DODMAC／正丁醇／水体系溶致液晶的^2H—NMR和DSC研究

在５０℃下，测定双十八烷基二甲基氯化铵（ＤＯＤＭＡＣ）／醇（正丙醇，正丁醇，正戊醇）／水体系的相平衡，确定了液晶区域的边界范围。在ＤＯＤＭＡＣ／正丁醇／水相图液晶区中，选取一系列样品点，用＾２Ｈ－ＮＭＲ和差示扫描量热法（ＤＳＣ），并与液晶纹理相互对照，研究了该体系结构的变化。结果表明：直链醇碳链长度增加，液晶相区域面积增加，恒定温度下，随含水量增加，体系从单一各向同性的Ｗ／Ｏ型微乳液→层状，六角状     

Study of Preferential Solvation in Binary Mixtures by Means of Frequency-Domain Fluorescence Spectroscopy

The preferential solvation of 8-N,N-(dimethylamino)-11H-indeno[2,1-a]pyrene, Py(S)DMA, in its transient charge transfer (CT) state in binary solvents such as toluene/DMSO liquid mixtures was studied by means of frequency-domain fluorometry. The data obtained were considered within the following kinetic scheme: the preferential solvation was described by the system of consecutive reversible reactions of which each step is associated with the absorption of one DMSO molecule in the first solvation shell of the fluoresent Py(S)DMA dipolar CT molecule. The rate constants of the first two reversible elementary processes (i.e., the decay of solvation complexes of Py(S)DMA with one and two polar molecules, k _–1 = 1.1 10⁹ s^–1 and k _–2 = 1.4 10⁹ s^–1) were determined.     

Spectral Investigations of Solvatochromism and Preferential Solvation on 1,4-Dihydroxy-2,3-Dimethyl-9,10-Anthraquinone

Solvatochromic and preferential solvation of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone (DHDMAQ) have been investigated using optical absorption and fluorescence emission techniques. Optical absorption spectra of DHDMAQ in different solvents show the intra molecular charge transfer band in the region 400–550nm. The observed blue shift with solvent polarity indicates the delocalisation of the excited state, owing to reduction in quasiaromaticity of the chelate rings formed by intra molecular hydrogen bonds, due to electrostatic or hydrogen bonding interaction. This is also confirmed by the observed low oscillator strength and the transition dipole moment. The observed quantum yield of DHDMAQ in different solvents is due to the inter molecular hydrogen bond in the excited state in addition to the intra molecular hydrogen bond. It also reveals from the low oscillator strength, which indicates that the radiative decay is low. Excited state dipole moment of DHDMAQ is calculated by solvatochromic data and it shows a lower value than ground state dipole moment. The preferential solvation parameter shows that in dimethyl formamide (DMF) + ethanol mixture, the DHDMAQ is preferentially solvated by ethanol in DMF rich region and by DMF in ethanol rich region. In the case of DMF + dichloromethane mixture DHDMAQ is preferentially solvated by DMF.     

Preferential Solvation of 1,4-Dimethoxy-2,3-Dimethyl-9,10-Anthraquinone-A Spectrophotometric and Fluorometric Study

Electronic absorption and fluorescence emission spectra of DMDMAQ (1,4-dimethoxy-2,3-dimethyl-9,10-anthraquinone) have been studied as a function of solvent composition in some binary mixtures and in different neat solvents. The binary mixtures consist CCl₄ (Carbon tetrachloride)-DMSO (Dimethylsulfoxide), EtOH (Ethanol)-DMSO, and CCl₄-EtOH combination of single solvents. The wavelength maxima of the absorption band for DMDMAQ are quite solvent sensitive in aprotic solvents. But, in protic solvent, there is no marked shift in absorption and emission maximum which shows the absence of specific interaction. Excited state shows increasing shift with increasing solvent polarity compared to ground state. The ratio of dipole moment in the excited state to that in the ground state was calculated. Different criteria were considered to analyse preferential solvation characteristics in different binary mixtures, viz., local mole fraction (), solvation index (δ_S2) and exchange constant (K₁₂).     

Solvatochromism,Preferential Solvation of 2,3-Bis(Chloromethyl)-1,4-Anthraquinone in Binary Mixtures and the Molecular Recognition Towards <Emphasis Type="Italic">p</Emphasis>-Tert-Butyl-Calix[4]arene

Optical absorption and fluorescence emission spectra of 2,3-bis(chloromethyl)-1,4-anthraquinone (DCMAQ) in single solvents namely, carbon tetrachloride, acetonitrile, chloroform, propan-2-ol and its binary mixtures [carbon tetrachloride/chloroform, chloroform/acetonitrile, chloroform/propan-2-ol] have been investigated. The preferential solvation of DCMAQ in above mixtures has been studied by monitoring the absorption and fluorescence spectra of DCMAQ. The spectral features indicate that DCMAQ is preferentially solvated by CHCl₃ in the above mixtures. This can be elucidated from the local mole fraction, non-linearity in transition energy plot, preferential solvation index (δ _s2) and (f ₂/f ₁) values. Molecular recognition properties of p-tert-butylcalix[4]arene (tBC) to DCMAQ via hydrogen bonding and π–π interaction were sensed successfully on the basis of absorption and fluorescence emission spectroscopies, by which the stoichiometry ratio and the binding constant of the tBC–DCMAQ complex were determined.     

离子液体存在下银的电沉积及其表面增强拉曼散射活性研究

离子液体作为一种绿色介质,在电化学领域的应用研究正在兴起,并已引起了研究者的浓厚兴趣。运用循环伏安法研究了离子液体(1-丁基-3-甲基咪唑硝酸盐,[bmim]NO₃)添加剂存在时,AgNO₃溶液中的Ag在玻碳电极上的电化学沉积行为。研究表明,离子液体的加入对Ag的沉积具有阻化作用。采用扫描电镜(SEM)对沉积层的表面形貌进行表征,结果显示离子液体的存在可使沉积层更加致密,Ag颗粒的尺寸减小。以甲基橙为探针分子,研究了在加入及不加[bmim]NO₃添加剂的AgNO₃溶液中电沉积所得银颗粒膜的表面增强拉曼散射(SERS)效应,增强因子分别为1.7×105和1.1×105,表明在离子液体存在下制得的Ag颗粒膜具有相对较好的SERS活性。     

水分胁迫对小麦光谱红边参数和产量变化的影响

在不同的水分胁迫梯度下,利用实验区小麦不同生长期光谱反射率观测数据,研究水分胁迫对小麦光谱反射率、红边参数及小麦产量的影响。首先分析水分胁迫对小麦光谱反射率的影响,然后利用小麦光谱反射率的一阶微分得到小麦光谱反射率的红边位置和红边幅度参数,分析了水分胁迫对小麦光谱红边参数的影响,最后利用水分胁迫下的红边幅度和小麦产量的关系,阐述了小麦水分胁迫下的光谱反射率特征与小麦产量的关系。研究结果表明,水分胁迫下小麦的红边位置在生长期前期出现红边位置红移现象,生长期后期出现红边位置蓝移现象。水分胁迫下的小麦的红边幅度在不同的生长期表现出不同的变化特征：生长期初期随着水分胁迫的增加而红边幅度增大,生长期后期随着水分胁迫的增加而红边幅度减小。小麦的红边幅度在拔节生长期前与小麦产量呈负相关而拔节生长期之后呈正相关,且不同生长期小麦的红边幅度与小麦的产量的相关系数不同。     

Solvatochromic dipolarity micro‐sensor behaviour in binary solvent systems of the (water + ionic liquid) type: application of preferential solvation model and linear solvation energy relationships

The type of specific intermolecular and interionic interactions that are established when an ionic liquid is dissolved in water was here analysed. The study of the solvatochromic response of dipolarity micro‐sensors based on Reichardt E_T(30) and Kamlet–Abboud–Taft solvent scales and the application of the solvent exchange model confirmed the formation of different intersolvent complexes in binary mixtures of (water + [C₄mim] [BF₄]/[Br]) type. These complexes provide H‐bond or electron pairs to the polar network, respectively. Moreover, for 4‐methoxybenzenesulfonyl chloride hydrolysis reaction in the (water + [C₄mim] [BF₄]) system, a higher inhibition (13 times) on the k_obs values was observed. Multiple linear regression analysis that allows confirming the solvent effect upon the reactive system is due to the hydrogen‐bond donor properties of intersolvent complex formed. Then, the correlation between two different solvent‐dependent processes proved to be successful. Copyright © 2014 John Wiley & Sons, Ltd.     

工矿业城市区域水质参数高光谱定量反演

工矿业城市区域易受工业活动、矿产开采影响,使其水环境遭受不同程度的破坏,以至于水体污染问题突出。当前常规水质监测主要采用“以点代面”的工作方式进行野外采样及其室内化验分析,然而环境复杂多变,空间差异大,导致调查点代表性受限,整体精度不高,效率低下,更难以实现区域性动态监测。以因矿兴市的矿业重镇湖北黄石大冶市为研究区,同步开展无人机高光谱航飞、地面光谱测量和水体样品采集测试,分别获得具有49个波段的高光谱影像数据和光谱分辨率为1 nm的水体光谱曲线,其中影像数据波谱范围为505~890 nm,光谱分辨率为7.78 nm,空间分辨率为30 cm。对获取的高光谱影像和光谱数据剔除异常值、光谱定标、辐射校正等预处理后,对比分析研究区内水体的不同光谱吸收、反射及光谱曲线形态特征信息,从而提取出高光谱影像和测量光谱的反射光谱曲线形态特征、去包络线后光谱曲线形态特征、三阶求导后光谱曲线形态特征和光谱四值编码共四大类25个光谱特征。采用皮尔森相关系数分析样品水质参数与光谱特征之间的相关性,以此筛选出存在显著相关的水质参数与光谱特征。在此基础上,采用逐步回归分析方法筛选出最大反射率及其波长位置、对称度、光谱编码Ⅲ、三阶导最大及最小值等光谱特征作为模型变量,构建出水质参数的多元线性反演模型,并对模型进行F检验和t检验。将检验后的反演模型推广运用于研究区内高光谱影像,获得尾矿库、河流、湖泊等典型区域的水质参数反演结果,从而实现“由点到面”水质参数信息的快速获取。结果显示水质参数pH、硬度（Ca2++Mg2+）、钾与氯离子比值（K+/Cl-）、镁与碱度比值[Mg2+/(HCO3-+CO2-₃)]的反演精度较高,其pH的判定系数R2最小为0.669,镁与碱度比值的判定系数R2最大为0.895,相对均方根误差均小于28%;而总溶解固体（TDS）反演精度较低,其判定系数R2仅为0.463,相对均方根误差达36.762%。提出了一种基于光谱曲线形态特征的高光谱遥感水质参数定量反演模型方法,实现了pH值、硬度、镁离子与碱度之比等水质参数的高光谱定量反演,为区域水环境动态监测提供了新方法。     

丙三醇浓溶液玻璃化转变与结构松弛参数DSC分析

利用差示扫描量热仪研究了5种高浓度丙三醇水溶液(60%、70%、80%、90%、100%)的玻璃化转变行为,以考察水分含量和升降温速率对其玻璃化转变行为和结构松弛参数的影响.采用4种线性升降温速率(10、15、20、25K/min)获得玻璃化转变的相关参数.利用GordonTaylor方程对玻璃化转变温度的分析结果表明,水对丙三醇增塑常数的计算结果与升降温速率和玻璃化转变温度的读取方法有很大关系.玻璃化转变过程的比热容变化不仅随水分含量的增加而增加,而且与升降温速率也有一定的依赖关系.结构松弛活化能的计算结果表明,随体系水分含量的增加,体系的结构松弛活化能和动力学脆度都逐渐降低.随水分含量的变化,热力学脆度和动力学脆度表现出相反的变化趋势.     

氯铝酸离子液体的酸性及其催化烷基化反应研究

分别采用吡啶探针和乙腈探针红外光谱法研究了氯铝酸离子液体的酸性,结合固体酸表征方法,研究了离子液体的酸性对吡啶探针各振动模式的影响。发现当氯铝酸离子液体AlCl₃的摩尔分数x为0.4～0.5时,离子液体显弱Lewis酸性,强碱性吡啶探针分子能很好地表征离子液体的酸性,而弱碱性乙腈探针分子只适用于表征酸性较强的离子液体。考察了氯铝酸离子液体酸强度对苯与长链烯烃烷基化反应的影响,结果发现,AlCl₃的摩尔分数x≤ 0.5时,离子液体没有催化活性;x>0.55时,随着离子液体酸性的增强,烯烃转化率升高,但2位烷基苯选择性下降。结合离子液体的酸强度对烷基化反应机理进行初步分析认为具有催化活性的物质是强Lewis酸Al₂Cl-₇。