Oxygen‐sensing properties of 5,10,15,20‐tetraphenylporphinato platinum(II) and palladium(II) covalently bound on poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate)

A novel methacrylate monomer bearing 5,10,15,20‐tetraphenylporphyrinato palladium(II) (PdTPP) (monomer 1a ) was synthesized and copolymerized with isobutyl methacrylate (IBM) and 2,2,2‐trifluoroethyl methacrylate (TFEM) to give poly (IBM‐co‐TFEM) bearing PdTPP (copolymer 2a ) as a dye‐conjugated oxygen‐permeable polymer for pressure‐sensitive paint applications. The introduction of PdTPP into copolymer 2a was confirmed by UV–vis spectroscopy and extended X‐ray absorption fine structure analysis. The Stern–Volmer plots of the copolymer 2a and a mixture of PdTPP and poly(IBM‐co‐TFEM) both showed downward curvature, unlike that of the platinum complex analogue (copolymer 2b ) previously reported. The plots were successfully fitted with a two‐site model to give two distinct Stern–Volmer constants (K_SV1 and K_SV2) and the partition ratio f₁. Interestingly, the f₁ values for the copolymer 2a were almost constant at about 0.98, whereas those of the mixture of PdTPP and poly(IBM‐co‐TFEM) increased from 0.889 to 0.967 as the temperature was increased. This finding suggests that there are two distinct microheterogeneities, one temperature‐dependent and the other temperature‐independent, in the mixture of PdTPP and poly(IBM‐co‐TFEM). The dye‐conjugation approach effectively eliminates the temperature‐dependent, but not the temperature‐independent microheterogeneity. The luminescence decays of copolymers 2a and 2b and the corresponding mixtures in the absence of oxygen indicated that the temperature‐dependent microheterogeneity involves an oxygen diffusion process, whereas the temperature‐independent one appears to be inherent nature in PdTPP. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 663–670, 2010     

Structural Characterization of a Pentacoordinate Monohydrosilane with the Apical Si-H Bond

A pentacoordinate phenyldibenzosilazocine containing the apical Si-H bond has been prepared and characterized by ¹H and ²⁹Si NMR spectra and X-ray analysis.     

Prediction of the lifetime of nitrile-butadiene rubber by FT-IR.

A quantitative measurement method with FT-IR was proposed for a thermal degradation analysis of nitrile-butadiene rubber (NBR). An NBR film was prepared as a model sample on a barium fluoride (BaF2) crystal plate, which was subjected to a heat treatment. The absorbances of various functional groups were measured directly by FT-IR after thermal degradation at high temperatures. By measuring the absorbances, it was possible to readily determine quantitatively each of the functional groups after the degradation of NBR. By assuming that the NBR lifetime was the point at which the absorbance of a carbon-carbon double bond reaches 45% of that prior to thermal treatment, a method for predicting the lifetime of NBR heated below 150 degrees C was proposed, by using an Arrhenius plot of the heating time versus heating temperature.     

Formation of a liquid organic ion associate in aqueous solution and its application to the GF-AAS determination of trace cadmium in environmental water as a complex with 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)phenol

The formation of a liquid organic ion associate in an aqueous sample was applied to the concentration and determination of cadmium in environmental water samples. Cadmium was converted into a complex with 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)phenol (5-Br-PAPS) in a 40-mL sample solution, and was extracted into a liquid ion associate of phenolsulfonate and benzethonium during phase formation. More than 400-fold enrichment was easily attained by this technique, because the volume of the liquid organic phase formed was very small, ca. 2 microL. After dilution of the organic phase with a small volume of 2-methoxyethanol, the cadmium in the solution was determined by GF-AAS. The detection limit was 0.09 ng/L (3sigma(b)). This method was applied to the determination of cadmium in river water and seawater.     

Synthesis and antiulcer activity of the metabolites of 2-(4-ethyl-1-piperazinyl)-4-phenylquinoline dimaleate (AS-2646), a novel gastric antisecretory and antiulcer agent

The metabolites 3 and 4 of 2-(4-ethyl-1-piperazinyl)-4-phenylquinoline dimaleate (AS-2646, 1), a candidate as a gastric antisecretory and antiulcer drug, were synthesized to confirm the proposed structures. The effects of the metabolites 2-4 on ulcer induced by stress were determined.     

Synthesis of an O-acyl isopeptide by using native chemical ligation to efficiently construct a hydrophobic polypeptide

By using dimethylformamide to suppress the O-to-N acyl migration, we efficiently synthesized an O-acyl isopeptide by native chemical ligation of a peptide-thioester and a Cys-O-acyl isopeptide. The reaction mixture was then loaded onto an octadecylsilane reverse-phase HPLC column, and the isopeptide was purified by using a linear gradient of CH₃CN in 0.1% aqueous trifluoroacetic acid. The recovery rate of the O-acyl isopeptide was considerably higher than that of the corresponding native polypeptide. Synthesis of O-acyl isopeptides via native chemical ligation, with O-to-N acyl migration as the final step to give the native form, has potential as an efficient method of constructing hydrophobic polypeptides.     

Effect of preparative conditions on crystallinity of apatite particles obtained from simulated body fluids

Preparation of colloidal hydroxyapatite (HAp) particles under body fluid conditions was investigated with focusing on the effect of preparative conditions on crystallinity of the resulting particles. Tris(hydroxymethyl)aminomethane was added to 1.5SBF (a solution having 1.5 times higher ion concentrations than those of a simulated body fluid, SBF) to increase the solution pH, which resulted in induction of homogeneous nucleation of HAp in the solution. Colloidal HAp particles having diameters about 300 nm were obtained. When the reaction was proceeded at 70°C and the sample was dried by heating, it was effective to obtain HAp particles having high crystallinity. Experimental results support that remaining water in the sample contributed to increase HAp crystallinity.     

Spatiotemporally controlled contraction of micropatterned skeletal muscle cells on a hydrogel sheet

We have developed gel sheet-supported C(2)C(12) myotube micropatterns and combined them with a microelectrode array chip to afford a skeletal muscle cell-based bioassay system. Myotube line patterns cultured on a glass substrate were transferred with 100% efficiency to the surface of fibrin gel sheets. The contractile behavior of each myotube line pattern on the gel was individually controlled by localized electrical stimulation using microelectrode arrays that had been previously modified with electropolymerized poly(3,4-ethylenedioxythiophene) (PEDOT). We successfully demonstrated fluorescent imaging of the contraction-induced translocation of the glucose transporter, GLUT4, from intracellular vesicles to the plasma membrane of the myotubes. This device is applicable for the bioassay of contraction-induced metabolic alterations in a skeletal muscle cell.     

Synthesis of poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate) with 5,10,15,20‐tetraphenylporphinato platinum(II) moiety as an oxygen‐sensing dye for pressure‐sensitive paint

Pressure‐sensitive paint (PSP), which consists of luminescent molecules embedded in an oxygen‐permeable polymer, has been developed for use in wind‐tunnel experiments. To improve the PSP technique, a novel luminescent methacrylate monomer, 5‐[4‐(2‐methacryloyloxyethoxycarbonyl)phenyl]‐10,15,20‐triphenylporphinato platinum(II), was synthesized and copolymerized with isobutyl methacrylate and 2,2,2‐trifluoroethyl methacrylate to produce a dye‐pendant copolymer ( 2 ). The introduction of 5,10,15,20‐tetraphenylporphinato platinum(II) (PtTPP) dye into 2 was confirmed by ultraviolet–visible spectroscopy and extended X‐ray absorption fine structure measurements. The extent of PtTPP dye incorporation in 2 was proportional to the molar fraction of the PtTPP‐pendant methacrylate monomer in the feed. The oxygen‐sensing property of 2 was compared with that of a PSP consisting of PtTPP dye embedded in poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate). Although the simple mixture of PtTPP and poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate) showed a marked deviation from a single Stern–Volmer relation, novel copolymer 2 gave a highly linear Stern–Volmer plot. This was unequivocal evidence of dye conjugation on the oxygen‐sensing polymer film. © 2005Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2997–3006, 2005