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《Carbohydrate research》1986,148(2):189-197
Five galactomannans obtained by aqueous extraction at different temperatures from the endosperm of the seed of Gleditsia triacanthos, and having different Gal:Man ratios, were submitted to a preliminary degradation, and the products analyzed by high resolution 13C-n.m.r. spectroscopy. In these spectra all carbon atoms yield several lines. C-6 (substituted Man) shows, for the first time, a clear splitting, which is explained by considering that this carbon atom is sensitive to whether or not its neighbors are branched; this provides a basis for determining the next-nearest-neighbor probabilities in the galactomannans (“triad frequencies”). Although diad frequencies are roughly consistent with a random arrangement, the values obtained for the triad frequencies indicate a more complex kind of arrangement of the lateral chains. 相似文献
3.
The 1H- and 13C-n.m.r. spectra of eledoisin and minor oligopeptides were measured and assigned. The proton spectra were interpreted on the basis of homonuclear decoupling, chemical shift criteria and spectra simulation. The information obtained was used in the assignment of the 13C spectrum via heteronuclear 1H-13C. The steric arrangement of proline residue was deduced from the 13C spectrum. Moreover the similarity of the 13C spectrum of eledoisin with that of component oligopeptides suggests that no considerable conformational change occurs in the undecapeptide relative to the component fragments. 相似文献
4.
《Carbohydrate research》1986,148(2):199-207
A complete, unambiguous assignment of all of the 13C-n.m.r.-spectral signals of agarose oligomers produced by enzymic hydrolysis has been achieved. The 1J13C-H coupling constants are reported, and the chemical shifts and coupling constants of both the agarose polymer and oligomers are compared. 相似文献
5.
13C-N.M.R. study of the conformation of helical complexes of amylodextrin and of amylose in solution
Amylose (average d.p. 1000) and amylodextrin (average d.p. 25) have identical 13C-n.m.r. spectra, except for some minor signals from the small amount of alpha-1----6 branch linkages present in amylodextrin. Amylodextrin can be obtained as stable solutions in much higher concentrations than amylose and so requires only 1/100th as many scans to obtain a spectrum comparable to that of amylose. 13C-N.m.r. spectroscopy has been used to study the formation of amylodextrin complexes with organic complexing agents in aqueous solution. A control study using dextran, which does not form helical complexes, showed that, when complexing agents are added, the signals from all of the carbons show a slight downfield shift due to a general solvent effect. In the case of amylodextrin, the addition of increasing concentrations of complexing agent also produced a downfield shift of the signals of all the carbons, but there was a greater shift of the signals for carbons 1 and 4 than for carbons 2, 3, and 6, indicating that something more than a solvent effect was occurring. The cycloamyloses (cyclic alpha-1----4 linked D-glucose oligosaccharides which may be considered as model for an amylose helix) in water have chemical shifts for carbons 1 and 4 that are comparable to those shown by the amylodextrin complexes. It is thus proposed that the formation of a helical complex with amylodextrin results in a change in the conformation of the glycosidic linkage, which is reflected by greater downfield shifts of the signals for carbons 1 and 4, relative to those for carbons 2, 3, and 6. It was observed that differences in the ratio of the downfield shifts of C-1 and C-4 of the different amylodextrin complexes indicate differences in the degree of compactness of the helical structures. A comparison of the 13C chemical shifts of methyl alpha-D-glucoside and methyl alpha-maltoside showed that, for a molecule as small as a disaccharide, there is a conformational change about the glycosidic linkage when complexing agents are added. 相似文献
6.
《Carbohydrate research》1986,147(2):247-264
l-(1-13C, 5-2H)Arabinose (6D) and l-(2-13C, 5-2H)arabinose (8D) have been synthesized by degradation of 2,3-O-isopropylidene-α-l-rhamnofuranose (2) to l-(4-2H)erythrose (5β,5αD), with subsequent chain elongation to 6D plus l-(1-13C, 5-2H)ribose (7D), the latter being converted into 8D. Intermediates were identified by complete assignment of the 13C chemical shifts employing carbon-carbon and carbon-deuterium coupling constants, deuteration shifts, differential isotope-shifts, and deuterium spectra. The anomeric carbon atoms of 2 and 2,3-O-isopropylidene-l-(1-2H) erythrose (4D) gave only single 13C resonances, suggesting that these two compounds exists in only one major anomeric configuration, clarifying previously reported work. The synthesis of 2,3-O-isopropylidene-l-(1-2H)rhmanitol (3D) facilitated the assignment of the signals in the 13C spectra of the nondeuterated analog. Specific deuterium-enrichment and the observed carbon-deuterium coupling (1JC,D ∼22 Hz) not only served to identify the deuterated carbon atom unambiguously in 3 but also permitted assignment of closely spaced resonances. The deuterium spectrum of 2,3-O-isopropylidene-l-(1-2H)erythrofuranose (4D) showed only a single resonance, indicating preponderance of one anomer, in accord with the observation of a single C-1 resonance in the 13C spectrum. 相似文献
7.
《Carbohydrate research》1987,163(1):91-98
O-(2-Hydroxyethyl)cellulose was converted into a mixture of the corresponding d-glucitol derivatives by hydrolysis followed by reduction of the sugars with NaBH4. On the basis of the spectra of individual O-(2-hydroxyethyl)-d-glucitols, the 13C-n.m.r. spectrum of this mixture was assigned to the extent that permitted quantitative analysis in terms of monomer composition of the polymer. The monomer mole-fractions conform to a statistical, kinetic model that assumes that the reactivity of the 3-hydroxyl group of the d-glucosyl residues of cellulose depends on the state of substitution at O-2. The relative rate-constants of the hydroxyl groups in the (hydroxyethyl)ation reaction are k2:k3:k3′:k6:kx = 6.0:1.0:4.0:11.1:34.6, indicating that the reactivity of OH-3 increases fourfold upon (hydroxyethyl)ation of OH-2. 相似文献
8.
Ronald J. Voll Theodore A.W. Koerner Paul A. Bartlett Norman S. Bhacca David C. Lankin Ezzat S. Younathan 《Carbohydrate research》1981,95(2):145-154
The reaction of two equivalents of diphenylchlorophosphate in cold pyridine with 2,5-anhydrohexitols has been assumed to result in only 1,6-bis(diphenylphosphate) products. However, by thin-layer, silica gel dry-column, and DEAE-Sephadex A-25 column chromatography, the products of this reaction have been shown to contain three major components; monophosphates (32 or 30%, by weight), 1,6-bis(phosphates) (40 or 56%), and 1,4,6-tris(phosphates) (28 or 14%): the former percentages for the product from 2,5-anhydro-d-mannitol (1) and the latter for the product from 2,5-anhydro-d-glucitol (10). The identity of each bis- and tris-(phosphate) of 1 or 10 was established by 31P- and 13C-n.m.r. spectroscopy. Acetylated bis- and tris-(diphenylphosphates) of 1 were also examined by 1H-n.m.r. The significance of these findings on the interpretation of studies of the anomeric specificity of enzymes and on the specificity of the reagent diphenylchlorophosphate are discussed. The formation of only a 1,4,6-tris(phosphate) of 10 suggests that the 1,6-bis(diphenylphosphate) of 10 may undergo formation of a 1,3-cyclic phosphate triester by transesterification with elimination of phenol. A method for the determination of the number of cyclohexylammonium groups crystallizing with a sugar phosphate is proposed that simplifies the elemental analysis of this type of salt. 相似文献
9.
D C Sabularse R L Anderson 《Biochemical and biophysical research communications》1981,100(4):1423-1429
Inorganic pyrophosphate: D-fructose-6-phosphate 1-phosphotransferase was detected in extracts of mung bean sprouts, the first such detection in C3 plants. The enzyme had an absolute requirement for a divalent metal (Mg++) as well as for D-fructose 6-phosphate and inorganic pyrophosphate. An examination of anomalous kinetics revealed that the enzyme was activated by a product of the reaction, D-fructose 1,6-bisphosphate; micromolar concentrations of this effector increased the activity of the enzyme about 20-fold. D-Glucose 1,6-bisphosphate at higher concentrations could substitute for D-fructose 1,6-bisphosphate as an activator, but not as a substrate in the reverse reaction. The enzyme was fully active under conditions wherein ATP: D-fructose-6-phosphate 1-phosphotransferase from the same source was inhibited >99% (e.g., in the presence of 10 μM phosphoenolpyruvate). 相似文献
10.
Effects of carbohydrate-structure changes on induced shifts in differential isotope-shift 13C-N.M.R.
Deuterium-induced, 13C-isotope shifts are shown to vary considerably from the initially predicted values calculated for ordinary pyranose and furanose sugars, when minor structural changes are introduced into the carbohydrate ring. Both substitution of C-OH groups or reduction of C-OH to CH2 permitted the evaluation of γ effects of OD without the contribution of β-OD-induced shifting. The observed γ-shift values for these modified structures were twice as large as those previously noted. This difference is most probably due to favored salvation. Substitution of OH at C-6 led to the predicted loss of differential isotope-shift (d.i.s.) at C-6 because of its isolation from all β and γ OD groups. The 31P resonances of d-glucose 6-phosphate show downfield deuterium shifts. Based on d.i.s. values, new 13C-shift assignments are proposed for isomaltose and 2-amino-2-deoxy-α-d-glucose. A study of acidic carbohydrates has demonstrated that isotope shifts are somewhat larger for sp2-hybridized carbon atoms whose OH groups are acidic. Relaxation times for sp2 carbon atoms isolated from dipolar interaction with protons were very long in D2O relative to their relaxation time in the H2O environment. 相似文献
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Glucose 1,6-bisphosphate, the powerful common regulator of several key enzymes in carbohydrate metabolism, was found to exert a potent inhibitory effect on the activity of 6-phosphogluconate dehydrogenase (decarboxylating) from yeast and several rat tissues. These findings suggest that glucose 1,6-bisphosphate may have a regulatory influence on the pentose phosphate pathway. 相似文献
13.
The nature of the inclusion complexes of several cyclomalto-oligosaccharides (cyclodextrins, CDs) with azo dyes has been studied on the basis of 13C-n.m.r. chemical shifts, relaxation times, correlation times, and broadening and doubling of the n.m.r. signals. All CDs show the azo dye-induced shifts at the narrow-rim side of the CD, indicating that the azo dyes protrude from the cavity. CD-induced shifts of azo dyes depend on the hydrophobic nature of the cavity, van der Waals forces, as well as ring-current and deformation effects, and suggest inclusion essentially from the hydrophobic site. The broadening and the doubling of the 13C-n.m.r. signals, the altered relaxation and correlation times, as well as the temperature dependence for these phenomena, also provide particular information about the characteristic host-guest interactions. 相似文献
14.
D-myo-inositol (1,4)-bisphosphate 1-phosphate. Partial purification from rat liver and characterization 总被引:3,自引:0,他引:3
J D Moyer O Reizes N M Dean N Malinowski 《Biochemical and biophysical research communications》1987,146(3):1018-1026
A specific 1-phosphatase acting on myo-inositol (1,4)-biphosphate with a high affinity (Km = 0.9 microM) has been purified 49-fold from soluble proteins of rat liver by anion exchange chromatography followed by gel filtration. This enzyme has a molecular weight of 58,000 as estimated by gel filtration, a pH optimum of 7.5, and requires Mg++ for activity. The only product formed from myo-inositol (1,4)-bisphosphate is the 4-monophosphate. Of 7 other inositol phosphates examined only myo-inositol (1,3,4)-triphosphate was a substrate. 相似文献
15.
《Carbohydrate research》1977,59(1):19-34
The1H- and13C-n.m.r spectra ofD-glucopyranose and 2-acetamido-2-deoxy-D-glucopyranose and its derivatives in D2O at 25° have been completely interpreted. Iterative analysis allowed accurate determination of the chemical shifts and coupling constants in the 270-MHz1H-spectra, and these are used to correlate the chemical shift changes with substitution patterns. The implications of the systematic errors from assuming first-order conditions for the p.m.r spectra of sugars are discussed in relation to measuring shift changes of sugar-enzyme complexes. 相似文献
16.
The rate of substrate cycling between fructose 6-phosphate and fructose 1,6-bisphosphate in skeletal muscle. 总被引:5,自引:4,他引:1
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Substrate cycling of fructose 6-phosphate through reactions catalysed by 6-phosphofructokinase and fructose-1,6-bisphosphatase was measured in skeletal muscles of the rat in vitro. The rate of this cycle was calculated from the steady-state values of the 3H/14C ratio in hexose monophosphates and fructose 1,6-bisphosphate after the metabolism of either [5-3H,6-14C]glucose or [3-3H,2-14C] glucose. Two techniques for the separation of hexose phosphates were studied; t.l.c. chromatography on poly(ethyleneimine)-cellulose sheets or ion-exchange chromatography coupled with enzymic conversion. These two methods gave almost identical results, suggesting that either technique could be used for determination of rates of fructose 6-phosphate/fructose 1,6-bisphosphate cycling. It was found that more than 50% of the 3H was retained in the fructose 1,6-bisphosphate; it is therefore probable that previous measurement of cycling rates, which have assumed complete loss of 3H, have underestimated the rate of this cycle. The effects of insulin, adrenaline and adrenergic agonists and antagonists on rates of fructose 6-phosphate/fructose 1,6-bisphosphate cycling were investigated. In the presence of insulin, adrenaline (1 microM) increased the cycling rate by about 10-fold in epitrochlearis muscle in vitro; the maximum rate under these conditions was about 2.5 mumol/h per g of tissue. The concentration of adrenaline that increased the cycling rate by 50% was about 50 nM. This effect of adrenaline appears to be mediated by the beta-adrenergic receptor, since the rate was increased by beta-adrenergic agonists and blocked by beta-adrenergic antagonists. From the knowledge of the precise rate of this cycle, the possible physiological importance of cycling is discussed. 相似文献
17.
Fred R. Seymour Roger D. Knapp Stephen H. Bishop Allene Jeanes 《Carbohydrate research》1979,68(1):123-140
Dextran fractions from NRRL strains Leuconostoc mesenteroides B-742, B-1299, B-1355, and Streptobacterium dextranicum B-1254 were examined by 13C-n.m.r. spectroscopy at 34 and 90°, and by methylation structural analysis. The native, structurally homogeneous dextran from L. mesenteroides NRRL B-1402 was also examined. The data allow correlations to be made between the structure and physical properties of the S (soluble) and L (less-soluble) fraction pairs of dextrans B-742, B-1254, B-1299, and B-1355. For the dextrans under consideration here, increasing solubility of the dextran (both in water and in aqueous ethanol) was found to correlate with decreasing percentages of α-d-(1→6)-linked d-glucopyranosyl residues. Both the diagnostic nature of the 70–75-p.p.m. spectral region with regard to type of dextran branching, and the increase in resolution of the polysaccharide spectra at higher temperatures, have been further confirmed. 相似文献
18.
Kinetic pathways of formation and dissociation of the glycerol-3-phosphate dehydrogenase-fructose-1,6-bisphosphate aldolase complex.
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Quantitative analysis of the time courses of fluorescence anisotropy changes due to the binding of fructose-1,6-bisphosphate aldolase to the dissociable cytoplasmic glycerol-3-phosphate dehydrogenase covalently labelled with fluorescent dye was carried out. The behaviour of the aldolase-dehydrogenase system seems to be consistent with a cyclic reversible model characterized by the formation and dissociation of complexes of both the monomeric and the dimeric forms of dehydrogenase with aldolase, and rapid equilibrium between the free monomeric and dimeric forms of dehydrogenase. The half-life time of the formation of dimeric dehydrogenase-aldolase complex at the concentration of the enzymes expected to exist in the cell (i.e. in the micromolar range) is some minutes, and the time needed for equilibration between the aldolase-bound dimeric and monomeric forms of dehydrogenase is a few minutes as well. Consequently, one may expect that both the formation and the dissociation of this heterologous enzyme complex have physiological relevance. 相似文献
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13C-N.m.r. spectral data as well as spin-lattice relaxation times (T1 values) are presented for the core glycopeptides beta-D-Gal-(1----3)-alpha-D-GalNAc----Ser, Thr. The binding of Gd3+ to these model compounds containing N-terminal blocking groups and esterified carboxyl groups indicates that the disaccharide contains a rather weak, but unique, binding-site in the vicinity of C-2 of alpha-D-GalNAc (possibly involving N-2', the acetamido carbonyl group, O-3' and/or possibly the glycosidic oxygen atom (O-3)). 相似文献