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Discrete oligo- and polyesters are highly attractive for a wide range of investigations because of their great fidelity on structure–property relationships. Even though numerous synthetic approache...

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.

Self-assembly of chiral block copolymers (BCPs*) can give rise to ordered chiral nanostructures, that is, a helical phase (H* phase), via chirality transfer from the molecular level to mesoscale. In the present work, we reported the self-assembly of BCPs* under one-dimensional spatial confinement. The morphological dependence of self-assembled BCPs* on the molecular weights and the film thickness was investigated. As chiral nanostructures, the H* phase can be formed in bulk, nonchiral nanostructures that were observed in the thin films. Also, the topology effect of self-assembly of BCPs* was examined. The self-assembly of BCPs* with a star-shaped topology exhibited a distinct morphology compared with that of linear BCPs*. The present work provides new insight into the chirality transfer of macromolecules under spatial confinement.

We have studied the self-assembly of two types of amphiphiles with one or two blocks composed of giant “monomers” of the cubic cage using dissipative particle dynamics (DPD) simulations with the ai...

Stereocomplexation critically depends on the chain length and stoichiometry of constituent enantiomeric chains. Quantitative understanding of their independent contribution, however, has long been ...

Bioinspired brush polymers containing α-2,6-linked sialic acids at the side chain termini were synthesized by protection-group-free, ring-opening metathesis polymerization. Polymers showed strain-selective antiviral activity through multivalent presentation of the sialosides. The multivalent effect was further controlled by independently varying the degree of polymerization, the number density of sialic acids, and the length of side chains in the brush polymers. Optimizing the three-dimensional sialoside spacing for better binding to hemagglutinin trimers was of critical importance to enhance the multivalent effect and the antiviral activity determined by hemagglutination inhibition assays and in vitro infection assays. By taking advantage of their structural similarities with native mucins, these brush polymers can be used as model systems to dissect the intricate design principles in natural mucins.

A series of shape amphiphiles based on functionalized polyhedral oligomeric silsesquioxane (POSS) head tethered with two polymeric tails of symmetric or asymmetric compositions was designed and synthesized using sequential "grafting-from" and "click" surface functionalization. The monofunctionalization of octavinylPOSS was performed using thiol-ene chemistry to afford a dihydroxyl-functionalized POSS that was further derived into precisely defined homo- and heterobifunctional macroinitiators. Polymer tails, such as polycaprolactone and polystyrene, could then be grown from these POSS-based macroinitiators with controlled molecular weight via ring-opening polymerization and atom transfer radical polymerization (ATRP). The vinyl groups on POSS were found to be compatible with ATRP conditions. These macromolecular precursors were further modified by thiol-ene chemistry to install surface functionalities onto the POSS cage. The polymer chain composition and POSS surface chemistry can thus be tuned separately in a modular and efficient way.

This letter reports a sequential triple “click” chemistry method for the precise synthesis of functional polyhedral oligomeric silsesquioxane (POSS)-based multiheaded and multitailed giant surfactants. A vinyl POSS-based heterobifunctional building block possessing two alkyne groups of distinct reactivity was used as a robust and powerful “clickable” precursor for ready access to a variety of POSS-based shape amphiphiles with complex architectures. The synthetic approach involves sequentially performed strain-promoted azide–alkyne cycloaddition (SPAAC), copper-catalyzed azide–alkyne cycloaddition (CuAAC), and thiol–ene “click” coupling (TECC). Specifically, the first SPAAC reaction was found to be highly selective with no complications from the vinyl groups and terminal alkynes in the precursor. The method expands the toolbox of sequential “click” approaches and broadens the scope of synthetically available giant surfactants for further study on structure–property relationships.

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.

Hierarchical structures are important for transferring and amplifying molecular functions to macroscopic properties of materials. In this regard, rodlike molecules have emerged as one of the most promising molecular building blocks to construct functional materials. Although the self-assembly of conventional molecules containing rodlike components generally results in nematic or layered smectic phases, due to the preferred parallel arrangements of rodlike components, extensive efforts have revealed that rational molecular design provides a versatile platform to engineer rich self-assembled structures. Herein, first successes achieved in polyphilic liquid crystals and rod-coil block systems are summarized. Special attention is paid to recent progress in the conjugation of rodlike building blocks with other molecular building blocks through the molecular Lego approach. Rod-based giant surfactants, sphere-rod conjugates, and dendritic rodlike molecules are covered. Future perspectives of the self-assembly of molecules containing rodlike components are also provided.

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.

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.

In this study, polyhedral oligomeric silsesquioxane (POSS) based giant triblock molecules with precisely defined regio-configuration are modularly prepared through highly efficient coupling reactions. The length of the linker connecting neighboring nanoparticles is elaborately designed to regulate the geometric constraints. The triblock molecules adopt a folded packing during phase separation, and the regio-configuration imparts direct influence on the self-assembly behaviors. The ortho-isomers form periodic structures with a larger domain size, larger interfacial curvature, and enhanced phase stability. The regio-effect is closely related to the length and symmetry of the linker. As the linker extends, the neighboring particles gradually decouple, and the regio-effect diminishes. The symmetry of the linker shows an even more profound impact. This work quantitatively scrutinized the role of the linker, opening an avenue for engineering the assembled structures with molecular precision.

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.

This work quantitatively explores the effect of chain length heterogeneity on self-assembly behaviors of block copolymer, focusing on the narrow distribution region. A library of discrete diblock copolymers consisting of oligo dimethylsiloxane (oDMS) and oligo lactic acid (oLA) blocks were modularly prepared with one monomer difference in composition, which form highly ordered nanostructures at room temperature. The molecular weight distribution of the oLA block was then precisely modulated through a reconstruction approach, achieving an absolute control on chain length heterogeneity. By meticulously tuning the breadth and symmetry of the distribution profile, the lattice dimension of the assembled nanostructure significantly expands, while no appreciable difference on the phase stability was observed. This work provides an explicit access to block copolymers with narrow dispersity that are not possible through conventional chemical approach, revealing the critical contribution of dispersity on self-assembly and bridging the existing gaps between experiments and theories.

As one of the most critical molecular parameters, molecular weight distribution has a profound impact on the structure and properties of polymers. Quantitative and comprehensive understanding, however, has yet to be established, mainly due to the challenge in the precise control and regulation of molecular weight distribution. In this work, we demonstrated a robust and effective approach to artificially engineer the molecular weight distribution through precise recombination of discrete macromolecules. The width, symmetry, and other characteristics of the distribution can be independently manipulated to achieve absolute control, serving as a model platform for highlighting the importance of chain length heterogeneity in structural engineering. Different from their discrete counterparts, each individual component in dispersed samples experiences a varied degree of supercooling at a specific crystallization temperature. Non-uniform crystal nucleation and growth kinetics lead to distinct molecular arrangements. This work could bridge the gap between discrete and dispersed macromolecules, providing fundamental perspectives on the critical role of molecular weight distribution.

This mini review summarizes recent progress on two-dimensional (2D) self-assembly of giant molecules. Two critical factors with significant impact on the formation of nanostructure are highlighted, i.e., the dimensional constraint of 2D geometry, and the conformational constraint imposed the rigid molecular nanoparticles (MNPs). Diverse 2D nanostructures have been fabricated in condensed state and solution by rational molecular design. The collective secondary interactions between functional groups on the periphery of the MNPs and their persistent shape, together with the dimensional limit, change the free energy landscape and lead to unconventional nanostructures. The unique molecular properties of giant molecules endow these 2D structures with promising technological applications.

Controlling self-assembled nanostructures in thin films allows the bottom-up fabrication of ordered nanoscale patterns. Here we report the unique thickness-dependent phase behavior in thin films of a bolaform-like giant surfactant, which consists of butyl- and hydroxyl-functionalized polyhedral oligomeric silsesquioxane (BPOSS and DPOSS) cages telechelically located at the chain ends of a polystyrene (PS) chain with 28 repeating monomers on average. In the bulk, BPOSS-PS28-DPOSS forms a double gyroid (DG) phase. Both grazing incidence small-angle X-ray scattering and transmission electron microscopy techniques are combined to elucidate the thin film structures. Interestingly, films with thicknesses thinner than 200 nm exhibit an irreversible phase transition from hexagonal perforated layer (HPL) to compressed hexagonally packed cylinders (c-HEX) at 130 °C, while films with thickness larger than 200 nm show an irreversible transition from HPL to DG at 200 °C. The thickness-controlled transition pathway sug...

The continuous demand for novel hybrid materials in specific technological applications inspires people to develop new synthetic strategies in a modular and efficient way. In the recent years, extensive efforts have been devoted to using polyhedral oligomeric silsesquioxane (POSS) to construct multifunctional nanohybrids and nanocomposites with tunable hierarchical structures and unparalleled properties. The shape-persistent nanostructure and diverse surface chemistry make those nanocaged materials ideal building blocks for such purposes. Functionalization of POSS cages are further facilitated by the introduction of “click” chemistry at the beginning of this century. “Click” reactions include several kinds of selective and orthogonal chemical ligations with high efficiency under mild reaction conditions. The concept has generated real stimulus not only in elegantly preparing materials of choice, but in making the leap from laboratory to industrial scale-up of POSS-based hybrid materials as well.

In nearly all biosensors, sensitivity is greatly reduced for measurements conducted in biological matrices due to nonspecific binding from off-target molecules. One method to overcome this issue is to design a sensor that enables selective size-based uptake of proteins. Herein, a protein-polymer conjugate thin-film biosensor is fabricated that self-assembles into lamellae containing alternating domains of protein and polymer. Analyte is captured in protein regions while polymer domains restrict diffusion of large molecules. Device sensitivity and size-based exclusion properties are probed using two analytes: streptavidin (SA, 52.8 kDa) and monomeric streptavidin (mSA2, 15.6 kDa). Tuning domain spacing by adjusting polymer molecular weight allows the design of films that relatively freely uptake mSA2 and largely restrict SA diffusion. Furthermore, when detecting the smaller mSA2, no reduction in the limit of detection (LOD) is observed when transitioning from detection in the buffer to detection in biological fluids. As a result, LOD measured in fluid samples is reduced by 2 orders of magnitude compared to a traditional surface-immobilized protein monolayer.

In biological systems, it is well-known that the activities and functions of biomacromolecules are dictated not only by their primary chemistries, but also by their secondary, tertiary, and quaternary hierarchical structures. Achieving control of similar levels in synthetic macromolecules is yet to be demonstrated. Most of the critical molecular parameters associated with molecular and hierarchical structures, such as size, composition, topology, sequence, and stereochemistry, are heterogenous, which impedes the exploration and understanding of structure formation and manipulation. Alternatively, in the past few years we have developed a unique giant molecule system based on molecular nanoparticles, in which the above-mentioned molecular parameters, as well as interactions, are precisely defined and controlled. These molecules could self-assemble into a myriad of unconventional and unique structures in the bulk, thin films, and solution. Giant molecules thus offer a robust platform to manipulate the hierarchical structures via precise and modular assemblies of building blocks in an amplified size level compared with small molecules. It has been found that they are not only scientifically intriguing, but also technologically relevant.

As one of the most fundamental features of synthetic polymer, molecular weight distribution profoundly influences the structures and properties. In this work, chain length heterogeneity was precisely regulated by a reconstruction approach using a library of discrete oligo l -lactide (oLLA). Crystallization of a series of binary blends were systemically investigated. At a specific crystallization temperature, each fraction experiences varied degrees of supercooling, leading to non-uniform nucleation and growth kinetics. Both oLLA fractions co-crystallize homogeneously when chain length heterogeneity is not significant, while partial segregation occurs when the difference is sufficiently large. The co-crystals consisting of non-uniform chains are metastable, which rearrange into a homo-crystal of longer chains by excluding the shorter components upon heating. This work highlights the profound contribution of chain length heterogeneity on crystallization, which not only provides insights into the importance of molecular weight distribution, but also bridges the intrinsic gap between discrete and disperse polymers.

In this work, for the first time, polymer chain growth and topology formation was monitored and quantitatively evaluated using a maleimide-based fluorogenic probe based on a photo-induced electron transfer (PET) mechanism. A fluorene-containing monomer bearing terminal maleimide and thiol functional groups was rationally designed. The fluorescence of fluorene was effectively quenched by the adjacent maleimide group, which was proved by model reactions. Firstly, the correlation between molecular weight and fluorescence intensity was established as a calibration curve using precisely synthesized monodisperse polymers with varying numbers of repeating units via an iterative exponential growth strategy. Secondly, step-growth polymerization of the maleimide–fluorene–thiol monomer progressively consumed the maleimide group during polymer chain propagation and led to a gradual increase of fluorescence. This provides a quantitative and robust approach to monitor polymerization processes in situ. Moreover, cyclic oligomers were produced via intramolecular thiol–maleimide Michael addition in highly diluted solutions of linear precursors, and the cyclization process resulted in gradual enhancements of fluorescence intensity due to the elimination of maleimide groups. The cyclic oligomer content at a determined time can thus be quantitatively calculated based on fluorescence emission, enabling a real-time approach for monitoring/surveilling the cyclization process. We further applied this fluorogenic probe method to quantitatively monitor the formation of polymers with more complicated topologies, such as “cyclic-brush-like” macromolecules. This work demonstrates a facile, robust, and versatile platform for monitoring polymerization processes in situ, which may inspire and facilitate diverse molecular design and preparation in the field of precision polymer synthesis.

Three-dimensional (3D) ordered arrays of human immunoglobulin G (IgG) were fabricated using well-defined full-length antibody–polymer conjugates (APCs). The conjugates were prepared through a two-step sequential click approach with a combination of oxime ligation and strain promoted alkyne–azide cycloaddition. They were able to self-assemble into lamellar nanostructures with alternating IgG and poly(N-isopropylacrylamide) (PNIPAM) nanodomains. As a proof-of-concept, these materials were fabricated into thin films and their specific binding ability was tested. The nanostructure not only improves the packing density and the proper orientation of the IgG, but also provides nanochannels to facilitate substrate transport.

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.

Wei Zhang received his BS degree from Peking University and PhD degree in polymer science from the University of Akron (UA). He is now a postdoc at Harvard Medical School. Xuehui Dong received his BS degree at the University of Science and Technology of China and PhD degree in polymer science from UA. After completing postdoctoral research at the Massachusetts Institute of Technology, he joined the South China Advanced Institute for Soft Matter Science and Technology (AISMST) as a professor. Stephen Z.D. Cheng received his PhD degree from Rensselaer Polytechnic Institute. He has been at UA for his entire career and also serves as dean for AISMST at the South China University of Technology. He has received a number of awards and has been a member of the US National Academic of Engineering since 2008. His research interests span condensed states in polymers, liquid crystals, and hybrid systems.

Spontaneous formation of concentric lamellae was observed in self-assembling giant surfactants consisting of a fluorinated polyhedral oligomeric silsesquioxane (FPOSS) head and flexible polymer tail(s). Owing to the asymmetrical sizes of the head and tail blocks and the rectangular molecular interface, the giant surfactants assumed a truncated-wedge-like molecular shape, which induced morphological curvature during self-assembly, thus resulting in the formation of curved and concentric lamellae. These curved/concentric lamellae were observed in FPOSS-based giant surfactants with different architectures and compositions. The spontaneous curvature formation not only promotes our fundamental understanding of assembly principles, but also provides a promising and efficient approach to the fabrication of a wide range of high-performance devices.