The Cauchy Problem for Non-linear Higher Order Hartree Type Equation in Modulation Spaces

Journal of Fourier Analysis and Applications - We study the Cauchy problem for Hartree equation with cubic convolution nonlinearity $$F(u) = (K \star |u|^{2k})u$$ under a specified condition on...     

Fluorination suppresses thermal quenching in perovskite QLEDs

正Perovskite nanocrystals and quantum dots(QDs) have attracted great attention due to their potential in optical and optoelectronic applications, especially in ultra-high definition displays because of their high purity of photo/electroluminescence(PL/EL) [1,2]. Although the external quantum efficiency(EQE) of light-emitting diodes(LEDs) based on perovskite quantum dots(PeQDs) has been over 20% [3,4],another key problem, the PL/EL stability, still remains open.The thermal PL/EL quenching phenomenon, which is ubiquitously observed, has not aroused enough attention in this     

Catechol oxidase activity of a series of new dinuclear copper(II) complexes with 3,5-DTBC and TCC as substrates: syntheses, X-ray crystal structures, spectroscopic characterization of the adducts and kinetic studies

A series of dinuclear copper(II) complexes has been synthesized with the aim to investigate their applicability as potential structure and function models for the active site of catechol oxidase enzyme. They have been characterized by routine physicochemical techniques as well as by X-ray single-crystal structure analysis: [Cu 2(H 2L2 (2))(OH)(H 2O)(NO 3)](NO 3) 3.2H 2O ( 1), [Cu(HL1 (4))(H 2O)(NO 3)] 2(NO 3) 2.2H 2O ( 2), [Cu(L1 (1))(H 2O)(NO 3)] 2 ( 3), [Cu 2(L2 (3))(OH)(H 2O) 2](NO 3) 2, ( 4) and [Cu 2(L2 (1))(N 3) 3] ( 5) [L1 = 2-formyl-4-methyl-6R-iminomethyl-phenolato and L2 = 2,6-bis(R-iminomethyl)-4-methyl-phenolato; for L1 (1) and L2 (1), R = N-propylmorpholine; for L2 (2), R = N-ethylpiperazine; for L2 (3), R = N-ethylpyrrolidine, and for L1 (4), R = N-ethylmorpholine]. Dinuclear 1 and 4 possess two "end-off" compartmental ligands with exogenous mu-hydroxido and endogenous mu-phenoxido groups leading to intermetallic distances of 2.9794(15) and 2.9435(9) A, respectively; 2 and 3 are formed by two tridentate compartmental ligands where the copper centers are connected by endogenous phenoxido bridges with Cu-Cu separations of 3.0213(13) and 3.0152(15) A, respectively; 5 is built by an end-off compartmental ligand having exogenous mu-azido and endogenous mu-phenoxido groups with a Cu-Cu distance of 3.133(2) A (mean of two independent molecules). The catecholase activity of all of the complexes has been investigated in acetonitrile and methanol medium by UV-vis spectrophotometric study using 3,5-di- tert-butylcatechol (3,5-DTBC) and tetrachlorocatechol (TCC) as substrates. In acetonitrile medium, the conversion of 3,5-DTBC to 3,5-di- tert-butylbenzoquinone (3,5-DTBQ) catalyzed by 1- 5 is observed to proceed via the formation of two enzyme-substrate adducts, ES1 and ES2, detected spectroscopically for the first time. In methanol medium no such enzyme-substrate adduct has been detected, and the 3,5-DTBC to 3,5-DTBQ conversion is observed to be catalyzed by 1- 5 very efficiently. The substrate TCC forms an adduct with 2- 5 without performing further oxidation to TCQ due to the high reduction potential of TCC (in comparison with 3,5-DTBC). But most interestingly, 1 is observed to be effective even in TCC oxidation, a process never reported earlier. Kinetic experiments have been performed to determine initial rate of reactions (3,5-DTBC as substrate, in methanol medium) and the activity sequence is 1 > 5 > 2 = 4 > 3. A treatment on the basis of Michaelis-Menten model has been applied for kinetic study, suggesting that all five complexes exhibit very high turnover number, especially 1, which exhibits turnover number or K cat of 3.24 x 10 (4) (h (-1)), which is approximately 3.5 times higher than the most efficient catalyst reported to date for catecholase activity in methanol medium.     

Surface and Structural Investigation of a MnOx Birnessite‐Type Water Oxidation Catalyst Formed under Photocatalytic Conditions

Catalytically active MnO_x species have been reported to form in situ from various Mn‐complexes during electrocatalytic and solution‐based water oxidation when employing cerium(IV) ammonium ammonium nitrate (CAN) oxidant as a sacrificial reagent. The full structural characterization of these oxides may be complicated by the presence of support material and lack of a pure bulk phase. For the first time, we show that highly active MnO_x catalysts form without supports in situ under photocatalytic conditions. Our most active ⁴MnO_x catalyst (～0.84 mmol O₂ mol Mn^?1 s^?1) forms from a Mn₄O₄ bearing a metal–organic framework. ⁴MnO_x is characterized by pair distribution function analysis (PDF), Raman spectroscopy, and HR‐TEM as a disordered, layered Mn‐oxide with high surface area (216 m²g^?1) and small regions of crystallinity and layer flexibility. In contrast, the ^SMnO_x formed from Mn²⁺ salt gives an amorphous species of lower surface area (80 m²g^?1) and lower activity (～0.15 mmol O₂ mol Mn^?1 s^?1). We compare these catalysts to crystalline hexagonal birnessite, which activates under the same conditions. Full deconvolution of the XPS Mn2p_3/2 core levels detects enriched Mn³⁺ and Mn²⁺ content on the surfaces, which indicates possible disproportionation/comproportionation surface equilibria.     

Invoking Pairwise Interactions in Water‐Promoted Diels–Alder Reactions by using Ionic Liquids as Cosolvents

Rate constants and derived activation parameters of organic reactions in aqueous media, in particular Diels–Alder reactions, are sensitive to the presence of cosolvents in water. To enhance the solubility window of water, we introduced ionic liquids as cosolvents in the aqueous Diels–Alder reaction between anthracene‐9‐carbinol and N‐ethylmaleimide. The reactive potentials of the organic compounds are parameterized by using semi‐empirical quantum chemical methods. The principle of Savage–Wood additivity of group interactions is used to quantify the pairwise group interactions among chemically inert ionic liquids and organic reactants, both at initial and transition states of the reaction. The present approach shows promise, as the use of simple calculations from easily available kinetic data can help researchers to understand the versatility of green ionic‐liquid alternatives to volatile organic solvents.     

Mathematical modeling of localized melting around graphite nodules during laser surface hardening of austempered ductile iron

An attempt has been made to mathematically predict the optimum conditions of laser surface hardening (LSH) of austempered ductile iron (ADI) that can ensure a predominantly martensitic microstructure and preclude partial/complete dissolution of graphite nodules in the laser hardened zone during laser irradiation. The exercise involves prediction of the thermal profile (using the Ashby and Easterling model), and consequently, the carbon diffusion profile around the graphite nodules at different depths from the surface for the given conditions of LSH. Microstructural investigations have been carried out by optical and scanning electron microscopy to study the morphology, shape and width of the partially/completely melted graphite nodules as a function of the LSH parameters. Finally, the predicted maximum width of the melted zone around the graphite nodules is compared with the relevant experimental data to validate the proposed model.     

Calorimetric investigation of the interaction between a macromolecular prodrug of diflunisal and human platelets

The thermal effect due to the interaction between human platelets and α,β poly(N-hydroxy-ethyl)-DL-aspartamide (PHEA) or the PHEA-Diflunisal conjugate was measured by the calorimetric technique at 25°C. The experimental data confirm that PHEA is a biocompatible macromolecule and that its conjugate influences the physiological activity of human platelets.     

Ratio dependent predation :A bifurcation analysis

In this study, we have considered a prey-predator model reflecting the predator interference with discrete time delay. This delay is regarded as the lag due to gestation. In absence of delay, the criteria for existence of interior equilibrium and its global stability are derived. By choosing the delay as a bifurcation parameter, we have shown that a Hopf bifurcation may occur when the delay passes its critical value. Finally, we have derived the criteria for stability switches and verified the results through computer simulation.     

Role of tunneling of hydrogen in photoenolization of a ketone

Photoenolization of a ketone in its lowest triplet state was examined using the AM 1 semiempirical molecular orbital method with complete geometry optimization at the configuration interaction level in the restricted Hartree–Fock frame. The theoretical barrier fits with a polynomial given by Eq. (1) and the probability of tunneling of hydrogen was calculated by the WKB method. The density of states above the zero-point level was estimated by the Whitten–Rabinovitch approximation. Rate constants for the hydrogen and deuterium-abstraction processes via tunneling were then computed at different temperatures. © 1994 John Wiley & Sons, Inc.