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51.
52.
The compression curve (to 200 kbars) and the ambient resistivity versus temperature (1.5K <T < 300K) of CeS have been measured. The results are compared to the analogous experiments on the compound CeAl2. A high pressure valence instability and ambient pressure crystalline electric field, spin fluctuation and magnetic order effects are found to be common to both compounds. 相似文献
53.
54.
Jayaraman Chandrasekhar Prem K. Mehrotra Sankaran Subramanian Periyakaruppan T. Manoharan 《Theoretical chemistry accounts》1979,52(4):303-310
Three valence-only schemes based on the Roby version of NDDO MO theory, which differ only in the core-valence treatment and the choice of the basis set, have been applied to the study of molecules containing first-row atoms. Orbital energies, charge distribution, dipole moments, field gradients, and a few other one-electron molecular properties are calculated to satisfactory accuracy. The schemes appear unreliable in the prediction of barriers to internal rotation in molecules, presumably due to errors in the core contribution to the total energy. An alternative treatment is suggested. 相似文献
55.
Juan G. Andrade Timothy Clark Jayaraman Chandrasekhar Paul von Ragué Schleyer 《Tetrahedron letters》1981,22(31):2957-2960
Mechanisms for the recently observed exchange of cyanide anion in acetonitrile have been investigated by means of semi-empirical MNDO molecular orbital calculations. A prototropic type mechanism a cyclopropane intermediate is the most likely candidate. The previously proposed concerted migration is indicated to be the least favourable reaction pathway. 相似文献
56.
Chou J Jayaraman S Ranasinghe AD McFarland EW Buratto SK Metiu H 《The journal of physical chemistry. B》2006,110(14):7119-7121
We deposit Pt particles electrochemically on an electrode covered with a Nafion membrane. Platinum ions travel through the hydrophilic channels of the membrane, and platinum deposits are formed at the place where the channels make contact with the planar electrode. This procedure deposits the catalyst only at the end of the hydrophilic channels that cross the membrane; no catalyst is placed under the hydrophobic domains, where it would not be in contact with the electrolyte. By performing a series of cyclic voltammograms with this system, we show that deposition of the platinum through the membrane achieves better platinum utilization than deposition of platinum on the naked electrode followed by the placement of the membrane on top. 相似文献
57.
Effect of homopolymer matrix on diblock copolymer grafted nanoparticle conformation and potential of mean force: A molecular simulation study
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We study the effect of homopolymer A or B matrix on the conformations and effective interactions of AB diblock copolymer grafted particles using coarse‐grained molecular dynamics simulations. In an A homopolymer matrix we observe patchy conformations within the AB diblock copolymer grafted layer, where the number of B patches is controlled by the A‐A attractive interaction strength. In a B homopolymer matrix the grafted particle takes on a core‐corona conformation, where the inner A block aggregates near the particle surface and the outer B block forms a corona that interacts with the B matrix. The potential of mean force (PMF) between two particles in an A homopolymer matrix has a long‐ranged attractive well with a minima at intermediate distances corresponding to the location of the outer B block patches. The PMF between two particles in a B homopolymer matrix has an attractive well at short interparticle distances corresponding to the size of the inner A block. We isolate the contribution of the homopolymer matrix on the PMF between the two diblock copolymer grafted particles, by deducting the PMF in the absence of a matrix, assuming the contributions of the grafted particle and matrix to the PMF to be additive. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 76–88 相似文献
58.
V.V. Sreenivasu Mummidivarapu Rakesh Kumar Pathak Vijaya Kumar Hinge Jayaraman Dessingou 《Supramolecular chemistry》2014,26(7-8):538-546
A triethylene glycol di-imine locked triazole linked bis-calix[4]arene conjugate L has been synthesised and characterised. Conjugate L exhibits high fluorescence enhancement towards Zn2+ among the 13 metal ions studied down to a lower detection limit of ~12 ppb. The absorption and visual colour change experiments differentiated the Zn2+ from the other metal ions studied. The isolated zinc complex, [Zn2L] has been used as a chemo-sensing ensemble for the recognition of anions based on their binding affinities towards Zn2+. [Zn2L] was found to be sensitive and selective towards phosphate-bearing species and in particular to adenosine triphosphate (ATP2 ? ) among the other 20 anions studied as observed based on the changes occurred in the fluorescence intensity. The selectivity of the ATP2 ? has been shown on the basis of the changes observed in the emission and absorption spectral studies. The lowest detectable concentration for ATP2 ? with the chemo-sensing ensemble [Zn2L] is 348 ppb in methanol. The fluorescence quenching by the phosphate-based anions has been modelled by molecular mechanics studies and found that the anions possessing two or more phosphate moieties can only bridge between the two zinc centres, and hence those possessing only one phosphate moiety (H2PO4? and AMP2 ? ) are ineffective. 相似文献
59.
Prasad Mishra G Venkata Ramana G Venkateswara Rao B 《Chemical communications (Cambridge, England)》2008,(29):3423-3425
A new, efficient and highly diastereoselective approach for the synthesis of 1,2,3,5-tetraacetylcarba-alpha-D-lyxofuranose from D-ribose is reported via one-pot conversion of to using Tebbe reagent which involves a cascade reaction sequence of methylenation, cleavage of isopropyl group, carbocyclization and again methylenation. 相似文献
60.
Govindasamy Rajarajan Natesan Jayachandramani Subramaniyan Manivarman Jayaraman Jayabharathi Venugopal Thanikachalam 《Transition Metal Chemistry》2008,33(3):393-397
The kinetics of oxidation of aldonitrones by 4-(dimethylamino)pyridinium chlorochromate (DMAPCC) has been studied in aqueous
N,N-dimethylformamide in the presence of perchloric acid. The reaction follows first-order kinetics with respect to each of DMAPCC
and nitrone. The order with respect to [H+] was found to be close to zero. The rate of oxidation was unaltered by the variation of [NaClO4] but addition of MnSO4 decreased the rate. The reaction rate was found to decrease with a decrease in dielectric constant of the medium. Electron-releasing
and electron-withdrawing groups perturb the reaction rate with a good Hammett correlation. The oxidation products were found
to be benzaldehyde and nitrosobenzene. The reaction was carried out at four different temperatures and the activation parameters
have been calculated. On the basis of the experimental findings, a suitable mechanism has been proposed. 相似文献