茯苓菌丝体多糖的分离及结构分析

由茯苓菌种在培养基中于 2 5℃下培养一周得茯苓菌丝体 .分别用 0 9%NaCl水溶液、热水、0 5mol/LNaOH和 88%甲酸从该茯苓菌丝体中提取出四种多糖 ,编号为PCM1 ,PCM2 ,PCM3和PCM4 .用红外光谱 (IR) ,高效液相色谱 (HPLC) ,气相色谱 (GC)及13 C 核磁共振 ( 13 C NMR)等方法分析了它们的组成和结构 .结果表明 ,PCM1 ,PCM2为酸性杂多糖由D 鼠李糖、D 木糖、D 甘露糖、D 半乳糖、D 葡萄糖及葡萄糖醛酸组成 .PCM3主要为线型 β ( 1→ 3 ) D 葡聚糖 ,其产率占茯苓菌丝体总量的 55 8% .PCM4由D 葡萄糖和葡萄糖醛酸组成 .茯苓菌丝体化学组成和结构基本同于茯苓菌核多糖 ,随提取过程进行葡萄糖含量逐渐增加的变化规律也相同 .     

灵芝菌丝体多糖的化学组成和溶液性质

用磷酸盐缓冲液在 80℃时从灵芝菌丝体中提取出多糖 -蛋白质缀合物 LM-A.成分分析表明 ,GLM-A主要由葡萄糖组成 ,蛋白质含量为 1 3 % . GLM-A在 1∶ 1水稀释的饱和镉乙二胺溶液中 3 0℃时的特性粘数 [η]和均方根旋转半径〈S2 〉1 /2 的分子量依赖关系分别为 [η]=5.1× 1 0 - 2 M0 .6 0w ( cm3· g- 1 )和〈S2 〉1 /2 =3 .9×1 0 - 2 M0 .5 0w ( nm) .按照 Yamakawa-Fujii-Yoshizaki蠕虫状圆筒模型的粘度理论和 Bohdanecky表达式 ,求得GLM-A的分子参数为 :单位围长摩尔质量 ML=( 53 0± 1 0 ) nm- 1 ,持久长度 q=( 2 .8± 0 .2 ) nm.链直径 d=0 .75nm.实验结果表明 ,GLM-A在该溶液中为无规线团构象     

β-1,2,3,4,6-五-O-倍酰-D-葡萄糖与人血清白蛋白的相互作用研究

应用红外光谱和荧光光谱方法研究了人血清白蛋白 (HSA)与 β 1,2 ,3 ,4,6 五 O 倍酰 D 葡萄糖 (PGG)的相互作用 .荧光光谱结果显示 ,PGG在CPGG/CHSA<0 5和 0 5 相似文献   

从鱿鱼顶骨β-甲壳素合成的丙酰化甲壳素的结晶结构

分别从α 甲壳素 (来源于蟹壳 )和 β 甲壳素 (来源于鱿鱼顶骨 )制备丙酰化甲壳素。丙酰化β 甲壳素的大角X光衍射图出现 2 0个衍射峰 ,而丙酰化α 甲壳素只在 2 0°左右出现弥散峰。发现丙酰化β 甲壳素的结晶属三斜晶系 ,a =7.997,b =1 3.0 67,c =6.31 6(任意单位 ) ,α =98°5 6′ ,β =1 0 4°1 9′,γ =82°2 6′。列表说明了各衍射峰的归属。据分析 ,每个单元晶胞内含一根分子链的 2 .5个葡萄糖残基单元。分子轴为b轴     

当归多糖XC-1的分离与结构研究

从中药岷当归 (Angelicasinensis)中用热水提取、乙醇沉淀、DEAE SephadexA 2 5柱层析分离得到多糖组分XC 1 ,凝胶色谱法测得分子量为 1 0× 1 0 5道尔顿 ,糖的组成分析表明XC 1只含葡萄糖 ,且经红外测定为α型葡萄糖 ,连接点分析证明葡萄糖主链是以 1 ,6位连接     

酸性深蓝5R的极谱分析方法及其与环糊精的超分子体系研究

建立并研究了酸性深蓝 5R(AC5R)的极谱分析法.结果表明,在pH=7. 0的Na2HPO4 KH2PO4底液中,AC5R产生一峰形好、稳定、灵敏的还原峰,其峰电位EP约 -0. 60V(vs.SCE),峰电流及二阶导数极谱峰高随AC5R浓度变化的线性范围在 3. 0×10-8 ~6. 0×10-5 mol/L(r=0. 992 6 ~0. 999 1 ),检测限为 6. 0×10-9mol/L.RSD为 1. 16% (n=10),标准回收率在 95. 85% ~103. 3%之间,可望用于AC5R的定量分析.此外,还应用极谱伏安法研究了各种环糊精对AC5R电化学行为的影响和超分子体系;利用电流法测定了AC5R与α CD、β CD、γ CD、DM β CD、TM β CD、HP γ CD的包结常数和包结比,比较AC5R与不同类型环糊精的包结能力,并初步研究影响包结能力大小的可能因素.     

辅酶I在钴/玻碳离子注入修饰电极上的电化学行为及其应用研究

辅酶I(NAD)在 0 .0 0 5mol/LTris 0 .0 1mol/LNaCl(pH =7.0 )缓冲溶液中 ,在Co/GC离子注入电极上有一良好的伏安还原峰 ,峰电位Ep=- 1 .0 7V (vs .SCE)。其峰电流与辅酶I (NAD)的浓度在 5 .0× 1 0 -5～ 1 .0×l0 -3 mol/L范围内呈线性关系 ;检出限为 2 .5× 1 0 -5mol/L ;回收率在 98.8%～ 1 0 1 .9%之间。用线性扫描和循环伏安法等方法研究该体系的电化学行为 ,实验表明 :该体系具有吸附性和催化性的不可逆过程。根据Laviron理论 ,求得电极表面反应速率常数Ks=0 .0 77/s;电子转移系数α =0 .4 35。     

[Cu(C8H4F3O2S)2(C12H8N2)]·C3H6O的合成及其晶体结构

标题配合物 [Cu(C8H4 F3O2 S) 2 (C12 H8N2 ) ]·C3H6 O属于三斜晶系 ,空间群为P1,并测得如下晶胞参数a =10 .5 77(3) ,b =15 .72 2 (4) ,c =10 .133(2 ) ,α =94 .5 3(2 ) ,β =10 0 .81(2 ) ,γ =96 .18(2 )° ,V =16 37.0 3 3,Z =2 ,Mr =74 4.18,Dx =1.5 1× 10 6 g·m- 3,F(0 0 0 ) =5 2 6 ,μ =8 2 4cm- 1,最终偏差因子为R =0 .0 83,Rw=0 .0 74。Cu(II)与 2个 4 ,4 ,4 三氟 1 (2 噻吩基 )丁二酮 1,3中的四个氧原子和菲咯啉中的两个氮原子 ,组成了一个畸变的八面体构型。     

新型激光晶体α—Nd：Ba3Y（BO3）3光谱性能研究

研究了高温相掺钕硼酸钇钡α Nd∶Ba3Y(BO3)3(α NBYB)晶体的光谱特性。α NBYB晶体具有R3空间群结构。吸收光谱表明:该晶体在808nm左右有比较强的吸收峰,其对应于4I9 2→4F5 2,2H9 2的能级跃迁,半峰宽(FWHM)15nm,相应的吸收截面为1.56×10-20cm2,荧光光谱表明:4F3 2→4I11 2能级跃迁有很强的荧光发射,其发射波长为1.058μm,相应的荧光寿命为70μs,发射跃迁截面为1.82×10-19cm2,并用J O理论计算了该晶体的振子强度参数:Ω2=1.43×10-20,Ω4=2.08×10-20,Ω6=2.45×10-20cm2。     

1-芳酰基-4-(1''''-N-β-D-吡喃型糖基)氨基硫脲类化合物的合成(英文)

通过 2 ,3,4 ,6 四 O 乙酰基 β D 吡喃型葡萄糖异硫氰酸酯和 2 ,3,4 三 O 乙酰基 β D 吡喃型木糖异硫氰酸酯与取代的芳基酰肼的亲核加成反应合成了 1 0个 1 芳酰基 4 ( 1′ N 2′,3′,4′,6′ 四 O 乙酰基 β D 吡喃型葡萄糖基 )氨基硫脲和 7个 1 芳酰基 4 ( 1′ N 2′,3′,4′ 三 O 乙酰基 β D 吡喃型木糖基 )氨基硫脲 ,所得化合物的结构经元素分析 ,IR ,1 HNMR确证 .     

COMPARISON OF POLYSACCHARIDES ISOLATED FROM THE MYCELIA OF A CULTIVATED STRAIN OF PORIA COCOS GROWN IN DIFFERENT LIQUID CULTURE MEDIA

Mycelium of a cultivated strain of Poria cocos was grown by submerged fermentation in a liquid mediumcontaining corn steep liquor with orbital shaking. Six polysaccharides coded as ac-PCM1, ac-PCM2, ac-PCM3-Ⅰ andⅡ, ac-PCM4-Ⅰand Ⅱ were isolated from the myelium by extracting with 0.9% NaCl aqueous solution, hot water, 0.5 mol/L NaOHaqueous solution and 88% formic acid. Exo-polysaccharide was obtained from the culture medium and coded as ac-PCM0.The monosaccharide composition and molecular weights of these polysaccharides were characterized by using infraredspectroscopy, gas chromaography, elemental analysis, ~(13)C-NMR, viscometry and light scattering. The results indicated thatac-PCM0, ac-PCM1 and ac-PCM2 are heteropolysaccharides containing glucose, galactose, mannose and fucose, and ac-PCM3-Ⅰ and ac-PCM3-Ⅱ mainly consist of D-glucose. The content of the glucose in the polysaccharides increased with theisolation progress. Remarkably, α-glucan and β-glucan coexisted in the extract by NaOH aqueous solution (ac-PCM3), andcould be separated by chemical methods. The protein in the ac-PCM polysaccharides cultured from the medium containingcorn steep liquor was higher than that in the ab-PCM from the medium with bran extract. Therefore, the polysaccharidesfrom Poria cocos mycelia cultured in different media have different chemical composition, molecular weights and conformations.     

Synthesis of stereoregular heteropolysaccharides having amino-groups by ring-opening copolymerization of 1,6-anhydro-azido-sugar derivatives

The cationic, ring-opening copolymerization of 1,6-anhydro-2-azido-3,4-di-0-benzyl-2-deoxy-(2-ABG), -3-azido-2,4-di-0-benzyl-3-deoxy- (3-ABG), -4-azido-2,3-di-0-benzyl-4-deoxy-β-D -glucopyranose (4-ABG) with 1,6-anhydro-2,3,4-tri-0-benzyl-β-D -glucopyranose (LGTBE) was investigated with phosphorus pentafluoride as catalyst at low temperatures, giving highly stereoregular, (1→6)-α-linked copolymers with number-average molecular weights of 3.90 × 10⁴?9.27 × 10⁴. Structure and composition of the copolymers were determined by ¹H- and ¹³C-NMR spectroscopies and elemental analysis, which indicated that copolymerization occurred in a stereoregular manner to give azido groups containing (1→6)-α-linked glucopyranan derivatives. The differences in polymerizability among the three azido monomers are discussed. Regioselective reduction of three kinds of heteropolysacharide derivatives which had different quantities of azido groups at C-2, -3, or -4 position with lithium aluminum hydride and subsequent debenzylation of the copolymers with sodium in liquid ammonia produced amino-group-containing heteropolysaccharides.     

PREPARATION AND STRUCTURE OFFIVE DERIVATIVES OFβ-(1→3)-D-GLUCAN ISOLATED FROM PORIA COCOS SCLEROTIUM*

A new solvent of cellulose (1.5 mol/L NaOH/0.5 mol/L urea aqueous solution) was used as one of the homogeneous reaction media of polysaccharides for methylation, hydroxyethylation and hydroxypropylation. A water insoluble β-(1→3)-D-glucan, sample PCS3-Ⅱ, isolated from fresh sclerotium of Poria cocos was sulfated in dimethyl sulfoxide (Me2SO), carboxymethylated in NaOH, isopropanol solution, as well as methylated, hydroxyethylated and hydroxypropylated in the new solvent system, respectively, to obtain five water-soluble derivatives coded as S-PCS3-Ⅱ, C-PCS3-Ⅱ, M-PCS3-Ⅱ, HE-PCS3-Ⅱand HP-PCS3-Ⅱ. Their chemical structure and distribution of substitution were characterized by infrared spectroscopy (IR), elementary analysis (EA), ^1H-NMR, ^13C-NMR, 2D-COSY, 2D-TOCSY and 2D-^1H-detected ^1H ^13C HMQC spectra. The results reveal that the relative reactivity of hydroxyl groups of the β(1→3)-D-glucan is in the order C-6 ＞ C-4 ＞ C-2 on the whole. The substitution of the samples S-PCS3-Ⅱ, C-PCS3-Ⅱ and M-PCS3-Ⅱ occurred mainly at C-6 position and secondly at C-4 and C-2 positions, and that of HE-PCS3-Ⅱ occurred at C-6 and C-4 positions and of HP-PCS3-Ⅱ almost completely occurred at C-6 position. The degrees of substitution (DS) obtained from ^13C-NMR range from 0.23 to 1.27. The water solubility of the derivatives is in the order S-PCS3-Ⅱ ＞ C-PCS3-Ⅱ ＞ M-PCS3-Ⅱ ＞ HE-PCS3-Ⅱ ＞ HP-PCS3-Ⅱ. This work provides a novel and nonpolluting process for the methylation, hydroxyethylation and hydroxypropylation of β-(1→3)-D-glucan.     

Spectres RMN des Polysaccharides et de leurs Dérivés: Influence des Substituants sur le Déplacement Chimique 13C

Methyl and acetyl substituent effects on ¹³C chemical shift have been determined on (α 1→3), (α 1→4), (β 1→3) and (β 1→4) linked polysaccharides such as pseudo-nigerane, β-cyclodextrine, amylose, laminarane and cellulose. Methyl α- and β-D -glucopyranoside have been used as monomer model compounds. Shift determination of hydroxylated and substituted polysaccharides requires unambiguous assignment of their ¹³C spectra. Selective heteronuclear spin decoupling and the isotope effect of deuterated hydroxyl have been used as assignment techniques.     

Synthesis of glycosaminoglycans via enzymatic polymerization

Hyaluronic acid and chondroitin were successfully synthesized as representative molecules of glucosaminoglycans and galactosaminoglycans found in a glycosaminoglycan family via enzymatic polymerization catalyzed by testicular hyaluronidases. A newly designed N-acetylhyalobiuronate oxazoline derivative with a β-D -glucuronyl-(1→3)-N-acetyl-D -glucosamine disaccharide structure served as a transition-state analogue substrate monomer for the enzyme, giving rise to artificial hyaluronic acid in 52% yields with a number-average molecular weight of 1.35 × 10⁴ through ring-opening polyaddition in a perfect regioselective and stereoselective manner. A novel N-acetylchondrosine oxazoline derivative with a β-D -glucuronyl-(1→3)-N-acetyl-D -galactosamine disaccharide structure also acted as a transition-state analogue substrate monomer for the enzyme, yielding artificial chondroitin in 35% yields with a number-average molecular weight of 2.5 × 10³. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3541–3548, 2003     

Pressure-products diagram of FexV1−xO2 system (0 ≤ x ≤ 0.5)

The pressure-products diagram of the Fe_xV_1?xO₂ system (0 ≤ x ≤ 0.5) was investigated under the conditions of 5 ～ 55 kbar and 800°C. In high-pressure synthesis, FeV₃O₈ phase (monoclinic), which is stable under ambient pressure, was converted to the O phase (orthorhombic) and the region of O phase was extended from x = 0.1 up to ～0.3. The O phase so obtained, showed the characteristic reversible temperature-induced phase transition to the high-temperature rutile phase under ambient pressure, prior to the decomposition to an ambient pressure form. At x = 0.5, successive transformations, FeVO₄-I (monoclinic) → -II (orthorhombic) → -III (α-PbO₂ type) → -IV (wolframite type), were observed with increasing pressure.     

碳纳米管修饰电极测定冬虫夏草有效成分含量

以多壁碳纳米管修饰金电极为工作电极测定了冬虫夏草胶囊有效成分的含量。结果表明,在pH值为7.0的缓冲溶液中,测得其极化电流与腺嘌呤核苷在浓度为1.0×10-4～1.0×10-8mol/L范围内呈良好的线性关系(R2=0.9947),检出限为1.0×10-9mol/L。所测的5批样品的平均回收率为101.5%,相对标准偏差RSD为1.5%。方法灵敏度高、简单、快速、重现性好、干扰小,而且节能、环保,无污染物排放。     

Carbohydrates ofAllium. IV. Glucofructans ofAllium longicuspis

Water-soluble polysaccharides have been isolated from the bulbs ofAllium longicuspis Rgl. By fractionating the combined water-soluble polysaccharides, homogeneous polysaccharides with molecular weights of 15,500 and 5100 have been isolated. It has been shown by spectral and chemical methods that they consist of glucofructans of a mixed type containing glycosidic bonds of the inulin (2 → 1) and levan (2→6) types in a ratio of 2.1:1.     

Electronic energy transfer from the S2 state of rhodamine 6G

In this paper we present the results of an experimental study of intermolecular electronic energy transfer (EET) from the short-lived Second excited singlet state of rhodamine 6G (R6G) to the ground state of 2,5-bis [5′-tert-butyl-2-benzoxazolyl] thiophene (BBOT). The S₂ state of the donor was excited by sequential, time-delayed, two-photon excitation (STDTPE) utilizing the second harmonic and the first harmonic of a mode-locked Nd³⁺: glass laser, while the EET process was interrogated by monitoring the enhancement of the S₁ → S₀ fluorescence of BBOT. The enhancement of the fluorescence intensity of BBOT was found to be linear in the energies of the two exciting pulses, and linear in the concentration of the energy acceptor (over the BBOT concentration range of (0.3–7) × 10^?5 M), which is in accord with the predictions of the Forster—Dexter mechanism for resonant EET from an ultrashort-lived donor state at low acceptor concentrations. Quantitative measurements of the S₂ → S₀ fluorescence yield in R6G solution directly excited by STDTPE and of the S₁ → S₀ fluorescence of BBOT from R6G + BBOT solutions resulting from EET led to the values of Y_D(S₂ → S₀) = (2.1 ± 0.5) × 10^?6 for the emission quantum yield of the S₂ state of R6G and τr_D(S₂) ≈ 3 × 10^?14 s for the lifetime of the metastable S₂ state of this molecule.