非标记液晶型免疫传感器检测赭曲霉素A

研制了一种基于液晶取向改变的非标记液晶型免疫传感器,并用于检测赭曲霉素A(0TA).采用戊二醛交联法将OTA同定在由自组装膜修饰的玻璃肇底表面.自组装膜能诱导液晶分子垂直排列,而连接OTA抗体后则扰乱了液晶分子取向的有序排列,导致液晶分子在化学敏感膜表面的取向发生变化,使光学信号的亮度及色彩发生变化,以此实现对OTA的...     

液晶型化学传感器检测甲基膦酸二甲酯的研究

液晶型化学传感器是利用传感器检测目标化合物前后,液晶分子在敏感膜表面的取向发生变化,改变液晶折射光线的能力,导致传感器的颜色和光亮度发生变化,实现对生物分子、有害化学物质的检测。本实验报道了一种以μm级沟槽状金膜为基底的液晶型化学传感器,通过在具有μm级沟槽(一个沟槽周期5μm)的玻璃基底上进行平面镀金,制备了具有相同沟槽周期的金膜,并在金膜上制备Cu2 修饰的巯基十一酸自组装敏感膜。通过检测甲基膦酸二甲酯时液晶织构的变化,阐明了液晶型化学传感器的作用机理,并证实微米级沟槽状金膜为基底制作的液晶型化学传感器可以用于检测目标化合物。传感器对甲基膦酸二甲酯检测的线性范围0.03~1.00g/m3;线性方程Y=0.14X 0.0035,相关系数r=0.9957。     

液晶型非标记免疫传感器检测天蚕素B

制备了一种基于液晶取向变化的非标记液晶型免疫传感器,用于检测天蚕素B。首先采用硅烷化试剂自组装膜法构建基底敏感膜诱导液晶分子呈均一垂直排列,再通过戊二醛交联法将天蚕素B固定到基底表面,当天蚕素B抗体与天蚕素B特异性结合后扰乱了液晶分子的取向,使液晶膜的颜色和亮度发生变化,以此实现对天蚕素B的检测,检测限可达0.1 ng/m L。本方法具有灵敏度高、特异性好、非标记和操作简单等优点。     

DNA在氨基功能化偶氮苯自组装膜表面的固定

采用简单快速的方法制备出将DNA固定在其表面的单分子层敏感膜.首先采用表面自组装技术将硅氧烷基偶氮苯衍生物H2NAzoCONHC3Si(OCH3)3(APDA-N-TMSPBA)组装在硅表面,在详细考察单分子层薄膜的化学结构、表面浸润性和分子表面形貌之后,又通过紫外吸收光谱(UV)在位考察了硅氧烷基偶氮苯衍生物的光学异构特性.在DNA在自组装薄膜固定后,X光电子能谱仪(XPS)结果显示出现了明显的磷元素信号,表明DNA分子可以成功固定在自组装膜表面.     

含氟光敏单体的液晶光控取向研究

制备了系列含氟光敏单体材料, 六氟双酚A双肉桂酸酯(6F-BADE)与含二氟亚甲基结构的肉桂酸酯(FDE-n, n=2, 3, 4). 材料在线性偏振紫外光辐照下均可发生定向光交联反应, 通过红外光谱和凝胶渗透色谱跟踪检测, 表明光交联类型为[2+2]环加成. 单体光聚后形成的取向膜对液晶分子排列效果不同, 6F-BADE取向膜诱导液晶分子垂直排列, FDE-n取向膜诱导液晶分子平行排列. 用原子力显微镜对取向膜表面进行表征, 均未观察到明显的各向异性分布现象. 应用量子力学半经验方法AM1分析发现单体分子极性有较大差异, 认为分子极性的差异是诱导液晶取向不同的主要原因.     

三聚磷酸二氢铝与有机胺的插层反应特征

采用IR、XRD、SEM、EDS、DT-TG和滴定实验等技术手段研究主体三聚磷酸二氢铝(ATP)与客体甲胺、乙胺、正丙胺和正丁胺等有机胺的插层反应特性。 实验结果表明,ATP与甲胺、乙胺、正丙胺、正丁胺发生了化学反应,有机胺中的N与ATP层间-OH上的H形成配位键。 这些有机胺通过插层反应改变了ATP的酸性、层间距和热分解温度,但没有改变颗粒的层状形貌。 层间距从0.795 nm增大至1.71 nm,层间距d与有机胺的碳原子数Cn呈线性关系：d=0.229Cn+0.811,R2=0.9986。 有机胺分子链越长则越具有剥离倾向。     

蒽衍生物自组装膜的制备及其对金属离子的识别作用

本文制备了石英基片表面的蒽甲基胺自组装膜，荧光光谱测试结果表明该膜在450～500 nm波段产生较强的excimer发射峰，这应与成膜分子的有序排列加强了蒽环间的相互作用有关。利用该自组装膜通过固/液界面相互作用实现了Zn^Ⅱ和Ag^Ⅰ的荧光识别。不同金属离子与膜分子结合对蒽环排列产生的不同影响是实现识别的主要机制。     

L-半胱氨酸和胱胺共自组装膜活体检测抗坏血酸

自组装单分子膜（SAM）由于其独特的物理化学性质近年来受到了极大的关注. SAM通过金硫键在电极表面形成高度有序的单分子膜,该稳定的分子膜不仅可以调节表面的亲疏水性质,而且可以促进电极表面氧化还原活性分子的反应速率. 本论文提出了一种简单有效的方法,在金微电极上构建半胱氨酸和胱胺共自组装单分子膜用于活体内抗坏血酸的检测. 研究发现,当混合单分子层中半胱氨酸和胱胺的摩尔比为1:1时,可以在低电位下（约为0.10 V）显著增强抗坏血酸氧化的电子转移动力学,同时该膜能在一定程度上抵抗蛋白质在电极表面的非特异性吸附. 将共自组装单分子膜应用到活体检测中,作者检测到鼠纹状体中抗坏血酸的基准值为257±30mmol·L^-1（n = 3）. 本论文为活体电化学检测提供了一种简单、有效的方法.     

杯芳烃-卟啉化合物及其金属配合物的Langmuir-Blodgett膜研究

通过对杯芳烃-卟啉化合物及其锌、钯配合物LB膜的表面压-表面积等温线、紫外可见光谱和傅里叶变换红外光谱的检测,研究了它们在气/液界面和Langmuir-Blodgett膜中的性质,并用量子力学方法优化了杯芳烃-卟啉化合物的构型.结果表明,成膜时3种化合物分子中卟啉环都倾斜地排列在亚相表面,且卟啉环间存在π-π相互作用.连接杯芳烃和卟啉之间的碳氢链在膜性质中起着重要的作用,杯芳烃-卟啉化合物分子中这种碳氢链的有序性小于其锌、钯配合物分子中的这种碳氢链有序性.     

硒杂环化合物(4,5-苯并苤硒脑)在金表面上的自组装

为了寻求新的自组装单分子膜体系,构建新的功能膜,研究了具备平面型的大环共轭硒杂环化合物-- 4,5-苯并苤硒脑(苯并[c]硒二唑,简称苤硒脑)在金表面的自组装单分子膜.通过X射线光电子能谱(XPS)和电化学手段对其进行表征.XPS研究结果表明,自组装形成单分子膜后,苤硒脑分子中Se3d结合能从57.4 eV下降到57.1 eV;表明硒杂环化合物是通过金硒键固定在金表面上的;电化学循环伏安法实验表明,金电极表面上自组装该有机硒后, Fe(CN)63-/4-的氧化还原峰几乎完全消失;以四硼酸钠为底液,测得该化合物自组装在金表面上时,其还原电位在-0.66 V,与在溶液中用裸金电极测得的还原峰电位基本一致.     

基于金纳米颗粒生长的液晶生物传感器检测酪氨酸

基于酶介导金纳米颗粒(AuNPs)生长构建了液晶生物传感器, 并用于检测酪氨酸(Tyr). 将酪氨酸酶(TR)固定于经戊二醛活化的二甲基十八烷基(3-[三甲氧基硅烷] 丙基)氯化铵/3-氨丙基三乙氧基硅烷(DMOAP/APTES)混合自组装修饰的玻片表面, 当向玻片表面滴加含Tyr的生长溶液时, TR催化Tyr羟基化为左旋多巴(L-Dopa), L-Dopa还原生长溶液中的AuCl₄^-生成AuNPs并沉积于玻片表面, 导致玻片表面地貌发生变化, 这一变化能诱导液晶取向发生变化进而调控透光量, 从而实现对Tyr的检测, 且检测浓度可低至6×10^-7 mol/L.     

Preparation and Characterizations of TiO2/Organically Modified Silane Composite Materials Produced by the Sol-Gel Method

TiO₂/organically modified silane (ORMOSIL) composite materials produced by the sol-gel method were studied for optical waveguide applications. High optical quality waveguiding films on different substrates, including silicon, gallium arsenide, silica/silicon substrates, and microscope glass slides, were prepared from high titanium content (0.2 molar) ÿ-glycidoxypropyltrimethoxysilane at low temperature. Scanning electron microscopy (SEM), atomic force microscopy (AFM), differential thermal analysis (DTA), thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) have been used to investigate the optical and structural properties of the composite films. The TGA/DTA results showed that the organic compounds in the film would tend to decompose in the temperature range from 200°C to 500°C. SEM and AFM results showed that a dense and porous-free composite material film could be obtained at the heat treatment temperature of 100°C. It was also shown that ORMOSIL is integrated in the glass, providing low shrinkage and high cracking resistance. The propagation loss properties of the composite films were also investigated. About 1.1 dB/cm propagation loss of the planar waveguide film was obtained at the wavelength of 633 nm.     

The effect of surface polarity of glass on liquid crystal alignment

The effects of the surface polarity of a glass substrate on the orientation of nematic liquid crystals (LCs) were studied using the polarised optical microscope and Fourier-transform infrared spectroscopy. On the surface of oxygen plasma treated glass, a homeotropic alignment of LCs was induced for LCs with negative dielectric anisotropy. This suggests that vertical orientation of LCs could be induced on a polar glass substrate without using an LC alignment layer. Upon cooling towards the isotropic–nematic transition, E7 with positive dielectric anisotropy changes its LC arrangement to isotropic, homeotropic, planar orientations in order. The nematic LC anchoring transition of E7 was interpreted by considering the competition between van der Waals forces and dipole interactions that control the alignment of LC molecules on a polar glass surface.     

Alignment and switching of nematic liquid crystals embedded in porous chiral thin films

Porous thin films with engineered microstructures have been fabricated using glancing angle deposition (GLAD). GLAD films with chiral microstructures have been previously shown to exhibit unique chiral optical response. The pores of these films were embedded with (non-chiral) nematic liquid crystals (LCs) to produce a new composite optical material wherein the GLAD film induces chiral nematic-like LC orientation. We demonstrate here reversible electro-optic switching of the LC component of these hybrid films. Unaddressed, cells of GLAD/LC hybrid films show enhanced chiral optic response compared with the unfilled GLAD film. When addressed, the chiral optic response vanishes.     

A simple strategy for detecting synthetic polymers on solid surfaces using liquid crystal

In this study, we developed a liquid crystal (LC)-based detection method for polymer films synthesized on solid surfaces. A dark to bright transition in the optical appearance of nematic 4-cyano-4′-pentylbiphenyl (5CB) was observed after transferring a poly(methyl methacrylate) (PMMA) film onto a glass substrate functionalized with n-octyltrichlorosilane (OTS). This phenomenon indicates an orientational transition of 5CB from a homeotropic to a planar-random state. The optical response of 5CB was then evaluated directly through polymerization reactions on the OTS-functionalized glass substrate. Polymer films of PMMA, poly(glycidyl methacrylate) (PGMA), and poly(dimethylsiloxane) (PDMS) were synthesized on OTS surfaces covered with their reaction mixtures. All polymer films displayed bright signals of 5CB, which corresponded to the planar-random orientation of LCs. However, no change in orientation was observed for the control experiments. We confirmed the formation of polymer films on the OTS surface using atomic force microscopy. Overall, our results suggest that LCs can be used to construct optical monitoring systems for the product of polymerization reactions.

Alignment of liquid crystals using Langmuir‒Blodgett films of unsymmetrical bent-core liquid crystals

ABSTRACT

The properties of the thin films of liquid crystal (LC) molecules can be governed easily by external fields. The anisotropic structure of the LC molecules has a large impact on the electrical and optical properties of the film. The Langmuir monolayer (LM) of LC molecules at the air–water interface is known to exhibit a variety of surface phases which can be transferred onto a solid substrate using the Langmuir?Blodgett (LB) technique. Here, we have studied the LM and LB films of asymmetrically substituted bent-core LC molecules. The morphology of LB film of the molecules is found to be a controlling parameter for aligning bulk LC in the nematic phase. It was found that the LB films of the bent-core molecules possessing defects favour the planar orientation of nematic LC, whereas the LB films with fewer defects show homeotropic alignment. The defect in LB films may introduce splay or bend distortions in the nematic near the alignment layer which can govern the planar alignment of the bulk LC. The uniform layer of LB film facilitates the molecules of nematic to anchor vertically due to a strong van der Waals interaction between the aliphatic chains leading to a homeotropic alignment.     

Determination of the molecular orientation of very thin films on solid substrates: surface liquid crystal layers and rubbed polyimide films

The molecular orientation of very thin films on solid substrates can be determined quantitatively by measuring the polarized infrared (IR) absorption spectra of samples as a function of angle of incidence. The quantitative molecular orientation is derived by fitting the incident angle dependence and the dichroic ratio with theoretical calculations. We applied this method to a technologically important system: liquid crystal (LC)/rubbed polyimide film. To understand the alignment mechanism of LC molecules in contact with rubbed polyimide films, we have quantitatively determined the molecular orientation of rubbed polyimide films and a surface LC layer in contact with a rubbed polyimide film. In this paper two relations are discussed: (1) correlation between the inclination angle of polyimide backbone structures in rubbed films and the pretilt angle of bulk LC in contact with them, and (2) relation among the molecular orientation of a rubbed polyimide film and those of surface and bulk LC layers in contact with it.     

Interfacial Interaction of Polymer/Liquid Crystal Molecules and Electrooptical Properties of their Composite Systems

Polymer/liquid crystal composite films were prepared from a solution of polymer and nematic liquid crystal (LC) by a solvent casting method. The phase-separated structure of the composite film was controlled by the solvent evaporation rate. The light-scattering profile of a poly(diisopropyl fumarate)/LC: 40/60 w/w solution during solvent evaporation exhibited a periodic structure, indicating that the phase-separated structure was formed by spinodal decomposition. The aggregation structure of the composite film was investigated with a scanning electron microscope (SEM). SEM observation of the composite film suggested the presence of periodicity and dual connectivity of polymer and LC phases. The faster the solvent was evaporated, the smaller the LC channel (domain) size in the composite film. The composite film, composed of poly(methyl methacrylate) (PMMA) and a nematic LC (E44) with a positive dielectric anisotropy, exhibited remarkable and reversible light-scattering-light-transmission switching, under the modulation of an ac electric field. The light-scattering state was dependent on such optical heterogeneities as spatial distribution of the nematic directors and/or mismatching in the refractive indices of the components. The electrooptical behavior of the composite film was strongly dependent on the LC channel (domain) size in the composite film. The transmittance increased and the rise and decay response times (τ_R and τ_D), decreased and increased, respectively, with an increase in the size of the LC channel (domain).

The electrooptical switching properties for the polymer/LC composite film should be influenced by miscibility between the polymer and the LC phases. The miscibility between both phases was evaluated from a distribution of relaxation time for interfacial polarization. The anchoring effect was also investigated by measuring the nonlinearity of the dielectric constant for the composite system.     

软光刻技术制备液晶显示用定向层

以偶氮聚合物光致表面起伏光栅为模板,制备聚二甲基硅氧烷(PDMS)弹性印章,再以可溶性聚酰亚胺(PI)为“墨水”,在石英玻璃上压印出具有规则起伏结构的PI薄膜.由此制备的PI薄膜显示出很好的使液晶分子定向排列的效果.此方法成本低、效率高,是一种实用的液晶定向层薄膜制备方法.     

还原石墨/氧化锌复合薄膜的制备及其光电转换性能

本工作研究不同过程还原的氧化石墨rGO/ZnO(reduced graphiteoxide/ZnO)复合膜的可见光激发光电转换性能。氧化石墨(GO)经KOH还原处理或NaBH4还原处理后,和氧化锌溶胶混合,通过旋涂法和热处理在F掺杂SnO2薄膜导电玻璃(FTO)衬底上形成复合薄膜。采用XRD、FTIR、FE-SEM、XPS、UV-Vis等方法对复合薄膜的晶相结构、微观形貌等进行表征,并测试了复合薄膜在可见光照射下的光电转换性能。GO的预处理过程对复合薄膜的结构影响显著,采用NaBH4对GO处理更有利于形成均匀薄膜。光电流测试结果表明不同复合薄膜均能实现可见光照射下产生光电流,其原理为rGO的光激发电子跃迁到ZnO,而空穴在rGO中迁移,在rGO与ZnO界面实现光生载流子分离。其中NaBH4处理后的rGO/ZnO复合薄膜光电流密度最大,达6×10-7A·cm-2。