Mass spectrometric identification of multihydroxy phenolic compounds in Tibetan herbal medicines

A highly selective and accurate method based on derivatization with dansyl chloride coupled with liquid chromatography-mass spectrometry has been developed for identification of natural pharmacologically active phenolic compounds in extracts of Lomatogonium rotatum plants (Tibetan herbal medicine) obtained by solid-phase extraction. The number of hydroxyl groups on the dansylated phenols was estimated by LC-MS-MS analysis in positive-ion mode. Dansyl derivatization of the compounds introduced basic secondary nitrogen into the phenolic core structures and this was readily ionized when acidic HPLC mobile phases were used. MS fragmentation of the derivatives generated intense protonated molecular ions of m/z [MH](+) (phenol aglycones were transformed into the corresponding free phenols by cleavage of an aglycone bond). Collision-induced dissociation of the protonated molecule generated characteristic product ions of m/z 234 and 171 corresponding to the protonated 5-(dimethylamino)naphthalene sulfoxide and 5 -(dimethylamino) naphthalene moieties, respectively. Selected reaction monitoring based on the m/z [MH](+) to 234 and 171 transitions was highly specific for these phenolic compounds. Characteristic ions with m/z values of [MH - 234](+), [MH 2 x 234](+), and [MH - 3 x 234](+) were of great importance for estimation of the presence of multihydroxyl groups on the phenolic backbone.

Docking and molecular dynamics studies toward the binding of new natural phenolic marine inhibitors and aldose reductase

Phenolic marine natural product is a kind of new potential aldose reductase inhibitors (ARIs). In order to investigate the binding mode and inhibition mechanism, molecular docking and dynamics studies were performed to explore the interactions of six phenolic inhibitors with human aldose reductase (hALR2). Considering physiological environment, all the neutral and other two ionized states of each phenolic inhibitor were adopted in the simulation. The calculations indicate that all the inhibitors are able to form stable hydrogen bonds with the hALR2 active pocket which is mainly constructed by residues TYR48, HIS110 and TRP111, and they impose the inhibition effect by occupying the active space. In all inhibitors, only La and its two ionized derivatives La_ion1 and La_ion2, in which neither of the ortho-hydrogens of 3-hydroxyl is substituted by Br, bind with hALR2 active residues using the terminal 3-hydroxyl. While, all the other inhibitors, at least one of whose ortho-sites of 3- and 6-hydroxyls are substituted by Br substituent which take much electron-withdrawing effect and steric hindrance, bind with hALR2 through the lactone group. This means that the Br substituent can effectively regulate the binding modes of phenolic inhibitors. Although the lactone bound inhibitors have relatively high RMSD values, our dynamics study shows that both binding modes are of high stability. For each inhibitor molecule, the ionization does not change its original binding mode, but it does gradually increase the binding free energy, which reveals that besides hydrogen bonds, the electrostatic effect is also important to the inhibitor–hALR2 interaction.

Dynamic constitutive equation of GFRP obtained by Lagrange experiment

The note presents a method of constructing dynamic constitutive equations of material by means of Lagrange experiment and analysis. Tests were carried out by a light gas gun and the stress history profiles were recorded on multiple Lagrange positions. The dynamic constitutive equations were deduced from the regression of a series of data which was obtained by Lagrange analysis based upon recorded multiple stress histories. Here constitutive equations of glass fibre reinforced phenolic resin composite(GFRP) in uniaxil strain state under dynamic loading are given. The proposed equations of the material agree well with experimental results.

酚醛树酯的热解动力学模型

建立了一种利用热重峰值分析进行酚醛树酯热解动力学研究的方法,这种方法利用热重谱峰上几个特征点的数据来确定动力学参数.根据酚醛树酯热解DTG曲线的特点,把酚醛树酯的热解过程分解成三个阶段,用峰值分析法对每个反应阶段分别建模,通过三个反应阶段的叠加得到了一个酚醛树酯分阶段热解动力学模型,该模型能够很好地描述酚醛树酯的热解过程. 

酚醛树脂激波管试验的高温热解研究

使用激波管作为加热手段研究酚醛树脂在1200～1800K温度范围内的热解特征.气相产物中主要碳氢产物是甲烷、乙烯、乙炔、苯和甲苯.获得试验温度范围内主要碳氢产物分布随热解温度的变化关系.结果表明,在试验温度范围内随着热解温度的升高酚醛树脂的热解机理发生重大变化.1400K以下热解断键过程主要发生在亚甲基桥链结构上;1400K以上芳环开环成为主要的热解通道,生成大量的乙炔.

酚醛树酯的热解动力学模型

建立了一种利用热重峰值分析进行酚醛树酯热解动力学研究的方法,这种方法利用热重谱峰上几个特征点的数据来确定动力学参数.根据酚醛树酯热解DTG曲线的特点,把酚醛树酯的热解过程分解成三个阶段,用峰值分析法对每个反应阶段分别建模,通过三个反应阶段的叠加得到了一个酚醛树酯分阶段热解动力学模型,该模型能够很好地描述酚醛树酯的热解过程.

激波管在酚醛树脂高温热解动力学研究中的应用

使用激波管作为加热手段,利用其加热速率快的优点,突破了传统方法在加热速率上的限制,研究了酚醛树脂在1400～1700K温度范围内的热解动力学.主要碳氢产物是甲烷、乙烯、乙炔和苯.通过对反应扩散过程的分析,考察了扩散对热解过程的影响.结果表明,实验中酚醛树脂的反应扩散过程迅速达到稳态,扩散影响可以忽略,首次获得了酚醛树脂在芳环开环热解机制下的热解速率常数.

酚醛树脂高温热解的激波管实验研究

采用激波管方法研究了酚醉树脂在温度1100K～1800K范围之间的热解过程.在激波管高温和短实验时间条件下,分析了实验样品颗粒在高温气相中的传热过程,讨论了样品颗粒达到热平衡的条件.通过色谱和质谱方法检测热解产物,获得了酚醛树脂高温热解产物分布和热解速率常数.酚醛树脂高温热解最主要的产物为水、一氧化碳、氢、乙炔和苯.温度1400 K将酚醛树脂热解分为高温和低温区,分别表现出不同的热解速率常数与温度的关系.

Anti-HIV Activities of the Compounds Isolated from Polygonum cuspidatum and Polygonum multiflorum

The 70% EtOH extract of Polygonum cuspidatum showed inhibitory action against HIV-1-induced syncytium formation at non-cytotoxic concentrations in vitro with a 50% effective concentration (EC50) of 13.94 +/- 3.41 mu g/mL. Through bioactivity-guided fractionation, 20 phenolic compounds, including eight stilbenoids, were isolated from the roots of Polygonum cuspidatum, and their anti-HIV-1 activities were evaluated. Results showed that compounds 1, 13, 14, and 16 demonstrated fairly strong antiviral activity against HIV-1-induced cytopathic effects in C8166 lymphocytes at non-cytotoxic concentrations, with EC50 values of 4.37 +/- 1.96 mu g/mL, 19.97 +/- 5.09, 14.4 +/- 1.34 mu g/mL, and 11.29 +/- 6.26 mu g/mL and therapeutic index (TI) values of 8.12, > 10.02, > 13.89, and > 17.71, respectively. Other compounds showed either weak or no effects. Compound 6 also showed weak inhibition (153.42 +/- 19.25 mu g/mL); however, it possesses very good water solubility and showed almost no cytotoxicity (> 2000 mu g/mL), therefore achieving a fairly good TI (13.04). The activities of the two compounds (3 and 18) from Polygonum multiflorum were also assayed. The relationship between molecular structures and their bioactivities was also discussed.

Relationship between the allelopathic activity and molecular structure of hydroxyl derivatives of benzoic acid and their effects on cyanobacterium Microcystis aeruginosa

The antialgal activities of benzoic acid, 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid (gallic acid) were studied on the growth of two strains of Microcystis aeruginosa (toxic FACHB 942 and non-toxic 469). The results showed that the sequence of 50% growth inhibition concentration (ErC50) of 6- compounds for both strains of M. aeruginosa followed the same order: gallic acid > 3,5-dihydroxybenzoic acid > 4-hydroxybenzoic acid > salicylic acid > 3-hydroxybenzoic acid > benzoic acid. The position and the numbers of hydroxy groups between the hydroxy group and carboxyl influenced the antialgal effects of phenolic acids. We also investigated the joint effects of benzoic acid, 4-hydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid on the growth of M. aeruginosa ( toxic FACHB 942). The mixture of phenolic allelochemicals showed the synergistic effects.

Evaluation of soot particles of biomass fuels with endocrine-modulating activity in yeast-based bioassay

Exposure to indoor air pollution (IAP) from the combustion of biomass fuels is an important cause of morbidity and mortality in developing countries. In the work discussed in this paper we evaluated the endocrine activity of soot particles from biomass fuels by using yeast bioassay. These pollutants could have beta-galactosidase activity with a relative potency (RP) about 10(-7)-10(-9) that of estradiol. Soot particles from wood and straw combustion only partially induced beta-galactosidase activity whereas others produced fully inductive activity in the yeast assay system. These pollutants did not have estrogen antagonist and progesterone agonist activity within the defined concentration range. However, these pollutants require 2-4 orders of magnitude higher IC50 to inhibit the activity of progesterone in a similar dose-response manner to mifepristone. We therefore propose that the endocrine activity of some environmental pollutants may be because of inhibition of the progesterone receptor (hPR). GC-MS results showed that substituted polycyclic aromatic hydrocarbon (PAH) compounds, substituted phenolic compounds and derivatives, aromatic carbonyl compounds, and phytosteroids in these soot particles may be mimicking endogenous hormones.

Presence of estrogenic activity from emission of fossil fuel combustion as detected by a recombinant yeast bioassay

Estrogenic activities of emission samples generated by fossil fuel combustion were investigated with human estrogen receptor (ER) recombinant yeast bioassay. The results showed that there were weak but clear estrogenic activities in combustion emissions of fossil fuels including coal, petroleum, and diesel. The estrogenic relative potency (RP) of fossil fuel combustion was the highest in petroleum-fired car, followed by coal-fired stove, diesel-fired agrimotor, coal-fired electric power station. On the other hand, the estrogenic relative inductive efficiency (RIE) was the highest in coal-fired stove and coal-fired electric power station, followed by petroleum-fired car and diesel-fired agrimotor. The estrogenic activities in the sub-fractions from chromatographic separation of emitted materials were also determined. The results indicated that different chemical fractions in these complex systems have different estrogenic potencies. The GC/MS analysis of the emission showed that there were many aromatic carbonyls, big molecular alcohol, PAHs and derivatives, and substituted phenolic compounds and derivatives which have been reported as environmental estrogens. The existence of estrogenic substances in fossil fuel combustion demands further investigation of their potential adverse effects on human and on the ecosystem. The magnitude of pollution due to global usage of fossil fuels makes it imperative to understand the issue of fossil fuel-derived endocrine activities and the associated health risks, particularly the aggregated risks stemmed from exposure to toxicants of multiple sources. (C) 2003 Elsevier Science Ltd. All rights reserved.

耐热树脂的增强与增韧研究

耐热树脂或称特种工程塑料主要包括聚芳飒类、聚醚酮类、聚芳酷、液晶类、聚酞亚胺和聚苯硫醚等。长春应化所已获得有关聚芳醚酮（PEK-C），聚芳醚砜（PES-C）和聚酞亚胺（PEI）等特种工程塑料的专利12项。在特种工程塑料中，PEK-C，PES-C和PEI有着最高的机械强度（室温下的拉伸强度在100MPa以上）。PES-C和PEI的耐热等级最高（热变形温度分别为225℃和220-260℃）。PE工有极好的阻燃性（氧指数为47）和耐磨性。而PEK-C的加工性好、韧性高、耐磨损和抗电击穿等性质突出，其综合物性与英国ICI公司的聚醚醚酮（PEEK）相近，是良好的高性能复合材料基体树脂。具有优异综合物性的PEK-C、PES-C、PEI及其改性系列材料在机械、电子电气、军工、医疗及食品等许多领域有着广泛的应用前景。近年来，长春应化所在酞侧基聚芳醚酮和聚芳醚矾的结构一加工一物性关系及开发应用等方面作了大量的研究工作，主要涉及此两种聚合物的粘弹性、屈服行为、断裂行为、转变与松弛以及复合与共混等方面内容。这些研究工作表明，酞侧基聚芳醚酮和聚芳醚矾经过共混和复合改性能够具有更优异的使用性能，而且这些研究中的一些方法同样可以应用于其它耐热树脂的改性。高分子材料科学的发展趋势就是在更深层次上把握材料的结构特点及其与宏观物性间的相互关耽达到高分子分子设计和材料设计的目标，实现高性能化和高功能化使现有的高分子材料找到更广泛而合理的应用。工程塑料的高性能化是高分子材料科学近年来发展的一个主要方向。为满足航天航空、电子信息、汽车工业家用电器以及机械等多方面技术领域的需要，要求材料的机械性能、耐热性、耐腐蚀性和长期使用性等性能进一步提高。在现有工程塑料品种的基础上通过共混增韧、复合增强等改性方法使其成为高性能的结构材料，是高分子材料私｝学的前沿课题及重要任务。本文采用熔融加工的方法制备了PEK-C和PES-C耐热树脂的共混与复合材料，利用热分析、力学性能检测、微观形貌观察、加工性能检测等手段研究了共混物及复合材料的结构与性能。通过对PEK-C和PES-C的冲击断裂过程的研究，我们发现，两种材料在裂纹起始扩展时所能承受的最大应力值相同，但PES-C的裂纹引发（ti）和扩展（tp）所需时间仅是PEK-C的一半，此即PES-C的冲击强度（I）和断裂韧性（KIC）较低的原因。因此，如能延长裂纹引发和扩展的时间，也就是说如能扩大断裂过程区，抑制裂纹的早期形成就能达到增韧的目的。在PES-C的增韧研究方面，我们可以借鉴通用塑料的增韧方法，即在高聚物基体中，以适当的手段掺加第二相粒子，通过粒子的变形和引发基体在粒子周围产生剪切屈服或银纹化等作用机理，实现增韧目的。所不同的是，对PES-C类耐热树脂来说，实现增韧的同时应保持材料原有的高强度和高耐热性等优良险质。另一方面，由于耐热树脂的加工温度极高，适合于通用塑料的偶联剂等界面改性技术已不再适用于特种工程塑料。针对PES-C的增韧方法和机理的研究工作可归纳为以下三个方面：①刚性有机粒子（PPS，LCP等）增韧；②柔性有机粒子（UHMWPE）增韧；③刚性无机粒子（硅灰石）增韧。物理老化或结构松弛效应使得高聚物材料的结构和宏观物性随时间而发生变化。随时间的增长，PES-C和PES-C／PPS共混物的拉伸强度增加、冲击韧性减小，而且这种变化趋势表现出物理老化过程的自衰减特性。研究结果表明，PES-C／pps共棍物的结构松弛速率比PES-C慢。具有良好界面相互作用的PES一C／PPS共混物材料的强度和韧性始终高于PES-C纯组份聚合物。因此说，pES-C／PPS共混物不仅具有良好的短期性能，而且在高温下长期使用过程中，其力学性能将始终优于纯组份聚合物。我们研究了热固性聚酞亚胺预聚物（P01）增容聚芳醚酮／聚苯硫醚共混物的热学性能、力学性能、形态结构及加工性，对POI在聚芳醚酮／聚苯硫醚共混物中所起的增容作用机理进行了初步探讨。实验发现，PEK-C／PPS共混物在保持PEK一C原有的高强度和高模量的同时，加工流动性和韧性得到一定程度的改善。PEK-C／ppS／Pm三元共混物中，少量的POI能够控制PPS分散相的相区尺寸，防止分散相粒子的自凝聚，起到了增容剂的作用。热固性高聚物预聚体可用于增容热塑性高聚物共混体系，这种增容方法有其特殊性和新颖性，增容后的聚芳醚酮／聚苯硫醚共棍物的力学性能得以改善。利用纤维可以作为结晶性高聚物的异相成核剂的特性，将合适的结晶性高聚物与非晶高聚物共混，可以在在一定程度上改善非晶高聚物与纤维间的界面粘结，提高纤维增强效率。这种方法对PEK-C类耐热树脂尤为重要。通过与即S共混，玻纤增强PEK-C复合材料中纤维与基体间的界面粘结以及纤维的长径比明显增加，因而复合材料的强度和模量显著提高，而且加工流动性也得到一定程度的改善。从考虑综合物性的角度出发，利用结晶性高聚物改善纤维与非晶树脂基体间的界面粘结时，结晶性高聚物的用量存在一个最佳值。与PEEK／GF复合材料相比，PEK-C／PPS／GF复合材料在加工能耗、价格等方面存在很大优势，可以预期这一高性能复合材料可应用于制造高强度、高耐热、耐腐蚀、耐磨损、耐疲劳的往复运动部件、振动或转动等机械零部件。

ABS树脂形态结构及力学性能的研究

ABS树脂具有优良的抗冲击性、耐热性和耐化学药品性，还具有易加工性、制品尺寸稳定性等特点，广泛应用于工业领域。ABS树脂的制备方法有许多种，目前应用最为广泛的是乳液接枝ABS共聚物一本体SAN掺混法。首先采用乳液聚合方法合成聚丁二烯胶乳，然后将其作为种子进行苯乙烯和丙烯睛的接枝共聚反应生成ABS接枝共聚物；采用本体法制备SAN树脂；最后将ABS接枝共聚物（冲击改性剂）和SAN树脂共混制得ABS树脂。由此看来，ABS接枝共聚物的合成是控制ABS树脂性能的关键。目前国产ABS树脂普遍存在的问题是ABS接枝共聚物的增韧效率低。影响其增韧效率的因素包括共聚单体的组成、橡胶相的组成及结构、橡胶与树脂之间的界面结合力等。因此为提高ABS冲击改性剂的增韧效率，拓宽ABS树脂的应用领域，应合理地控制ABS冲击改性剂的合成参数。本论文采用种子乳液聚合方法在PB（聚丁二烯）橡胶粒子上接枝共聚苯乙烯和丙烯睛合成ABS接枝共聚物，将其作为冲击改性剂与SAN树脂共混制备ABS树脂，对ABS树脂形态结构及力学性能进行了研究。主要研究内容和结论如下：1、研究ABS接枝共聚物中PB／SAN组成、TDDM（叔十二碳硫醇）链转移剂和CHP（过氧化氢异丙苯）用量、单体加料方式及引发剂类型对SAN在PB橡胶粒子上接枝度的影响。sAN在PB橡胶粒子上的接枝度随PB和TDDM含量的增加而降低；随CHP用量的增加先增加后降低；随单体滴加时间的延长而增加，但过分延长时间则对接枝度影响很小；与AIBN（偶氮二异丁睛）和K25208（过硫酸钾）相比，采用氧化一还原引发体系得到的接枝度较高。2、研究ABS接枝共聚物的力学性能。DMA结果表明，随着PB含量的增加，ABS接枝共聚物的储能模量降低，橡胶相的玻璃化转变温度向低温移动，内耗峰值增加。拉伸试验结果表明，当体系中没有TDDM时，不同橡胶含量的ABS接枝共聚物均没有发生明显的应变软化；当加入适量的TDDM后，材料发生应变软化，且随着TDDM用量的增加，材料的屈服应力提高。3、研究ABS接枝共聚物对ABS树脂形态结构及力学性能的影响。ABS接枝共聚物中PB／SAN组成及TDDM链转移剂用量影响ABs树脂中橡胶粒子的内部形态及橡胶粒子在基体中的分散。在合成ABS接枝共聚物的过程中，应合理地调节PB／SAN组成及TDDM的用量以使ABS接枝共聚物达到最大的增韧效率。4、研究ABS树脂在不同应变速率下的断裂行为及形变机理。结果表明，橡胶含量及应变速率影响ABS树脂的力学性能，但没有改变ABS树脂的形变机理。ABS树脂的形变机理包括银纹、橡胶粒子的空洞化及基体的剪切屈服，其中占主导地位的是橡胶粒子的空洞化及基体的剪切屈服。