对苯二甲酸、2-(3-吡啶基)苯并咪唑配位聚合物的合成、晶体结构和发光

在水热条件下,对苯二甲酸(H2Bdc)和2-(3-吡啶基)苯并咪唑(3-PyHBIm)与Cd(NO3)2、Zn(NO3)2反应,得到配合物{[Cd(3-PyHBIm)(Bdc)(H2O)2](H2Bdc)1/2}n (1)、[Zn(3-PyHBIm)2(Bdc)(H2O)2]n (2)。单晶X-射线衍射结构分析表明,两个化合物均呈一维聚合结构,3-PyHBIm配体采用吡啶氮原子单齿配位。在配合物1中,对苯二甲酸根作为四齿配体,桥联Cd(II)离子,形成一维锯齿链状配位聚合物,两个水分子呈顺式配位。该化合物含有对苯二甲酸客体分子,通过强的氢键,构成三维超分子框架。在配合物2中,对苯二甲酸根作为双齿配体,结合Zn(II)离子,形成直线链状配位聚合物,两个水分子呈反式配位。两个配位聚合物都对热稳定,在固体状态下,呈蓝色发光。     

2-甲基-2-丁醇的低温热容和热力学性质

本文用精密自动绝热量热仪测定了2-甲基-2-丁醇在80～305 K温区的热容,从热容曲线(Cp-T) 发现三个固－固相变和一个固－液相变, 其相变温度分别为T = 146.355, 149.929, 214.395, 262.706 K。从实验热容数据用最小二乘法得到以下四个温区的热容拟合方程。在80～140K温区, Cp,m = 39.208 + 8.0724X - 1.9583X2 + 10.06X3 + 1.799X4 - 7.2778X5 + 1.4919X6, 折合温度X = (T –110) / 30; 在 155 ～ 210 K温区, Cp,m = 70.701 + 10.631X + 12.767X2 + 0.3583X3 - 22.272X4 - 0.417X5 + 12.055X6, X = (T –182.5) /27.5; 在220 ～ 250 K温区, Cp,m = 99.176 + 7.7199X - 26.138X2 + 28.949X3 + 0.7599X4 - 25.823X5 + 21.131X6, X = (T – 235)/15; 在 270～305 K温区, Cp,m =121.73 + 16.53 X- 1.0732X2 - 34.937X3 - 19.865X4 + 24.324X5 + 18.544X6, X = (T –287.5)/17.5。从实验热容计算出相变焓分别为0.9392, 1.541, 0.6646, 2.239 kJ×mol-1; 相变熵分别为6.417, 10.28, 3.100, 8.527 J×K-1×mol-1。根据热力学函数关系式计算出80～305 K温区每隔5 K的热力学函数值 [HT –H298.15]和 [ST –S298.15]。     

A pure blue light emitting binaphthyl derivative：Synthesis and properties

A binaphthyl derivative with pyrene on 3 and 3＇ positions was synthesized and characterized via Suzuki coupling reaction. Emission maximum in solution was located at 390 nm with a quantum efficiency of 68% by taking 9,10-diphenyl anthracene as reference,while it is shifted to 450 nm with FWHM of 104 nm resulting from aggregation state in solid film.Glass transition temperature（Tg）and decomposition temperature were measured to be 184 and 447℃,respectively,by DSC and TGA.Unlike its photoluminescence spectrum,electroluminescent spectrum peaked at about 460 nm and shows a FWHM of 69 nm corresponding to a pure blue emission.The turn-on voltage,luminance and efficiency maximum were 5 V,2953 cd/m^2 and 1.37cd/A with CIE color coordinate of（0.16,0.15）,in the device structure of ITO/NPB（40nm）/PY-BN-PY（15nm）/BPhen（40nm）/Mg：Ag.     

纤维素超临界水预处理与水解研究

利用超临界水解工艺进行生物质废弃物(秸秆)能源转化, 使其主要成分纤维素在超临界水中快速水解为低聚糖, 为其进一步葡萄糖转化和乙醇发酵解决技术瓶颈. 其中纤维素在超临界水中的溶解是预处理与水解过程的限速步骤. 研究表明, 反应温度达到380 ℃及以上时, 纤维素可迅速溶解并进行水解, 液化比例可达100%; 在374～386 ℃范围内反应温度对纤维素的转化率有明显作用, 低聚糖和六碳糖的总产率在临界点附近出现最大值. 超临界条件下, 低聚糖和六碳糖转化率在较短反应时间内出现峰值, 而后随反应时间的延长快速下降, 固液比对于纤维素的低聚糖和六碳糖转化也有显著影响. 最优水解条件研究显示, 在380 ℃, 40 mg纤维素/2.5 mL水条件下反应16 s可获得最大的低聚糖产率, 为29.3%, 在380 ℃, 80 mg纤维素/2.5 mL水条件下反应18 s可获得最大的六碳糖产率, 为39.2%.     

溴化乙锭对B-DNA碱基对特异性识别的分子模拟研究

溴化乙锭是一种常用的DNA荧光探针, 其作用机制是通过插入作用与DNA分子形成稳定的复合物. 分子模拟显示, 溴化乙锭插入碱基对过程中有大小沟选择性, 对结合能的统计分析发现, 溴化乙锭分子更倾向从小沟方向插入到DNA分子中. 由溴化乙锭从小沟方向插入不同碱基对的结合能考察发现, 溴化乙锭对DNA碱基对有特异性识别, 并且与CA碱基对结合能最强. 对溴化乙锭插入DNA分子的驱动力和序列特异性识别的作用力分析, 揭示溴化乙锭插入DNA分子的驱动力和碱基对的特异性识别均以静电作用为主.     

两亲性D-π-A型有机染料在染料敏化太阳能电池中的应用

设计合成了6个带有烷基链的D-π-A型有机光敏染料应用于染料敏化太阳能电池. 发现长链烷基有利于电池开路光电压的提高. 利用脂肪酸共敏化可进一步提高染料分子的敏化效果, 且提高的程度与脂肪酸的链长有重要关系.     

配合物[Ni(IDB)2]2•(SO4)2•3CH3CH2OH•CH3OH•5H2O的合成、 晶体结构及其荧光光谱的研究

标题配合物是由三齿配体N,N-二(2-苯并咪唑甲基)亚胺(IDB)与NiSO4•6H2O在甲醇-乙醇溶液中反应得到的紫色晶体. X射线衍射测定了其单晶结构. 结构分析表明, 镍(II)分别与两个IDB配体中的苯并咪唑的四个氮和胺基的两个氮配位形成畸变的八面体构型. 研究了纳米金和小牛胸腺DNA对配合物荧光的影响, 探讨了配合物的荧光猝灭与恢复的可能机理.     

Kinetics and mechanism of the reactions of CH3CO and CH3C(O)CH2 radicals with O2. Low-pressure discharge flow experiments and quantum chemical computations

The reactions CH(3)CO + O(2)--> products (1), CH(3)CO + O(2)--> OH +other products (1b) and CH(3)C(O)CH(2) + O(2)--> products (2) have been studied in isothermal discharge flow reactors with laser induced fluorescence monitoring of OH and CH(3)C(O)CH(2) radicals. The experiments have been performed at overall pressures between 1.33 and 10.91 mbar of helium and 298 +/- 1 K reaction temperature. OH formation has been found to be the dominant reaction channel for CH(3)CO + O(2): the branching ratio, Gamma(1b) = k(1b)/k(1), is close to unity at around 1 mbar, but decreases rapidly with increasing pressure. The rate constant of the overall reaction, k(2), has been found to be pressure dependent: the fall-off behaviour has been analysed in comparison with reported data. Electronic structure calculations have confirmed that at room temperature the reaction of CH(3)C(O)CH(2) with O(2) is essentially a recombination-type process. At high temperatures, the further reactions of the acetonyl-peroxyl adduct may yield OH radicals, but the most probable channel seems to be the O(2)-catalysed keto-enol transformation of acetonyl. Implications of the results for atmospheric modelling studies have been discussed.     

Crystal Structure of the 1:2 Stoichiometric Nd: [α-SiW_(11)O_(39)]~(8-): K_5Na_5H_3[Nd(α-SiW_(11)O_(39))_2]·6H_2O

Single-crystal X-ray structural analysis of K5Na5H3[Nd(α-SiW11O39)2]·6H2O (triclinic, space group P1, a = 13.7738(10), b = 19.722(2), c = 20.6647(15) , α = 111.0090(10), β = 105.1740(10), γ = 98.6870(10)o, Z = 2, V = 4867.2(8), Mr = 5914.40, Dc = 4.026, μ = 26.754 mm-1, F(000) = 5076, R = 0.0750 and wR = 0.2077) reveals that two [α-SiW11O39]8- moieties are connected through one Nd atom which is in a square antiprismatic coordination environment by eight oxygen atoms from two [α-SiW11O391]8- moieties. The Nd(Ⅲ ) ion is substituted for a [WO]4+ unit in the "cap" region of the tungsten-oxygen framework of the parent Keggin ion. Disordered Na+ cations and water molecules reside outside these channels, leaving empty pores with an intersecting slot (13 × 10 ).     

Analysis of tensides in complex samples with comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry

Multidimensional gas-chromatographical analysis of various tensides of natural or synthetic origin in cosmetic products is demonstrated. Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry allows the qualitative and quantitative determination of alkyl polyglucosides (AG), fatty alcohol ethoxylates (FAEO), fatty alcohol sulfates (FAS), fatty alcohol ether sulfates (FAES) and cocamidopropyl betaines (CAPB) in shower gel and cleaning agents. The samples were aliquoted in two parts. The first part was silylated, diluted and analysed; then, in order to detect anionic tensides (FAES, FAS) too, the second aliquot was hydrolysed before being silylated for analysis. Because of their amphoteric character, the betaines can only be analysed by gas chromatography after thermal decomposition in the injector, which leads to the corresponding amidoamines among other products.