inhibition in the in vitro primary screening at 6.25 μg · cm⁻³. The most active compound was 3-(4-nitrophenyl)-2-(((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-hydrazono)-4-thiazolidinone. Corresponding author. E-mail: nurayulusoy@yahoo.com Received December 10, 2001. Accepted (revised) March 1, 2002     

Component B binding to the soluble methane monooxygenase hydroxylase by saturation-recovery EPR spectroscopy of spin-labeled MMOB

Spin-labeled Cys89 of the soluble methane monooxygenase regulatory protein (MMOB) from Methylococcus capsulatus (Bath) binds within 15 +/- 4 A of the hydroxylase (MMOH) diiron center, placing the MMOB docking site in the MMOH "canyon" region on iron-coordinating helices E and F of the alpha-subunit.     

Radiochemical studies of the sorption behavior of strontium and barium

The sorption behavior of strontium and barium on kaolinite, bentonite and chlorite-illite mixed clay was studied by radioanalytical techniques using the batch method.⁹⁰Sr (29.1 y) and¹³³Ba (10.5 y) were used as radiotracers. Characterization of the solid matrices was done by FTIR and XRD spectrometries and specific surface area measurements. Synthetic groundwater was used as the aqueous phase. The variation of the distribution ratioR _d, as a function of metal ion loading was examined. The sorption isotherms were fitted to various isotherm models. The sorption energies were calculated to be in the range of 8–10 kJ/mol suggesting an ion exchange type of sorption mechanism. In detailed experiments, chlorite-illite mixed clay was first presaturated with K⁺, Sr²⁺, Ca²⁺ and Al³⁺ ions, respectively, prior to sorption studies with Ba²⁺ ions. The results of Ca²⁺ pretreated chlorite-illite were very similar to those of natural chlorite-illite, suggesting that the Ba²⁺ ion exchanges primarily with the Ca²⁺ ion on the clay minerals.     

Rapid method for the isolation of the mature collagen cross-links, hydroxylysylpyridinoline and lysylpyridinoline

Hydroxylysylpyridinoline (HP) and lysylpyridinoline (LP) are two non-reducible cross-links of mature collagen which are formed by a sequence of post-translational modifications. HP is a derivative of three residues of hydroxylysine and is present in almost all mature tissues (e.g., tendons, vessel walls, cartilage, teeth and bone). LP is a derivative of two residues of hydroxylysine and one residue of lysine and is present only in dentine and bone. Neither cross-link is found in normal human skin. HP and LP were purified from commercially available bone gelatine (“ossein hydrolysate”) by preparative reversed-phase HPLC and the degree of purity was verified by amino acid determination ( > 98% dry mass). Hydroxylysylpyridinoline and lysylpyridinoline are promising markers in urine of collagen resorption because their levels in urine should reflect only the breakdown of collagen fibres of skeletal tissues. The two components were used as external standards and the determination of HP and LP in urine provides a good means for the specific evaluation of pathological conditions associated with increased bone resorption, e.g., high turnover post-menopausal osteoporosis.     

Stabilising small clusters: synthesis and characterisation of thermolabile [Gd4F7(15-crown-5)4][AsF6]5.6 SO2

Addition of 15-crown-5 to [GdF(AsF6)2], both dissolved in liquid SO2, and crystallisation at -30 degrees C has led to the isolation of the tetranuclear ionic complex [Gd4F7(15-crown-5)4][AsF6]5.6 SO2 which is stable up to--10 degrees C where SO2 loss leads to loss of crystallinity.