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151.
A series or γ- and δ-lactones could be found in the thermal oxidative products of normal saturated acids, aldehydes, and alcohols (C9, C10, and C12, respectively) heated at 180°C in the presence of 0.1% KMnO4. Their lactones were identified by gas chromatography, infrared spectroscopy, and mass spectroscopy. And they could be detected also in the volatile compounds occurred by heating of C10 acid, aldehyde, and alcohol mixed with pork fat. So it was expected that lactones in meat fat flavor described in the earlier papers could be secondary products converted from saturated acids, aldehydes, and alcohols formed by oxidative degradation of meat fats. This process was presumed to be one of the mechanisms of the lactone formation.It was discussed that lactones might be derived through mono or dihydroperoxides of acids, aldehydes, and alcohols. 相似文献
152.
Arti Baban Dumbrepatil Ji‐Hye Choi Jong Tae Park Myo‐Jeong Kim Tae Jip Kim Eui‐Jeon Woo Kwan Hwa Park 《Proteins》2010,78(2):348-356
The debranching enzyme Nostoc punctiforme debranching enzyme (NPDE) from the cyanobacterium Nostoc punctiforme (PCC73102) hydrolyzes the α‐1,6 glycosidic linkages of malto‐oligosaccharides. Despite its high homology to cyclodextrin/pullulan (CD/PUL)‐hydrolyzing enzymes from glycosyl hydrolase 13 family (GH‐13), NPDE exhibits a unique catalytic preference for longer malto‐oligosaccharides (>G8), performing hydrolysis without the transgylcosylation or CD‐hydrolyzing activities of other GH‐13 enzymes. To investigate the molecular basis for the property of NPDE, we determined the structure of NPDE at 2.37‐Å resolution. NPDE lacks the typical N‐terminal domain of other CD/PUL‐hydrolyzing enzymes and forms an elongated dimer in a head‐to‐head configuration. The unique orientation of residues 25–55 in NPDE yields an extended substrate binding groove from the catalytic center to the dimeric interface. The substrate binding groove with a lengthy cavity beyond the ?1 subsite exhibits a suitable architecture for binding longer malto‐oligosaccharides (>G8). These structural results may provide a molecular basis for the substrate specificity and catalytic function of this cyanobacterial enzyme, distinguishing it from the classical neopullulanases and CD/PUL‐hydrolyzing enzymes. Proteins 2010. © 2009 Wiley‐Liss, Inc. 相似文献
153.
Malene Bech Vester-Christensen Maher Abou Hachem Anette Henriksen 《Journal of molecular biology》2010,403(5):739-750
Barley limit dextrinase [Hordeum vulgare limit dextrinase (HvLD)] catalyzes the hydrolysis of α-1,6 glucosidic linkages in limit dextrins. This activity plays a role in starch degradation during germination and presumably in starch biosynthesis during grain filling. The crystal structures of HvLD in complex with the competitive inhibitors α-cyclodextrin (CD) and β-CD are solved and refined to 2.5 Å and 2.1 Å, respectively, and are the first structures of a limit dextrinase. HvLD belongs to glycoside hydrolase 13 family and is composed of four domains: an immunoglobulin-like N-terminal eight-stranded β-sandwich domain, a six-stranded β-sandwich domain belonging to the carbohydrate binding module 48 family, a catalytic (β/α)8-like barrel domain that lacks α-helix 5, and a C-terminal eight-stranded β-sandwich domain of unknown function. The CDs are bound at the active site occupying carbohydrate binding subsites + 1 and + 2. A glycerol and three water molecules mimic a glucose residue at subsite − 1, thereby identifying residues involved in catalysis. The bulky Met440, a unique residue at its position among α-1,6 acting enzymes, obstructs subsite − 4. The steric hindrance observed is proposed to affect substrate specificity and to cause a low activity of HvLD towards amylopectin. An extended loop (Asp513-Asn520) between β5 and β6 of the catalytic domain also seems to influence substrate specificity and to give HvLD a higher affinity for α-CD than pullulanases. The crystal structures additionally provide new insight into cation sites and the concerted action of the battery of hydrolytic enzymes in starch degradation. 相似文献
154.
Huacheng Zhang Zhaona Liu Jingcheng Hao Jian Shen Xiaohui Zhao Hongyuan Sun Lizhen Sun 《Carbohydrate research》2010,345(1):87-60
Redox-responsive vesicles self-assembled by supramolecular cyclodextrin amphiphiles, consisting of the guest (N-1-decyl-ferrocenylmethylamine, 1) and the host (2-O-carboxymethyl-β-cyclodextrin, CM-β-CD), were prepared. The morphologies and sizes of these novel vesicles in an aqueous solution were observed by transmission electron microscopy (TEM) and were confirmed by atomic force microscopy (AFM) and dynamic light scattering (DLS) measurements. The effects of the host-guest ratio, the concentration and the solvent composition of water and methanol on vesicles were investigated in detail. The interactions between the host and the guest, the complex stoichiometry, the stability constant and conformations of 1·CM-β-CD in aqueous solution were investigated by cyclic voltammetry (CV), UV and nuclear magnetic resonance (NMR) measurements. According to the complex stoichiometry and ‘tadpole-like’ spatial conformations, the supramolecular cyclodextrin amphiphiles made from 1·CM-β-CD were proposed to form the membranes of the vesicles. This kind of vesicle system was responsive to an oxidizing agent, which could pave the way to combine supramolecular host-guest chemistry and membrane chemistry for potentially functional applications. 相似文献
155.
Cholesterol and glycosphingolipid-enriched membrane domains, termed lipid rafts, were proposed to play important roles in trafficking and signaling events. These functions are inhibited following putative disruption of rafts by cholesterol depletion, commonly induced by treatment with methyl-beta-cyclodextrin (MbetaCD). However, several studies showed that the lateral diffusion of membrane proteins is inhibited by MbetaCD, suggesting that it may have additional effects on membrane organization unrelated to cholesterol removal. Here, we investigated this possibility by comparison of the effects of cholesterol depletion by MbetaCD and by metabolic inhibition (compactin), and of treatment with alpha-CD, which does not bind cholesterol. The studies employed two series of proteins (Ras and influenza hemagglutinin), each containing as internal controls related mutants that differ in raft association. Mild MbetaCD treatment retarded the lateral diffusion of both raft and non-raft mutants, whereas similar cholesterol reduction (30-33%) by metabolic inhibition enhanced selectively the diffusion of the raft-associated mutants. Moreover, alpha-CD also inhibited the diffusion of raft and non-raft mutants, despite its lack of effect on cholesterol content. These findings suggest that the widely used treatment with CD to reduce cholesterol has additional, cholesterol-independent effects on membrane protein mobility, which do not necessarily distinguish between raft and non-raft proteins. 相似文献
156.
Dissolution of hydrophobic rac-norgestrel in aqueous gamma-cyclodextrin (gamma-CyD) and hydroxypropyl-gamma-cyclodextrin (HP-gamma-CyD) solutions was investigated, and enantioselective dissolution was observed. (-)-Norgestrel, the eutomer molecule, was dissolved to a greater extent using each of the CyDs, although the effect was more significant in the case of HP-gamma-CyD. A circular dichroism (CD) spectroscopic method based on measurement of the anisotropy factor was applied for the determination of the enantiomer ratio. The concentration and the enantiomer ratio of norgestrel were determined indirectly in octanol after extraction. Optical rotation dispersion (ORD) measurements could confirm that neither the free CyDs nor their inclusion complexes could get into the organic phase during transport to octanol. Only the norgestrel molecules were able to get into the organic phase, although the enantiomer ratio remained the same as was obtained in the aqueous CyD solution. 相似文献
157.
George T. Taylor Jürgen Weiss Josef Pitha 《Molecular reproduction and development》1988,19(4):401-409
Both ejaculated semen and epididymal contents from an individual male contain sperm that differ in various physicochemical characteristics. An experiment is reported in which epididymides from rats 5–24 months old were subjected to density gradient centrifugation to separate gametes of different stages of maturity. The research was designed to examine typical changes in “profiles” of sperm maturity during the reproductive lifetime of rats. Also, testosterone complexed with cyclodextrin that mimics the episodic release of the endogenous hormone was used to supplement the decreased circulating titers of some of the old males. Results revealed clear ontogenetic patterns of gradually decreasing reproductive competence as measured by absolute numbers of sperm, circulating levels of testosterone, and various other physiological markers of fertility. Sperm profiles also revealed age-specific changes with a shift toward progressively more mature, perhaps senile, gametes that begins at middle age. Testosterone supplementation (400 μg/kg b.w./day for 30 days) failed to restore sperm numbers or other measures of physiology in the old males, but the steroid modified sperm profiles to approximate more closely the profiles characteristic of young adult males than either untreated middle-aged or old males. The data were interpreted as suggesting that epididymal sperm profiles clearly identify males of different ages, and that the aging epididymis retains its capacity to respond to manipulations that modify the endocrine milieu. 相似文献
158.
Aminoethylcarbamoyl-β-cyclodextrin (AEC-β-CD)-based nanoparticle is prepared by an interfacial polyaddition reaction. The
nanoparticle has high β-CD content and many amino groups on the surface. The β-CD cavity of this particle forms inclusion
complexes with aromatic molecules, where the uptake ability significantly depends on physicochemical factors such as hydrophobicity,
ionic charge, size, and shape of guest molecules. 相似文献
159.
Pavel Řezanka David Sýkora Michal Novotný Martin Havlík Vladimír Král 《Chirality》2013,25(11):810-813
Racemic mixtures of six Tröger's base derivatives were separated by chiral nonaqueous capillary electrophoresis. The separation protocol was optimized first for suitable solvents. Then the applicability of various salts dissolved in organic solvents and their mixtures was evaluated. As chiral selectors β‐cyclodextrin and heptakis(2,6‐di‐O‐methyl)‐β‐cyclodextrin at various concentrations were used. The best enantioselectivity for the studied analytes was obtained utilizing formamide as organic nonaqueous solvent containing a mixture of sodium citrate and tris(hydroxymethyl)aminomethane acetate as electrolytes, and β‐cyclodextrin as chiral additive. The experimental results demonstrated the feasibility of nonaqueous capillary electrophoresis for enantioseparation of Tröger's base derivatives. This technique represents a suitable alternative to more commonly used capillary electrophoresis in aqueous environment. Chirality 25:810–813, 2013. © 2013 Wiley Periodicals, Inc. 相似文献
160.
Sirantha Perera Yun‐Cheol Na Thomas Doundoulakis Victor J. Ngo Qing Feng Zachary S. Breitbach Carl J. Lovely Daniel W. Armstrong 《Chirality》2013,25(2):133-140
High performance liquid chromatography (HPLC) and capillary electrophoresis (CE) were used to examine the enantiomeric separation of a series of 17 racemic tetrahydrobenzimidazole analytes. These compounds were prepared as part of a synthetic program directed towards a select group of pyrrole‐imidazole alkaloids. This group of natural products has a unique framework of pyrrole‐ and guanidine‐containing fused rings which can be constructed through the intermediacy of a tetrahydrobenzimidazole scaffold. Several bonded cyclodextrin‐ (both native and derivatized) and derivatized cyclofructan‐based chiral stationary phases were evaluated for their ability to separate these racemates via HPLC. Similarly, several cyclodextrin derivatives and derivatized cyclofructan were evaluated for their ability to separate this set of chiral compounds via CE. Enantiomeric selectivity was observed for the entire set of racemic compounds using HPLC with resolution values up to 3.0. Among the 12 different CSPs, enantiomeric recognition was most frequently observed with the Cyclobond RN and LARIHC CF6‐P, while the Cyclobond DMP yielded the greatest number of baseline separations. Fifteen of the analytes showed enantiomeric recognition in CE with resolution values as high as 5.0 and hydroxypropyl‐γ‐cyclodextrin was the most effective chiral additive. Chirality 25:133–140, 2013. © 2012 Wiley Periodicals, Inc. 相似文献