加压毛细管电色谱法高效分离分析葛根多糖中的单糖

葛根多糖具有抗氧化、抗肿瘤等众多生物活性,对葛根多糖进行单糖组成分析对其活性研究具有重要意义。该研究利用响应面分析法考察了超声辅助提取法中液料比、超声温度、超声时间和超声功率对葛根多糖提取率的交互影响,并拟合数据得到多元二次回归方程。同时建立了柱前衍生加压毛细管电色谱检测糖类的方法,对分离8种中性单糖的色谱条件进行了探索与优化,并将此方法应用于两种葛根实际样品的单糖组成测定。响应面分析结果表明,4个试验因素中,超声温度对两种葛根多糖提取率的影响程度最大,其次为液料比,超声时间和超声功率影响程度较小。结合软件预测分析得到的最佳条件及设备实际情况,确定葛根多糖的最佳提取工艺条件为：超声温度90℃,粉葛多糖液料比20 mL/g,柴葛多糖液料比40 mL/g,超声时间30 min,超声功率180 W。优化后的色谱分离条件为：采用Halo-2.7 μm核壳型C18填料毛细管色谱柱,以乙腈-50 mmol/L pH 4.1的醋酸铵水溶液（18：82,v/v）为流动相,在250 nm波长下检测,施加电压-20 kV。在此条件下可以实现24 min内对葡萄糖等8种中性单糖衍生物的快速分离,相比传统液相色谱方法大大提升了分离检测速度和分离柱效。方法学考察表明此方法具有较好的线性关系和良好的重复性。对实际样品分离鉴定表明,粉葛多糖主要由葡萄糖、甘露糖、鼠李糖和岩藻糖组成,4种单糖物质的量之比为1.00：0.16：0.14：0.07;柴葛多糖主要由葡萄糖和甘露糖组成,2种单糖物质的量之比为1.00：0.70。该研究为单糖化合物快速高效分离检测提供了新方法,并为葛根多糖单糖组成分析提供了参考。     

半叶马尾藻粗糖中单糖的离子色谱法分析

以60～80 ℃的水从半叶马尾藻干粉中提取粗多糖,用Sevage溶剂去蛋白纯化后,将粗多糖用4.0 g/L 的三氟乙酸在 80 ℃下水解,水解液在CarboPacTM PA10离子色谱柱(2 mm i.d.×250 mm)上以14.0 mmol/L NaOH溶液为流动相进行 分离,以电化学检测器检测半叶马尾藻粗糖水解产生的单糖成分及含量。结果表明,半叶马尾藻粗糖中木糖、半乳糖、阿 拉伯糖、葡萄糖、鼠李糖和果糖的含量分别为2200,820,98,4560,358和740 mg/kg,加标回收率范围为86.0%~108.0%,检出限范围为5.6～89.6 μg/kg。该方法具有灵敏度高、精密度好、样品不需 要衍生化处理等优点,适合藻类样品中单糖的分析。     

HPLC法同时测定鸡腿菇水解液中单糖及多糖的研究

建立了HPLC法测定鸡腿菇水解液中单糖、低聚糖及多糖含量的分析方法.选用Aminex HPX-87H柱,示差折光检测器,柱温50 ℃,5 mmol/L的硫酸为流动相,流速0.4 mL/min,进样量20 μL,外标法定量.结果表明,单糖、低聚糖及多糖均得到较好分离,其峰面积与质量浓度线性关系良好,相关系数r~2值为0.991 2 ～0.999 7,回收率为98% ～106%.采用HPLC-示差法与气相色谱法测定多糖、低聚糖及单糖相比,样品无需衍生处理,过滤后可直接进样检测.该法可同时测定原料水解液中可能存在的主要单糖、低聚糖及多糖.     

毛细管型离子色谱-脉冲安培法检测枸杞多糖的单糖组成

采用ICS-5000毛细管离子色谱仪对枸杞多糖中的10种单糖进行了分离测定.优化了前处理过程中影响多糖水解的酸种类、酸浓度、水解温度和时间等参数,优化条件为使用2 mol/L三氟乙酸溶液在100℃下水解120min,在该条件下,果糖回收率约为50％,其余单糖回收率在84％～104％之间.采用新型淋洗液自动发生装置电解产生淋洗液,Capillary CarborPac PA20色谱柱分离,毛细管安培池检测,10种单糖成分标准曲线线性关系良好,相关系数均大于99.9％;检出限在2.5～75 μg/L之间,为枸杞多糖中单糖组分测定提供了新的可行方法.     

中药大黄多糖中单糖组成的毛细管区带电泳分析

以1-苯基-3-甲基-5-吡唑啉酮(PMP)为单糖的衍生化试剂,建立毛细管区带电泳(CZE)同时分离分析8种常见还原单糖PMP衍生物的方法。将该方法用于中药大黄多糖(RTP)的单糖组成及其摩尔比率的测定。结果表明,在pH 10.8和150 mmol/L硼砂缓冲溶液、10kV分离电压、25℃柱温的优化条件下,8种单糖衍生物实现了良好的分离,并证实RTP由阿拉伯糖、葡萄糖、半乳糖、葡萄糖醛酸和半乳糖醛酸5种单糖组成,其摩尔比为8.01∶5.01∶30.30∶1.00∶1.56;样品测定回收率为96.4%~105.3%。该方法灵敏、快速、准确,可用于中药RTP的组成分析。     

瑞香狼毒多糖中单糖组成的毛细管区带电泳分析

采用1-苯基-3-甲基-5-吡唑啉酮(PMP)和1-(2-萘基)-3-甲基-5-吡唑啉酮(NMP)为衍生试剂,以反相高效液相色谱(RP-HPLC)和毛细管区带电泳(CZE)法对9种单糖衍生物进行了分离研究,对比确定了NMP衍生化CZE法在植物多糖单糖组成分析中的优越性。以NMP为柱前标记试剂,建立了毛细管区带电泳定量测定9种单糖的新方法。方法具有较好的重复性(相对标准偏差RSD小于4.3%),单糖衍生物检测限为0.85～1.6μmol/L,回收率为96.4%～104%。已应用于瑞香狼毒多糖样品的单糖组成分析。     

高效液相色谱法分析新型细菌多糖中单糖和糖醛酸组成

建立了柱前1-苯基-3-甲基-5-吡唑啉酮(PMP)衍生-高效液相色谱法,分离检测新型细菌多糖中5种单糖及糖醛酸组成的分析方法。新型细菌多糖中加入单糖内标木糖后,经3mol/L三氟乙酸水解,再用PMP进行衍生化,采用XBridgeTMC18柱(250×4.6mm,5μm),以50mmol/L KH2PO4溶液(pH=5.5)和乙腈为流动相,在245nm波长检测。定量分析结果表明,该多糖由甘露糖、葡萄糖醛酸、葡萄糖、半乳糖和岩藻糖组成,其质量比为1.77∶0.44∶8.52∶1.32∶1.67。该方法重现性良好,能够快速对多糖样品进行组成分析。     

高效阴离子交换-脉冲安培检测同时分析单糖和糖醛酸

建立了高效阴离子交换-脉冲安培检测(HPAE-PAD)同时分离测定8种单糖和2种糖醛酸的分析方法。以CarboPacPA20阴离子交换柱为分离柱,以2mmol/LNaOH溶液将8种单糖从分离柱上洗脱,而后用NaAc(50~200mmol/L)梯度淋洗2种糖醛酸,淋洗液流速为0.5mL/min,总分析时间为30min。在优化的分离测定条件下,8种单糖和2种糖醛酸的检出限为2.5~14.4μg/L(进样体积25μL,峰面积定量)。5mg/L的10种化合物的混合标准溶液连续7次进样,峰面积的相对标准偏差为0.3%~1.5%。用所建立的方法测定了多糖水解液和木材半纤维素水解液中的单糖和糖醛酸含量。     

竹荪加工中废弃物多糖水解液的胶束毛细管电泳研究

本文建立了胶束毛细管电泳测定竹荪加工废弃物的多糖组成的新方法。考察了缓冲溶液、表面活性剂、运行电压、温度等因素对分离效果的影响。选择25mmol/L硼酸盐(pH=9.4)-20mmol/L十二烷基磺酸钠(SDS)为电泳介质,分离电压为15kV,分离温度为25℃,9min中内可实现对竹荪加工中废弃物中多糖的单糖组分的分离检测。     

离子色谱-脉冲安培法测定芦荟多糖中7种单糖的含量

采用水提醇沉法提取芦荟鲜叶中的多糖，经三氟乙酸水解，利用Dionex CarboPac PA10高效阴离子色谱柱分离，氢氧化钠梯度淋洗，积分脉冲安培检测，建立了芦荟多糖中岩藻糖、鼠李糖、阿拉伯糖、半乳糖、葡萄糖、甘露糖和木糖7种常见单糖的测定方法。结果表明：7种单糖在线性范围内的相关系数（R²）均高于0.997，检出限为0.007~0.024 mg/L，加标回收率为97.5%~102.5%，相对标准偏差（RSD）为0.1%~4.8%。该法简单、快速、灵敏、准确，可用于芦荟多糖中单糖含量的测定和多糖组成的研究。     

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%.     

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.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.     

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.