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This work demonstrates an effective and robust approach to regulate phase behaviors of a block copolymer by programming local features into otherwise homogeneous linear chains. A library of sequence-defined, isomeric block copolymers with globally the same composition but locally different side chain patterns were elaborately designed and prepared through an iterative convergent growth method. The precise chemical structure and uniform chain length rule out all inherent molecular defects associated with statistical distribution. The local features are found to exert surprisingly pronounced impacts on the self-assembly process, which have yet to be well recognized. While other molecular parameters remain essentially the same, simply rearranging a few methylene units among the alkyl side chains leads to strikingly different phase behaviors, bringing about (i) a rich diversity of nanostructures across hexagonally packed cylinders, Frank-Kasper A15 phase, Frank-Kasper σ phase, dodecagonal quasicrystals, and disordered state; (ii) a significant change of lattice dimension; and (iii) a substantial shift of order-to-disorder transition temperature (up to 40 °C). Different from the commonly observed enthalpy-dominated cases, the frustration due to the divergence between the native molecular geometry originating from side chain distribution and the local packing environment mandated by lattice symmetry is believed to play a pivotal role. Engineering the local chain feature introduces another level of structural complexity, opening up a new and effective pathway for modulating phase transition without changing the chemistry or composition.

The inherent statistical heterogeneities associated with chain length, composition, and architecture of synthetic block copolymers compromise the quantitative interpretation of their self-assembly process. This study scrutinizes the contribution of molecular architecture on phase behaviors using discrete ABA triblock copolymers with precise chemical structure and uniform chain length. A group of discrete triblock copolymers with varying composition and symmetry were modularly synthesized through a combination of iterative growth methods and efficient coupling reactions. The symmetric ABA triblock copolymers self-assemble into long-range ordered structures with expanded domain spacings and enhanced phase stability, compared with the diblock counterparts snipped at the middle point. By tuning the relative chain length of two end blocks, the molecular asymmetry reduces the packing frustration, and thus increases the order-to-disorder transition temperature and enlarges the domain sizes. This study would serve as a quantitative model system to correlate the experimental observations with the theoretical assessments and to provide quantitative understandings for the relationship between molecular architecture and self-assembly.

This work describes the first rigorous example of a single-component block copolymer system forming unconventional spherical phases. A library of discrete block polymers with uniform chain length and diverse architectures were modularly prepared through a combination of a step-growth approach and highly efficient coupling reactions. The precise chemical structure eliminates all the molecular defects associated with molar weight, dispersity, and compositional ratio. Complex spherical phases, including the Frank–Kasper phase (A15 and σ) and quasicrystalline phase, were experimentally captured by meticulously tuning the composition and architectures. A phase portrait with unprecedented accuracy was mapped out (up to one monomer resolution), unraveling intriguing details of phase behaviors that have long been compromised by inherent molecular weight distribution. This study serves as a delicate model system to bridge the existing gaps between experimental observations and theoretical assessments and to provide insights into the formation and evolution of the unconventional spherical phases in soft matter systems., Discrete block copolymers provide a precise model platform to explore complex spherical phases, correlating experimental observations with theoretical advances.

Molecular shape is an essential parameter that regulates the self-organization and recognition process, which has not yet been well appreciated and exploited in block polymers due to the lack of precise and efficient modulation methods. This work (i) develops a robust approach to break the intrinsic symmetry of linear polymers by introducing geometric features into otherwise homogeneous chains and (ii) quantitatively highlights the critical contribution of molecular geometry/architecture to the self-assembly behaviors. Iteratively connecting homologous monomers of different side chains according to pre-designed sequences generates discrete polymers with exact chemical structure, uniform chain length, and programmable side-chain gradient along the backbone, which transcribes into diverse shapes. The precise chemistry eliminates all the defects and heterogeneities, providing a delicate platform for fundamental inquiries into the role of molecular geometry. A rich collection of unconventional complex phases, including Frank-Kasper A15 and σ phases, as well as a dodecagonal quasicrystal phase, were captured in these rigorous single-component systems. The self-assembly behaviors are strikingly sensitive to subtle variations of geometry, such that simply migrating a few methylene units among the side chains would generate substantial differences in lattice size or phase stability, or even trigger a phase transition toward distinct structures. The phenomena can be rationalized with a geometric argument that nonuniform side chain distribution leads to conformational mismatch between two immiscible blocks, resulting in varied interfacial curvatures and distinct lattice symmetries. The profound contribution demonstrates that molecular geometry is an effective and robust parameter for structural engineering.

Polymeric chains made of "giant" monomers at a larger length scale provide intriguing insights into the fundamental principles of polymer science. In this study, we modularly prepared a library of discrete amphiphilic polymeric chains using molecular nanoparticles as repeat units, with exact control of composition, chain length, surface property, and regio-configuration. These giant polymeric chains self-assembled into a rich collection of highly ordered phases. The precise chemical structure and uniform chain length eliminate all the inherent molecular "defects", while the nanosized monomer amplifies minute structural differences, providing an ideal platform for a systematic scrutiny of the self-assembly behaviors at a larger length scale. The compositional and regio-configurational contribution was carefully studied. The regio-regularity is found to have a direct and profound impact on the chain conformation, leading to a distinct molecular packing scheme and therefore shifting the phase boundaries. With increasing the length of the linker, the regio-constraint gradually diminishes, and the neighboring particles would eventually be decoupled.

Research on superhydrophobic surfaces received continued attention due to more and more widely applications of superhydrophobic materials. Two parameters have been recognized for the rational design of the superhydrophobic materials: surface texture and chemical constitution. In this work, we fabricated composite membranes of polystyrene-block-poly (ethylene-co-butylene)-block-polystyrene (SEBS) and fluorinated polyhedral oligomeric silsesquioxane-block-polystyrene (FPOSS-PS) using a sequential electrospinning and electrospraying approach. Composite membranes with hierarchical geometries could be achieved by adjusting the formulation and/or fabrication protocols. Incorporation of fluorinated component enhances the surface property of the composite membranes due to its ultra-low surface energy, while micron particles attached on the surface further promotes the robustness of the membrane and enhanced the cell/tissue anti-adhesion efficiency. With a simple annealing treatment, the physical crosslinking was built up between the micron particles and underlying fibers, rendering the membranes with good stability and anti-adhesion properties. These superhydrophobic membranes are anticipated to have potential applications in wound-dressing and other related areas.