This work describes the first rigorous example of a single-component block copolymer system forming unconventional spherical phases. A library discrete polymers with uniform chain length and diverse architectures were modularly prepared through combination step-growth approach highly efficient coupling reactions. The precise chemical structure eliminates all molecular defects associated molar weight, dispersity, compositional ratio. Complex phases, including Frank–Kasper phase (A15 σ)...

Rationally introducing chain length heterogeneity, such as binary blending, is a robust approach to regulate phase behavior of block copolymers. This work designed library discrete linear–branched copolymers bearing two unequal branches. Diverse ordered nanostructures, including complex Frank–Kasper phases and quasicrystalline phase, were captured by tuning the compositional architectural asymmetry. The precise chemistry rules out interferences associated with statistical distribution, while...

Modulating MWD through precise blending of discrete macromolecules provides a model platform for highlighting the importance chain length heterogeneity.

Molecular shape is an essential parameter that regulates the self-organization and recognition process, which has not yet been well appreciated exploited in block polymers due to lack of precise efficient modulation methods. This work (i) develops a robust approach break intrinsic symmetry linear by introducing geometric features into otherwise homogeneous chains (ii) quantitatively highlights critical contribution molecular geometry/architecture self-assembly behaviors. Iteratively...

The Frank–Kasper phase and quasicrystalline are an intriguing class of complex crystalline structures, which so far sporadically observed only in a limited number block copolymers. Incorporation homopolymer into copolymer has recently been demonstrated as effective robust approach to regulate the formation evolution these spherical phases. experimental explorations, however, suffer from inherent chain length distribution blending stocks. In this study, we quantitatively assessed behaviors...

A lack of understanding interactions and the inability to effectively resolve conflicts continue impede progress Connected Autonomous Vehicles (CAVs) in their with Human-Driven (HDVs). To address this challenge, we propose Recognize then Resolve (RtR) framework. First, a Bilateral Intention Progression Graph (BIPG) is constructed based on CAV-HDV interaction data model evolution identify potential HDV intentions. Three typical breakdown scenarios are categorized, key moments defined for...

This work quantitatively explores the effect of chain length heterogeneity on self-assembly behaviors block copolymer, focusing narrow distribution region. A library discrete diblock copolymers consisting oligo dimethylsiloxane (oDMS) and lactic acid (oLA) blocks were modularly prepared with one monomer difference in composition, which form highly ordered nanostructures at room temperature. The molecular weight oLA was then precisely modulated through a reconstruction approach, achieving an...

Stereocomplexation critically depends on the chain length and stoichiometry of constituent enantiomeric chains. Quantitative understanding their independent contribution, however, has long been compromised by inherent molecular weight distribution. In this work, we prepared a library discrete oligo l-lactide D-lactide systematically explored stereocomplexation behaviors. The relative mole ratio two complementary oligomers can be precisely regulated with predesigned recipes. When enantiomers...

Conformational asymmetry of block copolymers is a critical molecular parameter dictating the self-assembly behaviors. This work develops an efficient approach to construct with uniform chain length and tunable conformational mismatch. Three model discrete diblock based on γ-alkyl-α-hydroxy glutaric acid lactide monomers were prepared through iterative growth approach. The can be adjusted via simple substitution hydrocarbon side chains. precise chemical structure rules out all uncertainties...

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 sequence-defined, isomeric copolymers with globally the same composition but locally different side chain patterns were elaborately designed prepared through iterative convergent growth method. The precise chemical structure uniform length rule out all inherent molecular defects associated statistical...

In the linear and three armed PLLA/PDLA blends, the<italic>G</italic>value increased firstly, then decreased as<italic>M</italic>_n,PLAincreased, and<italic>G</italic>reduced as PLAs added.

Despite being predicted to be a thermodynamically equilibrium structure, the absence of direct experimental evidence hexagonally close-packed spherical phase in single-component block copolymers raises uncomfortable concerns regarding existing fundamental principles. This work presents robust approach regulate behavior linear by deliberately breaking molecular symmetry, and lattice is captured rigorous system. A collection discrete A1BA2 triblock designed prepared through an iterative growth...

By attaching hydrophilic OEG on different conjugation sites of SN38, isomeric self-assembling prodrugs were developed and self-assembled into giant nanotubes filamentous assemblies, revealing the critical contribution sites.

Anisotropic patchy particles with molecular precision are exquisite building blocks for constructing diverse meso-structures of high complexity. In this research, a library clusters consisting collection functional polyhedral oligomeric silsesquioxane cages exact regio-configuration and composition were prepared through robust modular approach. By meticulously tuning the composition, symmetry, other parameters, these could assemble into nanostructures, including unconventional complex...

Current polymer network design suffers from intrinsic trade-offs, where networks with high modulus often turn out to be in short of stretchability or fracture toughness. Here, we show a novel through polymer-nanoparticle alternating hybrids that enable integrating the non-polymeric colloid deformation into design. The new class exhibits colloidal yielding at small before conformational change higher elongation ratios, enabling simultaneous achievement Young's E≈10−50MPa, yield strength...

This work develops an iterative growth approach to synthesize discrete oligo lactic acids with exactly defined stereoconfiguration by connecting enantiomeric monomers (i.e., L- and D-lactic acid) following a predesigned sequence. A library of diblock copolymers uniform chain length was modularly prepared conjugating the stereoisomeric blocks chemically incompatible chain. The precise chemical structure eliminates all molecular uncertainties associated statistical distribution decouples...

PLLA/PLLA-<italic>b</italic>-PBAT-<italic>b</italic>-PLLA/(PLLA-<italic>b</italic>-PGMA)₃ blends with different ratio.