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991.
Antimony(III) is determined by means of electrolysis at ?0.40 V vs. Ag/AgCl on a gold-coated gold fibre electrode for 0.5–10 min in a redox buffer containing 0.01 M iron(II) in 0.10 M hydrochloric acid, and subsequent stripping with a constant current of 0.50μA either in 2 M hydrochloric acid or in 4 M hydrochloric acid/4 M calcium chloride. Antimony(V) is determined by the same procedure in 4 M hydrochloric acid medium. Bismuth(III) is masked by the addition of iodide to the sample prior to electrolysis. Antimony(III) and antimony(V) are determined by standard addition methods; the whole procedure including digital and graphical evaluation of the results is fully automated. The antimony(V) concentrations in the river water reference sample SLRS-1 and the seawater reference sample NASS-1 were found to be 0.63 and 0.31 μg l?1 with standard deviations of 0.046 and 0.051 μg l?1, respectively (n=15). The certified value for SLRS- 1 is 0.63±0.05 μg l?1; no certified value is available for NASS-1. 相似文献
992.
Enrico Borgarello Jean Desilvestro Michael Grtzel Ezio Pelizzetti 《Helvetica chimica acta》1983,66(6):1827-1834
Conduction band electrons produced by band gap excitation of TiO2-particles reduce efficiently thiosulfate to sulfide and sulfite. \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm 2e}_{{\rm cb}}^ - ({\rm TiO}_{\rm 2}) + {\rm S}_{\rm 2} {\rm O}_3^{2 - } \longrightarrow {\rm S}^{2 - } + {\rm SO}_3^{2 - } $\end{document} This reaction is confirmed by electrochemical investigations with polycrystalline TiO2-electrodes. The valence band process in alkaline TiO2-dispersions involves oxidation of S2O to tetrathionate which quantitatively dismutates into sulfite and thiosulfate, the net reaction being: \documentclass{article}\pagestyle{empty}\begin{document}$ 2{\rm h}^{\rm + } ({\rm TiO}_{\rm 2}) + 0.5{\rm S}_{\rm 2} {\rm O}_{\rm 3}^{{\rm 2} - } + 1.5{\rm H}_{\rm 2} {\rm O} \longrightarrow {\rm SO}_3^{2 - } + 3{\rm H}^{\rm + } $\end{document} This photodriven disproportionation of thiosulfate into sulfide and sulfite: \documentclass{article}\pagestyle{empty}\begin{document}$ 1.5{\rm H}_{\rm 2} {\rm O } + 1.5{\rm S}_{\rm 2} {\rm O}_{\rm 3}^{{\rm 2} - } \mathop \to \limits^{h\nu} 2{\rm SO}_3^{2 - } + {\rm S}^{{\rm 2} - } + 3{\rm H}^{\rm + } $\end{document} should be of great interest for systems that photochemically split hydrogen sulfide into hydrogen and sulfur. 相似文献
993.
Bao‐Shiang Lee Sangeeth Krishnanchettiar Syed Salman Lateef Nabila Salman Lateef Shalini Gupta 《中国化学会会志》2006,53(3):745-750
Avidin functional affinity electrophoresis (AFAEP) is substituted for an avidin affinity column (AAC) to capture biotinylated peptides in the Isotope‐Coded Affinity Tagging (ICAT) technique which is a valuable tool in quantitative proteomics. In this new technique, the AFAEP‐captured ICAT‐labeled biotinylated peptides are extracted with the biotin tag intact from the polyacrylamide gel piece with aqueous 95% formamide (pH 8.2) at 65 °C for 20 min, and then detected by a matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometer. Bovine serum albumin (BSA) and the 12C‐ and 13C‐ICAT reagents are used to test this AFAEP‐ICAT technique. The results show that both AFAEP and AAC methods provide quantitative information of the relative amounts of 12C‐ and 13C‐ICAT‐labeled biotinylated tryptic peptides of BSA in a sample. Compared with AAC, the AFAEP is cheaper to perform, more stringent in capturing the biotinylated peptides, and capable of simultaneously processing multiple samples. 相似文献
994.
Turbiez M Frère P Allain M Videlot C Ackermann J Roncali J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(12):3742-3752
Hybrid oligothiophenes based on a various combinations of thiophene and 3,4-ethylenedioxythiophene (EDOT) groups have been synthesized. UV/Vis absorption spectra show that the number and relative positions of the EDOT groups considerably affect the width of the HOMO-LUMO gap and the rigidity of the conjugated system. Analysis of the crystallographic structure of two hybrid quaterthiophenes confirms that insertion of two adjacent EDOT units in the middle of the molecule leads to a self-rigidification of the conjugated systems by intramolecular SO interactions. Cyclic voltammetry data shows that the first oxidation potential of the oligomers decreases with increasing chain length and increasing number of EDOT groups for a given chain length. Electrochemical studies and theoretical calculations show that the positions of the EDOT units in the conjugated chain control the potential difference (DeltaE(p)) between the first and second oxidation steps. Moving the EDOT groups from the outer to the inner positions of the conjugated system increases DeltaE(p). Theoretical calculations confirm that this phenomenon reflects an increase of the intramolecular coulombic repulsion between positive charges in the dication. A thin-film field-effect transistor was fabricated by vacuum sublimation of a pentamer with alternating thiophene-EDOT structure, and the hole mobility was determined. 相似文献
995.
Mohy eldinAbdelFattah Samir ElRayes ElSayedAhmed Soliman Anthony Linden Khaled Abou‐Hadeed Hans‐Jürgen Hansen 《Helvetica chimica acta》2005,88(5):1085-1101
3‐(Phenylsulfonyl)benzo[a]heptalene‐2,4‐diols 1 can be desulfonylated with an excess of LiAlH4/MeLi?LiBr in boiling THF in good yields (Scheme 6). When the reaction is run with LiAlH4/MeLi, mainly the 3,3′‐disulfides 6 of the corresponding 2,4‐dihydroxybenzo[a]heptalene‐3‐thiols are formed after workup (Scheme 7). However, the best yields of desulfonylated products are obtained when the 2,4‐dimethoxy‐substituted benzo[a]heptalenes 2 are reduced with an excess of LiAlH4/TiCl4 at ?78→20° in THF (Scheme 10). Attempts to substitute the PhSO2 group of 2 with freshly prepared MeONa in boiling THF led to a highly selective ether cleavage of the 4‐MeO group, rather than to desulfonylation (Scheme 13). 相似文献
996.
Xiao‐Yan Chen Peng Cheng Shi‐Ping Yan Dai‐Zheng Liao Zong‐Hui Jiang 《无机化学与普通化学杂志》2005,631(15):3104-3107
A novel two‐dimensional cobalt complex, [Co(btrm)2(dca)]ClO4 ( 1 , btrm = 1,2‐bis(1,2,4‐triazole‐1‐yl)methane, dca = dicyanamide), was synthesized and characterized. X‐ray diffraction analyses reveal that the title complex crystallizes in the monoclinic space group C2/m with a = 29.507(13)Å, b = 17.804(8) Å, c = 14.709(7) Å, β = 119.916(7)°, Z = 12, and R1 = 0.0784, wR2 = 0.2041. The cobalt atom involves a six‐coordinated CoN6 environment, with a distorted octahedral coordination. Two btrm ligands connect the CoII atoms with the exodentate nitrogen atoms on the 4‐position of triazole rings to form a sixteen‐membered rhombic grid. The unprecedented double btrm bridges and μ1,5‐dca bridge connect the cobalt atoms to form a two‐dimensional grid‐like layered structure. The spectroscopic and magnetic properties have also been investigated. 相似文献
997.
Ai‐Hua Zhao Yan Zhang Zhao‐Hui Xu Jian‐Wen Liu Wei Jia 《Helvetica chimica acta》2004,87(12):3160-3166
Three new enmein‐type ent‐kaurenoids, i.e., the two pairs 1 and 2 of 20‐epimers and the (20R)‐isomer 3 , besides the seven known diterpenoids 4 – 10 , were isolated from the aerial parts of Isodon serra. Their structures were elucidated by spectroscopic techniques and X‐ray diffraction. The immunosuppressive effect for T‐lymphocytes proliferation induced by Con A in BALB/c mouse was evaluated for the isolates 1 – 10 . They all displayed a remarkable inhibitory effect, with multi‐glycosides of Tripterygium wilfordii as positive reference substance (Table 3). 相似文献
998.
Anne Vessieres Daniel Touchard Pierre Dixneuf 《Journal of organometallic chemistry》1976,118(1):93-100
Heterodienetricarbonyliron complexes react with ligands ( L = PMe2Ph, P(OMe)3 or P(OPh)3) to give the adducts (enone)Fe(CO)3L with the ethylenic double bond coordinated only to the iron(0). Electron-releasing and low-steric effects of L make the reaction which is specific for enones easier compared to that for dienes. PMe2Ph allows enone exchange and P(OPh)3 promotes carbonyl elimination. Ligand influence is shown by infrared spectroscopy and by the shielding of ethylenic protons in NMR spectroscopy. 相似文献
999.
M. Pilar Gamasa Mariano Laguna Daniel Miguel Víctor Riera 《Transition Metal Chemistry》1981,6(6):374-376
Summary Bidentate ligands can readily replace acetone in thefac-[Mn(CO)3(chel)(OCMe2)]+ complexes or the perchlorate group fromfac-[Mn(CO)3(chel)(OClO3)] yieldingfac-[Mn(CO)3(chel)(L-L)]+ or [{fac-Mn(CO)3(chel)}2(L-L)]2+ [chel = 1,10-phenanthroline (phen), 2,2-bipyridine (bipy), 1,2-bis(diphenylphosphine)ethane (dpe); L-L = bis(diphenylphosphine)methane (dpm), dpe, 1,4-bis(diphenylphosphine)butane (dpb), succinonitrile (suc), and glutaronitrile (glu)]. Some of these mononuclear complexes are precursors for binuclear complexes which are linked by bridging phosphines or nitriles. 相似文献
1000.
Henri Patin Gerard Mignani Christian Mahe Jean-Yves Le Marouille Alain Benoit Daniel Grandjean 《Journal of organometallic chemistry》1980,193(1):93-103
103Rh Chemical shifts of a variety of mono- and di-nuclear rhodium carbonyl complexes are reported together with the modifications to the probe and decoupler unit of a JEOL PS-100 PFT spectrometer which enable these 103Rh-decoupled 13C NMR measurements to be made. These data are discussed in conjunction with 13C NMR data on other rhodium carbonyls. 相似文献