Cinnamoyl shell‐modified poly(amidoamine) dendrimers

Poly(amidoamine)(PAMAM) dendrimers with a cinnamoyl shell were prepared by reacting full generation PAMAM dendrimers (G=3.0) with 2‐chloroethanol and cinnamoyl chloride, which resulted in densely packed polymerizable unsaturated groups on the periphery. The cinnamoyl shell of the dendrimers dimerized when irradiated under a UV light by using 5‐nitroacenaphthylene as an initiator in dilute dimethylformamide (DMF). FTIR, ¹H NMR, UV‐Vis, SEC, and a viscosity test certified that the photocycloaddition of the cinnamoyl shell of the dendrimers took place within the molecules with the disappearance of double bond signals in the FTIR. ¹H NMR spectra as well as the intrinsic viscosity and polydispersity value of the products both before and after irradiation showed no difference. It was further found that the cinnamoyl shell‐modified dendrimers possessed fluorescence property, and the fluorescence intensity became stronger when the shell was photocyclized under UV‐ irradiation. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4147–4153, 2000     

UV‐induced crosslinking of ring opening metathesis block copolymer micelles

Statistical and amphiphilic block copolymers bearing cinnamoyl groups were prepared by ring opening metathesis polymerization (ROMP). The UV‐induced [2 + 2] cycloaddition reaction of polymer bound cinnamic acid groups was studied in polymer thin films as well as in block copolymer micelles. In both cases, exposure to UV‐light for 10 min led to a crosslinking conversion of about 60%, as determined by FT‐IR spectroscopy and UV–vis absorption measurements. Time based IR‐spectroscopy revealed a maximum conversion of 78% reached after an irradiation time of about 16 min. For micelles obtained from polymers bearing 5 mol % or more cinnamoyl groups, the crosslinking reaction proceeded smoothly, yielding in crosslinked particles which were stable in a non‐selective solvent (CHCl₃). Diameters determined by dynamic light scattering in the selective solvent (MeOH) were similar for both, non‐crosslinked and crosslinked micelles, whereas diameters of crosslinked micelles in the non‐selective solvent (CHCl₃) were significantly larger compared to MeOH samples. This strategy of direct self assembly of block‐copolymers in a selective solvent followed by “clean” crosslinking, without the need for additional crosslinking reagents or crosslinking initiators, provides a straight forward approach toward ROMP‐based polymeric nano‐particles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2402–2413, 2008     

Surface patterned graft copolymerization of hydrophilic monomers onto hydrophobic polymer film upon UV irradiation

A random copolymer [p(MMA/DMAB)] composed of methyl methacrylate (MMA) and 2,2‐dimethoxy‐1,2‐di(4‐methacryloyloxy)phenylethane‐1‐one (DMAB), which can simultaneously act as a photoradical initiator and crosslinkable monomer, was prepared by free radical random copolymerization. A hydrophobic film on quartz glass was prepared using p(MMA/DMAB) by a spin‐coating technique. Hydrophilic methacrylic acid (MA) and 2‐methacryloyloxyethyl phosphorylcholine (MPC) were graft‐copolymerized from the hydrophobic p(MMA/DMAB) film in water by photo‐cleavage of the DMAB unit. The graft copolymer of MA and MPC was characterized by infrared and X‐ray photoelectron spectroscopies and contact angle measurements. To confirm that MPC can be grafted onto the surface of the film selectively at only UV‐irradiated sites, photoinduced graft copolymerization of MPC using a photomask was performed to prepare a pMPC patterned p(MMA/DMAB) film. The film was stained using a rhodamine 6G dye that can absorb specifically to pMPC to confirm the pMPC pattern. The p(MMA/DMAB) film can be applied to various fields including photolithography and biomedical applications, because the film surface properties can be controlled using various vinyl monomers selectively on UV‐irradiated sites. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2822–2829     

Rollable ferroelectric liquid crystal devices monostabilized with molecularly aligned polymer walls and networks

This paper describes a flexible monostabilized ferroelectric liquid crystal (FLC) device using molecularly aligned polymer walls and networks, which are sequentially formed with a two-step photopolymerization-induced phase separation. When ultraviolet (UV) light was irradiated through a photomask onto a heated nematic phase solution of FLC and monomer, monomer molecules that had flowed into the irradiated areas were photopolymerized, and polymer walls aligned along the rubbing direction of the polyimide alignment layers on plastic film substrates were formed. After uniform UV irradiation without a photomask, polymer networks aligned along the rubbing direction were formed in the FLC. The FLC molecules were monostabilized in the rubbing direction by the strong anchoring of the polymer networks. The device, which was sandwiched between crossed polarizers, exhibited a monostable electro-optic characteristic with a high contrast ratio of over 100:1 and a response time of less than 1 ms. The FLC device exhibited spatially uniform operation even when it was rolled up with a radius of curvature of 1.5 cm.     

Micropatterning of Inorganic-Organic Hybrid Coating Films from Various Tri-Functional Silicon Alkoxides with a Double Bond in Their Organic Components

Inorganic-organic hybrid coating films were prepared from various trifunctional silicon alkoxides with a C=C double bond in their organic components, such as vinyltriethoxysilane (VTES), allyltriethoxysilane (ATES) or trimethoxysilylpropylmethacrylate (TMSPM), and zirconium n-tetrapropoxide modified with methacrylic acid. UV light from a high-pressure mercury lamp was irradiated through a photomask on the hybrid films, and this irradiation increased refractive index and microhardness of the films and decreased solubility of the films in alcohol or alkaline solution. IR spectra of the coating films have shown that C=C bonds in these trifunctional silicon alkoxides were polymerized with the UV irradiation. Patterns with a width of about 10 m and thickness of about 5–15 m were formed by the etching of unirradiated region of the films. Since VTES and ATES have a shorter organic chain than TMSPM, the hybrid films prepared from VTES or ATES are expected to show small optical loss in the near-infrared region due to C—H bonds in their use as waveguides.     

Photodecomposition of Chloroform Catalyzed by Unmodified MCM‐41 Mesoporous Silica

Unactivated MCM‐41 mesoporous silica catalyzes the photodecomposition of chloroform to phosgene and hydrogen chloride under near‐UV (λ > 360 nm) irradiation. The rate of photodecomposition increases toward an asymptotic limit as the O₂ partial pressure is increased. Deuterochloroform does not decompose under the same experimental conditions. Low concentrations of both cyclohexane and ethanol quench the photodecomposition, whereas water, up to its solubility limit, does not. Dissolved tetraalkylammonium salts suppress photodecomposition. The data are consistent with a mechanism in which light absorption by an SiO₂ defect yields an electron‐deficient oxygen atom, which then abstracts hydrogen from chloroform. The resulting CCl₃ radicals react with oxygen to form a peroxy radical that decomposes, eventually yielding phosgene and hydrogen chloride.     

Synthesis and properties of biodegradable copolymers based on 4,4′‐(adipoyldioxy)dicinnamic acid, 1,6‐hexanediol,and poly(ethylene glycol)s

4,4′‐(Adipoyldioxy)dicinnamic acid (CAC) was synthesized by a condensation of adipoyl chloride and 4‐hydroxycinnamic acid. The CAC6 copolymers were prepared by a high‐temperature solution polycondensation of a diacyl chloride of CAC, 1,6‐hexanediol (6), and poly(ethylene glycol) (PEG) in which the molecular weights of PEG are 1000, 2000, and 8300. Differential scanning calorimetric curves of the copolymers exhibited a glass‐transition temperature because of PEG moiety and two melting endotherms (T_m's); the one at the higher T_m was due to CAC6 moiety, and the other at the lower T_m was due to PEG moiety, suggesting that these copolymers are the block type. The incorporation of the PEG component decreased the tensile strength and initial modulus, but increased the elongation extremely. The enzymatic degradation was performed in phosphate buffer solution (pH 7.2) with Ps. cepacia lipase at 37 °C. The degradation rate of the copolymers increased significantly with an increasing content of PEG, which was correlated to the water absorption of the copolymers. All copolymers could undergo photocuring by ultraviolet (UV) light irradiation (λ > 280 nm) at ambient temperature, as examined by UV spectroscopy and solubility. The CAC6/E2000(50/50) film photocured for 3 min exhibited a good elastic property with a maximum tensile strength of 3.7 MPa and maximum elongation of 640%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2930–2938, 2003     

New conjugated polymers comprising ortho‐phenylazonaphthols: Synthesis and chromogenic behaviors

A new series of poly(ortho‐phenylazonaphthol) derivatives linked with a phenylene or fluorene repeat unit was synthesized using the Suzuki cross‐coupling reaction and characterized. The synthesized polymers can be categorized by their structures, with a free hydroxyl group and with a t‐Boc‐blocked hydroxyl group, which exhibited completely different UV‐vis absorption properties according to the allowed or forbidden tautomerism. In both cases, a pronounced color change to deep violet (bathochromic shift) was induced upon exposure to fluoride anion, presumably because of electron transfer between the hydroxyl group and the fluoride anion. Interestingly, the chromogenic pattern could be produced directly by UV irradiation through a photomask on the flexible nanofiber web electrospun from poly(methyl methacrylate) blended with t‐Boc‐protected Polymer 8 and photoinduced acid generator. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4430–4440, 2007     

Determination of Tetracycline at a UV‐Irradiated DNA Film Modified Glassy Carbon Electrode

In this study, interaction of tetracycline (TC) and DNA in the Britton? Robinson buffer solution (BR) was studied by cyclic voltammetry. The experimental results reveal that TC can bind strongly to DNA and the association constant and binding number between TC and DNA was obtained. Then DNA was immobilized on a glassy carbon electrode by UV‐irradiation. Through this process, water‐soluble DNA was converted into insoluble materials, and a stable DNA film was formed on the electrode. The electrochemical oxidation behavior of TC was studied at UV‐irradiated DNA film modified glassy carbon electrode (UV‐DNA‐GCE). The response of modified electrode was optimized with respect to pH, accumulation time, ionic strength, drug concentration and other variables. TC at the surface of modified electrode showed a linear dynamic range of 0.30–90.00 µM and a detection limit of 0.27 µM. To demonstrate the applicability of the modified electrode, it was used for the analysis of real samples such as pharmaceutical formulations and milk.     

Encapsulation of nanomaterials using an intermediary layer cross‐linkable ABC triblock copolymer

For the preparation of core‐shell nanoparticles containing functional nanomaterials, a photo‐cross‐linkable amphiphilic ABC triblock copolymer, poly(ethylene glycol)‐b‐poly(2‐cinnamoyloxyethyl methacrylate)‐b‐poly(methyl methacrylate) (PEG‐PCEMA‐PMMA), was synthesized. This triblock copolymer was then used to encapsulate Au nanoparticles or pyrene. The triblock copolymer of PEG‐b‐poly(2‐hydroxyethyl methacrylate)‐b‐PMMA (PEG‐PHEMA‐PMMA) (M_n = 15,800 g/mol, M_w/M_n = 1.58) was first synthesized by activators generated by electron transfer atom transfer radical polymerization. Its middle block was then functionalized with cinnamoyl chloride. The degrees of polymerization of the PEG, PHEMA, and PMMA blocks were 45, 13, and 98, respectively. PMMA‐tethered Au nanoparticles (with an average diameter of 3.0 nm) or pyrene was successfully encapsulated within the PEG‐PCEMA‐PMMA micelles. The intermediary layers of the micelles were then cross‐linked by UV irradiation. The spherical structures of the PEG‐PCEMA‐PMMA micelles containing Au nanoparticles or pyrene were not changed by the photo‐cross‐linking process and they showed excellent colloidal stability. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4963–4970, 2009     

Photoinduced liquid crystal alignment by layer-by-layer ultrathin films with dual photoreaction moieties

A novel layer-by-layer (LBL) film containing dual photoreaction groups, cinnamoyl and azobenzene, was prepared from poly(diallyldimethylammonium chloride) (PDDA) and a photosensitive polyanion, PCAzo, in aqueous solution via electrostatic attraction. The film was able to induce uniform alignment of liquid crystals (LCs) with good stability and 2.3° pretilt angle by oblique irradiation with linearly polarised ultraviolet light (LPUVL). UV absorption and FTIR spectroscopic results indicate that the photoreactions of the two photoreactive groups jointly participate in generating the anisotropy of the film. The dichroic ratio of the film was found to depend on the number of adsorbed layers. The thicker film has the larger dichroic ratio after the LPUVL irradiation. The reorientation behaviour of the LC molecules was found to be associated with the LBL film thickness. Experiment results revealed that the photo-crosslinking of the cinnamoyl groups was responsible for the stability of the anisotropic orientation, and the isomerisation of the azobenzene chromophores led primarily to the appropriate pretilt angle.     

Cinnamoyl Alginate Microspheres: Effect of UV-Treatment on Release of FITC-Dextran

Cinnamoyl alginate microspheres were prepared using the water droplets of W/O emulsions as a template. Cinnamoyl alginates having variable content of the cinnamoyl group were prepared by a condensation reaction. The photo-dimerization degree of the cinnamoyl group increased as the molar ratio of pyranose unit/cinnamoyl group increased from 1:0.043 to 1:0.18. The air/water interfacial activity of cinnamoyl alginate also increased with increasing the molar ratio. Aqueous solution of cinnamoyl alginate was dispersed in mineral oil to obtain W/O emulsion. UV light (254 nm, 6 W) was irradiated to the emulsion to dimerize the cinnamoyl groups, and CaCl₂ was added to the emulsion to cross-link the cinnamoyl alginate. The surface of UV-treated microspheres was rougher than that of UV-untreated microspheres, possibly due to the photo-dimerization-induced tension on the alginate chains. The release degrees for 24 hours of fluorescein isothiocyanate-dextran (FITC-dextran; MW 4000) from UV-treated microspheres were markedly higher than those from UV-untreated ones. This is possibly due to the intramolecular dimerization of cinnamoyl group. The UV irradiation-induced percentage increase in the maximum release degree was greater as the content of cinnamoyl group was higher.     

Synthesis,characterization, photo‐induced alignment,and surface orientation of poly(9,9‐dioctylfluorene‐alt‐azobenzene)s

Three types of bi‐functionalized copolymers ( P1FAz , P2FAz , and P3FAz ) with different numbers of fluorene units and an azobenzene unit were synthesized and characterized using UV–vis and polarized absorption spectroanalysis. The trans‐cis photoisomerization was conformed under 400 nm light irradiation for all copolymers in chloroform. However, in the film state, only the trans‐cis photoisomerization occurred by mono‐fluorene attached copolymer poly[(9,9‐di‐n‐octylfluorenyl‐2,7‐diyl)‐alt‐4,4′‐azobenzene)] ( P1FAz ). Photo‐induced alignment was achieved using the P1FAz film after irradiation with linear polarized 400 nm light and subsequent annealing at 60 °C. Surface orientation of a spin‐coating film of poly(9,9‐didodecylfluorene) ( F12 ) was achieved using the photo‐induced alignment layer of the P1FAz film after annealing at 90 °C. The photo‐induced alignment layer of P1FAz has potential application to the surface orientation technique for appropriate polymers, which will be useful for the fabrication of optoelectronics devices. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

In situ photochemical conversion from cinnamoyl‐functionalized liquid‐crystalline monomers to liquid‐crystalline dimers

Liquid‐crystalline (LC) monomers, which were functionalized with a cinnamoyl group on their extremity, were synthesized and irradiated with UV light in their LC phases. In the presence of a triplet sensitizer, most LC monomers were converted into the corresponding dimers, which were produced by the cycloaddition reaction of the cinnamoyl group. The photodimerization reaction could proceed while the LC phases were maintained, because the dimers showed LC phases whose temperature ranges were wider than those of the corresponding monomers. A ¹H NMR study of the LC dimers indicated that the cyclobutane unit dominantly had an anti‐head‐to‐head configuration, that is, δ‐truxinate. As the LC monomers, which had a phenyl biphenyl‐4‐carboxylate moiety as a mesogen, showed smectic A phases and the corresponding dimers also exhibited smectic A phases, we estimated the smectic layer distances by X‐ray diffraction analysis and found that the dimers adopted the structure in which the two mesogens aligned laterally and existed in the same smectic layer in the LC phases.     

Synthesis and characterization of negative‐type photosensitive hyperbranched polyimides with excellent organosolubility from an A2 + B3 monomer system

A series of photosensitive hyperbranched polyimides (HB‐PIs) were prepared through facile end‐group modifications of the fully imidized polymer. A triamine, 1,3,5‐tris(4‐aminophenoxy)benzene, and a dianhydride, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, were condensed with a dropwise addition method in a molar ratio of 1/2 to afford an anhydride‐terminated poly(amic acid) precursor, which was then end‐capped by 4‐aminophenol and chemically imidized to yield a phenol‐terminated HB‐PI. The modifications of the terminal phenol groups of the polyimide by acyl chloride compounds (acryloyl chloride, methylacryloyl chloride, and cinnamoyl chloride) gave the target polymers. The photosensitive HB‐PIs showed good thermal properties and excellent solubility even in low‐boiling‐point solvents at room temperature, such as acetone, 1,1,2‐trichloroethane, tetrahydrofuran, and chloroform. Photosensitive property studies revealed good photolithographic properties with a resolution greater than 3 μm and a sensitivity of 650–680 mJ/cm². © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1735–1744, 2004     

Formation and dichroism of poly(vinyl alcohol)–iodine complex in photocurable film

The formation of polyiodine complexes was investigated in a photocurable poly(vinyl alcohol) modified N‐methyl‐4(4′‐formylstyryl)pyridinium methosulfate acetal (PVA‐SbQ), which is a photofunctional group that causes photodimerization. PVA‐SbQ films with polyiodine complexes were prepared to be photocured, iodinated and soaked in a boric acid solution. The formation of PVA–polyiodine complexes was studied during iodinating and while in the boric acid treatment through UV–vis absorption spectrometry, resonance Raman spectrometry and IR absorption spectrometry. As a result, polyiodines were formed in the photocurable PVA‐SbQ films, and the formation of PVA–polyiodine complexes was enhanced by boric acid treatment. It was found that the SbQ‐ratio of PVA‐SbQ affects the formation of PVA–polyiodine complexes. The photocrosslinking by the dimerization of SbQ groups helps to form the PVA–I₅⁻ complex during the boric acid treatment. Based on this effect, we demonstrated a unique recording method by the PVA–polyiodine complex formation. The PVA‐SbQ film cured by the irradiation of the liner polarized light showed that dichroism of the PVA–polyiodine complexes formed after iodination. Copyright © 2015 John Wiley & Sons, Ltd.     

Patterning of cells on a PVC film surface functionalized by ion irradiation

Micropatterns of cells on a poly(vinyl chloride) (PVC) film surface were created by using ion irradiation. A PVC film was irradiated with H⁺ ions through a pattern mask in order to create patterns of the hydrophilic/hydrophobic regions on the PVC surface. The effect of ion irradiation on the surface properties of the PVC film was characterized by using Fourier transform‐infrared spectroscopy (FT‐IR), water contact angle measurement, and X‐ray photoelectron spectroscopy (XPS). The results revealed that the chemical environment of the PVC film surface was effectively changed by ion irradiation due to dehydrochlorination and oxidation. The in vitro cell culture on the patterned PVC film surface showed selective adhesion and proliferation of the cells on the ion‐irradiated regions. Well‐defined 50 µm patterns of the cells were obtained on the PVC film surface irradiated to 1 × 10¹⁵ ions/cm². Copyright © 2009 John Wiley & Sons, Ltd.     

Degradation of polymer coating systems studied by positron annihilation spectroscopy. IV. Oxygen effect of UV irradiation

The effect of oxygen on the photodegradation of a polyurethane coating induced by accelerated UV irradiation was studied with two different light sources: 313‐nm UVB and Xe lamps. Doppler‐broadened energy spectra (DBES) and positron annihilation lifetimes were measured as a function of incident positron energy (0–30 keV) and irradiation time (0–100 h). The photodegradation of the coating was characterized in terms of subnanometer defect changes. Significant variations of the S parameter (a defect parameter from DBES) and the ortho‐positronium lifetime and intensity were observed as a function of oxygen concentration during exposure to UV irradiation. These results showed a significant enhancement in photodegradation due to the presence of oxygen, as indicated by a decrease in free volume and holes at the atomic level. Enhanced degradation in the presence of oxygen, as indicated by increased free‐radical production (observed with electron spin resonance spectroscopy), was also observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2035–2047, 2001     

Interfacial Rheological Property and Rheokinetics of a Novel Photoreversible Micellar System

A new photorheologically reversible micelle composed of a polymerizable cationic surfactant N-cetyl dimethylallyl ammonium chloride (CDAAC) and trans-4-phenylazo benzoic acid (trans-ACA) was prepared. Exposing the CDAAC/trans-ACA (14 mM/10 mM) micellar system to the UV light (365 nm) resulted in a decrease in the relative viscosity, and in turn, the relative viscosity increases to its initial value when the micellar system was exposed to visible light (460 nm), which is caused by the photoisomerization of ACA. The interfacial tension and modulus of the micellar system change significantly after UV irradiation and show the reversible interfacial rheological properties when irradiated by visible light. Furthermore, for the first time the dynamic changing of the rheological properties, i.e., the decreasing of viscosity and viscoelasticity during the UV irradiation, has been studied and well described by a rheokinetics model.     

Pyrogallic acid‐PLGA conjugate as new biodegradable material suitable for final sterilization by irradiation

This paper reports the feasibility to prepare a biodegradable material stable to γ‐irradiation by grafting of poly(lactide‐co‐glycolide) with pyrogallic acid (PLGA‐g‐PA) and ferulic acid (PLGA‐g‐FA) in mild condition. Only the grafting procedure with PA did not modify molecular weight (Mw) of the starting polymer and PLGA‐g‐PA showed antioxidant properties. The polymer degradation in pH 7.4 phosphate buffer saline (PBS) was mainly governed by a random chain scission mechanism according to a first‐order reaction. The irradiation at the dose of 25 kGy caused only a very slight decrease of Mw and the degradation patterns of the non‐irradiated and irradiated material were superimposable. PLGA‐g‐PA resulted a promising material to develop biodegradable drug delivery systems which would be sterilizable in the final container. Copyright © 2010 John Wiley & Sons, Ltd.