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. Herein, a facile strategy is proposed to realize the transient anticounterfeiting by constructing bivalent metal (M2+)-coordination complexes in poly(acrylic acid) gels, where the cloud temperature (Tc) of the gels can be feasibly tuned by M2+ concentration. Therefore, the multi-Tc parts in the gel can be locally programmed by leveraging the spatially selective diffusion of M2+ with different concentrations. With the increase of temperature or the addition of a complexing agent, the transparency of the multi-Tc parts in the gel spontaneously evolves in natural light, enabling the transient information anticounterfeiting process. This work has provided a new strategy and mechanism to fabricate advanced anticounterfeiting hydrogel materials.

An Efficiently Doped PEDOT:PSS Ink Formulation via Metastable Liquid-Liquid Contact for Capillary Flow-Driven, Hierarchically and Highly Conductive Films.

With commercial electronics transitioning toward flexible devices, there is a growing demand for high-performance polymers such as poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS). Previous breakthroughs in promoting the conductivity of PEDOT:PSS, which mainly stem from solvent-treatment and transfer-printing strategies, remain as inevitable challenges due to the inefficient, unstable, and biologically incompatible process. Herein, a scalable fabrication of conducting PEDOT:PSS inks is reported via a metastable liquid-liquid contact (MLLC) method, realizing phase separation and removal of excess PSS simultaneously. MLLC-doped inks are further used to prepare ring-like films through a compromise between the coffee-ring effect and the Marangoni vortex during evaporation of droplets. The specific control over deposition conditions allows for tunable ring-like morphologies and preferentially interconnected networks of PEDOT:PSS nanofibrils, resulting in a high electrical conductivity of 6,616 S cm-1 and excellent optical transparency of the film. The combination of excellent electrical properties and the special morphology enables it to serve as electrodes for touch sensors with gradient pressure sensitivity. These findings not only provide new insight into developing a simple and efficient doping method for commercial PEDOT:PSS ink, but also offer a promising self-assembled deposition pattern of organic semiconductor films, expanding the applications in flexible electronics, bioelectronics as well as photovoltaic devices.

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. Herein, a novel strategy is reported to fabricate hydrogels with multi-level information encryption/decryption functions through spatially programming the polymorphic crystal phases. As homocrystalline and stereocomplex crystal phases in fluorescent hydrogels have different solvent stabilities, the transparency and fluorescence of the hydrogels can be regulated, thereby enabling the multi-level encryption/decryption processes. Moreover, the structural origins behind these processes are discussed. It is believe that this work will inspire future research on developing advanced information-encryption materials upon programming the polymer crystal structure.

Thermoresponsive Water-in-Oil-in-Water Pickering Double Emulsions Stabilized with Biodegradable and Semicrystalline Poly(ethylene glycol)-b-poly(ε-caprolactone-co-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)-b-poly(ε-caprolactone-co-δ-valerolactone) (PEG-b-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. The melting points of PEG-b-PCVL copolymers and their lyophilized micelles were within a physiological range of temperatures, as determined by differential scanning calorimetry. Water contact angle measurements provided evidence that the surface wettability of PEG-b-PCVL micelles could be tuned by the PCVL block mass fractions or temperature stimulus. Such PEG-b-PCVL micelles were employed as a single particulate stabilizer to develop Pickering double emulsions through a one-step emulsification technique. W/O/W Pickering double emulsions could be generated using relatively hydrophobic PEG-b-PCVL micelles with high mass fractions (exceeding about 89%) of PCVL blocks, and they displayed excellent long-term physical stabilities at room temperature. However, the Pickering double emulsions underwent a rapid microstructural transition into simple oil-in-water Pickering emulsions instead of complete demulsification at elevated temperature (37 °C), which was attributed to the hydrophilicity of micelles enhanced when the core-forming PCVL melted realized by temperature stimulus. Consequently, such W/O/W Pickering double emulsions stabilized solely with semicrystalline PEG-b-PCVL micelles exhibit thermal responsiveness, enabling them to release vitamin B12 encapsulated within the internal aqueous phase rapidly.

Thermoresponsivity, Micelle Structure, and Thermal-Induced Structural Transition of an Amphiphilic Block Copolymer Tuned by Terminal Multiple H-Bonding Units.

Constructing noncovalent interactions has been a benign method to tune the stimuli responsivity and assembled structure of polymers in solution; this is essential for controlling the functions and properties of stimuli-responsive materials. Herein, we demonstrate a novel supramolecular strategy to manipulate the cloud point (Tcp) and assembled structure of thermoresponsive polymers in solution by using H-bonding interactions. We use poly(lactide-co-glycolide)-b-poly(ethylene glycol)-b- poly(lactide-co-glycolide) (PLGA-PEG-PLGA) as a model thermoresponsive polymer and functionalize its chain terminals by the self-complementary quadruple H-bonding motif, 2-ureido-4[1H]-pyrimidinone (UPy). UPy end functionalization and increasing PLGA block length decrease the Tcp of copolymer. Both UPy- and nonfunctionalized copolymers form the spherical micelles at low temperature. They undergo the intermicellar aggregation and form large compound micelles during heating; this thermally induced structural transition causes the presence of Tcp. Due to the UPy-UPy H-bonding interactions, UPy end functionalization leads to more copolymer chains to associate in one micelle, thus, enhancing the hydrodynamic, gyration radii, core size, as well as the packing density of PLGA in micelle core and grafting density of PEG on core-shell interface. The decreased Tcp of UPy-functionalized copolymer stemmed from the stronger intermicellar attractions at high temperature. Furthermore, UPy-functionalized copolymers exhibit higher drug loading content, slower drug release rate, and better separation efficiency in removing the hydrophobic substances from water than PLGA-PEG-PLGA precursors.

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

A graphene oxide/poly(N-isopropylacrylamide-co-ß-cyclodextrin) (GO/poly(NIPAM-co-ß-CD)) hydrogel has been synthesized through host-guest interaction between ß-cyclodextrin (ß-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 ß-CD, GO sheets and amide group of NIPAM acts as a secondary cross-linker. The volume phase transition temperature and NIR response rate of such a hydrogel are controlled by its contents of ß-CD and GO. The obtained hydrogels showing excellent properties might be applied in remote contactless control devices in advanced smart technologies. Based on the excellent characteristics of the hydrogels, remote light-controlled switches have been designed, and more applications will be explored, such as intelligent light-controlled drivers and soft robots.

Dual-Crosslink Physical Hydrogels with High Toughness Based on Synergistic Hydrogen Bonding and Hydrophobic Interactions.

Constructing dual or multiple noncovalent crosslinks is highly effective to improve the mechanical and stimuli-responsive properties of supramolecular physical hydrogels, due to the synergistic effects of different noncovalent bonds. Herein, a series of tough physical hydrogels are prepared by solution casting and subsequently swelling the films of poly(ureidopyrimidone methacrylate-co-stearyl acrylate-co-acrylic acid). The hydrophobic interactions between crystallizable alkyl chains and the quadruple hydrogen bonds between ureidopyrimidone (UPy) motifs serve as the dual crosslinks of hydrogels. Synergistic effects between the hydrophobic interactions and hydrogen bonds render the hydrogels excellent mechanical properties, with tensile breaking stress up to 4.6 MPa and breaking strain up to 680%. The UPy motifs promote the crystallization of alkyl chains and the hydrophobic alkyl chains also stabilize UPy-UPy hydrogen bonding. The resultant hydrogels are responsive to multiple external stimuli, such as temperature, pH, and ion; therefore, they show the thermal-induced dual and metal ion-induced triple shape memory behaviors.

Double network hydrogels with highly enhanced toughness based on a modified first network.

A novel double network (DN) hydrogel with highly enhanced toughness has been prepared using reversible addition-fragmentation transfer (RAFT)-modified poly(2-acrylamide-2-methylpropane sulfonic acid) (PAMPS) as the first network, and polyacrylamide (PAM) as the second network. The mechanical properties of the first-network-modified PAMPS/PAM DN hydrogels have been studied and the new DN hydrogel shows remarkably high fracture energy (3.3 MJ m-3) in tensile deformation, which is nearly 9 times larger than that of the unmodified PAMPS/PAM DN hydrogel. Synchrotron radiation small-angle X-ray scattering (SAXS) was used to study the microstructures of the first-network single network (SN) and DN hydrogels. It was demonstrated by the SAXS results that the introduction of the RAFT agent into the first network enlarges the size of the ordered cross-linked domains in the SN hydrogel. The large ordered domains are beneficial for entanglement and interpenetration between the first and the second networks to dissipate concentrated stress more efficiently, resulting in the enhanced toughness of the first-network-modified DN hydrogels.

Stereocomplexed physical hydrogels with high strength and tunable crystallizability.

Physical hydrogels crosslinked by non-covalent interactions have attained increasing attention due to their good mechanical properties and processability. However, the use of feasible and controllable non-covalent interactions is highly essential for preparing such hydrogels. In this article, we report on stereocomplexed physical hydrogels prepared by simple casting and swelling of amphiphilic graft copolymers bearing a poly(acrylic acid) (PAA) backbone and poly(l-lactic acid) (PLLA) or poly(d-lactic acid) (PDLA) stereocomplexable side chains. The microstructure, swelling behavior, and mechanical and shape memory properties of the obtained hydrogels can be tuned by varying the copolymer composition and stereocomplex (SC) crystallization of PLLA/PDLA enantiomeric chains. The long PLLA or PDLA chains segregate to form hydrophobic, crystallized domains in water, serving as physical crosslinking junctions for hydrogels. SC crystallization between PLLA and PDLA further enhances the number density of physical crosslinkers of enantiomerically mixed hydrogels. The SC content increases as the PLLA/PDLA ratio approaches 1/1 in enantiomerically mixed hydrogels. The average distance between crosslinking junctions declines for the hydrogels with a high PLLA (or PDLA) mass fraction (MPLA) and SC content, due to the increased number density of physical crosslinkers. Accordingly, the tensile strength and the Young's modulus increase but the swelling ratio and the elongation-at-break of the hydrogels decrease with an increase in MPLA and SC content. The hydrogels exhibit shape memory behavior; the shape fixing ability is enhanced by the SC crystallization of PLLA/PDLA side chains in the hydrogels.

Thermoresponsive physical hydrogels of poly(lactic acid)/poly(ethylene glycol) stereoblock copolymers tuned by stereostructure and hydrophobic block sequence.

CBABC-type poly(lactic acid) (PLA)/poly(ethylene glycol) (PEG) pentablock copolymers composed of a central PEG block (A) and enantiomeric poly(l-lactic acid) (PLLA, B), poly(d-lactic acid) (PDLA, C) blocks were synthesized. Such pentablock copolymers form physical hydrogels at high concentrations in an aqueous solution, which stem from the aggregation and physical bridging of copolymer micelles. These gels are thermoresponsive and turn into sols upon heating. Physical gelation, gel-to-sol transition, crystalline state, microstructure, rheological behavior, biodegradation, and drug release behavior of PLA/PEG pentablock copolymers and their gels were investigated; they were also compared with PLA-PEG-PLA triblock copolymers containing the isotactic PLLA or atactic poly(d,l-lactide) (PDLLA) endblocks and PLLA-PEG-PLLA/PDLA-PEG-PDLA enantiomeric mixtures. PLA hydrophobic domains in pentablock copolymer gels changed from a homocrystalline to stereocomplexed structure as the PLLA/PDLA block length ratio approached 1/1. The gel of symmetric pentablock copolymer exhibited a wider gelation region, higher gel-to-sol transition temperature, higher hydrophobic domain crystallinity, larger intermicellar distance, higher storage modulus, and slower degradation and drug release rate compared to those of the asymmetric PLA/PEG pentablock copolymers or triblock copolymers. SAXS results indicated that the PLLA/PDLA blocks stereocomplexation in pentablock copolymers facilitated the intermicellar aggregation and bridging. Cylindrical ordered structures were observed in all the gels formed from the PLA/PEG pentablock and triblock copolymers. The stereocomplexation degree and intermicellar distance of the pentablock copolymer gels increased with heating.

Core-shell structure, biodegradation, and drug release behavior of poly(lactic acid)/poly(ethylene glycol) block copolymer micelles tuned by macromolecular stereostructure.

Poly(ethylene glycol)-b-poly(L-lactic acid)-b-poly(D-lactic acid) (PEG-b-PLLA-b-PDLA) stereoblock copolymers were synthesized by sequential ring-opening polymerization. Their micelle formation, precise micelle structure, biodegradation, and drug release behavior were systematically investigated and compared with the PEG-b-poly(lactic acid) (PEG-b-PLA) diblock copolymers with various PLA stereostructures and PEG-b-PLLA/PEG-b-PDLA enantiomeric mixture. Stereoblock copolymers having comparable PLLA and PDLA block lengths and enantiomerically-mixed copolymers assemble into the stereocomplexed core-shell micelles, while the isotactic and atactic PEG-b-PLA copolymers formed the homocrystalline and amorphous micelles, respectively. The PLA segments in stereoblock copolymer micelles show smaller crystallinity than those in the isotactic and enantiomerically-mixed ones, attributed to the short block length and presence of covalent junction between PLLA and PDLA blocks. As indicated by the synchrotron radiation small-angle X-ray scattering results, the stereoblock copolymer micelles have larger size, micellar aggregation number, core radius, smaller core density, and looser packing of core-forming segments than the isotactic and enantiomerically-mixed copolymer micelles. These unique structural characteristics cause the stereoblock copolymer micelles to possess higher drug loading content, slower degradation, and drug release rates.

Preparation of Janus Pd/SiO2 nanocomposite particles in inverse miniemulsions.

Janus Pd/SiO2 nanocomposite particles (NCPs) were successfully synthesized through a combination of the sol-gel process of tetramethoxysilane in inverse miniemulsions and in situ reduction of Pd salts via a gas diffusion process of hydrazine. The formation of Pd nanoparticles (NPs) was verified by X-ray diffraction. The Janus morphology of the Pd/SiO2 NCPs was confirmed by microscopic observation. The Pd/SiO2 NCPs displayed a mesoporous structure. The content of Pd NPs in the NCPs could be conveniently adjusted by the K2PdCl4 loading. A formation mechanism of the Janus Pd/SiO2 NCPs was proposed. The mesoporous Janus Pd/SiO2 NCPs show good catalytic activity toward the reduction of p-nitrophenol with NaBH4.

Unique multiple soluble-insoluble phase transitions in aqueous two-phase copolymerization of acrylamide and a weakly charged comonomer.

A unique phenomenon of multiple soluble-insoluble phase transitions was found in the two-phase copolymerization of acrylamide (AM) and a weakly charged comonomer, N,N-dimethylaminoethyl methacrylate (DMAEMA), in the aqueous solution of poly(ethylene glycol) (PEG). As the DMAEMA molar fraction increased from 0 to 0.30, the insoluble-soluble (I-S) phase transition first appeared and then disappeared. Varying the PEG concentration, the salt concentration, or the pH of reaction mixture, the phase transitions were tuned dependently. The volume fractions and refractive indices of continuous and disperse phases, as well as the viscosity change in the phase transitions were investigated, and the results showed that phase reentrance had occurred in the I-S phase transition. The transitional conversion for the first S-I phase transition increased with the DMAEMA molar fraction, indicating the solubility enhancement of charged polyelectrolytes. The content of DMAEMA in the resulting copolymer first increased and then decreased as the polymerization progressed. Accordingly, the droplet size increased in the two S-I phase transitions and decreased in the I-S phase transition. And it was proved that the copolymers were molecularly solubilized after the I-S phase transition. The multiple soluble-insoluble phase transitions were ascribed to the synergistic effect of polymer concentration, solubility enhancement of charged copolymers, and the salting-out effect of ionic comonomers. A generalized mechanism for the multiple soluble-insoluble phase transitions was proposed, which showed that the effects of polymer concentration were dominant in the two S-I phase transitions, while the effects of solubility enhancement played a key role in the I-S phase transition.

A strong and tough interpenetrating network hydrogel with ultrahigh compression resistance.

A novel interpenetrating network (IPN) hydrogel with ultrahigh compressive strength and fracture strain has been prepared using the copolymer of 2-acrylamide-2-methylpropane sulfonic acid (AMPS) and acrylamide (AM) [P(AMPS-co-AM)] or N-isopropylacrylamide (NIPAM) [P(AMPS-co-NIPAM)] as the primary network and polyacrylamide (PAM) as the secondary network. The as-prepared IPN hydrogel of P(AMPS-co-AM)/PAM has a significantly high compressive strength (91.8 MPa), which is 4 times greater than that of the common PAMPS/PAM IPN hydrogel as well as the compressively strongest hydrogel reported in the literature. The P(AMPS-co-AM)/PAM IPN hydrogel is tough enough not to fracture even when the compressive strain reaches 98%. Synchrotron radiation small-angle X-ray scattering (SAXS) analysis has indicated that the presence of an AM comonomer changes the size of the physically cross-linked domains in the IPN hydrogel, which may partially account for its unique mechanical properties. This study has presented the compressively strongest hydrogel reported to date and also provided a novel and feasible method to prepare the highly strong and tough hydrogel.

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. We find that the thermal parameters of side-substituted polyamides vary linearly with the side group content, analogous to the isomorphic crystallization of random copolymers. All the solution-crystallized polyamides experience the α-γ Brill transition during heating, with the Brill transition temperature linearly decreasing as the side group content increases. Intriguingly, the γ-α transition of polyamides during cooling is suppressed with the presence of side methyl groups due to the difficulty in H-bond reorganization and gauche-trans conformational changes. This work has demonstrated the critical role of side substitution in the polymorphic crystallization and phase transition of long-chain polyamides.

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. Owing to the melt of polymer cocrystal domains and the tunable migration of ions in the resistance switching region, the obtained PTICs display ultrahigh temperature sensitivity with a superior temperature coefficient of resistance of -8.50% °C-1 around human body temperature, as compared to various ionic conductors previously reported. Therefore, the PTICs can detect tiny temperature variation, allowing for the intelligent applications for overheating warning and heat dissipation. It is believed that this work may inspire future researches on the development of advanced soft electrical devices.

Construction of a Soft Antifouling PAA/PSBMA Hydrogel Coating with High Toughness and Low Swelling through the Dynamic Coordination Bonding Provided by Al(OH)3 Nanoparticles.

Marine biofouling, resulting from the adhesion of marine organisms to ship surfaces, has long been a significant issue in the maritime industry. In this paper, we focused on utilizing soft and hydrophilic hydrogels as a potential approach for antifouling (AF) coatings. Acrylic acid (AA) with a polyelectrolyte effect and N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine (SBMA) with an antipolyelectrolyte effect were selected as monomers. By adjusting the monomer ratio, we were able to create hydrogel coatings that exhibited low swelling ratio in both fresh water and seawater. The Al(OH)3 nanoparticle, as a physical cross-linker, provided better mechanical properties (higher tensile strength and larger elongation at break) than the chemical cross-linker through the dynamic coordination bonds and plentiful hydrogen bonds. Additionally, we incorporated trehalose into the hydrogel, enabling the repair of the hydrogel network through covalent-like hydrogen bonding. The zwitterion compound SBMA endowed the hydrogel with excellent AF performance. It was found that the highest SBMA content did not lead to the best antibacterial performance, as bacterial adhesion quantity was also influenced by the charge of the hydrogel. The hydrogel with appropriate SBMA content being close to electrical neutrality exhibits the strongest zwitterionic property of PSBMA chains, resulting in the best antibacterial adhesion performance. Furthermore, the pronounced hydrophilicity of SBMA enhanced the lubrication of the hydrogel surface, thereby reducing the friction resistance when applied to the hull surface during ship navigation.

Role of poly(ethylene glycol) in surfactant-free emulsion polymerization of styrene and methyl methacrylate.

Through zeta potential and surface tension measurements and a series of polymerization experiments, the role of poly(ethylene glycol) (PEG) in the process of surfactant-free polymerization of styrene (St)/methyl methacrylate (MMA) has been investigated experimentally. Nanoscale and stable copolymer particles were formed after an abnormal process, in which the nucleation and growth of particles was different from that in previously proposed mechanisms. It has been observed that PEG can exist in both the monomer and the aqueous phases at high temperature. PEG in the aqueous phase could form copolymer particles with a loose structure, making them prone to enter the monomer phase. Entry of these copolymer particles into the monomer phase would introduce excess PEG. From the ternary phase diagram, a solubility curve could be delineated in the ternary system of PEG/monomer/copolymer. The system used the ternary solubility property to regenerate copolymer particles in the monomer phase, which maintained their morphology until the end of the polymerization. At the end, consumption of the monomer resulted in the volume contraction of the particles, and the surface potential increased. This increasing potential is a driving force to prevent particles from stacking, leading to the formation of nanoscale and stable particles.

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 trans-1,4-polyisoprene (tPI) as a model polymer system and elucidate the structures of the intermediate polymer melt and their strong effects on the following crystallization process. We find that the metastable ß crystals of the tPI melt first into an intermediate state and then recrystallize in new crystals upon thermal annealing. The intermediate melt shows multilevel structural order at the chain level depending on the melting temperature. The conformationally ordered melt can memorize the initial crystal polymorph and accelerate the crystallization process, while the ordered melt without the conformational order can only enhance the crystallization rate. This work provides deep insight into the multilevel structural order of polymer melts and its strong memory effects on the crystallization process.

Crystal Polymorphism of Isodimorphic Polyesters Tuned by cis- and trans-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 trans/cis-C═C units in tuning the chain conformation and crystal polymorphism of polymers. Both PBA-based trans- and cis-copolymers show isodimorphic crystallization behavior with the partial inclusion of C═C units in PBA crystals. The presence of trans-C═C units favors the formation of metastable ß-crystals of PBA and retards the ß-to-α crystal transition upon heating due to the highly conformational matching between trans-C═C units and ß-crystals. Conversely, the incorporation of cis-C═C units destroys the regularity of the trans conformation and favors the growth of α-crystals of PBA. This work has elucidated the crucial role of local chain conformation in the crystal polymorphism of polymers.