Synthesis,Characterization, and Antiproliferative Activity of Novel Chiral [QuinoxP*AuCl2]+ Complexes

Herein is reported the synthesis of two Au(III) complexes bearing the (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (R,R-QuinoxP*) or (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (S,S-QuinoxP*) ligands. By reacting two stoichiometric equivalents of HAuCl₄.3H₂O to one equivalent of the corresponding QuinoxP* ligand, (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (1) and (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (2) were formed, respectively, in moderate yields. The structure of (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (2) was further confirmed by X-ray crystallography. The antiproliferative activities of the two compounds were evaluated in a panel of cell lines and exhibited promising results comparable to auranofin and cisplatin with IC₅₀ values between 1.08 and 4.83 µM. It is noteworthy that in comparison to other platinum and ruthenium enantiomeric complexes, the two enantiomers (1 and 2) do not exhibit different cytotoxic effects. The compounds exhibited stability in biologically relevant media over 48 h as well as inert reactivity to excess glutathione at 37 °C. These results demonstrate that the Au(III) atom, stabilized by the QuinoxP* ligand, can provide exciting compounds for novel anticancer drugs. These complexes provide a new scaffold to further develop a robust and diverse library of chiral phosphorus Au(III) complexes.     

薄膜基荧光传感检测的研究进展

薄膜基荧光传感器是继离子迁移谱之后,业界公认的一种最具发展潜力的微痕量物质探测技术.由于其具有灵敏性、便携性、实时检测、响应速度快、易于制造、不污染待测体系等优点,在食品检测、环境监测、质量控制和生物医学分析等领域引起了广泛的关注和研究.本文主要综述了近年来薄膜基荧光传感在挥发性气体检测、有毒化学品检测、爆炸物检测、溶液相离子检测以及生物监测等领域的研究进展,并提出了薄膜基荧光传感所面临的挑战与未来的发展方向.     

Xe对NO(X)微分截面和非弹性散射中的碰撞诱导旋转准直

本文对NO(X)-Xe碰撞系统在碰撞能量为519 cm^-1,测量了完全?-双峰分解的微分截面和碰撞引起的旋转准直力矩. 同时结合初始量子态选择,使用六极杆的非均质电场,借助量子态分辨的测量,利用(1+1'')共振增强的多光子电离和速度离子成像. 结果显示,微分截面以及偏振相关的微分截面均显示与从头算势能面上进行的量子力学散射计算[J. K?os etal. J. Chem. Phys. 137, 014312 (2012)]一致. 通过与准经典轨迹、硬壳势能的量子力学散射以及运动近端模型的比较,评估了势能对所测微分截面和碰撞引起的旋转准直力矩的影响.     

Detection of water in jet fuel using layer-by-layer thin film coated long period grating sensor

The quantitative measurement of jet fuel additives in the field is of interest to the Air Force. The “smart nozzle” project was designed as a state-of-the-art diagnostics package attached to a single-point refueling nozzle for assessing key fuel properties as the fuel is dispensed. The objective of the work was to show proof of concept that a layer-by-layer thin film and long period grating fibers could be used to detect the presence of water in jet fuel. The data for the nafion/PDMA film and a long period grating fiber is a combination capable of quantitative measurement of water in kerosene. The average response (spectral loss wavelength shift) to the kerosene sample ranged from −6.0 for 15 ppm to −126.5 for 60 ppm water. The average calculated value for the check standard was 21.71 and ranged from 21.25 to 22.00 with a true value of 22.5 ppm water. Potential interferences were observed and are judged to be insignificant in real samples.     

Kinetics and mechanism of the reaction of propylene oxide with chlorine atoms and hydroxy radicals

The kinetics and mechanism of gas‐phase propylene oxide (PPO) reactions were studied in a 142‐L reaction chamber by long‐path Fourier transform infrared spectroscopy at atmospheric pressure and 298 K. Rate coefficients for the reaction of PPO with ozone (O₃), chlorine atoms (Cl), and hydroxyl radicals (OH) were measured using the relative rate technique. Product yields of acetic acid, acetic formic anhydride, formic acid, and carbon monoxide were determined for the following reactions: PPO with Cl both in the presence and absence of NO, PPO with OH and NO, methyl acetate with Cl both in the presence and absence of NO, and ethyl formate with Cl both in the presence and absence of NO. The measured rate coefficients for PPO with O₃, Cl, and OH are <3.5 × 10^?21 cm³ molecule^?1 s^?1, (3.0 ± 0.7) × 10^?11 cm³ molecule^?1 s^?1, and (3.0 ± 1.0) × 10^?13 cm³ molecule^?1 s^?1, respectively. The carbon balance for the products measured ranged from 10% (for OH + PPO) to 100% (for Cl + methyl acetate in the absence of NO). The mechanistic and atmospheric implications of these measurements are discussed. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 507–521, 2011     

Voltage-controlled optical switch in planar nematic liquid crystal film

This study presents an integrated device that consists of a directional coupler and an electro-optic switch. The device is designed to include a nematic liquid crystal cell, comprising a grating-like electrode. Applying the appropriate voltage to the cell yields a periodically distributed refractive index. An incident polarized beam will couple to an adjacent channel if it is parallel to the channel. The coupling efficiency is controlled by applied voltage. An obliquely injected polarized beam will be reflected and refracted in the channel, and propagated along a curved path. The route of the beam can be controlled by applying the voltage. A multiport routing was achieved for voltage modulation. In addition, the distribution of refractive index is also investigated by employing conoscopic technique experimentally and numerically.     

Synthesis of Structurally Varied 1,3‐Disiloxanediols and Their Activity as Anion‐Binding Catalysts

A series of new 1,3‐disiloxanediols has been synthesized, including naphthyl‐substituted and unsymmetrical siloxanes, and demonstrated as a new class of anion‐binding catalysts. In the absence of anions, diffusion‐ordered spectroscopy (DOSY) displays self‐association of 1,3‐disiloxanediols through hydrogen‐bonding interactions. Binding constants determined for 1,3‐disiloxanediol catalysts indicate strong hydrogen‐bonding and anion‐binding abilities with unsymmetrical siloxanes displaying different hydrogen‐bonding abilities for each silanol group.     

Combined Helmholtz equation-least squares method for reconstructing acoustic radiation from arbitrarily shaped objects

A combined Helmholtz equation-least squares (CHELS) method is developed for reconstructing acoustic radiation from an arbitrary object. This method combines the advantages of both the HELS method and the Helmholtz integral theory based near-field acoustic holography (NAH). As such it allows for reconstruction of the acoustic field radiated from an arbitrary object with relatively few measurements, thus significantly enhancing the reconstruction efficiency. The first step in the CHELS method is to establish the HELS formulations based on a finite number of acoustic pressure measurements taken on or beyond a hypothetical spherical surface that encloses the object under consideration. Next enough field acoustic pressures are generated using the HELS formulations and taken as the input to the Helmholtz integral formulations implemented through the boundary element method (BEM). The acoustic pressure and normal component of the velocity at the discretized nodes on the surface are then determined by solving two matrix equations using singular value decomposition (SVD) and regularization techniques. Also presented are in-depth analyses of the advantages and limitations of the CHELS method. Examples of reconstructing acoustic radiation from separable and nonseparable surfaces are demonstrated.     

Anion exchange in the channels of a robust alkaline earth sulfonate coordination network

The barium sulfonate network presented herein, [[Ba2(L)(H2O)5]Cl]infinity (1), represents the first metal sulfonate compound to possess a cationic framework. The network is layered with channels between pillaring ligands in which chloride ions reside. Compound 1 contracts slightly upon dehydration but retains its overall structural motif to 420 degrees C. Significantly, the chloride ions of the structure can be exchanged in 80% yield for fluoride ions in a facile manner. This exchange is quantified by elemental analyses, gravimetric determination, and 19F NMR spectroscopy. Confirmation of retention of structure is provided by standardized powder X-ray diffraction experiments. This last point is notable as the F-analogue of the structure is not attainable by a direct synthesis. These results illustrate one of the hallmark features of supramolecular chemistry, that a robust and functional framework can result through cooperative interactions between more weakly interacting units.