Enantioselective Diethylzinc Addition to Aromatic Aldehydes Catalyzed by Novel Ti(IV) Complex of Three-Dentate Chiral Sulfonamide Ligands

The synthesis of several novel three-dentate sulfonamide alcohol ligands is described, starting from camphorsulfonyl chloride. The influence of temperature and ligand structure on the asymmetric addition of dietylzinc to aromatic aldehydes has been studied. Enantioselectivities up to 76% have been obtained.     

Effect of block lengths on the association behavior of poly(l-lactic acid)/poly(ethylene glycol) (PLA–PEG–PLA) micelles in aqueous solution

A series of poly(l-lactic acid)/poly(ethylene glycol) triblock copolymers with a PLA–PEG–PLA architecture were synthesized by a ring-opening polymerization (ROP) process. The copolymers were characterized by ¹H NMR and GPC. The total number average molecular weights were in the range of 4,700–50,000, whereas the degrees of polymerization of the PLA and PEG blocks varied from 15 to 359 and from 68 to 136, respectively. The self-association of these copolymers in aqueous environment was studied by emission fluorescence spectroscopy of anilinonaphthalene probe and the critical association concentration (CAC) of the copolymers was measured. It was found that the micellization process of these copolymers was mainly determined by the length of the hydrophobic LA block, while the length of the hydrophilic PEG block had little effect. Furthermore, the low CAC values of the copolymers suggest that the copolymers form stable supramolecular structures in aqueous solutions.     

A Dimroth rearrangement approach for the synthesis of selenopheno[2,3-e][1,2,4]triazolo[1,5-c]pyrimidines with cytotoxic activity on breast cancer cells

Molecular Diversity - New selenopheno[2,3-e][1,2,4]triazolo[1,5-c]pyrimidine derivatives have been synthesized via Dimroth rearrangement by cyclocondensation of...     

Deuterium-tritium fuel impact ignition in the presence of degenerate plasma

The impact ignition model is proposed based on the collision of a deuterium-tritium (DT) layer accelerated to high velocities in a conical target. Simple mechanism, low cost, high coupling efficiency, and lack of the need for Petawatt laser pulses are the prominent advantages of this model. However, an increase in the productivity of this ignition mechanism is an important issue. In this regard, in this paper, the idea of impact ignition using the plasma degeneracy mechanism has been investigated. For this purpose, first, the ignition energy gain and stopping power of the DT beam in pure and impure fuels, by employing both degenerate and non-degenerate plasmas, have been examined numerically. Then, in order to assess the penetration depth and range of the incident beam, simulations have been carried out using a three-dimensional (3D) Monte Carlo code for two states of degenerate and non-degenerate pre-compressed pure fuel. The results imply that the state of degeneracy causes an increase by about 63% in the energy gain of impact ignition. In addition, the degeneracy condition leads to an approximate enhancement of 60% in the energy deposition of the pure fuel and about 67% for the impure fuel, with a mixed density ratio of 1.5%; therefore, the range and penetration depth decrease significantly in comparison to the non-degenerate one. This can be indicative of the increasing efficiency of impact ignition conditions in the presence of degenerate plasma. The results of the range for the pure fuel have also been confirmed by a 3D Monte Carlo simulation code.     

Enantioselective Addition of Diethylzinc to Aromatic Aldehydes Catalyzed by Pyrolidine and Piperidine β-Amino Alcohols

The enantioselective alkylation of aryl aldehydes by diethylzinc in the presence of catalytic amounts of several chiral pyrolidine- and piperidine-based amino alcohol ligands, synthesized from the reaction of (R)-2-amino-1-butanol and (S)-2-amino-3-phenylpropan-1-ol with appropriate dibromoalkanes, was studied. The influence of temperature and ligand structure has been investigated. Addition of diethylzinc to aromatic aldehydes under the optimized condition gave the corresponding products in excellent yields with ee values of up to 77%.     

Direct electron transfer enhancement of covalently bound tyrosinase to glassy carbon via Woodward's reagent K

This work describes the reaction mechanism for chemical modification of tyrosinase by Woodward's Reagent K and its covalent attachment to a glassy carbon electrode. The spectrophotometric studies revealed that the modification does not cause a significant structural change to tyrosinase. The direct electrochemistry of modified enzyme was achieved after immobilization on an oxidatively activated glassy carbon electrode. The enzyme film exhibited a pair of well-defined quasi-revesible voltammetric peaks corresponding to the Cu (II)/Cu (I) redox couple located in the active site of tyrosinase. The formal potential of immobilized enzyme was measured to be 90mV (vs. Ag/AgCl) in phosphate buffer solution at pH 7.0. The charge-transfer coefficient and apparent heterogeneous electron transfer rate constant were estimated to be 0.5 and 0.9±0.06s(-1), respectively. Finally, the electrochemical behavior of the immobilized enzyme in the presence of caffeic acid and L-3,4-dihydroxyphenylalanine as substrates was investigated. The amperometric study of biosensor toward L-3,4-dihydroxyphenylalanine resulted a linear response in the concentration range from 1.66×10(-6) to 8.5×10(-5)M with detection limit of 9.0×10(-5)M and sensitivity of 135mAμM(-1)cm(-2).     

Optimal design of shock ignition target in order to stop generated hot electrons within the cold fuel

Generation of hot electrons (HEs) within ignitor pulse interaction with pre-compressed fuel is an important challenge in the shock ignition approach. Target optimization in order to prevent the destructive effects of HE is the main goal of the present work. In the first stage, the spectrum of electron energy generated during the interaction of ignitor pulse at different widths with the HiPER pre-compressed target has been estimated by applying particle simulation tool. Then, by changing the thickness of the cold fuel in the range of 185–225 μm, the corresponding areal densities are calculated using 1D hydrodynamic simulations. Finally, in order to assess the energy fusion yield, the iso-gain curves are obtained for different ignitor time windows as well as target thicknesses. Simulation results indicate that by decreasing the baseline, target thickness leads to a 17–70% increase in the fuel areal density. Subsequently, it has been demonstrated that by properly adjusting the parameters of ignitor pulse launch time and its width and employing a target with areal density high enough to stop the HEs, energy gain above 140 can be achieved. Optimal areas for shell thickness and ignitor time window are identified.     

An efficient numerical approach to solve a class of variable‐order fractional integro‐partial differential equations

The main purpose of this work is to investigate an initial boundary value problem related to a suitable class of variable order fractional integro‐partial differential equations with a weakly singular kernel. To discretize the problem in the time direction, a finite difference method will be used. Then, the Sinc‐collocation approach combined with the double exponential transformation is employed to solve the problem in each time level. The proposed numerical algorithm is completely described and the convergence analysis of the numerical solution is presented. Finally, some illustrative examples are given to demonstrate the pertinent features of the proposed algorithm.     

A Straightforward Approach for the Synthesis of Novel Derivatives of Benzo[b]pyrazolo[5′,1′:2,3]pyrimido[4,5‐e][1,4]thiazine

Several derivatives of the novel benzo[b]pyrazolo[5′,1′:2,3]pyrimido[4,5‐e][1,4]thiazine ring system have been synthesized through the one‐pot cyclocondensation of 6‐bromo‐7‐chloro‐2‐(ethylthio)‐5‐methylpyrazolo[1,5‐a]pyrimidine‐3‐carbonitrile ( 4 ) with o‐aminothiophenol in the presence of Et₃N in CH₃CN. The true regio isomer ( 5 ) was also determined by X‐ray crystallographic analysis. The N‐alkylation of the synthesized compound ( 5 ) was also accomplished.