A Four-Component Model for Volume Phase Transition

Abstract

By means of the Flory-Huggins and Iwatsubo theory for macromolecules, a four-component model of a hydrogel, which consists of a copolymer network and a solution with two solvents, is given for discussing the “normal pattern” volume phase transition which was proposed by Katayama. Furthermore, the theoretical result shows that an ionic gel can also undergo a volume phase transition caused by the variation of the ratio of the two components in the copolymer network.     

相转移催化应用于催化裂化汽油氧化脱硫的研究

随着人们环境保护意识的增强及原油硫含量的增大, 生产满足环境保护要求的清洁燃料是全球炼油工业的发展趋势, 燃料油脱硫显得越来越重要. 在众多的脱硫方法中, 选择性氧化脱硫技术以其工艺条件温和, 脱硫效果明显等特点, 受到了炼油行业的极大关注[1~3], 但脱硫率偏低(30％), 其关键是水相氧化剂与含硫化合物的有效混合. 本文将相转移催化应用于催化裂化(FCC)汽油的氧化脱硫中, 并对脱硫的工艺和机理进行了研究.     

万古霉素手性固定相分离克伦特罗对映体

应用万古霉素手性固定相对克伦特罗对映体进行了分离,考察了洗脱模式、流动相组成、柱温等因素对分离的影响,并对其分离机制进行了探讨.最佳色谱条件为:甲醇-冰醋酸-三乙胺(体积比100:0.01:0.01),流速1.0mL/min,柱温20℃.在此条件下,克伦特罗对映体可实现基线分离,最大分离度可达2.67.克伦特罗对映体与固定相之间的离子相互作用是实现对映体分离的最主要分离机制.     

流动相组成对有机硒手性化合物拆分的影响

 在自制的涂敷型纤维素 三 (3,5 二甲基苯基氨基甲酸酯 ) (CDMPC)手性固定相上拆分了一些结构相似的有机硒手性化合物 ,详细考察了三元流动相对手性拆分的影响 ,并探讨了溶质分子与手性固定相相互作用的模式。实验结果表明 :在二元流动相中加入极少量的质子性改性剂 (醇 )或非质子性改性剂 (乙腈 ) ,可使溶质的保留和手性拆分发生较大的变化。     

磺酸基共聚凝胶在混合有机溶剂中的体积相变

2-丙烯酰胺基-2-甲基丙磺酸(AMPS)与甲基丙烯酸-2-羟基丙酯(HPM)在乙二醇/水(1:1,质量比)中70℃下进行共聚,AMPS/HPM(8:2,摩尔比)为该体系的恒比共聚点.在此组成加入交联剂N,N'-亚甲基双丙烯酰胺2%、3%和5%(摩尔分数)制备了凝胶试样GO2、GO3、GO5.它们在DMSO/THF混合溶剂中THF达55%～60%(体积百分数)时发生体积相变;在乙醇/THF混合溶剂中GO3的体积随THF的加入连续缩小,但不出现体积相变.此现象可用高分子链溶剂化层的变化以及低极性介质中离子对之间的偶极-偶极相互作用来说明.     

戊唑醇对映体在新型纤维素键合手性固定相上的拆分

利用4,4-二苯基甲基二异氰酸酯作为连接臂, 采用6-位选择键合法制备了键合型纤维素-(3,5-二甲基苯基氨基甲酸酯)固定相, 并将其应用于戊唑醇的手性分离, 还考察了异丙醇的浓度、不同的醇类改性剂、四氢呋喃以及三氯甲烷对戊唑醇在该固定相上的手性分离的影响.     

长棒状T形三组分双亲分子相行为的耗散粒子动力学模拟

采用耗散粒子动力学方法建立了以侧链长度和温度为变量的相图,计算了相关结构参数及每个液晶相对应侧链的有效体积分数,重现了实验上观察到的五边形、六边形柱状相及刚棒在层内位置的有序堆垛层状结构.研究发现,长棒状T形三组分双亲分子相图中的相序列和相结构符合相关报道,并且侧链有效体积分数f L与实验值一致.表明粗粒化模型反映了真实T形分子的主要特性,如分子的拓扑结构、排除体积效应及分相趋势、刚棒液晶基元的长径比和侧链的空间效应.证实了侧链尺寸对主/侧链非线性连接体系的自组装结构及各组成单元的位置分布的重要作用.     

Determination of Acetonitrile Volume Fraction in Mobile Phase by HPLC

This paper reports the development and validation of an assay for the determination of acetonitrile in the recycled mobile phase using high performance liquid chromatography（HPLC）. The method is based on that the retention in reversed-phase liquid chromatography increases with decreasing concentration of organic phase in the mobile phase. The natural logarithm of the capacity ratio for a given solute is linearly related to the volume fraction of the organic modifier in the mobile phase. For dimethylphthalate and diethylphthalate, the linearity range is 30%--60%, and for biphenyl and terphenyl, the range is 60%--95%. Precision values（RSD） were both 〈1% and the accuracy（RE） was in the range of ±1%. The assay was successfully applied to the determination of acetonitrile concentration of recycled mobile phase after the distillation of the column eluent in our laboratory.     

酰胺型手性固定相直接拆分克仑特罗对映体

 将酰胺型手性固定相用于正相高效液相直接拆分 β2 受体兴奋剂克仑特罗。讨论了三元流动相中正己烷、1,2 二氯乙烷和甲醇含量的变化以及柱温和流速对分离的影响 ;优化了实验条件 :流动相为V(正己烷 )∶V(二氯乙烷 )∶V(甲醇 ) =5 4∶38∶8,柱温为 17℃ ,流速为 1 0mL/min ;并对拆分的机理加以探讨。方法简单、快速。     

环境因素对正负表面活性剂体系相行为的影响

在1:1正负离子表面活性剂混合体系(十二烷基硫酸钠/辛基三甲基溴化铵 SDS-C8NM3Br; 十二烷基硫酸钠/十二烷基三甲基溴化铵,SDS-C12NM3Br)中加入短链脂肪醇 (乙醇,正丙醇,正丁醇),正负离子表面活性剂沉淀溶解,出现表面活性剂双水相.上相有液晶存在,下相有囊泡自发形成.折光率数据和电镜结果表明:上相为表面活性剂富集相,下相表面活性剂浓度较低.混合体系中,出现表面活性剂双水相所需短链脂肪醇的体积百分数,随短链脂肪醇的链长增加而降低.温度升高,出现表面活性剂双水相所需短链脂肪醇的体积百分数降低.对SDS/C8NM3Br/H2O体系的研究结果表明:超声处理,可使混合体系中沉淀向囊泡转化,与短链脂肪醇的加入后的作用类似.     

Novel Thermosensitive IPN Hydrogel Having a Phase Transition Without Volume Change

A novel thermosensitive interpenetrating network (IPN) hydrogel was prepared from an aqueous solution of poly[3,3‐dimethyl(methacryloyloxyethyl)propylammonium sulfonate] infiltrating a crosslinked sulfobetaine polymer, poly(2‐acrylamido‐2‐methylpropylsulfonic acid). The IPN gel shows an upper critical solution temperature (UCST) depending on the molar ratio of the components and the presence of salt. In contrast to conventional gels, the IPN gel exhibits no volume phase transition after traversing the UCST.     

栀子苷在乙腈水体系中诱导相分离分配行为

研究了栀子乙腈水提取液中的栀子苷在诱导相分离后在两相中的分配行为,建立了乙腈/水分相体系分离纯化栀子苷的新方法。 重点考察了能使乙腈/水体系分相的诱导剂的种类,分析了诱导剂的组成比例以及用量、乙腈的体积分数、样品加入量和温度对栀子苷分配行为的影响。 当温度为25 ℃时,栀子的乙腈/水（体积比1∶1）提取液中加入KCl与MgSO4组成的混盐（质量比2∶1）分相诱导剂后,栀子苷的萃取率达到81.63%,含量由分相前的3.05%提高至13.54%。     

1-Hexyl-3-Methylimidazolium Chloride-Potassium Carbonate Aqueous Two Phase System: Equilibrium Characteristics and BSA Partitioning Behavior

The partitioning behavior of the model protein (bovine serum albumin) was investigated in ionic liquid (1-hexyl-3-methylimidazolium chloride) -salt (potassium carbonate) based aqueous two phase system (ATPS). The phase diagram with binodal curve and tie lines for the selected ATPS was developed at different temperatures and analyzed through effective excluded volume (EEV) and Othmer-Tobias and Bancroft equations, respectively. The influence of various process parameters like the ionic liquid and salt concentration, system temperature, tie line length, phase volume ratio, and neutral salt addition on partition coefficient/extraction efficiency of BSA protein was evaluated.     

The Thermal Charging Performance of Finned Conical Thermal Storage System Filled with Nano-Enhanced Phase Change Material

A latent heat thermal energy storage (LHTES) unit can store a notable amount of heat in a compact volume. However, the charging time could be tediously long due to weak heat transfer. Thus, an improvement of heat transfer and a reduction in charging time is an essential task. The present research aims to improve the thermal charging of a conical shell-tube LHTES unit by optimizing the shell-shape and fin-inclination angle in the presence of nanoadditives. The governing equations for the natural convection heat transfer and phase change heat transfer are written as partial differential equations. The finite element method is applied to solve the equations numerically. The Taguchi optimization approach is then invoked to optimize the fin-inclination angle, shell aspect ratio, and the type and volume fraction of nanoparticles. The results showed that the shell-aspect ratio and fin inclination angle are the most important design parameters influencing the charging time. The charging time could be changed by 40% by variation of design parameters. Interestingly a conical shell with a small radius at the bottom and a large radius at the top (small aspect ratio) is the best shell design. However, a too-small aspect ratio could entrap the liquid-PCM between fins and increase the charging time. An optimum volume fraction of 4% is found for nanoparticle concentration.     

Effects of Mobile Phase Ratios on the Separation of Plant Carotenoids by HPLC with a C30 Column

Plant products are dietary sources of lutein and zeaxanthin. Lutein and zeaxanthin have been implicated in the protection of age related macular degeneration (AMD) and in cardiovascular diseases. However, xanthophylls and unidentified components (λ_max = 423 and 468 nm) in plant products are often not separated well, and affect an accurate quantitative determination of lutein and zeaxanthin. A high performance liquid chromatography (HPLC) system equipped with a Bischoff C30 column and a mobile phase of methanol, methyl-tert-butyl ether (MTBE) and water was used to separate lutein, zeaxanthin and other unidentified components in plant products. Mobile phase A containing methanol, MTBE and water with a ratio of 60:33:7 by volume (1.5% ammonium acetate, NH₄Ac), combined with mobile phase B with a ratio of 8:90:2 by volume (1.0% NH₄Ac) is optimal for the separation. This method was successfully applied to the quantitative determination of lutein and zeaxanthin in extracts of plant products, such as chlorella, spirulina, celery and mallow.     

液固相水热法制备氧化硅纳米线

利用液固相水热反应方法, 以硅溶胶为硅源, 在三价铁辅助下与乙二胺的水溶液在180 ℃反应4 d后生成具有P21212空间群结构的单晶氧化硅纳米线. 用扫描电子显微镜、透射电子显微镜和多晶X射线衍射对制备的样品进行了表征, 系统研究了有机胺、金属盐、反应时间及反应温度等条件对氧化硅纳米线生长的影响. 结果表明, 随着有机胺碳链的增长, 产物形貌逐渐由纳米线转变为纳米片; 金属阳离子的存在对纳米线形貌有较大的影响, 而阴离子的存在并不影响纳米线的生成; 过低的铁含量导致反应进行不完全, 而过多的铁盐加入则会导致反应中剩余铁氧化物吸附到氧化硅纳米线表面, 进而影响到产物纯度; 反应时间延长及反应温度的提高都有利于氧化硅纳米线的生长. 最佳反应条件为: 有机胺为乙二胺, 硝酸铁为铁源, 硅溶胶为硅源, 硅/铁摩尔比为1∶0.4, 乙二胺与水的体积比为8∶5, 温度为180 ℃.     

Phase Separation in Sol-Gel System Containing Mixture of 3- and 4-Functional Alkoxysilanes

The phase separation behavior of gelling systems containing the mixture of 3-functional and 4-functional alkoxysilanes has been investigated. The relation between the starting composition and resultant macroporous morphology was examined using tetramethoxysilane (TMOS) and vinyltrimethoxysilane (VTMS) as starting alkoxysilanes, formamide (FA) as an additive, under an acidic condition. Up to TMOS:VTMS molar ratio of 0.5:0.5, the phase relation remained almost unchanged from that of pure TMOS system which exhibits morphology with well-defined co-continuous macropores in a very limited concentration region. On the VTMS-rich side typically TMOS:VTMS = 0.2:0.8, however, the co-continuous macroporous morphology was obtained in a broader composition range than those of either pure TMOS or VTMS system. A dome-like pseudo binary region was obtained with the two-phase region extending toward FA-rich direction. The domain size and pore volume of the gels with macroporous morphology could be controlled by alkoxide:water ratio and total solvent fraction, respectively.     

温度梯度引起的聚合物共混物梯度相形态的研究

研究了两相不相容聚合物共混物在静态退火时,由温度梯度引起的分散相尺寸的空间分布梯度相形态,讨论了分散相体积分数和两相之间界面张力对梯度形态形成的影响.应用接触凝聚模型计算了在温度梯度作用下,分散相粒子的粗化过程.计算结果表明,界面张力越大,或者分散相体积分数越大,形成的梯度相形态越明显;并且在温度梯度存在下,分散相粒子粗化的速度加快.