Mixture diffusion of sulfonated dyes into cellulose membrane. III. Application of parallel diffusion model to binary system of direct dyes with different affinity

Mixture diffusion of two dyes (C.I. Direct Blue 15 (DB15) and C.I. Direct Yellow 12 (DY12)) with different affinity onto the substrate into cellulose membrane from the binary solution was studied at 55°C. Uptake curves and concentration–distance profiles were measured experimentally in the ratios (DB15:DY12) 1:0.5, 1:1 and 1:2. It was examined whether the diffusion of the dyes could be analyzed based on the parallel diffusion theory of surface and pore diffusion. It was revealed that the diffusion of DB15 with higher affinity could be analyzed based on the model in the ratios 1:0.5 and 1:1, although the theoretical value deviated slightly from the data in the concentration–distance profile in the ratio 1:1. On the other hand, the diffusion of DY12 with smaller affinity could not be described by the model, because the diffusivity of the dye changed during the adsorption process against the assumption of the model.     

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     

Synthesis of 1H‐quinazoline‐2,4‐diones from 2‐aminobenzonitriles by fixation of carbon dioxide with amidine moiety supported polymer at atmospheric pressure

1H‐Quinazoline‐2,4‐diones, which are key intermediates in the synthesis of medicines, were successfully synthesized from 2‐aminobenzonitriles by the fixation of CO₂ in the presence of a polystyrene derivative bearing amidine moiety [poly(amidine)]. A model reaction, that is, the reaction of 2‐aminobenzonitrile ( 1a ) with CO₂ in the presence of N‐methyltetrahydropyrimidine ( MTHP ) revealed that a catalytic amount of MTHP afforded 1H‐quinazoline‐2,4‐dione ( 2a ) quantitatively at atmospheric pressure. Several 1H‐quinazoline‐2,4‐diones ( 2a ‐ 2c ) were successfully synthesized from the corresponding 2‐aminobenzonitriles ( 1a ‐ 1c ) in the presence of poly(amidine). The poly(amidine) could easily be separated from the reaction mixture by filtration and reused in subsequent reactions owing to the heterogeneous system. These demonstrated that poly(amidine) is a useful heterogeneous polymer‐supported reagent for the synthesis of 1H‐quinazoline‐2,4‐diones from CO₂. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 653–657, 2009     

Photocontrollable cation extraction with crowned oligo(spirobenzopyran)s.

The photoinduced changes of metal-ion extractability of crown ether derivatives bearing three or four spirobenzopyran moieties and their analogues were studied using 1,2-dichloroethane as the organic solvent. Under dark conditions, these compounds extracted Cu2+, Ag+, and Pb2+ with their counteranions from the aqueous phase to the organic phase. The extraction equilibrium constants of the photochromic crown ether derivatives for Cu2+ and Ag+ were determined successfully. Under UV-light irradiation conditions, the extraction of Cu2+ by crowned tris(spirobenzopyran) was enhanced, while that of Ag+ was suppressed. During the competitive metal-ion extraction of crowned oligo(spirobenzopyran)s between Cu2+ and Ag+, the metal-ion selectivity was reversed explicitly by photoirradiation.     

Chaotic Vibrations of a Cylindrical Shell-Panel with an In-Plane Elastic-Support at Boundary

This paper presents numerical results on chaotic vibrations of a shallow cylindrical shell-panel under harmonic lateral excitation. The shell, with a rectangular boundary, is simply supported for deflection and the shell is constrained elastically in an in-plane direction. Using the Donnell--Mushtari--Vlasov equation, modified with an inertia force, the basic equation is reduced to a nonlinear differential equation of a multiple-degree-of-freedom system by the Galerkin procedure. To estimate regions of the chaos, first, nonlinear responses of steady state vibration are calculated by the harmonic balance method. Next, time progresses of the chaotic response are obtained numerically by the Runge--Kutta--Gill method. The chaos accompanied with a dynamic snap-through of the shell is identified both by the Lyapunov exponent and the Poincaré projection onto the phase space. The Lyapunov dimension is carefully examined by increasing the assumed modes of vibration. The effects of the in-plane elastic constraint on the chaos of the shell are discussed.     

Studies on cardiac ingredients of plants. IX. Chemical transformation of proscillaridin by utilizing its 1,4-cycloadducts as key compounds and biological activities of their derivatives.

Three aromatic compounds (2-4) possessing a carbomethoxyl group or a dimethoxyphthaloyl group, prepared by the Diels-Alder reaction of the cardiac glycoside, proscillaridin (1), with dimethyl acetylenedicarboxylate and methyl propiolate, were transformed into alcohols, carboxylic acids and amides. The biological activities of the resulting derivatives were evaluated by the use of Na+, K(+)-adenosine triphosphatase (Na+,K(+)-ATPase) from dog kidney and isolated guinea-pig papillary muscle. Although the biological activities of the resulting derivatives were less potent than that of 1, a para-substituted benzylalcohol (5), methylbenzamides (9a and 10a), and ethylbenzamides (9b and 10b) inhibited the activity of Na+,K(+)-ATPase almost as potently as naturally occurring cardiac glycosides such as digoxin and digitoxin.     

Assay for sialidase using erythrocytes and peroxidase-labeled peanut lectin

A rapid and sensitive sialidase assay method based on peroxidase-labeled peanut lectin (PNA) binding to desialylated erythrocyte is described. Formalinized sheep erythrocytes were used both as a stable substrate for sialidase and as a target for the lectin. In the case of sialidases from Vibrio cholerae and Arthrobacter ureafaciens, a linear relationship was observed between the amount of peroxidase-labeled PNA bound to erythrocytes and the enzyme amount. Binding of the lectin to sialidase-treated erythrocytes was completely prevented in the presence of 25 mM lactose and galactose. The method is particularly useful as a selective assay for sialidase which is active towards gangliosides or sialoglycoproteins, because a mammalian sialidase which is preferentially active towards sialooligosaccharides and sialoglycopeptides is not able to remove sialic acid from erythrocytes.     

Gas permeability and n‐butane solubility of poly(1‐trimethylgermyl‐1‐propyne)

The gas permeability and n‐butane solubility in glassy poly(1‐trimethylgermyl‐1‐propyne) (PTMGP) are reported. As synthesized, the PTMGP product contains two fractions: (1) one that is insoluble in toluene and soluble only in carbon disulfide (the toluene‐insoluble polymer) and (2) one that is soluble in both toluene and carbon disulfide (the toluene‐soluble polymer). In as‐cast films, the gas permeability and n‐butane solubility are higher in films prepared from the toluene‐soluble polymer (particularly in those films cast from toluene) than in films prepared from the toluene‐insoluble polymer and increase to a maximum in both fractions after methanol conditioning. For example, in as‐cast films prepared from carbon disulfide, the oxygen permeability at 35 °C is 330 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐soluble polymer and 73 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐insoluble polymer. After these films are conditioned in methanol, the oxygen permeability increases to 5200 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐soluble polymer and 6200 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐insoluble polymer. The rankings of the fractional free volume and nonequilibrium excess free volume in the various PTMGP films are consistent with the measured gas permeability and n‐butane solubility values. Methanol conditioning increases gas permeability and n‐butane solubility of as‐cast PTMGP films, regardless of the polymer fraction type and casting solvent used, and minimizes the permeability and solubility differences between the various films (i.e., the permeability and solubility values of all conditioned PTMGP films are similar). © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2228–2236, 2002