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1.
Food Chem ; 449: 139218, 2024 Aug 15.
Article in English | MEDLINE | ID: mdl-38579656

ABSTRACT

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". Meanwhile, P(LA-NI) contains numerous polar groups and unique nanoscale microphase structures to realize excellent CO2, O2 barrier, CO2/O2 selectivity, anti-fogging, and UV shielding functions. The atmosphere within the package spontaneously achieves the desirable low O2 and high CO2 levels when packaging button mushrooms with high respiratory metabolism. Eventually, the shelf life of button mushrooms reached 24 days, >3-fold extended. This PLLA-based film meets "dual carbon" and "food safety" goals and has vast potential for fresh food preservation.


Subject(s)
Carbon Dioxide , Food Packaging , Oxygen , Polyesters , Food Packaging/instrumentation , Polyesters/chemistry , Carbon Dioxide/chemistry , Oxygen/chemistry , Food Preservation/methods , Food Preservation/instrumentation , Permeability
2.
Small ; : e2401261, 2024 Mar 27.
Article in English | MEDLINE | ID: mdl-38533971

ABSTRACT

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.

3.
ACS Macro Lett ; 13(3): 354-360, 2024 Mar 19.
Article in English | MEDLINE | ID: mdl-38451171

ABSTRACT

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.

4.
Adv Mater ; 36(15): e2309568, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38227221

ABSTRACT

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.

5.
ACS Macro Lett ; 12(12): 1629-1635, 2023 Dec 19.
Article in English | MEDLINE | ID: mdl-37967041

ABSTRACT

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.

6.
ACS Macro Lett ; 12(10): 1324-1330, 2023 Oct 17.
Article in English | MEDLINE | ID: mdl-37713680

ABSTRACT

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 -CH3 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. The substituted polyesters grow in the thermally stable phase (form I) at a higher temperature. However, the polyesters crystallize in a metastable hexagonal phase (form II) with trans chain conformation at a lower temperature. The metastable form II transforms into the more stable form I during long-time annealing or upon heating; this phase transition is accompanied by chain tilting and crystal lamellar thickening. This study has elucidated the critical role of side groups in the polymorphic crystallization and phase transition of linear polyesters.

7.
ACS Macro Lett ; 12(8): 1138-1143, 2023 Aug 15.
Article in English | MEDLINE | ID: mdl-37503873

ABSTRACT

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. However, the impact of entanglement on folded crystalline chains has not been well understood due to experimental difficulties. In this work, chain-folding structures for seven 13C CH3 labeled poly(l-lactic acid)s with various molecular weights (Mws) were investigated by 13C-13C double quantum NMR spectroscopy. As a result, chain-folding events were categorized into three different Mw regimes: (i) The lowest Mw sample (2K g/mol) adopts an extended chain conformation (folding number, n = 0) (regime I); (ii) Intermediate Mw ones possess mixtures of non- and once-folded structures, and the once-folded fraction suddenly increases above the entanglement length (Me), up to Mw = 45K g/mol (regime II); (iii) The high Mw ones (Mw > 45K g/mol) adopt the highest chance for an adjacent re-entry structure with n = 1.0 in the well-developed entangled network (regime III). It was suggested that entanglement induces folding of the semicrystalline polymer.

8.
J Phys Chem Lett ; 14(22): 5181-5187, 2023 Jun 08.
Article in English | MEDLINE | ID: mdl-37253264

ABSTRACT

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.

9.
Small ; 19(9): e2205960, 2023 Mar.
Article in English | MEDLINE | ID: mdl-36538742

ABSTRACT

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.

10.
J Phys Chem Lett ; 13(50): 11703-11709, 2022 Dec 22.
Article in English | MEDLINE | ID: mdl-36512490

ABSTRACT

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. Herein, we synthesized the end-functionalized poly(lactic acid)s with a self-assemblable mesogenic termini (4-hexyloxy-4'-cyanobiphenyl) and investigated the structural evolution of mesogenic termini between crystal lamellae. Intriguingly, the mesogenic termini can organize into an ordered layer structure between polymer crystal lamellae; such a process strongly depends upon the interlamellar spacing. A higher crystallization temperature (Tc) of the polymer allows for a larger interlamellar region, favoring the formation of an ordered mesogenic layer. However, a lower Tc results in a restricted interlamellar region, in which the end groups are strongly confined without sufficient mobility to undergo structural ordering. This study provides evidence for the structural ordering of chain termini confined between polymer crystal lamellae.

11.
Langmuir ; 38(48): 14918-14927, 2022 12 06.
Article in English | MEDLINE | ID: mdl-36420614

ABSTRACT

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.


Subject(s)
Micelles , Water , Emulsions , Polyethylene Glycols/chemistry , Ethylene Glycol , Delayed-Action Preparations , Polyesters/chemistry , Polymers/chemistry , Drug Carriers/chemistry
12.
ACS Macro Lett ; 11(2): 193-198, 2022 Feb 15.
Article in English | MEDLINE | ID: mdl-35574768

ABSTRACT

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 (Tm). The observed phase separation induced by asymmetric molecular dynamics is similar to the phase separation of the miscible amorphous polymer blend; however, it is limited to two dimensions due to the parallel packing of the stems inside the cocrystal, as well as chain connectivity at the crystalline-amorphous boundary.

13.
ACS Macro Lett ; 11(2): 257-263, 2022 Feb 15.
Article in English | MEDLINE | ID: mdl-35574778

ABSTRACT

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. Herein, we use isotactic polybutene-1 (PB-1) as a model polymorphic polymer and present the crucial role of chain entanglement in the polymorphic crystallization kinetics and solid-solid phase transition. A series of less-entangled PB-1 with different entanglement degrees were successfully prepared by freeze-drying the polymer dilute solution. Compared to the bulk sample and re-entangled one, chain disentangling of PB-1 suppressed the crystallization kinetics of form II but significantly increased the phase transition rate and final transition degree from form II to form I. The disentangling-promoted II-I phase transition originated from the reduced nucleation barrier and enhanced chain mobility. This work would advance the in-depth understanding on the formation and transition mechanisms of polymorphic polymer crystals at the molecular level.

14.
ACS Macro Lett ; 11(6): 739-746, 2022 06 21.
Article in English | MEDLINE | ID: mdl-35603498

ABSTRACT

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. Various crystal size patterns in both plane and depth directions are introduced by the photothermal effect of printed ink and subsequent crystallization at different temperatures, which can be reprogrammed by repeated melting and crystallization. These obtained materials with well-defined crystal size heterogeneities exhibit diverse and regulable optics, mechanical and swelling properties, as manifested in applications including rewritable polymer paper, programmed mechanics, and advanced morphing devices. The light-induced crystal size heterogeneity of polymers has provided insights into developing advanced multifunctional materials.


Subject(s)
Polymers , Writing , Crystallization , Polymers/chemistry
15.
Food Chem ; 374: 131827, 2022 Apr 16.
Article in English | MEDLINE | ID: mdl-35021583

ABSTRACT

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. Relationship between the wettability of PEG-b-PCL copolymer micelles and their emulsification properties has been proved through phase diagram, optical microscopic observation, droplet sizes evolution and phase separation behavior of Pickering emulsion samples. Results show that both oil-in-water and water-in-oil Pickering emulsions, as well as water-in-oil-in-water (W/O/W) double-Pickering emulsions, may be controllably prepared through one-step homogenization. Double microstructure of W/O/W Pickering emulsion has proved to be extremely stable during long-term storage.


Subject(s)
Micelles , Polymers , Emulsions , Ethylene Glycols , Polyesters , Polyethylene Glycols
16.
Mater Horiz ; 9(2): 756-763, 2022 02 07.
Article in English | MEDLINE | ID: mdl-34881765

ABSTRACT

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. To break this limitation, a new principle for developing self-evolving materials from a commercialized polymorphic polyolefin via programmable crystal transition is proposed. The self-evolving materials can encode information on patterns and morphing by the metastable crystal phase. Dynamically, this phase transforms to the stable crystal phase so that the encoded information self-evolves with time, displaying the autonomous characteristic. Moreover, this process can be interrupted at an arbitrary time through solvent-induced recrystallization. These advantages have been demonstrated by fabricating an edible period indicator and imitating sophisticated human body language. It is believed that this work may inspire future research studies on self-evolving materials based on the non-equilibrium process of dry materials.


Subject(s)
Crystallization , Humans , Polyenes
17.
Nat Commun ; 12(1): 6155, 2021 10 25.
Article in English | MEDLINE | ID: mdl-34697306

ABSTRACT

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. During its temperature triggered shape-shifting event, the programmed stress induces uneven water diffusion, which pushes the hydrogel off the equilibrium based natural pathway. The resulting geometric change enhances the diffusion contrast in return, creating a self-amplifying sequence that drives the system into an FFE condition. Consequently, the hydrogel exhibits counterintuitive two opposite shape-shifting events under one single stimulation, at a speed accelerated by more than one order magnitude. Our discovery points to a future direction in creating FFE conditions to access otherwise unattainable shape-shifting behaviors, with potential implications for many engineering applications including soft robotics and medical devices.

18.
Adv Mater ; 33(24): e2008119, 2021 Jun.
Article in English | MEDLINE | ID: mdl-33960032

ABSTRACT

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. Inspired by this, live evolution of both optical and thermal images for temporal communication in which time is the encoded information is demonstrated. This system is based on a digitally light-cured polymeric phase-change material for which the crystallization kinetics can be controlled in a pixelated manner. Consequently, live evolution in optical transparency during the crystallization process enables temporal optical communication. Additionally, by harnessing the dynamic evolution of the thermal enthalpy, multiple sets of time-specific information can be reversibly retrieved as self-evolving infrared thermal images. The versatility of this dual-mode temporal system expands the scope for secured communication, with potential implications for various other areas including optics, thermal regulation, and 3D/4D printing.

19.
J Phys Chem Lett ; 12(18): 4378-4384, 2021 May 13.
Article in English | MEDLINE | ID: mdl-33938753

ABSTRACT

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). The LC can form the metastable phase at the lower PLLA crystallization temperature but the stable phase at the higher PLLA crystallization temperature in the PLLA/LC mixture. The formation of LC metastable and stable phases is attributed to the segregation of the LC material in the interlamellar and interspherulitic regions of polymer crystals, respectively. This study provides a potential way to evaluate the spatial segregation in the crystallization-induced microphase separation of polymer blends/mixtures.

20.
ACS Macro Lett ; 10(8): 1023-1028, 2021 08 17.
Article in English | MEDLINE | ID: mdl-35549120

ABSTRACT

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., poly(lactic acid)]. Despite extensive studies, why HMW enantiomeric blends have difficulty in SC crystallization has not been clarified. Herein, we chose the HMW poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) 1/1 blend as the model system and demonstrated the crucial role of chain entanglement in regulating SC crystallization. PLLA/PDLA blends with various entanglement degrees were prepared by freeze-drying. We observed that disentangling promoted not only the crystallization rate but also the crystallinity of SCs in both the nonisothermal and isothermal processes. The less-entangled samples crystallized exclusively as the high-crystallinity SCs at different temperatures, in contrast to the predominant homocrystallization that occurred in the common entangled samples. This study provides deep insight into the SC crystallization mechanism of polymers and paves the way for future research attempting to prepare SC materials.


Subject(s)
Polyesters , Polymers , Crystallization , Polyesters/chemistry , Polymers/chemistry , Stereoisomerism
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