十二烷基混合糖苷与其它表面活性剂二元体系表面吸附和胶束形成的顺序研究

摘要绿色表面活性剂烷基糖苷C₁₂G _1.46具有混合糖苷组成, 将其分别与十二烷基三氧乙烯磺酸钠C₁₂E₃S、 十二烷基三甲基氯化铵C₁₂TAC、 三硅氧烷非离子表面活性剂BE-6、 聚醚类表面活性剂 TMN-6复配, 在25 ℃下测定它们在0.1 mol/L NaCl溶液中的表面活性, 通过其混合表面层和混合胶束的分子交换能(ε, ε_m)的计算得出如下结论: (1) C₁₂G_1.46的活性高于C₁₂G₁和C₁₂G₂, 即烷基混合糖苷的活性高于相同烷基的纯糖苷的结论得到了进一步证实. 利用MM2分子力场计算的能量数据可合理地解释这种混合产品活性提高的原因. (2) 在该烷基混合糖苷的二元体系溶液中, 对其表面吸附和胶束化两个过程的顺序问题进行探讨, 一种情况是先建立表面吸附, 再形成胶束(C₁₂G_1.46/BE-6 和 C₁₂G_1.46/TMN-6 体系); 另一种情况是表面吸附和胶束化同时进行(C₁₂G_1.46/C₁₂TAC和C₁₂G_1.46/C₁₂E₃S体系).     

枝状分子表面组装结构的形成与结构转变

本文是对近期有关枝状分子在石墨表面吸附组装研究的综述.利用扫描隧道显微技术,系统研究了5-甲氧基间苯二酸类枝状分子在石墨表面组装结构的形成及结构转变,发现虽然该类枝状分子大都可以在石墨表面自发有序组装,但是最终形成的组装结构不仅与分子本身结构例如烷基链的数目有关,与分子浓度有关,还与所用溶剂有关.分子浓度和溶剂的变化,影响组装体系内的相互作用力如分子与基底间的作用力、分子间氢键的作用力等,影响分子迁移和结构转变的动力学过程,从而影响枝状分子组装的最终结构.研究揭示了特定体系中枝状分子组装结构与分子浓度、所用溶剂的定量和定性关系.研究结果有助于认识和掌握枝状分子组装规律,进而可以通过改变相关技术参数,调控得到不同的枝状分子表面组装体,为实现可控构筑分子表面组装结构提供了新的思路.     

介孔SiO2孔道内Gemini分子有序自组装构筑正相胶束辅助传递OH-离子

利用Gemini型阳离子表面活性剂(顺丁烯二酸二乙酯撑基双[辛烷基二甲基氯/溴化铵], G_8-2-8)在有机反离子水杨酸根(Sal^-)的诱导作用下, 于介孔SiO₂孔道内有序组装, 构筑表面带有季铵基团的正相蠕虫胶束. 胶束外表面有序排布的季铵基团与介孔SiO₂孔道内壁布满的硅羟基共同作用形成环形保水腔室, 即构筑了OH^-传递的有序通道. 通过对G_8-2-8/NaSal 胶束体系的流变学性质研究, 结果表明, 胶束网络结构已经形成. 将G_8-2-8/NaSal胶束网络形成过程引入聚砜(PSF)体系中, 制备出有序OH^-迁移通道的高耐碱性的阴离子导电膜. 相关性能测定结果表明, 随着G_8-2-8质量分数的增加, 电导率、 含水率及离子交换量均呈现上升趋势, 特别是在离子交换量和含水率均较低的情况下, OH^-的迁移效率得到明显提升. 经过400 h的耐碱性测试, 结果表明, 该系列膜的电导率降幅仅为1.5%左右, 且外观形貌无明显变化, 表现出优异的耐碱稳定性.     

Oxazine750对平行四股螺旋结构的识别与稳定作用

以d[TG₄T]₄、d[G₄T₄G₄]₂和c-myc序列为代表,采用竞争平衡透析、紫外光谱和圆二色光谱研究了oxazine750对四股螺旋结构的识别与稳定作用。 结果表明,oxazine750能够更好的结合在平行四股螺旋上,而对反平行四股螺旋结合较少。 热变性实验表明,oxazine750使d[TG₄T]₄形成的平行结构的四股螺旋的解旋温度提高了11 ℃,对c-myc形成的平行四股螺旋的解旋温度甚至提高了40 ℃。 而对d[G₄T₄G₄]₂形成的反平行结构解旋温度降低了近8 ℃。     

多体展开势能函数在碳族元素原子簇研究中的应用(Ⅳ)──Si9─Si16原子簇的分子结构与稳定性

多体展开势能函数研究表明,Si₄-Si₁₆原子簇分子间的结构衍生关系为:依次增加一个二配位或三配位的表面原子,分子表面被四元蝶形环Si₄(D_2d)所覆盖;Si_n(n=5-16)结构中多含有Si₅(D_3h)、Si₆(D_2d)区域结构单元,笼状Si₁₀及Si₁₆的表面原子均为三配位或三配位以上,预计Si₅、Si₆、Si₁₀及Si₁₆是硅原子簇碎片化产物分布中丰度较高的序列;在这一范围内的分子结构呈与晶体硅结构(金刚石)无关的密堆积,最高配位数为5,在小于半球的立体角内形成六配位的硅中心,使该簇合物在能量上不稳定。     

L-(-)-α-苯乙胺类立方烷结构2-萘甲酸二聚体盐的晶体结构

L-(-)-α-苯乙胺与消旋的类立方烷结构2-萘甲酸二聚体相互作用形成铵盐,其晶体结构表明,L-(-)-α-苯乙胺与类立方烷结构2-萘甲酸二聚体作用形成的铵离子通过氢键N_2A-HN_2B…O_5A和N_1A-HN_1A…O_3A与类立方烷结构2-萘甲酸二聚体结合在一起.同时类立方烷结构2-萘甲酸二聚体的两个对映异构体之间也存在分子间氢键O_1A-H_1AA…O_6A和O_1B-H_1AB…O_6B.这些氢键将类立方烷结构2-萘甲酸二聚体的两个对映异构体连在同一个晶胞中,呈现两条分子链状堆积.     

烷基链长及肽链电荷分布对脂肽双亲分子自组装及水凝胶化的影响

为阐明脂肽分子烷基链长及肽链电荷分布对其自组装及水凝胶化的影响, 设计合成了C_nV₃K₂ (n=12, 14, 16) 和C_mKV₃K (m=14, 16)两个系列的脂肽分子. 原子力显微镜(AFM)和透射电镜(TEM)结果表明, 两个系列的脂肽分子都可以自组装成一维纳米带结构. 圆二色(CD)光谱结果表明, C_nV₃K₂系列自组装体的二级结构为β折叠; C_mKV₃K系列自组装体中包括α螺旋和β折叠两种二级结构, 其中C14KV3K的α螺旋结构较多, C16KV3K的β折叠结构占优. 烷基链疏水作用的增强会抑制β折叠结构侧向堆积, 使纳米带随烷基链的变长而变窄; 电荷分布于肽链部分的两端有利于纳米带结构的侧向生长. 流变性测试结果表明, 在浓度10 mmol·L^-1、pH 8.4下, 脂肽分子可以形成自支撑水凝胶, 相比烷基链长度, 肽链部分的电荷分布对水凝胶性能影响更大.     

银纳米枝的合成及表面增强拉曼效应

利用硝酸银与铜之间发生置换反应原理, 在铜箔上得到了有序的银纳米枝结构, 用十二烷基磺酸钠(SDS)为表面活性剂, 通过调控前驱体硝酸银的浓度, 可在铜箔上得到不同密度的银纳米枝. 表面拉曼增强实验结果表明, 当分别以对巯基苯胺(4-ATP)、腺嘌呤和罗丹明G6为探针分子时, 有序的银纳米枝结构比无序的银纳米粒子具有更好的拉曼增强活性; 且随银纳米枝密度的增加, 表面拉曼增强活性有所提高. 该有序的银纳米枝结构是较好的表面增强拉曼(SERS)活性基底, 在有机分子和生物分子的SERS检测方面将具有一定的应用前景.     

氢键稳定的苯并菲盘状液晶的合成及介晶性

盘状液晶分子能自组装成高度有序的六方柱状介晶相. 其各向异性的载流子高速迁移率使其成为较理想的有机光电子材料. 采用分子间氢键锚定柱状相, 获得介晶相温度范围宽、有序度高的苯并菲盘状液晶是本研究的目的. 本文通过分子设计, 合成了3个系列, 共18个有两种不同软链的苯并菲盘状液晶化合物C₁₈H₆(OR)₅(OCH₂COOEt), C₁₈H₆(OR)₅(OCH₂COOBu)和C₁₈H₆(OR)₅(OCH₂CONHBu), 其中R＝C_nH_2n＋1, n＝4～9. 化合物的纯度和结构通过¹H NMR和元素分析确证. 化合物热稳定性通过热重分析(TGA)测定, 并显示出较高的热稳定性. 通过偏光显微镜(POM)和差示扫描量热法(DSC)对这些化合物的热致液晶性进行了研究. 结果显示对于分子中含有酰胺基的苯并菲液晶化合物C₁₈H₆(OR)₅(OCH₂CONHBu), 与具有同样软链长度的分子中不含酰胺键的化合物系列C₁₈H₆(OR)₅(OCH₂COOBu)相比较, 前者由于柱内分子间氢键的形成, 具有更高的熔点和清亮点.     

光致变色的PW12/1,10DAD自组装超晶格多层膜

本文报道了在固体基底表面上用PE方法连续自组装沉积PW₁₂和1,10-DAD分子,构建了PW₁₂/1,10-DAD自组装多层膜.紫外-可见吸收、X射线衍射等分析结果表明此多层膜有好的超晶格结构,层间距为3.19nm.与真空蒸镀WO₃薄膜相比,PW₁₂/1,10-DAD自组装多层膜表现出更好的光致变色特性.     

Scanning tunneling microscopy study of metal-free phthalocyanine monolayer structures on graphite

Low temperature scanning tunneling microscopy (STM) studies of metal-free phthalocyanine (H2Pc) adsorbed on highly oriented pyrolytic graphite (HOPG) have shown ordered arrangement of molecules for low coverages up to 1 ML. Evaporation of H2Pc onto HOPG and annealing of the sample to 670 K result in a densely packed structure of the molecules. Arrangements of submonolayer, monolayer, and monolayer with additional adsorbed molecules have been investigated. The high resolution of our investigations has permitted us to image single molecule orientation. The molecular plane is found to be oriented parallel to the substrate surface and a square adsorption unit cell of the molecules is reported. In addition, depending on the bias voltage, different electronic states of the molecules have been probed. The characterized molecular states are in excellent agreement with density functional theory ground state simulations of a single molecule. Additional molecules adsorbed on the monolayer structures have been observed, and it is found that the second layer molecules adsorb flat and on top of the molecules in the first layer. All STM measurements presented here have been performed at a sample temperature of 70 K.     

Self-assembly of PcOC8 and its sandwich lanthanide complex Pr(PcOC8)(2) with oligo(phenylene-ethynylene) molecules

Self-assemblies of octakis(octyloxy) phthalocyanine (PcOC8) and its sandwich lanthanide complex, substituted praseodymium bis(phthalocyanine) (Pr(PcOC8)(2)), with oligo(phenylene-ethynylene) (OPE) have been investigated by scanning tunneling microscopy (STM) on a highly oriented pyrolytic graphite (HOPG) surface. The assemblies were prepared by dissolving the molecules in phenyloctane solution. It was found that both PcOC8 and Pr(PcOC8)(2) can form 4-fold or 6-fold symmetrical adlayers on HOPG. The intramolecular structure of Pr(PcOC8)(2) molecule was revealed by a high-resolution STM image. When OPE molecules are added into phenyloctane solvent, Pr(PcOC8)(2) molecules prefer to form an ordered adlayer at the top of the OPE adlayer, while PcOC8 molecules adsorb on HOPG surface directly and form separated domains with OPE. These results may be helpful to construct surface assemblies and develop molecular electronic devices in the future.     

Atomic structure of highly ordered pyrolytic graphite doped with boron

Boron-doped carbon was prepared by the high-temperature reaction of B₂O₃ with the highly ordered pyrolytic graphite (HOPG). In order to reveal the effect of the boron doping on the HOPG structure, several experimental tools were employed such as X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning tunneling microscopy (STM), and atomic force microscopy (AFM). While the interlayer spacing of the graphite plane remains virtually unchanged, the boron doping makes the graphite plane of HOPG more disordered. Both the STM and the AFM studies show that the boron-doped HOPG surface is deformed not only in its bonding geometry, but also in its electronic structure. The overall results imply that the boron atom is substituted for the carbon atom rather than is intercalated into the graphite layers.     

Self-assembly of amphiphilic hexapyridinium cations at the air/water interface and on HOPG surfaces.

Mono- and multilayers of a novel amphiphilic hexapyridinium cation with six eicosyl chains (3) are spread at the air/water interface as well as on highly ordered pyrolytic graphite (HOPG). On water, the monolayer of 3 is investigated by recording surface pressure/area and surface potential/area isotherms, and by Brewster angle microscopy (BAM). Self-organized tubular micelles with an internal edge-on orientation of molecules form at the air/water interface at low surface pressure whereas multilayers are present at high surface pressure, after a phase transition. Packing motifs suggesting a tubular arrangement of the constituting molecules were gleaned from atomic force microscopy (AFM) investigations of Langmuir-Blodgett (LB) monolayers being transferred on HOPG at different surface pressures. These LB film structures are compared to the self-assembled monolayer (SAM) of 3 formed via adsorption from a supersaturated solution, which is studied by scanning tunnelling microscopy (STM). On HOPG the SAM of 3 consists of nanorods with a highly ordered edge-on packing of the aromatic rings and an arrangement of alkyl chains which resembles the packing of molecules at the air/water interface at low surface pressure. Additional details of the molecular packing were gleaned from single-crystal X-ray structure analysis of the hexapyridinium model compound 2b, which possesses methyl instead of eicosyl residues.     

Conformation Diversity of a Fused‐Ring Pyrazine Derivative on Au(111) and Highly Ordered Pyrolytic Graphite

Heterocyclic aromatic compounds have attracted considerable attention because of their high carrier mobility that can be exploited in organic field‐effect transistors. This contribution presents a comparative study of the packing structure of 3,6‐didodecyl‐12‐(3,6‐didodecylphenanthro[9,10‐b]phenazin‐13‐yl)phenanthro[9,10‐b]phenazine (DP), an N‐heterocyclic aromatic compound, on Au(111) and highly ordered pyrolytic graphite (HOPG). High‐resolution scanning tunneling microscopy (STM) combined with atomistic simulations provide a picture of the interface of this organic semiconductor on an electrode that can have an impact on the field‐effect transistor (FET) performance. DP molecules adsorb with different conformational isomers (R/S: trans isomers; C: cis isomer) on HOPG and Au(111) substrates. All three isomers are found in the long‐range disordered lamella domains on Au(111). In contrast, only the R/S trans isomers self‐assemble into stable chiral domains on the HOPG surface. The substrate‐dependent adsorption configuration selectivity is supported by theoretical calculations. The van der Waals interaction between the molecules and the substrate dominates the adsorption binding energy of the DP molecules on the solid surface. The results provide molecular evidence of the interface structures of organic semiconductors on electrode surfaces.     

Identification of a Peripheral Substitution Symmetry Effect in Self‐Assembled Architectures

Two complementary classes of molecules based on a triphenylene core are synthesized. The two‐dimensional (2D) assemblies of these molecules deposited on a highly oriented pyrolytic graphite (HOPG) surface are identified with scanning tunneling microscopy (STM). Structures with large cavities are formed by symmetric molecules, while uniform and closely packed stripe‐assembled structures are obtained for asymmetric molecules. X‐ray diffraction (XRD) results support the observation of an ordered hexagonal columnar mesophase for symmetric molecules and a rectangular columnar mesophase for asymmetric molecules. The study demonstrates that the substitution symmetry has significant effects on the assembly characteristics of molecular architectures and also on the three‐dimensional (3D) macroscopic properties of the molecular materials.     

β-联碳酰基类衍生物有序自组装膜的STM研究

在大气条件下, 利用扫描隧道显微镜研究了四个β-联碳酰基类衍生物在高定向裂解石墨(HOPG)表面的自组装结构. 研究分子的结构中均包含π电子共轭体系和烷基链. 实验研究了分子结构对自组装结构的影响, 并利用分子结构的变化实现了自组装膜结构的调控. 结果表明, 在甲苯溶剂中制备的这些自组装结构均长程有序, 分子间氢键和偶极相互作用是影响自组装膜结构变化的重要因素.     

Tetradecylferrocene: ordered molecular array of an organometallic amphiphile in the crystal and in a two-dimensional assembled structure on a surface

Tetradecylferrocene (4, Fc-(CH2)13CH3) was synthesized via lithiation of ferrocene by treatment with tert-butyl lithium, followed by alkylation with 1-bromotetradecane. Complex 4 forms a physisorbed ordered molecular monolayer on the surface of highly oriented pyrolytic graphite (HOPG) that was analyzed by scanning tunneling microscopy (STM). It features a lamellar structure with single rows of ferrocenyl moieties separating connecting areas formed by the long alkyl chains which are arranged parallel to each other. The ordering principle of 4 on the surface can be related to the arrangement of Fc-(CH2)13CH3 molecules in the three-dimensional crystal lattice.     

The self-assemblies of a newly designed star-shaped molecule end-capped with bromine atoms studied by scanning tunneling microscopy

A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface.We have obtained the high-resolution self-assembled STM images,from which the highly ordered and closely packed non-porous arrangements of the StOF-Br_3 molecular selfassemblies at the heptanoic acid/HOPG surface could be observed.The molecular models and selfassembled StOF-Br_3 architectures have been given in the following text.Besides,we have also figured out the surface free energy by the density functional theory(DFT) calculation,which proved that the halogen...halogen interaction was strong enough to stabilize the ordered molecular self-assemblies.This work verifies the existence of bromine...bromine interactions,and meanwhile provides a kind of effective approach for quickly building ordered molecular nanoarchitectures with large areas and different geometries.     

STM imaging of a heptanuclear ruthenium(II) dendrimer, mono-add layer on graphite

Scanning tunneling microscopy (STM) and molecular mechanics calculations were used to investigate the long-range packing and the structure of an heptanuclear ruthenium (II) dendritic species, as a PF6- salt. STM imaging was carried out on a mono-add layer of the ruthenium dendrimer formed by physisorption from a 1,2,4-trichlorobenzene solution at the liquid-graphite interface. The packing of the molecules on the surface was visualised by the formation of ordered patterns and a distance of 27 +/- 2 A was measured between two adjacent lamellae. The comparison of this dimension with the molecular-modelling data indicates that the lamellae were formed by rows of dendrimer molecules in which the counterions (PF6-) were strongly associated with the Ru atoms. The images acquired with higher spatial resolution revealed the presence of repeating units within the lamellae. The comparison of the STM images with the modelling results allowed the attribution of the repeating units observed in the imaged pattern to the STM signature of single dendrimer molecules.