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101.
A Ghavami B D Johnston M T Jensen B Svensson B M Pinto 《Journal of the American Chemical Society》2001,123(26):6268-6271
The syntheses of two nitrogen analogues (11 and 12) of the naturally occurring sulfonium ion, salacinol (7) are described. The latter compound is one of the active principles in the aqueous extracts of Salacia reticulata that are traditionally used in Sri Lanka and India for the treatment of diabetes. The synthetic strategy relies on the nucleophilic attack of a 1,4-dideoxy-1,4-imino-D- or L-arabinitol at the least hindered carbon of 2,4-O-benzylidene D- or L-erythritol-1,3-cyclic sulfate. The nitrogen analogues bear a permanent positive charge and serve as mimics of the sulfonium ion. We reasoned that these ammonium derivatives should function in a manner similar to that of known glycosidase inhibitors of the alkaloid class such as castanospermine (4) and deoxynojirimycin (5). Enzyme inhibition assays indicate that salacinol (7) is a weak (K(i) = 1.7 mM) inhibitor of glucoamylase, whereas compounds 11 and 12 inhibit glucoamylase with K(i) values in the range approximately 10-fold higher. The nitrogen analogues 11 and 12 showed no significant inhibitory effect of either barley alpha-amylase (AMY1) or porcine pancreatic alpha-amylase (PPA) at concentrations of 5 mM. In contrast, salacinol (7) inhibited AMY1 and PPA in the micromolar range, with K(i) values of 15 +/- 1 and 10 +/- 2 microM, respectively. 相似文献
102.
The development and validation of a numerical simulation model of the flow through embankment dams is described. The paper focuses on basic verification studies, that is, comparisons with analytical solutions and data from laboratory experiments. Two experimental studies, one dealing with the flow in a Hele–Shaw cell and the other with the flow through a bed of packed glass beads, are also described. Comparisons are carried out with respect to the phreatic surfaces, pressure profiles, seepage levels and discharges. It is concluded that the agreement between experimental, analytical and numerical results is generally satisfactory. 相似文献
103.
A formula of Walczak is applied to two situations in differentialgeometry. Holomorphic distributions on Kähler manifoldsare studied, and it is shown how the formula simplifies to aBochner type formula, which is particularly useful in the studyof integrable distributions. Then the Walczak formula is appliedin the context of harmonic morphisms, where it provides a meansof investigating the vertical Laplacian of the dilation. Itis shown that, under some additional conditions on the map andthe domain, the p-energy is infinite for p sufficiently large. 相似文献
104.
The basis set dependency of the core ionization potential of water was investigated for atomic optimized Cartesian Gaussian basis sets. Basis set parameters optimized for oxygen yielded better IP's than basis set parameters optimized for fluorine. Not much was gained by using different parameters for the ground state and for the 1s hole state. 相似文献
105.
J. Silverio E. Svensson Ann-Charlotte Eliasson G. Olofsson 《Journal of Thermal Analysis and Calorimetry》1996,47(5):1179-1200
In the present study, isothermal microcalorimetry was introduced as a tool to investigate properties of starch retrogradation during the first 24 h. The study was made on purified amylose and amylopectin from corn, as well as on native starches, such as wheat, potato, maize, waxy maize and amylomaize, differing in their amylose content. The results were obtained in the form ofP-t traces (thermal powervs. time), and integration of these traces gave a net exothermic enthalpy of reaction, caused by the crystallization of amylose and amylopectin. TheP-t traces reflected the quantities of amylose and amylopectin in the starch studied. Depending on the amylose content and the botanical source of the starch, the rate of crystallization of amylose was high and predominated over that of amylopectin during the first 5–10 h. The contribution from amylose crystallization to the measured exothermic enthalpy was very substantial during this period. After 10 h, amylose crystallized at a lower constant rate. During the first 24 h, amylopectin crystallized at a low steady rate. The exothermic enthalpies obtained by the isothermal microcalorimetric investigations during the first 24 h of retrogradation were generally low in relation to the endothermic melting enthalpies observed by differential scanning calorimetry (DSC) measurements after 24 h of storage. The discrepancies in enthalpy values between the two methods are discussed in relation to phase separation and the endothermic effects owing to the decrease in polymer-water interactions when polymer-rich regions in the starch gel separate. Besides the exothermic enthalpies obtained, theP-t traces also made it possible to study the initial gelation properties of amylose from different botanical sources. The present study further demonstrated that isothermal microcalorimetry can provide a possible way to investigate the antistaling effect of certain polar lipids, such as sodium dodecylsulphate (SDS) and 1-monolauroyl-rac-glycerol (GML), when added to starches of different botanical origin. The net exothermic heat of reaction for starch retrogradation during the first 24 h was decreased when GML or SDS was added to the starch gels. The recordedP-t traces also showed how the effect of the added lipid influenced different periods during the first 24 h of starch retrogradation, and that the effect depended mainly on the amylose content, the botanical source of the starch, and the type of lipid used. When GML or SDS was added to waxy maize, the isothermal microcalorimetric studies clearly indicated some interaction between amylopectin and the polar lipids. These results concerning the action of anti-staling agents are further discussed in relation to the helical inclusion complexes formed between amylose-polar lipid and amylopectin-polar lipid.The authors thank Eva Qvarnström at the Dept. of Thermochemistry and Eva Tjerneld at the Dept. of Food Technology for valuable practical assistance. Financial support was obtained from the Swedish Council for Forestry and Agricultural Research (SJFR) and the Swedish Farmer's Foundation for Agricultural Research (Stiftelsen Lantbruksforskning). 相似文献
106.
Szczepina MG Johnston BD Yuan Y Svensson B Pinto BM 《Journal of the American Chemical Society》2004,126(39):12458-12469
The syntheses of N-alkylated deoxynojirimycin and 1,5-dideoxy-1,5-iminoxylitol derivatives having either a D- or an L-erythritol-3-sulfate functionalized N-substituent are reported. The alkylating agent used was a cyclic sulfate derivative, whereby selective attack of the nitrogen atom at the least hindered primary center afforded the desired ammonium salt. In aqueous solution, these salts were configurationally labile at the ammonium center. Sulfonium and/or selenonium analogues of the ammonium salts were prepared by analogous reactions. The chalcogen salts were obtained as mixtures of diastereomers, separable in some cases, differing only in the stereochemistry at the configurationally stable sulfur or selenium atoms. Proof of configuration and conformation of each compound was obtained by detailed NMR experiments. The compounds are six-membered ring analogues of salacinol, a known sulfonium-salt glucosidase inhibitor. Evaluation of the target compounds for enzyme inhibition of the glucosidase enzyme glucoamylase G2 indicated that these compounds were either inactive or, at best, only weak inhibitors of maltose hydrolysis. 相似文献
107.
Folmer BM Svensson M Holmberg K Brown W 《Journal of colloid and interface science》1999,213(1):112-120
In this work the physicochemical behavior of a series of phytosterol ethoxylates in water is presented. The influence of the length of the polyoxyethylene chain is studied. The surfactant solutions have been examined by means of birefringent microscopy, surface tension, self-diffusion 1H NMR, dynamic and static light scattering, and rheology. The surfactants with a hydrophilic chain of 10 oxyethylene units or more gave a micellar region. The CMC values were generally very low and a reverse relationship between the CMC value and the polyoxyethylene chain length was obtained. The time required to reach equilibrium surface tension was very long, more than 150 min. For the hydrophobic surfactants large lamellar regions appeared while for the more hydrophilic surfactants cubic and hexagonal structures were present which remained stable up to temperatures of 100 degrees C. In the micellar region prolate aggregates were formed which showed "ghostlike" behavior, consisting of cross-linked micelles with very fast relaxation times. Copyright 1999 Academic Press. 相似文献
108.
109.
We have synthesized a new compound with formula Re4As6S3 and characterized its crystal structure by Rietveld powder diffraction methods. Re4As6S3 crystallizes in an face-centered cubic unit cell, space group (no. 216), with lattice constant a=9.8608(1) Å and Z=4. The rhenium atoms form tetrahedral clusters linked via tetrahedral arsenic clusters to produce an NaCl-type arrangement. The oxidation state of rhenium is IV and the number of electrons shared by the rhenium atoms in the cluster is 12. The structure is based on an ordered defect thio-spinel A(1−x)B2X4 where the B-type atoms form tetrahedral clusters. 相似文献
110.
L A Svensson A Bj?rklund O Lindvall 《Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry》1975,29(3):341-348
Strongly fluorescent 2-carboxymethyl-3,4-dihydro-7-hydroxyisoquinolin-6-ones are formed in high yields when catecholamines are reacted with glyoxylic acid. Formation of the fluorophores has been found to take place in two steps; i. e. via virtually non-fluorescent tetrahydroisoquinoline-1-carboxylic acids, which react to give the fluorophores in a subsequent, rapid reaction with glyoxylic acid. The rates of reaction (pseudo first-order) with glyoxylic acid for 6,7-dihydroxy-1,2,3,4-tetrahydroisoquinoline, 6,7-dihydroxy-1,2,3,4-tetrahydroisoquinoline-1-carboxylic acid, and 6,7-dihydroxy-1,2,3,4-tetrahydroisoquinoline-3- carboxylic acid show that introduction of a carboxyl group at either C-1 or C-3 in a tetrahydroisoquinoline highly facilitates the reaction with glyoxylic acid. This behaviour is discussed in terms of a mechanism involving both intramolecular acid catalysis by the C-1 or C-3-carboxyl groups during dehydration of the carbinolamine intermediate, and facilitation of the prototropic shifts of the resulting Schiff's base by decarboxylation. 相似文献