Macromolecular Rapid Communications最新文献

The development of multifunctional nanotheranostic platforms with stimuli-responsive capabilities holds significant potential for enhancing cancer diagnosis and treatment. Herein, a glutathione (GSH)-responsive semiconducting polymer (SP) nanotheranostic system, SP/DOX-SS-PEG nanoparticles (NPs), is presented, designed for combined near-infrared II (NIR-II) fluorescence imaging (FI) and chemo-photothermal therapy. The amphiphilic SP (SP-SS-PEG) is synthesized through a multi-step reaction sequence, including Suzuki coupling, amidation, and thiol-disulfide exchange reactions, and subsequently encapsulates the anticancer drug doxorubicin (DOX) through self-assembly, resulting in the formation of GSH-responsive SP/DOX-SS-PEG NPs. These SP/DOX-SS-PEG NPs exhibit high photothermal stability and significant GSH-triggered DOX release. In vitro studies demonstrate that SP/DOX-SS-PEG NPs display enhanced cellular uptake and robust cytotoxicity against 4T1 cancer cells under 808 nm laser irradiation. Upon intravenous injection in tumor-bearing mice, NIR-II FI reveals efficient tumor accumulation and prolonged retention of the NPs. In vivo anti-tumor efficacy studies indicate that SP/DOX-SS-PEG NPs combined with 808 nm laser irradiation achieve the most significant inhibition of tumor growth, with minimal systemic toxicity. Taken together, these findings highlight the promising potential of SP/DOX-SS-PEG NPs as a multifunctional platform for precision cancer theranostics, integrating efficient NIR-II imaging, GSH-triggered drug release, and dual chemo-photothermal therapy.

The conversion and utilization of greenhouse gases and other polluting gases in a green way represents a crucial strategy for developing C₁ chemistry and mitigating the dual crises of energy scarcity and the greenhouse effect. As a class of polyatomic molecules with a relatively simple structure, gas molecules are directly involved in the assembled process as the building blocks, converting them into polymer assemblies under mild and low energy consumption, and constructing recyclable functional assembled materials, which is of great significance to enrich the building block of assembly and promote the sustainable value-added of gas. The dynamic gas bridge is a new way of combining gas with other molecules, it provides the possibility for gas conversion and dynamic assembly. This perspective systematically introduces the formation mechanism and unique physicochemical properties of the dynamic gas bridge, and discusses the latest research progress of dynamic gas-bridged chemistry with a particular focus on three key aspects: gas-regulated assembled system, gas-constructed assembled materials, and green and efficient catalysis. Finally, a perspective on critical challenges and future directions of assembled materials based on dynamic gas bridge chemistry are also highlighted.

Although the chemical recycling of polymers synthesized by controlled radical polymerization enables the recovery of pristine monomer at low temperatures, it operates efficiently under strictly anaerobic conditions. Instead, oxygen-tolerant depolymerizations are scarce, and are either restricted to the use of a boiling co-solvent or are performed in closed vessels, often suffering from low conversions. Here, an open-vessel, oxygen-tolerant depolymerization of atom transfer radical polymerization (ATRP)-synthesized polymers is introduced, leading to high percentages of monomer regeneration (>90% depolymerization efficiency). Dissolved oxygen is eliminated by either utilizing high catalyst loadings, or lower catalyst loadings combined with a radical initiator. Notably, the methodology is compatible with various solvents (i.e., anisole, 1,2,4-trichlorobenzene (TCB), 1,2-dichlorobenzene (DCB), etc.) and a range of commercially available ligands including tris 2-(dimethylamino)ethylamine (Me₆TREN) and tris(2-pyridylmethyl)amine (TPMA), as well as more inexpensive alternatives such as tris(2-aminoethyl)amine (TREN) and N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA).

Electrospun functional nanofibers enable controlled release of the loaded active ingredient and an adjustable dissolution rate. However, the widespread use of toxic organic solvents in electrospinning poses risks to human health and the environment whereas increasing production costs and complexity. This article examines the application of eco-friendly electrospinning technologies in food engineering, with a focus on water-based and melt electrospinning methods. It provides a detailed analysis of water-soluble biopolymers and synthetic polymers, highlighting their current applications and challenges in food engineering. Water-based electrospinning is proposed as a sustainable alternative, offering scalability and reduced environmental impact. This transition is essential for advancing food engineering toward more sustainable and environmentally responsible practices.

Electrospinning is a well-established and widely adopted process for producing fine and continuous nanofiber networks. Electrospun nanofibers have gained significant attention owing to their advantages, including nanoscale fiber uniformity, tunable pore size with bimodal distribution, and versatility in integrating various inorganic and organic compositions. Recently, considerable efforts have been made to align nanofibers and enhance their functionality with improved mechanical properties, faster charge transport, and more efficient mass transport in well-organized spatial structures. This mini-review highlights the fabrication of precisely aligned nanofibers using insulating block-assisted electrospinning. By manipulating the electric field between the nozzle and substrate, combined with a moving substrate, insulating block-assisted electrospinning enables the biaxial alignment of the nanofibers. This review discusses recent advancements in insulating block-assisted alignment techniques and explores the applications of these aligned nanofibers in the environmental and energy fields, including air filtration media, lithium-ion battery electrodes, hybrid gel polymer electrolytes for aqueous batteries, and reinforced composite membranes for fuel cells. In addition, the perspectives associated with the extension of insulating block-driven aligned nanofiber applications to a wide range of fields and industries is summarized.

Epoxy resin is indispensable in various applications due to its outstanding properties. However, its limited recyclability and associated environmental issues pose significant challenges for sustainable development. To address this issue, integrating recyclable Schiff base groups into epoxy resin systems to construct epoxy vitrimer with dynamic properties has become a promising strategy. Herein, a rapid degradation, enhanced mechanical properties, and low dielectric constant epoxy vitrimer (EP-BOB) is proposed through a unique rigid-flexible structure bio-based curing agent (BOB). BOB is synthesized using siloxane as a flexible chain to bridge with vanillin in a one-pot process. The incorporation of the Schiff base structure imparted exceptional degradability to EP-BOB, allowing it to fully degrade within 45 min. In addition, due to the unique rigid-flexible structure, EP-BOB exhibited lower dielectric constant (1.2-2.6) and outstanding mechanical properties (60.5 MPa tensile strength). Furthermore, Raman spectroscopy and scanning electron microscopy shows that EP-BOB can be completely degraded in the amine solution to recycle carbon fibers (CFs) without damage. Especially, the Schiff base can endow EP-BOB UV-shielding and antibacterial properties. This work opens up a new strategy for designing a rigid-flexible structure epoxy vitrimer using silicone to achieve multifunctional and high-performance EP.

The novel chemically stable hybrid co-networks (PTA-Fe) of poly(thioctic acid) coordinated with molar content (C_Fe) of 1%∼12% Fe³⁺ generated from [FeCl₄·POH]^- can be in situ synthesized via controlled/living cationic ring-opening polymerization of α-thioctic acid (TA) with tert-butyl chloride(BCl)/FeCl₃/isopropanol(POH) initiating system at 0 °C. The polymerizations are all in first order with respect to monomer, initiator and co-initiator. The resulting PTAs with desired molecular weights and relatively narrow unimodal molecular weight distribution can be obtained via quantitative initiation by changing [BCl]₀. The livingness of polymerization without chain transfer and termination is confirmed from the linear relationship between molecular weights of the resulting PTAs and polymer yields and the unchanged average polymer chains during polymerization process by Incremental Monomer Addition and All Monomer In techniques. The possible mechanism of the above polymerization is proposed. Interestingly, it is found that the PTA-Fe hybrids can behave chemically stable during storage at room temperature for 24 months when C_Fe ≥ 6.9%. To the best of the knowledge, it is the first example of in situ green synthesis of PTA-Fe hybrid co-networks with excellent chemical stability. The PTA-Fe hybrids would have potential application in the field of elastomer, adhesive and self-healing materials.

Back Cover: In article 2400555, Yasuhito Koyama and co-workers report the synthesis and the molecular ligation capability of an orthogonal agent with a nitrile N-oxide and a phenyl carbamate. The orthogonal agent enables the catalyst-free grafting reaction of PEG onto poly(styrene-co-butadiene) resin.

Biogenic synthesis of metal nanoparticles offers a sustainable alternative to traditional methods that often rely on toxic reducing agents, offering an environmentally friendly approach to nanoparticle production. The use of nanofibrous substrates, algal nanofibers (Polyacrylonitrile (PAN)/Cystoseira barbata (Cb)), for the reduction process enhances the efficiency of nanoparticle formation, providing a larger surface area for reaction and ensuring uniform distribution of the synthesized nanoparticles. Following the biogenic synthesis of Ag nanoparticles and their stabilization with xanthan gum (XG), the resulting PAN/Cb/Ag@XG nanofibrous catalyst demonstrates excellent reusability, maintaining its activity and structural integrity even after multiple cycles of use. The stabilization with XG also ensures long-term shelf life by preventing nanoparticle aggregation. Additionally, the nanofibrous material exhibits antimicrobial activity against E. coli and S. aureus. Its dual functionality-targeting harmful pathogens while avoiding secondary pollution-positions them as a sustainable and eco-friendly solution for advanced water purification and disinfection systems.