Crystallization of Poly(l-lactic acid) on Water Surfaces via Controlled Solvent Evaporation and Langmuir-Blodgett Films.

Solvent evaporation is one of the most fundamental processes in soft matter. Structures formed via solvent evaporation are often complex yet tunable via the competition between solute diffusion and solvent evaporation time scales. This work concerns the polymer evaporative crystallization on the water surface (ECWS). The dynamic and two-dimensional (2D) nature of the water surface offers a unique way to control the crystallization pathway of polymeric materials. Using poly(l-lactic acid) (PLLA) as the model polymer, we demonstrate that both one-dimensional (1D) crystalline filaments and two-dimensional (2D) lamellae are formed via ECWS, in stark contrast to the 2D Langmuir-Blodgett monolayer systems as well as polymer solution crystallization. Results show that this filament-lamella biphasic structure is tunable via chemical structures such as molecular weight and processing conditions such as temperature and evaporation rate.

Fabrication of Surface Polymer Brushes Via Thin Film Crystallization and Solvent Annealing.

Polymer single crystals are used as templates to synthesize polymer brushes, known as the "polymer-single-crystal-assisted-grafting-to" (PSCAGT) approach. Polymer brushes with controlled grafting densities and spatial tethering locations are demonstrated. Previous works focused on solution crystallization, which involves large amounts of organic solvent, and the grafting density can only be tuned by varying crystallization temperatures. In this work, thin film crystallization is utilized to fabricate 2D polymer crystals on flat surfaces. Subsequent chemical tethering leads to polymer brushes that retain the original morphology of the crystals with high fidelity. Furthermore, it is shown that the grafting density of the polymer brushes fabricated using this method depends on the chain end distribution on the top/bottom surfaces of the crystal, which can be facilely controlled by annealing the crystals at various nonsolvent media. This work broadens the scope of the PSCAGT method and provides a new route to achieve polymer brushes with controlled structures.

Helical Crystals in Aliphatic Copolyesters: From Chiral Amplification to Mechanical Property Enhancement.

We demonstrate herein a bottom-up strategy for achieving helical crystals via chiral amplification in copolyesters by incorporating a small amount of (d)-isosorbide into semicrystalline polyester, poly(ethylene brassylate) (PEB). During bulk crystallization of poly(ethylene-co-isosorbide brassylate)s, the molecular chirality of isosorbide in the amorphous region is transferred to PEB crystal chirality and amplified by the formation of right-handed helical crystals. Increasing isosorbide content or reducing crystallization temperature leads to thinner PEB lamellae crystals, strengthening chiral amplification by forming superhelices with a smaller helical pitch. Moreover, the superhelices with smaller helical pitch (larger chiral amplification) endow aliphatic copolyesters with enhanced modulus, strength, and toughness without sacrificing elongation-at-break. The principle outlined here could apply to the design of strong and tough materials.

Crystallization-driven Nanoparticle Crystalsomes.

Nanoparticle (NP) assembly has been extensively studied, and a library of NP superstructures has been synthesized. These intricate structures show unique collective optical, electronic, and magnetic properties. In this work, we report a bottom-up approach for fabricating spherical gold nanoparticle (AuNP) assemblies that mimic colloidosomes. Co-crystallization of lipoic acid-end-functionalized poly(ethylene oxide) (PEO) and AuNPs in solution via a self-seeding method led to the formation of hollow spherical NP assemblies named nanoparticle crystalsomes (NPCs). Due to the spherical shape, the translational symmetry of PEO crystals is broken in NPCs, which can be attributed to the competition between NP close packing and polymer crystallization. This was confirmed by tuning the NPC morphology via varying the self-seeding temperature, crystallization temperature, and PEO molecular weight. We envisage that this strategy paves the way to attaining exquisite morphological control of NP assemblies with broken translational symmetry.

Insight on the Role of Poly(acrylic acid) for Directing Calcium Phosphate Mineralization of Synthetic Polymer Bone Scaffolds.

Bone is a complex tissue with robust mechanical and biological properties originating from its nanoscale composite structure. Although much research has been conducted on designing bioinspired artificial bone, the role of biological macromolecules such as noncollagenous proteins (NCPs) in influencing the formation of biominerals is not fully understood. In this work, we have designed nanofiber shish-kebab (NFSK) structures that can template mineral location by recruiting calcium cations from an ion-rich mineralization solution. Poly(acrylic acid) (PAA) is used as the NCP analogue to understand the role of polyelectrolytes in scaffold mineralization. We demonstrate that the addition of PAA in the mineralization solution suppresses the development of extrafibrillar minerals as well as slows down the accumulation and development of mineral phases within NFSKs. We probe the mechanism behind this effect by monitoring the free calcium ion concentration, investigating the PAA molecular weight effect, and conducting mineralization in membrane-partitioned solutions. Our results suggest the 2-fold effect of PAA as a solution stabilizer and physical barrier on the NFSK surface. This work could shed light on the understanding of the NCP effect in biomineralization.

Porous Crystalsomes via Emulsion Crystallization and Polymer Phase Separation.

Crystalsomes are crystalline capsules that are formed by controlling polymer crystallization to break translational symmetry. While recent studies showed that these crystalline capsules exhibit interesting mechanical properties, thermal behavior, and excellent performance in blood circulation, the closed capsule is undesired for drug delivery applications. We report the formation and characterization of porous crystalsomes where porosity is rendered on the crystalline shells. A miniemulsion is formed using two amphiphilic block copolymers (BCP). The competition between controlled crystallization and phase separation of the BCPs at the emulsion surface leads to multiphase crystalsomes. Subsequently removing one BCP produces porous crystalline capsules.

Multilayered Solid Polymer Electrolytes with Sacrificial Coating for Suppressing Lithium Dendrite Growth.

The practical application of lithium-metal batteries (LMBs) is hindered by the lithium dendrite formation during cycling. In this work, we report a multilayered solid polymer electrolyte (SPE) formed by sandwiching a comb-chain cross-linker-based network SPE (ConSPE) film with a linear poly(ethylene oxide) (PEO) SPE coating. Benefiting from the drastically different lithium dendrite resisting properties of the ConSPE and linear PEO SPE, the lithium dendrite growth in the multilayered SPEs could be tuned, with the linear PEO SPE effectively serving as a sacrificial layer to accommodate the lithium dendrite growth. Symmetrical lithium cells with the multilayered SPE exhibited an extended short-circuit time ∼4.1 times that for the single-layer ConSPE at a high current density of 1.5 mA cm-2. Li/LiFePO4 batteries with multilayered SPEs delivered superior cycling performance at extremely high C-rates of 2C and 10C. Our multilayered SPE architecture, therefore, opens up a new gateway for advancing SPE design for future LMBs.

Adaptable Multivalent Hairy Inorganic Nanoparticles.

We report a polymer brush-based approach for fabricating multivalent patchy nanoparticles (NPs) with the number of nanodomains (valency) from 6 to 10, potentially from 1 to 10, by exploiting the lateral microphase separation of binary mixed homopolymer brushes grafted on NPs with a radius comparable to the polymer sizes. Well-defined mixed brushes were grown on 20.4 nm silica NPs by two-step surface-initiated reversible deactivation radical polymerizations and microphase separated laterally upon casting from a good solvent, producing multivalent NPs on 2D surfaces. A linear relationship between valency and average core size for the corresponding valency was observed. The mixed brush NPs exhibited abilities to form "bonds" through the overlap of nanodomains and to change the valency when interacting with adjacent NPs. This method could open up a new avenue for studying patchy NPs.

MC3T3 E1 cell response to mineralized nanofiber shish kebab structures.

Block copolymers (BCPs) are of growing interest because of their extensive utility in tissue engineering, particularly in biomimetic approaches where multifunctionality is critical. We synthesized polycaprolactone-polyacrylic acid (PCL-b-PAA) BCP and crystallized it onto PCL nanofibers, making BCP nanofiber shish kebab (BCP NFSK) structures. When mineralized in 2× simulated body fluid, BCP NFSK mimic the structure of mineralized collagen fibrils. We hypothesized that the addition of a calcium phosphate layer of graded roughness on the nano-structure of the nanofiber shish kebabs would enhance preosteoblast alkaline phosphatase (ALP) activity, which has been shown to be a critical component in bone matrix formation. The objectives in the study were to investigate the effect of mineralization on cell proliferation and ALP activity, and to also investigate the effect of BCP NFSK periodicity, a structural feature describing the distance between PCL-b-PAA crystals on the nanofiber core, on cell proliferation, and ALP activity. ALP activity of cells cultured on the mineralized BCP NFSK template was significantly higher than the nonmineralized BCP NFSK templates. Interestingly, no statistical difference was observed in ALP activity when the periodic varied, indicating that surface chemistry seemed to play a larger role than the surface roughness.

Frustrated Layered Self-Assembly Induced Superlattice from Two-Dimensional Nanosheets.

Here we reported a hierarchical self-assembly approach toward well-defined superlattices in supramolecular liquid crystals by fullerene-based sphere-cone block molecules. The fullerenes crystallize to form monolayer nanosheets intercalated by the attached soft hydrocarbon cones. The frustration caused by cross-sectional area mismatch between the spheres and the somewhat oversize cones leads to a unique lamellar superlattice whereby each stack of six pairs of alternating sphere-cone sublayers is followed by a cone double layer. While such areal mismatch problems in soft matter are usually solved by interface curvature, the lamellar superlattice solution is best suited to systems with rigid layers. Meanwhile, formation of the superlattice significantly improves the material's transient electron conductivity, with the maximum value being among the highest for π-conjugated organic materials. The design principle of solving steric frustration by forming a superlattice opens a new avenue toward self-assembled optoelectronic materials.

Engineering long-circulating nanomaterial delivery systems.

One of the grand challenges at the forefront of bionanomaterials is their quick clearance in blood circulation. Progress has been made in understanding nanomaterial-biological system interactions and in developing new strategies to extend the blood circulation time of nanomaterials. Here, we first review interactions between the complement system and nanomaterials as well as clearance pathways in major organs such as the liver, spleen, and kidneys. We then discuss new approaches to prolong the blood circulation of nanomaterials with a focus on grafting polymers and biomimetic camouflages including cell membrane coating and hybrid vesicles. In the end, we provide insights into the pros and cons of these approaches and our perspectives for advancing this field.

Designing Comb-Chain Crosslinker-Based Solid Polymer Electrolytes for Additive-Free All-Solid-State Lithium Metal Batteries.

Developing solid polymer electrolytes (SPEs) is a promising approach to realize practical dendrite-free lithium metal batteries (LMBs). Tuning the nanoscale polymer network chemsitry is of critical importance for SPE design. In this work, we took lessons from the rubber chemistry and developed a series of comb-chain crosslinker-based SPEs (ConSPEs) using a preformed polymer as the multifunctional crosslinker. The high-functionality crosslinker increased the connectivity of nanosized cross-linked domains, which led to a robust network with dramatically improved toughness and superior lithium dendrite resistance even at a current density of 2 mA cm-2. The uniform and flexile network also dramatically improved the anodic stability to over 5.3 V versus Li/Li+. Additive-free, all-solid-state LMBs with the ConSPE showed high discharge capacity and stable cycling up to 10 C rate, and could be stably cycled at 25 °C. Our results demonstrated that ConSPEs are promising for high-performance and dendrite-free LMBs.

Fabrication of 2D Block Copolymer Brushes via a Polymer-Single-Crystal-Assisted-Grafting-to Method.

Block copolymer brushes are of great interest due to their rich phase behavior and value-added properties compared to homopolymer brushes. Traditional synthesis involves grafting-to and grafting-from methods. In this work, a recently developed "polymer-single-crystal-assisted-grafting-to" method is applied for the preparation of block copolymer brushes on flat glass surfaces. Triblock copolymer poly(ethylene oxide)-b-poly(l-lactide)-b-poly(3-(triethoxysilyl)propyl methacrylate) (PEO-b-PLLA-b-PTESPMA) is synthesized with PLLA as the brush morphology-directing component and PTESPMA as the anchoring block. PEO-b-PLLA block copolymer brushes are obtained by chemical grafting of the triblock copolymer single crystals onto a glass surface. The tethering point and overall brush pattern are determined by the single crystal morphology. The grafting density is calculated to be ≈0.36 nm-2 from the atomic force microscopy results and is consistent with the theoretic calculation based on the PLLA crystalline lattice. This work provides a new strategy to synthesize well-defined block copolymer brushes.

Brownian Diffusion of Individual Janus Nanoparticles at Water/Oil Interfaces.

Janus nanoparticles could exhibit a higher interfacial activity and adsorb stronger to fluid interfaces than homogeneous nanoparticles of similar sizes. However, little is known about the interfacial diffusion of Janus nanoparticles and how it compares to that of homogeneous ones. Here, we employed fluorescence correlation spectroscopy to study the lateral diffusion of ligand-grafted Janus nanoparticles adsorbed at water/oil interfaces. We found that the diffusion was significantly slower than that of homogeneous nanoparticles. We carried out dissipative particle dynamic simulations to study the mechanism of interfacial slowdown. Good agreement between experimental and simulation results has been obtained only provided that the flexibility of ligands grafted on the nanoparticle surface was taken into account. The polymeric ligands were deformed and oriented at an interface so that the effective radius of Janus nanoparticles is larger than the nominal one obtained by measuring the diffusion in bulk solution. These findings highlight further the critical importance of the ligands grafted on Janus nanoparticles for applications involving nanoparticle adsorption at an interface, such as oil recovery or two-dimensional self-assembly.

Breaking translational symmetry via polymer chain overcrowding in molecular bottlebrush crystallization.

One of the fundamental laws in crystallization is translational symmetry, which accounts for the profound shapes observed in natural mineral crystals and snowflakes. Herein, we report on the spontaneous formation of spherical hollow crystals with broken translational symmetry in crystalline molecular bottlebrush (mBB) polymers. The unique structure is named as mBB crystalsome (mBBC), highlighting its similarity to the classical molecular vesicles. Fluorescence resonance energy transfer (FRET) experiments show that the mBBC formation is driven by local chain overcrowding-induced asymmetric lamella bending, which is further confirmed by correlating crystalsome size with crystallization temperature and mBB's side chain grafting density. Our study unravels a new principle of spontaneous translational symmetry breaking, providing a general route towards designing versatile nanostructures.

Structure and Morphology of Poly(lactic acid) Stereocomplex Nanofiber Shish Kebabs.

We report the formation and structure of poly(lactic acid) (PLA) nanofiber shish kebabs (NFSKs) containing stereocomplex crystal (SC) shish and SC/homocrystal (HC) kebabs. PLA-based NFSKs were obtained by combining electrospinning and controlled polymer crystallization in order to investigate the interplay between PLA SC and HC formation. Nanofibers were produced by electrospinning poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) blends and were used as the shish. A secondary polymer (either PDLA or PLLA/PDLA blends) was decorated on the nanofiber by an incubation method to form kebab lamellae. We show that both SC and HC kebab crystals can be formed using a SC shish following a soft epitaxy mechanism, while the subtle morphological differences in the resultant NFSKs reveal the propensity of SC nuclei in SC/HC crystallization.

Confined Crystal Melting in Edgeless Poly(l-lactic acid) Crystalsomes.

Polymer single crystals tend to be quasi two-dimensional (2D) lamellae and their small lateral surfaces are the starting points of lamella melting and thickening. However, the recently discovered crystalsomes, which are defined for hollow single crystal-like spherical shells, are edgeless, self-confined, and incommensurate with translational symmetry. This work concerns the structure and melting behavior of these edgeless crystalsomes. Poly(l-lactic acid) crystalsomes were grown using a miniemulsion solution crystallization method. Differential scanning calorimetry and in situ wide-angle X-ray diffraction were used to follow the structural evolution of the crystalsomes upon heating. Our results demonstrated that the structure and melting behavior of crystalsomes are curvature-dependent and significantly different from their flat crystal counterpart.

Directed Nanoparticle Assembly through Polymer Crystallization.

Nanoparticles can be assembled into complex structures and architectures by using a variety of methods. In this review, we discuss recent progress of using polymer crystallization (particularly polymer single crystals, PSCs) to direct nanoparticle assembly. PSCs have been extensively studied since 1957. Mainly appearing as quasi-two-dimensional (2D) lamellae, PSCs are typically used as model systems to determine polymer crystalline structures, or as markers to investigate the crystallization process. Recent research has demonstrated that they can also be used as nanoscale functional materials. Herein, we show that nanoparticles can be directed to assemble into complex shapes by using in situ or ex situ polymer crystal growth. End-functionalized polymers can crystallize into 2D nanosheet PSCs, which are used to conjugate with complementary nanoparticles, leading to a nanosandwich structure. These nanosandwiches can find interesting applications for catalysis, surface-enhanced Raman spectroscopy, and nanomotors. Dissolution of the nanosandwich leads to the formation of Janus nanoparticles, providing a unique method for asymmetric nanoparticle synthesis.

Anomalous Ostwald Ripening Enables 2D Polymer Crystals via Fast Evaporation.

We demonstrate by molecular simulations that the Ostwald ripening of crystalline polymer nuclei within the fast-evaporation-induced 2D skin layer is retarded at suitable temperatures and evaporation rates. Such an anomalous ripening can be attributed to the interplay between the thermodynamically driven diffusion of noncrystalline fragments toward the growing nuclei and the diffusive current away from the free surface caused by the densification in the nonequilibrium skin layer. The growth orientation of the nuclei inside the skin plane can be adjusted during this anomalous ripening process, which is beneficial for fabricating 2D polymer crystals.

Decorin Regulates the Aggrecan Network Integrity and Biomechanical Functions of Cartilage Extracellular Matrix.

Joint biomechanical functions rely on the integrity of cartilage extracellular matrix. Understanding the molecular activities that govern cartilage matrix assembly is critical for developing effective cartilage regeneration strategies. This study elucidated the role of decorin, a small leucine-rich proteoglycan, in the structure and biomechanical functions of cartilage. In decorin-null cartilage, we discovered a substantial reduction of aggrecan content, the major proteoglycan of cartilage matrix, and mild changes in collagen fibril nanostructure. This loss of aggrecan resulted in significantly impaired biomechanical properties of cartilage, including decreased modulus, elevated hydraulic permeability, and reduced energy dissipation capabilities. At the cellular level, we found that decorin functions to increase the retention of aggrecan in the neo-matrix of chondrocytes, rather than to directly influence the biosynthesis of aggrecan. At the molecular level, we demonstrated that decorin significantly increases the adhesion between aggrecan and aggrecan molecules and between aggrecan molecules and collagen II fibrils. We hypothesize that decorin plays a crucial structural role in mediating the matrix integrity and biomechanical functions of cartilage by providing physical linkages to increase the adhesion and assembly of aggrecan molecules at the nanoscale.