聚{11-[(4'-正庚氧基-4-联苯基)羰基]氧-1-十一炔}的相结构与相转变

采用示差扫描量热法(DSC)、一维(1D)、二维(2D)广角X-射线衍射(WAXD)和偏光显微镜(PLM)等研究手段对聚{11-[(4'-正庚氧基-4-联苯基)羰基]氧-1-十一炔}(PA-9,7)的本体相转变和相结构进行研究,并采用分子动力学方法对相结构进行模拟.结果表明,样品的相转变为近晶B相(SmB)(→)近晶A相(SmA)(→)各向同性态(Iso).在近晶B相中,侧链在层状结构中排列成具有六次对称性的准长程有序结构.     

5-{[(4′-正戊基氧-4-联苯基基)羰基]氧}-1-戊炔的相转变与相结构

采用差示扫描量热(DSC)、一维(1D)广角X射线衍射(WAXD)、热台偏光显微镜(PLM-hotstage)等研究手段对含联苯液晶基元的侧链液晶聚炔单体5-{[(4′-正戊基氧-4-联苯基基)羰基]氧}-1-戊炔(A3EO5)的本体相转变和相结构进行了研究.DSC和1D-WAXD实验结果表明,A3EO5在升温和降温过程中均呈现四个相转变过程,形成双向性液晶.样品从各向同性态降温至室温过程中,首先形成近晶A相,随后进入层内排列具有准长程有序的近晶B相,继续降温将形成层内为正交排列的近晶E相,在此之后样品进入晶相.PLM结果指出样品在各向同性态降温过程中分别形成球状织构、角锥织构和同心圆弧织构.     

基于“甲壳”效应、不同尾链长度的离子液晶高分子的相行为和相结构

考察了一系列基于"甲壳"效应的离子液晶高分子poly(2,5-bis{[6-(4-butoxy-4?-imidazolium phenyl)k-alkyl]oxy carbonyl}styrene bis(fluoroborate)salts)Pk-6-BF4(k=4,8,12,16)的相行为和相结构.热重分析结果表明,该系列聚合物的热分解温度都在320?C以上,说明其均具有优异的热稳定性能.示差扫描量热仪结果表明,P4-6-BF4和P8-6-BF4仅表现出一个玻璃化转变,随着尾链的增长,P12-6-BF4和P16-6-BF4具有一个结晶熔融峰.偏光显微镜、一维广角X衍射、二维广角X衍射结果表明,该系列聚合物均形成稳定的近晶A相结构,并且随着烷烃尾链的增长,层间距增加、近晶结构内部分子堆积形式有所改变.     

4H晶相的Au纳米线的晶相重构及其电催化CO氧化的行为研究（英文）

本文利用液相合成的方法成功合成了4H晶相的Au纳米线.利用高分辨透射电镜、X射线衍射、铅-欠电位沉积和电化学循环伏安技术,在去除表面吸附的油胺分子前后,分别表征4H晶相的Au纳米线的晶相、表面结构和电催化CO氧化的性能.尽管尝试了不同的方法去除4H晶相的Au纳米线表面吸附的油胺分子,例如:醋酸清、电化学氧化清洗和二乙胺取代法,但是发现,一旦表面吸附的油胺分子被去除后,4H晶相的Au纳米线的形貌都将从纳米线状转变为哑铃形的大颗粒,并且晶相也会由4H晶相转变为面心立方相.铅-欠电位沉积结果表明,在去除吸附的油胺分子前后,411晶相的Au纳米线表面的晶面组成基本相同,但经过上限电位为1.3 V的电化学清洗后,4H晶相的Au纳米线的CO氧化活性明显提高.本文比较了4H晶相的Au纳米线的CO氧化活性与文献报道的三种金单晶基础晶面的活性,并讨论了其CO氧化活性增强的可能原因.     

晶相调控对金属纳米粒子催化性能的影响

尺寸在1–10 nm的金属纳米催化剂广泛地应用于石油化工,精细化学品合成,能源与环境保护等领域。大量研究表明,金属纳米粒子的催化性能与其微观结构,即尺寸、形貌和晶相等密切相关。近年来,对金属纳米粒子的尺寸和形貌效应已经有了较为系统深入的研究,但对晶相效应的研究则较少涉及。这主要是由于介稳晶相的金属纳米粒子在合成过程中或反应条件下极易转化为热力学稳定的晶相结构。根据金属原子密堆积形式,金属纳米粒子的晶相结构主要有立方面心(fcc)、立方体心(bcc)和六方密堆积(hcp)三种晶相;而金属合金由于d带电子存在着多种杂化方式,因而其晶相结构呈现出多样性且与单一金属有很大的不同。金属和合金纳米粒子晶相结构的调控,不仅会改变金属原子的配位环境,调控了其电子分布状态,还可影响反应物和产物的吸附、活化和脱附,进而调变催化性能。首先,我们简要总结了液相合成和固相转变调控金属纳米粒子晶相的原理和方法。纳米粒子的液相合成一般包括前驱体还原成核和晶核生长两个阶段,通过对液相合成条件的优化,尤其是表面活性剂的选择,可有效调控合成过程中的热力学和动力学因素,从而实现金属晶相的可控合成。固相转变则主要是对具有一定晶相结构的纳米粒子于一定气氛和温度条件下进行加热处理,利用金属粒子与活性气体之间(H2, CO等)的化学作用来实现晶相转变。利用上述方法,可以合成出fcc-Co、fcc-Ru、L10-AuCu等热力学介稳的金属或合金纳米粒子。在此基础之上,我们分别以Co纳米粒子(fcc和hcp晶相)催化FT合成, Fe模型催化剂(fcc和bcc晶相)活化N2和CO, Ru纳米粒子(fcc和hcp晶相)催化CO氧化和氨硼烷水解制氢, Pd纳米粒子(PdHx物种)催化加氢等为例分析了晶相对金属纳米粒子催化性能的影响;在合金催化剂方面,以Pt3Co(无序的fcc和有序的L12), AuPdCo(P3–m、Fm3–m和R3–m混合晶相)和FePt纳米粒子(fcc和fct相)催化O2电化学还原、PtRhSn (碲铂矿晶相和fcc晶相)和ZrPt3纳米粒子(hcp和fcc晶相)催化乙醇电氧化、Ag3In合金(无序的Fm3–m相和有序的Pm3–m晶相)催化对硝基苯酚加氢、PdRu纳米粒子(fcc和hcp混合晶相)催化CO氧化等为例分析了合金催化剂的晶相对催化性能的影响。上述研究进展表明,金属纳米粒子的晶相也是影响制备剂高效金属催化剂的主要因素。最后,我们结合纳米催化的发展现状,提出了金属纳米粒子的晶相调控在纳米催化和纳米材料领域可能的发展态势。第一,通过对金属纳米粒子溶液相合成机理的深入研究,有助于发展出尺寸、形貌和晶相同时可控的新合成方法。第二,金属纳米粒子在晶相转化过程中往往伴随着烧结及组分的偏析等难题。利用氧化物包覆的核壳型或蛋壳型纳米结构以及碳纳米管的空间限域效应,或许有助于解决上述难题。第三,具有亚稳晶相结构的金属纳米粒子在反应条件下极易转变为热力学稳定的结构,因此,利用原位、动态、实时的表征技术对催化剂在真实工作状态下的微观结构进行细致的分析是阐明晶相效应的前提。     

卷烟烟气粒相物芳香核结构的研究

采用电喷雾电离(ESI)傅里叶变换离子回旋共振质谱(FT-ICR MS)以及碰撞诱导解离(CID)的方法对卷烟烟气粒相物的芳香核结构进行了研究。CID可以对质谱中储存的分子离子进行碰撞,将分子离子的烷基侧链打断,而芳香核结构得以保留。利用此方法,本研究对比了卷烟主流烟气和侧流烟气粒相物在CID前后质谱图及化合物类型的变化。在CID之前,在卷烟烟气总共发现了28类化合物:N_1O_(0-6)、N_2O_(0-6)、N_3O_(0-4)、N_4O_(0-2)、O_(1-5)及少量烃类,共近4 600个可鉴别分子组成的谱峰。主流烟气中化合物的氧含量明显高于侧流烟气。在CID之后,谱图中化合物的类型降为6种:N_(1-3)、N_1O_1、O_1和多环芳烃,可鉴别分子组成的谱峰降为近180个。主流烟气和侧流烟气的芳香核结构非常类似,主要为含有一个或两个氮原子的稠环结构,芳环数量为2～4个(由于仪器条件所限,本研究没有给出单环芳香核结构的结果)。     

新型含氧亚甲基和亚胺桥键的液晶化合物的合成及介晶性

报道一类新的、结构通式为MeO₂CC₆H₄CH₂OC₆H₄CH＝NC₆H₄Y, Y＝OC_nH_2n＋1, Me, Cl, Br, NO₂, H 的棒状液晶化合物的合成. 通过DSC和偏光显微镜对其介晶性研究发现, 除Y＝H外, 这些化合物均具有介晶性. 当Y为非烷氧基时, 呈向列相液晶; 当Y为较短的烷氧基时(n＝1～3), 液晶化合物具有向列相(N); Y为较长烷氧基时(n＝4～16 ), 液晶化合物只有近晶B相(S_B)和近晶A相(S_A); S_A-I相变的熵变随烷氧链原子数而奇-偶变化, 但与N-I相变的“奇-偶效应”相反.     

12-4-12/tCA沉淀相的光响应溶解及聚集体结构转变

双子表面活性剂12-4-12与反式肉桂酸（tCA）由于强烈的静电吸引作用而生成12-4-12/tCA沉淀相。通过偏光显微镜和X射线衍射测定,我们发现12-4-12/tCA沉淀相具有六角和层状的复合晶体结构。在365 nm紫外光照射下,12-4-12/tCA沉淀相会逐渐溶解,依次经历晶体—囊泡—蠕虫状胶束的转变。我们对12-4-12/tCA沉淀相的光响应溶解及聚集体结构转变机理进行了讨论。     

无规聚丙烯腈纤维热处理过程相转变行为的同步辐射研究

使用在线同步辐射广角X射线衍射(WAXD)和原位变温傅里叶红外(FTIR)研究了无规聚丙烯腈(at-PAN)纤维热处理过程中晶区的相转变行为.研究发现,WAXD图像中由(110)晶面衍射形成的衍射弧在加热过程中其q值随温度的变化速率不完全一致,在110℃存在突变点,此温度下晶区的热膨胀率从4.15×10-4nm/K(α1)突变为1.13×10-3nm/K(α2),同时DSC曲线在110℃附近出现放热峰,说明发生了晶胞结构转变.通过升温FTIR测试发现1230 cm-1和1250 cm-1处吸收峰的相对强度随热处理过程也发生变化,两峰峰强分别对应纤维中31螺旋构象与平面锯齿构象的相对含量,通过C=I1250/I1230与热处理温度的关系发现C值在110℃突然急剧减小,说明at-PAN纤维晶区分子链在110℃附近发生了平面锯齿构象向31螺旋构象的剧烈转变,而正是由于这种转变导致晶区层间距的变化使得WAXD图像中衍射弧的位置随温度变化速率不一致,即相转变行为是由分子链构象的变化引起的.     

硅灰粉尘添加量对莫来石-堇青石复相材料晶相结构与性能影响

采用XRD和SEM法确定莫来石-堇青石复相材料的晶相结构及其含量。探讨不同含量硅灰粉尘对复相材料的晶相结构与性能的影响。实验结果表明:复相材料中存在α-堇青石、β-堇青石、μ-堇青石和莫来石四种晶相。堇青石含量随着硅灰粉尘结合剂含量的增加而增加。莫来石含量随着结剂含量的增加而减少。根据结构上的分析结果,确定2#为最隹的配方,其堇青石和莫来石含量分别为66.0%和33.7%,抗折强度为27.69Mpa,1次和10次热震抗折强度保持率分别为63.36%和33.7%,体积密度为2.69 g/cm3.     

Hole mobility and lifetime in a smectic liquid crystalline photoconductor of a 2-phenylnaphthalene derivative

We have investigated hole transport properties in the smectic mesophases of a 2-phenylnaphthalene derivative 6-(4'-octylphenyl)-2-dodecyloxynaphthalene in detail by using time-of-flight technique. The transient photocurrents were measured in liquid-crystal cells with various thickness from 5 to 700 microm. They were well defined and nondispersive in the smectic A (SmA) phase up to 500 microm and in the smectic B (SmB) phase within the entire thickness employed, while they exhibited an exponential decay in the SmA phase at 700 microm. The mobilities in the SmA and SmB phases were constant in each mesophase irrespective of the cell thickness, and were 2.5 x 10(-4) and 1.7 x 10(-3) cm2V s, respectively. The hole lifetimes were determined to be 10 ms and longer than 5 ms for the SmA and SmB phases, respectively. We discuss the origin of these lifetimes from the two points of view, i.e., hole trapping by a trace amount of existing impurities and recombination with negative ionic charges. We conclude that impurities are mainly responsible for the present hole lifetime test.     

Thermotropic liquid crystalline α-[bis(2-hydroxyethyl)amino]ω-(4 ′-methoxybiphenyl-4-oxy)alkane hydrochlorides

Liquid crystalline α-[bis(2-hydroxyethyl)amino]- ω -(4′-methoxybiphenyl-4-oxy)alkane hydrochlorides with different spacer lengths (6, 8, 10 methylene units) have been synthesized and characterized by NMR, DSC, polarizing optical microscopy and X-ray diffraction. The melting temperatures of the hydrochlorides decrease with increasing number of methylene units in the spacer. Highly ordered and very viscous liquid crystalline (LC1) smectic phases are formed on melting. Upon further heating these phases are transformed into a less viscous smectic C phase (LC2). The temperature of the LC1-LC2 transition decreases and the temperature of the LC2 to isotropic phase transition (LC2-I transition) increases with increasing number of methylene units in the spacer.     

Frustrated molecular packing in highly ordered smectic phase of side-chain liquid crystalline polymer with rigid polyacetylene backbone

Using poly(5-{[(4'-heptoxy-4-biphenylyl)carbonyl]oxy}-1-pentyne) as an example, we demonstrate the incorporative accommodation of the rigid polyacetylene backbones and the mesogenic pendants, which leads to a highly ordered smectic (Sm) phase with a frustrated structure. The polymer exhibits a recognizable sheetlike molecular shape due to its rigid backbone and relatively short spacer (three methylene units), and the building block of the liquid crystalline (LC) phase is the whole molecule. In the LC phase, five layers of the molecules stack as a smectic A (SmA) block, and adjacent SmA blocks glide halfway of the molecular width from one to another. In scanning tunneling microscopy (STM) experiments, the STM tip scrape is found to generate a regular nanopattern with periodic electron conductivity, of which the spacing is determined by the side-chain length.     

6-Hydroxyhexyl 4-(E)-4-alkoxy/halostyryl)benzoates: synthesis,characterisation and study of mesomorphic and fluorescent properties

Hydroxyhexyl esters of alkoxy and halostilbene carboxylic acids were prepared and studied for thermal, liquid crystalline and fluorescent properties. The decomposition temperatures were determined thermogravimetrically and the compounds were found stable at least up to 200°C. Differential scanning calorimetry (DSC) indicated two mesophases in alkoxystilbene caboxylates. The smectic nature of the liquid crystal (LC) compounds was identified from the optical textures and confirmed through X-ray diffraction (XRD) measurements, where SmA, SmB and CrE mesophases were observed. The compounds 3a-g and 3h-k show single absorption maxima in UV-visible spectra at around 338 and 322 nm, respectively. All the alkoxy compounds emit blue light in solution and in solid state in the wavelength range of 422–425 nm.     

Differences between smectic homo‐ and co‐polysiloxanes as a consequence of microphase separation

This paper compares smectic phases formed from LC‐homo‐ and LC‐co‐polysiloxanes. In the homopolysiloxane, each repeating unit of the polymer chain is substituted with a mesogen, whereas in the copolysiloxanes mesogenic repeating units are separated by dimethylsiloxane units. Despite a rather similiar phase sequence of the homo‐ and co‐polysiloxanes—higher ordered smectic, smectic C* (SmC*), smectic A (SmA) and isotropic—the nature of their phases differs strongly. For the copolymers the phase transition SmC* to SmA is second order and of the ‘de Vries’ type with a very small thickness change of the smectic layers. Inside the SmA phase, however, the smectic thickness decreases strongly on approaching the isotropic phase. For the homopolymer the phase transition SmC* to SmA is first order with a significant thickness change, indicating that this phase is not of the ‘de Vries’ type. This difference in the nature of the smectic phases is probably a consequence of microphase separation in the copolymer, which facilitates a loss of the tilt angle correlation between different smectic layers. This has consequences for the mechanical properties of LC‐elastomers formed from homo‐ and co‐polymers. For the elastomers from homopolymers the smectic layer compression seems to be rather high, while it seems to be rather small for the copolymers.     

Liquid crystallinity of newly synthesized glucose derivatives with mesogenic side chains

Synthesis of glucose derivatives by direct esterification of the five available sites on D-(+)-glucose with side chains containing a biphenyl mesogenic moiety, a pentyl spacer and an alkyl tail is reported for the first time. Liquid crystalline phase behaviour of these glucose derivatives was studied by optical microscopy, thermal and X-ray diffraction methods. A layered arrangement of the smectic A (SmA) type was commonly observed in the above materials. An increase in the length of the alkyl tail results in a change of the phase structure from smectic Ai(SmAi), intercalated layer phase, to smectic As(SmAs), segregated bilayer phase. From the transition temperature and enthalpy observations, the SmAs phase has higher order than the SmAi phase. Cholesteric and chiral smectic C phases were also observed in addition to the SmA for some of the glucose derivatives, demonstrating a potential for preparing chiral liquid crystals.     

端基含36个4-硝基偶氮苯介晶基元的二代树状碳硅烷的液晶性研究

液晶树状物的液晶相态分别为SA相、SC相、SC^*相、向列相、胆甾相、盘状相、立方相和群聚向列相,而SE相液晶树状物尚未见报道,本文报道含吸电性端基(硝基)偶氮苯介晶基元二代树状物(D2)的液晶行为。     

Thermotropic liquid–crystalline properties of 4,4′-dialkoxy-3,3′-diaminobiphenyl compounds and their precursors

A series of 4,4?-dialkoxy-3,3?-diaminobiphenyl compounds were synthesised by three-step procedure that involves alkylation, nitration and reduction reactions. Their chemical structures were characterised by FTIR, ¹H and ¹³C spectroscopy and elemental analysis. Their thermotropic liquid–crystalline (LC) properties were examined by a number of experimental techniques including differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), polarising optical microscopy (POM) and variable temperature X-ray diffraction (VT-XRD). The 4,4?-dialkoxy-3,3?-dinitrobipheyl compounds, precursors to the diamine compounds, were also examined for their thermotropic LC properties. POM studies of focal conic textures and VT-XRD of the 3,3?-diaminobiphenyl derivatives having flexible alkyl chains (C₆–C₁₂) exhibited the smectic A (SmA) phase independent of the length of alkyl chains. Similarly, the 3,3?-dinitrobiphenyl derivatives containing alkyl chains C₇, and C₉–C₁₁ exhibit the SmA phase, those containing C₈ formed the smectic C (SmC) phase and C₁₂ formed both the SmA and smectic B (SmB) phases, respectively. The 3,3?-diaminobiphenyl derivatives had excellent thermal stability in the temperature range of 237–329°C, while those of 3,3?-dinitrobiphenyl derivatives were in the temperature range of 270–321°C. The 3,3?-diaminobiphenyl derivatives emitted UV light both in chloroform and acetonitrile.     

Dimesogenic compounds consisting of cholesterol and azobenzene-based moieties: dependence of liquid crystal properties on spacer length and fluorination of the terminal chain

The liquid crystalline (LC) properties of two series of non-symmetric dimesogenic compounds consisting of cholesterol and azobenzene-based moieties interconnected by ω-oxyalkanoyl spacers of varying length are compared: one series (AOC-n) has an octyloxy chain attached to the azobenzene mesogen unit while the other (AOCF-n) has a perfluoroheptylmethyloxy chain. In general, compounds bearing the fluorinated alkoxy chain exhibited LC properties over a much broader temperature range than those with the alkoxy chain. In addition, the AOC-n series exhibited the chiral smectic C (SmC*), smectic A (SmA) and cholesteric (N*) phases depending on the length of the central spacer, whereas the AOCF-n series favoured the formation of only the SmA phase with the N* phase completely suppressed. Both series showed an odd-even dependence of the isotropization temperature on spacer length.