Helical Toroids Self‐Assembled from a Binary System of Polypeptide Homopolymer and its Block Copolymer

Toroids and helices are fundamental geometrical structures in nature. Polymers can self‐assemble into various nanostructures, including both toroids and helices; however, nanostructures combining toroidal and helical morphologies (that is, helical toroids) are rarely observed. A binary system is reported containing polypeptide homopolymer and its block copolymer, which can hierarchically self‐assemble into uniform helical nanotoroids in solution. The formation of the helical toroids is a successive two‐step process. First, the homopolymers aggregate into fibrils and convolve into toroids, thereby resembling the toroidal condensation of deoxyribonucleic acid (DNA) chains. Second, the block copolymers self‐assemble on the homopolymer toroids and result in helical surface patterns. Additionally, the chirality of the surface helical patterns can be varied by the chirality of the polypeptide block copolymers.     

Poly(3-alkylthiophene) diblock copolymers with ordered microstructures and continuous semiconducting pathways

Conjugated rod-coil diblock copolymers self-assemble due to a balance of liquid crystalline (rod-rod) and enthalpic (rod-coil) interactions. Previous work has shown that while classical block copolymers self-assemble into a wide variety of nanostructures, when rod-rod interactions dominate self-assembly in rod-coil block copolymers, lamellar structures are preferred. Here, it is demonstrated that other, potentially more useful, nanostructures can be formed when these two interactions are more closely balanced. In particular, hexagonally packed polylactide (PLA) cylinders embedded in a semiconducting poly(3-alkylthiophene) (P3AT) matrix can be formed. This microstructure has been long-sought as it provides an opportunity to incorporate additional functionalities into a majority phase nanostructured conjugated polymer, for example in organic photovoltaic applications. Previous efforts to generate this phase in polythiophene-based block copolymers have failed due to the high driving force for P3AT crystallization. Here, we demonstrate that careful design of the P3AT moiety allows for a balance between crystallization and microphase separation due to chemical dissimilarity between copolymer blocks. In addition to hexagonally packed cylinders, P3AT-PLA block copolymers form nanostructures with long-range order at all block copolymer compositions. Importantly, the conjugated moiety of the P3AT-PLA block copolymers retains the crystalline packing structure and characteristic high time-of-flight charge transport of the homopolymer polythiophene (μ(h) ~10(-4) cm(2) V(-1) s(-1)) in the confined geometry of the block copolymer domains.     

Glycyrrhizic acid based self-assembled helical nanostructures as scaffolds for asymmetric Diels-Alder reaction

Glycyrrhizic acid (GA), as a traditional herbal, can self-assemble into helical nanofiber in the water. The formed helical nanostructures can be employed as scaffolds for asymmetric Diels-Alder reaction.     

Hierarchical Self‐Assembly in Liquid‐Crystalline Block Copolymers Enabled by Chirality Transfer

Helical topological structures are often found in chiral biological systems, but seldom in synthesized polymers. Now, controllable microphase separation of amphiphilic liquid‐crystalline block copolymers (LCBCs) consisting of hydrophilic poly(ethylene oxide) and hydrophobic azobenzene‐containing poly(methylacrylate) is combined with chirality transfer to fabricate helical nanostructures by doping with chiral additives (enantiopure tartaric acid). Through hydrogen‐bonding interactions, chirality is transferred from the dopant to the aggregation, which directs the hierarchical self‐assembly in the composite system. Upon optimized annealing condition, helical structures in film are fabricated by the induced aggregation chirality. The photoresponsive azobenzene mesogens in the LCBC assist photoregulation of the self‐assembled helical morphologies. This allows the construction and non‐contact manipulation of complicated nanostructures.     

Spectroscopic investigation on chirality transfer in additive-driven self-assembly of block polymers

Chiral supramolecules prepared by the additive-driven self-assembly of block copolymers provide a facile method to construct helical nanostructures. In this study, we investigated the chiral transfer from chiral tartaric acid to poly(styrene)-b-poly(ethylene oxide) using small-angle X-ray scattering, transmission electron microscopy, circular dichroism, and vibrational circular dichroism. The results showed that the chirality was transferred to both the segments of block copolymer irrespective of the interaction with the chiral additives and formation of helical phase structure. However, the chirality transfer was carried out using different methods: for poly(ethylene oxide) segments, the chirality transfer was carried out via direct hydrogen bond formation; for polystyrene segments, the chirality transfer was carried out via the cooperative motion of block copolymers during the thermal annealing.     

Ultrahigh density arrays of toroidal ZnO nanostructures by one-step cooperative self-assembly processes: mechanism of structural evolution and hybridization with Au nanoparticles

A quick protocol for the fabrication of ultrahigh density arrays of toroidal ZnO nanostructures with tailored structures on a substrate surface is presented based on the one-step spin coating of a common solution composed of inverse micelles of polystyrene-block-poly(4-vinyl pyridine) copolymers (PS-b-P4VP) and sol-gel precursors without the need of conventional complex lithographic techniques. ZnO toroids decorated with gold nanoparticles are also obtained by subsequent loading and reduction of metallic precursors. It was elucidated that the diethanolamine moiety in the sol-gel precursors, which induces selective swelling and structural reorganization of the P4VP core blocks, plays a key role in the generation of toroidal nanostructures. Toroidal ZnO nanostructures embedded in a PS-b-P4VP matrix films or arrays of pure wurtzite ZnO nanorings are obtained by calcination under inert atmosphere. The structural parameters of the toroidal nanostructures such as the width, height, diameter of the rims as well as the spacing of their 2D arrays are controlled by employing PS-b-P4VP with different molecular weight and varying the mixing protocols.     

Macromolecular self-assembly in dilute sequence-controlled block copolymer/homopolymer blends

Conventional block copolymers consist of two long contiguous monomer sequences (‘blocks’) that can, in the same fashion as low-molar-mass surfactants, self-assemble into various microstructural elements (e.g., micelles at low copolymer concentrations) to minimize repulsive contacts in the presence of a parent homopolymer. In this work, we explore the existence of segment-specific interactions, as well as the possibility of tailoring these blend morphologies (and producing altogether new ones), with novel sequence-controlled block copolymers. These copolymers are comprised of at least one block that is a random segment composed of both constituent monomer species. Transmission electron microscopy is employed here to examine the bilayered membranes and channel structures that form in two different series of such copolymers in dilute copolymer/homopolymer blends.     

Self-assembly of amphiphiles with terthiophene and tripeptide segments into helical nanostructures

We previously reported a class of tripeptide amphiphiles known as peptide lipids that self-assemble into one-dimensional nanostructures with superhelical twisting. The pitch of this supramolecular twisting is controlled directly through sterics in the molecular structure of hydrophobic segments. In this work we study the supramolecular behavior of these nanoscale helices by substituting with a terthiophene conjugated segment of potential electronic interest and also through variations in the stereochemistry of the tripeptide. This terthiophene peptide lipid was shown to self-assemble into one-dimensional helical nanofibers with a regular diameter of 9±1 nm and helical pitch of 65±6 nm, and also found to form hierarchical double- and triple-stranded helices, which could be associated with terthiophene J-aggregate interactions among fibers. For stereochemical effects, we compared four diastereomers in the tripeptide sequence using l-glutamic acid and l- and d-alanine residues to probe their ability to control supramolecular organization. Interestingly, we found by atomic force microscopy that the LLD diastereomers formed cylindrical nanofibers without any twisting, whereas LDD diastereomeric segments self-assembled into helical nanofibers with a pitch of 40±6 nm. LDL diastereomeric segments formed, on the other hand, aggregates without any regular shape. We propose that these profound effects of chirality with amino acid sequence are related to changes in the β-sheet sub-structure within the nanofibers.     

Crystallization-Driven Asymmetric Helical Assembly of Conjugated Block Copolymers and the Aggregation Induced White-light Emission and Circularly Polarized Luminescence

Controlling the self-assembly morphology of π-conjugated block copolymer is of great interesting. Herein, amphiphilic poly(3-hexylthiophene)-block-poly(phenyl isocyanide)s (P3HT-b-PPI) copolymers composed of π-conjugated P3HT and optically active helical PPI segments were readily prepared. Taking advantage of the crystallizable nature of P3HT and the chirality of the helical PPI segment, crystallization-driven asymmetric self-assembly (CDASA) of the block copolymers lead to the formation of single-handed helical nanofibers with controlled length, narrow dispersity, and well-defined helicity. During the self-assembly process, the chirality of helical PPI was transferred to the supramolecular assemblies, giving the helical assemblies large optical activity. The single-handed helical assemblies of the block copolymers exhibited interesting white-light emission and circularly polarized luminescence (CPL). The handedness and dissymmetric factor of the induced CPL can be finely tuned through the variation on the helicity and length of the helical nanofibers.     

Formation of nanostructured materials via coalescence of amphiphilic hollow particles

A new, simplified route to amphiphilic core-shell nanotubes, microfibers, and microrods has been developed that does not involve the traditional utilization of well-defined block copolymers. Thus, amphiphilic graft copolymers (PEI-g-PMMA) are prepared by an aqueous free radical polymerization that self-assemble in situ to form uniform core-shell nanoparticles. The hydrophobic homopolymer (PMMA) that is also formed is incorporated in the cores. Slight cross-linking of the shells followed by extraction of the homopolymer results in hollow nanoparticles that coalesce to form nanotubes. When the shells are not cross-linked, the hollow particles coalesce to form microrods and microfibers. The sizes and shapes of the micromaterials can be controlled by varying the experimental conditions.     

Crystallization‐Driven Asymmetric Helical Assembly of Conjugated Block Copolymers and the Aggregation Induced White‐light Emission and Circularly Polarized Luminescence

Controlling the self‐assembly morphology of π‐conjugated block copolymer is of great interesting. Herein, amphiphilic poly(3‐hexylthiophene)‐block‐poly(phenyl isocyanide)s (P3HT‐b‐PPI) copolymers composed of π‐conjugated P3HT and optically active helical PPI segments were readily prepared. Taking advantage of the crystallizable nature of P3HT and the chirality of the helical PPI segment, crystallization‐driven asymmetric self‐assembly (CDASA) of the block copolymers lead to the formation of single‐handed helical nanofibers with controlled length, narrow dispersity, and well‐defined helicity. During the self‐assembly process, the chirality of helical PPI was transferred to the supramolecular assemblies, giving the helical assemblies large optical activity. The single‐handed helical assemblies of the block copolymers exhibited interesting white‐light emission and circularly polarized luminescence (CPL). The handedness and dissymmetric factor of the induced CPL can be finely tuned through the variation on the helicity and length of the helical nanofibers.     

双刚性共轭嵌段共聚物体系的自组装

棒杆-棒杆(rod-rod)共轭嵌段共聚物体系是近几年发展起来的一类新型共轭聚合物材料,由于其特有的电学活性以及通过自组装实现纳米尺度结构可控等特性正逐渐成为人们研究的热点.构筑单元的刚性棒状结构使得rod-rod共轭嵌段共聚物体系倾向于自组装形成囊泡或层状结构等低曲率聚集体.本文总结了近年来关于rod-rod共轭嵌段共聚物体系自组装行为的研究,分别介绍了溶液中以及薄膜状态下双刚性共轭嵌段共聚物体系的自组装行为,在此基础上进一步讨论了rod-rod共轭嵌段共聚物薄膜结构与性能的关系.     

Assembly of an Achiral Chromophore into Light‐Responsive Helical Nanostructures in the Absence of Chiral Components

The chirality found in living organisms is one of unsolved mysteries on Earth. It is crucial to understand the manner in which small achiral molecules evolve into helical superstructures in the absence of chiral components because this process can provide important insights regarding the origin of chirality in nature. 1) the uncommon helical assembly of an achiral trigonal chromophore into helical nanostructures with aggregation‐induced emission enhancement (AIEE) characteristics and 2) the tunability of the helical pitch and fluorescence intensity in response to light is reported. The Rietveld refinement of X‐ray diffraction (XRD) patterns and the growth process suggest that a striking transformation from an achiral to an asymmetric molecule can occur as a result of specific interactions with certain solvents, presumably leading to the unique helical assembly. More importantly, exposure to UV or visible light promoted not only the formation of irregular helical structures with a wide range of pitch lengths but also an increase in fluorescence intensity.     

Deuterium N.M.R. studies of polypeptides I. Sidechain orientation in poly(γ-benzyl L-glutamate) and the mechanism of the cholesteric sense inversion

The mechanism of thermally- and solvent-induced cholesteric sense inversions in lyotropic polypeptide liquid crystals has been discussed based on deuterium N.M.R. observations for poly(γ-benzyl L-glutamate) with perdeuteriated sidechain benzyl ester groups. Comparison of the deuterium quadrupolar splitting pattern with the macroscopic helical twisting power indicates that the sense inversion does not necessarily require sidechain conformational transitions (or changes in the helix surface chirality). The new data support a less specific mechanism for sense determination in polypeptide liquid crystals: anisotropic intermolecular interactions between helices are influenced by the solvent dielectric medium.     

乙烯基二联苯单体的螺旋选择性自由基聚合

为了深入理解乙烯基二联苯单体自由基聚合过程中的手性传递,进行了手性单体(+)-2-[(S)-异丁氧羰基-5-(4′-己氧基苯基)苯乙烯、非手性单体2-丁氧羰基-5-(4′-己氧基苯基)苯乙烯的均聚反应及它们二者的共聚反应,探讨了聚合温度和溶剂性质对手性单体均聚物旋光活性、手性单体含量对共聚物旋光活性以及聚合反应溶剂的超分子手性对共聚物旋光活性的影响.研究发现,降低聚合温度、采用液晶性反应介质有利于得到旋光度大的聚合物;少量手性单体的引入即可诱导共聚物形成某一方向占优的螺旋构象,比旋光度随手性单体的含量增加呈线性增长;在胆甾相液晶中制备的非手性单体聚合物不具有光学活性.这些结果表明,该类乙烯基二联苯聚合物具有动态螺旋构象,其光学活性主要依赖于主链的立构规整度和侧基不对称原子的手性.     

Fabrication of metallized nanoporous films from the self-assembly of a block copolymer and homopolymer mixture

Inorganic compound HAuCl4, which can form a complex with pyridine, is introduced into a poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) block copolymer/poly(methyl methacrylate) (PMMA) homopolymer mixture. The orientation of the cylindrical microdomains formed by the P2VP block, PMMA, and HAuCl4 normal to the substrate surface can be generated via cooperative self-assembly of the mixture. Selective removal of the homopolymer can lead to porous nanostructures containing metal components in P2VP domains, which have a novel photoluminescence property.     

Nanorings from the self-assembly of amphiphilic molecular dumbbells

We have prepared amphiphilic dumbbell molecules consisting of hydrophobic alkyl chains and hydrophilic oligoether dendrons at each end of the rod segment. The molecular dumbbells, in aqueous solution, self-assemble into toroids as an intermediate nanostructure between spherical and long cylindrical micelles. The formation of toroidal structure is likely to originate from side by side connections of discrete bundles through the combination of strong hydrophobic interactions and anisotropic aggregation of rod segments.     

Fine tuning the assembly and gel behaviors of PEGylated polypeptide conjugates by the copolymerization of l‐alanine and γ‐benzyl‐l‐glutamate N‐carboxyanhydrides

Tuning the secondary structure of polypeptide is an effective strategy to modulate the assembly behaviors of polypeptide‐based copolymers. In this study, ring‐opening polymerization of l ‐alanine (Ala) and γ‐benzyl‐l ‐glutamate (BLG) N‐carboxyanhydrides was adopted using mPEG‐NH₂ as the initiator to prepare mPEG‐poly(l ‐alanine‐co‐γ‐benzyl‐l ‐glutamate) (PEAB) copolymers with various Ala to BLG ratios. ¹H NMR spectra and GPC test confirmed their well‐defined chemical structures. FT‐IR spectra indicated that at the powder state, all copolymers adopted both β‐sheet and α‐helical conformations. With the content of PBLG increased, the crystallization temperature and melting points of PEAB copolymers first rose then fell indicated by DSC curves. The self‐assembly of PEAB copolymers in dilute aqueous solution studied by DLS, TEM and circular dichroism spectra showed that PEAB copolymers self‐assembled into nanostructures with diverse morphologies and sizes due to distinct polypeptide conformations. Rheological analysis indicated that the alteration of the polypeptide composition can effectively modulate the modulus of PEAB assemblies in concentrated solutions. In all, copolymerization of two hydrophobic amino acid N‐carboxyanhydrides into the polypeptide block maybe an effective approach for modulating the assembly properties of PEGylated polypeptide. Besides, nanosilver‐encapsulated PEA or PEAB hydrogel showed promising antibacterial effect against Staphylococcus aureus and Bacillus subtillis. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1512–1523     

Main-Chain Chirality and Optical Activity in Polymers Consisting of C?C Chains

Main-chain chirality is the optical activity resulting from the configurational or conformational arrangement in the main chain of a polymer. The chirality of the most important types of structures has been investigated on the basis of systematic considerations of symmetry. This has led to the surprising result that even in polymers derived from 1-substituted or nonsymmetric 1,1-disubstituted olefins (the technologically most important polymers) several types of chiral structures exist, which are expected to result in optical activity if a particular enantiomer is favorably formed. By carrying out an asymmetric cyclopolymerization, it has been possible to obtain certain structural types in the form of optically active copolymers or homopolymers (e.g., copolymers of styrene with methyl methacrylate, or even the homopolymer of styrene). Another new group of optically active polymers consists of the atropisomeric helical polyisocyanides, poly(trityl methacrylates), and polychlorals. Optically active polymers are already used as adsorbents for the chromatographic separation of racemic mixtures. Further applications are likely to emerge.     

Self-assembled architectures from biohybrid triblock copolymers

The synthesis and self-assembly behavior of biohybrid ABC triblock copolymers consisting of a synthetic diblock, polystyrene-b-polyethylene glycol (PSm-b-PEG113), where m is varied, and a hemeprotein, myoglobin (Mb) or horse radish peroxidase (HRP), is described. The synthetic diblock copolymer is first functionalized with the heme cofactor and subsequently reconstituted with the apoprotein or the apoenzyme to yield the protein-containing ABC triblock copolymer. The obtained amphiphilic block copolymers self-assemble in aqueous solution into a large variety of aggregate structures. Depending on the protein and the polystyrene block length, micellar rods, vesicles, toroids, figure eight structures, octopus structures, and spheres with a lamellar surface are formed.