2-(1-萘基偶氮)-咪唑的合成及组装Langmuir-Blodgett膜

合成了一个非典型两亲性分子,2-(1-萘基偶氮)-咪唑(2-NDIM),对它在气/液界面上的组装和LB膜性质进行了研究。结果表明:2-NDIM不能在水相表面形成Langmuir膜,在Ag NO3水溶液亚相中能形成稳定、均匀的配位聚合物单分子膜,组装的LB膜为J-聚集体,最大吸收波长为403nm,归属于反式-N=N-双键的π-π*电子跃迁,光激发LB膜中偶氮基团的反-顺异构化作用不明显,具有较低的反-顺光异构化量子产率。     

四(4-重氮基苯基)卟啉的合成及其与聚苯乙烯磺酸钠自组装的研究

卟啉是一类重要的功能性小分子染料,近年来,在光化学治疗^[1,2]、光电转换^[3,4]、传感元件^[5]、烯烃环氧化催化剂^[6]和光敏化剂^[7]等方面的研究与应用引起了人们的广泛注意.通过两亲卟啉分子衍生物,或带有负电荷的卟啉衍生物,特别是带磺酸基的卟啉分子与正离子聚电解质自组装,制备带有卟啉结构单元的LB膜和自组装膜已有很多报道^[8～14].     

4-(9-蒽基)-6-十六烷氧基-2-氨基-1,3,5-三嗪的合成及光谱行为的研究

从三氯均三嗪出发通过三步反应合成了4-(9-蒽基)-6-十六烷氧基-2-氨基-1,3,5-三嗪(AHTA),并通过红外、核磁、质谱、高分辨质谱对目标产物进行了表征.研究表明AHTA分子在基态下分子的蒽环与三嗪环不共平面,激发态下表现为ICT的荧光发射.由于分子间氢键作用的存在,AHTA在自组装膜和LB膜中均形成H-聚集体.     

手性药物(S)-布洛芬氢键自组装印迹聚合物识别机理

以含有单一结合基团的手性药物(S)-布洛芬作为模板分子,制备了系列印迹聚合物.采用紫外-可见光谱和红外光谱对印迹及识别机理进行了研究.结果表明,模板分子与功能单体分别通过形成蓝移氢键和红移氢键完成预组装过程和再识别吸附过程,且形成了主客体配比为1∶1的配合物.等温吸附实验结果表明,印迹聚合物对模板分子表现出明显的选择性吸附,特异性吸附容量为37.92μmol/g,印迹指数为3.06,且印迹聚合物内特定的三维空间结构对其特异性吸附性能具有显著影响.由手性分离实验考察了印迹聚合物的拆分性能,其对(R)-布洛芬的分离因子为1.79.     

酞菁铜阴阳离子分子沉积(MD)膜润湿性研究

酞菁及其衍生物等大环平面分子具有良好的化学稳定性和优异的光电性能 [1,2 ] ,利用酞菁进行模拟生物光合作用的研究 ,以期实现新的光电转换技术 ,近年来已引起人们的广泛重视[3～ 5] .分子沉积(MD)超薄膜[6～ 8] 是以阴阳离子间静电相互作用为成膜驱动力 ,通过相反离子体系的单层交替沉积制备的层状有序超薄膜 .分子沉积技术广泛应用在固体表面改性和生物传感技术等领域 ,沉积分子的物理化学性质是影响其应用的主要因素 .本文通过紫外 -可见光谱跟踪了酞菁铜阴阳离子 MD膜的均匀沉积 ,并根据酞菁 MD膜表面接触角的变化 ,探讨分子端基的…     

异氰衍生物在Au(111)表面吸附和自组装的研究

本文通过密度泛函理论和分子动力学模拟方法研究了异氰衍生物在Au(111)表面的吸附和自组装。分别采用平板模型和簇模型对苯异氰的吸附进行了密度泛函理论计算。利用自己建立的Au-C力场参数模拟了2-isocyanoazulene 和1,3-diethoxycarbonyl-2-isocyanoazulene 在 Au(111)的自组装。通过计算得到顶位吸附是最稳定的；通过模拟得出异氰衍生物确实能在Au(111)表面形成有序的面对边自组装单层，并且分子都能垂直位于Au(111)表面上。     

酸度对2-十八胺基甲酰基-8-羟基喹啉成膜性能的影响

两亲分子的成膜性能的研究主要集中在以羧基、磺酸基、磷酸基和第四铵盐等为亲水头基的化合物[1 ,2 ] ,而对亲水头基中兼有酸、碱性基团的两亲配体研究很少 ,本文报道了我们合成的一种新型两亲配体 2 -十八胺基甲酰基 - 8-羟基喹啉 (以下简写为 HL)在不同 p H的亚相溶液中单分子膜的形成。结果表明 ,HL在酸性亚相中不易成膜 ,而在碱性亚相中成膜性能较好 ,单分子膜由膨胀型向压缩型转变。并且讨论了亚相 p H对 HL单分子膜崩溃压的影响 ,以及 8-羟基喹啉头基在气 /液界面上的离解 -缔合情况。实　验　部　分一 .试剂与仪器2 -十八胺基甲…     

(-)-龙脑手性离子液体的合成

以(-)-龙脑为手性源,与溴乙酰溴通过酯化反应合成溴代乙酸龙脑酯(2);2与4,4'-联吡啶发生取代反应引入两个手性中心制得新型手性离子液体——N,N'-双(龙脑氧甲酰亚甲基)联吡啶.二溴(3.2Br-);3.2Br-与四氟硼酸钾或六氟磷酸钾盐进行阴离子交换制得相应的手性离子液体3.2BF4-或3.PF6-.3.2Br...     

四氯合锌酸二(正十一烷基铵)晶体相变的Raman光谱

用Raman光谱研究了[n-C_(11)H_(23)NH_3]_2ZnCl_4(简记为C_nZn)配合物的固-固相变.结果表明,配合物产生的固-固相变主要与烷烃链的堆积结构和分子构象变化有关.在 T_(c1)=25℃的相变是由于烷烃链的侧向堆积和分子构象的有序到部分无序变化.在中间相,分子链局部产生旁式构象.在T_(c2)=87℃的相变主要来源于烷烃链从部分构象有序到完全无序的变化.高温相形成了构象完全无序相.相应于烷烃链的“熔化”.     

4-(4-氨基苯氧基)-2-(烷基氨甲酰基)吡啶的合成

苯氧基胺酰基吡啶兼有芳基吡啶醚结构,因分子中吡啶环的亲脂性、酰胺基团的亲水性及醚键的存在而具有良好的生物活性,是制备抗癌新药索拉非尼[1]、吡啶醚类除草剂[2]等多种医药、农药的重要中间体,该类物质的合成已成为当今化学研究中最活跃和不断扩展的领域之一.     

Effect of counter-ion on the thermotropic liquid crystal behaviour of bis(alkyl)-tris(imidazolium salt) compounds

Recently, new thermotropic ionic liquid crystals (LCs) with a hexyl-linked tris(imidazolium bromide) core and two terminal alkyl chains were synthesised and characterised. To explore the effect of different counter-ions on the LC behaviour of this system, derivatives with BF₄^? and Tf₂N^? counter-ions were prepared and analysed. Five of the BF₄^? derivatives were found to exhibit thermotropic LC behaviour. The 12-, 14- and 16-carbon tail BF₄^? compounds form SmA phases. The 18- and 20-carbon tail homologues form what appears to be a smectic phase but are weakly mesogenic and harder to characterise. Only two of the Tf₂N^? derivatives exhibited mesogenic behaviour. The 18-carbon tail Tf₂N^? compound forms an as-yet unidentified, highly periodic smectic phase with positional order while the 20-carbon tail homologue forms a periodic SmA phase. The Tf₂N^? mesogens have much lower clearing points even though their LC phases have more order than the Br^? and BF₄^? mesogens. X-ray diffraction showed that these mesogens have different amounts of tail interdigitation between the smectic layers depending on the counter-ion present. Atomistic molecular dynamics simulations indicated that counter-ion size plays an important role in defining the density of the ionic region, which in turn affects the amount of interdigitation in the smectic phases.     

含4，4＇－二羟基二苯酮热致液晶四元共聚酯的合成与表征

含４，４＇－二羟基二苯酮热致液晶四元共聚酯的合成与表征董德文，韩平，倪玉山，丁孟贤，韩伟（中国科学院长春应用化学研究所长春１３００２２）（吉林化工学院化工系吉林）关键词　热致液晶，共聚酯，向列型，二羟基二苯酮关于热致液晶芳香族聚酯的研究已有大量的报道...     

Liquid–liquid phase separation in aqueous solutions of poly(ethylene glycol) methacrylate homopolymers

Here, the liquid–liquid phase separation (LLPS) in aqueous solutions containing poly(ethylene glycol) (PEG) methacrylate homopolymers is reported for the first time. In this study, the thermoresponse of concentrated solutions of DEGMA₆₀ (two ethylene glycol, EG, groups) TEGMA₇₁ (three EG groups), OEGMA300_x (4.5 in average EG groups) of varying molar masses (MM), and OEGMA500₂₈ (nine in average EG groups) is discussed. Interestingly, the temperature of LLPS (T_LLPS) is controlled by the length of the PEG side chain, the MM of the OEGMA300_x and the polymer concentration. More specifically, the transition temperature decreases with: (i) Decrease in the length of the PEG side chain, (ii) increase in MM of the OEGMA300_x, and increase in concentration. In addition, LLPS is also observed in mixtures of OEGMA300_x with Pluronic® F127. In conclusion, these systems present a thermally induced LLPS, with the transition temperature being finely tuned to room temperature when DEGMA is used. These systems find potential use in numerous applications, varying from purification to “water-in-water” emulsions.     

Preparation of thermo- and redox-responsive branched polymers composed of three-armed oligo(ethylene glycol)

We herein report the preparation of thermo- and redox-responsive branched polymers by the condensation reaction of three-armed oligo(ethylene glycol) (trisOEG) and cystamine (CA). The prepared branched polymers exhibited a soluble–insoluble transition at a lower critical solution temperature (LCST) and formed coacervate droplets through a liquid–liquid phase separation process. We then demonstrated control of the LCSTs of the branched polymers by varying the feed ratio of CA and the surrounding salt concentration close to body temperature. In addition, the trisOEG-cys _x polymer formed coacervate droplets above the LCST, in which hydrophobic molecules were condensed. The redox response of the branched polymers was also investigated. Interestingly, the branched polymers degraded to low-molecular-weight materials (i.e., trisOEG) in the presence of dithiothereitol as a reducing agent through cleavage of the disulfide bond of CA. This facile preparation of branched polymers is expected to be valuable in the context of functional biomedical materials and modifiers for materials surfaces, such as the bases for drug delivery carriers and separation materials. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2623–2629     

A sol-gel immobilization of nano and micron size sorbents in poly(dimethylsiloxane) (PDMS) microchannels for microscale solid phase extraction (SPE)

Sorbent particles consisting of nano and micro silica, and micron size octadecylsilica (ODS) were immobilized using sol-gel chemistry onto poly(dimethylsiloxane) (PDMS) microfluidic channels to serve as μ-chip solid phase extraction (SPE) devices. Extraction, preconcentration and purification of biological and chemical analytes were carried out using these. Micro and nano scale silica-immobilized μ-SPE were used for the extraction/purification of DNA from recombinant Escherichia coli crude lysate. The average DNA recovery was 77 ± 9% (X ± R.S.D.) for the micron size silica particles and 70 ± 5% (X ± R.S.D.) for the nano silica particles. The extracted DNA could be amplified by polymerase chain reaction (PCR) whereas the DNA from the crude lysate solution could not be. This was a testimony to the purification capability of the μ-SPE device. ODS immobilized μ-SPE were used to study the extraction efficiency (EE) and enhancement factor (EF) for three groups of organic compounds, aromatics, phenols and carboxylic acids. They showed poor recovery and low enrichment because the analytes sorbed into the PDMS and were not quantitatively extracted.     

Study on the thermotropic liquid crystalline polycarbonates. IV. Synthesis and properties of liquid crystalline poly(imide-carbonate)s

Two series of novel thermotropic liquid crystalline poly(imide-carbonate)s were prepared by melt polycondensation from various arylene or alkylene bis(phenylcarbonate)s by using N,N′-bis(hydroxyethyl)pyromellitimide and N,N′-bis(hydroxypropyl)pyromellitimide as monomers. Thermotropic liquid crystalline properties were characterized by a polarizing microscope with a heating stage and a differential scanning calorimeter (DSC). Nematic melts were found for the synthesized aromatic poly(imide-carbonate)s. In order to investigate whether the pyromellitimide unit could be used as a mesogenic unit for preparing LC polymers, a series of aliphatic poly(imide-carbonate)s was prepared in this study. However, no significant LC textures were found under the observation by polarizing microscope. It was suggested that the aspect ratio of the pyromellitimide unit was too short to form liquid crystalline poly(imide-carbonate)s. In addition, it was interesting that the aliphatic poly(imide-carbonate)s with a longer spacer (n = 3) in the pyromellitimide unit showed better crystallinity. Thermostabilities of all synthesized poly(imide-carbonate)s were measured by thermogravimetric analysis (TGA). © 1994 John Wiley & Sons, Inc.     

Using the solvation parameter model to characterize functionalized ionic liquids containing the tris(pentafluoroethyl)trifluorophosphate (FAP) anion

Ionic liquids (ILs) containing the tris(pentafluoroethyl)trifluorophosphate anion [FAP]⁻ have attracted increased attention due to their unique properties including ultrahigh hydrophobicity, hydrolytic stability, and wide electrochemical window. In this study, the solvation parameter model is used via gas chromatography to characterize the solvation interactions of seven ILs containing amino, ester, and hydroxyl functional groups appended to the cation and paired with [FAP]⁻, as well as three ILs containing the bis[(trifluoromethyl)sulfonyl]imide anion [NTf₂]⁻. The role of the functional groups, nature of the counter anion, and cation type on the system constants were evaluated. ILs containing [FAP]⁻ possessed lower hydrogen bond basicity than NTf₂-based ILs having the same cationic component; in the case of hydroxyl-functionalized cations, the presence of [FAP]⁻ led to an enhancement of the hydrogen bond acidity, relative to the NTf₂-analogs. The system constants support the argument that [FAP]⁻ weakly coordinates the cation and any appended functional groups, promoting properties of the cation which might be masked by stronger interactions with other anion systems. The chromatographic performance of the IL stationary phases was evaluated by examining the retention behavior and separation selectivity for chosen analytes. The results from this work can be used as a guide for choosing FAP-based ILs capable of exhibiting desired solvation properties while retaining important physical properties including high thermal stability and high hydrophobicity. Figure In this study, the solvation parameter model is used via gas chromatography to characterize the solvation interactions of seven ILs containing amino, ester, and hydroxyl functional groups appended to the cation and paired with tris(pentafluoroethyl)trifluorophosphate [FAP]⁻, as well as three ILs containing the bis[(trifluoromethyl)sulfonyl]imide anion [NTf₂]⁻. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

高效液相色谱对聚醚砜低聚物及其单体组分的分离与测定

In this work, the condition for the analysis of title compounds by HPLC was chosen.The componentcontent and average molecular weight of some kinds of poly(ether-sulfone)s oligomers were determined suc-cessfully. The optimum condition for the partial hydrolysis reaction from 4,4'-dichlorodiphenylsulfone to 4-chloro-4'-hydroxyldiphenylsulfone was obtained.In addition,the constituent changes of the oligomer can beobserved and determined by this method in the polymerization process.     

固相微萃取-高效液相色谱联用测定水样中的痕量苯并(k)荧蒽

研究了固相微萃取(SPME)-高效液相色谱(HPLC)联用测定水样中痕量苯并(k)荧蒽的的分析方法。对SPME的条件如萃取时间、萃取温度、离子强度、解吸方式、解吸溶剂、解吸时间和HPLC条件进行了优化，建立了SPME-HPLC联用分析水样中痕量苯并(k)荧蒽的方法，并用于自来水、雨水和纯净水等实际水样的分析。SPME优化的条件为室温、搅拌速度1100r／min、萃取时间30min、甲醇解吸溶剂、解吸时间2min。HPLC的条件为C18反相色谱柱、甲醇流动相、流速1mL/min、紫外检测器、波长244nm，以峰高为测量信号。方法的线性范围为0～8．00μg／L，检出限为0．014μg／L，相对标准偏差(n=6)为6．7％，回收率为82．0％～104．2％。该方法适合于水样中痕量苯并(k)荧蒽的分析。