二环己基-18冠-6加速锶离子在微米管支撑的水/1,2-二氯乙烷界面上的转移反应

采用玻璃微米管支撑的液/液界面通过循环伏安法(CV)研究了二环己基-18冠6(DCH18C6)加速Sr2+在水/1,2-二氯乙烷(W/DCE)界面上的转移反应,考察了DCH18C6加速Sr2+在W/DCE界面转移的影响因素,如DCH18C6和Sr2+浓度等,并求算其络合物的稳定常数。实验结果表明,Sr2+与DCH18C6发生的是一个1:1的扩散控制的界面络合转移过程,其络合常数β为5.31×1023。本研究可为理解溶剂萃取Sr2+行为提供基础理论数据。     

双通道微米管支撑的微-液/液界面上电荷转移反应的研究

将有机相和水相分别灌入双通道玻璃微米管θ管中的一个管中,利用θ管表面的亲水特征,在灌有有机相的微米管口附近形成微-液/液界面.利用循环伏安法研究了电荷在这种微-液/液界面上的转移反应,包括简单离子(四甲基铵离子TMA⁺)转移、加速离子转移(DB18C6加速K⁺离子)和电子转移(二茂铁/铁氰化钾+亚铁氰化钾体系)反应过程.结果表明,这种双通道微米管所得到的微-液/液界面具有不对称扩散场的特性.此装置是目前最简单的可用于研究液/液界面上的电荷转移反应的装置之一,即所谓的可进行"无溶液"液/液界面电化学及电分析化学研究的装置.     

普鲁士蓝膜电化学行为的EQCM研究

应用循环伏安法于铂电极上电化学沉积PB膜,并由电化学石英晶体微天平技术(EQCM)原位测量了PB膜电沉积过程的频率响应.研究表明,沉积液中添加邻菲咯啉对PB膜结构有影响.有邻菲咯啉参与沉积的PB Pt/QCM电极对H2O2的电催化还原性能优于不含邻菲咯啉沉积液制备的PB Pt/QCM电极.     

表面敏化TiO2基复合薄膜的能带结构与光致电荷转移的研究

采用离子束溅射方法制备出TiO₂/ITO, Zr^4＋掺杂的TiO₂(TiO₂-Zr)/ITO和ZrO₂/TiO₂/ITO复合薄膜. 利用表面敏化方法制备出(1,10-邻菲咯啉)₂(3,4,5-三氟苯基)咪唑并[5,6-f]邻菲咯啉钌混配配合物[Rup₂O](p＝1,10-邻菲咯啉, O＝(3,4,5-三氟苯基)咪唑并[5,6-f]邻菲咯啉)/TiO₂/ITO, Rup₂O/TiO₂-Zr/ITO和Rup₂O/ZrO₂/TiO₂/ITO表面敏化TiO₂基复合薄膜. 表面光电压谱(SPS)表明, 表面敏化TiO₂基复合薄膜在400～600和350 nm产生的SPS响应峰的峰高比与TiO₂基复合薄膜的结构密切相关. 利用电场诱导表面光电压谱(EFISPS)确定了复合薄膜的能带结构, 其结果分析表明, 400～600 nm的SPS响应峰主要源于Rup₂O分子的中心离子Ru 4d能级到配体邻菲咯啉p₁^*和配体咪唑并邻菲咯啉p₂^*跃迁|TiO₂禁带内Zr^4＋掺杂能级的存在减小了光生载流子的复合, 增加导带光生电子的数量|ZrO₂/TiO₂异质结构的存在有利于光生电子向ITO表面的转移, 从而导致400～600 nm和350 nm SPS响应峰的峰高比的增加, 意味着光致电荷转移效率的提高.     

应用扫描电化学显微镜研究极化液/液界面上的电子转移反应

将含有氧化还原电对的水溶液滴涂在铂盘电极表面, 然后将该电极插入到1,2-二氯乙烷溶液中, 形成稳定的油/水界面. 液滴中的K3Fe(CN)6和K4Fe(CN)6氧化还原电对既可以作为水相中的参比电对参与控制液/液界面上的电势差, 同时又可以作为水相的电子授受体参与界面上的电子转移反应. 结合扫描电化学显微镜电化学系统的特点, 利用其双恒电位仪分别控制界面电势差和现场扫描的优点, 通过扫描电化学显微镜的渐进曲线得到了不同界面电势差控制的电子转移反应速率常数. 实验结果表明, 应用此方法获得的液/液界面可以被外加电位极化, 在一定的电势差范围内, 反应速率常数与界面电势差的关系遵守Butler-Volmer公式.     

线性电流扫描过程中的液/液界面离子转移动力学

本文从理论上推导了在线性电流扫描过程中,离子在液/液界面转移的电位-电流方程。提出了利用线性电流扫描方法获取离子转移动力学参数的方法。并对液/液界面电化学中常用的基本电解质离子(TPAs~+)在水/硝基苯界面的转移进行了实际研究。     

钴(Ⅱ)-5-取代邻菲咯啉-α-氨基酸形成三元配合物的动力学研究

本文采用温度跃迁装置.即T-jump方法研究了钴(Ⅱ)-5-取代邻菲咯啉-α-氨基酸生成三元配合物的动力学性质.测定了该三元体系在25.0±0.1℃. 离子强度为0.1mol.dm^-^3(KNO~3)水溶液中的反应速率常数.结果表明反应速率常数与5- 取代邻菲咯啉的质子化常数之间存在着直线自由能关系. 讨论了具有不同取代基配体的电子效应对反应速率的影响.以及d-p反馈π键的强弱与该三元体系反应速控步骤速率常数之间的关系.     

新型混价铜配合物[CuⅠCuⅡ(Ophen)2Cl]·H2O(HOphen=2-羟基-1,10-邻菲咯啉)的水热合成和晶体结构

报道了一种新型混价铜配合物[CuⅠCuⅡ(Ophen)2Cl]·H2O(HOphen=2-羟基-1,10′-邻菲咯啉)的水热合成和晶体结构.该化合物属于三斜晶系,P1空间群,a=0.91667(18)nm,b=1.0546(2)nm,c=1.1705(2)nm,α=80.50(3)°,β=80.56(3)°,γ=66.87(3)°,V=1.0202(3)nm3,Z=2,Dc=1.872Mg/m3,R1=0.0508,(wR2)=0.1481.标题化合物由一种新型的双核铜配合物和一个结晶水组成.邻菲咯啉在水热反应中发生羟基化,形成新型的羟基化邻菲咯啉.两个这样的配合物通过Cu…Cu间的范德华力相互作用形成二聚体.二聚体之间通过Ophen基团的π-π堆积以及C—H…Cl弱相互作用构筑成三维超分子网络.水分子处于网络的孔穴中.该化合物为邻菲咯啉的羟基化提供又一个新的范例.     

阴离子交换膜修饰的水/1,2-二氯乙烷界面上SO42-离子的转移反应

将一种均相季铵型阴离子交换膜用于修饰水/1,2-二氯乙烷(W/DCE)界面,并利用循环伏安法、差分脉冲伏安法和计时电量法考察了该界面上强亲水性阴离子SO₄^2-的转移反应过程.研究结果表明,该阴离子交换膜所修饰的W/DCE界面比修饰前具有更宽的电化学窗口,而且在界面上可获得完整的SO₄^2-转移的循环伏安曲线和差分脉冲伏安曲线.其中,循环伏安曲线的峰电流与扫速平方根呈线性关系,SO₄^2-在膜内水相中的扩散系数为7.6×10^-8 cm²/s;差分脉冲伏安曲线的峰电流与SO₄^2-的浓度在5~25 mmol/L范围内呈线性关系.另外,利用计时电量法测得SO₄^2-在该界面上转移反应的标准速率常数为1.49×10^-3 cm/s.     

氨基酸在亚微米级液/液界面上的转移反应

应用循环伏安法和微、纳米管系统地研究了二苯并18冠6(DB18C6)加速20种氨基酸在水/1, 2-二氯乙烷(W/DCE)界面上的转移反应. 实验结果表明电位窗内只有10种氨基酸, 即苯丙氨酸(Phe)、亮氨酸(Leu)、异亮氨酸(Ile)、缬氨酸(Val)、色氨酸(Trp)、甲硫氨酸(Met)、丙氨酸(Ala)、甘氨酸(Gly)、半胱氨酸(Cys)和谷氨酰胺(Gln), 其质子化后的一价阳离子能给出很好的加速离子转移伏安图, 并且转移反应机理符合界面配合/界面离解反应. 由稳态伏安图可求出DB18C6与不同氨基酸在1,2-二氯乙烷中的配合常数和界面配合反应的动力学常数. 实验结果表明, 与碱金属离子和DB18C6配合相比, 这10种氨基酸与DB18C6的配合选择性较低, 主要原因是由于氨基酸支链所引起的位阻效应以及本体有机溶剂的亲脂化稳定效应的协同作用. 除了甘氨酸和甲硫氨酸以外, 不同氨基酸与DB18C6配合反应的配合常数以及反应速率常数与其亲脂性量度(π)有良好的对应关系, 这表明质子化的氨基酸与DB18C6的异相配合反应不仅决定于离子与冠醚环的键合强度, 而且与氨基酸在转移过程中的吉布斯转移能有关, 而吉布斯转移能又与氨基酸自身的结构密切相关. 这一研究将对人们理解在生命体中氨基酸在载体蛋白的推动作用下越过生物膜的主动运送过程有较重要意义.     

端烯基液晶冠醚推动钠离子在微液/液界面的转移

用循环伏安法研究新型载体端烯基液晶冠醚推动钠离子的转移,结果表明,钠离子的转移由扩散控制.探讨了影响钠离子转移的因素,如端烯基液晶冠醚和钠离子的浓度等.求算出端烯基液晶冠醚在1,2-二氯乙烷中的扩散系数为(2.61±0.12)×10^-6cm²/s,端烯基液晶冠醚和钠离子在1,2-二氯乙烷中所形成的配合物稳定常数lgβ_o=5.7.     

Amperometric proton selective sensors utilizing ion transfer reactions across a microhole liquid/gel interface

A new cost-effective amperometric proton selective sensor utilizing a single microhole interface between two immiscible electrolyte solutions (ITIES) is developed. The sensing methodology is based on measuring currents associated with proton transfer across the interface assisted by a proton selective ionophore. The ellipse shaped micro-interface was first fabricated by simple mechanical punching with a sharp needle on a thin PVC film (12 μm thick) commercially available as a food wrapping material. The microhole was then filled up with a gellified polyvinylchloride (PVC)-2-nitrophenyloctylether (NPOE) to create a single microhole liquid/liquid interface. Direct ion transfer reactions across the polarized interface serving as ion sensing platforms were studied using cyclic voltammetry. In order to enhance the selectivity of proton sensing, a proton selective ionophore, octadecyl isonicotinate (ETH1778), was incorporated into the organic gel layer and their electrochemical sensing characteristics were investigated using cyclic voltammetry and differential pulse stripping voltammetry. As an example, we employed the proton selective sensor for the determination of glucose concentrations. The detection scheme involves two steps: (i) protons are first generated by the oxidation of glucose with glucose oxidase in the aqueous phase; and (ii) the current associated with the proton transfer across the interface is then measured for correlating the concentration of glucose.     

Distribution mechanism of protonated l,10-phenanthroline between unbuffered aqueous and 1,2-dichloroethane phases

The faradaic ion transfer of protonated l.iO-phenanthroline [H(Phen)+] across the interface between unbuffered aqueous and 1,2-dichloroethane (DCE) solutions was investigated by means of current scan polarography at ascending aqueous electrolyte electrode, as well as chronopotentiometry. It follows from the splitting of the waves observed at the pH of aqueous phase (sodium sulfate solution) between 2.5–3.8 that neutral reagent (Phen) distributes into the aqueous phase, where it is protonated. The positive wave is associated with the mass transfer controlled by the H+influx, whereas the negative one is by the Phen influx. The reverse chronopotentiometry indicated that all the protonated transfer processes were reversible. A good agreement between experimental results and theoretical treatment was achieved. The aqueous acid dissociation constant of protonated Phen, K₂ can be evaluated from the dependence of the wave heights on the pH in the base of the equilibrium.     

Drop impact characteristics and structure effects of hydrophobic surfaces with micro- and/or nanoscaled structures

We report the drop impact characteristics on four hydrophobic surfaces with different well-scale structures (smooth, nano, micro, and hierarchical micro/nano) and the effects of those structures on the behavior of water drops during impact. The specimens were fabricated using silicon wet etching, black silicon formation, or the combination of these methods. On the surfaces, the microstructures form obstacles to drop spreading and retracting, the nanostructures give extreme water-repellency, and the hierarchical micro/nanostructures facilitate drop fragmentation. The maximum spreading factor (D*(max)) differed among the structures. On the basis of published models of D*(max), we interpret the results of our experiment and suggest reasonable explanations for these differences. Especially, the micro/nanostructures caused instability of the interface between liquid and air at Weber number We > ~80 and impacting drops fragmented at We > ~150.     

Fluorescence microscopy observation of self-organized microstructure formed by a rare earth compound

The morphologies of monolayers containing Eu(TTA)3Phen (TTA=thenoyltrifluoroace-tone, Phen = 1, 10-phenanthroline) were studied at the air/liquid interface on different subphases by fluorescence microscopy (FM). The composite subphase was the basic premise for the stable existence of the rare earth compound at air/liquid interface. The process that rare earth compound phase changes from liquid expanded state to liquid condensed state corresponded to a plateau in the π-A isotherm. In the pure Eu(TTA)3Phen monolayer, rod domains of Eu(TTA)3Phen formed and packed with no order. In the mixed monolayers with stearic acid (SA), phase transition of SA occurred first and formed domains with an electric gradient field, which induced the rare earth compound to form luminescent ring domains. Influence of intermolecular interaction on the self-organized microstructure was revealed.     

稀土—β—二酮配合物LB膜和三线态能量转移研究

在胶束体系中，Eu3+的发光强度可通过加入La3+－TTA－Phen（TTA：噻吩甲酰三氟丙酮；Phen：邻菲咯琳）而大大增强，这种发光增强作用被认为是由配体TTA经过三线态向EU3+的共振能级转移能量所致[1]．本文利用LB技术将这种Eu3+增强的发光转移到有序排列的LB膜中，研究了La（TTA）3Phen对Eu3+的发光增强作用，并用LB方法探讨了这种分子间的能量转移过程，发现这种能量转移距离小于3um，属经由三线态的短程交换能量转移过程．同时，用荧光光谱和低角X衍射对这种混合稀土配合物LB膜进行了表征．1实验部分配合物La（TTA）3Phen和Eu…     

Platinum Nanoparticle Impacts at a Liquid|Liquid Interface

Single nanoparticle (NP) electrochemistry detection at a micro liquid|liquid interface (LLI) is exploited using the catalyzed oxygen reduction reaction (ORR). In this way, current spikes reminiscent of nanoimpacts were recorded, which corresponded to electrocatalytic enhancement of the ORR by Pt NPs. The nature of the LLI allows exploration of new phenomena in single NP electrochemistry. The recorded impacts result from a bipolar reaction occurring at the Pt NP straddling the LLI. O₂ reduction takes place in the aqueous phase, while ferrocene hydride (Fc‐H⁺; a complex generated upon facilitated interfacial proton transfer by Fc) is oxidized in the organic phase. Ultimately, the role of reactant partitioning, NP bouncing, or the ability of NPs to induce Marangoni effects, is demonstrated.     

酸法制备杨木微/纳纤丝及其表征

近二十多年来,如何从天然纤维素中分离微/纳纤丝和用其来增强高分子聚合物受到许多学者的关注。本研究以杨木纤维素为原料,采用硫酸和盐酸的混合液水解、恒温水浴振荡处理制备杨木微/纳纤丝。利用扫描电子显微和X射线衍射仪对制备的杨木微/纳纤丝进行分析表征,结果表明当酸处理条件为杨木纤维3g、浓H2SO4体积分数为15%、浓HCl体积分数为5%、恒温水浴60℃、振荡8h,可得到杨木微/纳纤丝,杨木微/纳纤丝宽度分布在200nm到1μm之间,长宽比约60~120,相度结晶度为77.59%。     

LB膜中稀土配合物分子间能量转移研究

有关LB膜中的Forst。r型共振能量转移已有不少报导，这种能量转移一般可发生在给体（D）和受体（川两者相距50－100A以上．所以，可以用F0rS比r公式对临界转移距离进行计算h－’1．而对LB膜中涉及三线态的分子间能量转移报导则不多见，此类能量转移是发生在6－15A之间．Yalnamo     

Thermal and optical properties of ZTS single crystals in the presence of 1,10-phenanthroline (Phen)

The influence of heteroaromatic N-base (1,10-phenanthroline) (Phen), a new additive as complexing agent on tris(thiourea)zinc(II)sulphate (ZTS) crystals from aqueous solutions at 30 °C is investigated. Crystals were grown using low concentration of the dopant (0.005 M L^?1) in the aqueous growth medium and the growth promoting effect (GPE) is much greater because of an increase in the metastable zone width. High dopant concentration decreases GPE. The crystalline perfection of the grown crystals is quite good both in doped and undoped crystals as evaluated by high-resolution X-ray diffractometry (HRXRD). The diffraction curve of a typical Phen doped as-grown ZTS crystal was observed to contain a single peak indicating that the crystal does not contain any epitaxial layer on the surface or internal structural grain boundaries. Not much variation is observed in FT-IR and XRD of pure and doped ZTS. Phen depresses the NLO efficiency of ZTS. It could be ascribed due to the disturbance of charge transfer in the presence of the dopant. The grown crystals were also characterized by UV–Vis, SEM and TG–DTA techniques.