Orientational phenomena in comb-shaped liquid crystal polymers induced by laser beam irradiation

Action of the laser illumination on optical properties of liquid crystalline (LC) comb-shaped acrylic and methacrylic copolymers containing cyanobiphenyl mesogenic groups and azo dye fragments has been studied. Under an illumination the cis-trans configurational changes of dye fragments take place and reorientation of the side groups towards a direction perpendicular to the electric vector of the actinic light occurs. As a result the photoinduced optical birefringence (δn = 0.05-0.11) appears. The detailed study of dichrotic and optical properties of polymeric films, kinetics and relaxation of δn, as well as mechanism of orientational transformations during a laser illumination are discussed. The induced optical anisotropy of the films can be changed reversibly by rotating the electric vector of the laser beam in respect to the film that may be used in reversible optical data storage.     

Cure monitoring of two-component epoxy adhesives by terahertz time-domain spectroscopy

We report nondestructive measurements of the properties of two-component epoxy adhesives at terahertz wavelengths using a transmissive time-domain spectroscopy system. The results show that the different epoxies have measurably different THz properties, that the changes which occur during the curing process can be monitored by measurements of their refractive index and absorption at terahertz wavelengths, and that this technique is sensitive enough to record changes in the optical material parameters during the postcuring process.     

Optical data storage in Langmuir-Blodgett-Kuhn multilayer assemblies of azo-dye side chain LC-polymers

We describe the preparation of LB-films of novel polymers containing azobenzene dye side chains. X-ray refection measurements, surface-plasmon experiments were used to determine the structure of LB-films which had been transferred onto a substrate. Illumination with UV-light causes trans-cis isomerisation of the azobenzene side groups. This effect can be used for optical data storage and will be discussed in detail.     

Effect of preparation conditions on the optical and physical properties of an epoxy-functional inorganic-organic hybrid material system

A hybrid material system consisting of (3-glycidyloxypropyl)trimethoxysilane, dimethyldimethoxysilane and zirconium(IV) n-propoxide was prepared. The influence of processing parameters including Zr content, UV irradiation and sol ageing on the properties of the resultant thin films was discussed. Refractive index, at 633 nm, and reflectance measurements were performed and near-field waveguide images of the samples were taken. Optical propagation loss measurements, at 633 nm, were studied. Film thickness and cross-sectional scanning electron microscopy images were obtained as a function of process conditions. FT-IR spectroscopy was used to monitor chemical reaction pathways in the system during processing. It was demonstrated that the crosslinking of epoxy groups in the structure, along with inorganic network formation as a result of sol-gel reactions, was the primary reason for the changes in the optical and physical properties of the system. As Zr containing species and/or UV irradiation may be employed to crosslink the epoxy groups in the structure, the optical and physical properties of the system can be tuned by optimal combination of these two crosslinking methods, as well as sol ageing process.     

alpha and piDL helical states of alternating poly(gamma-benzyl D-L-glutamate) in solution.

As in solid state, strictly alternating poly(gamma-benzyl D-L-glutamate) in solution can adopt two different helical conformations. Besides the alpha helix, a second helical conformation is found at higher temperatures in dioxane and chloroform, the properties of which correspond to that of the piDL4 helix. As the molecules have a finite length a screw sense is favored for both helical forms thus giving rise to optical activity allowing the study of the transconformation by optical rotatory dispersion and circular dichroism besides infrared and dielectric measurements. Thus, as the temperature is raised the equilibria right-left handed alpha helices and alpha-piDL helical forms can be followed. The favored screw senses are determined by the number of interacting side chains for the alpha helix and by the number of hydrogen bonds which are formed in the piDL helical conformation. The side chain-side chain interactions in the alpha helix are experimentally shown to be attractive.     

线性脂环族聚酰胺化学结构对其力学和光学性能的影响

以重复单元结构不同的3种线性脂环族聚酰胺(LATPA)材料为研究对象,通过核磁共振谱、红外光谱、热分析、X射线衍射等技术,研究了链结构单元的侧基、端基对材料聚集态结构的影响,并对比研究了不同聚集态结构材料的宏观力学性能和光学透明性差异,建立了链结构、聚集态结构与力学性能、光学性能的关系.研究发现,侧基带来的大空间位阻降低了LATPA的结晶度,提高了材料的玻璃化转变温度;较长的柔性端基分子链有助于高分子链的有序规整排列,可生成尺寸很小的微晶;聚集态结构直接影响材料的力学和光学性能,无定形LATPA和含有微晶结构的LATPA都具有良好的光学透明性,前者的透明性更高,后者的综合力学性能更好.     

Versatile route for tuning optical properties of poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene)

In this contribution, we report a versatile method for tuning optical properties of poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene) (MEH‐PPV) in its solution with 1,2‐dichloroethane, accomplished by reacting with pyridinium formate (PF), a volatile organic salt. We can systematically control the positions of absorption and photoluminescent (PL) spectra of MEH‐PPV by adjusting the concentration of PF in the solution. The addition of 10 vol % PF caused a blue‐shift in the absorption spectra by about 65 nm. When the concentration of PF decreased to 0.1 vol %, the blue‐shift occurred to a lesser extent, about 25 nm. The measurements of PL spectra showed similar behaviors. The λ_max shifted from 558 nm to 546 and 552 nm when 10 and 0.1 vol % of PF were added, respectively. The changes of PL colors from orange to yellow and green, respectively, were observed by naked eyes. Structural investigation by nuclear magnetic resonance and Fourier‐transformed infrared spectroscopy indicated that the changes of the optical properties were due to chemical modifications along the main chain and the side groups of MEH‐PPV. These results implied a simple route for engineering the HOMO–LUMO energy gap of MEH‐PPV, which could be utilized in advanced applications such as organic light‐emitting devices and solar cells. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 696–705, 2009     

Thiophene-2-aryl-2H-benzotriazole-thiophene oligomers with adjustable electronic properties

The synthesis and the optical and electrochemical properties of 2-aryl-2H-benzotriazole based thiophene oligomers with chemical modifications either on the phenyl side group or on the backbone are presented. All data, supported by DFT calculations, show that modification on the backbone has a major impact on the electronic properties while the side groups can fine-tune the electronic properties. In addition, one compound exhibits a thermotropic mesophase.     

Liquid crystal comb polymer with polar mesogenic and aliphatic side groups II. Noise of the scattered light

Measurements of static light scattering and of the stationary noise of the scattered light have been performed as functions of temperature on the comb polymer whose synthesis and static structural properties are discussed in the preceding paper, Part I. The intrinsic optical noise strongly increases when the nematic phase is entered. An additional maximum in the noise, observed at lower temperatures, is attributed to a rearrangement of optical domains, introducing boundary regions where the fluctuations of loosely packed side groups are enhanced. The spectral density of the observed noise is definitely non-Lorentzian and can be fitted by the superposition of two pure Lorentzian components with different cut-off frequencies, attributed to the statistically independent random motion of mesogenic and aliphatic side chains. The noise level is reduced at all temperatures by an applied electrical field; in particular, the field is effective in selectively damping the fluctuations of polar side groups.     

Liquid crystal comb polymer with polar mesogenic and aliphatic side groups II. Noise of the scattered light

Measurements of static light scattering and of the stationary noise of the scattered light have been performed as functions of temperature on the comb polymer whose synthesis and static structural properties are discussed in the preceding paper, Part I. The intrinsic optical noise strongly increases when the nematic phase is entered. An additional maximum in the noise, observed at lower temperatures, is attributed to a rearrangement of optical domains, introducing boundary regions where the fluctuations of loosely packed side groups are enhanced. The spectral density of the observed noise is definitely non-Lorentzian and can be fitted by the superposition of two pure Lorentzian components with different cut-off frequencies, attributed to the statistically independent random motion of mesogenic and aliphatic side chains. The noise level is reduced at all temperatures by an applied electrical field; in particular, the field is effective in selectively damping the fluctuations of polar side groups.     

Photolabile carboxylic acid protected terpolymers for surface patterning. Part 2: Photocleavage and film patterning

The surface properties of films made of p-methoxyphenacyl derivative terpolymers, associated with photocleavage by UV irradiation, and their optical patterning are investigated. The deprotection reaction has been monitored by UV and FTIR spectroscopy, contact angle measurements, and X-ray photoelectron spectroscopy, revealing the photoremoval of the protecting p-methoxyphenacyl group in high yields under mild conditions. Parallel and serial patterning of the films has been performed by selective irradiation through optical masks and by laser irradiation via fiber tips of a scanning near-field optical microscope, respectively. By irradiation of photolabile protected functional groups, free carboxylic groups become exposed to the surface with which fluorescent dyes and proteins can be associated specifically.     

Effect of nonelectrostatic interactions on the macromolecular behavior of polyelectrolytes. III. Optical rotatory dispersion of PLL in water and aqueous-organic mixtures

We have investigated the optical rotatory dispersion of a stereo-irregular polyelectrolyte when neutralized with alkaline and N-tetraalkylammonium hydroxides, both in water and aqueousacetone mixtures. The variations of the optical activity properties during the neutralization can be well related to potentiometric and viscosity measurements. They are interpreted by assuming two kinds of solvation of the chiral centers located on the main chain, to which two partial optical rotary dispersions (ORD) of opposite signs are associated. The observed optical activity changes and specifically the discontinuity occurring in the neutralization range where a conformational transition between a compact structure and a more extended one is initiated, are thus accounted for in terms of the corresponding changes in the state of solvation of chains.     

Platinum‐segmented polydiacetylenes

We report the synthesis and characterization of a novel series of platinum‐segmented polydiacetylenes (Pt‐PDAs). These polymers can be considered PDAs having every other double bond replaced with a Pt center and fully conjugated side groups attached to the remaining double bonds. Physical, optical and electronic properties of these polymers can be systematically tuned by changing the side groups from alkyl to phenyl and to thienyl moieties. Application of these polymers in solution‐processed organic photovoltaic devices is attempted and evaluated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2662‐2668     

In vivo Spectroscopic Evaluation of the Intraperitoneal Cavity in Canines

As part of a preclinical trial for the treatment of peritoneal carcinomatosis (PC) with photodynamic therapy (PDT), we have assessed changes in optical properties, tissue oxygenation and drug concentration as a result of benzoporphyrin derivative (BPD)-mediated PDT using diffuse reflectance and fluorescence measurements. PDT can effectively treat superficial disease spread, but treatment efficacy is influenced by physical properties of the treated tissue which can change over the treatment time. In this study, healthy canines were given BPD and irradiated with 690 nm light during a partial bowel resection, and spectroscopic and fluorescence measurements were made using an in-house built spectroscopic probe. Hemoglobin concentration, oxygenation and optical properties were determined to be highly heterogeneous between canines and at different anatomical locations within the same subject, so further development of PDT dosimetry systems will need to address this patient and location-specific dose optimization. Compared to other photosensitizers, we found no apparent BPD photobleaching after PDT.     

Electrically-induced optical storage effects in smectic polysiloxanes A variable transmission device

Changes in the optical transmission induced by electric fields have been studied in a smectic side-chain polysiloxane liquid crystal. The transmission varied from effectively zero, for a highly scattering (opaque) texture, to total, for a homeotropic texture, on increasing the applied voltage across the material. The field-induced textures were durably stored in the smectic phase, enabling the order parameter of the side groups to be studied by dielectric relaxation measurements. For the highly transparent texture, a side group order parameter of 0-92 has been observed.     

Synthesis and nonlinear optical properties of side chain liquid crystalline polymers containing azobenzene push–pull chromophores

Azobenzene monomeric precursors bearing piperazine as donor moiety with different withdrawing groups and derived side chain polymethacrylates have been prepared and characterized. Monomers having terminal cyano or nitro groups, and the corresponding polymers, exhibited smectic A phases. Linear and nonlinear optical properties of every monomer and thin films of the cyano polymer ( pol‐PZ‐CN ) have been also studied. UV‐vis spectroscopy revealed out‐of‐plane orientation in the as prepared films, as confirmed by waveguide refractive index measurements. Moreover, absorption spectra indicated the presence of azo aggregates in these films. The initial molecular arrangement has been modified by applying thermal annealing within the mesophase range and UV‐blue irradiation. Although thermal annealing resulted in a significant amplification of the out‐of‐plane optical anisotropy due to thermotropic self‐organization of side chain azo moieties, irradiation with 440 nm light induced some disruption of aggregates. The nonlinear optical response of Corona poled films has been studied by second harmonic generation measurements, and the influence of the molecular arrangement on the nonlinear d_ij coefficients has been analyzed. The more efficient poling corresponded to preirradiated films. In any case, a noticeable degree of polar order (70% of the initial d₃₃ value) remained for several months after the poling in films kept at RT. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 232–242, 2010     

Anisotropic networks, elastomers and gels

Anisotropic networks, elastomers and gels exhibit piezoelectric, pyroelectric, ferroelectric and NLO properties of potential interest for use communication and processing technologies. The formation, properties and applications of such anisotropic, mainly liquid crystalline, networks are described. If some of the molecules in a liquid mixture contain at least two reactive groups which can be either photochemically or thermally polymerized, then crosslinked, anisotropic networks, elastomers and gels can be produced. Solid macroscopically aligned elastomers or networks can be formed as required beforehand or simultaneously by orientation of the sample. Anisotropic gels consist of a solid anisotropic network and non-covalently bonded, but strongly oriented domains of low molar mass liquid crystals. Anisotropic networks, elastomers preformed amorphous or liquid crystalline polymers incorporating additional reactive groups, which can be macroscopically oriented in the additional crosslinking reactions. Reversible networks, elastomers and gels can be prepared either non-covalently or covalently by thermally side group polymers and low molar mass molecules, liquid crystalline properties in the pure state. in many electro-optic devices for optical and gels can be prepared from liquid crystalline state and then fixed by reversible linkages between, for example, neither of which necessarily exhibit     

新型光取向液晶聚合物的制备及其性能表征

目前,液晶分子常规的定向方法是对涂有定向膜的基片进行摩擦,这种方法简单、方便,然而在摩擦过程中却难以避免产生机械划痕、污染或静电,影响了液晶分子取向的均匀性,光控取向方法是近年来发展起来的一种液晶定向新技术,即通过激光或偏振紫外光照射,引发基片上的聚合物薄膜发生光致聚合、光致异构或光致分解反应,产生表面的各向异性,进而诱导液晶分子取向。     

Electrically-induced optical storage effects in smectic polysiloxanes A variable transmission device

Abstract

Changes in the optical transmission induced by electric fields have been studied in a smectic side-chain polysiloxane liquid crystal. The transmission varied from effectively zero, for a highly scattering (opaque) texture, to total, for a homeotropic texture, on increasing the applied voltage across the material. The field-induced textures were durably stored in the smectic phase, enabling the order parameter of the side groups to be studied by dielectric relaxation measurements. For the highly transparent texture, a side group order parameter of 0-92 has been observed.     

Synthesis and phase behavior of side‐chain liquid‐crystalline polymers containing malachite green lactone groups

New side‐chain liquid‐crystalline polymers containing both cholesteric and thermochromic side groups were synthesized. Their chemical structures were confirmed with elemental analyses and Fourier transform infrared, proton nuclear magnetic resonance, and carbon‐13 nuclear magnetic resonance spectra. The mesogenic properties and phase behavior were investigated with differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction measurements. The effect of the concentration of dye side groups on the phase behavior of the polymers was examined. The polymers showed smectic or cholesteric phases. Those polymers containing less than 20 mol % dye groups had good solubility, reversible phase transitions, wider mesophase temperature ranges, and higher thermal stability. The experimental results demonstrated that the isotropization temperature and mesophase temperature ranges decreased with an increasing concentration of dye groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3870–3878, 2004