Photo-induced properties of anodic oxide films on Ti6Al4V

Photocatalytic activity and wettability of the anodic oxide layer on Ti6Al4V prepared by anodization in a sulfuric acid electrolyte are explored. The oxide is composed mainly of TiO₂ with V₂O₅, VO₂ and Al₂O₃. The crystal structure of the TiO₂ varies from anatase to rutile with the sulfuric acid concentration in the electrolyte. Anatase exhibits better photocatalytic activity compared with rutile, which is different from those on Ti and Ti-Nb-Sn alloy. Contact angles of the oxides decrease with ultraviolet light illumination, and hydrophilicity is observed in the rutile oxide. Both photocatalytic activity and hydrophilicity are inferior to the corresponding Ti and Ti-Nb-Sn alloy, which is explained by the presence of Al₂O₃ in the anodic oxide.     

Asymmetric anionic polymerization of n-diphenyl-methylitaconimide with chiral ligand-organometal complex

Summary Asymmetric anionic polymerizations of achiral N-diphenylmethylitaconimide (DPII) were performed with chiral ligand — organometal complexes in toluene. The obtained poly(DPII)s exhibited molecular weights of 1.5 × 10³ to 6.3 × 10³ and specific rotation between +7.5 to −18.4° (THF). The chirality of polymer was significantly affected by the organometals and chiral ligands. The poly(DPII) obtained with (4S)-2,2′-(1-ethylpropylidene)bis(4-benzyl-4,5-dihydrooxazole) (Bnbox) / n-butyllithium (n-BuLi) exhibited the highest specific rotation (−18.4°). The optical activities of the poly(DPII)s were attributed to configurational chirality of the main chain more than conformational chirality, judged from NMR, circular dichroism (CD) and GPC analyses using UV and polarimetric detectors. Received: 10 January 2002/ Revised: 12 April 2002/ Accepted: 22 April 2002     

Drying characteristics of porous material immersed in a bed of hygroscopic porous particles fluidized under reduced pressure

A relatively large wet material was immersed in a fluidized bed of hygroscopic porous particle (silica gel beads) under reduced pressure. And then the drying characteristics were compared with those in the case of inert particle (glass beads). The comparison of drying characteristics is performed experimentally and theoretically. In calculation, the water transfer from the sample to the fluidized bed was considered. The calculation results are in good agreement with the experimental data. The effects of the operational conditions (the pressure in the drying chamber and the temperature of the drying gas) on the drying characteristics were also examined in both fluidizing particles.The drying finishes earlier in the case of hygroscopic porous particle than in the case of inert particle regardless of pressure in the drying chamber, since the water transfer from the sample facilitates the drying in the case of hygroscopic porous particles. The temperature decrement in drying appears in the case of inert particle. This phenomenon is also observed in the case of hygroscopic porous particle, but the decrement degree of the temperature is much smaller than that in the case of inert particle. The difference of the minimum temperature in the sample in drying between the cases of hygroscopic porous particle and inert particle is very slight for different pressures in the drying chamber.     

Influence of ammonium salt on electrowinning of copper from ammoniacal alkaline solutions

In order to develop an energy-saving copper recycling process from wastes, electrochemical measurements were conducted in ammoniacal alkaline solutions containing Cu(I) ions and an ammonium salt of sulfate, chloride or nitrate. The results of each system were then compared. The polarization measurements suggested that the voltage required for the electrode process is lower in the chloride and nitrate systems than that in the sulfate system. The cathode current efficiency during the copper electrodeposition varied from 39 to 97% and increased with current density in the chloride and sulfate systems. In the nitrate system, the lowest cathode current efficiency of 30% was observed because of nitrate ion reduction. Based on these results, the power consumption required for the electrowinning stage of the copper recycling process was calculated. Among these three systems, the chloride system showed the lowest power consumption of 500 kWh t⁻¹ at the current density of 200 A m⁻², which is about 25% of the conventional copper electrowinning process from a copper sulfate-sulfuric acid solution.     

High speed and reproducible analysis of nitrosamines by capillary electrophoresis with a sulfonated capillary

Recently environmental control is regarded as important for good human health conditions, and toxic substances, including carcinogens and endocrine disruptors should be eliminated from our living environment. Hence easy quantitative methods are expected for a high level of environmental control. Our previous paper describes an easy quantitative analysis of nitrosamines (NAs) by capillary electrophoresis with an untreated fused silica capillary installed in an ordinary apparatus. In this paper, utilizing a novel type capillary column having sulfonated inner wall was investigated for improvements of separation performance and reproducibility. A sulfonated capillary causes fast and stabile electroosmotic flow because its inner wall is strongly negative charged. On a performance comparison of a sulfonated capillary with an untreated fused silica, analysis time reduction of c.a. forty percent was achieved, and relative standard deviations of migration times and peak responses were less than one third. In addition sample concentrations giving detection and quantitation limits were also reduced to a half.     

Enhanced growth inhibition of hepatic multicellular tumor spheroids by lactosylated poly(ethylene glycol)-siRNA conjugate formulated in PEGylated polyplexes

PEGylated polyplexes (lac-PEGylated polyplexes) composed of poly(L-lysine) and lactosylated poly(ethylene glycol)-small interfering RNA conjugate, which inhibits the RecQL1 gene product, were revealed to show an appreciable growth inhibition of multicellular HuH-7 spheroids (human hepatocarcinoma cell lines) for up to 21 days (IC(50)=6 nM); this system used as an in vitro three-dimensional (3D) model mimicking the in vivo biology of tumors. The PEGylated polyplexes thus prepared had a size of approximately 110 nm with clustered lactose moieties on their periphery as targeting ligands for the asialoglycoprotein-receptor-expressing HuH-7 cells. In contrast, OligofectAMINE/siRNA (cationic lipoplex) was observed to have almost no growth-inhibitory effect against HuH-7 spheroids, even though the lipoplex showed a stronger growth-inhibitory effect than the lac-PEGylated polyplexes on conventional monolayer-cultured HuH-7 cells. The FITC-tagged conjugate in the lac-PEGylated polyplexes showed smooth penetration into the HuH-7 spheroids compared with that in the lipoplexes, as observed by confocal fluorescence-scanning microscopy. This indicates that the small size of approximately 100 nm and the reduced nonspecific interaction due to the nonionic and hydrophilic lactosylated PEG layer contributes to the smooth penetration of the PEGylated polyplexes into the spheroid interior, eventually facilitating their uptake into the cells composing the spheroids. Cellular apoptosis indicating programmed cell death was also observed in the HuH-7 spheroids treated with the PEGylated polyplexes, revealing that the observed growth inhibition was indeed induced by the RNAi of the RecQL1 siRNA. These data suggest that the smart PEGylated polyplexes can indeed penetrate into the multiple cell layers of 3D tumor masses in vivo, exerting therapeutic effects through the RNAi.     

Cellulose nanofibrils as templates for the design of poly(l-lactide)-nucleating surfaces

The abilities of surface-grafted cellulose nanofibrils for the nucleation of poly(l-lactide) (PLLA) were investigated. Cellulose nanofibrils with a width of ∼3 nm were obtained from wood cellulose via the oxidation using 2,2,6,6-tetramethylpiperidiniyl-1-oxyl as a catalyst and successive mechanical treatment. The cellulose nanofibril surfaces were selectively modified with amine-terminated poly(ethylene glycol) chains, via simple ionic bonds. The PEG-grafted cellulose nanofibril/PLLA composite films were prepared using a solvent casting method with chloroform. The isothermal and non-isothermal crystallization kinetics of the PLLA in the composites was studied using differential scanning calorimetry and polarized optical microscopy. The PEG chains were densely immobilized on the surface of the cellulose nanofibril templates, which had extraordinarily large specific surface areas. As a result, the surface-PEG layers effectively increased the rate of crystallization of the PLLA in the composites. Because of the increased degree of crystallinity after the isothermal crystallization, the composites showed better heat resistance than neat PLLA.     

Oxidation kinetics for <Emphasis Type="Italic">cis</Emphasis>-9,<Emphasis Type="Italic">trans</Emphasis>-11 and <Emphasis Type="Italic">trans</Emphasis>-10,<Emphasis Type="Italic">cis</Emphasis>-12 isomers of CLA

The autoxidation processes of the cis-9,trans-11 (c9,t11) and trans-10,cis-12 (t10,c12) isomers of CLA were separately observed at ca. 0% RH and different temperatures. The t10,c12 CLA oxidized faster than the c9,t11 isomer at all tested temperatures. The first half of the oxidation process of t10,c12 CLA obeyed an autocatalytic-type rate expression, but the latter half followed first-order kinetics. On the other hand, the entire oxidation process of c9,t11 CLA could be expressed by the autocatalytic-type rate expression. The apparent activation energies and frequency factors for the autoxidation of the isomers were estimated from the rate constants obtained at various temperatures based on the Arrhenius equation. The apparent activation energies for the CLA isomers were greater than those for the nonconjugated n−6 and n−3 PUFA or their esters. However, the enthalpyentropy compensation held during the autoxidation of both the CLA and PUFA. This suggested that the autoxidation mechanisms for the CLA and PUFA were essentially the same.     

Oligomer-Rich Fraction from Polydisperse Sample of Poly(bis(β-phenoxyethoxy)phosphazene)

Poly[bis(-phenoxyethoxy)phosphazene] [PBPEP] had been shown in our previous paper to be a very useful polymer for investigating the crystallization mechanism of polymers, as the crystallization rate of PBPEP is extraordinarily small when isothermally crystallized from the melt. The crystallization of the low molecular weight oligomers of PBPEP was first studied in comparison to the high molecular weight polymers. The oligomer-rich fraction was obtained by fractionation of the as-polymerized sample, which had a broad molecular weight distribution. The fractions thus obtained were characterized by solution viscometry and size exclusion chromatography. The melting temperature and the growth rate of the spherulite from the melt were investigated by differential scanning calorimetry and optical microscopy. The growth rate was one or two orders of magnitude smaller in the oligomer-rich fraction than in the other high molecular weight fractions. A collapsed spherulite appeared in the oligomer-rich fraction at high crystallization temperatures. It is speculated that in the oligomer-rich fraction there is an excess free energy due to defects in the crystal phase. This defect is considerably larger in the oligomer-rich fraction than in the other fractions because a large quantity of short length chains is present.     

Trap Levels in Eu and other Rare‐Earth Ions Codoped CaAl2O4 Phosphors

Photoluminescence spectrum, trap depths, and densities of trapped carriers of CaAl₂O₄:Eu phosphor crystals doped with rare‐earth elements were studied using the thermally stimulated luminescence technique. Trap depths and densities of the specimens vary with rare‐earth elements doped as the auxiliary activators. Tm and Nd are found to be effective for the strong afterglow phosphorescence peaking at λ = 442 nm for several hours after the excitation. CaAl₂O₄:Eu phosphor crystals doped with Nd and Tm include high density of carriers trapped at E = 0.59 and 0.52 eV, respectively.