Experimental study for adsorption and photocatalytic reaction of ethyl methylphosphonate molecule as organophosphorus compound adsorbed at surface of titanium dioxide under UV irradiation in ambient condition

The adsorption and photocatalytic degradation of Ethyl methylphosphonate (EMPA) on powdery TiO₂ film has experimentally investigated using attenuated total reflection-infrared Fourier transform spectroscopy (ATR-FTIR) in ambient condition. Characteristic IR frequency as P-O-C vibration mode as EtO was observed by EMPA adsorbed at the surface of TiO₂. By TiO₂ photocatalysis, the adsorbed EMPA was decomposed to methyl phosphonic acid and phosphoric acid. The increment of IR intensity of which is assigned to Ti–O-P-O-Ti of EMPA was accompanied with increasing the IR peak intensity assigned to MPA. About that, we suggest that the appearance of the Ti–O-P-O-Ti of EMPA by the TiO₂ photocatalysis is regarded as acceleration of the hydrolysis of EMPA by the surface OH groups of TiO₂. The plausible adsorption structure and the photocatalytic reaction mechanism of EMPA at the surface of TiO₂ photocatalyst were elucidated.

     

Thermoanalytical characterization of carbon/carbon hybrid material, Apple Woodceramics

Woodceramics, a carbon/carbon composite of plant-originated carbon reinforced by glassy carbon from phenolic resin, was prepared from apple pomace at carbonizing temperatures of 1073 K (AWC800) and 1473 K (AWC1200), and characterized by thermoanalytical methods and X-ray diffraction (XRD). Simultaneous differential scanning calorimetry (DSC) and thermogravimetric (TG) showed complicated overlapping reactions similar to those of coal. The initial temperature of pyrolysis was obtained by fitting logistic functions to observed TG data. The results suggested that AWC1200 contained more volatile matter than AWC800. In an inert atmosphere, complicated devolatilization takes place. In an oxidizing atmosphere, thermal change occurs roughly in four steps: desorption of physically adsorbed matter; pyrolysis into aliphatic and aromatic fragments; ignition; combustion of char. The oxidation resistance of AWC1200 was superior to AWC800.     

Evolution of water vapor from indium-tin-oxide transparent conducting films fabricated by dip coating process

Tin-doped indium oxide In₂O₃ (indium-tin-oxide) transparent conducting films were fabricated on silicon substrates by a dip coating process. The thermal analysis of the ITO films was executed by temperature-programmed desorption (TPD) or thermal desorption spectroscopy (TDS) in high vacuum. Gas evolution from the ITO film mainly consisted of water vapor. The total amount of evolved water vapor increased on increasing the film thickness from approx. 25 to 250 nm and decreased by increasing the preparation temperature from 365 to 600°C and by annealing at the same temperature for extra 10 h. The evolution occurred via two steps; the peak temperatures for 250 nm thick films were approx. 100-120 and 205-215°C. The 25 nm thick films evolved water vapor at much higher temperatures; a shoulder at approx. 150-165°C and a peak at approx. 242°C were observed. The evolution temperatures increased by increasing the preparation and the annealing temperatures except in case of the second peak of the 25 nm thick films. The evolution of water vapor at high temperature was tentatively attributed to thermal decomposition of indium hydroxide, In(OH)₃, formed on the surface of the nm-sized ITO particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ab initio calculations of isomerization reaction of diphosphene 1-sulfide to thiadiphosphirane

Ab initio Calculations of the isomerization reaction of diphosphene 1-sulfide (2′) to thiadiphosphirane (3′) suggest that the energy barrier of the reaction in the ground state is 25 kcal/mol and that 2′ lies 21 kcal/mol above 3′, while the calculations show that there exists one local minimum on the lowest triplet energy surface.     

Surface effects on phase transition behavior and thermal polymerization of long-chain diynoic acids in micro DSC measurements

Effects of metal surfaces, such as aluminium, silver and gold, on the melting behavior and thermal polymerization of long-chain diynoic acids having a diacetylene group at different positions were investigated by thermal analyses using DSC, TG and other methods. The surface effects of metals were significant in the order of Ag, Al and Au. These effects are attributable to the anchoring of carboxyl group on the surface by chemisorption, which leads to unfavorable condition for polymerization of heptadeca-2,4-diynoic acid. In the case of tricosa-10,12-diynoic acid, containing a flexible methylene chain, inserted between COOH and C≡C?C≡C groups, the anchoring of COOH on the metal surface causes rather favorable effect on the polymerization.     

Studies on macrolide antibiotics I. Synthesis and antibacterial activity of erythromycin A 9-O-substituted oxime ether derivatives against Mycobacterium avium complex

A series of erythromycin A 9-O-substituted oxime ether derivatives have been synthesized and evaluated for antibacterial activity against Mycobacterium avium complex (MAC) and Staphylococcus aureus. These compounds possessed stronger in vitro activity against MAC including macrolide-resistant strains than clarithromycin (2), although in vitro antibacterial activities of these compounds were less than that of 2 against Staphylococcus aureus. Our studies found that several factors contribute to the antibacterial activity against MAC. The length and spatial orientation of the substituent at 9-position were found to significantly influenced the anti-MAC activity, especially against macrolide-resistant strains. Of all the compounds prepared, erythromycin A 9-[O-(4-phenylbutyl)oxime] (12q) and erythromycin A 9-[O-(3-phenoxypropyl)oxime] (12t) possessed 16 times stronger antibacterial activity than 2 against clarithromycin-resistant strains. Surprisingly, the minimum inhibitory concentrations (MICs) of 12q and 12t against the resistant strains were almost same as those against the susceptible strains. These results suggest that the erythromycin A 9-O-substituted oxime ether derivatives would be promising macrolide antibiotics.     

Synthesis and photochemical properties of photoactivated antitumor prodrugs releasing 5-fluorouracil

A new family of antitumor prodrugs (1-3) of 5-fluorouracil (5-FU) possessing photolabile 2-nitrobenzyl chromophores have been designed and synthesized to investigate the efficiency and mechanism of photoactivated 5-FU release upon UV-irradiation at lambda(ex)= 365 nm. The photoactivated prodrug 3 derived from conjugation of 2 with a tumor-homing cyclic peptide Cys-Asn-Gly-Arg-Cys (CNGRC) was so designed as to manifest a tumor-targeting function.     

Synthesis of spirodienones by intramolecular ipso-cyclization of N-methoxy-(4-halogenophenyl)amides using [hydroxy(tosyloxy)iodo]benzene in trifluoroethanol

Spirodienones bearing the 1-azaspiro[4.5]decane ring system have been synthesized from N-methoxy-(4-halogenophenyl)amides by the intramolecular ipso attack of a nitrenium ion generated with [hydroxy(tosyloxy)iodo]benzene in trifluoroethanol.     

A New Approach to the Construction of BEDT-TTF Derivatives Condensed with Heterocycles via BF3-promoted Reactions of Organotin Thiolates

The synthesis of BEDT-TTF derivatives fused with heterocycles (3–7) has been accomplished via the BF₃-promoted reaction of organotin thiolates (8 and 9) with electrophiles (10 and 11). Electrical conductivities of radical cation salts derived from some of them were also investigated.     

Spectrophotometric determination of lithium ion using a water-soluble octabromoporphyrin in aqueous solution

A water-soluble porphyrin, (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin; H(2)obtpps(4-)) was synthesized and developed for the determination of lithium ion in aqueous solution. The octabromo groups lower the basicity of the porphyrin by their electron-withdrawing effect, and enable the porphyrin to react with the lithium ion in alkaline solution to form the lithium complex along with a shift of absorption maximum: lambda max/nm (logepsilon/mol(-1) dm(3) cm(-1)) of the lithium porphyrin are 490.5 nm (5.31) and 734 nm (4.36). Sodium and potassium ions did not react with the porphyrin. The equilibrium constant for the reaction Li(+)+Hobtpps(5-)right harpoon over left harpoon[Li(obtpps)](5-)+H(+) was found to be 10(-8.80) and the conditional formation constant of the [Li(obtpps)](5-) at pH 13 is 10(4.21). The above results were applied to the determination of lithium ion in aqueous solution. The interference from transition and heavy metal ions was masked by using N,N'-1,2-ethanediylbis[N(carboxylmethy)glycinato]magnesium(II) ([Mg(edta)](2-)) solution. Absorbance at 490 nm was measured against a blank solution. A calibration graph was linear over the range of 0.007-0.7 mug cm(-3) (1x10(-6)-1x10(-4) mol dm(-3)) of lithium(I) with a correlation factor of 0.967. Lithium ion less than ppm level was determined spectrophtometrically in aqueous solution. The proposed method was applied to the determination of lithium in human serum and sea water samples.