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101.
We extend our recently developed inversion method to extract excited-state potentials from fluorescence line positions and line strengths. We consider a previous limitation of the method arising due to insufficient input data in cases where the relatively weaker emission data are not experimentally available. We develop a solution to this problem by ‘regenerating’ these weak transition lines via applying a model potential, e.g. a Morse potential. The result of this procedure, illustrated for the Q-branch emission from the lowest three vibrational levels of the B(1Π) state of LiRb, is shown to have an error of 0.29 cm?1 in the classically allowed region and a global error of 5.67 cm?1 for V ≤ E(ν′ = 10). The robustness of this procedure is also demonstrated by considering the statistical error in the measured line intensities. 相似文献
102.
Random overlap structures (ROSt’s) are random elements on the space of probability measures on the unit ball of a Hilbert space, where two measures are identified if they differ by an isometry. In spin glasses, they arise as natural limits of Gibbs measures under the appropriate algebra of functions. We prove that the so called ‘cavity mapping’ on the space of ROSt’s is continuous, leading to a proof of the stochastic stability conjecture for the limiting Gibbs measures of a large class of spin glass models. Similar arguments yield the proofs of a number of other properties of ROSt’s that may be useful in future attempts at proving the ultrametricity conjecture. Lastly, assuming that the ultrametricity conjecture holds, the setup yields a constructive proof of the Parisi formula for the free energy of the Sherrington–Kirkpatrick model by making rigorous a heuristic of Aizenman, Sims and Starr. 相似文献
103.
We report experimental evidence of mixed synchronization in two unidirectionally coupled chaotic oscillators using a scalar coupling. In this synchronization regime, some of the state variables may be in complete synchronization while others may be in anti-synchronization state. We extended the theory by using an adaptive controller with an updating law based on Lyapunov function stability to include parameter fluctuation. Using the scheme, we implemented a cryptographic encoding for digital signal through parameter modulation. 相似文献
104.
Sourav Maiti 《Tetrahedron letters》2009,50(27):3966-696
2-(Arylamino)-4-oxo-4H-chromene-3-carbaldehyde 3 (R2 = aryl) produces 12H-chromeno[2,3-b]quinolin-12-one 4 when treated with sarcosine, piperidine or diethylamine, but produces 3,3′-methylenebis(2-arylamino-4H-chromen-4-one) 8 when treated with the same amine in the presence of an excess of formaldehyde. Compound 3 (R2 = alkyl) was found to be less reactive than the N-aryl analogues towards the deformylative Mannich-type reaction. 相似文献
105.
Koushik Saha Sagar Ghorai Sourav Kar Suvam Saha Rajarshi Halder Beesam Raghavendra Eluvathingal D. Jemmis Sundargopal Ghosh 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(49):17848-17853
The room‐temperature reaction of [Cp*TaCl4] with LiBH4?THF followed by addition of S2CPPh3 results in pentahydridodiborate species [(Cp*Ta)2(μ,η2:η2‐B2H5)(μ‐H)(κ2,μ‐S2CH2)2] ( 1 ), a classical [B2H5]? ion stabilized by the binuclear tantalum template. Theoretical studies and bonding analysis established that the unusual stability of [B2H5]? in 1 is mainly due to the stabilization of sp2‐B center by electron donation from tantalum. Reactions to replace the hydrogens attached to the diborane moiety in 1 with a 2 e {M(CO)4} fragment (M=Mo or W) resulted in simple adducts, [{(Cp*Ta)(CH2S2)}2(B2H5)(H){M(CO)3}] ( 6 : M=Mo and 7 : M=W), that retained the diborane(5) unit. 相似文献
106.
Akbar Hossain Milan Skalicky Marian Brestic Sagar Maitra Sukamal Sarkar Zahoor Ahmad Hindu Vemuri Sourav Garai Mousumi Mondal Rajan Bhatt Pardeep Kumar Pradipta Banerjee Saikat Saha Tofazzal Islam Alison M. Laing 《Molecules (Basel, Switzerland)》2021,26(4)
The trace element selenium (Se) is a crucial element for many living organisms, including soil microorganisms, plants and animals, including humans. Generally, in Nature Se is taken up in the living cells of microorganisms, plants, animals and humans in several inorganic forms such as selenate, selenite, elemental Se and selenide. These forms are converted to organic forms by biological process, mostly as the two selenoamino acids selenocysteine (SeCys) and selenomethionine (SeMet). The biological systems of plants, animals and humans can fix these amino acids into Se-containing proteins by a modest replacement of methionine with SeMet. While the form SeCys is usually present in the active site of enzymes, which is essential for catalytic activity. Within human cells, organic forms of Se are significant for the accurate functioning of the immune and reproductive systems, the thyroid and the brain, and to enzyme activity within cells. Humans ingest Se through plant and animal foods rich in the element. The concentration of Se in foodstuffs depends on the presence of available forms of Se in soils and its uptake and accumulation by plants and herbivorous animals. Therefore, improving the availability of Se to plants is, therefore, a potential pathway to overcoming human Se deficiencies. Among these prospective pathways, the Se-biofortification of plants has already been established as a pioneering approach for producing Se-enriched agricultural products. To achieve this desirable aim of Se-biofortification, molecular breeding and genetic engineering in combination with novel agronomic and edaphic management approaches should be combined. This current review summarizes the roles, responses, prospects and mechanisms of Se in human nutrition. It also elaborates how biofortification is a plausible approach to resolving Se-deficiency in humans and other animals. 相似文献
107.
Dipolar relaxation within the protein matrix of the green fluorescent protein: a red edge excitation shift study 总被引:2,自引:0,他引:2
The fluorophore in green fluorescent protein (GFP) is localized in a highly constrained environment, protected from the bulk solvent by the barrel-shaped protein matrix. We have used the wavelength-selective fluorescence approach (red edge excitation shift, REES) to monitor solvent (environment) dynamics around the fluorophore in enhanced green fluorescent protein (EGFP) under various conditions. Our results show that EGFP displays REES in buffer and glycerol, i.e., the fluorescence emission maxima exhibit a progressive shift toward the red edge, as the excitation wavelength is shifted toward the red edge of the absorption spectrum. Interestingly, EGFP displays REES when incorporated in reverse micelles of sodium bis(2-ethylhexyl)sulfosuccinate (AOT), independent of the hydration state. We interpret the observed REES to the constrained environment experienced by the EGFP fluorophore in the rigid protein matrix, rather than to the dynamics of the bulk solvent. These results are supported by the temperature dependence of REES and characteristic wavelength-dependent changes in fluorescence anisotropy. 相似文献
108.
A central limit theorem is proved for the free energy of the random field Ising model with all plus or all minus boundary condition, at any temperature (including zero temperature) and any dimension. This solves a problem posed by Wehr and Aizenman (J Stat Phys 60:287–306, 1990). The proof uses a variant of Stein’s method.
相似文献109.
Saha S Flood AH Stoddart JF Impellizzeri S Silvi S Venturi M Credi A 《Journal of the American Chemical Society》2007,129(40):12159-12171
A multicomponent [2]rotaxane designed to operate as a molecular shuttle driven by light energy has been constructed, and its properties have been investigated. The system is composed of (1) a light-fueled power station, capable of using the photon energy to create a charge-separated state, and (2) a mechanical switch, capable of utilizing such a photochemically generated driving force to bring about controllable molecular shuttling motions. The light-fueled power station is, in turn, a dyad comprising (i) a pi-electron-accepting fullerene (C60) component and (ii) a light-harvesting porphyrin (P) unit which acts as an electron donor in the excited state. The mechanical switch is a redox-active bistable [2]rotaxane moiety that consists of (i) a tetrathiafulvalene (TTF) unit as an efficient pi-electron-donor station, (ii) a dioxynaphthalene (DNP) unit as a second pi-electron-rich station, and (iii) a tetracationic cyclobis(paraquat-p-phenylene) (CBPQT4+) pi-electron-acceptor cyclophane, which encapsulates the better pi-electron-donating TTF station. Diethylene glycol spacers were conveniently introduced between the electroactive components in the dumbbell-shaped thread to facilitate the template-directed synthesis of the [2]rotaxane. A modular synthetic approach was undertaken for the overall synthesis of this multicomponent bistable [2]rotaxane, beginning with the syntheses of the P-C60 dyad unit and the two-station TTF-DNP-based [2]rotaxane separately, using conventional synthetic methodologies. These two components were finally stitched together by an esterification to afford the target rotaxane. Its structure was characterized by 1H NMR spectroscopy and mass spectrometry as well as by UV-vis-NIR absorption spectroscopy and voltammetry. The observations reflect remarkable electronic interactions between the various units, pointing to the existence of folded conformations in solution. The redox-driven shuttling process of the CBPQT4+ ring between the two competitive electron-rich recognition units, namely, TTF and DNP, was investigated by electrochemistry and spectroelectrochemistry as a means to verify its operational behavior prior to the photophysical studies related to light-driven operation. The oxidation process of the TTF unit is dramatically hampered in the rotaxane, thereby reducing the efficiency of the shuttling motion. These results confirm that, as the structural complexity increases, the overall function of the system no longer depends simply on its "primary" structure but also on higher-level effects which are reminiscent of the secondary and tertiary structures of biomolecules. 相似文献
110.