Ring-opening polymerization of cyclic carbonates by alcohol–acid catalyst

Ring-opening reactions of 1,3-dioxepan-2-one ( 1 ) and 1,3-dioxan- 2 -one (2) with several alcohols were examined. The reactions proceeded without trifluoroacetic acid (TFA) in low conversions, while they proceeded smoothly with TFA to afford the ring-opened adducts and oligomers. Ring-opening polymerizations of 1 and 2 were also carried out by alcohol–acid catalysts to afford the corresponding polycarbonates (M _n = 2500−6800). The molecular weights increased with increase of the conversions of 1 and 2. The observed polymerization rates of 1 and 2 were determined as 24.4 × 10⁻⁶ and 0.8 × 10⁻⁶ s⁻¹, respectively. Mechanistic aspects were studied by NMR spectroscopy. The methylene protons α and β to the carbonate moieties shifted to lower fields in 0.06–0.11 ppm in the ¹H-NMR spectra by the addition of TFA. Downfield shifts of the carbonyl carbon signals of 1 and 2 were observed in 3.94–4.15 ppm in the ¹³C-NMR spectra. These results strongly suggest that the cyclic carbonates are activated by TFA. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2463–2471, 1998     

Radical addition of alkyl halides to formaldehyde in the presence of cyanoborohydride as a radical mediator. A new protocol for hydroxymethylation reaction

Hydroxymethylation of alkyl halides was achieved using paraformaldehyde as a radical C1 synthon in the presence of tetrabutylammonium cyanoborohydride as a hydrogen source. The reaction proceeds via a radical chain mechanism involving an alkyl radical addition to formaldehyde to form an alkoxy radical, which abstracts hydrogen from a hydroborate anion.     

N-(2-Alkoxyphenyl)-substituted double rhodanine indoline dyes for zinc oxide dye-sensitized solar cell

The effect of N-(2-alkoxyphenyl) group in double rhodanine indoline dye on the performance of zinc oxide dye-sensitized solar cell was examined. Both J_sc and V_oc were improved by introducing long alkoxy group due to prevention of H-aggregates formation and inhibition of electron recombination from zinc oxide surface to electrolyte.     

Improved MALDI‐MS method for the highly sensitive and reproducible detection of biomarker peaks for the proteotyping of Salmonella serotypes

The rapid identification and classification of pathogenic microorganisms, including Salmonella enterica, is important for the surveillance and prevention of foodborne diseases. Matrix‐assisted laser desorptionionization time‐of‐flight mass spectrometry (MALDI‐TOFMS) has been shown to be an effective tool for the rapid identification of microorganisms. In a previous report, a mass database consisting of 12 biomarker proteins, S8, L15, L17, L21, L25, S7, superoxide dismutase (SodA), peptidylprolyl cis‐trans isomerase C, Gns, YibT, YaiA, and YciF, was introduced for the serotyping of S. enterica via MALDI‐MS (Applied Microbiology and Biotechnology, 2017, 101, 8557‐8569). However, the reproducibility of peak detection of biomarkers such as SodA at mz 23 000 was poor. We report here an optimized MALDI‐MS method for detecting these biomarkers with high sensitivity and reproducibility. The issue was solved by controlling the bacterial concentration at 1 × 10 to 1 × 10² MFU (3 × 10⁶ to 3 × 10⁷ CFUμL, as calculated from the MFU), using the colony suspension supernatant obtained by centrifugation, and using matrix additives such as methylenediphosphonic acid and N‐decyl‐β‐D‐maltopyranoside. We propose that the method including the above steps is one of the best for detecting biomarkers with high sensitivity and reproducibility.     

Carbonylation of Alkyl Radicals Derived from Organosilicates through Visible‐Light Photoredox Catalysis

Primary, secondary, and tertiary alkyl radicals formed by the photocatalyzed oxidation of organosilicates underwent efficient carbonylation with carbon monoxide (CO) to give a variety of unsymmetrical ketones. This study introduces the possibility of radical carbonylation under a photooxidative regime.     

Ruthenium-catalyzed C-H/CO/Olefin coupling reaction of N-arylpyrazoles. Extraordinary reactivity of N-arylpyrazoles toward carbonylation at C-H bonds

The reaction of 1-arylpyrazoles with CO and ethylene in the presence of Ru(3)(CO)(12) resulted in regioselective carbonylation at the ortho C-H bonds. While it is found that the pyrazole ring also functions as the directing group for C-H bond cleavage, the efficiency of the reaction depends on the position of the pyrazole ring.     

Stereocontrolled total synthesis of (−)-aspidophytine

The enantioselective stereocontrolled total synthesis of aspidophytine is described. The key indole intermediate was prepared by radical cyclization of 2-alkenylphenylisocyanide, followed by Sonogashira-coupling with a highly functionalized terminal acetylene. The 11-membered cyclic amine, a precursor for the formation of the aspidosperma skeleton, was synthesized using nitrobenzenesulfonamide chemistry. After construction of the pentacyclic skeleton, the lactone ring was formed to complete the total synthesis.     

Designing interfaces that function to facilitate charge injection in organic light-emitting diodes

Layer-by-layer (LbL) assembly of triarylamine (TAA)-containing polymers has been applied for anode functionalizations in organic light-emitting diodes (OLEDs). Surface work function of the ITO electrodes was significantly altered with the functionalizations, and the values changed depending on electron affinity of the substituents (X) on the TAA units. When the functionalized ITO electrodes were utilized for the conventional TPD/Alq OLED, the multilayers of P1 (X = 4-OMe) and P2 (X = none) were found to promote better energy matching at the ITO/TPD interface to reduce the hole injection barrier. Furthermore, the multilayers having heterodeposited structure of several TAA polymers provided stepped and graded electronic profiles to facilitate hole mobility from ITO to TPD, so that the resulting OLED devices can exhibit appreciably reduced turn-on voltage and higher luminous intensities.     

Efficient Synthesis of a Water-Soluble Glucoamide Inhibitor Against Human Aldose Reductase by Click Chemistry

While D-glucose is the natural substrate of aldose reductase (AR) in the polyol pathway, the K _m value of D-glucose against AR is large. A glucoamide 1 was designed as a tool to investigate whether AR has a strong affinity for the open form of D-glucose. Glucoamide 1 was synthesized in high yield by modification of the reaction condition for click chemistry. It was found that our modified condition was applicable for highly polar alkynes and gave coupling products in excellent yield (90% to 100%). Although weak inhibitory activity against AR was observed, kinetic studies showed that AR does not accept glucoamide 1 in its active site.     

高羧基含量无皂多孔聚合物乳胶粒的研究

功能性聚合物乳液的性能与其功能基的含量密切相关. 采用完全无皂种子乳液聚合技术合成了具有不同羧基含量并且粒径分布均一的交联型聚甲基丙烯酸甲酯-丙烯酸乙酯因为甲基丙烯酸 [P(MMA-EA-MAA)]乳胶粒, 然后通过碱后处理, 制备出了高羧基含量的无皂多孔P(MMA-EA-MAA)乳胶粒. 系统研究了MAA对聚合反应、胶粒特性及胶粒多孔结构形态的影响. 结果表明: 在交联剂二乙烯基苯用量一定(0.3 g)的条件下, 随着MAA用量从4.0 mol%增加到 10.0 mol%, 聚合物交联程度(P_x)从28.26%迅速增大至90.95%, 当其用量超过10.0 mol%后P_x增大趋势变缓; 随着MAA用量的增加, 处理后胶粒体积膨胀百分率(ΔV)逐渐增大, 在MAA用量为12.0 mol%时ΔV达到42.1%的最大值, 当MAA用量增大到14.0 mol%时, 尽管P_x高达95.44%, 胶粒仍具有完好的孔状结构.