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The impact of tetragonal crystal symmetry on the two-dimensional (2D) confined polymer nanostructure is demonstrated. Our research shows that this chain packing defect in the tetragonal cell can be controlled to develop along the rod long axis in 2D confinement., The symmetry of polymer crystals greatly affects the optical, thermal con­ductivity and mechanical properties of the materials. Past studies have shown that the two-dimensional (2D) confined crystallization of polymer nanorods could produce anisotropic structures. However, few researchers have focused on understanding confined nanostructures from the perspective of crystal sym­metry. In this research, we demonstrate the molecular chain self-assembly of tetragonal crystals under cylindrical confinement. We specifically selected poly(4-methyl-1-pentene) (P4MP1) with a 41 or 72 helical conformation (usually crystallizing with a tetragonal lattice) as the model polymer. We found a coherent crystal branching of the tetragonal crystal in the P4MP1 nanorods. The unusual 45°- and 135°-{200} diffractions and the meridional 220 diffraction (from 45°-tilted crystals) have shown a uniform crystal branching between the a 1-axis crystals and the 45°-tilted crystals in the rod long axis, which originates from a structural defect associated with tetragonal symmetry. Surprisingly, this chain packing defect in the tetragonal cell can be controlled to develop along the rod long axis in 2D confinement.

We have successfully synthesized a series of monodispersed chain-like giant molecules with precisely controlled macromolecular composition and sequence based on polyhedral oligomeric silsesquioxane (POSS) nanoparticles using an orthogonal “click” strategy. Their nonspherical supramolecular structures, such as lamellae, double gyroids, and hexagonal packed cylinders, are mainly determined by the composition (namely, the number of incorporated amphiphilic nanoparticles). In addition, by precisely alternating the sequence of arranged nanoparticles in the giant molecules with identical chemical compositions, the domain sizes of their supramolecular structures could be fine-tuned. This is attributed to the macromolecular conformational differences caused by collective hydrogen bonding interactions in each set of sequence isomeric giant molecules. This work has demonstrated multilevel manipulation of supramolecular structures of giant molecules: coarse tuning by composition and fine-tuning by sequence.

Controlled assembly of nanoscale building blocks is a promising approach to obtain functional materials with unique properties. Here, we report a way to manipulate the supramolecular structures of ...

It has been recognized that macromolecular chains can self-assemble into a hierarchical structure from lamellae to spherulites in bulk crystallization. However, little account has been taken of crystal symmetry effects on the hierarchical nanostructure in polymers under cylindrical confinement. In this research, a model polymer, nylon 6,12, most commonly occurring in the triclinic α phase, was chosen in order to demonstrate the effect of triclinic symmetry on the 2D-constrained polymer nanostructure. The self-arranging unit of nylon 6,12 takes various forms, including stems, unit cells, hydrogen-bonded sheets, lamellae and complex spherulites, which is an essential structural feature for investigating hierarchical nanostructure. The rod nanostructure in confinement was examined by cross-checking electron and X-ray diffraction techniques. It is found that the a* axis of the α-phase cell is inclined at about ±6–11° to the rod long axis within the a*b* plane around the c axis (c axis ⊥ rod long axis). The rotation of the a*b* plane most likely results from the impact of the triclinic symmetry on the molecular chain packing under 2D confinement. A mechanism for this a*b* plane tilting is proposed.

In this work, we studied the linker effect on the nanostructures of a serious of specifically designed, functionalized polyhedral oligomeric silsesquioxane (POSS) based Dendron-like macro-isomers. The varying linkers between hydrophilic and hydrophobic POSS cages lead to topological isomers with identical composition but different molecular shapes. Their unique phase behaviors highlight remarkable effects of molecular architectures on the formation of nanostructures. Due to topological constraints, these macro-isomers assume either a fan- or a cone-molecular shape, which assembles into either hexagonally packed cylindrical phase (HEX) or Frank-Kasper A15 phase. This work provides guiding rules on designing precise molecular nanostructures with desired properties via linker engineering.

How biomembranes are self-organized to perform their functions remains a pivotal issue in biological and chemical science. Understanding the self-assembly principles of lipid-like molecules hence becomes crucial. Herein, we report the mesostructural evolution of amphiphilic sphere-rod conjugates (giant lipids), and study the roles of geometric parameters (head-tail ratio and cross-sectional area) during this course. As a prototype system, giant lipids resemble natural lipidic molecules by capturing their essential features. The self-assembly behavior of two categories of giant lipids (I-shape and T-shape, a total of 8 molecules) is demonstrated. A rich variety of mesostructures is constructed in solution state and their molecular packing models are rationally understood. Giant lipids recast the phase behavior of natural lipids to a certain degree and the abundant self-assembled morphologies reveal distinct physiochemical behaviors when geometric parameters deviate from natural analogues.

The bottom-up construction of Frank–Kasper (FK) phases in soft matter requires intricating tuning to balance entropic and enthalpic interactions. In contrast, sophisticated rules have been established in Metallurgy to dictate the packing structures of metal alloys. Inspired by alloy metallurgy, we develop a new self-sorting approach to construct nanostructures in condensed soft matters. This approach utilizes blends of nano-sized giant molecules to construct supramolecular motifs (“mesoatoms”) with controlled size heterogeneity, which is the key in rational design of diverse FK nanostructures. Especially, the scarcely observed thermodynamically stable Laves C14 and C15 phases are widely found. This approach sheds light on next-generation material engineering which allows nanostructure construction in a more predictable and straightforward way

We have designed and synthesized a pair of sequence isomeric giant surfactants based on polystyrene (PS) and polyhedral oligomeric silsesquioxane (POSS) nanoparticles. Although these two macromolecules possess identical compositions as “sequence isomers”, the distinctly arranged POSS sequences lead to different molecular packing conformations, and further induce distinguished self-assembly behaviors in DMF/water solutions.

Visible-light-induced living radical polymerization of acrylates (MA, nBA, tBA), acrylamides (DMA, AMO), and vinyl acetate (VAc) at ambient temperature mediated by (salen)Co(II)/TPO was described. Effects of light intensity, feeding ratio of monomer and equivalent of TPO for the polymerization of MA were investigated. Well-defined homopolymers and block polymers with predetermined molecular weight and narrow polydispersity were obtained under mild conditions. The mechanism of the polymerization was proposed based on polymerization behavior and polymer structure analysis. The (salen)Co(II)/TPO system was suitable for both conjugated and unconjugated monomers under mild conditions.

The control of the polymerization of a wide range of monomers under mild conditions by a single catalyst remains a major challenge in polymer science. We report a versatile, well-defined organocobalt salen complex to control living radical polymerization of different categories of monomers, including acrylates, acrylamides and vinyl acetate, under visible light irradiation at ambient temperature. Both household light and sunlight were effectively applied in the synthesis of polymers with controlled molecular weights and narrow polydispersities. Narrowly dispersed block copolymers (Mw/Mn < 1.2) were obtained under various conditions. The structures of the polymers were analyzed by 1H NMR, 2D NMR, 13C NMR, GPC, MALDI-TOF-MS and isotopic labeling experiments, which showed that the ω and α ends of the polymer chains were capped with (salen)Co and -CO2CH3 segments, respectively, from the photoinitiator (salen)Co-CO2CH3. The ω end was easily functionalized through oxygen insertion followed by hydrolysis from 18O2 to -18OH. This robust system can proceed without any additives, and offers a versatile and green way to produce well-defined homo and block copolymers.

Visible light induced living radical polymerization of a wide scope of acrylates mediated by organocobalt porphyrins was developed. The photocleavage of the Co–C bond of organocobalt porphyrin produced carbon centered radicals, which initiated polymerization, and porphyrin cobalt(II), a persistent metal-centered radical. The organocobalt porphyrins were highly sensitive to external visible light irradiation so that photostimulus was used to control the initiation steps and regulate chain growth by reversibly activating the Co–C bond. Polymerization occurred spontaneously under irradiation and stopped promptly once shutting down light source. The scope of monomers was successfully extended from acrylamides to various hydrophobic and hydrophilic acrylates via the control of the light intensity. The structure of polyacrylate obtained was confirmed by 2D NMR, 13C NMR, GPC, and MALDI-TOF-MS. One of the unique features of this neat visible light induced polymerization process is that organocobalt porphyrins pla...

Understanding polymer nanostructures is a prerequisite to manipulate their physical properties. Molecular self-assembly under confinement effectively generates novel polymer nanostructures. However, in one confined system, diffraction signals of different nanostructures are merged in a typical two-dimensional (2D) wide-angle X-ray diffraction (WAXD) measurement. For comparison, selected-area electron diffraction (SAED) of transmission electron microscopy can precisely capture the “local” diffraction signal of an individual nanoscale entity. Here, using isotactic polypropylene (i-PP) as a model polymer, we have demonstrated a cross-analysis of global X-ray and local electron diffraction results to fully reveal the structural details of i-PP nanorods. For the first time, we have decomposed completely the “mixed” 2D WAXD patterns of i-PP nanorods into five types of α-phase nanostructures: (a). Left-tilted daughter crystals; (b) Right-tilted daughter crystals; (c) Double-tilted daughter crystals; (d) a*-axis oriented crystals; (e) b-axis oriented crystals.

A well-defined organocobalt salen complex (salen)Co–CO2CH3 is used as a versatile photoinitiator for visible light-initiated living radical polymerization., The control of the polymerization of a wide range of monomers under mild conditions by a single catalyst remains a major challenge in polymer science. We report a versatile, well-defined organocobalt salen complex to control living radical polymerization of different categories of monomers, including acrylates, acrylamides and vinyl acetate, under visible light irradiation at ambient temperature. Both household light and sunlight were effectively applied in the synthesis of polymers with controlled molecular weights and narrow polydispersities. Narrowly dispersed block copolymers (M w/M n < 1.2) were obtained under various conditions. The structures of the polymers were analyzed by 1H NMR, 2D NMR, 13C NMR, GPC, MALDI-TOF-MS and isotopic labeling experiments, which showed that the ω and α ends of the polymer chains were capped with (salen)Co and –CO2CH3 segments, respectively, from the photoinitiator (salen)Co–CO2CH3. The ω end was easily functionalized through oxygen insertion followed by hydrolysis from 18O2 to –18OH. This robust system can proceed without any additives, and offers a versatile and green way to produce well-defined homo and block copolymers.