κ-卡拉胶琥珀酰基化衍生物的抗氧化活性研究

对κ-卡拉胶进行酸降解得到三种卡拉胶低聚糖,并进一步琥珀酰基化得到分子量分别为2720、4000和5960的κ-卡拉胶琥珀酰衍生物(A、B和C)。对产物进行FT-IR表征,并测得其琥珀酰基取代度(DS)分别为0.61、0.29和0.83。检测了三种κ-卡拉胶琥珀酰衍生物对超氧阴离子自由基O2.-、DPPH自由基、羟基自由基.OH以及过氧化氢的清除活性。结果表明:随着取代度的增加,其清除超氧阴离子自由基O2.-和DPPH自由基的能力增强;随着分子量的增加,其清除羟基自由基.OH和过氧化氢的能力增强。这可能与衍生物的羟基含量、取代基团的性质以及取代度等因素有关。     

不同取代度N-马来酰低聚壳聚糖的抗氧化活性的研究

低聚壳聚糖(COS)酰化得到三种取代度(DS)不同的N-马来酰低聚壳聚糖衍生物NMCOSA、NMCOSB和NMCOSC,其DS分别为0.25、0.67和0.89。对其结构进行红外表征。并考察了NMCOSA、NMCOSB和NMCOSC对羟基自由基(.OH)、1,1-二苯基苦基苯肼(DPPH)的清除活性以及还原能力。结果表明:N-马来酰衍生物有明显的抗氧化活性,随着取代度的升高,N-马来酰衍生物清除DPPH的能力以及还原能力增强,即NMCOSCNMCOSBNMCOSA;清除.OH的活性顺序为NMCOSBNMCOSANMCOSC,即取代度为0.67的表现出最强的活性。这可能与氨基和羟基的数目、取代基团的性质以及清除自由基的机理不同有关。     

κ-卡拉胶邻苯二甲酰基化衍生物的抗氧化活性研究

对κ-卡拉胶进行酸降解得到三种卡拉胶低聚糖,并进一步与苯二甲酰基合成制得三种分子量分别为1450、2520和3430的κ-卡拉胶邻苯二甲酰衍生物(LA、LB和LC)。对产物进行IR表征并对其取代度(DS)进行测定,并检测了产物对羟基自由基.OH、DPPH自由基和过氧化氢的清除活性以及还原能力。结果表明,上述三种κ-卡拉胶邻苯二甲酰衍生物的抗氧化能力强弱顺序依次为:LC>LA>LB,这可能与衍生物的羟基含量、取代基团的性质以及取代度等因素有关。     

N-琥珀酰低聚壳聚糖的抗氧化性能研究(英文)

低聚壳聚糖经化学改性得到三种取代度不同的N-琥珀酰低聚壳聚糖(NSCOSA、NSCOSB和NSCOSC,取代度(DS)分别是为0.25、0.57和0.70。对其结构进行红外表征,并且并考察了其对超氧阴离子自由基(O-·2)、羟基自由基(·OH)、DPPH的清除活性以及还原能力。结果表明:N-琥珀酰低聚壳聚糖衍生物的抗氧化活性与低聚壳聚糖相比有所降低。随着DS的升高,琥珀酰衍生物对·OH的清除能力下降;对O-·2的清除能力大小顺序为NSCBNSCANSCC;对DPPH的清除能力以及还原能力大小顺序均为:NSCANSCCNSCB。这可能是由于N-琥珀酰低聚壳聚糖的取代度、引进基团的性质以及对自由基的清除机理不同所致。     

款冬花多糖的羧甲基化衍生物合成工艺研究

本文应用响应面法优化制备款冬花多糖羧甲基化衍生物的合成工艺条件。采用碱性条件的氯乙酸法,以羧甲基的取代度为考察指标,最佳合成工艺为:氯乙酸浓度为2.5 mol/L,反应温度52℃,反应时间3.1 h。羧甲基化后的多糖清除DPPH的能力提高,抗氧化性提高,为今后多糖衍生物的产业化工艺开发有较好的参考价值和依据。     

裂褶多糖的羧甲基化

采用氢氧化钠-氯乙酸反应体系,以异丙醇为溶剂,利用L9(34)正交试验合成mg级的不同取代度(DS)的羧甲基化裂褶多糖。研究表明试验条件下各因素对DS值影响由大到小的顺序为:氯乙酸/裂褶多糖(g/g)>氢氧化钠/裂褶多糖(g/g)>反应时间>反应温度。其红外光谱在1600 cm-1出现-COO-特征吸收;其紫外光谱在200~300 nm没有明显的吸收峰。对其13C NMR化学位移进行了归属。     

制备条件对魔芋葡甘聚糖硝酸酯取代度的影响及产物热重分析

以魔芋葡甘聚糖(KGM)为底物,浓H2SO4为催化剂,发烟HNO3为改性剂,制备了高取代度的KGM硝酸酯(KGMN)。考察了制备条件对产物取代度(DS)的影响,在最佳条件下所得产物的DS为2.63。FTIR图谱显示,-NO2已成功引入到KGM分子中;SEM照片表明,KGMN的表观形貌变为疏松絮状,这与-NO2基的引入导致其疏水性增强有关;TGA测试表明,KGMN的热稳定性与KGM相比明显下降,且DS越高,下降程度越显著,更为重要的是,KGMN的热重曲线表现出瞬间热失重和/或表观增重的特性。本研究结果初步表明,KGMN有望作为一种新型环保含能材料应用于相关领域。     

不同功能基团对3型肺炎球菌荚膜多糖免疫原性影响的初步研究

目的比较3型肺炎链球菌荚膜多糖不同基团活化对多糖抗原性及结合物免疫原性的影响。方法分别采用1-氰基-4-二甲氨基-吡啶四氟硼酸(1-cyano-4-dimethylaminopyridinium tetrafluoroborate, CDAP)活化多糖羟基,碳二亚胺(1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, EDC)活化多糖羧基,再与己二酰肼(adipic dihydrazide, ADH)偶联获得活化度相近的多糖衍生物。用三硝基苯磺酸方法(trinitrobenzene sulfonic acid, TNBS)测定多糖活化度;高效液相分子排阻与多角度激光散射仪联用(HPLC-SEC-MALLS)分析衍生物分子分布和大小;Zeta电位仪与滴定仪联用分析其表面电荷变化;速率比浊法和免疫双扩散法比较其抗原性变化;利用多糖衍生物与载体蛋白偶联获得的不同结合物免疫小鼠,间接ELISA分析不同结合物免疫后的IgG抗体浓度,进一步阐述活化过程中多糖抗原性的变化对结合物免疫原性的影响。结果 TNBS结果显示,获得同一基团不同活化度(5%～30%)、不同基团(羟基和羧基)活化度相近的多糖衍生物;等电点分析结果显示,不同基团的活化会导致多糖表面不同的电荷变化;而速率比浊和免疫双扩散的结果显示,多糖羟基的活化会导致多糖抗原性略有下降,但不同活化度之间差异较小;在相似活化度情况下,羧基衍化物的抗原性更低,随着羧基活化度的增加,多糖抗原性下降明显(约60%)。小鼠ELISA结果显示,对羧基不同程度活化得到的结合物,其免疫原性较多糖明显提高,差异具有统计学意义(P<0.05);随着多糖羧基活化度的增加,结合物免疫原性先增加后降低。结论 3型多糖重复单位上的羧基的改变对抗原性影响较羟基更大,对羧基的过度活化会影响结合物的免疫原性。     

薤白多糖的硫酸化修饰及体外抗氧化活性

为探讨薤白多糖硫酸化修饰的最佳条件,以及硫酸化修饰提高薤白多糖活性的可能性,采用氯磺酸-吡啶法对醇沉法得到的薤白多糖和柱层析纯化的3种分级薤白多糖进行硫酸化修饰,以氯磺酸-吡啶配比、反应温度和反应时间为自变量,修饰产物的硫酸基取代度(DS)为响应值,应用响应面设计法确定硫酸化修饰的最佳条件,用H2O2/Fe2+体系法和邻苯三酚自氧化法测定修饰产物的抗氧化活性。结果表明:薤白多糖氯磺酸-吡啶法修饰的最佳条件为氯磺酸∶吡啶=1∶3,反应温度65℃,反应时间2 h,此条件下硫酸根取代度为0.470,硫酸化修饰能提高薤白多糖的体外抗氧化活性。     

不同诱导子对怀牛膝细胞生长及多糖含量的影响

为提高怀牛膝(Achyranthes bidentata)悬浮培养细胞中牛膝多糖的含量,以酵母提取物、榆黄蘑(Pleurotus citrinopileatus)及水杨酸作为诱导子,分别在同一时期以不同浓度或在不同时期以相同浓度添加至细胞培养物中,收获时测定细胞生长量和牛膝多糖含量。结果显示,在培养12天时添加2.5%(v/v)酵母诱导子,细胞干重最大,可达46.75 g·L–1,多糖含量为5.76 mg·g~(–1);在培养9天时添加5 mg GE·L–1榆黄蘑诱导子,收获时细胞中多糖含量可达6.56 mg·g~(–1),细胞干重达28.3g·L–1;1 mg·g~(–1)水杨酸对牛膝多糖的诱导效果不如以上2种诱导子明显。     

牛膝多糖的组分分析及抗衰老活性研究

牛膝多糖 (Achyranthesbidentatapolysaccharides ,ABPS)是苋科植物牛膝 (AchyranthesbidentataBl.)根中的水溶性多糖 ,先后用DEAE_Sepharosefast_flow柱和SephadexG_10 0柱将牛膝粗多糖分为 4个组分 ,分别命名为 :Con .1、Con .2、Con .3和Con .4。Micro_Kjeldahl试验表明 ,Con .1中含有氮元素 3 .95 % ,另 3个小分子组分不含氮元素。以果蝇为动物模型研究了该 4个牛膝多糖组分的抗衰老作用 ,结果表明 ,大分子组分Con .1对果蝇无抗衰老作用 ,而另3个小分子量组分在培养基中浓度为 2和 5mg/g(多糖质量 /培养基质量 )时 ,都可显著或极显著地使果蝇平均体重增加 3 .85 % - 5 .47% ,并使果蝇平均寿命延长 2 .6 1% - 3.16 %。     

牛膝不同密度群体光合速率与干物质积累和品质的关系

在大田条件下,探讨不同种植密度(A,500 000;B,330 000;C,250 000;D 200 000株/hm2)与牛膝的群体光合速率、干物质积累、产量及多糖含量之间的关系.结果表明:群体光合速率B处理较高,各群体日变化在开花期均呈双峰型,籽盛期均为单峰型;单株根干重和单位面积根产量的拟合均呈Logistic曲线变化;不同密度处理单株根干重增加速率为D>C>B>A,而单位面积根产量增加速率为B>C>D>A;密度与产量呈负相关,与多糖呈正相关;各处理群体光合速率与产量呈显著正相关,与多糖含量在开花和籽末期呈负相关.综合分析显示,330 000株/hm2为牛膝最佳种植密度;密度对牛膝产量和多糖含量影响较大,适当地提高籽粒期群体光合速率有利于提高牛膝产量和质量.     

Structure and characteristics of glucomannans from Eremurus iae and E.zangezuricus: detection of acetyl group localization in macromolecules]

Water-soluble glucomannans from roots of Eremurus iae and E. zangezuricus were studied. These polysaccharides were shown to contain 28.8; 69.0, and 2.2% (E. iae) and 22.6; 74.8, and 2.6% (E. zangezuricus) of D-glucose, D-mannose and acetyl groups, respectively. Their IR spectra were identical and revealed the presence of 1,4-beta-glycosidic bonds and ester carbonyl groups. 13C-NMR spectroscopy revealed both polysaccharides to be linear partially acetylated 1,4-beta-D-glucomannans. Acetyl groups substituted C-2- and C-3-hydroxyls of mannopyranose residues. Comparison of 13C-NMR data and the results of correlation analysis enables a conclusion to be made that acetyl groups can substitute no more than one OH-group in the mannopyranosyl residue. [alpha]D = -34.0 degrees, [eta] and molecular weights (MW) for E. iae polysaccharide were determined to be -34.0, 6.5 dl/g, and 265.5 kDa, respectively, and for E. zangezuricus polysaccharide -38.2, 5.4 dl/g, and 233.5 kDa, respectively. A correlation between intrinsic viscosities of polysaccharides and their molecular masses determined by HPLC was revealed.     

Optical polarization reveals different ultrastructural molecular arrangement of polysaccharides in the yeast cell walls.

The topo-optical aldehyde bisulfite-toluidine blue (ABT) reaction of vicinal OH and amino-OH groups offers new ways to study the ultrastructure of polysaccharides in different biological substrates. Through oriented dye binding on the reacting groups, the ABT reaction induces strong birefringence on the linearly ordered polysaccharides, which is negative with respect to their chain length. Using this method, two types of molecular order of the polysaccharides could be distinguished in the cell walls and capsules of yeasts. (1) The optically negative spherulitic character of the yeasts after the ABT reaction indicated that the toluidine blue molecules were bound tangentially (in a surface-parallel pattern) while the polysaccharide chains of the cell walls and capsules were oriented mainly radially. This structural pattern may be explained as resulting from a helicoid conformation of the polysaccharide component. (2) Acid or alkali hydrolysis removed the radially oriented polysaccharide component of the cell wall. The remaining, resistant polysaccharides showed up in the form of optically positive spherulites indicating radially oriented dye molecules on a circularly ordered, micellar polysaccharide texture.     

猴头菌子实体和菌丝体多糖的分离纯化与理化特征的比较*

人工栽培的猴头菌子实体和固体培养的菌丝体分别经热水提取,浓缩、醇析后得子实体粗多糖（HFP）和菌丝体粗多糖（HMP）,HFP的得率和多糖含量均高于HMP;两者再经透析、Sevag法脱蛋白、乙醇分级沉淀、SephadexG-100柱层析纯化,得子实体纯多糖hfp-1和菌丝体纯多糖 hmp-2,经HPLC检测hfp-1和hmp-2为单一均匀多糖。气相色谱分析表明hfp-1的单糖组成为阿拉伯糖、甘露糖、半乳糖和葡萄糖,摩尔比为：0.12：0.04：1.00：0.71;hmp-2的单糖组成为阿拉伯糖、木糖、甘露糖、半乳糖和葡萄糖,摩尔比为：0.25：0.41：0.31：1.00：0.29。紫外光谱分析表明组成中不含核酸和蛋白质,红外光谱分析二者均有多糖特征吸收峰,hfp-1有β-型连接的吸收峰,hmp-2无明显的β-型连接的吸收峰;经HPLC进行分子量测定,hfp-1的分子量为54000,hmp-2的分子量为68000。猴头菌子实体多糖和菌丝体多糖在化学组成上有一定的差异。     

Structure-activity relationship study of WSS25 derivatives with anti-angiogenesis effects

WGEW, an α(1-4) linked glucan with an α(1-4) linked branch attached to C-6, was isolated from the rhizoma of Gastrodia elata Bl. WSS25, a sulfated derivative of WGEW, was reported to inhibit angiogenesis by disrupting BMP2/Smad/Id1 signaling pathway. However, the structure-activity relationship (SAR) for WSS25 is not known. To study the SAR, seven sulfated saccharides derived from WGEW degradation products, six sulfated polysaccharides with varying degrees of substitution, and four aminopropylated, carboxymethylated, phosphorylated, and acetylated derivatives of WGEW were prepared. A sulfated, unbranched product of polysaccharide was also obtained. The structural features of these derivatives were characterized by infrared spectroscopy and nuclear magnetic resonance spectroscopy. An HMEC-1 cell tube formation assay was employed to measure the antiangiogenic effect of the derivatives. The results indicated that only sulfated polysaccharides with molecular weights of more than 41,000?Da could inhibit HMEC-1 cell tube formation. The inhibition effect was dependent on the presence of a sulfate group, since the tube formation was not blocked by aminopropylated, carboxymethylated, phosphorylated, or acetylated WGEW. A higher degree of sulfate substitution on the polysaccharide led to a stronger inhibitory effect, and the degree of sulfate substitution between 0.173 and 0.194 was found to be optimal. Interestingly, the WGEW side chain was not required for anti-tube formation activity. All these preliminary results may provide a clue for further modification of the core structure of WSS25 to discover polysaccharide derivatives as novel anti-angiogenic inhibitors.     

Chemical characterization and Ameliorating effect of polysaccharide from Chinese jujube on intestine oxidative injury by ischemia and reperfusion

A water-soluble polysaccharide was extracted from the fruits of Chinese jujube by boiled water extraction and ethanol precipitation. Monosaccharide composition and the structure of the polysaccharide were determined by gas spectroscopy and Fourier transform IR (FT-IR) spectroscopy. The components were glucose (23%), xylose (31.3%), mannose (12.9%) and fructose (21.6%). Six distinct-absorbance peaks, at 3290.20, 2928.66, 1616.20, 1342.96, 1254.35cm(-1), 1025.43, 917, 28 and 816.57cm(-1) in the infrared (IR) spectra of Chinese jujube polysaccharides were the characteristic of polysaccharide compound. Chinese jujube polysaccharides have effective reducing power, free radical scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, and metal chelating activities. This antioxidant property depends on concentration and increases with increased amount of sample. In addition, ischemia/reperfusion could stimulate oxidative injury in rabbits' intestine. Chinese jujube polysaccharides could still effectively reduce intestine MDA level and increase antioxidant enzyme activities in rabbits with ischemia/reperfusion (I/R) of the small intestine.     

Mediator facilitated,laccase catalysed oxidation of granular potato starch and the physico-chemical characterisation of the oxidized products

The primary hydroxyl groups in potato starch were selectively oxidized to the corresponding aldehyde and carboxylic acid functionalities by mediators like TEMPO, using laccase from fungi as catalytic oxidant and oxygen as the primary oxidant. Oxidized starch products with degree of substitution (DS_CHO ranging from 0.16 to 16.4/100AGU and DS_COOH from 0.01 to 3.71 carboxyl groups/100AGU) were obtained with mediator facilitated enzymatic oxidation. Maximum conversion of the primary alcohol group was obtained at a pH of 5, with TEMPO as mediator, under oxygen bubbling and two step administration of Trametes versicolor laccase (200 + 200 nkat/g of starch). The oxidized products were characterised by IR spectroscopy, XRD and thermal studies. In the oxidized samples, the larger starch granules exhibited cracks and fractures in comparison to the smaller granules which were relatively unaffected, as observed from the microstructural studies.     

淫羊藿多糖的分离纯化及结构初步分析

从淫羊藿中提取多糖并鉴定其初步结构和单糖组成.采用超声-水提醇沉法提取粗多糖、Sevag法去蛋白、DEAE-52纤维素及Sephadex G-100柱层析法纯化得到淫羊藿多糖EPSⅠ-1和EPSⅡ-1.应用紫外光谱法和红外光谱法对其结构做初步分析.采用高效液相色谱法(HPLC)测定其单糖组成及摩尔比.均一的EPSⅠ-1和EPSⅡ-1多糖在紫外和红外中具有多糖的特征吸收峰,组成中含有吡喃环结构;EPSⅠ-1的单糖组成为鼠李糖和葡萄糖,摩尔比为1:1.13;EPSⅡ-1的单糖组成为果糖、葡萄糖和一个不确定的糖,摩尔比为1:1.91.有效地分离纯化了淫羊藿多糖,这为淫羊藿多糖的广泛应用奠定了实验基础.     

怀牛膝挥发油成分分析

用气相色谱-质谱联用法定性,气相色谱法定量,首次分析了牛膝(Achgranthesbidentata B1.)干燥根的挥发油的化学成分.共鉴定了45个化合物.特征性成分为2,6-二甲基吡嗪,2-甲氧基-3-异丙基吡嗪和2-甲氧基-3-异丁基吡嗪.