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131.
Dey GR El Omar AK Jacob JA Mostafavi M Belloni J 《The journal of physical chemistry. A》2011,115(4):383-391
The detailed kinetics of the multistep mechanism of the Au(III) ion reduction into gold clusters have been investigated by radiation chemistry methods in 2-propanol. In particular, a discussion on the steady state radiolysis dose-dependence of the yields concludes to a comproportionation reaction of nascent gold atoms Au(0) with excess Au(III) ions into Au(II) and Au(I). This reaction should be achieved through Au(III) consumption before the coalescence of atoms Au(0) into gold clusters may occur. Then gold clusters catalyze the reduction of Au(I) by 2-propanol. It was also found that a long-lived Au(II) dimer, (Au(II))(2), was transiently formed according to the quantitative analysis of time-resolved absorbance signals obtained by pulse radiolysis. Then the disproportionation of Au(II) is intramolecular in the dimer instead of intermolecular, as usually reported. The yields, reaction rate constants, time-resolved spectra, and molar extinction coefficients are reported for the successive one-electron reduction steps, involving especially the transient species, such as Au(II), (Au(II))(2), and Au(I). The processes are discussed in comparison with other solvents and other metal ions. 相似文献
132.
Olsen JC Fahrenbach AC Trabolsi A Friedman DC Dey SK Gothard CM Shveyd AK Gasa TB Spruell JM Olson MA Wang C Jacquot de Rouville HP Botros YY Stoddart JF 《Organic & biomolecular chemistry》2011,9(20):7126-7133
A limited range of redox-active, rotaxane-based, molecular switches exist, despite numerous potential applications for them as components of nanoscale devices. We have designed and synthesised a neutral, redox-active [2]rotaxane, which incorporates an electron-deficient pyromellitic diimide (PmI)-containing ring encircling two electron-rich recognition sites in the form of dioxynaphthalene (DNP) and tetrathiafulvalene (TTF) units positioned along the rod section of its dumbbell component. Molecular modeling using MacroModel guided the design of the mechanically interlocked molecular switch. The binding affinities in CH(2)Cl(2) at 298 K between the free ring and two electron-rich guests--one (K(a) = 5.8 × 10(2) M(-1)) containing a DNP unit and the other (K(a) = 6.3 × 10(3) M(-1)) containing a TTF unit--are strong: the one order of magnitude difference in their affinities favouring the TTF unit suggested to us the feasibility of integrating these three building blocks into a bistable [2]rotaxane switch. The [2]rotaxane was obtained in 34% yield by relying on neutral donor-acceptor templation and a double copper-catalysed azide-alkyne cycloaddition (CuAAC). Cyclic voltammetry (CV) and spectroelectrochemistry (SEC) were employed to stimulate and observe switching by this neutral bistable rotaxane in solution at 298 K, while (1)H NMR spectroscopy was enlisted to investigate switching upon chemical oxidation. The neutral [2]rotaxane is a chemically robust and functional switch with potential for applications in device settings. 相似文献
133.
Saha R Biswas S Steele IM Dey K Mostafa G 《Dalton transactions (Cambridge, England : 2003)》2011,40(13):3166-3175
The metal complexes, [M(Hdammthiol)(2)]Cl·3H(2)O [M = Cr(III) (1), Fe(III) (2)] [where H(2)dammthiol is the thiol form of the ligand, diacetylmonoxime morpholine N-thiohydrazone] were synthesized by metal template reactions of diacetylemonoxime with morpholine N-thiohydrazide in the presence of CrCl(3)·6H(2)O and FeCl(3)·6H(2)O. Both the complexes (1 and 2) were characterized by single crystal X-ray crystallography, spectroscopic (IR and UV-vis), M?ssbauer and TGA analyses. The single crystal X-ray studies of both complexes show that the supramolecular hosts, constructed by the discrete mononuclear complexes, form supramolecular channels along the c-axis which are filled up by water-chloride clusters. In both complexes, the 1D water-chloride chain with chair-like architecture within the supramolecular hosts presents novelty. The magnetic measurement study of Fe(III) complex shows a spin crossover from S = 1/2 at 2.5 K to S = 5/2 at 300 K. At very low temperature, the presence of strong cooperative hydrogen bonding interactions stabilizes the S = 1/2 state. 相似文献
134.
Ahmad S Dey SS Jousseaume B Toupance T 《Dalton transactions (Cambridge, England : 2003)》2011,40(2):457-462
The preparation of hexamethylated and hexabenzylated arylene or heteroarylene bridged dinuclear di(cyclopentadienyltitanium) compounds from the reaction of the corresponding hexachlorides with methyllithium or benzylmagnesium chloride is described. The spacers between the cyclopentadienyl rings consist of one, two or three phenylene groups, a dioctyloxyphenylene group or a 2,2'-bithienylene group. The corresponding hexachlorides and hexaisopropoxides have also been prepared. 相似文献
135.
Nucleophilic C-S bond formation using easily available β-hydroxysulfonate derivatives allowed direct access to new mono- and disubstituted divinyl sulfones. Our strategy uses thioethanol (HSCH(2)CH(2)OH) and its analogues such as HSCH(2)CH(Y)OH generated in situ. The strategy also allows the synthesis of modified divinyl sulfones attached to chiral appendages like carbohydrates. Bis-heteronucleophilic Michael addition reactions with 1 equiv of a primary amine afforded new generations of S,S-dioxothiomorpholine derivatives known for their therapeutic applications. Further synthetic manipulations of some of these cyclic compounds led to the synthesis of novel bicyclic derivatives. 相似文献
136.
Dey A Das K Karan S De SK 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,83(1):384-391
Structure, morphology and thermal properties of polyethylene oxide (PEO) with sodium perchlorate (NaClO(4)) as electrolytic salt have been investigated by incorporating cupric monoxide (CuO) nanoparticles. Monoclinic CuO affects melting and glass transition temperatures of PEO-NaClO(4). Crystallinity and free ion concentration change with the variation of CuO concentration. The maximum ionic conductivity is observed for 10 wt.% CuO. Ionic conductivity follows Arrhenius type behavior as a function of temperature. 相似文献
137.
138.
Carolina Estarellas Prof. Antonio Frontera Dr. David Quiñonero Prof. Dr. Pere M. Deyà 《Chemphyschem》2011,12(15):2742-2750
This article analyzes the interplay between lone pair–π (lp–π) or anion–π interactions and halogen‐bonding interactions. Interesting cooperativity effects are observed when lp/anion–π and halogen‐bonding interactions coexist in the same complex, and they are found even in systems in which the distance between the anion and halogen‐bond donor molecule is longer than 9 Å. These effects are studied theoretically in terms of energetic and geometric features of the complexes, which are computed by ab initio methods. Bader′s theory of “atoms in molecules” is used to characterize the interactions and to analyze their strengthening or weakening depending upon the variation of charge density at critical points. The physical nature of the interactions and cooperativity effects are studied by means of molecular interaction potential with polarization partition scheme. By taking advantage of all aforementioned computational methods, the present study examines how these interactions mutually influence each other. Additionally, experimental evidence for such interactions is obtained from the Cambridge Structural Database (CSD). 相似文献
139.
Let (E,θ) be a stable Higgs bundle of rank r on a smooth complex projective surface X equipped with a polarization H. Let C⊂X be a smooth complete curve with [C]=n⋅H. If where , then we prove that the restriction of (E,θ) to C is a stable Higgs bundle. This is a Higgs bundle analog of Bogomolov's restriction theorem for stable vector bundles. 相似文献
140.
Arjun Berera 《Contemporary Physics》2013,54(1):33-49
In the past decade, the importance of dissipation and fluctuation to inflationary dynamics has been realized and has led to a new picture of inflation called warm inflation. Although these phenomena are common to condensed matter systems, for inflation models their importance has only recently started to be appreciated. The article describes the motivation for these phenomena during inflation and then examines their origins from first principles quantum field theory treatments of inflation models. Cosmology today is a data intensive field and this is driving theory to greater precision and predictability. This opens the possibility to consider tests for detecting observational signatures of dissipative processes, which will be discussed. In addition, it will be discussed how particle physics and cosmology are now working in tandem to push the boundaries of our knowledge about fundamental physics. 相似文献