Closed-loop recyclable membranes enabled by covalent adaptable networks for water purification.

In the state-of-the-art membrane industry, membranes have linear life cycles and are commonly disposed of by landfill or incineration, sacrificing their sustainability. To date, little or no thought is given in the design phase to the end-of-life management of membranes. For the first time, we have innovated high-performance sustainable membranes, which can be closed-loop recycled after long-term usage for water purification. By synergizing membrane technology and dynamic covalent chemistry, covalent adaptable networks (CANs) with thermally reversible Diels-Alder (DA) adducts were synthesized and employed to fabricate integrally skinned asymmetric membranes via the nonsolvent-induced phase separation technique. Due to the stable and reversible features of CAN, the closed-loop recyclable membranes exhibit excellent mechanical properties and thermal and chemical stabilities as well as separation performance, which are comparable to or even higher than the state-of-the-art nonrecyclable membranes. Moreover, the used membranes can be closed-loop recycled with consistent properties and separation performance by depolymerization to remove contaminants, followed by refabrication into new membranes through the dissociation and reformation of DA adducts. This study may fill in the gaps in closed-loop recycling of membranes and inspire the advancement of sustainable membranes for a green membrane industry.

Knoevenagel C═C Metathesis Enabled Glassy Vitrimers with High Rigidity, Toughness, and Malleability.

Thermosets, characterized by their permanent cross-linked networks, present significant challenges in recyclability and brittleness. In this work, we explore a polarized Knoevenagel C═C metathesis reaction for the development of rigid yet tough and malleable thermosets. Initial investigation on small molecule model reactions reveals the feasibility of conducting the base-catalyzed C═C metathesis reaction in a solvent-free environment. Subsequently, thermosetting poly(α-cyanocinnamate)s (PCCs) were synthesized via Knoevenagel condensation between a triarm cyanoacetate star and a dialdehyde. The thermal and mechanical properties of the developed PCCs can be easily modulated by altering the structure of the dialdehyde. Remarkably, the introduction of ether groups into the PCC leads to a combination of high rigidity and toughness with Young's modulus of ∼1590 MPa, an elongation at break of ∼79%, and a toughness reaching ∼30 MJ m3. These values are competitive to traditional thermosets, in Young's modulus but far exceed them in ductility and toughness. Moreover, the C═C metathesis facilitates stress relaxation within the bulk polymer networks, thus rendering PCCs excellent malleability and reprocessability. This work overcomes the traditional limitations of thermosets, introducing groundbreaking insights for the design of rigid yet tough and malleable thermosets, and contributing significantly to the sustainability of materials.

Recyclable, Malleable, and Strong Thermosets Enabled by Knoevenagel Adducts.

Plastic recycling is critical for waste management and achieving a circular economy, but it entails difficult trade-offs between performance and recyclability. Here, we report a thermoset, poly(α-cyanocinnamate) (PCC), synthesized using Knoevenagel condensation between terephthalaldehyde (TPA) and a triarm cyanoacetate star, that tackles this difficulty by harnessing its intrinsically conjugated and dynamic chemical characteristics. PCCs exhibit extraordinary thermal and mechanical properties with a typical Tg of ∼178 °C, Young's modulus of 3.8 GPa, and tensile strength of 102 MPa, along with remarkable flexibility and dimensional and chemical stabilities. Furthermore, end-of-life PCCs can be selectively degraded and partially recycled back into one starting monomer TPA for a new production cycle or reprocessed through dynamic exchange aided by cyanoacetate chain-ends. This study lays the scientific groundwork for the design of robust and recyclable thermosets, with transformative potential in plastic engineering.

Ionogels: recent advances in design, material properties and emerging biomedical applications.

Ionic liquid (IL)-based gels (ionogels) have received considerable attention due to their unique advantages in ionic conductivity and their biphasic liquid-solid phase property. In ionogels, the negligibly volatile ionic liquid is retained in the interconnected 3D pore structure. On the basis of these physical features as well as the chemical properties of well-chosen ILs, there is emerging interest in the anti-bacterial and biocompatibility aspects. In this review, the recent achievements of ionogels for biomedical applications are summarized and discussed. Following a brief introduction of the various types of ILs and their key physicochemical and biological properties, the design strategies and fabrication methods of ionogels are presented by means of different confining networks. These sophisticated ionogels with diverse functions, aimed at biomedical applications, are further classified into several active domains, including wearable strain sensors, therapeutic delivery systems, wound healing and biochemical detections. Finally, the challenges and possible strategies for the design of future ionogels by integrating materials science with a biological interface are proposed.

Catalyst-Free α-Acetyl Cinnamate/Acetoacetate Exchange to Enable High Creep-Resistant Vitrimers.

Vitrimers represent an emerging class of polymeric materials that combine the desirable characteristics of both thermoplastics and thermosets achieved through the design of dynamic covalent bonds within the polymer networks. However, these materials are prone to creep due to the inherent instability of dynamic covalent bonds. Consequently, there are pressing demands for the development of robust and stable dynamic covalent chemistries. Here, we report a catalyst-free α-acetyl cinnamate/acetoacetate (α-AC/A) exchange reaction to develop vitrimers with remarkable creep resistance. Small-molecule model studies revealed that the α-AC/A exchange occurred at temperatures above 140 °C in bulk, whereas at 120 °C, this reaction was absent. For demonstration in the case of polymers, copolymers derived from common vinyl monomers were crosslinked with terephthalaldehyde to produce α-AC/A vitrimers with tunable thermal and mechanical performance. All resulting α-AC/A vitrimers exhibited high stability, especially in terms of creep resistance at 120 °C, while retaining commendable reprocessability when subjected to high temperatures. This work showcases the α-AC/A exchange reaction as a novel and robust dynamic covalent chemistry capable of imparting both reprocessability and high stability to cross-linked networks.

Fatty Acid-Based Coacervates as a Membrane-free Protocell Model.

Membrane-less scenarios that involve liquid-liquid phase separation (coacervation) provide clues for how protocells might emerge. Here, we report a versatile approach to construct coacervates by mixing fatty acid with biomolecule dopamine as the protocell model. The coacervate droplets are easily formed over a wide range of concentrations. The solutes with different interaction characteristics, including cationic, anionic, and hydrophobic dyes, can be well concentrated within the coacervates. In addition, reversible self-assemblies of the coacervates can be controlled by concentration, pH, temperature, salinity, and bioreaction realizing cycles between compartmentalization and noncompartmentalization. Through in situ dopamine polymerization, the stability of coacervate droplets is significantly improved, leading to higher resistance toward external factors. Therefore, the coacervates based on fatty acid and dopamine could serve as a bottom-up membrane-less protocell model that provides the links between the simple (small molecule) and complex (macromolecule) systems in the process of cell evolution.

Paper-based device for the selective determination of doxycycline antibiotic based on the turn-on fluorescence of bovine serum albumin-coated copper nanoclusters.

An enhanced ratiometric fluorescence sensor was built for on-site visual detection of doxycycline (DOX) through the interaction with bovine serum albumin on the surface of red emissive copper nanoclusters. Upon the addition of weakly fluorescent DOX, the red fluorescence from copper nanoclusters gradually decreased through the inner-filter effect (IFE), while a green fluorescence appears and significantly increases, forming an interesting fluorescent isosbestic point, which was assigned to DOX due to sensitization effect of bovine serum albumin. On the basis of this ratiometric fluorescence, the system possessed good limit of detection (LOD) of 45 nM and excellent selectivity for DOX over other tetracyclines. Based on these findings, a paper-based sensor has been fabricated for distinct visual detection of trace DOX and combined with smartphone color recognizer for quantitative detection of DOX (LOD = 83 nM). This method shows broad application prospects in environmental monitoring and food safety.

Temperature and pH Responsive Light-Harvesting System Based on AIE-Active Microgel for Cell Imaging.

A highly emissive microgel is synthesized by polymerizing tetraphenylethene (TPE) based comonomers, acrylic acid, NIPAM, and permanent crosslinker ethylenebisacrylamide (BIS) (named as TPE microgel), which exhibited temperature responsive fluorescence emission. Rhodamine B (RhB), a positively charged molecule, is then inserted onto the surface of fabricated microgels through electrostatic interaction. As a result, a novel artificial light harvesting system with high energy transfer efficiency is constructed (named as TPE microgel-RhB light harvesting system), which is the first light harvesting system based on TPE microgels presenting dual response to pH and temperature. MTT assay indicates the fabricated TPE microgel and TPE microgel-RhB light harvesting system has good cytocompatibility. The strong fluorescence and good cytocompatibility make them perfect candidates for cell imaging. The prepared emissive microgel and light-harvesting system with desirable fluorescent property not only provide a new strategy for the fabrication of tunable luminescent nanomaterials, but also expand potential applications in the fields of stomach recognition, temperature sensors, and drug delivery.

Hybridized 2D Nanomaterials Toward Highly Efficient Photocatalysis for Degrading Pollutants: Current Status and Future Perspectives.

Organic pollutants including industrial dyes and chemicals and agricultural waste have become a major environmental issue in recent years. As an alternative to simple adsorption, photocatalytic decontamination is an efficient and energy-saving technology to eliminate these pollutants from water environment, utilizing the energy of external light, and unique function of photocatalysts. Having a large specific surface area, numerous active sites, and varied band structures, 2D nanosheets have exhibited promising applications as an efficient photocatalyst for degrading organic pollutants, particularly hybridization with other functional components. The novel hybridization of 2D nanomaterials with various functional species is summarized systematically with emphasis on their enhanced photocatalytic activities and outstanding performances in environmental remediation. First, the mechanism of photocatalytic degradation is given for discussing the advantages/shortcomings of regular 2D materials and identifying the importance of constructing hybrid 2D photocatalysts. An overview of several types of intensively investigated 2D nanomaterials (i.e., graphene, g-C3 N4 , MoS2 , WO3 , Bi2 O3 , and BiOX) is then given to indicate their hybridized methodologies, synergistic effect, and improved applications in decontamination of organic dyes and other pollutants. Finally, future research directions are rationally suggested based on the current challenges.

Recent Advances in Complex Coacervation Design from Macromolecular Assemblies and Emerging Applications.

Coacervation is a process during which a homogeneous aqueous solution undergoes liquid-liquid phase separation, giving rise to two immiscible liquid phases composed of a colloid-rich coacervate phase in equilibrium with a colloid-poor phase simultaneously. Recent attempts to develop complex coacervation from macromolecular self-assemblies have diversified a large group of novel coacervate-related materials with sophisticated properties and emerging applications. In this review, the most recent progress in the design strategies of macromolecular complex coacervation is discussed with respect to different key parameters, including macromolecular structure, mixing ratio, ionic strength, pH, and temperature, etc. Furthermore, the applications of these multiple-functional coacervate materials, oriented toward advanced encapsulation, are further summarized into several active domains in wastewater treatment, protein purification, food formulation, underwater adhesives, drug delivery, and cellular mimics. Finally, perspectives and future challenges related to the further advancement of macromolecular complex coacervates are proposed.

Using Artificial Skin Devices as Skin Replacements: Insights into Superficial Treatment.

Artificial skin devices are able to mimic the flexibility and sensory perception abilities of the skin. They have thus garnered attention in the biomedical field as potential skin replacements. This Review delves into issues pertaining to these skin-deep devices. It first elaborates on the roles that these devices have to fulfill as skin replacements, and identify strategies that are used to achieve such functionality. Following which, a comparison is done between the current state of these skin-deep devices and that of natural skin. Finally, an outlook on artificial skin devices is presented, which discusses how complementary technologies can create skin enhancements, and what challenges face such devices.

Polymeric Janus Nanoparticles: Recent Advances in Synthetic Strategies, Materials Properties, and Applications.

Polymeric Janus nanoparticles with two sides of incompatible chemistry have received increasing attention due to their tunable asymmetric structure and unique material characteristics. Recently, with the rapid progress in controlled polymerization combined with novel fabrication techniques, a large array of functional polymeric Janus particles are diversified with sophisticated architecture and applications. In this review, the most recently developed strategies for controlled synthesis of polymeric Janus nanoparticles with well-defined size and complex superstructures are summarized. In addition, the pros and cons of each approach in mediating the anisotropic shapes of polymeric Janus particles as well as their asymmetric spatial distribution of chemical compositions and functionalities are discussed and compared. Finally, these newly developed structural nanoparticles with specific shapes and surface functions orientated applications in different domains are also discussed, followed by the perspectives and challenges faced in the further advancement of polymeric Janus nanoparticles as high performance materials.

pH-Responsive Poly(dimethylsiloxane) Copolymer Decorated Magnetic Nanoparticles for Remotely Controlled Oil-in-Water Nanoemulsion Separation.

A smart and recyclable oil absorber based on pH-responsive block copolymer modified magnetic nanoparticles is constructed for effective separation of oil-in-water emulsions. Superparamagnetic iron(III) oxide (Fe3 O4 ) nanoparticles are designed as the core materials for providing the separation force, and surface modification with poly(4-vinylpyridine-b-dimethyl siloxane-b-4-vinylpyridine) (P4VP-PDMS-P4VP) block copolymer is performed to supply switchable oil wettability. The mean hydrodynamic radius of the nanoparticles increases from 43.8 ± 3.6 to 75.2 ± 5.3 nm when the neutral pH is reduced to 3, due to the protonation and subsequent swelling of P4VP segments at lower pH. The nanoparticles show excellent separation performance and can absorb octadecene up to 78.2 times of their own weight, simply by switching the pH of the oil-in-water emulsion treated with the nanoparticles and using a magnetic field. The different dipole of P4VP-PDMS-P4VP and protonated P4VP-PDMS-P4VP, as confirmed by density functional theory calculations, is responsible for the different oil miscibility and wettability of the nanoparticles.

Recent Progress in Macromolecule-Anchored Hybrid Gold Nanomaterials for Biomedical Applications.

Gold nanoparticles (AuNPs), with elegant thermal, optical, or chemical properties due to quantum size effects, may serve as unique species for therapeutic or diagnostic applications. It is worth mentioning that their small size also results in high surface activity, leading to significantly impaired stability, which greatly hinders their biomedical utilizations. To overcome this problem, various types of macromolecular materials are utilized to anchor AuNPs so as to achieve advanced synergistic effect by dispersing, protecting, and stabilizing the AuNPs in polymeric-Au hybrid self-assemblies. In this review, the most recent development of polymer-AuNP hybrid systems, including AuNPs@polymeric nanoparticles, AuNPs@polymeric micelle, AuNPs@polymeric film, and AuNPs@polymeric hydrogel are discussed with respect to their different synthetic strategies. These sophisticated materials with diverse functions, oriented toward biomedical applications, are further summarized into several active domains in the areas of drug delivery, gene delivery, photothermal therapy, antibacterials, bioimaging, etc. Finally, the possible approaches for future design of multifunctional polymer-AuNP hybrids by combining hybrid chemistry with biological interface science are proposed.

Targeted and Sustained Corelease of Chemotherapeutics and Gene by Injectable Supramolecular Hydrogel for Drug-Resistant Cancer Therapy.

Coadministration of chemotherapeutics as well as therapeutic gene could play a synergistic effect on cancer treatment. It is noteworthy that targeted and sustained codelivery of chemotherapeutic and therapeutic gene was rarely achieved in previous reports, while it might serve as an important platform for treating solid tumor with possible surrounding lesions. Herein, an injectable supramolecular hydrogel formed by α-cyclodextrin (α-CD) and cationic amphiphilic copolymer made of methoxy-poly(ethylene glycol)-b-poly(ε-caprolactone)-b-poly(ethylene imine) with folic acid targeted group (MPEG-PCL-PEI-FA), is rationally designed to achieve sustained codelivery of chemotherapeutic paclitaxel (PTX) and B-cell lymphoma-2 (Bcl-2) conversion gene Nur77 in the form of nanocomplex up to 7 days, to effectively inhibit the growth of folate receptor overexpressing H460/Bcl-2 therapeutic-resistant tumors (induced by overexpression of anti-apoptotic Bcl-2 protein), with peritumoral injection rather than direct intratumoral injection of hydrogel. To the best of our knowledge, this is a pioneer report on injectable MPEG-PCL-PEI-FA/α-CD supramolecular hydrogel with the ability to codeliver and sustainedly release PTX and Nur77 gene to combat Bcl-2 overexpressed therapeutic-resistant tumors in a targeted manner, which might be beneficial for further design in personalized medicine.

Precise Synthesis of PS-PLA Janus Star-Like Copolymer.

In this work, an efficient strategy is designed for the precise synthesis of novel Janus star-like copolymer (polystyrene)8 -b-(poly(l-lactide))8 , (PLLA)8 -b-(PS)8 , consisting of two types of chemically distinct polymer arms, PS and PLLA, in an asymmetric structure. During the synthesis, PLLA hemisphere carrying protected hydroxyl groups at the focal point was first synthesized via a combined reactions of esterification, light-induced "Click" chemistry, and ring opening polymerization (ROP) using a specially designed dendron as initiator. After removing the protecting moiety, the terminal hydroxyl groups on the dendron segment is increased fourfold and further modified into bromopropionate-based macroinitiator through a two-step end group transformation reaction, followed by atom transfer radical polymerization (ATRP) of styrene to obtain the desired (PLLA)8 -b-(PS)8 Janus star-like copolymer. The versatility and efficiency of the designed synthetic strategy are demonstrated by the well-defined molecular characteristics and high yields of the targeted product. In addition to the controlled degradation behavior of the PLLA segments, the remaining bromide groups located at the distal end of PS arms could allow for further fabrication of diverse building blocks through consecutive ATRP of various monomers. This work signifies the first time for facile and precise synthesis of Janus star-like copolymer with unique biphasic structure and function control.

Hydrophilicity-Controlled Conjugated Microporous Polymers for Enhanced Visible-Light-Driven Photocatalytic H2 Evolution.

To take advantage of high surface area of network conjugated microporous polymers, four linear or network conjugated polymers L-PDBT, L-PDBT-O, N-PDBT, and N-PDBT-O are designed in terms of water-compatibility, and it turned out that microporous network N-PDBT-O exhibited the highest hydrogen evolution rate (HER) at 366 µmol h-1 under visible light irradiation (λ > 420 nm, one of best reported pristine polymer-based photocatalysts), which is three times higher than the corresponding linear L-PDBT-O. Water contact angle measurements revealed that benzothiophene-sulfone-based conjugated polymers display better water compatibility and adsorption, and the synergic effect of better hydrophilic surface and higher surface area of N-PDBT-O might eventually lead to more exposed active sites in comparison to linear L-PDBT-O in the H2 evolution suspension system. The hydrophilicity-controlled strategy could be applied to design of other network conjugated microporous polymer photocatalysts in an attempt to improve the activity.

Cyclodextrin-Based Star-Like Amphiphilic Cationic Polymer as a Potential Pharmaceutical Carrier in Macrophages.

Effective delivery of therapeutic genes or small molecular drugs into macrophages is important for cell based immune therapy, but it remains a challenge due to the intracellular reactive oxygen species and endosomal degradation of therapeutics inside immune cells. In this report, the star-like amphiphilic biocompatible ß-cyclodextrin-graft-(poly(ε-caprolactone)-block-poly(2-(dimethylamino) ethyl methacrylate)x (ß-CD-g-(PCL-b-PDMAEMA)x ) copolymer, consisting of a biocompatible cyclodextrin core, hydrophobic poly(ε-caprolactone) PCL segments and hydrophilic PDMAEMA blocks with positive charge, is optimized to achieve high efficiency gene transfection with enhanced stability, due to the micelle formation by hydrophobic PCL segments. In comparison with lipofetamine, a currently popular nonviral gene carrier, ß-CD-g-(PCL-b-PDMAEMA)x copolymer, shows better transfection efficiency of plasmid desoxyribose nucleic acid in RAW264.7 macrophages. More interestingly, this delivery platform by ß-CD-g-(PCL-b-PDMAEMA)x not only shows low toxicity but also better dexamethasone delivery efficiency, which might indicate its great potential in immunotherapy.

Polymeric Encapsulation of Turmeric Extract for Bioimaging and Antimicrobial Applications.

As a herb of the ginger family, the turmeric plant has been used as spice and colorant in the Oriental countries. The rhizome part of the plant is rich in curcumin, which has been proven to be the main ingredient responsible for turmeric's biological effects. Most research endeavors have been upon the investigation of pharmaceutical activities of curcumin, yet the fluorescence of curcumin is a bit far from well-studied. The major drawbacks associated with curcumin are its poor aqueous solubility and low stability. In this communication, the encapsulation of fluorescent turmeric extract into polymeric nanoparticles (NPs) for bioimaging and antibacterial applications is reported. Through poly(d,l-lactic-co-glycolic acid) (PLGA) encapsulation, solubility of curcumin is greatly increased, and the biodegradable nature of PLGA further enhances the biocompatibility of curcumin. These Cur-PLGA NPs are successfully demonstrated to be efficient fluorescence probes for bioimaging, and promising for antibacterial application.

Polyester elastomers for soft tissue engineering.

Polyester elastomers are soft, biodegradable and biocompatible and are commonly used in various biomedical applications, especially in tissue engineering. These synthetic polyesters can be easily fabricated using various techniques such as solvent casting, particle leaching, molding, electrospinning, 3-dimensional printing, photolithography, microablation etc. A large proportion of tissue engineering research efforts have focused on the use of allografts, decellularized animal scaffolds or other biological materials as scaffolds, but they face the major concern of triggering immunological responses from the host, on top of other issues. This review paper will introduce the recent developments in elastomeric polyesters, their synthesis and fabrication techniques, as well as their application in the biomedical field, focusing primarily on tissue engineering in ophthalmology, cardiac and vascular systems. Some of the commercial and near-commercial polyesters used in these tissue engineering fields will also be described.