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41.
Summary. A highly efficient, selective, fast, and cheap protocol is developed for oxidation of aromatic amines and alcohols utilizing
34% hydrogen peroxide in water catalyzed by some W- and Mo-based heteropolyoxometalates. Findings showed that dodecatungstophosphoric
acid, H3PW12O40, was the most efficient catalyst in the examined oxidation reactions. This methodology may prove to be a valuable alternative
for eco-friendly green oxidation. Inherent simplicity, easy work up, and using regenerable catalysts were other key aspects
of this oxidation protocol. 相似文献
42.
Hindered internal rotation about the C‐N single bonds joining the thiuram disulfide was studied by 1H NMR complete line‐shaped analysis in different dimethyl sulfoxide‐chloroform (DMSO‐CDCl3) mixtures. From the temperature dependence of methyls proton spectra, activation parameters (Ea, ΔH≠, ΔS≠, and ΔG≠) were obtained. The Arrhenius plots showed a distinct isokinetic temperature at about 35 °C at which the exchange rate is more or less independent of the solvent composition. The resulting ΔH≠ against TΔS≠ plot showed a firmly good linear correlation, indicating the existence of an enthalpy‐entropy composition in an exchange process. 相似文献
43.
Behzad Haghighi Mohammad Reza Hussaindokht Mohammad Reza Bozorgmehr Naser Seyed Matin 《中国化学快报》2007,18(9):1154-1158
In this paper five equations of state are tested for checking their ability to predict the Joule-Thomson inversion curve.These five equations of state are:Mohsennia-Modarres-Mansoori(MMM),Ji-Lemp(JL),modified Soave-Redlich-Kwang(SRK)equation of state by Graboski(MSRK1),modified SRK equation of state by Peneloux and Rauzy(MSRK2),and modified Peng-Robinson (PR)equation of state by Rauzy(PRmr).The investigated equations of state give good prediction of the low-temperature branch of the inversion curve,except for MMM equation of state.The high-temperature branch and the peak of the inversion curve have been observed,in general,to be sensitive to the applied equation of state.The values of the maximum inversion temperature and maximum inversion pressure are calculated for each component used in this work. 相似文献
44.
Single bacterial cells, each expressing a different library variant, were compartmentalized in aqueous droplets of water-in-oil (w/o) emulsions, thus maintaining a linkage between a plasmid-borne gene, the encoded enzyme variant, and the fluorescent product this enzyme may generate. Conversion into a double, water-in-oil-in-water (w/o/w) emulsion enabled the sorting of these compartments by FACS, as well as the isolation of living bacteria cells and their enzyme-coding genes. We demonstrate the directed evolution of new enzyme variants by screening >10(7) serum paraoxonase (PON1) mutants, to yield 100-fold improvements in thiolactonase activity. In vitro compartmentalization (IVC) of single cells, each carrying >10(4) enzyme molecules, in a volume of <10 femtoliter (fl), enabled detection and selection despite the fast, spontaneous hydrolysis of the substrate, the very low initial thiolactonase activity of PON1, and the use of difusable fluorescent products. 相似文献
45.
Balakumar A Lysenko AB Carcel C Malinovskii VL Gryko DT Schweikart KH Loewe RS Yasseri AA Liu Z Bocian DF Lindsey JS 《The Journal of organic chemistry》2004,69(5):1435-1443
A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols. 相似文献
46.
Summary Three polarographic micro-methods are described for the determination of sulphur in organic compounds after oxygen-flask combustion. The products are converted into sulphuric acid by oxidation with hydrogen peroxide, the excess of which is expelled through boiling. The methods are based upon allowing the sulphuric acid to react with an excess of barium iodate or bromate, then recording polarographically the cathodic reduction wave of the iodate or bromate ion. The bromate methods are superior to the iodate method being simpler and more rapid, and the results are correct to within ca. ±0.5%.
Zusammenfassung Drei polarographische Mikromethoden zur Bestimmung von Schwefel in organischen Verbindungen nach deren Verbrennung im Sauerstoffkolben wurden beschrieben. Die Verbrennungsprodukte werden durch Oxydation mit Wasserstoffperoxid in Schwefelsäure umgesetzt. Der Überschuß des Oxydationsmittels wird durch Kochen zerstört. Die Schwefelsäure läßt man mit überschüssigem Bariumjodat oder -bromat reagieren und mißt dann polarographisch die kathodische Reduktionswelle des Jodats oder Bromats. Die Bromatmethode ist der Jodatmethode überlegen, da sie einfacher und rascher zu Resultaten führt, die innerhalb ±0,5% korrekt sind.相似文献
47.
Benzofuro[2,3-b]benzofuran-2,3,8,9-tetracarboxylic dianhydride (BBTDA) is introduced as a monomer for the synthesis of a series of novel polyimides with enhanced high thermal stability. Polyimides derived from BBTDA and aromatic diamines showed high glass transition (Tg>296 °C) and degradation (T5>455 °C) temperatures, and were soluble in organic solvents (i.e. N-methyl pyrrolidone (NMP), N,N′-dimethylformamide (DMF), N,N′-dimethylacetamide (DMAc)). The polymerization yielded high-molecular-weight polyimides with inherent viscosities ranging from 1.75 to 2.14 dl/g. The polymers were characterized by IR and elemental analysis. 相似文献
48.
Mostafa M. Amini Amirreza Azadmher Hamid Reza Bijanzadeh Nasser Hadipour 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(1-2):77-80
Behavior of {[(CH3)2SnCl2·H2O]2·18-crown-6}n in solution have been investigated by HMBC NMR. The results show that coordination of water to tin containing species and
its hydrogen bonding to crown ether remains intact in non-coordinating solvent in contrast to coordinating solvent. H-NMR
reveals that the chemical shift of water in complex varies by solvent of crystallization. 相似文献
49.
Josephsohn NS Snapper ML Hoveyda AH 《Journal of the American Chemical Society》2003,125(14):4018-4019
An efficient Ag-catalyzed method for asymmetric addition of the Danishefsky diene to various aryl imines to afford cycloadducts in > or =89% ee and > or =85% isolated yield is reported. Reactions are effected with 0.1-1 mol % catalyst (4 degrees C), and the chiral ligand is readily prepared from commercially available materials, including the inexpensive i-Leu. These catalytic asymmetric cycloadditions can be carried out without the use of solvent or with undistilled THF in air. A first generation supported chiral catalyst that effectively promotes the cycloaddition reaction and can be recycled (five cycles) is described. 相似文献
50.
Heidari AH Braun RJ Hirsa AH Snow SA Naire S 《Journal of colloid and interface science》2002,253(2):295-307
The drainage of a thin liquid film with an insoluble monolayer down a vertical wall is studied. Lubrication theory is used to develop a model where the film is pinned at the top with a given thickness and the film drains into a bath at the bottom. A nonlinear equation of state is used for the surface tension and the surface viscosity is a nonlinear function of the surfactant concentration; these are appropriate for some aqueous systems. The three partial differential equations are solved via discretization in space and then the resulting differential algebraic system is solved. Results are described for a wide range of parameters, and the conditions under which the free surface is immobilized are discussed. 相似文献