Simulation of texture evolution for nematic liquid crystalline polymers under shear flow

The development of microstructure in nematic liquid crystalline polymers under shear flow is investigated through computational simulation. By using a tensorial expression for the elastic torque, the nemato-dynamic equation is numerically resolved. The simulation shows that elastic anisotropy has a strong influence on the evolution of the director and that the ‘log-rolling’ orientation of the directors emerges for tumbling nematics if the twist constant is smaller than the splay and the bend constants, even though one starts from a structure in which the directors are aligned within the velocity and velocity gradient plane. The interaction of wedge disclination pairs subject to a shear flow field is also simulated. The generation, multiplication and interaction of inversion wall defects during shearing have been revealed. In general the wall moves to the boundaries and is absorbed by the boundaries. When two walls of opposite orientation meet, a loop may form, then shrink, and finally collapse. Correspondingly, if they have the same orientation, commutation will occur.     

Enrichment of solubility by esterification: Metal-free and metallo-porphyrazines with polyfluorinated units

Metal-free and metallo-porphyrazines (M = 2H, Mg, Cu, Zn or Co) carrying eight hydroxypropylsulfanyl units at the peripheral positions were synthesized from 2,3-bis(3-hydroxypropylthio)maleonitrile. The reactivity of the hydroxypropyl units was demonstrated by the esterification of porphyrazine derivatives with 3,5-bis(trifluoromethyl)benzoic acid in the presence of dicyclohexylcarbodiimide and toluene-p-sulfonic acid. The symmetrical porphyrazine derivatives with eight ester units were soluble in common organic solvents such as chloroform, dichloromethane, THF, acetone, and toluene and insoluble in water and n-hexane. The complexes were characterized by several spectroscopic methods.     

Conformational Studies of Dibenzo-30-crown-10 Complexes. Syntheses and Crystal Structures of Potassium and Ammonium Hexafluorophosphate Complexes

Abstract

Crown ether complexes formed by the dibenzo–30-crown–10 (DB30C10) with potassium and ammonium hexafluorophosphate have been prepared and their crystal structures have been determined by single crystal X-ray analyses. The potassium complex (compound 1) consists of [K(DB30C10)]⁺ cation and PF₆ ^? anion. Crystals are monoclinic, space group P2/n, with a = 11.9106(3), b = 9.8382(5), c = 14.3062(3) Å, β = 97.581(3)°, V = 1661.7(1) ų, D_c = 1.440 g cm^?3, Z = 4, R = 0.0675 for 2528 unique observed reflections. The potassium atom is coordinated to the ten oxygen atoms of the crown ligand at the distance from 2.859(3) to 2.930(3) Å. The ammonium complex (compound 2) has also 1:1 crown—cation ratio. Crystals are monoclinic, space group P2₁/n, with a = 12.5061(6), b = 19.3724(5), c = 14.2203(9) Å, β = 102.476(5)°, V = 3363.8(3) ų, D_c = 1.501 g cm^?3, Z = 4, R = 0.0677 for 4172 unique observed reflections. The ammonium cation is completely enclosed with crown oxygen atoms forming seven hydrogen bonds. The conformation of previously reported dibenzo-30-crown-10 complexes with potassium salts were investigated using polar coordinate maps.     

磷钼酸铵分光光度法测定药物中6-巯基嘌呤

建立了磷钼酸铵分光光度法测定6-巯基嘌呤(6-MP)的方法。结果表明,在一定条件下,6-MP可以定量地与磷钼酸铵反应生成磷钼蓝,通过测定磷钼蓝的吸光度,从而间接地测定6-MP的含量。显色体系最大吸收波长为710nm,6-MP质量浓度在0.004～0.06 mg/mL范围内与A呈良好的线性关系,线性回归方程为A=0.0258+10.655ρ(mg/mL),线性相关系数r=0.9986。方法用于实际药品中6-PM的含量测定,结果与药典法一致。     

Preparation and application of a polythiophene solid‐phase microextraction fiber for the determination of endocrine‐disruptor pesticides in well waters

A robust solid‐phase microextraction fiber was fabricated by electropolymerization of thiophene on a stainless steel wire. This fiber was applied for the determination of endocrine‐disruptor pesticides, namely, chlorpyrifos, penconazole, procymidone, bromopropylate, and λ‐cyhalothrin in well waters by a headspace solid‐phase microextraction procedure. Operational parameters, namely, pH, sample volume, adsorption temperature and time, desorption temperature, stirring rate, and salt amount were optimized as 7.0, 8 mL, 70°C and 20 min, 250°C, 600 rpm, and 0.3 g/mL, respectively. The separation power of GC was coupled with the excellent sensitivity of the developed fiber enabling us to determine pesticide mixtures simultaneously in a ng/mL range. The LOD was in the range of 0.02–0.64 ng/mL. The method was successfully applied for the selective and sensitive determination of target pesticides in well water samples with acceptable recovery values (92–110%). The polythiophene fiber gives satisfactory results compared with commercial fibers. Commonly used pesticides with different polarities were chosen as representative compounds to search the applicability of the fiber for well water analysis collected from vineyards.     

Asymmetric [3+2]-Cycloaddition of Morita–Baylis–Hillman Carbonates with Maleimides Catalyzed by Chiral Ferrocenylphosphines

New chiral ferrocenylphosphines LB1–LB9 were designed and prepared through simple synthetic approaches. These air-stable ferrocenylphosphines were applied to promote asymmetric [3+2]-cycloaddition of Morita–Baylis–Hillman carbonates with maleimides, among which LB7 was shown to have good catalytic activity to afford the corresponding multifunctional cyclopentenes in up to 59% yield and up to 53% ee under mild reaction conditions. A plausible reaction mechanism was proposed.     

Synthesis,characterization and X-ray structures of N-heterocyclic carbene palladium complexes based on calix[4]arenes: highly efficient catalysts towards Suzuki–Miyaura cross-coupling reactions

A new series of calix[4]arene supported N-heterocyclic carbene palladium complexes were developed and fully characterized. A mono-substituted calix[4]arene was prepared through conventional procedures, following with the attachment of imidazolyl derivative groups to compose the precursors of novel NHCs ligands. Undergoing the alkylation with n-butylbromide and corresponding metallation with palladium and pyridine, original complexes were obtained. After a full characterization in solution and solid state, the evaluation of catalytic activity was taken out in Suzuki–Miyaura cross-coupling reactions, which revealed good performances.     

Global Exponential Stability of a Neural Network for Inverse Variational Inequalities

Journal of Optimization Theory and Applications - We investigate the convergence properties of a projected neural network for solving inverse variational inequalities. Under standard assumptions,...     

Facile synthesis of indole- or benzofuran-fused benzo[a]carbazole-1,4-diones using a tandem two-step reaction sequence

Abstract  

An efficient three-step approach was developed to assemble indole- or benzofuran-fused benzocarbazole-1,4-diones in 42–53% overall yield. This approach includes AgOAc-promoted oxidative cyclization of 2,6-di-bromocyclohexene-1,4-dione with indol-3-ylpropanoid acid, condensation of the resulting bromocarbazole intermediates with phenols or anilines, followed by Pd(OAc)-catalyzed cyclization. Such convenient synthetic protocol and the novelty of the corresponding products will largely assist our drug design and development program.     

Performance enhancement of a pulse detonation rocket engine

Utilizing liquid kerosene as the fuel, oxygen as oxidizer and nitrogen as purge gas, a series of multi-cycle detonation experiments was conducted to improve the performance of pulse detonation rocket engine (PDRE). In order to improve the performance of the engine, it is crucial to develop an effective DDT enhancement device with less flow loss and higher survival in hostile detonation tube; therefore, three spiraling internal grooves were tested. The three spiraling internal grooves were semicircle, square and inversed-triangle grooves, respectively. The results showed that the spiraling internal groove can effectively enhance DDT and prolong the operation time of PDRE. The effect of groove shape on thrust enhancement of PDRE and the optimum length of spiraling groove were then investigated. To improve the detonability of liquid kerosene and prolong the durability of PDRE, experiments on the kerosene preheating based on active cooling were conducted. The results demonstrated that with the aid of fuel preheating, the detonation initiation time for liquid kerosene was noticeably reduced and a fully-developed detonation wave was achieved in the position away from igniter 4.67 times the diameter of the detonation tube. By adding the additive to liquid kerosene, the detonation initiation time from 0.75 ms decreased to 0.34 ms and the detonability of fuel was dramatically improved. Finally, experiments were conducted to investigate the effects of the operating frequency on the detonation parameters, the fill fraction and PDRE performance. The results indicated that detonation pressure and temperature vary with the operating frequency of PDRE, and the fill fraction has a significant influence on the specific impulse of PDRE. With the strategy of partial filling in detonation tube, the specific impulse can be remarkably enhanced.