Uptake kinetics of 3-buten-1-ol, 4-penten-1-ol and 3-methyl-3-buten-1-ol into sulfuric acid solutions

Unsaturated alcohols are important components in complex mixtures of oxygenated volatile organic compounds, and play a significant role in atmospheric chemistry. The uptake kinetics of 3-buten-1-ol (BO31), 4-penten-1-ol (PO41) and 3-methyl-3-buten-1-ol (MBO331) into 20 wt%-80 wt% H₂SO₄ solutions were studied, using a rotated wetted-wall reactor coupled to a differentially pumped single-photon ionization time of flight mass spectrometer (SPI-TOFMS). With increasing acidity, the uptake processes changed from reversible to irreversible (reactive). Reactive uptake was observed in 60 wt%-80 wt%, 50 wt%-80 wt% and 30 wt%-80 wt% H₂SO₄ solutions for BO31, PO41 and MBO331, respectively. Reactive uptake coefficients were acquired and are reported here for the first time. Reactivity order followed the trend: BO31<PO41<MBO331. An electrophilic addition mechanism of H₂SO₄ to the C=C double bond was used to explain this trend. Atmospheric implications were discussed, based on the reactive uptake coefficients. This heterogeneous reaction with sulfuric acid aerosols may be a potential degradation pathway of unsaturated alcohols, and should not be neglected.     

非饱和混凝土中氯离子输运问题的边界元算法

氯离子侵蚀对混凝土结构耐久性造成极大危害,研究混凝土中氯离子输运问题的计算方法,对于完善混凝土结构寿命预测与评估方法具有重要意义.针对非饱和混凝土中氯离子输运问题,综合考虑了渗透和扩散对输运过程的影响.将相应的控制方程转化为积分弱形式,采用径向积分法和基于紧支径向基函数的函数逼近方法,得到仅包含边界积分的积分方程.采用中心差分格式表示非稳态项中的湿度梯度和浓度梯度,进而建立该问题的无网格边界元方程.通过求解系统方程,得到混凝土中氯离子输运问题的解答.计算表明,混凝土未饱和之前,渗透过程对氯离子输运的影响显著高于扩散过程,渗透对扩散过程的影响时间远长于混凝土达到饱和的时间.这为进一步研究干湿循环作用下混凝土中氯离子输运问题奠定了基础.     

旋转模塑成型不饱和聚酯树脂的表面质量及工艺探究

为了解决旋转模塑成型中,不饱和聚酯树脂因其相对较高的初始黏度和反应热而难以操作的问题,利用实验室小型单轴旋转成型机加工成型不饱和聚酯树脂模制品;通过三维显微镜、厚度均匀性分析和热重量分析等方法确定其最佳加工条件。实验结果表明：在体积填充分数0.049~0.065、模具转速15~20 r/min、模具温度30~50 ℃条件下,可得到内外表面质量较好的模制品。     

ACLY抑制剂脱氢弯孢霉菌素肝微粒体代谢

该文主要研究了潜在抗肿瘤候选化合物脱氢弯孢霉菌素的体外肝微粒体代谢特点.建立了脱氢弯孢霉菌素含量的HPLC测定方法,考察了脱氢弯孢霉菌素在不同种属来源的肝微粒体中的代谢速率差异.依据UPLC-MS结果推测脱氢弯孢霉菌素中α、β不饱和双键经环氧化反应,亲和反应和分子内脱水反应,生成epoxycurvularin、 10,11-邻二羟基弯孢霉菌素和curvulopyran,且脱氢弯孢霉菌素在溶液中可能发生非酶催化的化学转化.考虑到脱氢弯孢霉菌素结构中的α,β不饱和双键既是重要的活性结构又是主要的代谢位点,合理的前药设计可能是提高该化合物可药性的有效方法.     

非饱和土壤水流问题的半离散间断有限体积元方法

讨论了二维非饱和土壤水分运动的间断有限体积元方法，给出了该格式的离散最优L2模估计和H1模估计。     

液晶p-BDAB的合成及其在不饱和聚酯树脂改性中的应用

以烯丙基溴、对羟基苯甲酸乙酯和联苯二酚为原料合成了二对烯丙基醚苯甲酸联苯二酚酯.用DSC,1H-NMR,FTIR,POM和XRD对其进行了表征,结果表明:该化合物熔点为185℃,在178℃出现一个晶型转变,清亮点为278℃,为近晶型液晶.以此液晶化合物与普通不饱和聚酯(UP)共聚合固化,研究了液晶化合物用量对产物微观形态和性能的影响,结果表明:液晶化合物的加入可提高共聚物的抗冲击强度,但当液晶加入的质量分数超过8%时会产生相分离.     

微藻资源的综合开发与应用

本文简要介绍了海洋微藻中可开发利用资源如不饱和脂肪酸、多糖、蛋白、色素等,并对其应用前景进行了展望。     

滇西典型土质滑坡饱和-非饱和渗流稳定性研究

降雨是滇西土质滑坡灾害的主要诱发因素,而滑坡土体中孔隙水压力的存在使得岩土体的力学性状变得更加复杂.选择滇西红层典型土质滑坡-思铺滑坡做深入的调查,考虑降雨入渗的影响,基于饱和-非饱和渗流理论,选择9月份的降雨量监测资料,对强降雨条件下思铺滑坡地下水动态渗流场进行了数值模拟,将其孔隙水压力结果用于滑坡稳定性分析.同时,又基于非饱和土强度理论,采用GLE通用条分法,对滑坡稳定性的时空效应进行了评价,从而得出降雨入渗与土质滑坡的内在联系:滑坡稳定性与其渗流滞后性有较好的对应关系,最危险滑动面随含水量不同而呈空间的演变.     

基于修正Mohr Coulomb模型考虑非饱和效应的基坑开挖

建筑施工的第一步便是开挖基坑,影响基坑及周边建筑稳定性的因素众多,而针对基坑的研究往往忽略了降水渗流的影响以及由此带来的非饱和效应。基于北斗GNSS监测参数反演,在考虑非饱和效应的基础上,以湖南常德某基坑开挖项目为背景对施工全过程进行了仿真模拟。并对内支撑轴力、渗流以及非饱和效应、坑外土应力分布进行了分析研究。研究表明：①基坑开挖阶段对坑外土体的扰动相对支护施工阶段更大;②非饱和效应对基坑稳定性的影响较小且主要体现在对其坑外土体沉降的影响;③矩形基坑四个角位置的内支撑会出现拉应力集中。     

非饱和粉土的力学和水力特性试验

By using a triaxial testing apparatus for unsaturated soils, the stress-strain relation and water drainage or absorption during shear were obtained from a series of triaxial tests on unsaturated compacted silt under suction control. By changing the specimen density, triaxial shear tests on unsaturated compacted specimens with different initial void ratios were performed to determine the critical void ratio for indentifying positive or negative dilatancy. By changing the applied suction, triaxial shear tests on compacted specimens at different suctions were performed to determine the critical suction for indentifying water drainage or absorption during shear. Finally, by changing the confining pressure, the stress-strain relation and water drainage or absorption were obtained from the results of triaxial shear tests at different net confining pressures, with the change in water content being almost the same during shear