新型鸟嘌呤类似物y-鸟嘌呤及其异构体电子光谱性质的理论研究

荧光核酸碱基类似物的设计合成是众多研究领域的热点课题. 本文利用密度泛函理论(DFT)和含时密度泛函理论(TDDFT)考察了新型鸟嘌呤类似物y-鸟嘌呤(yG-t1) 及其五个异构体(yG-t2到yG-t6)的结构性质、电子性质和光谱性质, 同时考察了甲醇溶剂和碱基配对对其光谱性质的影响. 研究表明, 气相中y-鸟嘌呤的标准结构并不是最稳定的结构, 其具有三个能量相近的异构体, y-鸟嘌呤最有可能以这三种形式存在. 光谱性质研究表明y-鸟嘌呤的最大吸收波长比天然鸟嘌呤大得多, 人们可以对其进行选择性激发. y- 鸟嘌呤的标准结构与其异构体显示出不同的光谱特性, 因此可以利用其电子光谱指纹对它们进行区分. 研究发现甲醇溶剂将使y-鸟嘌呤标准结构的最大吸收波长和荧光发生蓝移, 而使其他异构体相应值发生红移; 与胞嘧啶配对将使yG-t1, yG-t2, yG-t5 和yG-t6的最大吸收波长和荧光波长发生蓝移, 表明y-鸟嘌呤的电子光谱性质受环境影响较大.     

质子与金属布线层核反应对微纳级静态随机存储器单粒子效应的影响分析

金属布线层对微纳级静态随机存储器(static random access memory, SRAM) 质子单粒子效应敏感性的影响值得关注. 利用Geant4针对不同能量(30 MeV, 100 MeV, 200 MeV和500 MeV)的质子与微纳级SRAM器件的核反应过程开展计算, 研究了核反应次级粒子的种类、线性能量传输值(linear energy transfer, LET)及射程情况, 尤其对高LET 值的核反应次级粒子及其射程开展了详细分析. 研究表明, 金属布线层的存在和质子能量的增大为原子序数大于或等于30的重核次级粒子的产生创造了条件, 器件体硅区中原子序数大于60的重核离子来源于质子与钨材料的核反应, 核反应过程中的特殊作用机理会生成原子序数在30至50之间的次级粒子, 且质子能量的增大有助于这种作用机理的发生, 原子序数在30至50之间的次级粒子在器件体硅区的LET值最大约为37 MeV·cm²/mg, 相应射程可达到几微米, 对于阱深在微米量级的微纳级SRAM器件而言, 有引发单粒子闩锁的可能. 研究结果为空间辐射环境中宇航器件的质子单粒子效应研究提供理论支撑.     

燃烧系统的离散Boltzmann建模与模拟研究进展

燃烧系统的诸多模拟依托于流体建模, 离散Boltzmann方法(discrete Boltzmann method, DBM) 是近年来发展起来的一种新的流体介观建模方法. 本文简要评述DBM发展的两个方向——Navier-Stokes等偏微分方程的数值逼近解法和复杂系统的微介观动理学建模. 主要介绍在燃烧系统模拟方面DBM已有的工作、新近的思路、与传统流体建模的异同以及近期的研究成果. 本文重点传递的信息为: 作为复杂系统微介观动理学建模出现的DBM在模拟过程中同时给出“流动”及其相伴随的、关系最密切的那部分“热动”非平衡效应; 它为燃烧等复杂系统中各类非平衡行为的描述、非平衡信息的提取、非平衡程度的度量提供了一种简洁、有效的方法; 它所提供的热动非平衡测量量有两类: 一类是直接比较分布函数和平衡态分布函数的动理学矩关系得到的, 一类是来自于Chapman-Enskog多尺度分析给出的热传导和黏性项. 基于第二类DBM, 可以实现(燃烧等)一大类复杂流体系统的多尺度物理建模.     

Limit circle invariance for two differential systems on time scales

In this paper we consider two linear differential systems on a time scale. Both systems depend linearly on a complex spectral parameter λ. We prove that if all solutions of these two systems are square integrable with respect to a given weight matrix for one value λ₀, then this property is preserved for all complex values λ. This result extends and improves the corresponding continuous time statement, which was derived by Walker (1975) for two non‐hermitian linear Hamiltonian systems, to appropriate differential systems on arbitrary time scales. The result is new even in the purely discrete case, or in the scalar time scale case, as well as when both time scale systems coincide. The latter case also generalizes a limit circle invariance criterion for symplectic systems on time scales, which was recently derived by the authors.     

Improved synthesis of disaccharides with Escherichia coli β-galactosidase using bio-solvents derived from glycerol

A noticeably increase in activity, keeping total regioselectivity was found in the synthetic behaviour of Escherichia coli β-galactosidase in glycerol-based solvents using a 1:7 molar ratio of donor (pNP-β-Gal): acceptor (GlcNAc). Yields of up to 97% of β(1→6) with different solvents were found. These reactions take place without noticeable hydrolytic activity and with total regioselectivity, representing a considerable improvement over the use of aqueous buffer or conventional organic solvents. There is a clear dependence of the catalytic results on the solvent structure, which is analysed in terms of polarity and hydrophobicity.     

New approach in the synthesis of M6G

Morphine-6-glucuronide (M6G) is the primarily active metabolite of morphine, produced endogenously by the UGT enzyme, which displays analgesic activity. For this reason, M6G is a promising drug candidate for the treatment of severe pain. We described herein a new, efficient and scalable synthesis of M6G using dimorphinic derivatives. This preparation of M6G could be performed on multigram scale with good yield and high purity.     

Towards the reduction of matrix effects in inductively coupled plasma mass spectrometry without compromising detection limits: The use of argon-nitrogen mixed-gas plasma

The multivariate optimization of a mixed-gas plasma was conducted in an attempt to find conditions minimizing matrix effects without sacrificing the detection limits that are observed with an all argon plasma optimized for maximum sensitivity in inductively coupled plasma mass spectrometry. Compared to the latter, where 49.1 ± 7.1% (n = 17) analyte signal suppression resulted in the presence of 0.1 M Na, 3.8 ± 3.2% suppression (and 2.8 ± 2.1% enhancement in some cases) was observed in the optimized mixed-gas plasma with 0.13% v/v N₂ in the plasma gas and 0.11% in the central channel as a sheath gas around the nebulizer gas flow. Furthermore, improved detection limits were observed for Al, Co, Pd, and V with the optimized mixed-gas plasma compared to an argon plasma at maximum sensitivity. The robustness of this mixed-gas plasma was further demonstrated through the accurate determination of U and Mo in NASS-5 seawater certified reference material using a simple external calibration, without matrix-matching or internal standardization. Indeed, the result obtained for Mo (9.1 ± 1.9 μg/L) was within the 95% confidence interval of the certified value of 9.6 ± 1.0 μg/L, while that obtained for U (3.0 ± 0.2 μg/L) was close to the information value of 2.6 μg/L. Spatial profiling results suggest better energy transfer between the toroidal zone and the central channel in the mixed-gas plasma.     

Synthesis of new intramolecular charge transfer A-D-A tetrathiafulvalene-fused triads exhibiting large solvent sensitive emission behavior

We have synthesized three new acceptor-donor-acceptor (A-D-A) triads incorporating the donor tetrathiafulvalene (TTF) fused with acceptors quinoxaline and dipyrido[3,2-a:2′,3′-c]phenazine (dppz) systems. Solution emission spectral studies of all these compounds show large solvent sensitive behavior with huge Stokes shifts. The large solvent dependence of the emission indicates that the excited state is stabilized in more polar solvents due to the intramolecular charge transfer. We have also described electrochemical studies of one of the title compounds (compound 1b) exhibiting two oxidation responses at 1.02 and 1.31 V versus Ag/AgCl, that correspond to the oxidized species of TTF monocation and dication, respectively.     

Characterization of sugar juice heat exchanger tube deposit

Fouling of heat exchanger surfaces during sugar manufacture reduces productivity and increases energy demand. This study characterizes a deposit (including its internal structure) formed in a sugar factory's evaporator unit using a variety of X‐ray diffraction and scanning electron microscopy techniques (including X‐ray powder diffraction, X‐ray fluorescence, elemental mapping with energy dispersive spectroscopy and backscattered electron imaging). Calcium sulfate dihydrate, calcium oxalate mono‐ and dihydrate, hydroxyapatite, amorphous silica and organic matter are present in the deposit. The composition of the deposit (which contains three layers) varies along the height of the tube. There are noticeable differences in the composition and porosity among the layers in the deposit. A porous structure consisting of a mixture of amorphous silica, calcium oxalate dihydrate and organic matter is attached to the surface of the deposit in contact with sugar juice, while a denser morphology of amorphous silica and hydroxyapatite is attached to the tube wall. Elemental mapping identifies an association between Si, Al, Mg, Fe and O, suggesting the presence of a silicate compound as a minor component in the deposit. An attempt is made to rationalize the formation of the observed phases. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of two new asymmetrical branched amines and related Mn(II) and Ni(II) Schiff base complexes containing pyridine moieties: Crystal structures of Mn(II) and Ni(II) complexes and their antibacterial properties

Two new branched pentadentate amines (N₅), 3,7-bis(2-pyridylmethyl)-5,5-dimethyl-3,7-diazaheptane-1-amine (1) and 4,8-bis(2-pyridylmethyl)-6,6-dimethyl-4,8-diaza octane-1-amine (2) have been prepared. These have been used to synthesis two new Schiff base complexes containing a pyridine and 2-pyridylmethyl pendant arm, by template [1+1] condensation of pyridine-2-carbaldehyde with the amines in the presence of Mn(II) in methanol. Elemental and spectral results are used to characterize the complexes and their structures are confirmed by single crystal X-ray diffraction studies. The structure of MnL¹(ClO₄)₂ indicates that in the solid state the Mn(II) ion adopts a slightly distorted octahedral geometry. The crystal structure of [Ni(1)(MeCN)](ClO₄)₂ is also reported and exhibits a slightly distorted octahedral geometry. Also the synthesized complexes were screened for their antibacterial activity against Escherichia coli (Lio), Serratia marcescens (PTCC 1330), Staphylococcous aureus (ATCC 6633), and Proteus vulgaris (Lio) and results showed that the all complexes have antibacterial effects and [NiL¹](ClO₄)₂, [MnL²](ClO₄) and [MnL¹](ClO₄)₂ have more effective ones against E. coli.