The intercalation of ethidium bromide in the chromonic lyotropic phases of drugs and nucleic acids

Chromonic liquid crystalline phases are formed by a variety of drug and dye/water systems. In contrast to conventional lyotropic phases (where micelle formation underlies the mesogenic properties), in chromonic systems the molecules stack in columns. The different chromonic phases are different arrangements of these columns. We have examined the solution of ethidium bromide (EB) in the well-documented chromonic Intal/water system. EB is a widely used nucleic acid stain which changes colour when intercalated into DNA and which becomes fluorescent.

We have charted the changes in the temperature/composition phase diagram of the Intal/water system caused by adding EB. Although there are changes in the position of the phase boundaries, the overall pattern remains qualitatively the same—implying that the host phase is accepting EB as a similar chromonic molecule. The intercalation of EB molecules in the chromonic host phase results in optical effects—a metachromic colour change and fluorescence, similar to those occurring when the dye stains DNA.

These observations strengthen our belief that the central stack of bases in DNA can be regarded as being chromonic in nature.     

Preparation and Properties of Sol–Gel Thin Film Containing Rhodamine B Derivative with Ethoxy Silano Group on Organic Substrate and its Application to Surface-Treatment Thin Film for Display

A thin film containing rhodamine B derivative with ethoxy silano group was formed on organic film substrate using the sol–gel method. Rhodamine B derivative with a triethoxysilano group, SiO₂ sol and acrylic polymer having a triethoxy group were reacted in alcohol to give a coating solution for film formation, followed to be roll-coated on polyethylene terephthalate (PET) film and heat-treated at 130°C. This thin film consists of inorganic polymer (SiO₂), organic polymer (acrylic resin) and organic dye. These component parts become interconnected through mutual chemical bonding. This thin film has an absorption peak at 578 nm and superb water resistant characteristics (almost no dye elution in 50°C water for 150 min) as a result of chemical bonding between the organic dye and the matrix skeleton. It also has good flexibility. The film can be used as a wavelength-selective absorption film for displays to improve contrast.     

Chromonic mesophases

Over the last 10 years, there has been a growing acceptance of the concept of chromonic phases and a wider recognition that they form a well-defined family of lyotropic liquid crystalline phases, with a package of properties distinct in almost every aspect, from those of conventional amphiphiles. New chromonogenic compounds have appeared and new technological uses for chromonic systems are being actively explored. Recent promising investigations include the synthesis of a chromonic dye, C.I. Direct Blue 67, which has an N phase of high order parameter and which can be dried down to give well-oriented films of solid. When dried down on a ‘command surface’ of photoaligned substrate this can produce a highly patterned film. The use of chromonic phases in the construction of compensating plates for improving the viewing characteristics of twisted nematic displays has been explored. Although this technology may not be suitable for commercially exploitation in its present form, the success of the devices is significant. It is suggested that current studies of the way in which the temperature range of thermotropic discotic mesophases is enhanced in 1:1 CPI mixtures may well lead to improved formulations for chromonic dyes. It is predicted that the marriage of chromonic phase technology with current biochemical analytical techniques will give rise to a new generation of medical diagnostic tests.     

Formation and study of thin films oftert-butyl-substituted thiopyrylium dyes

The formation of thin films of symmetrical and asymmetrical thiopyrylium dyes, containingtert-butyl substituents, on glass supports was studied. The films were deposited by centrifugation of solutions of individual dyes or dye—polymer [poly(methyl methacrylate)] compositions. The dye: polymer ratios necessary for the formation of WORM recording layers based on these dyes were determined. The use of a polymeric matrix increases the film thickness and optical density but decreases its reflection power and does not allow crystallization of the dye on the support to be completely avoided. An increase in the number oftert-butyl groups in the dye molecule prevents crystallization of the recording layer in the case of symmetrical dye molecules, but does not prevent it for asymmetrical molecules. The data obtained were interpreted in terms of geometrical views on the interaction of dye molecules in thin layers. Translated fromIzestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1343–1349, July, 1998.     

Oriented monolayers prepared from lyotropic chromonic liquid crystal

We use a layer-by layer electrostatic self-assembly technique to obtain in-plane oriented aggregates of mesogenic dye molecules cast from lyotropic chromonic liquid crystals (LCLCs) on mica substrates. The aqueous solutions of dye used for deposition are in the nematic phase. Atomic force microscopy and X-ray photoelectron spectroscopy of the dried film reveal that the LCLC molecules adsorb at the charged substrate preserving ordered aggregates of elongated shape characteristic of the nematic phase in the aqueous solution. These elongated aggregates of LCLC molecules form films with in-plane orientational order and are compositionally distinct from the substrate.     

Polymer-surfactant layered heterostructures by electropolymerization of phenosafranine in Langmuir-Blodgett films

Langmuir-Blodgett (LB) films of the water-soluble dye phenosafranine (PS) have been prepared by its adsorption from aqueous dye solution to an arachidic acid (AA) monolayer at the air-water interface. Atomic force microscopy (AFM) images of the LB films revealed the effect of change in pH of deposition on the degree of complexation of AA with the PS dye. Well-defined circular islands and holes were observed which disappeared with the increase in pH. Polarized absorption studies indicated that the dye molecules are oriented uniaxially with their long axis titled at a constant angle to the surface normal of the LB film. Within the restricted geometry of the LB film, the PS dye was electropolymerized to form a two-dimensional film of poly(phenosafranine) sandwiched between arachidic acid layers. The film was characterized by IR spectroscopy, cyclic voltammetry, and AFM. X-ray diffraction studies reveal the presence of a layer structure in the AA-PS LB film before and after polymerization. The polymer film showed highly anisotropic electrical conductivity of ca. 10 orders of magnitude. This indicates the formation of two-dimensional polyPS layers between arachidic acid layers resulting in a layered heterostructure film having alternate conducting and insulating regions. Also, the conductivity of the polyPS prepared from LB film was found to be approximately 2.5 times higher than the conductivity of polyPS prepared by solution polymerization method.     

Local dynamic mechanical properties in model free-standing polymer thin films

High-frequency sinusoidal oscillations of a coarse-grained polymer model are used to calculate the local dynamic mechanical properties (DMPs) of free-standing polymer thin films. The storage modulus G(') and loss modulus G(") are examined as a function of position normal to the free surfaces. It is found that mechanically soft layers arise near the free surfaces of glassy thin films, and that their thickness becomes comparable to the entire film thickness as the temperature approaches the glass transition T(g). As a result, the overall stiffness of glassy thin films decreases with film thickness. It is also shown that two regions coexist in thin films just at the bulk T(g); a melt-like region (G(')G(")) in the middle of the film. Our findings on the existence of a heterogeneous distribution of DMPs in free-standing polymer thin films provide insights into recent experimental measurements of the mechanical properties of glassy polymer thin films.     

Polymer-based bilayer interfaces for electrochemical rectification

In this paper, the electrochemical current rectification phenomenon exhibited at an electrochemical interface constituted by a glassy carbon electrode covered with a bilayer of polymer films is discussed. The authors have shown that Methylene Blue (MB) redox species can be confined to a very thin insulating polymer film formed from orthophenylene diamine. The poly(opd) film exhibited excellent blocking properties to redox molecules in solution. On the other hand, the insulating poly(opd) film trapped with MB could mediate electron transfer between the redox molecules in solution and the electrode. Further, a second polymeric layer (Nafion film) trapped with ferrocene redox species was formed as the outer layer over the inner poly (opd) film containing MB. This bilayer-modified electrode, due to the significant difference in the redox potentials of the MB and ferrocene species immobilized in the inner and outer layers, respectively, exhibits unidirectional current flow and the results of the voltammetric investigations on the modified electrodes are described in this communication.     

“Surface-photografting”: new applications to synthetic fibers

“Surface-photografting” with UV-irradiation of polypropylene (PP) fiber and film and high-strength polyethylene (HSPE) yarn has been made with acrylic acid (AA) and acrylamide (AM) as monomers and benzophenone (BP), 4-chlorobenzophenone (4-BCP) and hydroxylcyclohexylacetophenone (HHA) as photoinitiators using a new continuous method. The grafting reaction occurs in a thin liquid layer on the fiber or film substrate, which is presoaked in a solution containing initiator and monomer. After irradiation with a highpressure mercury lamp, HPM 15 (2 kW) from Philips, for 5–20 sec at about 50°C the fiber and film surface is completely covered with a 2–8 nm thick layer of grafted polymer, analyzed by electron spectroscopy for chemical analysis. The grafting efficiency is 70–80%, i.e. only 20–30% of the polymer is homopolymer which can be removed by extraction. The grafted layers are so thin that they cannot be analyzed as weight increase (<0.1% of fiber weight). Absolute values for the amount of grafted AA polymer is analyzed by microtitration of the COOH groups at the fiber surface. The results agree well with the relative ESCA values. Grafting of commercial PP yarn with AA increases the adsorption of Crystal Violet dye with a factor of about 6. Grafting the same yarn with AM increases the adhesion to epoxy resin by a factor of 3–4 without affecting the mechanical properties of the fiber more than a few percent. For comparison, strips of blown PP film (5 mm wide) are modified by “surface-photografting” with AM. With increasing grafting, the contact angle for drops of distilled water decreases from 90° to 20°, indicating extensive wetting. The adhesion to epoxy resin increases from about 0.35 to 1.7 N/mm², i.e. with a factor of about 5 when the film surface is completely covered. Other comparisons are made with grafting of commercial HSPE yarn. Grafting with AA increases the adsorption of Crystal Violet dye by a factor of about 6. Grafting with AM increases the adhesion to epoxy resin from 0.25 to 1.3 N/nm², i.e. with a factor of 5. The bulk mechanical properties of the HSPE filaments are not affected by the grafting measured as tensile strength 2.7±0.1 GPa, elongation at break 4.8±0.3%, and Young's modulus 55±3 GPa, both before and after “surface-photografting”.     

Impedance change induced by varying polymerization temperature of conducting polymer thin films

In this study, we use a conducting polymer precursor to build layer-by-layer (LbL) films. Thermal conversion of the polymer precursor to conducting polymer makes the LbL films intractable, so the LbL films can be used as protective layers in salt solution. The conducting polymer LbL film shows stabilizing effect on top of another LbL thin film that contains nanoparticles. The LbL film prepared in this study shows a 35-fold increase of conductivity than the literature values obtained from non-conducting polymer films. The stabilization of the films is the result of the polymerization of the conducting polymer, so other anionic polymers or nanoparticles may be used to afford additional functionalities.     

Entropic Mixing Allows Monomeric-Like Absorption in Neat BODIPY Films

Intermolecular interactions play a crucial role in materials chemistry because they govern thin film morphology. The photophysical properties of films of organic dyes are highly sensitive to the local environment, and a considerable effort has therefore been dedicated to engineering the morphology of organic thin films. Solubilizing side chains can successfully spatially separate chromophores, reducing detrimental intermolecular interactions. However, this strategy is also significantly decreasing achievable dye concentration. Here, five BODIPY derivatives containing small alkyl chains in the α-position were synthesized and photophysically characterized. By blending two or more derivatives, the increase in entropy reduces aggregation and therefore produces films with extreme dye concentration and, at the same time almost solution like absorption properties. Such a film was placed inside an optical cavity and the achieved system was demonstrated to reach the strong exciton-photon coupling regime by virtue of the achieved dye concentration and sharp absorption features of the film.     

(苄基三乙基铵)双(1,3-二硫杂环戊烯-2-硫酮-4,5-二硫基)-金的三阶非线性光学性质

合成了一种新的配位化合物(苄基三乙基铵)双(1,3-二硫杂环戊烯-2-硫酮-4,5-二硫基)-金(BTEAADT). 利用旋涂技术制备了该材料与聚甲基丙烯酸甲酯(PMMA)掺杂的复合薄膜, 该材料在复合薄膜中的质量分数为1%. 采用Z扫描方法, 分别测试了该材料的乙腈溶液和该材料与PMMA复合薄膜在波长为1064 nm, 脉宽为20 ps条件下的三阶非线性光学特性. 同时还研究了复合薄膜的线性光学性质. Z扫描的结果表明, 复合薄膜和该材料的乙腈溶液都具有自散焦效应, 非线性折射率都是负值. 在实验条件下, 两者的非线性吸收效应都是可以忽略的. 经过计算得出溶液样品的非线性折射率为-1.459×10^-18 m²·W^-1, 复合薄膜样品的非线性折射率为-3.978×10^-15 m²·W^-1. 该材料在1064 nm处的非线性光学器件方面有潜在应用价值.     

Gas permeability in polymer- and surfactant-stabilized bubble films

The gas permeabilities of thin liquid films stabilized by poly(N-isopropylacrylamide) (PNIPAM) and PNIPAM-SDS (sodium dodecyl sulfate) mixtures are studied using the "diminishing bubble" method. The method consists of forming a microbubble on the surface of the polymer solution and measuring the shrinking rates of the bubble and the bubble film as the gas diffuses from the interior to the exterior of the bubble. PNIPAM-stabilized films exhibit variable thicknesses and homogeneities. Interestingly, despite these variable features, the gas permeability of the film is determined principally by the structure of the adsorbed polymer layer that provides an efficient gas barrier with a value of gas permeability coefficient that is comparable to that of an SDS Newton black film. In the presence of SDS, both the film homogeneity and the gas permeability coefficient increase. These changes are related to interactions of PNIPAM with SDS in the solution and at the interface, where coadsorption of the two species forms mixed layers that are stable but that are more porous to gas transfer. The mixed PNIPAM-SDS layers, studied previously for a single water-air interface by neutron reflectivity, are further characterized here in a vertical free-draining film using X-ray reflectivity.     

Spectral characteristics and nonlinear studies of crystal violet dye

Solid-state dye-doped polymer is an attractive alternative to the conventional liquid dye solution. In this paper, the spectral characteristics and the nonlinear optical properties of the dye crystal violet are studied. The spectral characteristics of crystal violet dye doped poly(methylmethacrylate) modified with additive n-butyl acetate (nBA) are studied by recording its absorption and fluorescence spectra and the results are compared with the corresponding liquid mixture. The nonlinear refractive index of the dye in nBA and dye doped polymer film were measured using z-scan technique, by exciting with He-Ne laser. The results obtained are intercompared. Both the samples of dye crystal violet show a negative nonlinear refractive index. The origin of optical nonlinearity in the dye may be attributed due to laser-heating induced nonlinear effect.     

Elastomeric flexible free-standing hydrogen-bonded nanoscale assemblies

Poly(ethylene oxide) (PEO) is a key material in solid polymer electrolytes, biomaterials, drug delivery devices, and sensors. Through the use of hydrogen bonds, layer-by-layer (LBL) assemblies allow for the incorporation of PEO in a controllable tunable thin film, but little is known about the bulk properties of LBL thin films because they are often tightly bound to the substrate of assembly. The construction technique involves alternately exposing a substrate to a hydrogen-bond-donating polymer (poly(acrylic acid)) and a hydrogen-bond-accepting polymer (PEO) in solution, producing mechanically stable interdigitated layers of PEO and poly(acrylic acid) (PAA). Here, we introduce a new method of LBL film isolation using low-energy surfaces that facilitate the removal of substantial mass and area of the film, allowing, for the first time, the thermal and mechanical characterization that was previously difficult or impossible to perform. To further understand the morphology of the nanoscale blend, the glass transition is measured as a function of assembly pH via differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The resulting trends give clues as to how the morphology and composition of a hydrogen-bonded composite film evolve as a function of pH. We also demonstrate that LBL films of PEO and PAA behave as flexible elastomeric blends at ambient conditions and allow for nanoscale control of thickness and film composition. Furthermore, we show that the crystallization of PEO is fully suppressed in these composite assemblies, a fact that proves advantageous for applications such as ultrathin hydrogels, membranes, and solid-state polymer electrolytes.     

Preparation and properties of poly[9-hexadecyl-3-phenyl-6-(4-vinylphenyl)-9H-carbazole]

Preparation of new carbazole-containing polymer, poly[9-hexadecyl-3-phenyl-6-(4-vinylphenyl)-9H-carbazole], is reported. The optical properties of the product have been studied in comparison with those of the starting compounds. Electrochemical properties of the polymer solution and its thin film have been investigated. The polymer film images were obtained by atomic force and scanning tunneling microscopy. Thermogravimetric analysis has shown high thermal stability of the obtained polymer.     

Ultrathin film characterization: photoreactive polyacrylamide

The structure and properties of photoreactive polyacrylamide thin films suitable for medical devices are presented. Using a solution deposition process, we report on the influences of polymer concentration, substrate residence time in solution and UV illumination upon the film structure, wettability and frictional properties. Ellipsometry, atomic force microscopy and lateral force microscopy show that increasing polymer concentration and illumination increased the film thickness and uniformity. Dynamic contact angles and frictional coefficients of the modified surfaces depend upon the film structure and thickness for films less than 40Å thick. We also demonstrate the potential of lateral force microscopy for investigating tribology at the nanoscale level.     

Immobilization of a hyperbranched polyester via grafting-to and electron beam irradiation

Stable thin films of an aromatic-aliphatic hyperbranched polyester with hydroxyl groups were fabricated on silicon substrates using electron beam irradiation and a grafting-to approach. We present a detailed study on the influence of the dose, dose rate, and temperature on the film properties and degradation behavior of the polyester immobilized by electron beam irradiation. A patterned polyester film was prepared on the substrate using a masking technique. In the second part of this work, we report on a method for the strong binding of the hyperbranched polyester onto the surface of an "activated" silicon substrate without using any coupling agent. The results are compared with the grafting-to of the hydroxyl-terminated polyester using thin PGMA anchoring layers ( Reichelt et al. Macromol. Symp. 2007, 254, 240- 247 ). The optimal conditions and mechanism of the anchoring procedures were investigated. The surface and film properties of all immobilized polymer films were characterized by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), electrokinetic measurements, contact-angle measurements by drop-shape analysis, spectroscopic and imaging ellipsometry, and infrared spectroscopy. It is shown that all immobilization methods can be optimized in such a way that the polymer surface properties remain unchanged compared to those of nongrafted polyesters.     

Tuning the electronic properties of conjugated polymer by tethering low‐bandgap rhenium(I) complex on the main chain

Low‐bandgap rhenium(I) complex with absorption onset at 795 nm in solution was tethered onto π‐conjugated polymer. The conjugated copolymer provides solution processability of the metallopolymer, and the pendant allows the low energy‐absorbing Re(I) complex units to be evenly distributed on the thin film. The copolymer tethered with low‐bandgap rhenium complex was synthesized by Suzuki cross‐coupling reaction. The metal‐free polymer ( poly‐1 ) tethered with functionalized intramolecular charge transfer dye, 2‐phenyl‐3‐pyridin‐2‐yl‐5,7‐di‐2‐thienylthieno[3,4‐b]pyrazine, exhibited high molecular weight, good film‐forming properties, and excellent solution processability. The pendants of the conjugated polymer possess donor–acceptor characters and broaden the absorption band. These pendants can function as bidentate ligands for metal chelation. The solubilizing groups on the monomers provide good solubility to the polymer even with high content of metal chelation. Upon the complexation with rhenium(I) pentacarbonyl chloride, the absorption spectrum of the resulting metallopolymer was further extended toward the near‐infrared region. Photovoltaic performances based on this metallopolymer have been studied. The design approach of these metallopolymers provides synthetic feasibility for coordinating wide range of metal ions on the pendant, and the resulting low‐bandgap polymer can be a potential candidate for light harvesting material in solar cell applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2311–2319, 2010     

Colloidal TiO2 nanocrystals/MEH-PPV nanocomposites: photo(electro)chemical study

An extensive optical and photoelectrochemical study of blended systems composed of organic-capped TiO(2) nanocrystals with either a spherical or rodlike morphology and a conjugated polymer, MEH-PPV, is presented. The absorption and emission properties of the heterojunctions have been characterized both in solution and in thin films. The blended structures deposited onto conductive substrates have been employed as active layers in photoelectrochemical systems. The investigation has been focused on the photoinduced charge transfer and recombination processes at the interface between the two components, as a function of the nanocrystal shape and surface coating, and of the film thickness. The presence of a large number of interfaces available for charge transfer is believed to play a fundamental role in enhancing the photoelectrochemical performances of the dispersed heterojunctions. The reported results suggest that such MEH-PPV/TiO(2) heterojunctions may be exploited as potential active layers in future photovoltaic and photoelectrochemical devices.