KINETICS OF DYNAMIC HOLOGRAM RECORDING IN POLYMER FILMS WITH IMMOBILIZED BACTERIORHODOPSIN

Abstract
Polymer films with immobilized photosensitive membrane protein, bacteriorhodopsin (BR), were prepared and investigated. A sensitive holographic interferometer with phase modulated optical beams was used for investigation of kinetics of dynamic hologram recording in BR polymer films. It was found that phase hologram formation consisted of two quasi-exponential stages demonstrating existence of a diffusive process in obtained films. It was shown that the kinetics of a phase hologram recording by high intensity beams do not correlate with the exponential law. The applicability of BR polymer films as reversible photorefractive materials for dynamic holography and real-time interferometry was discussed.     

Dynamic holography in bacteriorhodopsin/gelatin films: effects of light-dark adaptation at different humidity

This work examines the kinetics of dynamic holography responses in light-adapted and dark-adapted bacteriorhodopsin (BR) films at different humidity. We have demonstrated that the kinetics of the diffraction efficiency in wild type BR films is quite different in dark-adapted and light-adapted samples. The holographic recording kinetics, which depends on the duration of incubation in the dark after light adaptation at different humidity values, was studied in depth. A specially designed miniature cell containing a BR film was mounted inside the holographic set up to allow controlled humidity changes over a broad range. The diffraction efficiency kinetics at humidity values of 96-99% were quite different from the kinetics at 60-93% humidity. We found that humidity values of 90-93% were most optimal for dynamic holography recording using a gelatin film containing BR. In agreement with a calculation of the wavelength-dependent changes of the refractive index for dark-adapted and light-adapted BR samples using the Kramers-Kronig relation, the maximum difference in the refractive index and thus in the diffraction efficiency for dark-adapted and light-adapted BR films takes place at 630 nm, close to the wavelength of the He-Ne laser used.     

14-Fluoro-bacteriorhodopsin gelatin films for dynamic holography recording

The first dynamic holography recording using 14-fluoro-(14-F) bacteriorhodopsin (BR) gelatin films has been achieved. 14-F BR is an artificial BR pigment made by reconstitution of bacterioopsin (native BR without chromophore) with synthetic 14-F retinal. Low-intensity red light from a cw He-Ne laser was used for dynamic holography recording on the 14-F wild type (WT) BR and 14-F D96N mutant BR in gelatin films. There is not true comparing the diffraction efficiency for 14-F D96N BR and 14-F WT gelatin film, unlike the increased diffraction efficiency for D96N BR gelatin film with native chromophore relative to the WT BR gelatin film with native chromophore. Pre-illumination with blue light of the 14-F BR gelatin films significantly increases the diffraction efficiency of both the 14-F WT and the 14-F D96N BR pigments. The sequential application of blue and red laser beams indicates that 14-F BR gelatin films can be useful for optical memory.     

Optical Characteristics of Polymer Films Based on Bacteriorhodopsin for Irreversible Recording of Optical Information†

Bacteriorhodopsin (BR)‐containing polymer films have been developed in which photoinduced transformations of BR molecules take place during the process of photoinduced hydroxylaminolysis (PHA). The routine simplified scheme of the phototransformation is B?M ₄₁₂ in the case of polymer films based on nonmodified BR. In the case of polymer films based on BR modified by hydroxylamine (HA), this scheme is changed to where retinal oxime ( RO ) is a final product of chemical trapping of retinal by the HA molecule. Under certain conditions, the rate of RO to B regeneration is infinitely low. So, the irreversibility of RO formation allows one to use PHA for the preparation of films for irreversible write once recording. Some optical sensitometric characteristics are compared for polymer‐BR films and polymer‐BR–HA films. It has been shown that the photosensitivity level for polymer‐BR–HA films depends on the time after film preparation. A method is offered to increase the photosensitivity of polymer‐BR–HA films and to avoid the photosensitivity decrease with the time after film preparation.     

Molecularly imprinted polymer using beta-cyclodextrin as functional monomer for the efficient recognition of bilirubin

Bilirubin (BR) imprinted polymer was successfully prepared using supramolecular host compound β-cyclodextrin (β-CD) as functional monomer. The adsorption equilibrium was attained in about 4 h, which indicated that the adsorption kinetics was comparatively fast. The results of adsorption and selectivity experiments indicated that BR-imprinted β-CD polymer was able to bind BR specifically and reversibly. The specific recognition of BR-imprinted β-CD polymer for BR may be due to the cooperative effects of inclusion interaction and hydrogen bonding. This BR-imprinted β-CD polymer was further applied to eliminate BR in human serum sample. It was verified that the binding specificity of the BR-imprinted polymer for BR was essentially sufficient in the presence of other compounds coexisting in serum sample. Therefore, as a reusable material possessing high affinity and selectivity, BR-imprinted β-CD polymer has a potential application perspective as a clinical hemoperfusion material.     

Peculiar properties of photoinduced hydroxylaminolysis in different bacteriorhodopsin-based media using O-substituted hydroxylamines

The process of photoinduced hydroxylaminolysis has been re-examined in different bacteriorhodopsin (BR)-based media using O-substituted hydroxylamines, in particular, O-(4-nitrobenzyl) hydroxylamine hydrochloride (NBHA), O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride (FBHA) and O-(t-butyl) hydroxylamine hydrochloride (BHA). Both wild type (WT) and D96N BR-based gelatine films and gels were studied. The expected increase in the bleaching rate of BR in gelatin films by using O-substituted hydroxylamines in place of HA was not achieved. On the other hand, it was shown that in gels HA derivatives NBHA and FBHA (as against HA itself) do provide about three- to four-fold higher bleaching rate. By contrast to that in films, D96N BR in gels demonstrates more effective bleaching as compared to WT BR. The plausible interpretation for the results is discussed in frames of reduced mobilities of large-sized molecules of O-substituted hydroxylamines in dehydrated media. FBHA- or NBHA-modified gels possess higher photosensitivity both with D96N and WT BR (as compared with that for HA-modified gels) and offer a potentiality for application as an irreversible-recording medium. As anticipated, it is specifically D96N BR gel modified with FBHA that may present a promising medium suitable for write-once recording thus extending the range of recording materials in the optical processing field.     

The effect of the resultant microphase-separated structures of polymer matrices on the electro-optical properties of polymer dispersed liquid crystal films by Iniferter polymerization

Iniferter polymerization was employed to prepare polymer dispersed liquid crystal (PDLC) films and an additional photoinitiator was introduced to induce the phase separation of polymer matrices themselves on the process of preparing the PDLC. The effect of the polymerization kinetics and the resultant microphase-separated structures of polymer matrices on the electro-optical properties of PDLC films were studied. It was found that the bigger length scale of phase separation of polymer matrices induced strong light-scattering resulting in low ON-state transmittance. And faster polymerization kinetic induced higher threshold and saturation voltages.     

含手性末端基偶氮聚合物膜的全息光栅研究

偶氮苯侧链型高分子由于其含有偶氮苯基团 ,在光作用下会发生可逆的顺反异构过程 ,具有光致取向特性 ,在光学处理、衍射光学、投影显示、光开关等许多方面具有潜在的应用性[1] .近 1 0多年来国内外学者对此类化合物进行了广泛的研究 ,已有文献报道可利用Ａｒ+激光束在偶氮苯聚合物薄膜上直接“写入”表面凸起光栅 ,并且通过原子力显微镜观测到光栅起伏 .这种光栅很稳定 ,并可以利用光学方法“擦去” .偶氮苯聚合物上述独有的性质引起了许多学者的兴趣[2 ,3] .另一方面 ,由于旋光性聚合物在光学物理性质上的优势 ,我们已将手性基团引入偶氮苯…     

Preliminary Ultrasonication Affects the Rate of the Bacteriorhodopsin Bleaching and the Effectiveness of the Reconstitution Process in Bacterioopsin

The formation process of polymer films based on bacteriorhodopsin (BR) analogs requests a high amount of BR samples one time only. The common technique for apomembrane formation (preparation of bacterioopsin, BO) is not designed to be operated with high concentrations and high volumes of BR, so the use of this technique results in a low rate of BR bleaching. To accelerate the process of BR bleaching preliminary sonication was used. It was used just as preliminary sonication before bleaching of BR samples, so also sonication was used before reconstitution of resulted BO samples. These modifications of the common technique lead to an acceleration of BR bleaching and an increase in effectiveness of reconstitution of BO in comparison with the nonmodified technique. The quantitative results of sonication's effect on the bleaching acceleration and the effectiveness of reconstitution are different depending on the BR strains.     

Bragg-type polarization gratings formed in thick polymer films containing azobenzene and tolane moieties

Holographic gratings were formed in thick polymer films containing azobenzene and diphenylacetylene (tolane) moieties in the Bragg regime. Amorphous polymers containing various contents of the azobenzene moiety with photosensitivity and the tolane moiety with large birefringence in the side chain were synthesized, and optically transparent thick polymer films were prepared. The films were irradiated with a linearly polarized beam from an Ar+ laser (488 nm), and the transmittance of a He-Ne laser beam (633 nm) through a pair of crossed polarizers, with the film between them, was measured to estimate a photoinduced birefringence (deltan). The value of deltan increased with an increase in the tolane moiety content in the polymer films. When two linearly polarized beams at 488 nm were interfered in the film, a diffraction beam was observed, and the maximum diffraction efficiency (eta) increased with the tolane moiety content. In the film containing 70 mol% of the tolane moiety, the highest eta of 99% was achieved, and angular selectivity due to Bragg diffraction was clearly observed. We consider the cooperative molecular motion of the tolane moieties to be induced by the photoinduced change in alignment of the azobenzene moieties even if the polymers show no liquid-crystalline phase. When two orthogonal circularly polarized beams were allowed to interfere in the film, a Bragg-type polarization grating was formed. It was found that the value of eta reached 90% within 920 ms.     

Photopolymerisation kinetics and electro-optical properties in mixtures of dichroic dye-doped nematic liquid crystal and photocurable polymer

This work reports the effect of dye on the photopolymerisation and electro-optical properties of polymer dispersed liquid crystal (PDLC) composite films. Dichroic PDLC (DPDLC) films based on a photocurable polymer and nematic liquid crystal (LC) with an azo dichroic dye were prepared by photopolymerisation-induced phase separation method. Polarising optical microscopy has been used for monitoring the phase separation kinetics and two-phase morphology evolution in the DPDLC system. LC domains with radial structures during initial period of phase separation adopted a resultant morphology of bipolar configuration over the course of polymerisation. The phase separation and morphology of LC domains was found to be dependent on the amount of dye used. Moreover, the addition of small amount of dye reduced the switching voltage, and enhanced the contrast ratio with improved switching time in the PDLC films. It was shown that, under the application of an electric field, the molecular orientation and absorbance of dichroic dye can be controlled in DPDLC to induce non-linearity and colour contrast without the use of polarisers.     

Monte Carlo simulation of phase separation kinetics in a concentrated polymer solution

Ｔｈｅｐｈａｓｅｂｅｈａｖｉｏｒｉｎｍｕｌｔｉｐｌｅｃｏｍｐｏｎｅｎｔｐｏｌｙｍｅｒｓｃｏｎｓｔｉｔｕｔｅｓａｌｏｎｇｓｔａｎｄｉｎｇａｃｔｉｖｅａｃａｄｅｍｉｃｓｕｂｊｅｃｔｂｏｔｈｉｎｐｏｌｙｍｅｒｓｃｉｅｎｃｅａｎｄｃｏｎｄｅｎｓｅｄｓｔａｔｅｐｈｙｓｉｃｓ.Ｉｔｉｓｅｓｐｅｃｉａｌｌｙｓｉｇｎｉｆｉｃａｎｔｉｎｇｕｉｄｉｎｇｔｈｅｆａｂｒｉｃａｔｉｏｎｏｆｐｏｌｙｍｅｒａｌｌｏｙｓ[1].Ｄｕｒｉｎｇｔｈｅｌａｓｔｄｅｃａｄｅｓｍｕｃｈａｔｔｅｎｔｉｏｎｈａｓｂｅｅｎｐａｉｄｔｏｔｈｅｃｏｍ…     

Analysis of the kinetics of diffraction efficiency during the holographic grating recording in azobenzene functionalized polymers

The laser-assisted holographic grating recording process in films of azobenzene functionalized polymers is usually studied by observation of the efficiency of light scattering on a developing in time diffraction grating. Various possible mechanisms contributing to grating formation as well as the bulk or surface origin (bulk refractive index and/or relief grating) of light scattering make the analysis of kinetics of grating recording, from the light scattering data only, difficult and ambiguous. To fully explain experimentally observed various and complex (frequently nonexponential) kinetics of the first-order light diffraction intensity, we considered a simple single-exponential growth of the two phase gratings in the same polymer film. In modeling we assumed that the bulk refractive index grating Deltan(t) and the surface relief grating Deltad(t) differ considerably in their growth rates and we allowed for a nonstationary phase shift Deltaphi(t) between them which was experimentally observed during the recording process. The origin of the nonstationary phase shift is a result of a slow shift of interference pattern due to delicate symmetry breaking in illumination conditions (e.g., difference in beam intensities and deviation of exact symmetrical beam incidence angles on the sample). Changing only such parameters as stationary amplitudes of refractive index and relief gratings for a span of phase shifts (0-pi) between them, we obtained a series of kinetic responses which we discuss and interpret. The various examples of temporal evolution of diffraction efficiency for the same grating formation kinetics, modeled in our work, supply evidence that great care must be taken to properly interpret the experimental results.     

The oxidative polymerization of aniline as topochemical process. The statistical analysis of grain growth

The films of polyaniline (PANI) on the glass slides with granular morphology were prepared by oxidative polymerization with ammonium peroxydisulfate in strong acidic conditions. The kinetics of polymerization was monitored recording of scanning electron microscopy images of deposit PANI films on glass slides. Statistical analysis of the PANI grain size was successfully applied for characterization of the polymerization process. It was shown that oxidative PANI polymerization could be described as a topochemical process. This allowed us explaining the existence of three phase of process (induction period, acceleration stage and decay) and finding the kinetics parameters of these stages. The model of phenazine nucleates was used to described induction stage. It was shown that phenazine nucleation process can be described kinetically as zero-order reaction. The acceleration stage of PANI polymerization was connected with increase of PANI grain surface during reaction and the mechanism of this acceleration was discussed. The decay stage of process was attributed with formation fuse loose PANI film with reduced available interphase surface for polymerization process.     

Precise and fast secondary ion mass spectrometry depth profiling of polymer materials with large Ar cluster ion beams

We demonstrate depth profiling of polymer materials by using large argon (Ar) cluster ion beams. In general, depth profiling with secondary ion mass spectrometry (SIMS) presents serious problems in organic materials, because the primary keV atomic ion beams often damage them and the molecular ion yields decrease with increasing incident ion fluence. Recently, we have found reduced damage of organic materials during sputtering with large gas cluster ions, and reported on the unique secondary ion emission of organic materials. Secondary ions from the polymer films were measured with a linear type time‐of‐flight (TOF) technique; the films were also etched with large Ar cluster ion beams. The mean cluster size of the primary ion beams was Ar₇₀₀ and incident energy was 5.5 keV. Although the primary ion fluence exceeded the static SIMS limit, the molecular ion intensities from the polymer films remained constant, indicating that irradiation with large Ar cluster ion beams rarely leads to damage accumulation on the surface of the films, and this characteristic is excellently suitable for SIMS depth profiling of organic materials. Copyright © 2009 John Wiley & Sons, Ltd.     

偶氮苯聚合物膜的光致高密度存储及其三维微结构的研究

设计、合成及表征了一种偶氮苯聚合物(PGMAA-20)。研究了该偶氮苯聚合物薄膜中的高密度光学存储和三维微结构,并成功地将20套光栅储存在样品中同一个点上,储存密度是已报道的两倍;用简单的2波混频光路在该材料中刻写出长方格子和六角星型的微结构,在制作多重不同周期不同角度的高密度光栅结构的实验过程中,观察到不同周期光栅的刻写顺序对整个微结构形成的最终结果具有决定性的影响。     

Prediction of microclimate pH in poly(lactic-co-glycolic acid) films

An equilibrium mathematical model that accurately predicts microclimate pH (mupH) in thin biodegradable polymer films of poly(lactic-co-glycolic acid) (PLGA) is described. mupH kinetics was shown to be primarily a function of: (i) kinetics of water-soluble acid content and composition in the polymer matrix and (ii) polymer/water partition coefficient of water-soluble degradation products (P(i)). Polymers were coated on standard pH glass electrodes, and mupH was measured potentiometrically. Water-soluble acid distribution and content in PLGA films were determined by pre-derivatization HPLC. Polymer degradation products partitioned favorably in the polymer phase relative to water (P(i) range: approximately 6-100), and P(i) increased with increasing hydrophobicity of the acidic species according to a linear free energy law related to reversed phase HPLC retention time for the corresponding derivatized bromophenacyl esters. The mupH predicted by the model was in excellent agreement with experimental mupH for several PLGAs as a function of time and PLGA lactic/glycolic acid ratio. These data may be useful to slowly release pH-sensitive PLGA-encapsulated bioactive substances and provide a general framework for predicting partitioning behavior of degradation products in biodegradable polymers.     

辐射增强PP／BR共混体系的力学性能

研究了在多官能团单体－三烯丙基异氰酸酯存在下，共混体系聚丙烯／１．４－聚丁二烯橡胶的辐射效应，用ＤＳＣ，动态粘弹谱对其进行表征。结果显示，三烯丙基异氰酸酯主要分布于聚丙烯／１．４－聚丁二烯橡胶共混物的界面自高能射线作用下，被引发参与界面反应，从而改善了共混体系的相容性，增强也界面粘接，提高了共混物的力学性能。     

The Influence of Electrolyte Type on Kinetics of Redox Processes in the Polymer Films of Ni(II) Salen-Type Complexes

Electrodes modified with polymers derived from the complexes [Ni(salcn)], [Ni(salcn(Me))] and [Ni(salcn(Bu))] were obtained in order to study the kinetics of electrode processes occurring in polymer films, depending on the thickness of the films, the type of electrolyte and the solvent. FTIR and EQCM methods were used to determine the type of mass transported into polymer films during anode processes and the number of moles of ions and solvent. The rate of charge transport through films was determined by the cyclic voltammetry method, by the quantity cD^1/2. It was shown that the charge transport was determined by the transport of anions. The kinetics were most efficient for poly[Ni(salcn(Bu))] modified electrodes, obtained from TBAPF₆ and working in TBAClO₄ and TBABF₄. It was also shown that a solvent with a higher DN value and lower viscosity (MeCN) facilitated the transport of the charge through polymer films.     

The chemical effects of photo-oxidation on butadiene rubber

The photo-oxidation of butadiene rubber (BR) was studied in detail using films of a commercially available material, containing 33% cis-1,4-, 56% trans-1,4- and 12% 1,2-vinylic units. The spectral data of the products showed that during photo-oxidation the following functional organic groups are formed: hydroperoxides, alcohols, ketones, carboxylic acids and esters. ¹³C-NMR spectroscopic evidence for the formation of epoxides is presented. By comparison with spectra of model compounds, signals were assigned to ester and carboxylic acids in the allylic position of the oxidized polymer. The presence of ketones and carboxylic acids was also proved by chemical methods. It could be demonstrated that the formation of ketones, carboxylic acids and esters occurs from the photolysis of the OO bond of the hydroperoxides. Kinetic measurements with films containing benzophenone showed a strong increase in the quantum yield for the formation of products in comparison with the pure polymer sample. The opposite effect is observed with films containing the commercially used anti-oxidant, 2,6-di-t-butyl-p-hydroxytoluene. Also, the quantum yield for formation of the oxidation products decreases with increase in the light intensity. This result shows that cross-linking plays an important role in the photo-degradation of BR.