Effect of halogen substitution on azo-naphthol dye based poly(alkyloxymethacrylate)s and their Z-scan measurements

A series of photo addressable polymers bearing azo-naphthol moiety in the polymer side chain containing polymethacrylate backbone were synthesized for NLO applications. Various halogen atoms were substituted in the para position of the side chain azobenzene, and the effects of the substituents were investigated. The polymers were characterized by UV, FT-IR, ¹H-NMR and ¹³C-NMR spectroscopy. The photoisomerization property of all the polymers shows a clear dependence on the size of the halogen, indicating the rate of the switching time in the increasing order of F > Cl > Br > I. The glass transition temperature and thermal stability of the polymers were analyzed by DSC and TGA respectively. The third order nonlinear optical properties of the polymer film were measured by the Z-scan technique using Ar-ion laser and exhibited negative optical nonlinearity. The results revealed that these polymers possess potential applications in nonlinear optics and the value of nonlinear susceptibility for the iodine substituted polymer is higher than the other halogen substituted polymers chosen in the study.     

Holographic grating studies in pendant xanthene dyes containing poly(alkyloxymethacrylate)s

A series of xanthene dyes based poly(alkyloxymethacrylate)s were synthesized with even number of side-chain methylene spacers by free radical addition polymerization method for holographic grating studies. Chemical structure of monomers and polymers were confirmed by FTIR and ¹H-NMR spectroscopy. Thermal property was investigated by TGA and DSC. Lengthy spacers favor improved optical quality film formation than shorter spacer length containing polymers; however, thermal stability and Tm decreased. Absorption and emission spectra have been studied in different polar solvents. UV–vis absorption maxima were broad and red-shifted with increasing spacer length. Life-time decay analysis exhibited double exponential decay. Polymer films were tested for holographic grating formation and their diffraction efficiency compared. Photo bleaching mechanism of polymer films was disclosed by measuring electrochemical potential value.     

Biomolecular optical data storage and data encryption

The use of bacteriorhodopsin (BR) as an active layer in write-once-read-many optical storage is presented. This novel feature of BR materials may be used on a wide variety of substrates, among them transparent substrates but also paper and plastics. The physical basis of the recording process is polarization-sensitive two-photon absorption. As an example for this new BR application, an identification card equipped with an optical recording strip is presented, which has a capacity of about 1 MB of data. The recording density currently used is 125 kB/cm/sup 2/, which is far from the optical limits but allows operation with cheap terminals using plastic optics. In the examples given, data are stored in blocks of 10 kB each. A special optical encryption procedure allows the stored data to be protected from unauthorized reading. The molecular basis of this property is again the polarization-sensitive recording mechanism. The unique combination of optical storage, photochromism, and traceability of the BR material is combined on the single-molecule level. BR introduces a new quality of storage capability for applications with increased security and anticounterfeiting requirements.     

Large two-beam coupling effect in poly(methylmethacrylate) doped with hemicyanine dye

Unexpected asymmetric energy exchange (two-beam coupling) between two writing beams in two-wave mixing experiments was observed in poly(methylmethacrylate) doped with hemicyanine dye. It was found that photobleaching of hemicyanine dyes was responsible for the formation of refractive index gratings. Instability of the laser-based optical system could be the cause of the phase shift between the interference pattern of the writing beams and the refractive index gratings, such a phase shift being a necessary condition for the two-beam coupling.     

Poly(etherimide)s and poly(esterimide)s containing azobenzene units: Characterization and study of photoinduced optical anisotropy

In this paper novel processable, photoresponsible aromatic polymers with imide rings and covalently boned azobenzene units are presented. Prepolymerization strategy based on polycondensation of two diamines with azobenzene group, that is, 2,4-diamino-4′-cyanoazobenzne and 2,4-diamino-4′-nitroazobenzene and two dianhydrides, was utilized for preparation of the new photochromic polyimides. The obtained polymers differ in the chemical structure of polymer backbone and the kind of substituents on azobenzene moieties. Polymers were characterized and evaluated by FT-IR, ¹H NMR, X-ray, UV-vis, DSC, and TGA methods. The synthesized azopolymers exhibited glass transition temperatures in the range of 140-170 °C, thermal stability with initial decomposition temperatures (T_d) in the range of 266-290 °C, and excellent solubilities in common organic solvents, providing optical-quality films. The light-induced optical anisotropy was studied in obtained polymers by photoinduced birefringence measurements. The birefringence was generated by the femtosecond pulses at 400 nm via a linear absorption of the trans-azobenzene. A large light-induced birefringence (Δn = 0.02) was achieved in poly(esterimide)s contrary to poly(etherimide)s. The birefringence exhibited a very stable behavior after switching off the writing light indicating a permanent storage capacity.     

Polymeric nanomedicines based on poly(lactide) and poly(lactide-co-glycolide)

Small molecule chemotherapeutics often have undesired physiochemical and pharmacological properties, such as low solubility, severe side effect and narrow therapeutic index. To address these challenges, polymeric nanomedicine drug delivery technology has been routinely employed, in particular with the use of biodegradable and biocompatible polyesters, such as poly(lactide) (PLA) and poly(lactide-co-glycolide) (PLGA). Here we review the development and use of PLA and PLGA for the delivery of chemotherapeutic agents in the forms of polymer–drug conjugates and nanoconjugates.     

Solvent dependent triphenylamine based D-(pi-A)n type dye molecules and optical properties

D-(pi-A)n type dyes of triphenylamine derivatives were synthesized and their absorption and luminescence in different solvents were examined to investigate solvent dependent properties observed for their emissions in solvents with different dielectric constants. The emission wavelengths showed a dramatic blue shift with increasing solvent polarity. The results of molecular orbital calculations by computer simulation, based on Material Studio suite of programs, were found to reasonably account for the spectral properties. Relative levels of HOMO and LUMO were measured and calculated and all derivatives exhibited strong solid fluorescence with distinctively different FWHMs.     

光致变色材料及其在光存储中的应用

介绍了光致变色原理及各类无机、有机光致变色材料,并就其在双光子、多波长、超分辨光存储中的应用进行了讨论.     

Chalcogenide glasses as prospective materials for optical memories and optical data storage

This paper first reviews recent progress in the understanding of the nanometer-scale mechanism of reversible photostructural changes in chalcogenide glasses, and its relevance to various photo-induced phenomena. Then the principles of phase-change optical recording are described. Finally, a novel technique for overcoming the diffraction limit in optical recording is considered, namely the super-resolution near-field structure. This technique, used in combination with multicomponent Te-based chalcogenides as a recording medium, is believed to be a prototype for future optical-storage devices.     

Effect of dye doping in poly(vinyl alcohol) waveguides

Dye-doped poly(vinyl alcohol) (PVA) waveguides have been fabricated and characterized. The waveguiding parameters of PVA film, for example the refractive index, thickness, birefringence, polarization conversion and propagation losses, were evaluated using the various concentration of dyes in polymeric solution. It has been shown that the dyes can affect the basic waveguiding parameters considerably. However, birefringence in PVA waveguides remains unaffected irrespective of any dyes and any concentration of dye used.     

Soft X-ray image storage in poly (methylmethacrylate)

Images stored in resist for soft X-ray lithography or microradiography were found to show a background noise which limits the resolution. This is due to the statistically variable spatial distribution of the photons incident on the resist surface. An estimate of the fundamental noise-limited resolution has been made from the experimental measurement of photon flux incident on the surface and the accurate development rate curves. Monochromatic radiation from a synchrotron source was used.     

Electrospinning of novel biodegradable poly(ester urethane)s and poly(ester urethane urea)s for soft tissue-engineering applications

The development of biomimetic highly-porous scaffolds is essential for successful tissue engineering. Segmented poly(ester urethane)s and poly(ester urethane urea)s have been infrequently used for the fabrication of electrospun nanofibrous tissues, which is surprising because these polymers represent a very large variety of materials with tailored properties. This study reports the preparation of new electrospun elastomeric polyurethane scaffolds. Two novel segmented polyurethanes (SPU), synthesized from poly(ε-caprolactone) diol, 1,6-hexamethylene diisocyanate, and diester-diphenol or diurea-diol chain extenders, were used (Caracciolo et al. in J Mater Sci Mater Med 20:145–155, 2009). The spinnability and the morphology of the electrospun SPU scaffolds were investigated and discussed. The electrospinning parameters such as solution properties (polymer concentration and solvent) and processing parameters (applied electric field, needle to collector distance and solution flow rate) were optimized to achieve smooth, uniform bead-free fibers with diameter (~700 nm) mimicking the protein fibers of native extracellular matrix (ECM). The obtained elastomeric polyurethane scaffolds could be appropriate for soft tissue-engineering applications.     

Solution properties of poly(decylmethacrylate)s

Samples of poly(decylmethacrylate)s (PDMA) of a narrow molecular weight distribution were characterized by means of light-scattering, osmotic pressure, intrinsic viscosity and gelpermeation chromatography. The Kuhn-Mark-Houwink equation for molecularly uniform PDMA in THF at 25°C was calculated to be log [η] (ml/g) = ?2.67 + 0.80 logM (g/mol). The following Θ-solvents were found: 2-propanol, 2-propylacetate, 1-butanol and 1-pentanol. The molecular weight dependence of the demixing behaviour yields a Θ-temperature of 9.6°C for 1-pentanol and of 37.4°C for 1-butanol. Flow curves were measured in various solvents of different thermodynamic quality. A first valuation of the observed non-Newtonian behaviour is given.     

Hot-press molded poly(methyl methacrylate) matrix for solid-state dye lasers

A hot-press molding method was used to fabricate dye-doped poly(methyl methacrylate) (PMMA) slabs. Three rhodamine dyes, Rh640 (ClO(4)), Rh6G(ClO(4)), and Rh6G (Cl), were impregnated into the PMMA matrix first by dissolving the dye and granular PMMA in a solvent mixture of chloroform and methanol and then heating the mixture in vacuo at 175 degrees C to obtain a spongy preform. The powdered preform was molded into slabs at 175 degrees C and at <1 mbar, to eliminate the formation of bubbles in the slabs. We annealed the slabs for several hours to improve its optical homogeneity and hence its lasing efficiency. When pumped by a 1.5-mJ nitrogen laser, we obtained peak lasing efficiencies of 8% and 7.8%, respectively, for Rh6G (ClO(4)) and Rh640 (ClO(4)) in PMMA matrices. The lasing efficiency of Rh6G (ClO(4))-doped PMMA suffered a reduction rate of 0.012%/shot compared with 0.15%/shot for Rh640 (ClO(4))-doped PMMA. In contrast, Rh6G (Cl) in a hot-press molded PMMA slab suffered thermal bleaching that resulted in a low lasing efficiency of <1%; this can be explained by its absorption and fluorescence characteristics.     

Synthesis and characterization of polyester copolymers based on poly(butylene succinate) and poly(ethylene glycol)

A series of polyester copolymers was synthesized from 1,4-succinic acid with 1,4-butanediol and poly(ethylene glycol) through a two-step process of esterification and polycondensation in this article. The composition and physical properties of copolyesters were investigated via GPC, ¹HNMR, DSC and PLM. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T_m), crystallization temperature (T_c), and crystallinity (X_c) of these copolyesters decreased gradually as the content of PEG unit increased. Otherwise, experimental results also showed that the contents of PEG in copolymers had an effect on the molecular weight, distribution, thermal properties, hydrolysis degradation properties, and crystalline morphology of polyester copolymers.     

The surface characteristics of organoclays and their effect on the properties of poly(trimethylene terephthalate) nanocomposites

Biobased materials developed in conjunction with nanotechnology are poised to achieve a significant presence in the world market for polymeric materials. An example of an engineering polymer that can be partially derived from biomass is poly(trimethylene terephthalate). One of its raw materials, 1,3-propanediol, can be derived from corn sugar. In the present study we used a fully petroleum-based resin as an analog to the biobased material. Five organically modified montmorillonite clays were characterized via moisture uptake studies to determine the hydrophilic/hydrophobic nature of their surfaces. Nanocomposites were produced via melt compounding followed by injection molding with 5 wt.% organoclay loading to determine which modification gave the best balance of mechanical and thermal properties. It was found that the tensile modulus increased by up to 35% and the tensile stress at break by up to 50%. The heat deflection temperature of the nanocomposites versus the neat polymer increased by up to 33 °C. From these results, one organoclay was selected for detailed study over a loading range of 0–5 wt.%. The testing revealed that over this range, changes in the mechanical properties may go through a maximum (e.g. strength) or increase/decrease to a plateau (e.g. modulus, elongation at break). X-ray diffraction and transmission electron microscopy were also used to characterize the nature of the organoclay/polymer interaction. Biobased poly(trimethylene terephthalate)/organoclay nanocomposites are expected to exhibit properties similar to the petroleum-based resin.     

Phase-to-amplitude data page conversion for holographic storage and optical encryption

A new phase-to-amplitude data page conversion method is proposed for efficient recovery of the data encoded in phase-modulated data pages used in holographic storage and optical encryption. The method is based on the interference between the data page and its copy shifted by an integral number of pixels. Key properties such as Fourier plane homogeneity, bit error rate, and positioning tolerances are investigated by computer modeling, and a comparison is provided with amplitude-modulated data page holographic storage with and without static phase masks. The feasibility and the basic properties of the proposed method are experimentally demonstrated. The results show that phase-modulated data pages can be used efficiently with reduced system complexity.