Study on extraction of agaropectin from Gelidium amansii and its anticoagulant activity

Gelidium amansii agar was fractionated on DEAE-cellulose and four fractions were obtained sequentially. The yields of 1.0 mol/L NaCl fraction and 2.5 mol/L NaCl fraction were 2.80% and 2.03%. They are highly sulfated agar, and named as agaropectin with sulfate content being 22.8% and 32.5%, respectively. The anticoagulant experiment results show that agaropectin could effectively prolong the coagulation time in a dose-dependent manner in vitro. Agaropection could be absorbed and effectively prolong the plasma coagulation time in vivo. After intragastric administration at the doses of 100, 200, and 400 mg/kg.d in rats for 15 days, TT (thrombin time), CT (coagulation time), PT (prothrombin time), and APTT (activated partial thromboplastin time) could be effectively prolonged and the plasma Fib level could be significantly lowered.

Chemical constituents from euphorbia wallichii

Eleven known compounds were isolated from the roots of Euphorbia wallichii for the first time. They were elucidated to be three triterpenoids, β-amyrin (1), β-amyrin acetate (2) and 3β-acetoxy-lupenol (3), one nor-triterpene peroxide baccatin (4), two caffeic esters (5a, 5b), palmitic acid-2,3-dihydroxypropanenyl ester (6), palmitic acid (7), scopoletin (8), β-sitosterol (9) and daucosterol (10) on the basis of spectral methods. Among them, compound 5a, 5b were reported firstly in the spurge family. And the NMR assignments of compounds 5a and 5b were given for the first time.

Determination of 30 free fatty acids in two famous Tibetan medicines by HPLC with fluorescence detection and mass spectrometric identification

A simple and sensitive high-performance liquid chromatographic (HPLC) method with fluorescence detection and mass spectrometric identification has been developed for analysis of 30 long-chain and short-chain free Fatty acids (FFAs). The fatty acids were derivatized to their esters with 1-[2-(p-toluenesulfonate)ethyl]-2-phenylimidazole-[4,5-f]-9,10-phenanthrene (TSPP) in N,N-dimethylformamide (DMF) at 90 degrees C with anhydrous K2CO3 as catalyst. A mixture Of C-1-C-30 fatty acids was completely separated within 60 min by gradient elution on a reversed-phase C-8 column. Qualitative identification of the acids was performed by atmospheric-pressure chemical ionization mass spectrometry (APCI-MS) in positive-ion mode. The fluorescence excitation and emission wavelengths were 260 and 380 nm, respectively. Quantitative determination of the 30 acids in two Tibetan medicines Gentiana straminea and G. dahurica was performed. The results indicated that the medicines contained many FFAs. Linear correlation coefficients for the FFA derivatives were > 0.9991. Relative standard deviations (RSDs, n = 6) for the fatty acid derivatives were < 3%. Detection limits (at a signal-to-noise ratio of 3:1) were 3.1-38 fmol. When the fatty acid derivatives were determined in the two real samples results were satisfactory and the sensitivity and reproducibility of the method were good.

Chemical constituents from the whole plant of Euphorbia altotibetic

Four new jatrophane diterpenoids, altotibetin A (1), altotibetin B (2), altotibetin C (3), altotibetin D (4), and nine known compounds, beta-sitosterol, cycloart-23-ene-3beta,25-diol, cycloart-25-ene-3beta,24-diol, lupeol acetate, scopoletin, kaempferol, uracil, uridine, astragalin, and daucosterol have been isolated from the whole plant of Euphorbia altotibetic PAULS. Their structures were established by spectral methods, and the configurations of 1 and 2 were confirmed by X-ray analysis.

中国中部全新世气候变化的泥炭同位素记录--以湖北神农架大九湖为例

泥炭作为一种地质档案，其发育形成过程中包含了丰富的古气候和古环境的变化信息。由于泥炭沉积中植物残体的碳、氧等稳定同位素组成与气候变化之间存在着密切关系，其稳定同位素时间序列已作为气候变化的代用指标逐渐用于古气候的恢复和重建，尤其是在以高时间分辨率重建全新世以来的气候环境变化方面已取得一些重要进展。 本论文通过对湖北省神农架地区大九湖泥炭中植物残体的氧、碳同位素的研究，同时以温度和湿度这两种重要的气候参数代用指标，恢复和重建全新世以来中国中部地区的气候状况。通过本论文的工作并与其它相关成果综合对比研究，对从末次冰消期晚期和全新世以来中国中部地区气候状况有如下的认识： 1. 末次冰消期晚期至全新世阶段，大九湖泥炭纤维素δ18O敏感地记录了发生在约14.67～12.89 cal. kaBP的BA暖期以及在此期间所发生的两次冷事件：Oder Dryas冷事件和Intra-Allerød冷事件；并指示随后的Allerød暖期明显较Bølling暖期偏冷；在新仙女木时期（YD），神农架地区温度较低，事件中后期温度开始回升；在11.0～9.0 cal. kaBP的早全新世时期，大九湖泥炭δ18O在波动中升高，指示了整体上的温暖气候，期间存在一系列的气候变冷事件。这些冷事件基本都是叠加在一种长期的、相对较暖的变化趋势上，有别于末次冰消期的突然变冷事件；在9.0～5.0 cal. kaBP的中全新世阶段，神农架地区总体上处于相对温暖的适宜阶段，但波动较为频繁，期间记录到了著名的“8.2ka”冷事件；约5.0 cal. kaBP开始，大九湖泥炭δ18O值持续升高，指示以一次快速的升温过程开始了晚全新世阶段并保持在一个相对较高的温度水平；在整体温暖的气候背景下也明显记录有“4.2ka”、“小冰期”等全球性冷事件；大九湖泥炭纤维素δ18O所记录的温度变化趋势与中国大陆地区其他一些气候代用指标所记录的温度变化趋势有很好的相似性，说明中国大陆地区温度变化的趋势基本一致。 2. 大九湖泥炭δ18O温度变化序列所记录到的历次突然气候变冷事件，与格陵兰冰芯和北大西洋冷事件的发生具有很好的一致性，这说明对应于北半球高纬度区域的气候变化，在中低纬度的中国地区同样存在响应和变化，并且这种响应贯穿于整个全新世阶段。 3. 大九湖泥炭纤维素δ13C敏感地记录了末次冰消期以来东亚季风的演变历史。东亚季风在整个末次冰消期至晚全新世阶段始终处于一种强弱交替的波动态势。在末次冰消期至全新世早期，其整体上表现为一种由弱转强的态势；在全新世早期和中期阶段，东亚季风活动强度整体较高，表现为整个时间序列中的高活动时段，而其中也出现了数次明显的减弱迹象；全新世晚期阶段，东亚季风的活动强度较中期和早期为弱，整体上表现出低幅的波动但没有恢复到前两个时期的活动强度。在中世纪温暖期阶段的中后期，东亚季风的活动强度开始在波动中逐渐升高。 4. 该泥炭纤维素代用指标所记录的一些东亚季风突变（增强）事件与同一时期所发生的印度季风的突变（减弱）事件具有很好的对应关系；进一步证实这两个季风系统之间所存在的反相变化关系；同时，这些突变事件与北大西洋IRD冷事件在发生时间段也具有较好的对应关系，即每当北大西洋地区气候变冷时，东亚季风都表现出增强的迹象。 5. 综合分析中国泥炭同位素古气候记录和其它研究结果，对气候驱动机制有如下认识：当太阳活动发生百年至千年时间尺度的减弱时，由大气臭氧层变化所触发的影响向大气层下部延伸，导致北半球气候变冷；同时，减弱的太阳活动可能在赤道太平洋触发类厄尔尼诺状态出现，并引发印度洋夏季风减弱和东亚夏季风增强；早全新世北半球冰盖周围大冰湖冰岸坍塌，湖中巨量体积淡水突然流入北大西洋，导致海洋温盐环流传送带运转放慢甚致停顿，通过跨赤道的温盐环流向北输送的热量大大减少，引起北半球气候变冷；由于海洋温盐环流的变化改变了全球热量的分配，暖水在地球南部积累，导致西太平洋暖池区域海表面水与深层水温度之间反差的增加，从而有利于类厄尔尼诺状态出现，同样将可能引起印度洋夏季风减弱和东亚夏季风增强。

单种属泥炭纤维素碳稳定同位素组成与全新世青藏高原东部西南季风变化

泥炭的形成和积累主要受控于气候，其次是地质、地貌和水文等因素。作为一种重要和理想的气候信息载体，泥炭己经与冰芯、海洋及湖泊沉积、黄土堆积、洞穴碳酸盐沉积、树轮和珊瑚礁等其它类型的自然地质档案一样，逐渐为国内外致力于古气候变化研究的学者所接受，并将其重点应用于全新世以来气候变化信息的提取。本研究在已有的泥炭混合植物残体纤维素碳稳定同位素记录青藏高原东部地区气候信息的基础上，首次提取泥炭中单一种属植物残体一木里苔草（Calexmulieensis）纤维素，测定其碳稳定同位素，并以其时间序列作为一种新的西南季风代用指标，揭示该区域全新世以来气候变化。研究表明：1．木里苔草的碳稳定同位素时间序列是西南季风强度变化的敏感代用指标。约11800～11加0 cal aBP期间，木里苔草纤维素的613C记录处于最大值，表明该时段西南季风活动鼻弱，气候干冷，对应于普遍发生并存在的新仙女木事件；它清晰地指示了该区全新世的下限年龄为约11200 cal aBP（14c年龄约9900aB玲从约11200 oal aBP起该区迅速进入湿暖的全新世阶段，季风活动迅速增强；在约10800～5500 cal aBP期间，季风总体保持在强盛状态，但其间有4次突然减弱，气候变干冷；约从5500 cala即起季风活动在波动中逐渐减弱，其中有4次减弱最为明显。2．木里苔草纤维素碳同位素所记录的犯000年以来的所有9次西南季风活动的突然减弱与同时期北大西洋发生的冰力｝漂移碎屑沉积物事件（IRD事件）一一对应。这种密切的相关关系表明，西南季风强度的波动可能是对全球气候变化特别是对海洋热盐环流引起的地球南北方气撇动变化的响应。3．木里苔草纤维素碳稳定同位素所指示的西南季风有952，乓57，475，312，211和77年等一系列周期。其中557年和77年两个周期分别与北大西洋深层海水环流的550年的周期和76年的气候周期非常吻合。这表明西南季风与北大西洋气候间有很好的相关关系。由于557年和77年的季风周期又都分别类似于53。年和80年的太阳活动周期，这表明太阳活动可能对西南季风和北大西洋气候间的联系有着影响。4．红原泥炭木里苔草纤维素和泥炭混合纤维素别3c时间序列在千年至万年时间尺度上的变化趋势很相近。两种代用记录都一致反映了冰后期的气候变化，即均指示西南季风强度变化可分为三个明显的大阶段。这说明它们对过去12000年的西南季风变化具有相同的响应。对于目前经过较详细研究的那些全球大范围发生的突然气候变化事件，木里苔草纤维素δ~(13)C代用记录与泥炭混合纤维素δ~(13)C代用记录一样，都有相同的响应，但是，相对于泥炭中单一的木里苔草敏感地记录到历次北大西洋I劝事件而言，泥炭混合纤维素δ~(13)C记录对其中的几次突然气候变化事件似乎没有表现出明显的响应。这个结果表明对数百年尺度的突然气候变化，木里苔草纤维素比混合纤维素的酬3c指标似乎要更敏感一点。因此，在能获得足够数量的单种植物·残体的情况下，单种植物残体纤维素的δ~(13)C指标有很好的使用价值。

Simple derivatization method for sensitive determination of fatty acids with fluorescence detection by high-performance liquid chromatography using 9-(2-hydroxyethyl)-carbazole as derivatization reagent

A simple and sensitive method for the determination of short and long-chain fatty acids using high-performance liquid chromatography with fluorimetric detection has been developed. The fatty acids were derivatized to their corresponding esters with 9-(2-hydroxyethyl)-carbazole (HEC) in acetonitrile at 60 degreesC with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride as a coupling agent in the presence of 4-dimethylaminopyridine (DMAP). A mixture of esters of C-1-C-20 fatty acids was completely separated within 38 min in conjunction with a gradient elution on a reversed-phase C-18 column. The maximum fluorescence emission for the derivatized fatty acids is at 365 nm (lambda (ex) 335 nm). Studies on derivatization conditions indicate that fatty acids react proceeded rapidly and smoothly with HEC in the presence of EDC and DMAP in acetonitrile to give the corresponding sensitively fluorescent derivatives. The application of this method to the analysis of long chain fatty acids in plasma is also investigated. The LC separation shows good selectivity and reproducibility for fatty acids derivatives. The R.S.D. (n = 6) for each fatty acid derivative are <4%. The detection limits are at 45-68 fmol levels for C-14-C-20 fatty acids and even lower levels for

Removal of endotoxin from human serum albumin solutions by hydrophobic and cationic charged membrane

A novel matrix of macropore cellulose membrane was prepared by chemical graft, and immobilized the cationic charged groups as affinity ligands. The prepared membrane Fan be used for the removal of endotoxin from human serum albumin (HSA) solutions. With a cartridge of 20 sheets affinity membrane of 47 mm diameter, the endotoxin level in HSA solution can be reduced ro 0.027 eu/mL. Recovery of HSA was over 95%.

Determination of alcohols by high-performance liquid chromatography with fluorimetric detection after pre-column derivatisation with carbazole-9-N-acetic acid and chromatographic behaviour of alcoholic derivatives

Alcohols were derivatised to their carbazole-9-N-acetic acid (CRA) esters with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC . HCl) as the dehydrating agent. Studies on derivatisation conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives. The retention behaviour of alcohol derivatives was investigated by varying mobile phase compositions (ACN-water and MeOH-water). The parameters from the equation log k'=A-BX were evaluated by retention data of derivatives using an isocratic elution with different mobile phases. The results indicated that the parameters derived allowed computation of retention factors in good agreement with experiments. At the same time, a general equation was derived that makes possible predictions of partition coefficient in binary mobile phases with different proportions of organic solvent to water based on some simple regression analysis. The LC separation for the derivatised alcohols containing higher carbon alcohols showed good reproducibility on a reversed-phase C-18 column with gradient elution. The detection limits (excitation at 335 nm, emission at 360 nm) for derivatised alcohols (signal-to-noise ratio=3:1) were in the range of 0.1-0.4 pg per injection. (C) 2001 Elsevier Science B.V. All rights reserved.

Synthesis of chiral 3-acylcamphors

3-Acylcamphors were synthesized in moderate yields by the condensation of camphor with esters using sodium hydride as a base.

Modeling of protein adsorption in membrane affinity chromatography

For the design of affinity membranes, protein adsorption in membrane affinity chromatography (MAC) was studied by frontal analysis. According to fast mass transfer, small thickness of affinity membranes and high affinity between the protein and the ligand, an ideal adsorption (IA) model was proposed for MAC and was used together with equilibrium-dispersive (E-D) model to describe the adsorption of bovine serum albumin (BSA) onto cellulose diacetate/polyethyleneimine (CA/PEI) blend membranes with and without Cu2+ chelating. E-D model was found to better describe the initial region of experimental breakthrough curves. The influence of axial dispersion was revealed and it showed the importance of design of the module to homogenously distribute feed solution. IA model was found to be better for the whole experimental breakthrough curve. According to it, the capacity of affinity membranes and the specificity of the interaction are of equal importance for the design of affinity membranes. An optimum feed concentration was also found in the operation of MAC. The discrepancy between experimental optimum feed concentrations and predicted ones from IA model may be due to the ignorance of some experimental effects such as axial dispersion.

Lipase-catalyzed regioselective acylation of diosgenyl saponins

Diosgenyl saponins were regio selectively acylated by Novozyme 435 with vinyl esters as acylating agents in THF to afford the corresponding mono- or diacyl diosgenyl saponins. (C) 2001 Elsevier Science Ltd. All rights reserved.

Morphology transcription process from CMC micelles to inorganogel and its effect on the properties of alumina particle

In this study, a carboxymethyl cellulose (CMC)-mediated sol-gel process was developed to synthesize the alumina hydoxide whiskers. During the process, inexpensive inorganic salts were used as precursors and supercritical drying method was used to extract the water in hydrogel. The influences of CMC on the gel formation and the particle morphology were investigated. The results show that the formation of CMC-aluminium hydroxide organic-inorganic hybridgels led to a morphology transcription process from CMC micelles to aluminium hydroxide gel, as a result, the precursor with whiskerious morphology was obtained.