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21.
Summary Rate constants for the oxidation of thiosulphate by hexachloroplatinate(IV) have been measured. The kinetics of the oxidation of thiosulphate follow a second-order rate law, first order with respect to thiosulphate and first order with respect to platinum(IV). The influence of pH is small. The rates are found to depend on the nature and concentration of the cations and follow the order: Cs+>Rb+>K+>Na+>Li+. The activation parameters calculated from the temperature studies are: H=42.9 k J mol–1 and S=–102 JK–1 mol–1. A mechanism of the reaction in terms of intermediate formation of free radicals followed by the formation of tetrathionate is postulated to explain the kinetic behaviour. 相似文献
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Nair S Dimeo RM Neumann DA Horsewill AJ Tsapatsis M 《The Journal of chemical physics》2004,121(10):4810-4819
The methyl rotational tunneling spectrum of p-xylene confined in nanoporous zeolite crystals has been measured by inelastic neutron scattering (INS) and proton nuclear magnetic resonance (NMR), and analyzed to extract the rotational potential energy surfaces characteristic of the methyl groups in the host-guest complex. The number and relative intensities of the tunneling peaks observed by INS indicate the presence of methyl-methyl coupling interactions in addition to the methyl-zeolite interactions. The INS tunneling spectra from the crystals (space group P2(1)2(1)2(1) with four crystallographically inequivalent methyl rotors) are quantitatively interpreted as a combination of transitions involving two coupled methyl rotors as well as a transition involving single-particle tunneling of a third inequivalent rotor, in a manner consistent with the observed tunneling energies and relative intensities. Together, the crystal structure and the absence of additional peaks in the INS spectra suggest that the tunneling of the fourth inequivalent rotor is strongly hindered and inaccessible to INS measurements. This is verified by proton NMR measurements of the spin-lattice relaxation time which reveal the tunneling characteristics of the fourth inequivalent rotor. 相似文献
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In this study, a novel concept of picture fuzzy threshold graph (PFTG) is introduced. It has been shown that PFTGs are free from alternating 4-cycle and it can be constructed by repeatedly adding a dominating or an isolated node. Several properties about PFTGs are discussed and obtained the results that every picture fuzzy graph (PFG) is equivalent to a PFTG under certain conditions. Also, the underlying crisp graph (UCG) of PFTG is a split graph (SG), and conversely, a given SG can be applied to constitute a PFTG. A PFTG can be decomposed in a unique way and it generates three distinct fuzzy threshold graphs (FTGs). Furthermore, two important parameters i.e., picture fuzzy (PF) threshold dimension (TD) and PF partition number (PN) of PFGs are defined. Several properties on TD and PN have also been discussed. Lastly, an application of these developed results are presented in controlling medicine resources. 相似文献
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Synthesis,characterization and biological screening studies of mixed ligand complexes using flavonoids as precursors 下载免费PDF全文
Flavonoids are a group of plant phenolics that provide various health benefits through cell signalling pathways and antioxidant effects. In the present study, a new series of mixed ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) were synthesized by incorporating curcumin and quercetin flavonoid precursors. The structural features of the synthesized complexes were explored using elemental analysis, thermogravimetric analysis, UV–visible, infrared, NMR, mass and electron paramagnetic resonance spectral analyses and conductivity measurements. These data support an octahedral geometry of the synthesized complexes. In silico biological activity score for the ligand was predicted using PASS online software. ADMET properties were studied using VLS3D online software. Anti‐inflammatory and antioxidant activities were experimentally validated which prove that theoretical predictions are in agreement with the experimental results. Interestingly the synthesized complexes interact with calf thymus DNA through groove binding mode. Moreover, they have good potential to cleave pUC19 DNA. Minimum inhibitory concentration values of the synthesized complexes reveal that they have better antimicrobial efficacy than the ligands. 相似文献
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Deshabrata Roy Mahapatra Sankar Kumar Roy Mahendra Prasad Biswal 《Applied Mathematical Modelling》2013
In this paper a multi choice stochastic transportation problem is considered where the supply and demand parameters of the constraints follow extreme value distribution. Some of the cost coefficients of the objective function are multi-choice type. At first all the probabilistic constraints are transformed into deterministic constraints. Further using the binary variables, multi-choice type cost coefficients are handled. Then the transformed problem is considered as a deterministic multi-choice transportation problem. Finally, a numerical example is presented to illustrate the solution procedure. 相似文献
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Akhil Kumar Singh Dr. Mohammad Usman Dr. Giuseppe Sciortino Prof. Dr. Eugenio Garribba Prof. Dr. Sankar Prasad Rath 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(43):10098-10110
Metallophilic interactions between closed-shell metal ions are becoming a popular tool for a variety of applications related to high-end materials. Heavier d8 transition-metal ions are also considered to have a closed shell and can be involved in such interactions. There is no systematic investigation so far to estimate the structure and energy characteristics of metallophilic interactions in AgII/AgII (d9/d9), AgIII/AgIII (d8/d8), and mixed-valent AgII/AgIII (d9/d8) complexes, which have been demonstrated in the present study. Both interporphyrinic and intermetallic interactions were investigated on stepwise oxidation by using a rigid ethene-bridged cis silver(II) porphyrin dimer and the results compared with those for highly flexible ethane-bridged analogues. By controlling the nature of chemical oxidants and their stoichiometry, both 1e and 2e oxidations were done stepwise to generate AgII/AgIII mixed-valent and AgIII/AgIII porphyrin dimers, respectively. Unlike all other ethene-bridged metalloporphyrin dimers reported earlier, in which 2e oxidation stabilizes only the trans form, such an oxidation of silver(II) porphyrin dimer stabilizes only the cis form because of the metallophilic interaction. Besides silver(II) ⋅⋅⋅ silver(II) interactions in cis silver(II) porphyrin dimer, stepwise oxidations also enabled us to achieve various hitherto-unknown silver(II) ⋅⋅⋅ silver(III) and silver(III) ⋅⋅⋅ silver(III) interactions, which thereby allow significant modulation of their structure and properties. The strength of Ag ⋅⋅⋅ Ag interaction follows the order AgII/AgII (d9/d9)<AgII/AgIII (d9/d8)<AgIII/AgIII (d8/d8). Single-crystal XRD, X-ray photoelectron spectroscopy (XPS), 1H NMR and EPR spectroscopy, and variable-temperature magnetic investigations revealed various oxidation states of silver and metallophilic interactions, which are also well supported by computational analysis. 相似文献
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