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1.
The quantum density of states of the Henon-Heiles potential displays a pronounced beating pattern. This has been explained by the interference of three isolated classical periodic orbits with nearby actions and periods. A singular magnetic flux line, passing through the origin, drastically alters the beats even though the classical Lagrangian equations of motion remain unchanged. Some of the changes can be easily understood in terms of the Aharonov-Bohm effect. However, we find that the standard periodic orbit theory does not reproduce the diffraction-like quantum effects on those classical orbits which intersect the singular flux line, and argue that corrections of relative order variant Planck's over 2pi are necessary to describe these effects. We also discuss the changes in the distribution of nearest-neighbor spacings in the eigenvalue spectrum, brought about by the flux line. (c) 1995 American Institute of Physics. 相似文献
2.
Sumit Bhaduri Krishna R. Sarma Bikshandarkovil A. Narayan 《Transition Metal Chemistry》1981,6(4):206-210
Summary Four-coordinate nickel nitrosyl complexes of the general formula Ni(NO)X(Dppe) (Dppe=Ph2PCH2CH2PPh2) have been prepared byin situ formation of Ni(NO2)X(Dppe), (X= Cl, Br, I or SCN) followed by reduction with triphenylphosphine, or carbon monoxide, and/or DMF. Oxygenation of the nitrosyl complexes gives the corresponding nitro products and as indicated by u.v.-vis spectroscopy involves formation of an intermediate. The oxygenation rate increases markedly in the presence of light or of a catalytic amount of benzoyl peroxide and a tentative explanation is offered for these observations. Ionic adducts are formed in reactions between the nitrosyl complexes and donor molecules.Paper presented in part at the XXth ICCC Conference. 相似文献
3.
Turbid emulsion systems of ethylacrylate/sodium dodecyl sulphate/water with monomer to surfactant (M/S) ratios 10 and 40 were transformed into stable transparent/translucent nanolatexes through emulsion polymerisation using potassium persulphate as an initiator. The latex particle size was observed to be similar to that obtained by true microemulsion polymerisation where M/S ratio is one. The kinetic plots exhibited two intervals upto M/S ratios 10. AIBN initiated systems showed separation of two phases for the M/S ratio ?10. M/S ratios were varied from 1 to 54 for the comparative study of polymerisation in emulsion and microemulsion media. Gel effect dominance was observed around 40-60% conversion for the microemulsion polymerisation of ethylacrylate. Only one chain per particle was observed for microemulsion system with M/S ratio 1 and three to four chains per particle were observed for the systems with M/S ratios 10 and 40. Unlike M/S=1 system, higher dependency of polymerisation rate on initiator concentration was observed for the systems with M/S=10 and 40. A possible mechanism for such a transformation has been proposed. 相似文献
4.
Tripathi RP Rastogi SK Kundu B Saxena JK Reddy VJ Srivastava S Chandra S Bhaduri AP 《Combinatorial chemistry & high throughput screening》2001,4(3):237-244
A library of 24 glycoconjugates related to glycosylated beta-amino acid derivative (I) was been prepared and screened against DNA topoisomerase-II of the filarial parasite S. cervi. Among these, compound 6 was found to be a potent inhibitor of DNA topoisomerase-II with 95% inhibition at 1.09 microM. Furthermore, compound 6 was at least three times more potent than the lead compound, glycosylated beta-amino acid derivative I. 相似文献
5.
Rao PV Bhaduri S Jiang J Hong D Holm RH 《Journal of the American Chemical Society》2005,127(6):1933-1945
The construction of a synthetic analogue of the A-cluster of carbon monoxide dehydrogenase/acetylcoenzyme synthase, the site of acetylcoenzyme A formation, requires as a final step the formation of an unsupported [Fe(4)S(4)]-(mu(2)-SR)-Ni(II) bridge to a preformed cluster. Our previous results (Rao, P. V.; Bhaduri, S.; Jiang, J.; Holm, R. H. Inorg. Chem. 2004, 43, 5833) and the work of others have addressed synthesis of dinuclear complexes relevant to the A-cluster. This investigation concentrates on reactions pertinent to bridge formation by examining systems containing dinuclear and mononuclear Ni(II) complexes and the 3:1 site-differentiated clusters [Fe(4)S(4)(LS(3))L'](2-) (L' = TfO(-) (14), SEt (15)). The system 14/[{Ni(L(O)-S(2)N(2))}M(SCH(2)CH(2)PPh(2))](+) results in cleavage of the dinuclear complex and formation of [{Ni(L(O)-S(2)N(2))}Fe(4)S(4)(LS(3))]- (18), in which the Ni(II) complex binds at the unique cluster site with formation of a Ni(mu(2)-SR)(2)Fe bridge rhomb. Cluster 18 and the related species [{Ni(phma)}Fe(4)S(4)(LS(3))](3)- (19) are obtainable by direct reaction of the corresponding cis-planar Ni(II)-S(2)N(2) complexes with 14. The mononuclear complexes [M(pdmt)(SEt)]- (M = Ni(II), Pd(II)) with 14 in acetonitrile or Me(2)SO solution react by thiolate transfer to give 15 and [M(2)(pdmt)(2)]. However, in dichloromethane the Ni(II) reaction product is interpreted as [{Ni(pdmt)(mu(2)-SEt)}Fe(4)S(4)(LS(3))](2-) (20). Reaction of Et(3)NH(+) and 15 affords the double cubane [{Fe(4)S(4)(LS(3))}(2)(mu(2)-SEt)](3-) (21). Cluster 18 contains two mutually supportive Fe-(mu(2)-SR)-Ni(II) bridges, 19 exhibits one strong and one weaker bridge, 20 has one unsupported bridge (inferred from the (1)H NMR spectrum), and 21 has one unsupported Fe-(mu(2)-SR)-Fe bridge. Bridges in 18, 19, and 21 were established by X-ray structures. This work demonstrates that a bridge of the type found in the enzyme A-clusters is achievable by synthesis and implies that more stable, unsupported single thiolate bridges may require reinforcement by an additional covalent linkage between the Fe(4)S(4) and nickel-containing components. (LS(3) = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3-); L(O)-S(2)N(2) = N,N'-diethyl-3,7-diazanonane-1,9-dithiolate(2-); pdmt = pyridine-2,6-methanedithiolate(2-); phma = N,N'-1,2-phenylenebis(2-acetylthio)acetamidate(4-); TfO = triflate.). 相似文献
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9.
An expedient three‐step procedure for the synthesis of trichlorophenol derivatives based on the acid‐catalyzed rearrangement of the bicyclic ketone precursors 6a–e in high overall yield is described. The bicyclic ketone precursors 6a–e were obtained from Diels–Alder cycloadducts of β‐substituted vinyl acetates with tetrachloro‐5,5‐dimethoxycyclopentadiene in two steps. 相似文献
10.
Priti Kumar Roy Sumit Nandi Mithun Kumar Ghosh 《Journal of mathematical chemistry》2013,51(10):2704-2717
Double substrate enzyme kinetics has a leading role for product quantification and optimization in different chemical and biochemical sectors. Mathematical approach for controlling these reactions in different stages by suitable parameters adds a new dimension in this interdisciplinary field of research. Applying control theoretic approach in the reversible backward stages of double substrate enzymatic model, time economization with regard to product formation is significant. In this article, we formulate a double substrate mathematical model of enzymatic dynamical reaction system with control measures with a view to observe the effect of changes of these measures with respect to the concentration of substrates, enzyme, complexes and finally product. Here, Pontryagin Minimum Principle is used for observing the effect of control measures in the system dynamics with the help of Hamiltonian. We compare the relevant numerical solutions for the substrates, enzyme, complexes and product concentration profile for a specified time interval with respect to control factors. 相似文献