Non-monotonic Information and Shape Evolution of Polymers Enabled by Spatially Programmed Crystallization and Melting.

Stimuli-responsive polymer materials are a kind of intelligent material which can sense and respond to external stimuli. However, most current stimuli-responsive polymers only exhibit a monotonic response to a single constant stimulus but cannot achieve dynamic evolution. Herein, we report a method to achieve a non-monotonic response under a single stimulus by regionalizing the crystallization and melting kinetics in semicrystalline polymers.

Poly(lactic acid)-based materials with enhanced gas permeability for modified atmosphere packaging of Chinese bayberry.

Biodegradable plastics are increasingly utilized in packaging, driven by green chemistry and environmental responsibility. Among them, poly(L-lactic acid) (PLLA) stands out due to its biodegradability and biocompatibility. However, its limited gas permeability and selectivity hinder its application in produce preservation.

Moisture-responsive ultralow-hysteresis polymer ionogels for adhesion-switchable strain sensing.

Adhesion-switchable ultralow-hysteresis polymer ionogels are highly demanded in soft electronics to avoid debonding damage and signal distortion, yet the design and fabrication of such ionogels are challenging. Herein, we propose a novel method to design switchable adhesive ionogels by using binary ionic solvents with two opposite-affinity ionic components. The obtained ionogels exhibit moisture-induced phase separation, facilitating switchable adhesion with a high detaching efficiency (>99%).

Defect Crystal Formation and Thermal-Induced Structural Ordering of Semicrystalline Copolymers Induced by Comonomer Inclusion/Exclusion.

Comonomer defects can induce semicrystalline polymers to form unique crystalline structures (., defect crystals), which can greatly influence the materials' physical properties. However, the formation mechanism and structural evolution of defect polymer crystals are not yet well understood.

Development of ultra-thin poly(L-lactic acid)-based films integrating toughness, barrier properties, and gas selectivity: Towards gas-permeation controllable green food packaging.

High costs and low performance have constrained the application of bio-based materials in food packaging. Herein, a series of ultra-thin poly(L-lactic acid-iconic acid N-diol) (P(LA-NI)) copolymer films were developed using a "one-step" polycondensation process with integrated toughness, barrier properties, gas selectivity, and quality control features. The massive branched structure and gg conformers in P(LA-NI) act as "internal chain expansion" and "internal plasticization".

Spatially and Temporally Programmable Transparency Evolutions in Hydrogels Enabled by Metal Coordination toward Transient Anticounterfeiting.

Hydrogels have emerged as promising candidates for anticounterfeiting materials, owing to their unique stimulus-responsive capabilities. To improve the security of encrypted information, efforts are devoted to constructing transient anticounterfeiting hydrogels with a dynamic information display. However, current studies to design such hydrogel materials inevitably include sophisticated chemistry, complex preparation processes, and particular experimental setups.

Linearly-Changed Thermal Behavior and Depressed Brill Transition in Long-Chain Polyamides Substituted by Methyl Side Groups.

Side substitution is an effective way of functionalizing and modifying the properties of polyamides. Meanwhile, side substitution would significantly influence the crystallization kinetics and polymorphic phase transition of polyamides, which, however, has not been well elucidated. Herein, we synthesized the side-substituted long-chain polyamides with various content of methyl pendent groups and investigated their crystallization and phase transition behaviors.

Ultrasensitive Ionic Conductors with Tunable Resistance Switching Temperature Enabled by Phase Transformation of Polymer Cocrystals.

Phase-transformable ionic conductors (PTICs) show significant prospects for functional applications due to their reversible resistance switching property. However, the representative design principle of PTICs is utilizing the melt-crystallization transition of ionic liquids, and the resistance switching temperatures of such PTICs cannot be tuned as desired. Herein, a new strategy is proposed to design PTICs with on-demand resistance switching temperatures by using the melt-crystallization transition of polymer cocrystal phase, whose melting temperature shows a linear relationship with the polymer compositions.

Crystal Polymorphism of Isodimorphic Polyesters Tuned by - and -C═C Comonomer Units.

Polymorphism is ubiquitous in polymer crystallization due to the diversified chain conformations and interchain packings in polymer crystals. Controlling chain conformation is effective in tailoring the crystal polymorphism of polymers, which, however, is challenging at the molecular level. Herein, we have synthesized poly(butylene adipate) (PBA)-based copolymers containing C═C units and demonstrated the important role of /-C═C units in tuning the chain conformation and crystal polymorphism of polymers.

Hexagonal Phase Formation and Crystalline Structural Transition in Long-Spaced Aliphatic Polyesters with Side Groups.

Side substitution is an effective method for the chemical modification and functionalization of linear polyesters. The presence of side groups can have a profound effect on the crystalline structure and phase transition of semicrystalline polyesters. Herein, we synthesized the long-spaced polyesters with -OH and -CH side groups and various methylene segment lengths and studied the effects of the side groups on the crystal polymorph and phase transition of substituted polyesters.

Impact of Entanglement on Folding of Semicrystalline Polymer during Crystallization.

Upon cooling, semicrystalline polymers experience crystallization and form alternatively stacked layers consisting of thin crystal lamellae and amorphous ones. The unique morphology, crystallinity, and crystallization kinetics highly depend on the molecular weight. Therefore, it is deduced that entanglement impacts crystallization kinetics, as well as hierarchically crystalline structures.

Tunable Crystallization Kinetics and Crystal Polymorphism in Semicrystalline Polymers: Insight into the Multilevel Structural Order of Polymer Melts.

The melting of semicrystalline polymers is a typical multistep process and involves a series of intermediate melt states. However, the structural characteristics of the intermediate polymer melt is unclear. Herein, we choose polymorphic -1,4-polyisoprene (PI) as a model polymer system and elucidate the structures of the intermediate polymer melt and their strong effects on the following crystallization process.

Multi-Level Information Encryption/Decryption of Fluorescent Hydrogels Based on Spatially Programmed Crystal Phases.

The growing urgence of information protection promotes continuously the development of information-encryption technique. To date, hydrogels have become an emerging candidate for advanced information-encryption materials, because of their unique stimulus responsiveness. However, current methods to design multi-level information-encrypted hydrogels usually need sophisticated chemistry or experimental setup.

Structural Organizations of a Mesogen-Terminated Semicrystalline Polymer: Chain Termini Ordering between Polymer Crystal Lamellae.

In polymer crystallization, the chain end groups are generally excluded into the nanoscaled amorphous regions confined between crystal lamellae. Understanding the structural characteristic and evolution of interlamellar end groups is of great importance to control the macroscopic properties of polymers. However, the structural evolution of those confined end groups and related physical evidence remain unclear.

Thermoresponsive Water-in-Oil-in-Water Pickering Double Emulsions Stabilized with Biodegradable and Semicrystalline Poly(ethylene glycol)--poly(ε-caprolactone--δ-valerolactone) Diblock Copolymer Micelles for Controlled Release.

Water-in-oil-in-water (W/O/W) Pickering double emulsions are promising materials for the construction of carriers for water-soluble and oil-soluble molecules or drug delivery systems if the contradictive trade-off between their extreme stability and controlled release properties can be resolved. In this study, biodegradable and biocompatible poly(ethylene glycol)--poly(ε-caprolactone--δ-valerolactone) (PEG--PCVL) diblock copolymers with predesigned hydrophilic to hydrophobic block length ratios and nearly identical ε-caprolactone/δ-valerolactone molar ratio (8/2), were synthesized by ring-opening copolymerization. Then, they self-assembled to create semicrystalline micelles.

Light-Induced Crystalline Size Heterogeneity of Polymers Enables Programmable Writing, Morphing, and Mechanical Performance Designing.

Constructing the spatio-selective crystalline structures has been an effective strategy to diversify the functions and applications of polymers. However, it is still challenging to program the crystalline heterogeneity into commercialized polymers and realize associate functions by a simple yet generalizable method. Herein, we propose a facile approach to fabricate multifunctional materials by programming the spatial distribution of crystal size in semicrystalline polymers.

Retarded Crystallization and Promoted Phase Transition of Freeze-Dried Polybutene-1: Direct Evidence for the Critical Role of Chain Entanglement.

Polymorphism and crystal transition are common phenomena of semicrystalline polymers. These two behaviors are known to be controlled by the nucleation and chain mobility of polymers, both of which are constrained by the chain entanglement at the molecular level. However, the role of chain entanglement in polymorphic crystallization and crystal phase transition of polymers has not been well understood.

Asymmetric Molecular Dynamics and Anisotropic Phase Separation in the Cocrystal of the Crystalline/Crystalline Polymer Blend.

Semicrystalline polymers are categorized as either mobile or fixed crystals, depending on chain mobility in the crystalline region. In this work, we investigate molecular dynamics and phase structure in the cocrystal consisting of fixed and mobile polymer crystals by solid-state (ss) nuclear magnetic resonance (NMR) spectroscopy. It is demonstrated that (i) the mobile component begins large amplitude motions associated with crystal-crystal transition, while fixed ones keep their rigidity in the cocrystal, and (ii) asymmetric molecular dynamics leads to nanosegregations into mobile- and fixed-rich domains in the cocrystal below the melting temperature ().

Role of Chain Entanglements in the Stereocomplex Crystallization between Poly(lactic acid) Enantiomers.

Stereocomplex (SC) crystallization between polymer enantiomers has opened a promising avenue for preparing high-performance materials. However, high-crystallinity SCs are difficult to achieve for high-molecular-weight (HMW) enantiomeric blends of chiral polymers [e.g.

Microstructurally tunable pickering emulsions stabilized by poly(ethylene glycol)-b-poly(ε-caprolactone) diblock biodegradable copolymer micelles with predesigned polymer architecture.

Poly(ethylene glycol)-b-poly(ε-caprolactone) diblock copolymers (PEG-b-PCL) with predesigned hydrophilic/hydrophobic block length ratios have been synthesized and self-assembled to form micelles, then used to emulsify medium-chain triglycerides with an aqueous phase. The morphologies and sizes of PEG-b-PCL copolymer micelles have been characterized by transmission electron microscopy and dynamic light scattering. Interfacial tension testing between micellar dispersions and oil, combined with water contact angle measurements, have been performed to assess the ability of these micelles to adjust interfacial tension and micellar hydrophobicity, respectively.

Self-evolving materials based on metastable-to-stable crystal transition of a polymorphic polyolefin.

Living organisms can self-evolve with time in order to adapt to the natural environment. Analogically, self-evolving materials also show similar properties based on non-equilibrium structural transformation. The common design of these materials tends to rely on solutions and hydrogels, yet only little attention has been paid to dry materials.

Differential diffusion driven far-from-equilibrium shape-shifting of hydrogels.

Far-from-equilibrium (FFE) conditions give rise to many unusual phenomena in nature. In contrast, synthetic shape-shifting materials typically rely on monotonic evolution between equilibrium states, limiting inherently the richness of the shape-shifting behaviors. Here we report an unanticipated shape-shifting behavior for a hydrogel that can be programmed to operate FFE-like behavior.

Bioinspired Dual-Mode Temporal Communication via Digitally Programmable Phase-Change Materials.

Switchable optical properties are essential for numerous technologies including communication, anticounterfeiting, camouflage, and imaging/sensing. Typically, the switching is enabled by applying external stimulation such as UV light for fluorescence detection. In contrast, ground squirrels utilize spontaneous live infrared emission for fencing off predators as a unique way of communication.

Polymorphic Phase Formation of Liquid Crystals Distributed in Semicrystalline Polymers: An Indicator of Interlamellar and Interspherulitic Segregation.

Amorphous and melted components can segregate into the interlamellar or interspherulitic regions of polymer crystals in their blends/mixtures; this phase behavior strongly influences the physical properties and functions of materials. However, it is experimentally difficult to evaluate the spatial distributions of the other components in polymer crystals. Herein, we use a small-molecule liquid crystal (LC) as a probe and find that it forms different solid phases when mixed with the semicrystalline polymer poly(l-lactic acid) (PLLA).

Fast photothermal poly(NIPAM-co-β-cyclodextrin) supramolecular hydrogel with self-healing through host-guest interaction for intelligent light-controlled switches.

A graphene oxide/poly(N-isopropylacrylamide-co-β-cyclodextrin) (GO/poly(NIPAM-co-β-CD)) hydrogel has been synthesized through host-guest interaction between β-cyclodextrin (β-CD) and the isopropyl group of N-isopropylacrylamide (NIPAM). The product exhibits rapid responses to the stimuli of temperature and near-infrared (NIR) irradiation, self-healing properties, and excellent mechanical properties. The host-guest interaction serves as the main physical cross-linker, while a hydrogen bond between the hydroxyl group of β-CD, GO sheets and amide group of NIPAM acts as a secondary cross-linker.