含对硝基偶氮苯偶基的丙烯酸酯类液晶聚合物的超分子结构

利用ＤＳＣ、偏光显微镜和广角Ｘ射线衍射等手段研究了含对硝基偶氮苯侧基的丙烯酸酯类均聚物ＨＰｎ（ｎ＝３，４，６）及其与丙烯酸的共聚物Ｐｎ＝（ｎ＝３，４，６，８）的相行为，结果表明：ＨＰ６可形成向列型液晶相，其相态特征可表示为：Ｔｒ３０８．９Ｋ，ＴＫＮ３４２Ｋ、ＴＮＴ４０１Ｋ，ＨＰ３和ＨＰ１为非液晶聚合物；Ｐ可形民近晶型液晶相，ＷＡＸＤ结果指出其ｄ／ｌ介于１．４０－１．５４之间，故其液晶相具在ＳＡdisp     

鞘磷脂和神经节苷脂对磷脂酰乙醇胺混合脂超分子体系液晶态立方相Im3m和Pn3m结构影响的研究

用磷脂酰乙醇胺(DEPE)、鞘磷脂(Sphingomyeline, Sph)、神经节苷脂(Gm1)和胆固醇(Chol)模拟了生物膜超分子体系液晶态结构, 通过用小角X射线衍射(SAXD)对混合脂体系液晶态结构进行了研究, 鉴定出了两种立方相: 即Im3m(Q²²⁹)和Pn3m(Q²²⁴)结构. 实验发现, 鞘磷脂的含量对DEPE膜的结构有一定的影响, 随着鞘磷脂浓度的增加, 混合脂体系的液晶态结构发生了由Im3m(Q²²⁹)到Pn3m(Q²²⁴)的变化. 神经节苷脂(Gm1)的含量对混合脂体系的液晶态结构也有一定的影响, 当神经节苷脂(Gm1)含量达到某一临界值时, 混合脂体系的液晶态结构发生了从Im3m(Q²²⁹)到Pn3m(Q²²⁴) 的变化. 当DEPE-Shp-Gm1超分子聚集体中含有胆固醇时, 胆固醇的极性头部(—OH)与磷脂酰乙醇胺(DEPE)、鞘磷脂(Shp)、神经节苷脂(Gm1)的极性头部通过氢键相互作用形成液晶态立方相Im3m(Q²²⁹)结构, 再通过疏水/亲水相互作用形成稳定的Pn3m (Q²²⁴)结构.     

三维超分辨荧光和形貌显微镜联用系统的研制

搭建了一种联用超分辨荧光和三维形貌显微成像系统(Correlative super-resolution fluorescence and three-dimensional topography imaging microscopy),以聚合纤维状肌动蛋白(F-actin)为例,评价了此联用系统的性能。实验结果表明,此联用仪器具有纳米级分辨率的三维形貌及具体成分的定位分布成像功能,可实现在形貌图中定位具体成分的功能,表明此联用仪器可应用于研究分析细胞骨架及细胞亚结构(如细胞膜蛋白质聚集体的组成和分布特性等)方面,此联用系统在生命科学和材料科学等领域具有广泛的应用前景。     

用原子力显微镜研究磷脂酸Langmuir-Blodgett双层膜中超分子结构

用原子力显微镜研究了二棕榈酰磷脂酸(DPPA)双层LB膜的分子排列结构,发现DPPA双层膜的分子排列具有长程的位置和取向有序,为有序六方结构;同时,在DPPA双层膜的极性区磷酸基团间存在局域超分子结构.     

磷脂酸Langmuir-Blodgett膜分子结构的原子力显微术研究——分子排列有序性,分子间氢键作用,超分子结构以及晶格结构转变

利用原子力显微镜(AFM)研究了二棕榈酰磷脂酸(DPPA)的单层,双层和三层Langmuir-Blodgett膜的分子排列结构,发现相邻的(2～6个)DPPA分子的极性头磷酸基团通过分子间氢键形成局域超分子结构.分子分辨的AFM图象表明,DP-PA LB膜中分子排列具有长程的取向和位置有序.DPPA分子的晶格排列随着LB膜层数的增加由单层和双层的六方晶格转变成三层的正交(四方)晶格.探讨了不同的pH下的DPPA极性头磷酸基团的分子间氢键作用及其对膜分子有序排列以及云母基片对DPPALB膜中分子排列的晶格结构的影响.     

双亲性三嵌段共聚物/水体系超分子结构的研究

利用小角 X-射线散射技术研完了双亲性聚氧化乙烯-聚二甲基硅氧烷-聚氧化乙烯三嵌段共聚物/水体系在高浓度的溶致性液晶相,测定了亲水区、疏水区随浓度和结构变化的尺寸等超分子结构参数。用简单的几何模型可满意地解释实验结果。     

原子力显微镜对细胞色素C分子结构的形态研究

用原子力显微镜(AFM)对不同浓度下细胞色素C的分子形态,以及加入蛋白质降聚和变性剂脲后的形态变化进行了考察。实验结果显示,在50μmol/L的低浓度溶液中细胞色素C分子主要以直径为3nm的类球形单体形式存在。浓度增大,细胞色素C分子发生聚集,且随着浓度的进一步增大,细胞色素C分子倾向于形成更大的聚集体。浓度为200μmol/L时,聚集体分子间相互缠绕,形成链状结构。浓度低于0.8mol/L的脲的加入基本不影响细胞色素C分子的形态。加入较高浓度的脲,细胞色素C聚集体的聚集数降低,聚集体分子间没有明显的链状结构。     

液晶态磷脂酰乙醇胺脂质体和LB膜结构的研究

用原子力显微镜、小角X射线散射和³¹PNMR分别对液晶态磷脂酰乙醇胺脂质体和LB膜结构进行了研究.用原子力显微镜观察到了液晶态脂质体的立方相和双层膜共存的结构图像.研究结果表明,两相共存的状态与双亲性分子的结构、浓度以及介质的组分和pH等因素有关.用小角X射线散射和³¹PNMR研究发现,在DEPE液晶态中,钠盐诱导形成Q²²⁹(Im3m)立方相.DEPE液晶态分别在37.5℃出现L_β→L_α可逆相变,在63.5℃出现L_α→H_Ⅱ可逆相变.     

丁烯和丁烷自由基阳离子的分子结构和超精细结构的 理论研究

用密度函数理论B3LYP方法和6-31G(d,p),6-311G(d,p)及6-311+G(d,p)基组，分别对1-C4H^+~8,2-C4H^+~8和C4H^+~10进行了构型优化和频率分析计算，预言1-C4H^+~8具有非平面构型，与以往报道的从头算和密度函数理论计算结果不同。在各自由基阳离子的B3LYP构型上，进行了B3LYP、MP2及MRSDCI方法的超精细偶合常数计算，得到了比以往更好的结果，特别是MP2/B3LYP计算值是至今与实验值符合得最好的理论计算结果。     

超分子结构草甘膦插层水滑石的组装及结构研究

提出了一种新的绿色农药缓释剂模型——超分子结构草甘膦缓释剂.依据插层组装理论,以阴离子层状材料镁铝水滑石(MgAl-LDH)为插层主体,以除草剂草甘膦为插层客体,由共沉淀法一步组装得到超分子结构草甘膦插层镁铝水滑石(MgAl-LDH-gly).通过对MgAl-LDH-gly的结构、主客体相互作用及化学组成确认,建立了MgAl-LDH-gly的近似超分子结构模型,并对其缓慢释放草甘膦的可行性进行了分析.     

有序介孔氧化硅膜的制备及结构研究

本文介绍了在α-Al₂O₃中空纤维载体上制备担载有序氧化硅膜的方法。应用LXRD、HRTEM、TG-DTA、SEM、氮气吸附等测试手段对膜的结构、形貌进行了表征。LXRD和HRTEM结果显示所制备的非担载膜具有高度有序的二维六方结构。SEM分析发现担载膜表面完整、无缺陷。气体渗透实验表明中空纤维担载膜具有一定的气体选择性，在0.1 MPa下对H₂/N₂和CH₄/N₂的分离因子分别为2.80和1.65，气体透过膜孔的扩散由努森机制所控制。等温氮气吸附实验显示：500 ℃热处理后非担载膜的比表面积为548.84 m²·g^-1，孔容为0.57 mL·g^-1。     

脱乙酰基对天然魔芋葡甘聚糖分子形貌的影响

通过原子力显微镜直接观察魔芋葡甘聚糖（KGM）分子的三维结构形貌，KGM水溶液铺展在经Ca^2 处理的云母片上，干燥固定后，可获得稳定，重复的图像，实验结果表明，稀溶液中KGM分子具有伸展的螺旋链状结构，单股的长度达200－400nm，厚度为1．0nm，宽度为35．0－35．2nm，脱乙酰后分子链卷曲成直径约40－50nm,厚3．5－5．0nm的弹性圆台状。     

Effect of the length of the substituents on the phase structure and transition behavior of a series of laterally attached side‐chain liquid‐crystalline polynorbornenes

A series of polynorbornenes (PNBEs) with 1,4‐bis[(3′‐fluoro‐4′‐n‐alkoxyphenyl)ethynyl]benzene mesogens (n = 1–12, where n is the number of methylene units in the substituents of the mesogens) laterally attached to polymer backbones through a one‐carbon spacer were previously synthesized by the ring‐opening metathesis polymerization of the corresponding norbornene‐based monomers. Differential scanning calorimetric results showed that the first‐order transition temperatures exhibit an odd–even alternation, especially when PNBEs have lower values of n. PNBE (n = 8), similar to the previously studied PNBEs (n = 9–12), shows a smectic C (S_C) phase at room temperature (Kim, Pugh, and Cheng, Macromolecules, 33, 8983, 2000.) According to one‐ and two‐dimensional wide‐angle X‐ray scattering experiments, PNBEs (n = 2–7) exhibit a nematic (N) phase with S_C fluctuations, whereas for PNBE (n = 1), only an N phase is observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 3029–3037, 2001     

Normal and Lateral Deformation of Lyotropically Ordered Polymer Brush

Summary: Planar polymer brush formed by semirigid chains of freely jointed rigid segments and immersed into a solvent is considered. Brush collapse induced by deterioration of the solvent quality and its deformation by external normal or lateral force is studied. It is demonstrated that these three different situations can be described in the framework of the common approach. It is shown that the collapse is accompanied by liquid‐crystalline (LC) ordering within the brush. The LC transition can be jump‐like (the first order) or continuous, depending on the segment's aspect ratio and grafting density. Transition point is investigated in detail, the corresponding phase diagrams are calculated. It is shown that the phase diagrams of a normally deformed brush have different structures, with a narrow ‘leg’ in the good solvent region for sparsely grafted brush, with two coexistence regions and a triple point, in addition, for shorter segment length or without these features if the chains are densely grafted. For the laterally deformed brush, phase diagrams have similar structures with a critical point in the good solvent regime.

Polymer brush subjected to deformation by normal (top) and lateral (bottom) external force.     

Effect of the Linking Structure of Nonlinear Optical Side Groups on the Phase Behavior of an Aromatic Polyester Backbone

Summary: The phase behavior of poly(p‐phenylene terephthalate)s (PPT) with pendant side groups, N‐(4‐nitrophenyl)ethylaminoethanol (NPE) and N‐(4‐nitrophenyl)‐L ‐prolinol (NPP) has been studied by using differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXS), and second harmonic generation (SHG). PPT‐NPE showed a layered liquid crystalline morphology while PPT‐NPP showed a completely amorphous structure. Compressive or shear stress applied on the polymer melt surface at 210 °C induced a more prominent layered structure of PPT‐NPE whereas the amorphous structure of PPT‐NPP remained unchanged under the stress. In order to understand this phase difference in terms of the repeat structure, we attempted theoretical ab initio Hartree‐Fock, and DFT calculations for the monomers and molecular dynamics for the bulk state. The results indicated that molecular configurations are a good way of microscopically understanding the phases of rigid backbone polymers with functional side groups: The NPT (constant particle number, pressure, and temperature) simulation data at 210 °C agree qualitatively with the experimental data and the difference between PPT‐NPE and PPT‐NPP could be understood using rotational energy barrier, steric hindrance and inter‐chain interactions. X‐ray diffractometer (XRD) simulation patterns for the oligomers are also in qualitative agreement with the experimental WAXS data and the structural parameters of stacks of PPT‐NPE chains are estimated to be layer distance (4.6 Å), backbone distance (21.5 Å), and side distance (12 Å).

     

Effect of a lateral methyl group on azo-mesogens containing the naphthalene moiety

Two mesogenic homologous series, 2-[4-(4-n-alkoxybenzoyloxy)-2-methylphenylazo]-naphthalenes (I) and 2-[4-(4-n-alkoxybenzoyloxy)-3-methylphenylazo]naphthalenes (II) with a lateral methyl group have been synthesized. Both series are purely nematogenic. The mesomorphic properties of both series are compared with each other and also with the properties of other structurally related series to evaluate the effect of the lateral methyl group on mesomorphism. The chiral nematic (N*) mesophase was induced in the system by doping with a derivative of naturally occurring chiral menthol.     

脂双层膜表面结构与稳定性的原子力显微镜研究

用原子力显微镜研究了1,2－二油酸甘油－3－磷酸－1甘油（DOPG）脂双层膜 的表面结构与稳定性。实验结果表明,原子力显微镜的探针与脂双层膜的相互作用 导致脂双层膜表面产生一个永久的损伤。静电相互作用对脂双层膜结构和稳定性的 影响表明,在NaCl溶液中制成的脂质体,随着NaCl浓度的增加,它们的双层膜更稳 定。在低的NaCl浓度则经常被损伤,在1 mol/L NaCl溶液中制备的指双层变得更稳 定。在KCl溶液中结果恰好相反。在高的KCl浓度中经常被损伤,随着KCl浓度的降 低,它们的双层膜更稳定。葡萄糖和蔗糖对脂双层膜结构有稳定作用。     

Effect of quenching on the structural and dynamic properties of non-aqueous lyotropic mesophases

We focused to highlight the effect of quenching on the development and ordering of non-aqueous lyotropic liquid crystalline phases. Lyotropic mesophases are prepared from binary mixtures of sodium dodecyl sulphate and ethylene glycol at varying concentrations 30:70 and 50:50 wt%. The obtained self-assembled phases are characterised by X-ray diffraction, polarisation optical microscopy, differential scanning calorimetry and dielectric spectroscopy to evaluate the structural, optical, thermal and dielectric behaviours. Structural and textural measurements confirmed mesomorphic and crystalline phases for both mixtures. Calorimetric study gives insight about the growth of new phases at ≈335 K and isotropic temperatures of these mixtures. Both the mixtures are quenched from 335 K to the 303 K to analyse the effect of quenching on the structure and ordering of mesophases. We noticed well-defined hexagonal liquid crystalline mesophases for both concentrations after quenching at 303 K. Dielectric and relaxation behaviours of quenched mesophases were also examined. Higher capacitance and dielectric strength are noticed for quenched mixtures. The application prospective of such phases is also discussed.     

Molecular Organization of Various Collagen Fragments as Revealed by Atomic Force Microscopy and Diffusion‐Ordered NMR Spectroscopy

Heterogeneous mixtures of collagen fragments can be used as nutrition supplement or as key ingredients for ointments with therapeutic relevance in wound healing. Some mixtures of collagen fragments are referred to as collagen hydrolysates owing to the production process with hydrolytic enzymes. Since the precise composition of collagen hydrolysates is generally unknown, it is of interest to analyze samples containing various collagen fragments with appropriate biophysical methods. Any product optimization without a profound knowledge concerning the size and the molecular weight distribution of its components is nearly impossible. It turned out that a combination of AFM methods with NMR techniques is exceptionally suited to examine the size range and the aggregation behavior of the collagen fragments in the hydrolysates of fish, jellyfish, chicken, porcine and bovine collagen. Supported by molecular modeling calculations, the AFM and NMR experiments provide a detailed knowledge about the composition of collagen hydrolysates and collagen ointments. Furthermore, the data allow a correlation between the size of the fragments and their potential bioactivity.