Thermal analysis of polymer networks consisting of different homopolymers

TG and DSC were carried out on PMAA-net-POTM in order to elucidate the relation between the heterogeneity and the thermal changes; moreover, TG and DSC were carried out on PPOTMDM and PMAA to compare the results. The onset temperature in the last stage in the TG curve of PMAA-net-POTM increases as the concentrations of DMF and POTMDM in the polymerization decrease. This is explained in terms of plasticizers effects. A single peak due to fusion of POTM chains appears in the DSC curves of most copolymers. However, it is not seen in the DSC curves of copolymers with high heterogeneity. This is explained in terms of the freezing of POTM chains by frozen heterogeneous moieties.     

Surface design for precise control of spatial growth of a mesostructured inorganic/organic film on a large-scale area

A microfabrication technique is presented to fabricate a mesostructured inorganic/organic composite film, i.e., silica/cetyltrimethylammonium chloride (CTAC) film, with near-perfect site-selectivity on a large surface area based on a spatially regulated growth method. To precisely regulate the site-selective growth of this mesocomposite film at the solid/liquid interface, we designed a novel microtemplate consisting of a "dual-component" self-assembled monolayer (SAM) with alternating hydrophobic trifluorocarbon (CF3) and cationic amino (NH2) groups. First, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane (FAS)-SAM was formed onto Si substrate covered with native oxide (SiO2/Si) from vapor phase. The substrate was then photolithographically micropatterned using 172 nm vacuum UV light. Finally, the micropatterned FAS-SAM was immersed in a solution of 1 vol % (aminoethylaminomethyl)phenethyltrimethoxysilane (AEAMPS) in absolute toluene. Due to these treatments, a dual-SAM microtemplate with CF3- and NH2-terminated surfaces was fabricated, as evidenced by lateral force microscopy, ellipsometry, and X-ray photoelectron spectroscopy. Using this template, the microfabrication of a mesocomposite film was demonstrated. As a control, the micropatterned hydrophobic FAS-SAM template (composed of CF3- and OH-terminated surfaces) was also treated under the same conditions. Optical microscopy and atomic force microscopy confirmed that the formation of the continuous mesocomposite film proceeded only on the FAS-SAM-covered regions, while the AEAMPS-SAM-covered regions remained free of deposits. This shielding effect also remained constant regardless of the pattern's geometry, i.e., the interval distance between the FAS-SAM-covered areas in the pattern. Through this approach, we were able to obtain well-defined 5-, 10-, and 20-mum wide mesocomposite microlines over the entire 10 x 10 mm2 area with high area-selectivity. On the other hand, when the SiO2 regions were not terminated with the cationic NH2 groups, cluster formation proceeded not only on the hydrophobic CF3 regions but also on the SiO2 regions, particularly with an increase in the pattern interval distance, resulting in lower final pattern resolution.     

Coptidis rhizoma extract protects against cytokine-induced death of pancreatic beta-cells through suppression of NF-kappaB activation

We demonstrated previously that Coptidis rhizoma extract (CRE) prevented S-nitroso-N-acetylpenicillamine-induced apoptotic cell death via the inhibition of mitochondrial membrane potential disruption and cytochrome c release in RINm5F (RIN) rat insulinoma cells. In this study, the preventive effects of CRE against cytokine-induced beta-cell death was assessed. Cytokines generated by immune cells infiltrating pancreatic islets are crucial mediators of beta-cell destruction in insulin-dependent diabetes mellitus. The treatment of RIN cells with IL-1beta and IFN-gamma resulted in a reduction of cell viability. CRE completely protected IL-1beta and IFN-gamma-mediated cell death in a concentration-dependent manner. Incubation with CRE induced a significant suppression of IL-1beta and IFN-gamma-induced nitric oxide (NO) production, a finding which correlated well with reduced levels of the iNOS mRNA and protein. The molecular mechanism by which CRE inhibited iNOS gene expression appeared to involve the inhibition of NF-kappaB activation. The IL-1beta and IFN-gamma-stimulated RIN cells showed increases in NF-kappaB binding activity and p65 subunit levels in nucleus, and IkappaB alpha degradation in cytosol compared to unstimulated cells. Furthermore, the protective effects of CRE were verified via the observation of reduced NO generation and iNOS expression, and normal insulin-secretion responses to glucose in IL-1beta and IFN-gamma-treated islets.     

Vicinal C-functionalization of alkenes. Pd/light-induced multicomponent coupling reactions leading to functionalized esters and lactones

Under photoirradiation conditions using a xenon light, and in the presence of PdCl(2)(PPh(3))(2) as a catalyst, four-component coupling reactions comprising of α-substituted iodoalkanes, alkenes, carbon monoxide, and alcohols proceeded smoothly to give functionalized esters in good yields. When alkenyl alcohols were used as acceptor alkenes, three-component coupling reactions accompanied by intramolecular esterification proceeded to give lactones in good yields. The present reaction system represents the vicinal C-functionalization of alkenes.     

Carboxylic acid recognition of diamidine having a fluorescent 1,8-diphenylanthracene unit and its detection of amidinium-carboxylate and amidinium formation

A diphenylanthracene-based diamidine (1a) fluorescent probe for the detection of dicarboxylic acids has been designed and synthesized, which has an extended π-conjugation rather than a simple anthracene ring, in order to observe highly different fluorescence wavelengths after complex formation with dicarboxylic acids. The fluorescence spectra of the mixed solution of the diamidine 1a and carboxylic acids showed two different fluorescence bands, which corresponded to the complex formation (amidinium-carboxylate formation, λ_em?=?450?nm, light blue color) and dissociated amidinium formation (λ_em?=?510?nm as a broad band, green color). The complexed and dissociated states were confirmed by DOSY NMR and TD-DFT calculations. These different fluorescence wavelengths may come from the differences in the dihedral angles between the phenyl rings at the 1,8-position and anthracene ring (difference in π-conjugation) of 1a under complex formation and dissociated amidinium formation. The proposed mechanism for the observation of the different fluorescence wavelengths (complex formation and amidinium formation) was also confirmed by the fluorescence study of diamidine 1b which causes restricted rotation of the phenyl rings by substitution of the steric methyl groups, and observed the same fluorescence spectra for the complex formation and amidinium formation (400, 420, 450?nm as a vibrational structure of anthracene ring). These fluorescence characteristics of the diamidine 1a are also applicable for the detection of α,ω?dicarboxylic acids.     

Catalyzing methanolysis of alkyl halides in the interior of an amphiphilic molecular basket

A molecular basket with four cholate units assembled on a cone-shaped calix[4]arene assumed reversed micelle-like conformation in 5% methanol/carbon tetrachloride. The inwardly facing hydroxyl groups on the cholates concentrated the polar solvent from the mostly nonpolar mixture. Methanolysis of alkyl halides benefited from the concentrated pocket of methanol if the substrate was capable of entering the basket. Substrates that were too large or too hydrophobic to fit within the basket showed no rate acceleration.     

Gold-catalyzed intramolecular hydroalkoxylation/cyclization of conjugated dienyl alcohols

Catalytic intramolecular additions of hydroxyl groups to tethered conjugated dienes are described. The reactions proceed smoothly at 60 °C in the presence of 5 mol % of (PPh₃)AuCl/AgOTf as a catalyst. A broad range of structurally diverse conjugated dienes produce substituted tetrahydrofurans and tetrahydropyrans in good yields. This reaction represents an atom-economic route to construct five- and six-membered cyclic ethers.     

Conformational analysis of N-aryl-N-(2-azulenyl)acetamides

Aromatic amides bearing 2-azulenyl group on the amide nitrogen were synthesized and their structures were investigated. The π-electron density of the N-aryl group was found to influence the cis-trans conformational preferences of these compounds in solution. X-ray crystallography revealed that the plane of the 2-azulenyl ring has a strong tendency to lie coplanar with the amide plane when the azulene group is located on the same side as the amide oxygen atom.