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1.
Free amino groups in β-chitin from squid pen were acetylated to obtain N-acetylated β-chitin. After careful control of degree of acetylation, thermal and mechanical properties of β-chitin and N-acetylated β-chitin were compared. The structural differences of β-chitin and N-acetylated β-chitin were characterized by Fourier transform infrared (FTIR) and wide-angle x-ray diffraction (WAXD) analysis. The results indicated that the crystallinity of N-acetylated β-chitin was higher than that of β-chitin and N-acetylated β-chitin exhibited characteristics similar to α-chitin. Equilibrium water content (EWC) of β-chitin reached to about 50% and this hydrophilic nature was assumed to be caused by a relatively weak hydrogen bonding force of β-chitin with parallel main chains. On the other hand, EWC of N-acetylated β-chitin was 40% due to the introduction of ordered structure. β-chitin and N-acetylated β-chitin have the tensile strength of 0.4 and 0.7 Mpa in the swollen state, respectively. Viscoelastic properties and thermal relaxation behaviors were investigated by dynamic mechanical thermal analysis (DMTA). DMTA spectra of these samples showed that α-transition peaks of β-chitin and N-acetylated β-chitin were observed at 170 and 190°C, respectively. These relaxation peak maxima were assigned to be their glass transition temperature. In addition, a second relaxation peak of β-chitin resulting from acetamide groups was found at 112°C and a broad relaxation peak of N-acetylated β-chitin at around 81–100°C. As a result of thermogravimetric analysis, 10% weight loss temperatures of β-chitin and N-acetylated β-chitin were 270 and 285°C, respectively. © 1996 John Wiley & Sons, Inc.  相似文献   

2.
A series of β,γ‐unsaturated ketones were isomerized to their corresponding α,β‐unsaturated ketones by the introduction of DABCO in iPrOH at room temperature. The endo‐cyclic double bond (β,γ‐position) on ketone was rearranged to exo‐cyclic double bond (α,β‐position) under the reaction conditions.  相似文献   

3.
Sulfamic acid was used as a catalyst in the synthesis of β‐amino carbonyl compounds from amines, acetophenone and aldehyde. The reaction was carried out at room temperature. High selectivity, mild reaction temperature, cost‐effective catalyst, simple product separation and catalyst recycle were notable achievements in the reaction. Another feature was that the reaction could be performed on a relatively larger scale to the model reaction (50 times), which also gave good yields. In particular, the first preparation of β, β'‐diamino diketone derivatives via the direct coupling of amines, acetophenone and isophthalic aldehyde promoted by sulfamic acid has been developed.  相似文献   

4.
A new styrene derivative having an L -gulonic moiety, N-(p-vinylbenzyl)-6-L -gulonamide (VB-6-Glco, 3) was synthesized from L -gulono-1,4-lactone and p-vinylbenzylamine. The styrene derivative (3) was subjected to the radical homopolymerization and copolymerization with acrylamide and acrylic acid. The hydrolysis of p-nitrophenyl β-D -glucuronide with β-glucuronidase was scarcely inhibited in the presence of the glycopolymer prepared from 3 and acrylamide (P(VB-6-Glco-co-AAm), 4), whereas the glycopolymer prepared from 3 and acrylic acid (P(VB-6-Glco-co-AAK), 5) was found to suppress the enzyme activity strongly as well as a polystyrene derivative having pendant D -glucaric moieties (P(VB-6-GlcaH-co-AAm), 6). From the kinetic analysis of the hydrolysis, the glycopolymers 6 and 5 were postulated to inhibit the enzyme competitively and uncompetitively, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2773–2779, 1999  相似文献   

5.
A sweet almond β-glucosidase (EC 3.2.1.21) isozyme was purified from commercial crude product. The process of purification consisted of a Protein-Pak Q anion exchange chromatography following by a Superdex 75 HR gel filtration separation. The purified enzyme is a monomeric glycoprotein with molecular weight of 58 kDa and pI=4.55 which is distinguished from reported isozymes. The enzyme has apH optimum in the range of 5.2-5.6 when p-nitrophenyl-β-D-glycopyranosides are used as substrate and is stable up to 50 °C at that pH range. The purified protein also exhibits profound β-galactosidase and σ-L-arabinosidase activity. The study of substrate specificity revealed that lacking of hydroxymethyl group at C-5 of glycosides resulted in higher affinity for substrate binding to enzyme, whereas the chemical step of hydrolysis (kcst) was prevented significantly. The pH activity profile displayed a bell-shaped curve for all measured p-nitrophenyl-β-D-glycopyranosides with apparent pK1 and pK2 values of 4.4-4.7 and 6.2-6.4, respectively. This isozyme was strongly inhibited by δ-gluconolactone (Ki = 160 μM) and 4-phenylimidazole (Ki = 17.8 μM) reversibly at pH 6.2. Among the tested glycoses, the binding affinity of N-acetyl-β-D-glucosamine to the enzyme (Kl = 52 mM) was 6 times stronger than that of glucose and its epimers.  相似文献   

6.
The condensation of β-phenylpyruvic acid with amides gave olefinic intermediates in good yields (75-80%). The asymmetric catalytic hydrogenation of α-acetamidocinnamic acid with high enantioselectivity is described.  相似文献   

7.
The isolation and identification of eleven crystalline components from the aerial part of Cynanchum taiwanianum Yamazaki (Asclepiadaceae) are described. Their structures were determined on the basis of spectral evidence and chemical transformation. Besides caffeic acid, β-amyrin, and methyl phaeophorbide a, the isolated flavonoid components are classified into two groups, i.e. kaempferol derivatives (kaempferol, astragalin, afzelin, trifolin) and quercetin derivatives (quercetin, isoquercitrin, quercitrin, hyperin).  相似文献   

8.
Forty one terpenoidal compounds were isolated from the essential oil of Chamaecyparis formosensis Matsum. The dominant component is α-pinene. Other major components include β-pinene, 3-carene, α-terpineol, γ-muurolene, and kaurene.  相似文献   

9.
Twelve peptides, 1 – 12 , have been synthesized, which consist of alternating sequences of α‐ and β‐amino acid residues carrying either proteinogenic side chains or geminal dimethyl groups (Aib). Two peptides, 13 and 14 , containing 2‐methyl‐3‐aminobutanoic acid residues or a ‘random mix’ of α‐, β2‐, and β3‐amino acid moieties were also prepared. The new compounds were fully characterized by CD (Figs. 1 and 2), and 1H‐ and 13C‐NMR spectroscopy, and high‐resolution mass spectrometry (HR‐MS). In two cases, 3 and 14 , we discovered novel types of turn structures with nine‐ and ten‐membered H‐bonded rings forming the actual turns. In two other cases, 8 and 11 , we found 14/15‐helices, which had been previously disclosed in mixed α/β‐peptides containing unusual β‐amino acids with non‐proteinogenic side chains. The helices are formed by peptides containing the amino acid moiety Aib in every other position, and their backbones are primarily not held together by H‐bonds, but by the intrinsic conformations of the containing amino acid building blocks. The structures offer new possibilities of mimicking peptide–protein and protein–protein interactions (PPI).  相似文献   

10.
A supramolecular recognition functionalized electrode (βCD‐nanoAu/Fc‐ITO) which exhibits redox‐activity was prepared through supramolecular assembly of β‐cyclodextrin (βCD) capped gold nanoparticles (βCD‐nanoAu) on the ITO previously coated with a monolayer of ferrocene residues (Fc‐ITO). The immobilization of βCD‐nanoAu on Fc‐ITO was confirmed by atomic force microscopy (AFM), and the supramolecular nature of the immobilization approach was also confirmed by cyclic voltammetry. On the other hand, the electrocatalytic activity of βCD‐nanoAu/Fc‐ITO electrode was also studied. The electrocatalytic activity toward ascorbic acid (AA) was enhanced compared with that at the Fc‐ITO electrode, and a linear relationship existed between the anodic peak and the concentration of AA in the range of 5.3×10?5 to 3.0×10?3 M with a detection limit (S/N=3) of 4.1×10?6 M.  相似文献   

11.
The direct condensation of amines with β-ketoesters to produce functional enamine derivatives has been investigated with iron Lewis acid catalysts. FeCl3·6H2O shows good catalytic activity and makes possible the chemo- and stereoselective formations of (Z)-enamine derivatives from aliphatic and aromatic primary amines under mild conditions.  相似文献   

12.
The structure of the N-linked oligosaccharide chain of β-momorcharin, a ribosome-inactivating protein from the seeds of Momordica charantia Linn (Cucurbitaceae) was determined. A glycopeptide liberated by pronase digestion of the glycoprotein was subjected to amino acid and neutral carbohydrate analysis to establish the composition of amino acid and sugar residues. The sequences and glycosylation linkages of the sugar and amino acid residues in the glycopeptide were determined as Manal-6(Xylβ1-2)-Manβ1-4GlcNAcβ1-4(Fucal-3)-GlcNAc-Asn-Leu by 2D-NMR spectroscopy and FAB-MS data.  相似文献   

13.
A series of α-, β,β-, and α,β,β-deuterium-labelled acrylonitrile monomers were prepared and polymerized. Secondary deuterium isotope effects on the polymerization and on the pyrolysis reactions that precede carbon fiber formation were observed. When deuterium is in the α-position, the polymerization rate is greater and the molecular weight is higher. It is proposed that either the propagation rate constant or both that constant and the termination rate constant are increased on deuterium substitution. In differential scanning calorimetry, the polyacrylonitrile exotherm occurs at higher temperatures and is narrower when deuterium is substituted at the α-position. On the other hand, the thermal gravimetric analysis activation energy for weight loss of polymer at temperatures below the acrylic exotherm is lower when deuterium is in the α-position, relative to the α-hydrogen polymers. As there is no correlation between the weight loss energy of activation and the various exotherm parameters, the weight loss energy of activation and the various exotherm parameters, the weight loss and exotherm are considered to be independent events. Examination of the distribution of deuterium substituted ammonia species evolved during 100–240°C thermal treatment of the α-and β, β-deuterated polyacrylonitriles provides a clear indication that both the α- and β-positions are directly involved in hydrogen migration to nitrogen, but the mechanism of ammonia generation remains unclear. © 1995 John Wiley & Sons, Inc.  相似文献   

14.
Enantiomeric separations of several β-amino alcohol drugs, i.e., phenylephrine, epinephrine, norepinephrine, synephrine, and chlorprenaline were performed by capillary electrophoresis using DM-β-CD as a chiral selector. Five test solutes were baseline resolved in six minutes. The effects of DM-β-CD concentration, pH value, ionic strength of the buffer, and the type of β-CDs on resolution were investigated. The results indicated that DM-β-CD is suitable for enantiomeric separation of β-amino alcohols containing a phenyl group on the chiral atom. Enantiorecognition mechanisms for test solutes are also discussed.  相似文献   

15.
The era of β-lactam antibiotics, which represent the most important class of drugs against infectious diseases caused by bacteria, began more than fifty years ago with the discovery of penicillin G. Further improvements by isolation and structure elucidation of new natural compounds, and systematic chemical modification of these, is a striking example of to what extent chemistry can contribute to the progress of drug therapy. The complex relationship between structure and activity requires, even today, a largely empirical approach. The minimum structural unit for antibiotic activity had to be revised several times over decades. Both the activated β-lactam ring with an acidic group and the nature and spatial arrangement of the other substituents and rings decisively affect the potency, antibacterial spectrum, pharmacokinetics, and toxicity. Totally synthetic mono- and bicyclic compounds from the series of monobactams, penems, carbapenems, 1-oxacephems, and 1-carbacephems are increasingly joining the classic groups obtained by semisynthesis from 6-amino-penicillanic acid and 7-aminophalosporanic acid.  相似文献   

16.
α,β‐Hybrid oligomers of varying lengths with alternating proteogenic α‐amino acid and the rigid β2,3,3‐trisubstituted bicyclic amino acid ABOC residues were studied using both X‐ray crystal and NMR solution structures. While only an 11/9 helix was obtained in the solid state regardless of the length of the oligomers, conformational polymorphism as a chain‐length‐dependent phenomenon was observed in solution. Consistent with DFT calculations, we established that short oligomers adopted an 11/9 helix, whereas an 18/16 helix was favored for longer oligomers in solution. A rapid interconversion between the 11/9 helix and the 18/16 helix occurred for oligomers of intermediate length.  相似文献   

17.
Soluble polypyrrole (PPy) with high conductivity (27 S/cm) has been prepared by chemical polymerization of pyrrol monomer in the presence of β-naphthalene sulphonic acid (NSA) as a dopant. The solubility of the resulting conducting polymer of PPy-NSA in m-cresol increases with increasing the concentration of NSA in the polymerization media, and the highest solubility of PPy-NSA in m-cresol is about 1.2 g/100 mL. The room-temperature conductivity of PPy-NSA significantly increases with the concentration of NSA when the concentration of NSA is less than 0.1 mol/L, while it slightly decreases with increasing the concentration of NSA after the concentration of NSA is higher than 0.1 mol/L. UV-VIS spectra and ESR measurements demonstrate that both polaron and bipolaron are present as a charge carrier. The resulting PPy-NSA exhibits unusual fibrillar morphology with a diameter of about 0.5 μm, which is quite different from the granular morphology of PPy doped with dodecyl benzene sulfonic acid (DBSA) and HCl. Moreover, the polymerization conditions greatly influence the morphology of the obtained PPy-NSA. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3689–3695, 1997  相似文献   

18.
The effects of sodium caprate on the gelation of β-lactoglobulin B and a β-lactoglobulin B/β-casein mixture at ambient temperature were investigated using ultrasonic spectroscopy and rheology. A 12% β-lactoglobulin B solution gelled in the presence of 3.6% sodium caprate. Conversely, sodium caprate did not induce the formation of a gel when β-casein was in isolation, regardless of the protein concentration. Although a 6% β-lactoglobulin B/1.8% sodium caprate solution did not form a gel, a gel was formed when 6% β-casein was added to a mixture containing 6% β-lactoglobulin B and 3.6% sodium caprate. This gel showed comparable rheological properties to that of a gel containing 12% β-lactoglobulin B. The results clearly indicated that β-casein aids in the gelation of a β-lactoglobulin B/sodium caprate mixture, when the concentration of β-lactoglobulin B is insufficient to allow for gelation. It appears that β-casein self-aggregation is also inhibited. Therefore, it could be concluded that β-casein can be used as a texture modifier for β-lactoglobulin gelation induced by sodium caprate.  相似文献   

19.
Tri-n-butylphosphine-catalyzed polyadditions of activated internal diynes (bifunctional β-substituted propiolate, 1B and 1C ) with diols are described. Although a terminal bispropiolate ( 1A ) could not produce soluble polymers, with secondary diols, the polyaddition of 1B or 1C with primary as well as secondary diols gave corresponding polymers ( 3 , only composed of E isomeric units) in high yield. The rate of the present polyaddition was estimated by a model reaction of benzyl alcohol with methyl 2-heptynoate ( 4 ), from which the introduction of alkyl groups at the β-position of propiolate moieties was found to decrease the rate of the reaction by 80 times. Furthermore, the rate-determining step on this polymerization system was speculated to be a protonation step of zwitterionic intermediates with protons from diols. © 1996 John Wiley & Sons, Inc.  相似文献   

20.
A review of research on snake neurotoxin is presented, with emphasis on the chemical modification studies and molecular cloning of postsynaptic and presynaptic neurotoxins from Naja naja atra (Taiwan cobra) (Fig. 1a) and Bungarus multicinctus (Taiwan banded krait) (Fig. 1b). Cobrotoxin and α-bungarotoxin are the primary postsynaptic neurotoxins isolated from the venom of N. naja atra and B. multicinctus, respectively. Although they share a common three-dimensional structure, the functional elements essential for the manifestation of their toxicity are different. Selective and stepwise chemical modification of cobrotoxin indicate that at least two cationic groups, an ?-amino group of Lys-47 and a guanidino group of Arg-33 common to all known postsynaptic neurotoxins, are functionally important for its neuromuscular blocking activity. However, for α-bungarotoxin, the side chains of several basic amino acid residues are involved in the multipoint contact between the toxin and acetylcholine receptor. Moreover, the conserved Trp residue is essential for the neurotoxicity of cobrotoxin, but not for α-bungarotoxin. The cDNAs encoding cobrotoxin and α-bungarotoxin was constructed from the cellular RNA isolated from the venom glands of N. naja atra and B. multicinctus by polymerase chain reaction. The sequence of their 3′-untranslational region, signal peptide and 5′-untranslational region share a high degree of homology, suggesting that they are evolutionarily related. Expression of both neurotoxic protein in E. coli generated polypeptide chains for reactions with the antisera against the native neurotoxins. Presynaptic neurotoxins constitute a different group of neurotoxic proteins in snake venom proteins. These presynaptic neurotoxins are either basic phospholipase A2 (PLA2) per se or contain basic PLA2 as an indispensible part of their structures. Thus, the presynaptic neurotoxins usually show both PLA2 activity and presynaptic neurotoxicity. β-Bungarotoxin (β-Bgt), the main presynaptic PLA2 neurotoxin isolated from the venom of B. multicinctus (Taiwan banded krait), consists of two dissimilar polypeptide chains, a PLA2 subunit (A chain) and potassium channel recognition subunit (B chain). Chemical modification studies show that the toxin might possess two functional sites, one responsible for the catalytic activity and the other for its pharmacological properties. Molecular cloning and expression of the A chain and B chain of β-Bgt reveal that the A chain of β-Bgt is an active subunit with PLA2 activity, and that the B chain is involved in voltage-gated potassium channel blocking action observed with β-Bgt.  相似文献   

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