Synthesis and Characterization of Fluoro- and Chloro- bimetallic Alkoxides as Precursors for Luminescent Metal Oxide Materials via Sol-Gel Technique

Heterobimetallic alkoxides are broadly recognized as versatile precursors for luminescence materials, and efforts are being made to develop novel routes by applying the concept of geometrical molecular design, for their synthesis and to design a single source precursor suited to photoluminescent materials. Novel and new series of bimetallic alkoxides has been prepared by metathesis route. They exhibit a lower sensitivity towards hydrolysis and so they are easier to handle as compared to other alkoxides. All the compounds were characterized by elemental analysis, FT-IR and multinuclear NMR spectroscopies. FT-IR revealed that the molecular structure of these metal alkoxides was retained to a large extent in 4 ： 1 halogenated alcohol-benzene solution. The heteronuclear NMR spectroscopy provided useful information about chemical shifts for better understanding the likely structure based on interactions with their coordinate metals. The mass spectra show similar types of fragmentation pattern. SEM-EDS analyses showed consistency with the formulation. XRD patterns show an enhanced homogeneity at high temperature. TGA measurements show that thermal decomposition occured in steps that depended entirely on the chemical compositions and the synthesis routes. SEM observation reveals that the morphology and particle size strongly depend on synthesis routes for their precursors.     

In situ Fe K-edge X-ray absorption fine structure of a nitrosyl adduct of iron phthalocyanine irreversibly adsorbed on a high area carbon electrode in an acidic electrolyte

Key aspects of the microenvironment surrounding the Fe center in the nitrosyl adduct of iron phthalocyanine, [Fe(Pc)(NO)], have been elucidated from the analysis of the Fe K-edge extended X-ray absorption fine structure (EXAFS) of the material adsorbed on the surface of a high area carbon electrode recorded in situ, in 0.5 M H(2)SO(4). Statistical best fits to the EXAFS data place the Fe center in a five-coordinated square pyramidal configuration shifted away from the Pc plane toward the axially bound NO bent at an angle of ca. 40 degrees with respect to the normal to the Pc plane. This environment is analogous to that of Fe in the nitrosyl adduct of crystalline [Fe(TPP)], where TPP = meso-tetraphenylporphyrinato(2-), determined from X-ray diffraction.     

Catalytic combustion of chlorobenzene over V2O5/TiO2 catalysts prepared by the precipitation-deposition method

Catalytic combustion of chlorobenzene over supported vanadium oxides has been investigated. TiO₂ was prepared by the sol-gel method from titanium isopropoxide. The supported vanadium oxide catalysts have been prepared by precipitation-deposition and impregnation method and characterized by XRD, FT-Raman and TPR. In the VO_x/TiO₂catalysts prepared using the impregnation method, when vanadium loading reaches 3 wt.%, the activity shows a maximum. However, in the VO_x/TiO₂catalysts prepared by precipitation-deposition, when vanadium loading reaches 7 wt.%, the activity shows a maximum. This result suggests that the precipitation-deposition can yield a higher metal loading on the support and a high dispersion compared to the impregnation method. This revised version was published online in August 2006 with corrections to the Cover Date.     

Photochemical reactions of a dimethacrylate compound containing a chalcone moiety in the main chain

We synthesized the new photosensitive oligomer containing a chalcone moiety in the main chain by end-capping reaction of diepoxide compound with methacrylic acid. The chalcone-epoxy oligomeric compound was synthesized with 4,4^′-dihydroxychalcone and epichlorohydrin. Investigation of the photosensitivity of the newly synthesized chalcone oligomer was carried out by using UV-Vis absorption and infrared spectroscopies under UV exposure. We observed the photodimerization behavior under UV irradiation. At the same time, we could also observe the photopolymerization of the compound with a trace amount of dimethoxyphenyl acetophenone. Thermal properties of UV-cured dimethacrylate compounds were also studied.     

A novel method for the synthesis of the PEG-crosslinked chitosan with a pH-independent swelling behavior

In this study, a simple method was developed to crosslink chitosan using poly(ethylene glycol) (PEG) with different molecular weights. Crosslinking of chitosan was confirmed by various spectral analyses. The differential scanning calorimetric (DSC) study indicated that the rigid crystalline structure of chitosan was decreased after crosslinking with PEG. The PEG-crosslinked chitosan (PEG-Ch) showed a pH-independent swelling behavior: swelled in both the simulated stomach (pH 1.1) and intestinal (pH 7.4) solutions. The swelling ratio of PEG-Ch increased significantly with a higher molecular weight of PEG used. In contrast, chitosan dissolved completely in a simulated stomach solution and showed a comparatively less swelling in a simulated intestinal solution. Thus, the prepared PEG-Ch could be a better biomaterial than chitosan in the development of orally sustained drug-delivery devices.     

Synthesis and crystal structures of novel calix[4]azacrowns

A series of novel 1,3‐altemate calix[4]arene azacrowns having mono and bis crown ethers on the lower rim of the calix[4]arene framework were synthesized. Solid‐state structures confirmed the three dimensional conformation of compounds 1–3.     

The use of a thermally reversible bond for molecular imprinting of silica spheres

A silica monomer-estrone complex (EstSi) having a thermally cleavable urethane bond and a cross-linkable triethoxysilane group was synthesized. From EstSi and TEOS, spherical silica particles with sizes of 1.5-3 mum were prepared. The template molecules were removed from the silica matrix by heating at 180 degrees C in DMSO in the presence of water, generating a cavity with an amino group. The control silica particles that had the same sizes and shapes were obtained with aminopropyl triethoxysilane and TEOS. When ethylene glycol was added in place of H2O, an ethyl alcoholic group was formed in the cavity. Their recognition ability and specific binding for estrone were characterized by uptake experiments. The estrone-imprinted silica particles showed a much higher recognition ability than the control silica particles and higher selectivity for estrone than testosterone propionate.     

Depigmenting activity and low cytotoxicity of alkoxy benzoates or alkoxy cinnamte in cultured melanocytes

To obtain effective and safe topical depigmenting agents, we synthesized hydroxybenzoates, alkoxybenzoates, and 3,4,5-trimethoxycinnamate containing a thymol moiety and screened then for high-level inhibitory activity against melanin synthesis in cultured melanocytes. Eight compounds were tested for their depigmenting effect and cytotoxicity using a murine melanocyte cell line. We found that 3,4,5-trialkoxybenzoates and 3,4,5-trimethoxycinnamate, synthesized by conjugating 3,4,5-trialkoxybenzoic acids and 3,4,5-trimethoxycinnmic acid with thymol, showed a potent depigmenting effect and low cytotoxicity. Compound 4h, 5-methyl-2-(methylethyl)phenyl (2E)-3-(3,4,5-trimethoxyphenyl)prop-2-enoate, showed the most potent depigmenting effect (IC50=10 microM) with low cytotoxicity (IC50=200 microM).