电解质浓度改变对心磷脂囊管结构稳定性的影响

心磷脂是构成线粒体内膜的特殊磷脂组分, 是线粒体内膜不同功能态下的拓扑结构变化的主要参与者. 本实验通过溶剂自然蒸发与微操注射两种途径, 原位研究了溶液中电解质浓度改变程度对心磷脂构成的囊管结构稳定性的影响, 以期对线粒体功能状态的变化机理有进一步的认识. 实验发现, 即使没有蛋白质对膜曲率的调制作用, 单纯由溶液浓度改变造成的刺激也可以引起心磷脂膜组装形态的改变. 皱缩的发生与膜表面的电势变化有关, 是可受浓度调控的可逆过程.     

C12EO4与氨丙基三乙氧基硅烷水溶液自组装和流变性研究（英文）

研究了3-氨丙基三乙氧基硅烷(APTES)和非离子表面活性剂十二烷基聚氧乙烯(C12EO4)水溶液的相行为、溶液自聚集作用和流变性,小角度X-射线散射(SAXS)、低温透射电子显微镜(cryo-TEM)和氘谱核磁共振(2H NMR)测定确定了溶液中聚集体结构,测定了聚集体混合物溶液的流变性质.结果表明:随着溶液混合物组分的变化,溶液聚集体结构发生了改变,在Lα相区内,恒定C12EO4浓度,随着APTES浓度增加聚集体结构由高曲率聚集体转变为低曲率的层状结构;而在恒定APTES浓度时,随着C12EO4增加,Lα相由低粘弹性的囊泡溶液转变为粘弹性极高的密堆积囊泡和平面层状结构共存的类凝胶相,溶液聚集体结构和结构转变是由于APTES水解产物插入至C12EO4胶束引起的.非离子表面活性剂和氨基硅烷混合物溶液相结构及结构转变的新结果对于完全理解该类混合物的实际应用,特别是作为模板合成硅材料的应用具有重要理论意义.     

C12EO4与氨丙基三乙氧基硅烷水溶液自组装和流变性研究

研究了3-氨丙基三乙氧基硅烷(APTES)和非离子表面活性剂十二烷基聚氧乙烯(C₁₂EO₄)水溶液的相行为、溶液自聚集作用和流变性, 小角度X-射线散射(SAXS)、低温透射电子显微镜(cryo-TEM)和氘谱核磁共振(²H NMR)测定确定了溶液中聚集体结构, 测定了聚集体混合物溶液的流变性质. 结果表明: 随着溶液混合物组分的变化, 溶液聚集体结构发生了改变, 在L_α相区内, 恒定C₁₂EO₄浓度, 随着APTES浓度增加聚集体结构由高曲率聚集体转变为低曲率的层状结构; 而在恒定APTES浓度时, 随着C₁₂EO₄增加, L_α相由低粘弹性的囊泡溶液转变为粘弹性极高的密堆积囊泡和平面层状结构共存的类凝胶相, 溶液聚集体结构和结构转变是由于APTES水解产物插入至C₁₂EO₄胶束引起的. 非离子表面活性剂和氨基硅烷混合物溶液相结构及结构转变的新结果对于完全理解该类混合物的实际应用, 特别是作为模板合成硅材料的应用具有重要理论意义.     

磺酸型双子表面活性剂的溶致液晶结构研究

合成了一种磺酸型双子表面活性剂6,6 -(丁基-1,4-二基双氧)双(3-壬基苯磺酸)(9BA-4-9BA), 利用偏光显微镜和X射线衍射分析仪研究了其在水溶液和乙酸乙酯溶液中的溶致液晶结构变化. 结果表明, 9BA-4-9BA在两种溶剂及其混合溶剂中均可出现溶致液晶态结构, 并且双子表面活性剂的溶致液晶相态与溶液浓度和溶剂种类密切相关. 随着浓度增加, 9BA-4-9BA水溶液溶致液晶结构由立方相经由片层立方相转变为层状液晶相, 乙酸乙酯溶液中主要以层状液晶相存在.     

糖和盐类物质对生物膜超分子结构稳定性影响的研究

用原子力显微镜(AFM)和小角X射线(SAXS)技术, 研究了NaCl、KCl、胆固醇、葡萄糖和蔗糖等与膜脂的相互作用. 研究发现它们能引起脂质膜超分子体系液晶态结构的变化. 葡萄糖和蔗糖对脂双层膜结构有稳定作用. 在NaCl溶液中制成的脂质膜, 随着NaCl浓度的增加, 它们的双层膜更稳定. 在KCl溶液中结果恰好相反. AFM研究发现液晶态脂双层膜结构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. 在1,2-反十八碳-3-磷脂酰乙醇胺(DEPE)液晶态中, 钠盐诱导形成Q²²⁹(Im3m)立方相. 油酸的含量对DEPE-PVP(聚乙烯吡咯烷酮)超分子结构也有一定的影响, 当油酸含量达到某一临界值时, 则发生从Im3m(Q²²⁹)到Pn3m(Q²²⁴)的转变. 胆固醇能促使形成Pn3m(Q²²⁴)和六角相H_II共存相. 研究结果表明, 生物膜超分子聚集体的氢键、分子van der Waals力、离子的静电力等这些弱相互作用的协同性、方向性和选择性, 可能决定着生物膜的结构和功能.     

小角X射线散射表征AOT/水层状溶致液晶的有序性

用小角X射线散射研究了AOT/水层状溶致液晶的有序性. 通过对散射曲线的解析, 讨论了表面活性剂浓度、温度和助表面活性剂等三个方面对溶致液晶层状相结构有序性的影响. 在一定的范围内, 提高温度, 改变表面活性剂浓度和加入少量助表面活性剂可使碳氢链排列由稀疏转变为密实, 层状相也相应地由“柔性双层”过渡到更加有序化的“平面双层”. 基于形状因子和体系内分子间作用力, 提出了层状相形成与有序化的机理, 同时采用分子模拟的方法展现了不同浓度下的液晶结构.     

CTAB在云母表面吸附的AFM研究

应用原子力显微镜技术(AFM)对十六烷基三甲基溴化胺(CTAB)在云母表面的吸附行为进行了研究. 结果表明在2 cmc的CTAB溶液中, CTAB分子在云母表面的吸附经历了从胶团→圆柱形→层状膜结构形貌的转变; 在0.5 cmc的CTAB溶液中, 表面活性剂分子在云母表面形成层状膜结构, 没有明显的结构转变; 同时CTAB分子在云母表面的吸附和云母表面脱落的周期性现象也被观察到.     

两亲分子溶液聚集体结构的冷冻刻饰电子显微镜研究

利用冷冻刻饰电子显微镜(FF-TEM)技术研究了两亲分子溶液不同有序聚集体的结构, 特别对一些两亲分子溶液体系形成的泡囊结构进行了详细的研究, 探讨了聚集体结构的演变规律. 对无剪切力下化学反应诱导L3-相(海绵相)到层状Lα-相, 手振荡层状Lα-相到多双层泡囊相及高剪切力作用下多双层泡囊相到单双层泡囊相的结构演变进行了冷冻刻饰电子显微镜追踪研究. 首次报道了-诱导的单链长表面活性剂溶液中泡囊相的形成.     

两亲分子溶液聚集体结构的冷冻刻饰

利用冷冻刻饰电子显微镜(FF-TEM)技术研究了两亲分子溶液不同有序聚集体的结构, 特别对一些两亲分子溶液体系形成的泡囊结构进行了详细的研究, 探讨了聚集体结构的演变规律. 对无剪切力下化学反应诱导L₃-相(海绵相)到层状Lα-相, 手振荡层状Lα-相到多双层泡囊相及高剪切力作用下多双层泡囊相到单双层泡囊相的结构演变进行了冷冻刻饰电子显微镜追踪研究. 首次报道了Zn²⁺-诱导的单链长表面活性剂溶液中泡囊相的形成.     

辛基三甲基溴化铵与辛基硫酸钠混合水溶液的相行为

对辛基三甲基溴化铵(OTAB)与辛基硫酸钠(SOS)正、负离子混合表面活性剂水溶液的相行为进行了研究.在高浓度的溶液中,混合表面活性剂形成液晶相,随着混合摩尔比OTAB/SOS接近于1,液晶结构由六角相转层状相,同时夹杂少量沉淀物;在中等浓度时,任意混合摩尔比例下皆为均相透明溶液;在低浓度下,在很宽的OTAB/SOS混合摩尔比的范围,出现双水相,其中的表面活性剂稀薄相,为不同大小的胶团与囊泡组成的稀溶液,另一表面活性剂富集相中则为数密度很大的囊泡聚集体,富集相对油溶性染料的增溶作用比非富集相高得多.     

Preparation of superhydrophobic silica films with honeycomb-like structure by emulsion method

Silica films with honeycomb-like structure were successfully obtained by emulsion method. Emulsion films prepared by the Dip-Withdrawing method were dried at 180 °C for 2 h and sintered at 500 °C, the films turned from superhydrophilic to superhydrophobic after being modified by octyltrimethoxysilane (OTMS) to form a self-assembled monolayer (SAM) with low surface energy. The surface structures and the thickness of the silica emulsion films were observed by scanning electron microscopy (SEM), and the results showed that the emulsion method had a similar effect to the phase separation one on producing the honeycomb-like structure that highly influenced the wettability of solid surface.     

Morphology control of polyacrylonitrile (PAN) fibers by phase separation technique

Based on the constructed theoretical ternary phase diagrams of water/dimethyl sulfoxide (DMSO)/polyacrylonitrile (PAN) terpolymer system, the phase separation behavior for PAN fibers preparation was investigated. Theoretical ternary phase diagrams were determined by the extended Flory‐Huggins theory. To investigate the temperature dependence of theoretical ternary phase diagrams, all binary interaction parameters at different temperatures were determined accurately and thoroughly revisited. From numerical calculations, it was found that a small quantity of water was needed to induce phase demixing. Meanwhile, the cloud point data of the system for more dilute PAN terpolymer solutions were determined by cloud point titration, and the cloud point data for more concentrated PAN terpolymer solutions were calculated by Boom's linearized cloud point (LCP) curve correlation. Furthermore, the morphology of PAN fibers was investigated by using scanning electron microscopy (SEM). With increasing the concentration of PAN terpolymer solutions as well as the quenching depth, the morphology of PAN fibers turns from large open channels to small bead‐like structures, accompanying with a reduction of the porosity of PAN fibers. Judging from our investigation, it was clear that the final morphology of PAN fibers was mainly determined by phase separation in fiber‐forming process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 261–275, 2009     

3D analysis of the lattice defects in the gyroid network structure of a block copolymer/homopolymer blend – The line-like defects in the gyroid network structure

The line-shaped defects formed in the gyroid bicontinuous microdomain structures in the solution-casting process of a blend of polystyrene-block-polyisoprene (SI) diblock copolymer and homopolystyrene (HS) were investigated using 3D electron tomography. The inclusion-type lattice defects composed of segregated HS formed during the morphological transition from the preexisted sponge phase to the stable gyroid phase induced by the phase separation between SI and HS. The gyroid grains grew by consuming the sponge phase and expelling excess HS as well as by impinging each other. Consequently, some expelled HS was trapped as the line-like inclusions in the gyroid grains. Structural rearrangement occurred so that low energy planes of the gyroid phase are facing the HS inclusions while the gyroid structure became continuous across/around the inclusions.     

Effect of cellulose nanofiber on the dynamically asymmetric phase separation in epoxy/polysulfone blends

Significant effect of cellulose nanofibers (CNFs) on cure‐induced phase separation in dynamically asymmetric system is reported. An epoxy/polysulfone blends with typical layered structure formation was chosen as the polymer matrix, and morphology evolution and rheological behavior of systems with different nano‐size fiber loadings upon curing reaction were investigated using optical microscopy and rheological measurement. CNF distributed uniformly in the polymer matrix and had good interaction with polymer chains. Curing reaction of epoxy was promoted by CNF, making the system gel and phase separate earlier. Meanwhile, system viscosity was increased with CNF addition, and the movement of polymer chains and component diffusion were constrained, as a result, the structure evolution process was slowed down. The CNF altered the final morphologies, resulting in refined structures with smaller characteristic length scales or even completely change the morphologies from the layered structures to a bicontinuous structure when the CNF concentration reached to a relatively high level. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1357–1366     

基于高分子软物质特性构建嵌段共聚物的非平衡相

利用高分子的弱影响强响应、熵致相变和多分散等软物质特性,以嵌段共聚物为例介绍了高分子非平衡相构建的研究结果:实现了特定化学组成的嵌段共聚物显示出多种有序相形貌,讨论了不依赖于嵌段组成的非平衡相的形成原因及演变规律.期望单一组成的高分子构成的多样性有序相结构能经济地满足高分子材料的多需求性.     

Phase Separation in Methylsiloxane Sol-Gel Systems in a Small Confined Space

The organo-siloxane gel with co-continuous structure derived from methyltrimethoxysilane (MTMS) was synthesized in a confined space between parallel plates by inducing spinodal decomposition during sol-gel transition. The resultant gel morphology was 3-dimensionally observed by laser scanning confocal microscopy (LSCM). The sliced LSCM photographs revealed that the confined gels have inhomogeneity perpendicular to the plate, exhibiting a layered structure. The layered structure can be divided into three regions according to their morphology; interface, near-surface layer, bulk phase. The organo-siloxane depletion layer had formed in the vicinity of both hydrophobic and hydrophilic plates, and the bulk phase had formed slight away from the plates exhibited co-continuous structure. In addition, the confined gels exhibited no shrinkage during drying process that resulted in the larger domain size compared to the monolithic gel. The attractive interaction between the plates and the resultant organo-siloxane phase accounts for the inhibition of shrinkage of confined gels.     

A Novel Solid-Solid Phase Change Material Based on Poly(styrene-co-acrylonitrile) Grafting With Palmitic Acid Copolymers

(SAN-g-PA) as new solid-solid phase change materials (SSPCMs) were synthesized starting from poly(styrene-co- acrylonitrile) (SAN) and palmitic acid (PA). The chemical structure of the synthesized SAN-g-PA were characterized with Fourier transform infrared (FTIR), and Nuclear Magnetic Resonance (¹H-NMR), their thermal energy storage properties and thermal stability were investigated with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. Moreover, the crystalline morphology and crystal structures were also measured with polarized optical microscopy (POM) and X-Ray Diffraction (XRD). The result shows that the PA molecule was grafted onto the SAN, SAN-g-PA were obtained successfully. The crystalline morphology and crystal structures of the synthesized SAN-g-PA are different from palmitic acid and SAN. As novel SSPCMs, SAN-g-PA possess suitable phase transition temperature, the higher enthalpy value, and good heat stability.     

Stimuli-Responsive Polymers in Solution Investigated by NMR and Infrared Spectroscopy

Summary: Temperature-induced and solvent composition-induced phase separation in solutions of poly(N-isopropylmethacrylamide) (PIPMAm) and other thermoresponsive polymers as studied by NMR and infrared (IR) spectroscopy is discussed. The fraction p of phase-separated units (units with significantly reduced mobility) and subsequently, e.g., thermodynamic parameters characterizing the coil-globule phase transition induced by temperature, were determined from reduced integrated intensities in high-resolution ¹H NMR spectra. This approach can be especially useful in investigations of phase separation in solutions of binary polymer systems. Information on behaviour of water during temperature-induced phase transition was obtained from measurements of ¹H NMR relaxation times of HDO molecules. NMR and IR spectroscopy were used to investigate PIPMAm solutions in water/ethanol (D₂O/EtOH) mixtures where the phase separation can be induced by solvent composition (cononsolvency). Some differences in globular-like structures induced by temperature and solvent composition were revealed by these methods.     

溶剂热合成法制备纳米颗粒自组装的线形和球形铜的硫化物

在130 ℃, 以水和乙二醇混合体系为溶剂, 无水硫酸铜和硫脲反应, 制备了不同物相结构和形貌的铜的硫化物. 通过扫描电镜(SEM)、透射电镜(TEM)、电子衍射(SAED)及X射线衍射(XRD)等技术, 对所得产物进行了表征. 结果表明, 溶剂中水含量的变化对铜的硫化物的物相影响不明显, 但显著影响其形貌; 反应时间对其物相和形貌都产生影响. 并对其形成机理进行了探讨.