吡嗪衍生物在石墨表面上的自组装单层膜结构

利用扫描隧道显微镜研究了荧光液晶分子2, 5-二-[2-(3, 4-二-十二烷氧基-苯基)-乙烯基]-3, 6-二甲基吡嗪(BPDP12)在石墨表面上自组装单层膜的结构. 实验结果表明, 该化合物在石墨表面形成两种自组装结构：一种是稳定的, 分子的共轭中心相互平行, 烷基链相互交错的密排结构；另一种是不稳定的, 分子的共轭中心彼此为烷基链所分隔的非密排结构. 分子之间较强的π-π作用和分子烷基链之间的范德华作用力对分子组装的取向形成竞争, 是产生两种不同组装结构的根本原因.     

硫醇分子链长对氧化还原自组装多层膜电化学行为影响的初步研究(英文)

以烷基硫醇和二茂铁衍生物构建的氧化-还原自组装多层膜为模型体系,研究烷基硫醇分子链长对多层膜电化学行为的影响.实验表明,二茂铁基团和电极之间的电子传递反应速率随两者距离的增加呈现指数级下降的趋势;烷基硫醇分子链长对自组装膜电化学行为的影响于不同情况下表现不同.本实验条件下,当多层膜上的电活性基团与电极比较接近时,长链分子自组装膜呈现较强的电化学响应.而当电极与电活性基团之间的距离较远时,短链烷基硫醇分子自组装膜呈现较强的电化学响应.     

金表面不同链长烷基硫醇自组装单分子膜表面电势的变化规律

从Helmholtz模型出发,对生长在金表面不同链长烷基硫醇自组装单分子膜(SAM)表面电势的变化规律进行了理论研究.利用量子化学软件Gaussian03和MOPAC,讨论了分子偶极矩、相对介电常数以及分子的倾斜角对SAM表面电势的影响.研究表明,不同链长烷基硫醇SAM中分子的倾斜角随烷基链长度的规律性变化是引起SAM表面电势变化的主要原因.从SAM形成机制出发,对金表面不同链长烷基硫醇SAM表面电势的变化规律及其成因提出了新的解释.     

系列长链烷氧基苯甲醛的合成研究

以长链正烷基醇为原料与氢溴酸作用 ,合成了长链正烷基溴 6个 ;再与对或间羟基苯甲醛反应 ,合成了烷氧基苯甲醛 9个、间烷氧基苯甲醛 8个 .由于烷基链长的不同 ,其产率为 70 %～ 94% .考察了催化剂、烷基链长、羟基位置对长链烷氧基甲醛合成的影响 .解析了各种产物的红外光谱 .     

含烷基柔性链的n型刚棒-线团分子的合成、表征与自组装

含多个对苯撑作为刚棒,齐聚烷基或烷氧基作为柔性链的刚棒-线团(rod-coil)分子,由于具有很强的微相分离和π-π堆积作用,可以在本体和溶液中产生有效的自组装。研究表明,刚棒嵌段的形状影响着分子排列的方式、自组装性能和微结构,因此本文设计了n型芳香嵌段、柔性链全部为烷基的n型刚棒-线团分子,通过红外光谱、NMR和MALDI-TOF-MS对其结构进行了表征,利用DSC、POM和SAXS对此化合物的自组装行为进行了研究。结果表明,含烷基柔性链的n型分子在固态时能形成双分子的层状结构。     

三取代直链烷基苯磺酸钠的界面扩张性质

利用悬挂滴方法研究了五种表面活性剂3,4-二己基苯磺酸钠(66)、3,4-二庚基苯磺酸钠(77)、2-乙基-4,5-二己基苯磺酸钠(266)、2-丙基-4,5-二己基苯磺酸钠(366)和2-丁基-4,5-二己基苯磺酸钠(466)在空气-水和癸烷-水界面上的扩张流变性质,考察了烷基取代在苯环不同位置对分子界面行为的影响.研究发现,苯环不同位置的取代烷基链长变化对扩张弹性模量和扩张粘性模量影响不同.随着烷基链长增长,表面扩张弹性模量均增加,而扩张粘性模量表现则不同:邻位短链烷基碳数从2变化到4,对粘性模量贡献不大;而间位长链烷基增长对表面弛豫过程影响较大,粘性模量明显增大.油分子的插入能大大削弱间位长链烷基间的强相互作用,一方面导致界面弹性模量和粘性模量远低于表面,同时使得同分异构分子77和266的界面扩张粘性模量数值接近.     

一种反铁电液晶薄膜相变过程的变温红外光谱研究

通过变温红外光谱对反铁电液晶MHOCPOOB薄膜相变过程中的分子构象、排布及相互作用的变化进行了研究.结果表明,室温时,薄膜中的分子烷基链同时含有zigzag和gauche两种构象.随着温度的升高,有序的zigzag构象转化为无序的gauche构象,链的扭曲程度增加.但S^*IA到S^*CA的转变并不引起烷基链构象和取向发生明显变化.刚性核中的羰基与相邻的苯环形成共轭体系,苯环之间相互倾斜排列,在相变过程中羰基与苯环的共平面作用逐渐被打破,且在相变点苯环间的二面角明显增大.     

不同链长直链烷基硫醇自组装的吸附动力学

本文利用电化学方法,并结合接触角和原子力显微镜表征手段对直链烷基硫醇自组装的吸附动力学进行了研究。分别考察了短链正六烷基硫醇、中链正十二烷基硫醇和长链正十八烷基硫醇三种链长硫醇分子的组装动力学,每种链长考察了四个浓度。实验结果表明:硫醇自组装由快速吸附和缓慢重组两个过程组成,其组装过程符合扩散控制的Langmuir模型。表观吸附动力学常数kobs与吸附动力学常数ka都显示了浓度相关性,由此估算出烷基硫醇链每增加一个CH2单元,吸附自由能变化约0.09kJ/mol。     

Graphene功能分子在HOPG上自组装结构的密度泛函研究

Graphene自组装超分子结构,是指FTBC-Cn(n=4,6,8,12)分子有序自组装在高定向裂解石墨(HOPG)上形成的自组装超分子结构,是一种新型二维固体表面材料.其中FTBC-Cn分子是由三角形扶手椅型graphene每边添加2条含有n(n=4,6,8,12)个C原子的烷基链所形成具有曲面结构的一种分子.采用...     

“拟双子”阴离子表面活性剂在癸烷/水界面的分子动力学模拟

采用全原子分子动力学模拟方法研究了壬基酚取代的系列烷基磺酸盐表面活性剂在癸烷/水界面的微观聚集行为,通过分析界面厚度、界面生成能和界面张力以及表面活性剂分子与水分子之间的径向分布函数和配位数,讨论了不同磺烷基链长度对壬基酚基取代烷基磺酸盐表面活性剂界面性质的影响.结果表明,磺烷基链长为12时,表面活性剂的界面张力最低,界面厚度和界面生成能最大.     

ORDERED STRUCTURAL EVOLUTION AND RELAXATION BEHAVIORS OF A SERIES MICROPHASE SEPARATED “HAIRY-ROD” POLYIMIDES WITH MULTIPLE ALKYL SIDE CHAINS

A series of “hairy-rod” polyimides, BBPA(n), with multiple alkyl side chains was prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-biphenyldiamine substituted in the 2,2′-positions with benzoate, which was substituted in the 3,4,5-positions with ether side chains of varying lengths. The number of the methylene units, n, in these alkyl side chains were in even numbers ranging from 8 to 18. Combining techniques of one-dimensional (1D) and 2D wide angle x-ray diffraction, 1D small angle X-ray scattering, differential scanning calorimetry experiments, it was found that this series of “hairy-rod” polyimides possess a micro-phase separation between the backbones and side chains. This led to the formation of ordered structures in two different length scales, of which both are hexagonal packing: one is attributed to the alkyl side chains on the sub-nanometer scale, and another is for the whole polymer chains on the nanometer scale. The development of the hexagonal structure on the sub-nanometer scale was critically dependent upon the lengths of the alkylside chains. Three relaxation processes were captured by dynamic mechanical analysis, i.e., segmental motion of the backbones, α the melting of the side chain crystals, β1, which exits only for the materials with longer side chains(n=18,16); and the subglass relaxation of side chains, β2- The peak relaxation temperature of the α process decreased with increasing the length of side chains, while the one of the β2 process increased. The activation energy of the α relaxation was relatively independent on the length of side chain, whereas, β2 process showed the increasing of activation energy with increasing the length of side chains.     

Self-assembling bilayers of palladiumthiolates in organic media

Alkylthiolates of palladium forming a homologous series (butyl to octadecyl) have been prepared and characterized using X-ray diffraction and STM. The thiolates adopt an unusual bilayered lamellar structure, whose thickness is governed by the length of the alkyl chain. These mesophases melt in the temperature range, 60° to 100°C, with the melting point increasing linearly with the thiol chain length. There is evidence to suggest that the alkyl chains are orientationally disordered especially prior to melting.     

Two-dimensional structure control by molecular width variation with metal coordination

The self-assembled monolayer of bipyridine derivative 1, which has two alkyl chains on each end, at the HOPG/1-phenyloctane interface was studied by in situ scanning tunneling microscopy (STM). The detailed mechanism of a spontaneous change in the monolayer packing pattern by Pd coordination was studied. Uncomplexed 1 existed in a bent form in the monolayer, and the alkyl chains were interdigitated, whereas Pd-complexed 1 was in a straight form and the alkyl chains were not interdigitated. An intermediate state of 1 was successfully observed during metal coordination. The structure was the bent form with noninterdigitated alkyl chains. Equilibrium intermolecular distances reported from ab initio calculations indicate that the molecular width of the central aromatic part of uncomplexed 1 (7.5 A) is substantially smaller than that of the peripheral alkyl chain part (9.2 A). The bent form was suitable for covering up the surface to maximize the packing density. However, the molecular width of the aromatic unit of Pd-complexed 1 (9.1 A) was almost identical to that of the alkyl chain unit (9.2 A). Therefore, Pd-complexed 1 took the straight form in the monolayer. The observation of surface coverage by STM suggests that the bent form increases the packing density by as much as 16% compared with that of the straight form. These results indicate that the control of molecular width can be used to design molecular templates for nanostructure formation.     

N-烷基化聚对苯二甲酰对苯二胺梳状高分子中烷基侧链对刚性主链堆积行为的影响

基于聚对苯二甲酰对苯二胺(PPTA), 采用N-烷基化方法制备了系列PPTACns(烷基侧链碳原子数n=8, 10, 12, 14, 16, 18)刚性主链梳状高分子, 利用DSC, XRD和FTIR等方法研究了其主链堆积行为、 分子链构象及热性能等与烷基侧链长度及结晶特性之间的关系. XRD和DSC结果表明, 当烷基侧链碳原子数达到14时, 烷基侧链发生结晶. XRD结果显示, PPTACns具有层状结构, 烷基侧链长度对主链层间距影响显著. FTIR研究发现, 烷基侧链的聚集状态对PPTACns分子链的构象产生较大影响, 伴随着烷基侧链结晶的熔融, PPTACns的分子链构象发生显著改变. 烷基侧链处于熔融状态的PPTACns的ν_C=O和γ_C-H谱带峰位与烷基侧链不结晶的PPTACn接近.     

Structure and mobility of a series of poly(alkyl l-glutamate)s studied by VT 13C CPMAS NMR spectroscopy

VT CPMAS NMR measurements were carried out for a series of poly(alkyl l-glutamate)s (PALG) which have n-alkyl side chains with carbon numbers ranging from 2 to 12 in order to investigate the structure and mobility of the main and the side chains. From the temperature dependencies of the peak intensities for the PALGs, the relative mobilities of the main and side chains are discussed. For PG-2 and PG-4, the molecular motions of both the main and side chains are not very fast. From the amount ratio between the main and side chains, the main chain dominates the entire mobility of the polymer. As the side chain length increases, the side chain motion is drastically activated by a temperature change. In addition, the main chain motion is induced by the side chain motion. For PALGs with long alkyl side chains, the mobilities of the polymers are governed by the structure and mobility of the side chain.     

Limited Fraction of Crystallized Side Chains in Bottlebrush Poly(n-alkyl methacrylate)s

Crystallinity of bottlebrush polymers due to side chain crystallization has been considered to be related to the length of the side chains only under the assumption of complete participation of crystallization by all side chains.Recent experimental results revealed that in poly(n-alkyl methacrylate)s a fraction of side chains could not crystallize due to constraints imposed by the trapped main chain entanglements and required expansion of main chain-main chain distance.This result renders the original simplified consideration of the origin of crystallinity in bottlebrush polymers questionable.In this work,we introduce a new parameter fc,the fraction of crystallizable side chains,to better describe the crystallinity of bottlebrush polymers.A linear relationship between the melting enthalpy and the number of alkyl groups in side chains for bottlebrush polymers reported repeatedly indicates that fc remains essentially unchanged when bottlebrush polymers had the same main chain structure and grafting degree but different side chain lengths.The slope of the above-mentioned linear relationship is thus AHCH2×fc,where AHCH2 stands for the melting enthalpy of one mole alkyl group packed into the crystal.With a known value of fc,it is possible to estimate the value of AHCH2.In case of poly(n-alkyl methacrylate)s,we estimated AHCH2 of hexagonal crystal being at most 5.74 kJ/mol with the knowledge of possibly smallest fc of 0.67 obtained from small angle X-ray scattering data.Therefore,the crystallinity of bottlebrush polymer would be calculated based on the equation Xc = fc×Nc/N with N and Nc being the number of alkyl groups in a side chain and those packed in the crystalline structure,respectively.Both chemical structure and grafting degree of bottlebrush polymers affect fc.     

The photophysical properties and morphology of fluorene-alt-benzene based conjugated polymer

A series of fluorene-alt-benzene based conjugated main chain polymers chemically attached with alkyl side chains of different lengths on phenylene rings were designed and synthesized by a palladium catalyzed Suzuki coupling reaction. The UV-vis absorption and fluorescence spectra, thermal stability of spectral property, phase transition behavior and morphology of the synthesized polymers were investigated. With increasing the length of the alkyl side chain, the UV and fluorescence spectra exhibit an obvious blue shift compared with those of the unsubstituted polymer. The alkyl substitution improves the thermal spectral stability of the polymers due to the steric hindrance of the alkyl side chains, thus leading to efficient separation of the main chain backbones. The phase transition behavior is closely related to the length of the alkyl side chains attached on the phenylene rings. The annealed films of the polymers display characteristic nematic liquid crystalline texture. TEM observations indicate that solvent-cast thin deposits of all the polymers show typical fibrillar morphology.     

Revisiting the crystallization of poly(2‐alkyl‐2‐oxazoline)s

Poly(2‐alkyl‐2‐oxazoline)s (PAOx) exhibit different crystallization behavior depending on the length of the alkyl side chain. PAOx having methyl, ethyl, or propyl side chains do not show any bulk crystallization. Crystallization in the heating cycle, that is, cold crystallization, is observed for PAOx with butyl and pentyl side chains. For PAOx with longer alkyl side chains crystallization occurs in the cooling cycle. The different crystallization behavior is attributed to the different polymer chain mobility in line with the glass transition temperature (T_g) dependency on alkyl side chain length. The decrease in chain mobility with decreasing alkyl side chain length hinders the relaxation of the polymer backbone to the thermodynamic equilibrium crystalline structure. Double melting behavior is observed for PButOx and PiPropOx which is explained by the melt‐recrystallization mechanism. Isothermal crystallization experiments of PButOx between 60 and 90 °C and PiPropOx between 90 and 150 °C show that PAOx can crystallize in bulk when enough time is given. The decrease of T_g and the corresponding increase in chain mobility at T > T_g with increasing alkyl side chain length can be attributed to an increasing distance between the polymer backbones and thus decreasing average strength of amide dipole interactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 721–729     

Synthesis of dehydrobenzo[18]annulene derivatives and formation of self-assembled monolayers: implications of core size on alkyl chain interdigitation

The synthesis of a series of dodecadehydrotribenzo[18]annulene ([18]DBA) derivatives is reported, together with their steady-state absorption and fluorescence properties. The main focus, though, is on the self-assembly of these compounds at the liquid-solid interface as investigated with scanning tunneling microscopy (STM), highlighting the effect of alkyl chain orientation and alkyl chain length on the molecular ordering. Owing to the large triangular pi-electron system of the [18]DBAs, two different types of alkyl chain orientation are observed. The observed changes in the monolayer networks upon elongation of the alkyl chains are attributed to the increased van der Waals interactions between molecules and substrate. The effect of the core size on the alkyl chain orientation and, as a result, the monolayer structure is discussed in relation to the results obtained previously for triangularly-shaped dehydrobenzo [12]annulene ([12]DBA) derivatives and triphenylene derivatives. A guideline for substituent spacing allowing control of molecular alignment for large planar pi-electron systems utilizing directional alkyl chain interdigitation is also discussed.     

Low molecular weight organogels based on long-chain carbamates

Thermoreversible organogels were prepared from carbamates with alkyl side chains of different lengths. Gelation was possible only up to an alkyl side chain length of 12 carbons, beyond which crystallization occurs, due to the dominant van der Waals interaction between the alkyl chains. This is in contrast to other alkane-based organogels, in which gelating efficiency increased with the length of the alkane chain (see Abdallah, D. J.; Weiss, R. G. Adv. Mater. 2000, 12, 1237). The critical concentration for gelation decreases drastically with an increase in the side chain length. Xerogels of these show birefringent fibers with uniform cross section and unlimited growth in one direction. The extent of this unlimited growth is affected by the length of the alkyl side chain in the carbamate, which finally ceases the gel formation ability of the carbamate. Cryogenic scanning electron microscopy images of the gels are similar to those of xerogels. From X-ray diffraction of the fibers, we propose that the growth direction is along the plane of hydrogen bonds between the carbamate molecules. The thickness of the fibers depends on the length of the alkyl side chain. Morphological differences are seen between gels prepared by slow cooling and quenching of the solution. Thus, the morphology of the fibrous xerogels of the carbamates can be tailored for specific applications, by the choice of the alkyl side chain length and the rate of cooling the solution.