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1.
Amylose, a putative linear α-(1→4)-glucan and a component of most starches, was isolated from potato, rice, and wheat starches by forming the 1-butanol complex in a solution of the starches. It previously had been found that these amyloses were incompletely hydrolyzed by β-amylase, indicating that it was partially branched. Solubilization of the butanol complex in water and steam distillation of the 1-butanol, followed by cooling to 4 °C gave precipitation of the double helical, linear, retrograded amylose over a 15 h period, leaving the soluble amylose in solution. The soluble amyloses were precipitated with two volumes of ethanol, and the precipitate was solubilized and reprecipitated to remove traces of linear amylose. The precipitated, soluble amyloses, were partially branched and had properties intermediate between linear amylose and amylopectin. The water solubility of the potato amylose was 10.52 mg/mL, with a number-average degree of polymerization (DPn) of 8440 and 2.1% branch linkages that had a DPn of 48; the water solubility of the rice amylose was 8.83 mg/mL, with a DPn of 2911 and 1.4% branch linkages that had a DPn of 72; and the water solubility of wheat amylose was 6.33 mg/mL, with a DPn of 1160 and 1.6% branch linkages that had a DPn of 64. The three soluble amyloses have structures and properties intermediate between the nearly water insoluble (?1 mg/mL), linear amylose, and the highly water-soluble, 4-5% branched, amylopectin.  相似文献   

2.
《Carbohydrate polymers》1997,33(1):19-26
Commercial potato amylose was used to study temperature effects on the retrogradation of amylose solutions (3.5mg/ml). The retrogradation rate decreased as incubation temperature increased (5 to 45 °C). The degree of retrogradation within 24 h decreased from 58.8 to 7.1% as incubation temperature increased from 5 to 45 °C. In the amylose solution, different-sized molecular subfractions retrograded at different rates. After incubating at 5 °C for 100 days, the majority of the amylose molecules retrograded and precipitated from the solution; at 45 °C, only amylose of the small-molecular subfraction (number average, DPn = 110; weight average, DPw = 150) retrograded and precipitated. Entanglement of molecules was observed in size exclusion chromatograms. The morphology of retrograded amylose observed by using a scanning electron microscope differed with the retrogradation temperature. The chain length of amylose crystalline segments, prepared by hydrolysis of retrograded amylose, showed a narrow distribution (polydispersity from 1.21 to 1.67). The chain lengths of resistant segments increased DPn from 39 to 52 and DPw from 47 to 72 for α-amylolysis and DPn from 34 to 40 and DPw from 48 to 67 for 16% sulfuric acid hydrolysis, when incubation temperature increased from 5 to 45 °C.  相似文献   

3.
A series of pullulan fractions with molecular weights in the range 5 × 103 to 8 × 105 were prepared. The weight-average molecular weight (Mw) of all the samples was determined by sedimentation equilibrium. The hydrodynamic properties of pullulan in aqueous solution were investigated by viscometry and ultracentrifugation. The experimental results indicate that pullulan molecules in water are fairly stable and behave as expanded random coils when Mw is above 2 × 104. The molecular weight distributions of the fractions were measured by gel filtration. The ratio Mw/Mn was close to 1·1, except for a sample with the highest Mw.It is concluded that the pullulan fractions prepared by the present work are well characterized and have a narrow molecular weight distribution. They may be useful as standard samples for studies of water-soluble polymers.  相似文献   

4.
Thermally induced aggregates of α-chymotrypsinogen A and bovine granulocyte-colony stimulating factor in acidic solutions were characterized by a combination of static and dynamic light scattering, spectroscopy, transmission electron microscopy, and monomer loss kinetics. The resulting soluble, high-molecular weight aggregates (∼103-105 kDa) are linear, semiflexible polymer chains that do not appreciably associate with one another under the conditions at which they were formed, with classic power-law scaling of the radius of gyration and hydrodynamic radius with weight-average molecular weight (Mw). Aggregates in both systems are composed of nonnative monomers with elevated levels of β-sheet secondary structure, and bind thioflavine T. In general, the aggregate size distributions showed low polydispersity by light scattering. Together with the inverse scaling of Mw with protein concentration, the results clearly indicate that aggregation proceeds via nucleated (chain) polymerization. For α-chymotrypsinogen A, the scaling behavior is combined with the kinetics of aggregation to deduce separate values for the characteristic timescales for nucleation (τn) and growth (τg), as well as the stoichiometry of the nucleus (x). The analysis illustrates a general procedure to noninvasively and quantitatively determine τn, τg, and x for soluble (chain polymer) aggregates, as well as the relationship between τn/τg and aggregate Mw.  相似文献   

5.
《Biomass》1989,18(2):109-126
In a comparative investigation of the chemical composition of Arundo donax L. and Miscanthus sinensis Anderss. the following experiments were performed: ash determination and ash characterization by energy dispersive X-ray analysis; determination of solubility in cyclohexane/ ethanol, hot water, 1% hydrochloric acid and sodium hydroxide; C, H and N determination; determination of Klason lignin and acid soluble lignin content; sulfuric acid hydrolysis followed by borate complex ion exchange chromatography of the monomeric sugars; isolation of milled wood lignins (MWL) and dioxane lignins (DIL) and their analysis by C, H, and OMe determination; quantitative FTIR spectroscopy of MWL; recording the molecular weight distribution curves using high performance size exclusion chromatography (HPSEC); calculation of average molecular weights, such as Mw and Mn; calculation of the heating values of the lignocellulosics and their components. The quantitative composition of the lignin from the three basic phenylpropane units is presented.M. sinensis was submitted to hydroliquefaction. The conversion process yielded 35% of a net product oil (NPO) with low oxygen content (11%), low viscosity (10−2 NS m−2), low asphaltene content (3·5%) low molecular weight (Mw 200) and with a specific gravity of c. 0·93 g cm−3. The NPO has a heating value of 39·4 MJ kg−1 and contains 55% of the carbon of the starting material and 59% of the combined heating value from the biomass and the hydrogen used for hydroliquefaction. The process yields 28% water which contains 58% of the original oxygen of the biomass. The process gives rise to 9 g solids and 32–35 g gases, whose energy content can easily be recovered.  相似文献   

6.
Comb-shaped copolymers with cellobiose acetate or cellulose triacetate (CTA) side-chains, PPMA-g-(CTA2-C15) and PPMA-g-(CTA13-C15), were prepared by grafting N-(15-azidopentadecanoyl)-2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)-β-d-glucopyranosylamine (CTA2-C15-N3) and N-(15-azidopentadecanoyl)-tri-O-acetyl-β-cellulosylamine (CTA13-C15-N3, number average degree of polymerization (DPn= 13) onto poly(2-propyn-1-yl methacrylate) (PPMA, weight average degree of polymerization (DPw, X + Y = 5.59 × 102)) via “click chemistry”. The copolymers were characterized by 1H, 13C and two-dimensional NMR and size exclusion chromatography-multi-angle laser light scattering (SEC-MALS) measurements. The numbers of CTA side-chains (X) of PPMA-g-(CTA2-C15) and PPMA-g-(CTA13-C15) were calculated as 4.03 × 102 and 2.45 × 102, respectively. Copolymers with cellulosic side-chains, PPMA-g-(CELL2-C15) and PPMA-g-(CELL13-C15), were successfully obtained after deacetylation of PPMA-g-(CTA2-C15) and PPMA-g-(CTA13-C15), respectively. X-ray diffraction measurements revealed that PPMA-g-(CELL13-C15) showed crystalline pattern of cellulose II, which is believed to have anti-parallel orientation.  相似文献   

7.
Sonicated calf thymus DNA was fractionated by rate zonal centrifugation into seven fractions with weight average molecular weights ranging from 0.28 to 1.3 × 106 daltons, as determined by sedimentation equilibrium and light scattering measurements (the latter are described in the accompanying paper). Electron microscopy and sedimentation equilibrium analysis revealed these fractions to be narrowly disperse with Mw/Mn ratios averaging about 1.06. Intrinsic viscosities and sedimentation rates were measured and found to vary linearly with molecular weight in double-logarithmic plots in fair agreement with previously published functions relating these parameters for low molecular weight DNA. The average value for β from the Mandelkern— Flory equation was 2.59 × l06, also agreeing with reported estimates of this parameter for short DNA. These data will be used in the second paper of this series to calculate the persistence length of the DNA fragments in each of the seven fractions by light scattering and hydrodynamic theories for the Kratky—Porod worm-like coil.  相似文献   

8.
《Inorganica chimica acta》1988,151(2):153-161
Two crystalline forms of the [Cu(II) (IMP) (DPA) (H2O)]2·nH2O (IMP=inosine 5′-monophosphate, DPA=2,2′-dipyridylamine) complex were obtained from aqueous solution at pH=6.2. The crystals of the two forms belong to the monoclinic system, space group P21. The cell parameters are: a=9.445(2), b=33.902(4), c=7.802(2) Å, β=90.48(2)°, Z= 2, Dc=1.69g cm−3 and μ(Mo Kα) = 10.49cm−1 (form α, n=4), and a=7.828(2), b=18.552(3), c=17.378(3) Å, β=91.16(2)°, Z=2, Dc=1.66 g cm−3, μ(Mo Kα) = 10.40 cm−1 (form β, n=3.62). Bau and coworkers reported the preparation of form α by vapor diffusion of CH3CN into aqueous solution containing Cu(NO3)2, Na2IMP and DPA in a 1:1:1 molar ratio and the analysis of the compound by single crystal X-ray diffraction [1].Intensities for 3412 reflections were collected from a crystal of form β in the present work. Graphite-monochromatized Mo Kα radiation was employed. The structure was refined to final R and Rw values of 0.1000 and 0.1115 respectively. The dimeric units contain two copper ions in square-pyramidal coordination polyhedra. Each polyhedron consists of two nitrogen atoms of DPA, two oxygen atoms from two phosphate groups and a water molecule in the axial position. A statistical disorder was found in a nucleotide moiety of the dimer. Two sets of atomic positions corresponding to the purine system were refined with site occupation factors of 0.62(1) and 0.38(1) respectively. Also the ribose ring shows a disorder with two possible conformations. The puckering mode of the prevailing conformation is C(3′)-endo. In the other nucleotide molecule of the dimer the furanose puckering mode is C(3′)-endo. The rotation around the glycosyl linkages can be described as ‘anti’ in the structure of form β. The C(4)N(9)C(1′)O(4′) torsion angle values are −97(2) and −94(3)° for the disordered nucleotide molecule and +91(2)o for the other nucleotide moiety. Strong intermolecular DPADPA and purine-purine stacking interactions stabilize the crystal lattice. The differences on the nucleotide conformation between the structure of form α and form β can probably be ascribed to differences in the hydrogen bonds and stacking interactions.  相似文献   

9.
Chitosan is a linear heteropolymer consisting of β 1,4-linked N-acetyl-D-glucosamine (GlcNAc) and D-glucosamine (GlcN). We have compared the antifungal activity of chitosan with DPn (average degree of polymerization) 206 and F A (fraction of acetylation) 0.15 and of enzymatically produced chito-oligosaccharides (CHOS) of different DPn alone and in combination with commercially available synthetic fungicides, against Botrytis cinerea, the causative agent of gray mold in numerous fruit and vegetable crops. CHOS with DPn in the range of 15–40 had the greatest anti-fungal activity. The combination of CHOS and low dosages of synthetic fungicides showed synergistic effects on antifungal activity in both in vitro and in vivo assays. Our study shows that CHOS enhance the activity of commercially available fungicides. Thus, addition of CHOS, available as a nontoxic byproduct of the shellfish industry, may reduce the amounts of fungicides that are needed to control plant diseases.  相似文献   

10.
Data are presented which show that bromegrass mosaic virus has a particularly low molecular weight and nucleic acid content. A molecular weight of 4.6 × 106 was calculated from the sedimentation coefficient, S°20,w = 86.2S, the diffusion coefficient, D20,w = 1.55 × 10-7 cm2/sec., and an assumed partial specific volume, [UNK] = 0.708 ml/gm. The virus has a ribonucleic acid content of 1.0 × 106 atomic mass units. Electrophoresis experiments showed that the virus is stable in 0.10 ionic strength buffers in the pH range 3-6. Breakdown of the virus was observed outside this pH range. Some characteristics of the breakdown products are described.  相似文献   

11.
P18, the sole component of T4 tail sheath, has been isolated in a monomeric active form from extended sheaths of intact tails which were dissociated at low ionic strength. The molecular weight of P18 is determined to be 65,000 from sedimentation equilibrium and 73,000 from sodium dodecyl sulphate/gel electrophoresis. Combining the diffusion constant (D20,w = 5·5× 10?7cm2s?1)and the sedimentation constant (s020,w = 4·2 S) a value of 67,000 is obtained. The circular dichroism spectra reveal a striking similarity of the structure of P18 in the monomeric state and in the extended sheath conformation.The purified P18 is found to reassemble into extended sheaths if the core-baseplate complex is present, forming normal length tails. Structures similar to polysheath are formed in the absence of core-baseplates.  相似文献   

12.
The molecular weight (Mw) and molecular-weight distribution of the extracellular polysaccharide xanthan, synthesized by the bacterium Xanthomonas campestris, have been determined from measurements of the sedimentation coefficient, s20,itw, and the intrinsic viscosity, [η], with the aid of the Mandelkern-Flory-Scheraga equation. The sedimentation coefficient of native xanthan was measured by band-sedimentation of polysaccharide molecules that had been tagged with a fluorescent group; the fluorescent label permits the use of very low concentrations of polymer. A typical, native-xanthan sample has Mw  15 x 106; the polydispersity index Mw/Mn is 2.8. Measurement of s and [η] for a homologous series of five xanthan samples having Mw ranging from 0.40 to 15 X 106, prepared by sonication of native xanthan, shows that, for low molecular weight, the intrinsic viscosity [η] obeys the relation [η]  KM1.35. The high value of the Staudinger exponent in this relation demonstrates that xanthan is a rod-like molecule having stiffness similar to that of native DNA, which has a Staudinger exponent of 1.32. Moreover, the absolute values of [η] suggest that xanthan has a mass per unit length of about 1900 daltons/nm, which is twice the mass per unit length of the single-stranded structure proposed from X-ray work.  相似文献   

13.
Cerebral aneurysms form preferentially at arterial bifurcations. The vascular optimality principle (VOP) decrees that minimal energy loss across bifurcations requires optimal caliber control between radii of parent (r0) and daughter branches (r1 and r2): r0n=r1n+r2n, with n approximating three. VOP entails constant wall shear stress (WSS), an endothelial phenotype regulator. We sought to determine if caliber control is maintained in aneurysmal intracranial bifurcations. Three-dimensional rotational angiographic volumes of 159 middle cerebral artery (MCA) bifurcations (62 aneurysmal) were processed using 3D gradient edge-detection filtering, enabling threshold-insensitive radius measurement. Radius ratio (RR)=r03/(r13+r23) and estimated junction exponent (n) were compared between aneurysmal and non-aneurysmal bifurcations using Student t-test and Wilcoxon rank-sum analysis. The results show that non-aneurysmal bifurcations display optimal caliber control with mean RR of 1.05 and median n of 2.84. In contrast, aneurysmal bifurcations had significantly lower RR (0.76, p<.0001) and higher n (4.28, p<.0001). Unexpectedly, 37% of aneurysmal bifurcations revealed a daughter branch larger than its parent vessel, an absolute violation of optimality, not witnessed in non-aneurysmal bifurcations. The aneurysms originated more often off the smaller daughter (52%) vs. larger daughter branch (16%). Aneurysm size was not statistically correlated to RR or n. Aneurysmal males showed higher deviation from VOP. Non-aneurysmal MCA bifurcations contralateral to aneurysmal ones showed optimal caliber control. Aneurysmal bifurcations, in contrast to non-aneurysmal counterparts, disobey the VOP and may exhibit dysregulation in WSS-mediated caliber control. The mechanism of this focal divergence from optimality may underlie aneurysm pathogenesis and requires further study.  相似文献   

14.
Size exclusion chromatography coupled with triple detection (online laser light scattering, refractometry, and viscosimetry) (SEC-TDA) was applied for the study of hyaluronan (HA) fragments produced during hydrolysis catalyzed by bovine testicular hyaluronidase (BTH). The main advantage this approach provides is the complete hydrodynamic characterization without requiring further experiments. HA was hydrolyzed using several BTH amounts and for increasing incubation times. Fragments were characterized in terms of weight and number average molecular weights (Mw and Mn, respectively), polydispersity index (Mw/Mn), hydrodynamic radius (Rh), and intrinsic viscosity ([η]). The Mark-Houwink-Sakurada (MHS) curves (log [η] versus log Mw) were then derived directly. Fragments covering a whole range of Mw (10-900 kDa) and size (Rh = 4-81 nm) and presenting a rather narrow distribution of molar masses (Mw/Mn = 1.6-1.7) were produced. From the MHS curves, HA conformation resulted in a change from a random coil toward a rigid rod structure while decreasing the Mw. HA enzymatic hydrolysis in the presence of a BTH inhibitor was also monitored, revealing that inhibition profiles are affected by ionic strength. Finally, a comparison of the kinetic data derived from SEC-TDA with the data from rheological measurements suggested different strengths of the two methods in the determination of the depolymerization rate depending on the hydrolysis conditions.  相似文献   

15.
Donald B. Siano 《Biopolymers》1978,17(12):2897-2908
Light-scattering studies on buffered aqueous solutions of the triple-stranded polyribonucleic acid poly(A)·2poly(U) were carried out at neutral pH and during titration. At pH 7.1 and 22°C, a sample of commercially available polymer in 0.005M phosphate buffer gave a Zimm plot which yielded values for the weight-average molecular weight, M w, of 874,000 ± 1800 g/mol, a root-mean-square radius, ρ of 930 ± 22 Å, and a second viral coefficient of 0.51 ± 0.05 × 10 ?3 cm3g?1 mol. The light-scattering data were also analyzed by serval linear and nonlinear least-squares programs which were devised to determine the model (e.g., rod, coil, or zigzag) which could best describe the shape of the molecule. It was found that a rodlike model, perhaps with a few bends, was in best overall agreement with the data. The assumption that the molecule is a thin rod leads to a value for the linear density of 206 g mol?1 Å?1 and a translation of 3.3 Å per residue. These values are also in close agreement with those expected for a triple-stranded, thin, base-stacked molecule. During titration from neutral pH with 0.1M HCl, the observed apparent molecular weight slowly increased until at about pH 3.5 a sudden, large increase (about 30-fold) occurred. The root-mean-square radius, on the other hand, after an initial small decrease (of about 25%), also exhibited a large increase (about 4-fold). Upon back titration with 0.1M NaOH, the molecular parameters did not retrace the original path, but instead exhibited hysteresis—the M w and ρ z are both larger on the basic branch than on the acid branch at a corresponding pH. A plot of long ρ z against log(M w) during the interval in which the high-moelcular-weight form was present (below pH 3.5 on the acid branch, and on the basic branch) gave a straight line with a slope of ?. This suggests that the aggregates were composed of some tens of rather open radom coils, presumably of poly(A)·poly(A), and that the hysteresis may be caused under conditions by the metastability of the entangled coils.  相似文献   

16.
The physico-chemical properties of the DNA released from bacteriophage G (active on Bacillus megatherium) are described. Phage G, an unusually large bacteriophage, has a nucleic acid content of 4 to 6 × 108 daltons.Sedimentation velocity analysis at low angular speed and examination by electron microscopy, indicate that a single DNA molecule, sedimenting with s20, w0 = 125 ± 1.5 S and at least 200 ± 20 μm long, is released upon thermal or osmotic shock. Melting temperature data and chromatographic analysis indicate a mean base composition of 70% A + T. CsCl and Cs2SO4 buoyant density data, circular dichroism spectra and sensitivity to specific nucleases indicate that phage G DNA is similar to the DNAs from T-even phages and is more glucosylated than phage T6 DNA. Direct glucose determination indicates a 185% molar ratio of glucose to cytosine. Linear density extrapolated from literature data and contour length measurement yield a lower limit for the molecular weight of phage G DNA of 4.9 × 108. Comparison of this value with the s20,w0 measured with the analytical ultracentrifuge seems to confirm the validity of the empirical relationship proposed by Freifelder (1970), between s20, w0 and molecular weight, over a larger range than that previously known. A possible systematic error in defect in length determination, however, prevents a discrimination between this and other empirical formulae proposed by various authors, which predict a molecular weight that is 20 to 25% higher.  相似文献   

17.
Salmonella spp. are reported to have an increased heat tolerance at low water activity (aw; measured by relative vapor pressure [rvp]), achieved either by drying or by incorporating solutes. Much of the published data, however, cover only a narrow treatment range and have been analyzed by assuming first-order death kinetics. In this study, the death of Salmonella enterica serovar Typhimurium DT104 when exposed to 54 combinations of temperature (55 to 80°C) and aw (rvp 0.65 to 0.90, reduced using glucose-fructose) was investigated. The Weibull model (LogS = −btn) was used to describe microbial inactivation, and surface response models were developed to predict death rates for serovar Typhimurium at all points within the design surface. The models were evaluated with data generated by using six different Salmonella strains in place of serovar Typhimurium DT104 strain 30, two different solutes in place of glucose-fructose to reduce aw, or six low-aw foods artificially contaminated with Salmonella in place of the sugar broths. The data demonstrate that, at temperatures of ≥70°C, Salmonella cells at low aw were more heat tolerant than those at a higher aw but below 65°C the reverse was true. The same patterns were generated when sucrose (rvp 0.80 compared with 0.90) or NaCl (0.75 compared with 0.90) was used to reduce aw, but the extent of the protection afforded varied with solute type. The predictions of thermal death rates in the low-aw foods were usually fail-safe, but the few exceptions highlight the importance of validating models with specific foods that may have additional factors affecting survival.  相似文献   

18.
Bacterial cellulose-chitosan (BC-C) films were developed by immersing purified BC pellicles in 1.5 ~ 2.0% (w/v) acetic acid solutions containing chitosan of varying molecular weights. Effects of different molecular weight of chitosan on physical, biological and antimicrobial properties of the composite films were investigated. The cumulative chitosan absorption capacities with Mw of 141,000, 199,000, and 263,000 were 38.43, 24.65, and 23.89 mg/cm3 of dry BC film, respectively. The cumulative release profiles of chitosan from the films strongly depended on molecular weight of chitosan and pH of solution. The order of release of chitosan from the BC-C films was dependent on molecular weight as follows: Mw 141,000 > Mw 199,000 > Mw 263,000. All BC-C films showed the antimicrobial abilities against Staphylococcus aureus and Aspergillus niger but had no inhibitory effect on the growth of Escherichia coli. The BC-C films supported for adhesion, spreading and proliferation of both human skin keratinocytes and fibroblasts. The antibacterial activity against S. aureus of the BC-C with the highest Mw chitosan (263,000) was higher than those of the others. On the other hand, the BC-C films with the lowest Mw chitosan (141,000) promoted the growth of human skin cells more than those of the others.  相似文献   

19.
Mesembryanthemum edule is an edible medicinal halophyte traditionally used to treat several human diseases. In this study, particular importance was attached to the influence of environmental conditions on phenolic composition and antioxidant activities of two M. edule provenances from contrasting climatic regions (Djerba and Monastir sampled from arid and superior semi-arid bioclimatic stages, respectively). Shoot phenolic content was evaluated using colorimetric method and its composition was identified by HPLC analysis with or without thiolysis. Antioxidant activities were assessed by five in vitro antioxidant systems. Results showed that the two M. edule provenances were significantly different according to their antioxidant activity as well as their polyphenol profiles. Indeed, plants from Djerba (lack of rainfall and long light hour periods) exhibited stronger antioxidant activity together with higher phenolic content. For instance, Djerba provenance shoots showed much lower IC50 (4.8 μg ml−1) and EC50 (80 μg ml 1) values for DPPH and Fe-reducing tests, respectively. In addition, the superiority of this provenance (Djerba) was more marked as compared to positive controls (BHT, BHA, and VitC). HPLC identification revealed also an important difference between the two provenances on major flavonoid components. This difference was confirmed by the mean degrees of tannin polymerization (DPn) which was higher in Djerba plants. These data suggest that M. edule adaptation to environmental stresses proceeds through induced particular phenol quality and DPn for the improvement of their antioxidant capacities to protect plant tissues against oxidative stress.  相似文献   

20.
A glucan of DPnca 80 has been isolated from the hypocotyls of mung bean plants (Phaseolus aureus). Methylation analysis and periodate oxidation studies showed that the glucan has (1 → 3) and (1 → 4) linked d-glucopyranosyl residues in the molar ratio 1·0:1·7. Oligosaccharides containing both β(1 → 3) and β(1 → 4) linked residues were isolated from partial hydrolysates.  相似文献   

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