Study on the difference of photochromic and thermochromic mechanism of ethylenediamine trimolybdate

Ethylenediamine trimolybdate ((C2H10N2)[Mo3O10], denoted as ENTMo) shows unusual photochromic and thermochromic properties. The color of the white ENTMo compounds becomes reddish brown gradually under UV irradiation, and changes gradually to blue-black upon annealing. XRD patterns and FT-IR spectra verify that the crystal structure of the colored samples is almost unchanged except distortion. UV-vis diffuse reflectance spectra (DRS) and ESR spectra of the photochromic and the thermochromic samples could confirm that there must exist difference between thermochromic and photochromic mechanism.

Luminescent self-assembled thin films based on rare earth-heteropolytungstate

earth (Eu3+, Dy3+)-heteropolytungstate thin films were fabricated by self-assembly method successfully. The thin films give off strong fluorescence, which can be observed by eyes upon UV irradiation. The characteristic emission behaviors of the rare earth ions in self-assembled thin film were investigated compared with those of the corresponding solids. It is noticed that the intensity ratio between D-5(0) --> F-7(2) and D-5(0) --> F-7(1) of Eu3+ and the intensity ratio between F-4(9/2) --> H-6(13/2) and F-4(9/2) --> H-6(15/2) of Dy3+ in the self-assembled films are different from those of the corresponding solids. Furthermore, the self-assembled films present shorter fluorescence lifetimes than the corresponding solids. The reasons for these results have been discussed.

Novel indigo light emitting long-lasting phosphors CdSiO3: RE3+ (RE = Y, La, Gd, Lu)

A series of novel indigo light emitting long-lasting phosphors CdSiO3: RE3+ (RE = Y, La, Gd, Lu) was prepared by the conventional high-temperature solid-state method. The XRD, photoluminescence (PL) spectra and afterglow intensity decay were used to characterize the synthesized phosphors. These phosphors emitted indigo light and showed long-lasting phosphorescence. The phosphorescence can be seen with the naked eye in the dark clearly even after the 254-nm UV irradiation have been removed for more than 30 min.

Study on highly ordered luminescent Langmuir-Blodgett films of heteropolytung state complexes containing lanthanide

Luminescent thin films of heteropolytungstate complexes containing lanthanide (europium or samarium) were successfully fabricated by the Langmuir-Blodgett (LB) technique. The pressure-area isotherm of the monolayer of dimethyldioctadecylammonium. bromide (DODA) is modified rather markedly when the subphase contains the complex of Na9EuW10O36 or Na9SmW10O36. The above results indicate that the monolayer of DODA has a strong interaction with the polyanions of EuW10O369-. (or SmW10O369-). X-ray photoelectron spectra and fluorescent spectra verify that europium and tungsten atoms are 36 36 incorporated into the LB films. Ultraviolet (UV), fluorescent spectra and low-angle X-ray diffraction experiments demonstrate that these LB films have a well-defined lamellar structure. The LB film containing EuW10O369- can give off strong fluorescence 16 on UV irradiation. The characteristic emission behaviors of europium ions in LB films and in the powder of Na9EuW10O369- are discussed. It is found that the intensity ratio of the D-5(0)-F-7(2) transition to the D-5(0)-->F-7(1) transition in LB film is quite different from that in the powder of Na9EuW10O36. The difference of the ratio indicates that the site symmetry of europiurn is distorted in LB film, which is probably due to the strong electrostatic interactions between DODA and polyanions.

Preparation and luminescence properties of the mesoporous MCM-41s intercalated with rare earth complex

Rare earth complex Eu(DBM)(3)phen (DBM: dibenzoylmethane, phen: 1.10-phenanthroline) hits been incorporated into unmodified MCM-41 and modified MCM-41s by aminopropyltriethoxysilane (APTES) or N-[(3-triethoxysilyl)propyl]ethylenediamine(TEPED). Thus, the assemblies of unmodified or modified MCM-41s with rare earth (RE) complex have been obtained. XRD spectra. NMR spectra. diffuse reflectance spectra. and the luminescence spectra were used to characterize the pure RE complex and the corresponding assemblies. The assemblies have better luminescence properties under UV irradiation. and their fluorescence lifetimes on the excited state are longer than that of the corresponding pure complex. The possible mechanisms are also discussed in the context.

Covalently attached multilayer assemblies containing photoreactive diazo-resins and conducting polyaniline

We reported on the multilayer architecture containing diazo-resins (DAR) as polycations and polyaniline poly(aniline-co-N-propanesulfonic acid aniline) (PAPSAH) as polyanions held together by electrostatic interaction. Upon UV irradiation, the adjacent interfaces of the multilayer reacted to form a covalently crosslinking structure which greatly improved the stability of the films as confirmed by solvent etching experiments. These changes were confirmed by UV-Vis and FTIR spectroscopy. The thickness of the covalently attached films were characterized with small angle X-ray diffraction (SAXD) and a value of 30.0 Angstrom per bilayer was obtained. This type of film was further characterized by cyclic voltammetry which showed that the electroactive property of PAPSAH was still kept in the films after photoreaction. (C) 2000 Elsevier Science B.V. All rights reserved.

Effect of crosslinking distribution on gas permeability and permselectivity of crosslinked polyimides

Crosslinking modification of polyimide, prepared from 3,3'4,4'-benzophenone tetracarboxyl dianhydride (BTDA) and 2,3,5,6-tetramethyl-1,4-diphenylenediamine (4MPDA), was performed by two methods, putting the polyimide in ambient environment for 4 months, and under UV irradiation for 2 or 8 h. The gas permeation properties of the crosslinked polyimides were investigated. The crosslinked polyimides induced by UV irradiation, in which crosslinking occurs in the surface layer, are of much higher gas permselectivity of hydrogen to nitrogen than that induced by the ambient environment, in which crosslinking takes place in the whole matrix, but their gas permeabilities for hydrogen are similar. (C) 1999 Elsevier Science Ltd. All rights reserved.

Main-chain photosensitive polyamic acids using alkaline aqueous solution as developer

In order to develop photosensitive polyimides (PSPIs) imaged in alkaline aqueous solution, a photosensitive diamine and relevant polymer containing conjugated double bonds in the main chain have been synthesized. The photosensitive characteristics and thermal stability of the polymers were investigated. These polymers possess good thermal stability and sensitivity to UV irradiation, and could be used to form a PSPI resist using alkaline aqueous solution as developer. (C) 1999 Society of Chemical Industry.

GAS PERMEABILITIES AND PERMSELECTIVITY OF PHOTOCHEMICALLY CROSS-LINKED POLYIMIDES

Photosensitive polyimide BTDA-3MPDA was modified by UV irradiation. The structure of UV-irradiated polyimides was investigated by FTIR and gel fraction measurements. The results showed that longer UV exposure time resulted in a higher extent of crosslinking. The gas permeabilities of hydrogen, oxygen and nitrogen through UV-irradiated polyimides were characterized in a temperature range from 30 degrees C to 90 degrees C. Photocrosslinking resulted in a sharp decline in gas permeability for hydrogen, oxygen, and nitrogen through polyimide in the initial stage of photocrosslinking. Then, as the crosslinked benzophenone percentage amounted to 28-38% for hydrogen, 17-31% for oxygen and 3-28% for nitrogen, the gas permeabilities showed another sharp decline. Gas permselectivity increased significantly with the progress of photocrosslinking, and it can be adjusted in a wide range by controlling the extent of crosslinking. Arrhenius plots of gas permeability for hydrogen and oxygen through UV-irradiated polyimides are straight lines; for nitrogen, however, change in the slope of the straight line is observed and activation energies for hydrogen and oxygen permeation show abrupt increases when crosslinked benzophenone percentage amounts to about 30%. UV-irradiated polyimides with simultaneous high gas permeability and permselectivity make them ideal candidate materials for gas separation. (C) 1995 John Wiley & Sons, Inc.

SYNTHESIS AND PHOTOCHROMISM IN SOLUTION OF PHENOXYNAPHTHACENEQUINONE DERIVATIVES

Two new phenoxynaphthacenequinone derivatives, 6-[4-(2-(4-hydroxyphenyl)isopropyl)phenoxy] -5,12-naphthacenequinone (7) and 6-[4-(potassium sulfophenylazo)phenoxy]-5,12-naphthacenequinone (8), were synthesized, and their photochromism in solution was investigated and compared with that of 6-phenoxy-5,12-naphthacenequinone (1). On the basis of the spectral data and the selective irreversible reaction of ammonia with the colored phenoxy-ana-naphthacenequinone, the concentrations of the ana forms at the photostationary state (PSS), achieved by 365 nm UV irradiation, and the molar extinction coefficients of the pure ana forms at 481-482 nm of compounds 1, 7 and 8 in dimethylsulfoxide (DMSO) were found to be 83 mol.% and 1.70x10(4) mol(-1) dm(3) cm(-1), 82 mol.% and 1.62x10(4) mol(-1) dm(3) cm(-1) and 16 mol.% and approximately 1.34x10(4) mol(-1) dm(3) cm(-1) respectively; the absorption spectra of the colored ana forms of 7 and 1 in DMSO were estimated; the rate;constants of photoconversion induced by 365 nm light were obtained. The results show the strong effect of the structure of the phenoxynaphthacenequinones on their photochromism in solution. In addition to DMSO solution, compound 7 exhibited normal photochromism in toluene, benzene, chloroform and a DMSO-ethanol mixed solvent, but not in dimethylformamide (DMF) in which a photoinduced reaction occurred between 7 and DMF or impurities.

Comparative analysis of astaxanthin and its esters in the mutant E1 of Haematococcus pluvialis and other green algae by HPLC with a C30 column

A gradient reversed-phase high-performance liquid chromatography (HPLC) method using a C30 column was developed for the simultaneous determination of astaxanthin, astaxanthin monoesters and astaxanthin diesters in the green algae Chlorococcum sp., Chlorella zofingiensis, Haematococcus pluvialis and the mutant E1, which was obtained from the mutagenesis of H. pluvialis by exposure to UV-irradiation and ethyl methanesulphonate (EMS) with subsequent screening using nicotine. The results showed that the contents of total astaxanthins including free astaxanthin and astaxanthin esters ranged from 1.4 to 30.9 mg/g dry biomass in these green algae. The lower total astaxanthin levels (< 2 mg/g dry biomass) were detected in the green algae Chlorococcum sp. and C. zofingiensis. The higher total astaxanthin levels (> 16 mg/g dry biomass) were found in the green alga H. pluvialis and its mutant E1. It is notable that the mutant E1 is found to have considerably higher amounts of total astaxanthin (30.9 mg/g) as compared to the wild strain of H. pluvialis (16.1 mg/g). This indicates that UV-irradiation and EMS compound mutagenesis with subsequent screening using nicotine is an effective method for breeding of a high-producing astaxanthin strain of H. pluvialis. In addition, the green alga C. zofingiensis had a remarkably higher percentage of astaxanthin diesters (76.3% of total astaxanthins) and a remarkably lower percentage of astaxanthin monoesters (18.0% of total astaxanthins) in comparison with H. pluvialis (35.5% for diesters and 60.9% for monoesters), the mutant E1 (49.1% and 48.1%) and Chlorococcum sp. (18.0% and 58.6%).

Induction of diploid gynogenesis in turbot Scophthalmus maximus with left-eyed flounder Paralichthys olivaceus sperm

Turbot Scophthalmus maximus exhibits sexually dimorphic growth, with females growing faster and reaching larger adult sizes than males. Thus, development of techniques for preferentially producing females is necessary to optimize production of these species. In this paper, gynogenetic diploids of turbot were induced by activating egg development with ultraviolet (UV)-irradiated left-eyed flounder Paralichthys olivaceus sperm combined with cold shock to prevent extrusion of the second polar body. The results of UV irradiation experiments showed that survival, motility, and duration of activity of P. olivaceus sperm generally decreased with increase in UV dose. The typical Hertwig's effect was observed after fertilized turbot eggs with UV-irradiated P. olivaceus sperm and the optimal UV dose for gynogenetic haploid production was 36,000 erg mm(-2). At 15 degrees C, appropriate timing of cold shock for retention of the second polar body in turbot eggs was at 6 min after fertilization. Results of different combinations of two shock temperatures (1 or 3 degrees C) and four shock durations (15, 25, 35 or 45 min) at 6 min after fertilization demonstrated that shock of 25 min at 1 degrees C gave the highest production of diploid gynogens (39.58% relative to its diploid control). The results of this study reveal that the use of UV-irradiated P. olivaceus sperm for activation of turbot eggs and cold shock for polar body retention is an effective method to produce gynogenetic offspring.

Strain H-2-419-4 of Haematococcus pluvialis induced by ethyl methanesulphonate and ultraviolet radiation

Two strains H-2-410 and H-2-419 were obtained from the chemically mutated survivors of wild Haematococcus pluvialis 2 by using ethyl methanesulphonate (EMS). Strains H2-410 and H2-419 showed a fast cell growth with 13% and 20% increase in biomass compared to wild type, respectively. Then H-2-419-4, a fast cell growth and high astaxanthin accumulation strain, was obtained by exposing the strain H2-419 to ultraviolet radiation (UV) further. The total biomass, the astaxanthin content per cell, astaxanthin production of H-2-4194 showed 68%, 28%, and 120% increase compared to wild H. pluvialis 2, respectively. HPLC (High Performance Liquid Chromatography) data showed also an obvious proportional variation of different carotenoid compositions in the extracts of H2-4194 and the wild type, although no peak of carotenoids appeared or disappeared. Therefore, the main compositions in strain H-2-419-4, like its wild one, were free of astaxanthin, monoester, and diester of astaxanthin. The asexual reproduction in survivors after exposed to UV was not synchronous, and different from the normal synchronous asexual reproduction as the mother cells were motile instead of non-motile. Interestingly, some survivors from UV irradiation produced many mini-spores (or gamete?), the spores moved away from the mother cell gradually 4 or 5 days later. This is quite similar to sexual reproduction described by Elliot in 1934. However, whether this was sexual reproduction remains questionable, as no mating process has been observed.

Effect of nano-TiO(2)on MP-25 resin

MP-25 resin is a chlorine-containing polymer widely used in coatings. The effects of two types of nano-TiO2 (P-25 and RM301 LP) on MP-25 were studied with saline immersion, UV irradiation, and electrochemical impedance spectroscopy. UV irradiation was evaluated in terms of gloss change and X-ray photoelectron spectroscopy (XPS). The results indicate that, compared to pigment R-930 TiO2, P-25 reduced the immersion resistance and accelerated UV aging of the MP-25 coating, whereas RM301 LP showed the opposite effects. XPS analysis showed that MP-25 resin degraded under UV irradiation via dechlorination and C-C bond breakage, similarly to poly(vinyl chloride), but RM301 LP could inhibit the aging of MP-25 to a certain extent. A skin effect of oxygen and chlorine was identified in MP-25 resin by XPS. RM301 LP could improve the impedance of the MP-25 coating because of its excellent fill capacity. Hence, rutile nano-TiO2 RM301 LP represents an excellent additive for MP-25 resin. (c) 2007 Wiley Periodicals, Inc.

Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid

To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction pathways can be established; i.e., SiH3 adds to the terminal carbon atom of the alkene (-CH=CH2) to form an anti-Markovnikov addition product, or adds to the oxygen atom of the carboxy group (-COOH) to form silyl acetate (CH3-COOSiH3). Because the barrier in the reaction of the carboxy group (39.9 kJ/ mol) is much larger than that of alkene (11.97 kJ/mol), we conclude that the reaction of bifunctional molecules (e.g., omega-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH= CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction.