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91.
Devendra Kumar 《Journal of polymer science. Part A, Polymer chemistry》1980,18(4):1375-1385
With a view to understanding the structure of aromatic polyimide backbone, model compound N,N-bis(4-phenoxyphenyl)-1,2:4,5-benzenetetracarboxdiimide was synthesized by the condensation of pyromellitic dianhydride and 4-aminodiphenyl ether in solvent N,N-dimethylacetamide or N,N-dimethylformamide. Various side products formed during the reaction were isolated and identified by spectroscopical methods. This study reveals that the polymer backbone contains nearly 85% imide rings. The uncyclizable residues in the backbone are those derived by the chemical interaction of polymerization solvent or by the modification of intermediate orthoamido acid. The uncyclizable nature of the latter was explained in mass and infrared (IR) spectral studies. The role of the dipolar solvent appears to be vital to imidization. 相似文献
92.
Tapan Kumar Lal John F. Richardson Mark S. Mashuta Robert M. Buchanan Rabindranath Mukherjee 《Polyhedron》1997,16(24):1248-4336
Synthesis and characterization of a nitrite-bound copper(II) compound [CuL4)2(ONO)]ClO4 have been achieved (L4 = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L4 provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the dx2−y2 orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible CuII---CuI response [cathodic peak potential, Epc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible CuII---CuI redox response [
]. 相似文献
93.
Broja M. Mandal Joseph P. Kennedy Rodney Kiesel 《Journal of polymer science. Part A, Polymer chemistry》1978,16(4):821-831
An improved synthesis of trivinylaluminum (V3Al) is described. The proton magnetic resonance (PMR) spectrum of V3Al was recorded and analyzed. A new vinylation method involving the use of V3Al as the vinylating agent has been developed, and the vinylation of organic halides by V3Al was studied at ?30, ?50 and ?70°C. Primary alkyl chlorides, such as methyl and methylene chloride, do not react with V3Al and were used as solvents. Secondary chlorides such as 2-chloropropane also do not react. t-Butyl chloride gives rise to t-butylethylene (70–98%), depending on reaction conditions, and the allylic chlorides, 3-chloro-1-butene, and 3-chloro-3-methyl-1-butene, yield the expected vinylated products and their isomers (~90%). Allyl and benzyl chloride do not react under the conditions tried. The reaction between V3Al and the ditertiary dichloride 2,6-dichloro-2,6-dimethylheptane yields several isomeric C13H24 and C11H20 hydrocarbons; however, surprisingly, C9H16 does not form. The C13 hydrocarbons arise by divinylation at the termini of the dichloride, while the C11 hydrocarbons are formed by vinylation at one and proton elimination at the other terminus of the dichloride. The presence of unsaturated C13H24 and C11H20 isomers is most likely due to proton induced isomerization. These results are explained by a proximity effect involving vinylation at one end of the dichloride by V3Al followed by rapid reaction of the second chlorine (mostly) by V2AlCl generated in situ during the first vinylation in the proximity of the chloride. At the other chlorine terminus V2AlCl causes either a second vinylation (leading to C13 hydrocarbons) or a proton elimination (leading to C11 hydrocarbons). The absence of C9H16 among the reaction products indicates that V3Al exclusively effects vinylation. The RCl + V3Al ← RV + V2AlCl reaction may be regarded as a model for initiation followed by immediate termination in cationic olefin polymerization, a process leading to vinyl-ended polymers. 相似文献
94.
Summary The coagulation concentration for silver iodide sol, both in presence of pyridine and dioxane, increases for mono- and bivalent
coagulating electrolyte. In presence of a mixture of pyridine and dioxane in equal volume, the coagulation concentration assumes
an intermediate value, which is nearer to dioxane. However, in presence of dioxane more bivalent electrolyte is needed than
in presence of pyridine. If a bivalent coagulating electrolyte is added to a sol containing a mixture of pyridine and dioxane,
the amount of electrolyte required to coagulate is less than pyridine and greater than dioxane. Thus silver iodide sol is
more stable toward mono- and bivalent coagulating electrolytes. The degree of stabilization increases with the decrease of
the dielectric constant of the dispersing medium. The intermediate values for dioxane pyridine mixture is accountable by the
fact that dioxane acts as a solvent for pyridine. The PH value of the sol increases up to the coagulation point. Beyond this,
there is an abrupt decrease. When the particles settle down completely a rise in PH is again noted on the further addition
of electrolytes. The increase in the electrical conductance is more significant after coagulation. These changes have been
explained by adsorption of the ions and due to the release of ions from the electrical double layer.
Our thanks are due to Prof. R. C. Mehrotra for providing all the facilities for this work and to Prof. S. Ghosh of Allahabad University for helpful discussions. Thanks are also due to the University Grants Commission, Government of India, for the award of a research scholarship to one of us (V. K. S.). 相似文献
Zusammenfassung Die Koagulationskonzentration für Silberjodidsol in Gegenwart von Pyridin und Dioxan steigt für ein- und zweiwertige Elektrolyte an. In Gegenwart einer Mischung zu gleichen Volumen erh?lt man mittlere Werte, n?her denen zu Dioxan. Für Koagulation in Gegenwart von Dioxan ist jedoch mehr zweiwertiger Elektrolyt notwendig als in Gegenwart von Pyridin. Bei Koagulation mit zweiwertigem Elektrolyt verbraucht ein Sol mit der Mischung von Pyridin und Dioxan weniger als für Pyridin und mehr als für Dioxan. Daher ist das Silbersol gegenüber ein- und zweiwertigen Elektrolyten stabiler. Der Grad der Stabilisierung w?chst mit abnehmender Dielektrizit?tskonstante des Dispersionsmediums. Die Zwischenwerte der Dioxan-Pyridin-Mischungen lassen sich verstehen durch die Tatsache, da? Dioxan als L?sungsmittel für Pyridin wirkt. Der PH-Wert des Sols w?chst bis zum Koagulationspunkt, darüberhinaus erfolgt ein steiler Abfall. Wenn die Teilchen vollst?ndig absetzen, ist bei weiterer Zugabe von Elektrolyt ein erneuter Anstieg im PH feststellbar. Der Anstieg der elektrolytischen Leitf?higkeit wird nach der Koagulation ausgepr?gter. Diese ?nderungen lassen sich durch Ionenadsorption und Freiwerden von Ionen aus der elektrischen Doppelschicht erkl?ren.
Our thanks are due to Prof. R. C. Mehrotra for providing all the facilities for this work and to Prof. S. Ghosh of Allahabad University for helpful discussions. Thanks are also due to the University Grants Commission, Government of India, for the award of a research scholarship to one of us (V. K. S.). 相似文献
95.
D. Rekha K. Suvardhan K. S. Kumar G. R. K. Naidu P. Chiranjeevi 《Journal of Analytical Chemistry》2006,61(12):1177-1182
A simple, sensitive, and rapid flow-injection spectrophotometric method was developed for the determination of trace amounts
of selenium(IV). The method is based on the oxidation reaction of 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH)
by selenium(IV) followed by the coupling reaction with chromotropic acid (4.5-dihydroxy naphthalene-2.7-disulphonic acid)
in a basic medium (phosphate buffer, pH 10.5) to give a pink derivative with λmax 530 nm that is stable for more than 7 days at 35°C. The reaction and flow conditions of the full experimental design were
optimized. A detection limit (2s) of 0.25 μg/L Se(IV) was obtained at a sampling rate of 10 samples per hour. Beer’s law is
obeyed for a Se(IV) concentration range of 0.05–0.5 μg/mL at the wavelength of maximum absorption. The detailed study of various
interference ions indicates that the method is highly selective. The method was successfully applied to the determination
of traces of selenium(IV) in various water samples. The results obtained were in good agreement with those obtained by the
reported methods at the 95% confidence level.
The text was submitted by the authors in English. 相似文献
96.
The kinetics of substitution of aqua ligands fromcis-diaqua-bis(biguanide)cobalt(III) and chromium(III) ions by aspartic acid in EtOH–H2O media have been studied spectrophotometrically in the 30 to 45°C range. We propose the following rate law for the anation
相似文献
97.
Titanium oxide on silica-alumina support is described to be an efficient regenerable catalyst for alkylation of aromatic compounds with alkyl halides, alcohols and olefins, and the reaction is proposed to be initiated by the protonated metal active species present in the catalyst. 相似文献
98.
Raj Kumar 《Colloid and polymer science》1979,257(1):95-97
Summary Estimation of zeta potential from experimental data on electroosmotic and electrophoretic effects for Zeokarb 225 (Na+ form)/methanol-water system has been made and discussed. Results indicate that zeta potentials estimated from electroosmotic flux and electrophoretic mobility are not in agreement and vary with applied potential difference in a linear manner. Reasons for the variation of zeta potential with electrical field have been discussed. It has been argued that zeta potentials estimated from electroosmotic data are more reliable in comparison to the values obtained from electrophoretic data.With 2 figures and 2 tables 相似文献
99.
Sachindra Kumar Datta 《Fresenius' Journal of Analytical Chemistry》1959,168(6):418-424
Summary Eighteen anilic acids have been prepared from maleic anhydride and various aromatic amines and their properties and analytical reactions with various metal ions have been studied. The acid prepared from benzidine was insoluble in all common solvents and, hence, its application could not be studied. Most of these reagents, except those obtained from aniline, o- and p-chloroanilines, nitranilines, p-amino-acetanilide and o-phenylenediamine, produced more or less quantitative precipitations with both thorium and zirconium. Their actions towards thorium and zirconium were very much alike. They also gave precipitations with mercury(I), lead and cerium(IV), but such precipitations were not complete. Ferrous iron showed greyish turbidity with most of the reagents, but ferric iron produced colourations varying from brown to violet, such colours were, however, found to be unstable either on standing for a while or on heating. Gold and platinum underwent reduction in presence of these reagents.Part VIII: See Z. analyt. Chem. 163, 403 (1958).The work has been carried out in the chemical laboratories of Darjeeling Government College, Darjeeling. The author is grateful to the authorities of the College for the laboratory facilities. 相似文献
100.
K. Chabita P. C. Mandal S. N. Bhattacharyya 《Journal of Radioanalytical and Nuclear Chemistry》1994,188(2):133-148
Dilute aqueous solutions of cytosine were irradiated with60Co -rays under N2O saturated conditions at different pH and in the presence of Cu(II) ions at neutral pH. The base degradation decreased from neutral to acidic and basic conditions. In the presence of metal ions at neutral pH conditions there was a significant increase in the base degradation compared to that in the absence of metal ions under similar conditions. From the difference absorption spectra and fluorescence behavior of the irradiated solutions it was observed that the major radiolytic products of cytosine under different conditions are cytosine glycols, 5-hydroxycytosine, hydroxy-hydrocytosine and cytosine dimers. The yields of dimers is maximum in neutral conditions and it decreased from basic to acidic conditions. However, in the presence of Cu(II) ions formation of cytosine dimers is completely restricted and there is an increase in the yields of cytosine glycol, hydroxy-hydrocytosine and 5-hydroxycytosine. From the post-radiolytic changes in absorption and fluorescence behavior of irradiated solutions, it is revealed that some of the radiolytic products, namely cytosine glycol and hydroxy-hydrocytosine decompose to 5-hydroxycytosine and cytosine, respectively. 相似文献
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