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     

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     

Effect of absorption promoters in intranasal administration of human fibroblast interferon as a powder dosage form in rabbits

The utility of the absorption promoters, sodium glycocholate (GC-Na), ethylenediamine dihydrochloride (EDTA-2Na), sodium caprylate (Cap-Na) and sodium salicylate (Sal-Na), in the intranasal administration of human fibroblast interferon-beta (HuIFN-beta) in rabbits was investigated. The optimal amount of added EDTA-2Na, Cap-Na and Sal-Na with respect to HuIFN-beta was examined for nasal absorption in the powder dosage form. Formulations of HuIFN-beta with GC-Na showed greatly enhanced intranasal HuIFN-beta absorption, as compared to the other absorption promoters. The results of a stability study on HuIFN-beta in homogenates of nasal mucosa suggested that GC-Na behaved as a hydrolysis inhibitor in the nasal mucosa and maintained the activity of HuIFN-beta.     

Water revealed as molecular mirror when measuring low concentrations of sugar with near infrared light

Near infrared spectroscopy is an overtone spectroscopy regarded as a quick and non-destructive method that provides analytical solutions for components that represent approximately 1% or more of the total mass of the investigated composite samples. Aquaphotomics offers the possibility for disentanglement of information remaining hidden in the spectra when conventional data evaluation methods are used, since this concept utilizes changes of the water structure induced by the measured solute as specific molecular vibrations at water bands. Here, near infrared technique and aquaphotomics are applied for non-destructive identification and quantification of mono- and di-saccharide solutes at 100–0.02 mM concentration that is accepted as unachievable with near infrared spectroscopy. The results presented in this study support the aquaphotomics' water molecular mirror concept that explores spectral changes related to water molecular rearrangements caused by minute changes of the solutes in the aqueous systems. The method provides quick and accurate alternative for classical analytical measurements of saccharides even at millimolar concentration levels.     

Total synthesis of citridone A

The first total synthesis of citridone A has been achieved through regioselective intramolecular iodocyclization and regio- and stereoselective Pd(0)-catalyzed coupling as key reactions.