碱提鬼毛针多糖的研究

治疗癌症的方法主要有三种:手术、化疗和放疗,但近十年来世界上普遍认为癌的免疫疗法更为优越,所以寻找免疫促进剂成为当今发展新药的方向之一.多糖作为药物最早是1943年,但作为广谱免疫促进剂是60年代以后.近年来研究发现多糖不但能治疗机体的免疫系统受到严重损伤的癌症,也能治疗多种免疫缺损病症如病毒性肝炎,风湿症,甚至可以辅助治疗爱滋病等.多糖将在治疗癌症、爱滋病和减缓衰老等领域有着广阔的应用前景[1].所以我们选取了药用真菌鬼毛针作原料,从中提取多糖R-1并对其一级结构、分子量、理化性质等进行研究.     

树脂对防风粗多糖脱色效果

树脂对防风粗多糖脱色效果;防风;多糖;树脂;脱色     

6-叠氮-6-脱氧凝聚多糖的选择性一步合成

由于含氨基或氨基衍生物的多糖对细胞表面及细胞之间的生理功能具有特殊的作用,在研究细胞之间有效作用的促进剂和抑制剂方面具有潜在的应用价值,因而叠氮化多糖作为制备氨基多糖及其衍生物的中间体受到人们的重视,含乙酰氨基的天然多糖（如Chitin）和氨基多糖（如Chitosan）,由于具有抗感染和医治创伤作用,广泛用于医疗领域,含氨基和硫酸酯的多糖肝素有很好的抗凝血作用和降血脂活性,已用于动脉硬化病的治疗,我们发现含乙酰氨基的硫酸化核聚糖具有很高的抗艾滋病毒活性,而且没有抗凝血的副作用。     

关白附中1,6-葡聚糖及其硫酸酯的抗补体活性

为研究关白附多糖及其硫酸酯的经典途径抗补体活性, 以关白附[Aconitum coreanum(Lévl.) Raipaics]为原料, 经水提醇沉、 DE-32、 Superdex-200和Superdex-75凝胶柱分离纯化, 得到1个均一的中性多糖KMPS-2A. 采用高效凝胶渗透色谱法、 甲基化、 核磁共振和红外光谱等手段对KMPS-2A的结构进行了鉴定; 采用氯磺酸吡啶法制备了多糖硫酸酯, 并测定了多糖及硫酸酯的抗补体活性. 结果表明, KMPS-2A的平均相对分子量为6.76×10⁵, 结构为α-1,6-D-Glc链接的线性多糖; 在氯磺酸与吡啶的体积比为1.75∶1.0时制备的多糖硫酸酯1.75B的取代度最高为1.79. 碳核磁谱分析结果表明, 硫酸基团先后取代C2, C3及C4位. 该多糖硫酸酯的抗补体活性与其硫酸基团取代度呈现一定的相关性, 多糖硫酸酯1.75B的经典途径抗补体活性优于阳性对照药肝素, 表明其具有开发成为补体抑制剂的潜力.     

复合酶法提取大蒜多糖及其抗氧化活性研究

用复合酶法对大蒜多糖的提取工艺进行研究,并考察了不同浓度沉淀多糖的抗氧化活性;以多糖提取得率为指标,苯酚-硫酸法测定多糖的总糖含量,采用正交实验确定纤维素酶、木瓜蛋白酶和果胶酶的最佳配比,然后在单因素试验的基础上,采用正交实验优化复合酶提取大蒜多糖的最佳工艺;分别用羟基自由基(·OH)和1-二苯基-2-苦基肼基(DPP...     

甘草多糖螺旋结构的原子力显微镜研究

用原子力显微镜(AFM)对甘草多糖的微观结构进行观察, 实验结果表明, 甘草多糖主要由葡萄糖、阿拉伯糖和半乳糖组成. 甘草多糖分子的稀溶液铺展在Ni^2＋处理的云母片上, 经干燥, 乙醇固定后, 获得稳定、重复的图像. 甘草多糖分子具有高度分枝的结构, 并且糖链间形成环状、柱状或近似于螺旋状的结构. 甘草多糖链呈多股紧密的螺旋结构, 这种现象可能与该多糖中分子间的Van der Waals相互作用以及糖链间氢键缔合有关.     

茶多糖的纯化及结构分析

从茶多酚生产的下脚料中,通过有机溶剂洗涤和凝胶色谱分离,得到一种水溶性多糖.经高效液相色谱分析,为单一茶多糖,其相对分子量为(10～10.5)×105;气相色谱分析表明,糖基由葡萄糖、半乳糖、阿拉伯糖、甘露糖和鼠李糖组成,其摩尔比为6.97:5.34:8.11:2.76:1.14;比色法测其总糖含量、蛋白含量、糖醛酸含量分别为90%、8.52%、27.65%.红外光谱和核磁共振分析表明,该多糖足由单糖通过β-糖苷键连接的,多糖链上络有糖醛酸、氨基或蛋白基团,同时含有α和β异头碳;x-衍射分析显示,随多糖纯度的提高,茶多糖更易结晶,且有不同的品体聚合物出现;DSC的分析表明,随茶多糖纯度的提高,热焓增加,峰温向高温漂移.     

庐山石韦叶中多糖提取初探

用蒸馏水、10 g/L氢氧化钠、1%三氯乙酸分别从庐山石韦叶中提取多糖.通过苯酚-硫酸法进行多糖含量测定并比较它们的多糖得率.结果表明10g/L氢氧化钠的提取效果比蒸馏水和1%三氯乙酸的提取好.     

毛细管气相色谱法测定多糖的单糖组成

多糖是生命代谢不可缺少的重要物质,是多个单糖或其衍生物聚合而成的大分子活性化合物。近年来,各种多糖所具有的抗肿瘤、免疫、抗凝血、降血糖和抗病毒活性已相继被发现。一般来说,多糖所具有的药理活性是和其结构密切相关的[1,2],故对多糖的单糖组成和摩尔比测定是研究多糖性     

黑木耳酸性杂多糖的超声波辐射降解

黑木耳酸性杂多糖的超声波辐射降解李翔，张俐娜（武汉大学化学系武汉４３００７２）关键词黑木耳多糖，超声波辐射，特性粘数，糖醛酸含量，凝胶渗透色谱黑木耳多糖具有抗肿瘤，抗炎症，抗凝血及免疫功能［１～５］，黑木耳子实体含两种酸性杂多糖和３种有不同支链和相对...     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.