Macromolecular Rapid Communications最新文献

Large quantities of crab shells are generated in food-processing plants. In this review, the authors summarize a series of research findings on the production of nanochitin, its physical properties, chemical modifications, and functions, which have not been fully addressed in existing literature. Nanochitin, which has a width of 10 nm, is derived from chitin, the main component of crab shells, using a technology similar to that used to produce nanocellulose from wood. Unlike conventional chitin, nanochitin is well dispersed in water, making it easy to mold and process into various products for different applications. They can also be modified for specific uses through processes such as acylation and etherification to enhance their physical properties and add functionality. Nanochitin, which are known for their exceptional mechanical strength, can be blended with resins to create composite films with improved strength and elasticity. These films maintain the transparency of the resin, reduce its thermal expansion, and offer reinforcement. Chitin and its derivative chitosan are used as wound dressings, hemostatic agents, and health foods. Nanochitin and its deacetyl derivatives have diverse functions such as topical medicine for the skin, ingestion as a health food, and use as pesticides or fertilizers for plants.

Polymer gel-based ionic thermoelectric (i-TE) devices, including thermally chargeable capacitors and thermogalvanic cells, represent an innovative approach to sustainable energy harvesting by converting waste heat into electricity. This review provides a comprehensive overview of recent advancements in gel-based i-TE materials, focusing on their ionic Seebeck coefficients, the mechanisms underlying the thermodiffusion and thermogalvanic effects, and the various strategies employed to enhance their performance. Gel-based i-TE materials show great promise due to their flexibility, low cost, and suitability for flexible and wearable devices. However, challenges such as improving the ionic conductivity and stability of redox couples remain. Future directions include enhancing the efficiency of ionic-electronic coupling and developing more robust electrode materials to optimize the energy conversion efficiency in real-world applications.

Compared with other sequence structure polymers, alternating polymers usually have several unique properties, but their properties are more sensitive to changes in structure. By investigating the relationship between the structure and properties of alternating polymer chains, polymers with desired properties can likely be synthesized. In this study, a series of alternating copolymers of 1,1-diphenylethylene (DPE) derivatives and styrene derivatives, which exhibit nontraditional intrinsic luminescence (NTIL), are synthesized using living anionic polymerization. By changing the bridge plane structure of the DPE derivatives and the substituent groups of the styrene derivatives, the rigid chain structure of the alternating copolymers containing styrene derivative with a large steric hindrance is altered, and this change is observed by the altered fluorescence properties. Based on the results from experimental tests and theoretical simulations, copolymers with bridge plane structures have higher fluorescence emission intensities; moreover, a balance is observed between the electronic and steric hindrance effects of substituents on the fluorescence intensities, and polymer chains that are too rigid cause a decrease in the fluorescence intensities. Thus, the influence of the chain structure on the fluorescence properties of NTIL polymers cannot be disregarded.

The synthesis of well-defined hyperbranched aromatic polymer by Kumada-Tamao catalyst-transfer condensation polymerization of AB₂ monomer is investigated. Grignard monomer 2 is generated by treatment of 2-(3,5-dibromophenyl)-3-hexyl-5-iodothiophene (1) with 1.0 equivalent of isopropylmagnesium chloride in THF at 0 °C for 1 h and subsequently polymerized with Ni(dppe)Cl₂ at room temperature for 1 h. The molecular weight of the obtained polymer increases linearly up to ≈30 000 in proportion to the ratio of [consumed 2] /[Ni(dppe)Cl₂]₀ and in proportion to the conversion of 2, while a narrow molecular weight distribution is maintained (M_w/M_n ≤ 1.12). The matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrum shows almost a single series of peaks due to polymer with hydrogen at one end and bromine at the other, as in the case of Kumada-Tamao catalyst transfer condensation polymerization of AB monomers. The degree of branching (DB) of the obtained polymers is 0.70-0.75, irrespective of the degree of polymerization. These results indicate that the polymerization of 2 proceeds in a chain-growth polymerization manner through the intramolecular catalyst transfer mechanism, affording hyperbranched polymer with higher DB than the theoretical DB value of 0.5 in conventional polycondensation of AB₂ monomers.

In this study, a series of conjugated homopolymers (P1 and P5) and random copolymers (P2-P4) by copolymerizing naphthalene diimide (NDI) as the acceptor with varying ratios of two donor units, thiophene-imine-thiophene (TIT) and thiophene-vinylene-thiophene (TVT) is developed. The inclusion of TIT imparted degradability to the random copolymers under acidic conditions, offering a sustainable solution for electronic waste management. Structural analysis revealed that TIT favored edge-on molecular orientation, while TVT promoted face-on and end-to-end orientations. The synergistic combination of TIT and TVT in copolymerization resulted in balanced structural and functional properties with partial degradability conferred using the TIT units. The random copolymer P3, with an optimal equimolar TIT/TVT ratio, demonstrates superior electrical and mechanical performance. P3 exhibits an initial charge mobility of 0.10 cm² V⁻¹ s⁻¹ and maintained mobility of 0.0017 cm² V⁻¹ s⁻¹ under 20% strain, significantly outperforming P1 in mobility at almost strain levels. P3 also achieved a mobility retention of 31.3% under 20% strain, compared to 12.2% for P5. This study demonstrates that the copolymerization of TIT and TVT enables the fine-tuning of solid-state packing modes and molecular orientations, thereby improving both the stretchability and environmental sustainability of the materials.

Novel amphiphilic π-conjugated polymer nanoparticles tailored to efficiently absorb in the near-infrared II (NIR-II) region of the electromagnetic spectrum (>1000 nm) are presented. To achieve this, it is statistically introduced triethylene glycol substituted bithiophene moieties in various contents into a polymer backbone consisting of alternating thiophene and [1,2,5]thiadiazolo[3,4-g]quinoxaline. Through systematic modifications of monomer ratios, four amphiphilic conjugated polymers are produced. The presence of hydrophilic side chain, like triethylene glycol monomethyl ether, enhanced the polymer's concentration in aqueous media of up to 470%, versus the D-A thiophene and [1,2,5]thiadiazolo[3,4-g]quinoxaline hydrophobic analog polymer, enabling the production of surfactant-free conjugated polymer nanoparticles (CPNs) with higher concentrations (20.3 ppm maximum). Subsequently, the impact of this structural fine-tuning on the optical properties of the polymers and their corresponding CPNs are meticulous investigated. In both cases, it is identified the minimum bithiophene content that maintained the absorption spectra above 1000 nm at significantly higher concentrations. So, these findings contribute to the extensive prospects of these materials in multiple fields including biomedical and optoelectronic applications.

Metal ions, which are naturally occurring in food, soil, and water, are present in every part of the environment. Therefore, it is imperative to identify those using accessible and economical methods. In this study, a novel two-step chemical modification process for pullulan, a natural polymer, is presented. This process yields a macromolecular derivative with considerably increased fluorescence, enabling efficient detection of specific metal ions. Furthermore, the recently synthesized polymer displays distinctly divergent characteristics in comparison with the native pullulan, a consequence of the undergone chemical reactions. These include the existence of fluorescence and solubility in organic solvents, which are lacking from the initial polymer. Subsequent to exhaustive thermal and spectral analysis, the synthesized polymer's capacity to discern disparate metal ions is investigated. The interaction between metal ions and the pullulan derivative is monitored to ascertain the extent of fluorescence quenching during this process. The synthesized polymer exhibits the greatest sensitivity to Fe³⁺ and Cu²⁺ among the various cations that are examined, while Pb²⁺ and the other ions demonstrate satisfactory results. The paper also discusses the underlying quenching mechanism and possible future applications.

Nanospace has been used as a specific field for syntheses and assemblies of molecules, polymers, and materials. Free volume space among polymer chains is related to their properties, such as permeation of gas and small molecules. However, the void has not been used as a functional nanospace in previous works. The present work shows synthesis of guest conductive polymers in free volume space of conventional synthetic resins and rubbers as a new nanospace. Vapor of heteroaromatic monomer and oxidative agent is diffused into the soft dynamic nanospace among the polymer chains under ambient pressure at low temperature. The oxidative polymerization provides the conductive polymers, such as polypyrrole (PPy), in the free volume space of poly(methyl methacrylate) (PMMA), polypropylene (PP), silicone rubber (SR), and polyurethane rubber (PU). The ratio of the free volume decreases with the infiltration of the conductive polymers. The composites exhibit the improved mechanical and gas barrier properties. The rubbers containing PPy are used as mechanical-stress sensors with both the conductivity and flexibility. The free volume space of resins and rubbers can be used as a new dynamic nanospace for synthesis of functional polymer composites.

Flexible wearable electronic devices, capable of real-time physiological monitoring for personalized health management, are increasingly recognized for their convenience, comfort, and customization potential. Despite advancements, challenges persist for soft electrodes due to the skin's complex surface, biocompatibility demands, and modulus mismatch. In response, a mussel-inspired polydopamine-nanoclay-silk fibroin hydrogel (DA-C-SFH) is introduced, synthesized via a two-step process. The initial polydopamine oxidation introduces free catechol groups through polydopamine-incorporated nanoclay, followed by integration with silk fibroin, refining the fibroin network at the mesoscopic scale. This DA-C-SFH exhibits low modulus, high elasticity, adhesive properties, and biocompatibility, enabling conformal skin adhesion. It effectively detects subtle signals, such as pulse waves, and serves as a soft epidermal electrode, capable of recording various electrophysiological signals, including electrocardiograms and electromyograms, thus underscoring its potential in medical electronics and health monitoring applications.

Crystalline colloidal arrays (CCAs) composed of core-shell microspheres with thermoresponsive structural iridescence governed by Bragg's law have garnered significant attention for diverse applications. While core-shell microspheres with lower critical solution temperature (LCST) properties are extensively studied, upper critical solution temperature (UCST) counterparts remain unexplored, offering the potential to expand the application scope of thermoresponsive CCAs. In this study, poly(N-acryloyl glycinamide) (PNAGA), a UCST homopolymer, is employed for the first time to synthesize core-shell microspheres. By copolymerizing NAGA with the hydrophilic co-monomer acrylamide (AM) to form the shell, microspheres with soft shells capable of assembling into CCAs with bright iridescence are obtained. Owing to Bragg's law and the UCST properties of the shell, the diffraction wavelength of these CCAs depends on concentration, observation angle, and temperature. The CCAs exhibit thermoresponsive behavior, with a size transition temperature around 14°C. Upon heating, the shells swell, and the microspheres transition from a rigid to a soft state, leading to an increase in interparticle distance and enhanced stabilization of the ordered microsphere packing. This process results in a red shift and a significant increase in the intensity of the diffraction peak. The thermoresponsive properties of these CCAs highlight their potential as intelligent temperature-sensing materials.