Novel Azobenzene-Functionalized Polyelectrolytes of Different Substituted Head Groups 2: Control of Surface Wetting in Self-Assembled Multilayer Films

A novel set of light-responsive polyelectrolytes has been developed and studied, to control and tune surface wettability by introducing various types of substituted R head-groups of azo polyelectrolytes in self-assembled multilayer (SAMU) films. As part of a larger project to develop polymer surfaces where one can exert precise control over properties important to proteins and cells in contact, photo-reversibly, we describe here how one can tune quite reliably the contact angle of a biocompatible SAMU, containing a photo-reversible azo chromophore for eventual directed cell growth. The azo polyelectrolytes described here have different substituted R head-group pairs of shorter-ionized hydrophilic COOH and SO₃H, shorter non-ionized hydrophobic H and OC₂H₅, and larger non-ionized hydrophobic octyl C₈H₁₇ and C₈F₁₇, and were employed as polyanions to fabricate the SAMU onto silicon substrates by using the counter-charge polycation PDAC. The prepared SAMU films were primarily characterized by measurement of their contact angles with water. The surface wetting properties of the thin films were found to be dependent on the type of substituted R-groups of the azo polyelectrolytes through their degree of ionization, size, hydrophobicity/hydrophilicity, solubility, conformation, and inter-polymeric association and intra-polymeric aggregation. All these factors appeared to be inter-related, and influenced variations in hydrophobic/hydrophilic character to different extents of aggregates/non-aggregates in solution because of solvation effects of the azo polyanions, and were thus manifested when adsorbed as thin films via the SAMU deposition process. For example, one interesting observation is significantly higher contact angles of 79° for SAMU films of larger octyl R groups of PAPEA-C₈F₁₇ and PAPEA-C₈H₁₇ than for others with contact angles of 64° observed for non-polar R-groups of OC₂H₅ and H. Furthermore, lower contact angle values of 59° for SAMU films with polar R-groups of COOH and SO₃H relative to that of non-polar R-groups are in accordance with their expected order of the hydrophilicity or hydrophobicity. It is possible that the large octyl groups are more effective in shielding the ionic functional groups on the substrate surface, and contributed less to the water drop-molecule interactions with ionic groups of the PDAC and/or AA groups. In addition, higher hydrophobicity of the SAMU films may be due to the incorporation of bulky and hydrophobic groups in these polyelectrolytes, which can produce aggregates on the surfaces of the SAMU films. Through understanding and controlling the complex aggregation behavior of the different substituted R-groups of these azo polyelectrolytes, and hence their adsorption on substrates, it appears possible to finely tune the surface energy of these biocompatible films over a wide range, enhance the photo-switching capabilities of the SAMU films, and tailor other surface properties for the development and application of new devices in diverse areas of microfluidics, specialty coatings, sensors, and biomedical sciences.     

Powder‐XRD and 14N magic angle‐spinning solid‐state NMR spectroscopy of some metal nitrides

Some metal nitrides (TiN, ZrN, InN, GaN, Ca₃N₂, Mg₃N₂, and Ge₃N₄) have been studied by powder X‐ray diffraction (XRD) and ¹⁴N magic angle‐spinning (MAS) solid‐state NMR spectroscopy. For Ca₃N₂, Mg₃N₂, and Ge₃N₄, no ¹⁴N NMR signal was observed. Low speed (ν_r = 2 kHz for TiN, ZrN, and GaN; ν_r = 1 kHz for InN) and ‘high speed’ (ν_r = 15 kHz for TiN; ν_r = 5 kHz for ZrN; ν_r = 10 kHz for InN and GaN) MAS NMR experiments were performed. For TiN, ZrN, InN, and GaN, powder‐XRD was used to identify the phases present in each sample. The number of peaks observed for each sample in their ¹⁴N MAS solid‐state NMR spectrum matches perfectly well with the number of nitrogen‐containing phases identified by powder‐XRD. The ¹⁴N MAS solid‐state NMR spectra are symmetric and dominated by the quadrupolar interaction. The envelopes of the spinning sidebands manifold are Lorentzian, and it is concluded that there is a distribution of the quadrupolar coupling constants Q_cc's arising from structural defects in the compounds studied. Copyright © 2015 John Wiley & Sons, Ltd.     

Crystal planes and reciprocal space in Clifford geometric algebra

This paper discusses the geometry of kD crystal cells given by (k+ 1) points in a projective space ?^{n+ 1}. We show how the concepts of barycentric and fractional (crystallographic) coordinates, reciprocal vectors and dual representation are related (and geometrically interpreted) in the projective geometric algebra Cl(?^{n+ 1}) (see (Die Ausdehnungslehre von 1844 und die Geom. Anal. Teubner: Leipzig, 1894)) and in the conformal algebra Cl(?^{n+ 1, 1}). The crystallographic notions of d‐spacing, phase angle, structure factors, conditions for Bragg reflections, and the interfacial angles of crystal planes are obtained in the same context. Copyright © 2011 John Wiley & Sons, Ltd.     

Adsorption of azacrown ethers at solid–liquid interface. Contact angle and neutron reflectivity study

Adsorption of two alkylated N,N′-diaza-18-crown-6 ethers (decyl- and hexadecyl-derivatives, ACE-10 and ACE-16, respectively) on solid surfaces was studied by using contact angle and neutron reflectivity measurements. The solid substrates used were (a) Si covered with a native oxide layer (Si/SiO₂) and (b) Si with sputtered Pt layer (Si/Pt). The sensitivity of neutron reflectivity was drastically improved by applying the intermediate Pt layer of 150 Å, which gave rise to several Kiessig fringes in the experimentally accessible q-range. The position of the fringes is very sensitive to slight changes of the interfacial composition induced by adsorption of a thin monolayer, otherwise very difficult to detect. Unfortunately, in the studied case this sensitivity is immediately lost due to undesired adsorption of a protonated material on the Pt surface exposed to the lab air. A decrease of surface energy (increase of contact angle) of both Si/SiO₂ and Si/Pt upon exposure to toluene solutions of ACEs suggests that the latter are attached to the surface via the hydrophilic azacrown ether head with alkyl chains standing upright towards the liquid phase.     

Effect of barium titanate nanoparticles of different particle sizes on electro-optic and dielectric properties of ferroelectric liquid crystal

A comparative study of two different particle sizes of ferroelectric barium titanate (BaTiO₃) nanoparticles as a dopant on the molecular structure, spontaneous polarization and dielectric behavior of a pure ferroelectric liquid crystal 6F₆T have been studied. It has been found that there is a remarkable decrease in isotropic temperature of both doped samples as compared to the pure 6F₆T sample. The spontaneous polarization also decreases for both the doped samples and the reduction is more pronounced in case of the dopant with large particle size. The dielectric spectroscopy confirms the presence of soft mode as well as Goldstone mode and also shows the decrease in the value of dielectric permittivity ?' as a function of frequency for both doped samples. The improvised properties of liquid crystal host doped with BaTiO₃ nanoparticles mainly depend upon the synthesis method of nanoparticles and also upon the particle size of dopant.     

负性VA-LCD视角特性研究

液晶材料具有双折射效应,因此偏振光在液晶材料中各个方向上发生双折射的程度不同,这决定了LCD的视角特性和对比度随视角的变化有所不同。用光栅光谱仪测量在不同电压驱动下负性VA-LCD的电光特性,以及测量其电光特性随视角的变化;并对其三基色的电光特性和视角特性进行分析。结果表明,三基色的透过率在驱动电压2.2 V之前很小;在2.2 V后,透过率随电压的升高而增大;其中红基色和绿基色的透过率是一直升高,在电压达到5.0 V后,就是趋于平缓,而蓝基色的透过率是在3.7 V左右达到最大,而后慢慢变小,最后在电压达到6.0 V后,趋近一个稳定值。负性VA-LCD三基色的视角特性:红基色的视角范围最宽,绿基色次之,蓝基色的视角范围最窄。     

改进的极化SAR点散射目标扰动滤波检测方法

为完成极化合成孔径雷达(PolSAR)图像中点散射像素目标的检测,从几何扰动滤波检测点散射像素的基本原理出发,分析了经典方法存在的相干度参数阈值无法自适应获取和不同散射机制共享同一阈值两个问题,提出利用Cloude-Pottier分解结果中熵参数的分布情况计算得到阈值,利用平均阿尔法角参数完成不同散射机制的初分类,对初分类的结果排序得到的某种散射机制对应的相干度参数的比例因子,根据比例因子计算得到该类散射机制的阈值,从而完成点散射目标的检测。对机载合成孔径雷达（AIRSAR）数据集中的San Francisco Bay图像进行了实验,结果表明,改进方法在检测性能上优于经典方法。     

基于不同散射相函数的紫外光传输特性研究

为了研究三种不同散射相函数下紫外光大气传输特性,文章采用非直视紫外光通信的单次散射简化模型,对系统接收机接收到的能量及紫外光传输路径损耗随传输距离和散射角的变化情况进行分析.结果表明:三种相函数下,都表现为随传输距离的增大,接收能量减小,路径损耗增大,但三者之间存在一定的差异,对于紫外光通信系统,其传输性能的影响以前向散射为主,后向散射作用很小;随着散射角增大,后向散射作用相对明显;三种散射相函数下,紫外光通信链路的最佳散射角不同,但均随发射仰角的增大或接收仰角的增大最佳散射角增大,而接收能量减小.     

一种新的视角可控的液晶显示仿真研究

在PVA显示模式的基础上,研究了一种新型的液晶显示视角切换技术。通过增大液晶分子在暗态下的倾斜角度控制暗态亮度,实现了宽视角下暗态低,显示对比度高;窄视角下暗态高,在相同白态亮度下,显示对比度低。实施可行性:在时序控制芯片系统(Timing Controling,Tcon)中烧录两版code,使用者根据不同环境下对宽窄视角的特性需求选择相应的显示模式,通过宽窄视角下分别采用不同的Tconcode编译驱动电压以实现宽窄视角的面板显示。模拟结果表明:宽视角显示上下左右视角达到80°以上,而窄视角显示上下左右视角均不足40°,从模拟结果看本文提供的宽窄视角显示方法是有效的。