Fabrication of virus-like particles with strip-pattern surface: A two-step self-assembly approach

Spherical nanostructures with striped patterns on the surfaces resembling the essential structures of natural virus particles were constructed through a two-step self-assembly approach of polystyrene-boligo(acrylic acid)(PS-b-oligo-AA) and poly(γ-benzyI L-glutamate)-b-poly(ethylene glycol)(PBLG-bPEG) copolymer mixtures in solution.On the basis of difference in hydrophilicity and self-assembly properties of the two copolymers,the two-step self-assembly process is realized.It was found that PS-boligo-AA copolymers formed spherical aggregates by adding a certain amount of water into polymer solutions in the first step.In the second step,two polymer solutions were mixed and water was further added,inducing the self-assembly of PBLG-b-PEG on the surfaces of PS-b-oligo-AA spheres to form striped patterns.In-depth study was conducted for the indispensable defects of striped patterns which are dislocations and +1/2 disclinations.The influencing factors such as the mixing ratio of two copolymers and the added water content in the first step on the morphology and defects of the striped patterns were investigated.This work not only presents an idea to interpret mechanism of the cooperative self-assembly behavior,but also provides an effective approach to construct virus-like particles and other complex structures with controllable morphology.     

Self-assembly behavior of rod-coil-rod triblock copolymers within a planar slit

The self-assembly behavior of sphere-forming R₅C₃₀R₅ triblock copolymers within a planar slit is studied by performing dissipative particle dynamics simulations. A sequence of novel structures which are not observed in bulk are formed within slits, including wetting layers, island-like structure, parallel cylinders, perpendicular cylinders and cross-cylindrical structures. Perpendicular cylinders are always formed before the increase in the layers of parallel cylinders. A phase diagram of the assembled structures with respective to the slit property and height is thus presented. The rod length is found to have a significant impact on the rod alignment, and a disordered-ordered transition of rod orientation occurs with an increase in the length of rod blocks. Some special structures, such as parallel half-cylinders and arrowhead-shaped morphology, are observed when the rod length increases to a certain extent. Our results show that the property and height of the slit and rod length all influence the self-assembly of rod-coil-rod triblock copolymers.     

掺杂态聚苯胺蜂窝状有序多孔薄膜的制备及形成机制的探讨

近年来,由于微米、亚微米及纳米级有序多孔结构薄膜可以用于催化、生物培养基材、分离或吸附介质、光子晶体等诸多方面从而引起了科学家们极大的研究兴趣^[1～6].微制作是使材料表面具有新性能的重要手段,激光刻蚀及其相关技术已经被应用于不同表面的微图案化和微器件的制作^[7],另外,还可通过自组装技术进行多孔薄膜的制备^[8,9].Francois等^[10]于1994年首次提出了水辅助方法(Water-A ssisted Fab-rication),即在高湿度的环境下,以冷凝水滴为模板,在固体基片上制备了孔径分布均一,排列紧密的蜂窝状有序多孔薄膜.继而人们对此方法做了进一步的研究,不仅突破了最初的聚苯乙烯及其共聚物体系^[10～13],而且使用双亲共聚物^[14]、聚离子复合物^[15]和TiO₂前驱体的混合物^[16]等成功地获得了蜂窝状有序多孔薄膜,同时系统地研究了成膜体系及成膜条件对形成蜂窝状有序多孔薄膜的影响,并对形成机制进行了探讨.聚苯胺是典型的导电高分子,有关聚苯胺有序多孔结构薄膜的研究已有报道^[17～19].本文采用水辅助方法,在高湿度环境下,使用4-十二烷基苯磺酸掺杂的聚苯胺(PANI-DBSA)为成膜材料,制备了双层蜂窝状有序多孔薄膜,并通过原子力显微镜(A FM)对薄膜的形貌和电学性质进行了表征.同时在已有成膜机制的基础上,提出了该双层蜂窝状有序多孔薄膜的形成机制.     

Self-Assembly Behaviors of Heterogemini Surfactant in Aqueous Solution Investigated by Dissipative Particle Dynamics

As a preliminary study, self-assembly behaviors of heterogemini surfactant in aqueous solution are explored tentatively by means of dissipative particle dynamics simulation. Five kinds of heterogemini molecules are involved, and a variety of novel morphologies have been obtained. Results based on detailed comparisons among themselves and with traditional symmetric gemini surfactant show the proportion of hydrophilic to hydrophobic chain lengths in one monomer is the most important, more difference between proportions in the two monomers can induce more diverse self-assembly morphologies. The second important is the hydrophilic chain length, in which a small change can lead to obvious difference in self-assembly behaviors. While the length of hydrophobic chain has a less important influence, only the concentration for self-assembly morphologies appearing can be affected by its change. The microscopic morphology of heterogemini surfactant in its self-assembly structure can be embodied through its radius of gyration. Our simulation results can undoubtedly provide a theoretical guide to further research towards self-assembly behaviors of heterogemini surfactants and practical applications of these matters.     

Self-assembly of poly(ionic liquid)s: polymerization, mesostructure formation, and directional alignment in one step

This paper reports on the highly ordered and tunable inner structure of poly(ionic liquid) nanoparticles, which formed spontaneously by precipitation polymerization from water. Without added stabilizer, these "latexes" are much smaller (20-40 nm in diameter) than usual polymer latexes and exhibit either multilamellar or unilamellar vesicular morphology, depending on the tail length of the quaternizing alkyl chains. The simplicity in the synthesis and composition and the high complexity of the ordered structures that resemble liposomes expand the classical profile of homopolymer self-assembly. In addition, unidirectional superassembly to a nanoworm mesostructure is found at elevated concentrations, indicating that the ionic liquid liposomes are apt to integrate into further hierarchical assembly schemes.     

原位透射电子显微镜观察电荷驱动的氧化物纳米颗粒水中自组装

以四氧化三钴Co_3O_4纳米棒为研究对象,我们利用液体环境透射电子显微镜,原位观察了四氧化三钴纳米棒在水中的自组装过程。研究发现在电子束辐照的水环境下,四氧化三钴纳米棒的晶面存在互补式自组装现象。随着纳米棒之间的距离越来越近,纳米棒之间的相对运动速率逐渐增加,纳米棒之间的相互作用力逐渐增加。通过进一步分析纳米棒的形貌发现,纳米棒的暴露晶面大多数为{100}、{110}以及{111}晶面,而Co_3O_4属于极性氧化物,这些晶面往往会带有一定的电荷。在液体环境下,正是由于这些易暴露面都带有不同大小的电荷,在晶面电荷的驱动下,电荷属性相反的四氧化三钴纳米棒会互相吸引,形貌结构上进行互补,实现快速驱动的纳米棒之间自组装。     

Rapid self-assembly of oligo(o-phenylenediamine) into one-dimensional structures through a facile reprecipitation route

The self-assembly of oligo(o-phenylenediamine) (OPD) into 1-D nanostructures on a macroscopic length scale was found when they were transferred from N-methyl pyrrolidone to deionized water. Field emission scanning electron microscopy and confocal fluorescence microscopy were used to investigate the morphology of the precipitates. Results showed that large amounts of OPD 1-D supertructures could be obtained through the simple reprecipitation route, and the length of the fibers could be tuned from microscale to macroscale by adjusting the ratio of two solvents. X-ray diffraction patterns and UV-vis spectra revealed that pi-pi interactions between OPD molecules that facilitated the formation of 1-D structures became predominant when they were transferred from a good solvent to a bad one. Accordingly, a possible formation mechanism was proposed.     

Fabrication of functional nano-objects via self-assembly of nanostructured hybrid materials

A simple route to fabricate functional nano-objects via self-assembly of block copolymer-based hybrid materials is described. In water–toluene mixtures, spheres, rod-like morphologies, and ring-like morphologies as well as vesicles of metal loaded block copolymers micelles are fabricated. The concept is generic to realize different functionalities by incorporating various inorganic components (Au, Ag, Pt, Co…) into the block copolymer matrix. A mechanism describing the formation of micellar aggregates with different morphologies is presented based on a simple force balance approach. Moreover, the composition of the solvent mixture is modified to gain control over the morphology of micellar aggregates. It was found that swelling of the micelle core with a selective cosolvent is the driving force to induce morphology transitions from spherical to rod- and ring-like structures as well as vesicles. These nano-objects can be further used as building blocks to construct well-defined structures via self-assembly in spin coated thin films. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1642–1650, 2010     

有序自组装聚合物纳米结构

采用水辅助方法(water-assisted fabrication method),分别以4-十二烷基苯磺酸掺杂的聚苯胺(PANI-DBSA)和聚2-甲氧基-5-(2′-乙烯基-己氧基)苯乙炔(MEH-PPV)两种功能高聚物为成膜材料,冷凝水滴为模板,利用水滴在聚合物溶液表面的自组装,制备出了两种纳米层次以上的蜂窝状有序多孔聚合物薄膜.通过原子力显微镜和共聚焦荧光显微镜对其形貌、电学性质和荧光图像进行了表征.     

端基结构对超支化聚合物静电吸附自组装行为的影响

研究了3种具有相同骨架结构、不同端基的超支化聚合物与线型聚阳离子(PDAC)的静电吸附自组装.结果表明,超支化聚合物的组装过程与线型弱酸聚合物相似,都受溶液pH值与无机盐浓度的影响,但影响程度随端基结构不同而变化.此外,对以超支化聚合物为最外层的不同自组装膜的表面形貌及接触角进行了表征,其表面形貌及亲水性随端基结构的不同而不同.     

含蜜胺基团的新型苝酰亚胺染料的合成及纳米纤维的构筑

合成了一种含三嗪基团的新型苝酰亚胺染料(T-PTCD), 并对其分子结构进行了确认. 考察了溶剂的极性和溶剂体积比等因素对相转移法和快速溶剂扩散法制备的T-PTCD聚集体形貌结构的影响. 结果表明, 以甲醇和三氯甲烷分别作为"不良"溶剂和"良"溶剂, 低体积比甲醇/氯仿在一定程度上有利纳米纤维的形成; 当体积比为1:4时, 采用相转移法可制备出直径大约100 nm左右, 长度为几十微米的结构规整的纳米纤维.     

两亲性Janus粒子在蜂窝状多孔聚合物膜上的自组装性能

采用具有两亲性的两面体(Janus)粒子实现稳定的粒子界面组装与水滴模板法自组装过程相结合的方法获得了粒子在蜂窝状多孔聚合物薄膜内壁的高效定向修饰.通过与均质粒子组装形貌的对比,证明了Janus粒子因其特殊的界面自组装活性,可以获得高粒子加量条件下的规则多孔结构,解决了使用均质粒子时存在的结构有序性和粒子修饰密度之间的矛盾.而在较低粒子加量的条件下,Janus粒子也展示出与均质粒子极为不同的组装形貌.这一方法的建立,为新型表面功能化材料的制备提供了一个新的思路.     

Effect of ionic strength on the self-assembly, morphology and gelation of pH responsive β-sheet tape-forming peptides

Molecular self-assembly is an intrinsic property of proteins central to their biological functionality. One important industrially interesting property is the ability to control and switch on and off self-assembly using a variety of external chemical and physical triggers. Model peptides have been developed with significantly reduced chemical and structural complexity compared to biological proteins. These are ideal systems for exposing the fundamental principles that drive protein-like self-assembly, as well as for establishing in a quantitative manner their structure-function relationship. We investigate simple, short model peptides that adopt a purely β-strand conformation, align in an antiparallel manner and self-assemble in one dimension in solution into long β-sheet nanotapes and higher order aggregates with no other conformation (i.e., helices, turns or random coils) present in the aggregates. These micrometre-long nanostructures gel in solutions at concentrations as low as 0.2% v/v. Their gel-fluid transition has been previously shown to be controlled by pH, temperature, or by mixing with complementary peptides. Here we show the dramatic effect of another chemical trigger, that of physiological-like salt concentration, on the self-assembly, morphology and gelation of a series of systematically designed charged self-assembling tape-forming peptides, each 11 amino acid residues in length, in the pH range of 2-14. This study provides a detailed understanding of the self-assembly of this class of peptides in aqueous solutions of biologically relevant pH and ionic strength. This insight has led to the development of injectable self-assembling peptide lubricants as potential therapeutics for the treatment of early stage knee joint osteoarthritis.     

Design and characterization of programmable DNA nanotubes

DNA self-assembly provides a programmable bottom-up approach for the synthesis of complex structures from nanoscale components. Although nanotubes are a fundamental form encountered in tile-based DNA self-assembly, the factors governing tube structure remain poorly understood. Here we report and characterize a new type of nanotube made from DNA double-crossover molecules (DAE-E tiles). Unmodified tubes range from 7 to 20 nm in diameter (4 to 10 tiles in circumference), grow as long as 50 microm with a persistence length of approximately 4 microm, and can be programmed to display a variety of patterns. A survey of modifications (1) confirms the importance of sticky-end stacking, (2) confirms the identity of the inside and outside faces of the tubes, and (3) identifies features of the tiles that profoundly affect the size and morphology of the tubes. Supported by these results, nanotube structure is explained by a simple model based on the geometry and energetics of B-form DNA.     

银纳米粒子的一步合成与表征

在水和乙醇溶液中,以对巯基苯胺作为还原剂,利用一步法合成了银纳米微粒,并利用拉曼光谱仪考察了对巯基苯胺在银纳米微粒表面的自组装行为.结果表明,合成的银纳米微粒的形貌与介质的pH值密切相关;对巯基苯胺可在银纳米微粒表面自组装.     

SELF-ASSEMBLY OF ROD-COIL DIBLOCK COPOLYMERS——INFLUENCE OF THE ROD LENGTH

The self-assembly of five narrowly distributed novel rod-coil diblock copolymers, poly(styrene-block-(2, 5-bis[4-methoxy-phenyl]oxycarbonyl) styrene) (PS-b-PMPCS), in p-xylene, a selective solvent at room temperature, was studied. Therod-coil copolymers, which have the same PS length but different PMPCS length, were synthesized by 2,2,6,6-tetramethyl-I-piperidinyloxy (TEMPO) mediated living free radical polymerization. The influence of the rod length on the self-assemblymorphology was studied by transmission electron microscopy (TEM). At a concentration of 2.0 mg/mL, those copolymerswith relatively shorter PMPCS length (copolymers 1 and 2) form individual spherical micelles; those with relatively longerPMPCS length (copolymer 3 and 4) form "pearl chains" coexisting with individual spherical micelles; the ones with longestPMPCS length form "pearl chains" coexisting with occasionally formed nanofibers. The diameter of all the morphologieswas controlled by the rod length. This gives us a way to govern the self-assembly morphology by altering the length of oneblock in the block copolymer.     

离子液体表面活性剂在水溶液中的自组装及其调控研究进展

离子液体表面活性剂在化学合成、材料制备和环境污染控制等方面的应用与它们在水溶液中的自组装及其微观结构密切相关。因此,研究离子液体表面活性剂在水溶液中的自组装行为具有重要的意义。本文重点综述了阳离子的结构、阴离子的类型、外加电解质、有机添加剂、环境因素(温度、溶液pH值和光)等对离子液体表面活性剂在水中的自组装行为以及对组装体结构影响的研究进展,总结了这些因素对离子液体表面活性剂在水中自组装的调控规律,展望了该领域的发展方向及面临的挑战。     

Tuning of Morphology by Chirality in Self-Assembled Structures of Bis(Urea) Amphiphiles in Water

We present the synthesis and self-assembly of a chiral bis(urea) amphiphile and show that chirality offers a remarkable level of control towards different morphologies. Upon self-assembly in water, the molecular-scale chiral information is translated to the mesoscopic level. Both enantiomers of the amphiphile self-assemble into chiral twisted ribbons with opposite handedness, as supported by Cryo-TEM and circular dichroism (CD) measurements. The system presents thermo-responsive aggregation behavior and combined transmittance measurements, temperature-dependent UV, CD, TEM, and micro-differential scanning calorimetry (DSC) show that a ribbon-to-vesicles transition occurs upon heating. Remarkably, chirality allows easy control of morphology as the self-assembly into distinct aggregates can be tuned by varying the enantiomeric excess of the amphiphile, giving access to flat sheets, helical ribbons, and twisted ribbons.     

The self-assembly of asymmetric block copolymers in films contacting a patterned surface

The preparation of ordered high-density polymer layers via the combined method of templated self-assembly is discussed. This approach combines the advantages of guided self-assembly of block copolymers and lithography on a topographical or chemical pattern. To implement the approach, a simulation has conducted for the first time through the use of the dissipative particle dynamics method in the NPAT ensemble. The pattern replication by asymmetric copolymers that form cylindrical phases in the bulk owing to their self-assembly near the patterned surface is studied. The effects of three patterns are described, i.e., hexagonal, rectangular, and triangular, which are characterized by one or two length scales. It is shown that the dense hexagonal pattern and the sparse rectangular and triangular patterns induce vertically oriented cylindrical domains in a thin film. The control of the orientation and ordering in the formed morphology heavily depends on the interaction between the minority component and the pattern. This effect is global in nature: The surface pattern propagates into the bulk of a film. In the case of rectangular and triangular patterns, two- and fourfold increases in their quantitites in the bulk are observed.     

Tubular or subsurface morphology of octabutoxyphthalocyanine upon self-assembly in polymer matrices: effect of the casting solvent

Spontaneous phase-separated, controlled aggregate structures of photo- and electroactive molecules in polymer matrices are of interest for device fabrication. We show that the self-assembly of octabutoxyphthalocyanine (Pc) in polymer matrices leads to tubular morphology of Pc when the film is prepared with tetrachloroethane (TCE) and subsurface droplet morphology with chloroform. The same morphology is seen with both bisphenol A polycarbonate (BPAPC) and poly(methyl methacrylate) (PMMA) as the matrix. The subsurface morphology results from the rapid association of Pc in the polymer matrix, as the film forms. With the tubular morphology in the films prepared with TCE, percolation threshold is reached with a concentration of Pc as low as 3% (wt) in the polymer. Such phase-separated self-assembly occurs, without any annealing of the films. Even in the absence of the polymer, Pc crystallized from TCE also shows tubular morphology, whereas it exhibits a columnar morphology with chloroform. X-ray diffraction of Pc crystallized from either solvent shows the columnar stacking of the Pc molecules. However, the morphology is tubular when TCE is used. We attribute the difference in the morphology to the higher viscosity of TCE and the diffusion-limited growth, which causes the tubular morphology, whereas the instantaneous self-assembly in less-viscous chloroform leads to droplets. The solvent effect observed here could be used to tailor the morphology of such photoconductive molecules in polymer matrices.