保留时间两点校正反相高效液相色谱法测定持久性有机污染物的正辛醇-水分配系数

采用改进的反相高效液相色谱法(RP-HPLC)测定了持久性有机污染物(POPs)包括多环芳烃(PAHs)、多氯二苯并二恶英(PCDDs)、多氯二苯并呋喃(PCDFs)和十溴二苯乙烷(DBDPE)等的正辛醇-水分配系数(logKow)。采用保留时间双点校正法(DP-RTC)校正因色谱柱老化等引起的保留时间漂移。以37种有可靠logKow实验值的苯系物、PAHs、PCDD/Fs类似物为模型化合物,建立了logKow和外推至纯水相的保留因子logkw的定量结构-色谱保留关系(QSRR)模型,回归方程为logKow=(1.18±0.02)logkw+(0.36±0.11),其相关系数(R2)为0.985,交叉验证相关系数(R2cv)为0.983,标准偏差(SD)为0.16。进而,用4个已有可靠logKow实验值的验证化合物(联苯、芴、PCDD 1和PCDF 114)对模型进行了外部验证,表明RP-HPLC测得的logKow值与摇瓶法/慢搅法结果有很好的一致性,尤其是对疏水性强的化合物。采用该模型测定了29种特别受关注的POPs的logKow值,这些化合物的logKow实验值均未见报道。所建立的DP-RTC-HPLC是测定强疏水性POPs的logKow值的一种值得推荐的方法。     

在划分系统下集合对策值的结构

A set game, in which the worth of a coalition is expressed by a set instead of areal number, is a new type of cooperative game.A F-restricted set game is a set game restricted by partition system.The main theorems show the structures of IM-value,OIM-value,SCM-value and ICM-value respectively,and the equivalency of IM-value and the OIM-value for monotonicset games restricted by partition system as well.     

正整数的一类三分拆的应用

利用正整数n的一类特殊的3分拆n=n1+n2+n3,n1>n2>n3≥1,且n2+n3>n1的Ferrers图将不定方程4x1+3x2+2x3=n(n≥9)的正整数解与这种分拆联系起来,从而得到了该不定方程的正整数解数公式;同时也给出了正整数n的一类4分拆的计数公式.此外,还给出了周长为n的整边三角形的计数公式的一个简单证明.     

攒尖四坡屋面风致雪漂移的数值模拟

为获得攒尖四坡屋面的风致雪漂移规律,基于欧拉-欧拉方法和风雪单向耦合假定,运用计算流体动力学软件,选取Mixture模型分别对立方体周边和高低屋面上的风致雪漂移运动进行数值模拟,将模拟结果与两者的实地观测数据对比,探讨分析数值风洞的关键技术和参数设置,验证数值模拟方法的合理性与可靠性。依据攒尖四坡房屋的使用功能要求,设计分析模型与分析工况,在试算的基础上对屋面进行分区。以风速5 m/s,7 m/s,9 m/s,11 m/s,13 m/s和15 m/s,风向角0°,15°,30°和45°以及屋面坡度25°,30°,34°,40°和45°为分析参数,对攒尖四坡房屋的120种工况进行数值模拟,得到屋面各分区侵蚀沉积的基本规律,提出可用于抗雪设计的屋面积雪分布系数。研究表明,风向角的改变会使屋面积雪分布状态发生较大程度的变化,风速和屋面坡度的变化对屋面整体积雪量有较大影响。     

甲基丙烯酸3-三甲氧基硅丙酯在乳液体系中的分配

通过气相色谱(GC)研究了甲基丙烯酸3_三甲氧基硅丙酯(MPS)在乳液体系各相中的分配行为,并测得了MPS在各种情况下的分配系数.发现当MPS加入量达到聚合物种子的约10 wt%时,体系进入饱和状态,且大部分MPS分配在粒子相中.通过对单体相分配行为的理论分析,并结合实验数据,发现种子乳胶粒粒径、聚合物种子中的化学组成对MPS的分配行为影响很小,而温度则使MPS在各相中的饱和浓度增加.     

Electron paramagnetic resonance study of amphiphiles partitioning behavior in desiccation-tolerant moss during dehydration

Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance (EPR) spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorum was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly, from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.     

用胶束液相色谱模拟生物膜预测药物的醇-水分配系数log P

通过比较药物在不同类型表面活性剂的胶束液相色谱中的容量因子与药物的醇-水分配系数(log P)的相关性, 发现药物在非离子型表面活性剂Brij35作为流动相的胶束液相色谱中的容量因子与其文献中报道的log P间有一定的相关性, 进一步考察了Brij35浓度对药物保留的影响, 并建立了药物在不同浓度的Brij35胶束液相色谱中的容量因子与文献中log P的相关关系, 该方法简单、快速, 将为药物的疏水性评价提供重要的参考价值.     

三嗪类化合物溶解度参数及毒性构—效关系

测定了１２种三嗪类化合物的水溶解度，辛醇水分配系数和对发光菌的毒性，并用分子连结性指数建立了预测三嗪类化合物的溶解度，辛醇水分配系数及对发光菌毒性的定量结构活性相关方程，其中１０种化合物献中未见报道。e     

Improvement in the Physicochemical Properties of Ketoconazole through Complexation with Cyclodextrin Derivatives

Highly-soluble cyclodextrin derivatives, such as hydroxypropyl--cyclodextrin(HP--CD) and methyl--cyclodextrin (MEB), were tested as solubilizingagents for ketoconazole, with the aim of improving the physicochemical andbiopharmaceutical properties of this lipophilic imidazole antifungal agent. Productswere prepared in four molecular ratios by physical mixing, kneading and spray-dryingmethods. The kneaded products in a ratio of 1:2 and the spray-dried products exhibitedthe highest dissolution rates. The phase solubility diagrams of ketoconazole with thesecyclodextrins at 25 °C in water and in simulated intestinal medium wereconstructed. A solubility diagram of A_L type was obtained with HP--CD, and one of A_P type with MEB. The complexes were characterized by thermal methods(DSC, TG, DTG and DTA). Multicomponent systems were prepared with tartaric acid.The effects of water-soluble polymers, e.g., polyvinylpyrrolidone, on the aqueous solubility of ketoconazole were investigated. Particle size distribution, surface area, partition coefficient, heat of dissolution and wettability studies were also carried out. The formation of inclusion complexes was observed by means of thermoanalytical studies.