Photoresponsive peptide and polypeptide systems: part II. Photochromism of poly(l-ornithine) containing various azo-contents in side chains

Poly(L-ornithine)s having various azo-contents in the side chains were synthesized by the water-soluble carbodiimide procedure. The photochemical properties of the polypeptides poly[N^δ-p-(phenylazo)benzoyl-L-ornithine] (PPABLO) containing 3–77 mol% azobenzene were investigated by absorption and circular dichroism spectroscopy in hexafluoro-2-propanol (HFIP) or water, and in HFIP-water or methanol-water solvent mixtures. The photochromism of the dichroic bands of the PPABLOs containing 20–77 mol% azobenzene in the visible and ultraviolet wavelength regions was found to be mostly reversible as a function of irradiation time at different wavelengths due to the photostationary state (above 80% trans-cis photoisomerization) of the azo aromatic moieties. The PPABLO containing 3.2 mol% azobenzene in water exhibited conformational changes from random coil to helix by the addition of methanol or sodium dodecyl sulphate (SDS). The photo-induced conformational change was observed in HFIP-water-SDS solvent mixtures, while no conformational change was seen in water and HFIP-water solvent mixtures.     

Formation of Small-Sized CdSxSe1-x Crystals in Sol-Gel-Derived SiO2 Glasses

Silica glasses doped with small-sized CdS_x-Se_1-x crystals were prepared by the sol-gel method. Gels synthesized by the hydrolysis of Si(OC₂H₅)₄, in the presence of CdSeO₄ with NH₄SCN dissolved in HNO₃ or NH₄OH, were heated in H₂-N₂ atmosphere. The pH value of solutions for CdSeO⁴ and NH⁴SCN primarily determined the fraction of anions in CdS^xSe^1-x crystals. The anion content in crystals was dependent on the pH value of the solvent and/or heat-treatment temperature, and the sulfur fraction changed from 0.1 to 0.6. The optical absorption spectra were red-shifted as the selenium content and the crystal size increased, and the emission spectra showed a sharp band near the absorption edge position and a broad tail extending into the long wavelength. The optical band gap energies increased reciprocally proportional to the square of the crystal size.     

Radical polymerization of butyl acrylate and random copolymerization of styrene and butyl acrylate and styrene and methyl methacrylate mediated by monospiro- and dispiropiperidinyl-N-oxyl radicals

Radical polymerization of butyl acrylate (BA) and random copolymerizations of styrene (St) and BA and St and methyl methacrylate (MMA) in the presence of 7-aza-15-hydroxydispiro[5.1.5.3]hexadecane-7-yloxyl (1) and 1-aza-2,2-dimethyl-4-hydroxyspiro[5.6]dodecane-1-yloxyl (2) were carried out. Radical polymerization of BA at 120 °C in the presence of 1 gave poly(BA) with M_n=20200 and M_w/M_n=1.30 at 23% conversion. The termination of polymerization observed around ∼20% conversion was solved to a certain extent by an addition of small amounts of dicumyl peroxide, and poly(BA) with M_n=37400 and M_w/M_n=1.33 was obtained in 46% yield. Random copolymerizations of St and BA and St and MMA in the presence of 1 and 2 at 80 °C gave the corresponding random copolymers with narrow polydispersities of 1.12-1.38 at the molar fraction above 0.30 of St in feed. The kinetic study for the NO-C bond homolysis of the corresponding alkoxyamines prepared from 1 and 2 were carried out, and evaluation of the preexponential factors (A_act) and the activation parameters (E_act) showed that the steric factors of the nitroxides are reflected mainly on E_act.     

Characterization of Hydroxyapatite Film on Titanium Substrate by Sputtering Technique

Radiofrequeut magnetron sputtering technique was used to produce calcium phosphate coated on the titurdum substrates, and the sputtered coating films were crystallized in an autoclave at 110℃ using a low temperature hydrothermal technique. The crystallization of as-sputtered coating film on the titanium substrates were amorphous calcium phosphate film. However, after the hydrothermal technique, calcium phosphate crystals grew and these were cohumnar crystal. The Ca/P ratio of sputtered coating films in 1.6 to 2.0.     

Experimental examination of the characteristics of bright-field scanning confocal electron microscopy images

We experimentally examined the characteristics of bright-field (BF) scanning confocal electron microscopy (SCEM) images by changing the observation conditions and comparing the images with those obtained by BF transmission electron microscopy (TEM) and BF scanning TEM (STEM) modes. The observation of 5-nm-diameter Au nanoparticles demonstrated that BF-SCEM produces object elongation of more than 2000?nm along the optical axis, as do BF-TEM and BF-STEM. We demonstrated the relationship between elongation length and geometric effects such as convergence and collection angles of a probe and the lateral size of an object; the relationship is consistent with previous theoretical prediction. Further, we observed interesting features that are seen only in the BF-SCEM images; the film contrast was strongly enhanced, compared with that of BF-STEM. In addition, a bright contrast appeared around the object position in the elongated images. Using this characteristic, we could determine the object position and structure.     

Visible Light Irradiation of [60]Fullerene Causes Killing and Initiation of Transformation in Balb/3T3 Cells

Abstract

Cell transformation in vitro is a model of carcinogenesis in vivo. Two-stage transformation assay increases the sensitivity of cells to chemicals and permits detection of carcinogens acting as initiating agents. [60]Fullerene (C₆₀) was cytotoxic in BALB/3T3 cells when it was irradiated by visible light, but not without light irradiation. Under conditions when C₆₀ was cytotoxic, it acted as an initiating agent for cell transformation, but it did not act as a complete transforming agent. the initiating activity of visible-light-irradiated C₆₀ was statistically significant in a modified two-stage transformation assay including a procedure for replating cells treated by C₆₀ and light, but it was equivocal in the standard two-stage transformation assay.     

Characterization of Proteoglycan and Hyaluronan in Hot Water Extract from Salmon Cartilage

Salmon cartilage proteoglycan fractions have recently gained favor as ingredients of functional food and cosmetics. An optimal hot water method to extract proteoglycan from salmon cartilage has recently been developed. The extracted cartilage includes hyaluronan and collagen in addition to proteoglycan as counterparts that interact with each other. In this study, biochemical analyses and atomic force microscopical analysis revealed global molecular images of proteoglycan in the hot water extract. More than seventy percent of proteoglycans in this extract maintained their whole native structures. Hyaluronan purified from the hot water extract showed a distribution with high molecular weight similar to hyaluronan considered to be native hyaluronan in cartilage. The current data is evidence of the quality of this hot water cartilage extract.     

Analysis of Plasmalogen Species in Foodstuffs

Ethanolamine plasmalogen (PlsEtn), which is present at high levels in brains, is believed to be involved in neuronal protection. The present study was performed to search for PlsEtn resources in foodstuffs. The foodstuffs examined showed a wide range of PlsEtn contents from 5 to 549 μmol/100 g wet wt. The marine invertebrates, blue mussel, and ascidian had high PlsEtn contents (over 200 μmol/100 g wet wt). Profiling of the molecular species showed that the predominant fatty acids of PlsEtn species were 20:5 (EPA) and 22:6 (DHA) at the sn‐2 position of the glycerol moiety in marine foodstuffs, whereas major PlsEtn species in land foodstuffs were 20:4. Following quantitative analysis by multiple reaction monitoring, the ascidian viscera were shown to contain the highest levels of 18:0/20:5‐PlsEtn and 18:0/22:6‐PlsEtn (86 and 68 μmol/100 g wet wt, respectively). In order to evaluate a neuronal antiapoptotic effect of these PlsEtn species, human neuroblastoma SH‐SY5Y cells were treated with ethanolamine glycerophospholipid (EtnGpl), purified from the ascidian viscera, under serum starvation conditions. Extrinsic EtnGpl from ascidian viscera showed stronger suppression of cell death induced by serum starvation than with bovine brain EtnGpl. The EtnGpl from ascidian viscera strongly suppressed the activation of caspase 3. These results suggest that PlsEtn, especially that containing EPA and DHA, from marine foodstuffs is potentially useful for a therapeutic dietary supplement preventing neurodegenerative diseases, such as Alzheimer's disease (AD).     

Preparation of Fe-based monodisperse spherical particles with fully glassy phase

In this study, we prepared monodisperse spherical particles of a desired diameter using [(Fe_0.5Co_0.5)_0.75B_0.2Si_0.05]₉₆Nb₄ alloy; the particles were prepared by using an atomization process developed by us. The particles have perfect sphericity and narrow size distribution along with a homogeneous composition. The phase transitions of particles from the fully glassy phase to the crystalline phase via mixed phase structures occurred as the particle diameter was increased; the particles produced in the fully glassy phase in an argon atmosphere had a diameter of less than 300 μm. This allowed the estimation of the intrinsic critical cooling rate for the particles with a fully glassy phase, R_c:R_c varied in the range of 700-900 K/s and depended only on the initial temperature of the alloy melt.     

Photooxidative degradation of polyethylene containing flame retardants by monochromatic light

Photodegradation of incombustible polymer materials [high-density (HD) and low-density (LD) polyethylene (PE) containing 0.5 to 2.0 phr of decabromodiphenyl ether (DBDE) or tetrabromobisphenol A (TBA) as a flame retardant] were studied using an Okazaki Large Spectrograph (OLS). Samples were irradiated in air at 23°C with monochromatic light of wavelengths at 260, 280, 300, 320, 340, and 360 nm. Ultraviolet and Fourier transform infrared (FTIR) spectra were taken to estimate the chemical changes caused by photoirradiation. Molecular weight change was followed by gel permeation chromatography (GPC) measurements. It was found that the photostability of PE samples was reduced by the addition of flame retardants. The threshold wavelengths of photodegradation are 320 nm and 360 nm for PE–TBA samples and PE–DBDE samples, respectively. Main-chain scission is favored when the irradiation was carried out with the light of wavelength 300 nm for HDPE–DBDE and HDPE–TBA samples. The most effective irradiation wavelengths for crosslinking are found to be 300 nm and 280 nm for LDPE–DBDE and LDPE–TBA samples, respectively. 1995 John Wiley & Sons, Inc.