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1.
Starch belongs to the polyglucan group. This type of polysaccharide shows a broad β-relaxation process in dielectric spectra at low temperatures, which has its molecular origin in orientational motions of sugar rings via glucosidic linkages. This chain dynamic was investigated for α(1,4)-linked starch oligomers with well-defined chain lengths of 2, 3, 4, 6, and 7 anhydroglucose units (AGUs) and for α(1,4)-polyglucans with average degrees of polymerization of 5, 10, 56, 70, and so forth (up to 3000; calculated from the mean molecular weight). The activation energy (Ea) of the segmental chain motion was lowest for dimeric maltose (Ea = 49.4 ± 1.3 kJ/mol), and this was followed by passage through a maximum at a degree of polymerization of 6 (Ea = 60.8 ± 1.8 kJ/mol). Subsequently, Ea leveled off at a value of about 52 ± 1.5 kJ/mol for chains containing more than 100 repeating units. The results were compared with the values of cellulose-like oligomers and polymers bearing a β(1,4)-linkage. Interestingly, the shape of the Ea dependency on the chain length of the molecules was qualitatively the same for both systems, whereas quantitatively the starch-like substances generally showed higher Ea values. Additionally, and for comparison, three cyclodextrins were measured by dielectric relaxation spectroscopy. The ringlike molecules, with 6, 7, and 8 α(1,4)-linked AGUs, showed moderately different types of dielectric spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 188–197, 2004 相似文献
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The formation of the 28-membered ring cyclo[(6-amino-6-deoxy-d-galactonic acid)4] by cyclisation of a protected open chain fully hydroxylated nylon 6 linear tetramer in modest yield provides the first example of a new class of carbopeptoid-cyclodextrin. 相似文献
4.
The N-benzoyl-l-tyrosine ethyl ester (BTEE) anchored in cyclodextrin (β and β-methyl CD) serves as an excellent substrate for subtilisin
Carlsberg catalysis. The rate of hydrolysis was found to be approximately twofold higher than that of the methanolic substrate.
The Kmapp and Vmax values for the CD anchored substrates were significantly higher than the methanol-solubilized BTEE. 相似文献
5.
Immobilized polysiloxane-anchored permethyl-β-cyclodextrin (Chirasil-Dex) with a cyclodextrin content of approximately 30 % by weight, previously employed as a versatile chiral stationary phase for the separation of enantiomers by GC, has been used for the separation of enantiomers by capillary supercritical fluid chromatography (SFC). A considerable number of racemates could be resolved, e.g. aromatic alcohols, amino alcohols (TFA derivatives), and underivatized acids. Many pharmaceutical compounds were among those analyzed, including several NSAIDs (e.g. ibuprofen and ketoprofen), a steroidal drug (nor-gestrel), a barbiturate (hexobarbital), and others. Among the racemates resolved were many which cannot be analyzed by GC owing to low volatility or decomposition at elevated temperatures. For two racemates, analysis temperature and mobile phase density were systematically varied to give constant analysis times or capacity factors k. Low temperatures (ca 60 °C) yielded the best separation in term of separation factor, α, or resolution, Rs, even though higher densities had to be used. In comparison with GC, capillary SFC was able to furnish higher separation factors and similar resolution. The applicability of capillary SFC for the analysis of mixtures of cyclodextrin derivatives, e.g. those used in the synthesis of Chirasil-Dex, was, furthermore, demonstrated. 相似文献
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7.
Yingjin liu Naoto Horiuchi Yoshimi Sueishi Shunzo Yamamoto 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(3-4):233-239
The kinetics of the hydride transfer reaction between Methylene Blue (MB+) and 1-benzyl-1,4-dihydronicotinamide (BNAH) were studied in 10% ethanol-90% water mixed solvents containing β- and γ-cyclodextrins (β-CD and γ-CD). The pseudo-first order rate constant shows kinetic saturation at high initial concentration of BNAH. This indicates the formation of a complex between MB+ and BNAH. The reaction was suppressed by addition of β-CD, but enhanced by addition of γ-CD. MB+ and BNAH were separately accommodated within the β-CD cavity and the cavity walls may protect the activity site of the reactants. On the other hand, in the MB+-BNAH-γ-CD system, the inclusion of the complex between MB+ and BNAH with γ-CD occurred. This effect of γ-CD can distinguish between the productive and non-productive nature of the complex. 相似文献
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Reported here is an analytical method enabling the stereochemical resolution of a new antianginal compound possessing two stereogenic centers, leading to four stereoisomers. Only one of these isomers is currently under development as a novel antianginal agent and consequently, the other three isomers are considered as unwanted chiral impurities. Therefore, an enantioselective method is required in order to check its enantiomeric purity. This paper presents a method exploiting the high efficiency of capillary electrophoresis and the complexing properties of cyclodextrins to achieve the separation of the four stereoisomers of this weakly basic compound (pKa = 7.4). For this purpose, the combination of a neutral cyclodextrin, hydroxypropyl-gamma-cyclodextrin (HP-gamma-CD), and an anionic cyclodextrin, carboxymethyl-beta-cyclodextrin (CM-beta-CD), was added to the separation buffer running in an uncoated silica capillary. After selection of the suitable cyclodextrin system, satisfactorily separation conditions were as follows: 30 mM phosphate buffer (pH 6.4) containing 10 mM of HP-gamma-CD and 10 mM of CM-beta-CD, running voltage +30 kV. The resulting run time and resolutions were respectively about 17 min and between 1.95 and 2.84. Linearity curves (0.993 < r2 < 0.998) are also shown. 相似文献
10.
Margarita Valero Silvia M. B. Costa José R. Ascenso M. Mercedes Velázquez Licesio J. Rodríguez 《Journal of inclusion phenomena and macrocyclic chemistry》1999,35(4):663-677
The inclusion of the anti-inflammatory drug, Nabumetone, in -, - and hydroxypropyl--cyclodextrin (CDs) is studied using UV-VIS absorption and steady-state fluorescence emission. Binding constants and thermodynamic parameters of complex formation are determined by spectrofluorimetry. The inclusion phenomena of Nabumetone with the three cyclodextrins is compared with that of the well known similar anti-inflammatory drug Naproxen. In the case of Nabumetone pronounced differences are observed in the complexation process with each cyclodextrin whereas the respective Naproxen complexes are nearly identical. 1H-NMR experiments show that the inclusion process in Nabumetone can occur either through the substituents in the -2 (butanone) or -6 (methoxy) positions in the naphthalene ring. 相似文献