Possible Role of Carboxyl and Imidazole Groups in the Catalysis of Pummelo Limonoid Glucosyltransferase

 Limonoid bitterness is a serious problem in the citrus industry worldwide. Limonoid glucosyltransferase is an enzyme that catalyzes the conversion of bitter limonoid into non-bitter limonoid glucoside while retaining the health benefit of limonoids in the juice. The immobilization of this enzyme in a column can solve the juice bitterness problem. More information about the catalytic residues of the en-zyme is needed in this immobilization process. Glutamate/aspartate, histidine, lysine, tryptophan, serine, and cysteine residues were chemi-cally modified to investigate their roles in the catalytic function of limonoid glucosyltransferase. Inactivation of the enzyme following modi-fication of carboxyl and imidazole moieties was a consequence of a loss in substrate binding and catalysis in the glucosyltransfer reaction. The modification of a single histidine residue completely destroyed the ability of limonoid glucosyltransferase to transfer the D-glucopyranosyl unit. Tryptophan seemed to have some role in maintaining the active conformation of the catalytic site. Lysine also seemed to have some direct or indirect role in this catalysis but the modification of serine and cysteine did not have any effect on catalysis. There-fore, we conclude that the carboxyl and imidazole groups contain amino acids are responsible for the catalytic action of the enzyme.     

膜乳化-溶剂挥发法制备表面羧基功能化苯乙烯-马来酸酐共聚物微球

以苯乙烯-马来酸酐共聚物(PSMA)为原料,利用膜乳化-溶剂挥发法,成功制备了表面光滑、尺寸均一的表面羧基功能化聚合物微球.研究表明:将膜乳化法和溶剂挥发法相结合,可以有效提高微球粒径的均一性,乳化剂种类及浓度、连续相流速、分散相中聚合物浓度等参数对微球粒径及粒径分布有显著影响.此外,利用盐酸使微球酸酐基团水解,可以得...     

Water Sorption to Hydroxyl and Carboxylic Acid Groups in Carboxymethylcellulose (CMC) Studied with NIR-spectroscopy

In carbohydrate systems which contain polar groups such as hydroxyl and carboxylic acid groups, water molecules are adsorbed in a specific way which varies with the type of polar group. Near infrared Spectroscopy (NIR) combined with multivariate statistical analysis was used to study the interactions between water molecules and carboxymethylated cellulose (CMC) with various degrees of substitution of the carboxylic acid groups, in two ionic forms (CMC-Na and CMC-Ca). The adsorbed water molecules were clearly influenced by the counterion; i.e. the nature of the ion-pair. A principle component analysis (PCA) identified variations in the registered spectra related to: the nature of the counter-ion, the degree of substitution (DS), the relative humidity (RH) and the type of polar group to which water was adsorbed. It was, possible furthermore, through the use of partial least square analysis (PLS), to extract spectral information related to the non-freezing bound water adsorbed on hydroxyl and carboxyl groups respectively. Loading spectra indicated that the obtained spectral information indeed correlated to the two kinds of polar groups studied (hydroxyl groups and carboxylic acid groups). The results support the view that, in the humidity range of 0–100%, water molecules are specifically adsorbed to individual polar groups, which characteristics are dependent on the nature of the polar group.     

Synthesis of Hydroxymethyl Side-Chained α-Aminoxy Diamide

Unnatural polar α-aminoxy acid residue with proteingenous hydroxymethyl side chain, a building block of the peptidomimetic foldamer of α-aminoxy peptide, was synthesized starting from natural amino acid L-serine. The starting material, L-serine, undergoes a reaction sequence to produce compound 1 in three steps: (1) the neighboring carboxyl group participates in diazotization/bromination to transform the amino group to a bromo group, (2) the C-terminal carboxyl group is protected, and (3) bromide is S_N2-displaced by N-hydroxyl phthalimide to introduce a N?O bond. After several conventional deprotection/coupling reactions, compound 1 is easily transformed to an α-aminoxy diamide, which can be widely used in peptidomimetics design.     

Synthesis of oligomeric urethane dimethacrylates with carboxylic groups and their testing in dental composites

Carboxyl urethane dimethacrylate oligomers with poly(ethylene oxide) sequences in the structure were synthesized and examined in photopolymerizable resins that could better adhere to various kinds of materials, including tooth substrates. Aspects of the morphogenesis of dental composites formed through a photochemically initiated radical copolymerization of the carboxylic derivatives, in addition to other partners encountered frequently in such materials, were studied comparatively with the corresponding urethane dimethacrylate monomer. The effect of a small quantity of a carboxylic macromer (ca. 10%) on the formation of a network with a non‐carboxyl urethane dimethacrylate oligomer (90%) as a potential substitute for diglycidyl methacrylate of bisphenol A and a filler (1/1 70% Aerosil/glass) was visualized by fluorescence spectroscopy with a pyrene methanol probe. The results showed the following: (1) the degree of conversion in the formulations into which carboxyl urethane dimethacrylate was incorporated decreased with increasing poly(ethylene oxide) chain length, (2) the formation of excimers was inhibited in the derived composites, and (3) an important quenching of the monomer fluorescence emission with the UV–vis irradiation time was observed in the formulation containing a filler (Aerosil+Zr/Sr glass). Preliminary testing of the resin composites suggested that all urethane oligomers containing carboxylic acid could lead to dental materials with reduced polymerization shrinkage and good mechanical properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1956–1967, 2007     

Synthesis of end‐functionalized AB copolymers. II. Synthesis and characterization of carboxyl‐terminated poly(ethylene glycol)–poly(amino acid) block copolymers

AB block copolymers composed of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic poly(amino acid) with a carboxyl group at the end of PEG were synthesized with α‐carboxylic sodium‐ω‐amino‐PEG as a macroinitiator for the ring‐opening polymerization of N‐carboxy anhydride. Characterizations by ¹H NMR, IR, and gel permeation chromatography were carried out to confirm that the diblock copolymers were formed. In aqueous media this copolymer formed self‐associated polymer micelles that have a carboxyl group on the surface. The carboxyl groups located at the outer shell of the polymeric micelle were expected to combine with ligands to target specific cell populations. The diameter of the polymer micelles was in the range of 30–80 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3527–3536, 2004     

Synthesis and pH‐responsive assembly of methoxy poly(ethylene glycol)‐b‐poly(ε‐caprolactone) with pendant carboxyl groups

pH‐responsive methoxy poly(ethylene glycol)‐b‐poly(ε‐caprolactone) bearing pendant carboxyl groups mPEG‐b‐P(2‐CCL‐co‐6‐CCL) was synthesized based on our newly monomer benzyloxycarbonylmethly functionalized ε‐caprolactone. Their structure was confirmed by ¹H NMR, ¹³C NMR, and Fourier transform infrared spectrum spectra. In addition, SEC results indicated that the copolymers had a relatively narrow polydispersity. WXRD and DSC demonstrated that the introduction of carboxymethyl groups had significant effect on the crystallinity of the copolymers. Furthermore, the solution behavior of mPEG‐b‐P(2‐CCL‐co‐6‐CCL) has been studied by various methods. The results indicated that mPEG‐b‐P(2‐CCL‐co‐6‐CCL) had a rich pH‐responsive behavior and the micelles could be formed by pH induction, and the mPEG‐b‐P(2‐CCL‐co‐6‐CCL) could existed as unimers, micelles or large aggregates in different pH range accordingly. The mechanism of which was supposed to depend on the counteraction between the hydrophobic interaction from PCL and the ionization of the carboxyl groups along the polymer chain. Moreover, the mPEG‐b‐P(2‐CCL‐co‐6‐CCL) copolymers displayed good biocompatibility according to the preliminary cytotoxicity study. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 188–199     

羧基取代类立方烷结构的萘光二聚体与芳香胺的反应性

本文利用羧基取代类立方烷结构的萘光二聚体2与芳香胺3反应研究这类结构化合物的反应活性。X-单晶衍射分析表明二环已基碳二亚胺（DCC）与2生成了具有类立方烷骨架的稳定化合物4,而且DCC能够作为一种有效的缩合剂催化2与3的反应,得到单独用光化学方法或热化学方法都无法获得的单边缩合或双边缩合的类立方烷酰胺化合物5和6。研究发现芳香胺3的电子效应显著影响反应产物的分布。     

取代苯甲酸羧基中的17O-NMR化学位移研究

提出了计算取代苯甲酸羧基¹⁷O NMR化学位移的公式：δ_cal（¹⁷O）=250.0+Δo+Δm+Δp,通过线性回归法确定了8种取代基参数.经回归检验表明该公式计算结果置信度为99.5 %,羧基¹⁷O NMR化学位移计算值与实验值的偏差Δδ全部在2.0以内.