Synthesis of functionalized mesoporous silica nanoparticles for colorimetric and fluorescence sensing of selective metal (Fe3+) ions in aqueous solution.

The fabrication of red fluorescent hybrid mesoporous silica-based nanosensor materials has promised the bioimaging and selective detection of toxic pollutants in aqueous solutions. In this study, we present a hybrid mesoporous silica nanosensor in which the propidium iodide (PI) was used to conveniently integrate into the mesopore walls using bis(trimethoxysilylpropyl silane) precursors. Various characterization techniques including X-ray diffraction (XRD), Fourier-transform infrared (FTIR), N2 adsorption-desorption, zeta potential, particle size analysis, thermogravimetric, and UV-visible analysis were used to analyze the prepared materials. The prepared PI integrated mesoporous silica nanoparticles (PI-MSNs) selective metal ion sensing capabilities were tested with a variety of heavy metal ions (100 mM), including Ni2+, Cd2+, Co2+, Zn2+, Cr3+, Cu2+, Al3+, Mg2+, Hg2+ and Fe3+ ions. Among the investigated metal ions, the prepared PI-MSNs demonstrated selective monitoring of Fe3+ ions with a significant visible colorimetric pink color change into orange and quenching of pink fluorescence in an aqueous suspension. The selective sensing behavior of PI-MSNs might be due to the interaction of Fe3+ ions with the integrated PI functional fluorophore present in the mesopore walls. Therefore, we emphasize that the prepared PI-MSNs could be efficient for selective monitoring of Fe3+ ions in an aqueous solution and in the biological cellular microenvironment.

High-Performance Engineered Composites Biofabrication Using Fungi.

Various natural polymers offer sustainable alternatives to petroleum-based adhesives, enabling the creation of high-performance engineered materials. However, additional chemical modifications and complicated manufacturing procedures remain unavoidable. Here, a sustainable high-performance engineered composite that benefits from bonding strategies with multiple energy dissipation mechanisms dominated by chemical adhesion and mechanical interlocking is demonstrated via the fungal smart creative platform. Chemical adhesion is predominantly facilitated by the extracellular polymeric substrates and glycosylated proteins present in the fungal outer cell walls. The dynamic feature of non-covalent interactions represented by hydrogen bonding endows the composite with extensive unique properties including healing, recyclability, and scalable manufacturing. Mechanical interlocking involves multiple mycelial networks (elastic modulus of 2.8 GPa) binding substrates, and the fungal inner wall skeleton composed of chitin and ß-glucan imparts product stability. The physicochemical properties of composite (modulus of elasticity of 1455.3 MPa, internal bond strength of 0.55 MPa, hardness of 82.8, and contact angle of 110.2°) are comparable or even superior to those of engineered lignocellulosic materials created using petroleum-based polymers or bioadhesives. High-performance composite biofabrication using fungi may inspire the creation of other sustainable engineered materials with the assistance of the extraordinary capabilities of living organisms.

Structure-Activity Relationship of Benzophenazine Derivatives for Homogeneous and Heterogenized Photooxygenation Catalysis.

Singlet oxygen is a powerful oxidant used in various applications, such as organic synthesis, medicine, and environmental remediation. Organic and inorganic photosensitizers are commonly used to generate this reactive species through energy transfer with the triplet ground state of oxygen. We describe here a series of novel benzophenazine derivatives as a promising class of photosensitizers for singlet oxygen photosensitization. In this study, we investigated the structure-activity relationship of these benzophenazine derivatives. Akin to a molecular compass, the southern fragment was first functionalized with either aromatic tertiary amines, alkyl tertiary amines, aromatic sulfur groups, alkyl sulfur groups, or cyclic ethers. Enhanced photophysical properties (in terms of triplet excited-state lifetime, absorption wavelength, triplet state energy, and O2 quenching capabilities) were obtained with cyclic ether and sulfur groups. Conversely, the presence of an amine moiety was detrimental to the photocatalysts. The western and northern fragments were also investigated and slightly undesirable to negligible changes in photophysical properties were observed. The most promising candidate was then immobilized on silica nanoparticles and its photoactivity was evaluated in the citronellol photooxidation reaction. A high NMR yield of 97 % in desired product was obtained, with only a slight decrease over several recycling runs (85 % in the fourth run). These results provide insights into the design of efficient photosensitizers for singlet oxygen generation and the development of heterogeneous systems.

Towards Sustainable Materials: A Review of Acylhydrazone Chemistry for Reversible Polymers.

Transitioning towards a circular economy, extensive research has focused on dynamic covalent bonds (DCBs) to pave the way for more sustainable materials. These bonds enable debonding and rebonding on demand, as well as facilitating end-of-life recycling. Acylhydrazone/hydrazone chemistry offers a material with high stability under neutral and basic conditions making it a promising candidate for materials research, though the material is susceptible to acid degradation. However, this degradation under acidic conditions can be exploited, making it widely applicable in self-healing and biomedical fields, with potential for reprocessing and recycling. This review highlights studies exploring the reversibility of acylhydrazone/hydrazone bonds in various polymers, altering their properties, and utilizing them in applications such as self-healing, reprocessing, and recycling. The review also focuses on how the mechanical properties are affected by the presence of dynamic linkages, and methods to improve the mechanical performance.

Carbohydrate-Based Reprocessable and Healable Covalent Adaptable Biofoams.

Polymeric foams derived from bio-based resources and capable of self-healing and recycling ability are of great demand to fulfill various applications and address environmental concerns related to accumulation of plastic wastes. In this article, a set of polyester-based covalent adaptable biofoams (CABs) synthesized from carbohydrates and other bio-derived precursors under catalyst free conditions to offer a sustainable alternative to conventional toxic isocyanate-based polyurethane foams is reported. The dynamic ß-keto carboxylate linkages present in these biofoams impart self-healing ability and recyclability to these samples. These CABs display adequate tensile properties especially compressive strength (≤123 MPa) and hysteresis behavior. The CABs swiftly stress relax at 150 °C and are reprocessable under similar temperature conditions. These biofoams have displayed potential for use as attachment on solar photovoltaics to augment the output efficiency. These CABs with limited swellability in polar protic solvents and adequate mechanical resilience are suitable for other commodity applications.

Preparation and Characterization of Novel Poly(thiourethane)-Poly(isocyanurate) Covalent Adaptable Networks: Effect of the Catalysts.

Poly(thiourethane)-based covalent adaptable networks are synthesized by reacting a trimer of hexamethylene diisocyanate (Desmodur N3300) containing isocyanurate groups in its structure with 1,6-hexanedithiol. The catalysts evaluated for this process include dibutyltin dilaurate (DBTDL), lanthanum triflate (La(OTf)3), and a thermal precursor of 1,8-diazabicyclo[5.4.0]undec-7-ene (BGDBU). The use of DBTDL results in the initiation of curing upon mixing, while the other two catalysts exhibit a latency period in the reactive mixture, with curing starting at about 90 °C. Notably, the use of the lanthanum salt produces an additional minor exothermic reaction at 80 °C. This phenomenon corresponds to the trimerization of isocyanates rending isocyanurates, leaving a portion of unreacted thiols. Materials prepared with BGDBU or La(OTf)3 present shorter relaxation times than those prepared with DBTDL. Nevertheless, the materials containing the lanthanum salt do not reach complete relaxation, likely due to the reinforcement of the permanent network through increased isocyanurate content. The formation of isocyanurates produces a stoichiometric imbalance, leaving unreacted thiols. This transforms the exchange process into a dual mechanism involving a dissociative process of thiourethanes to isocyanate and thiol, along with an interchange through thiol attacking the thiourethane group. The materials exhibit good recyclability and self-healing characteristics.

Strengthening-Durable Trade-Off and Self-Healing, Recyclable Shape Memory Polyurethanes Enabled by Dynamic Boron-Urethane Bonds.

Addressing the demand for integrating strength and durability reinforcement in shape memory polyurethane (SMPU) for diverse applications remains a significant challenge. Here a series of SMPUs with ultra-high strength, self-healing and recyclability, and excellent shape memory properties through introducing dynamic boron-urethane bonds are synthesized. The introducing of boric acid (BA) to polyurethane leading to the formation of dynamic covalent bonds (DCB) boron-urethane, that confer a robust cross-linking structure on the SMPUs led to the formation of ordered stable hydrogen-bonding network within the SMPUs. The flexible crosslinking with DCB represents a novel strategy for balancing the trade-off between strength and durability, with their strengths reaching up to 82.2 MPa while also addressing the issue of durability in prolonged usage through the provision of self-healing and recyclability. The self-healing and recyclability of SMPU are demonstrated through rapid dynamic exchange reaction of boron-urethane bonds, systematically investigated by dynamic mechanical analysis (DMA). This study sheds light on the essential role of such PU with self-healing and recyclability, contributing to the extension of the PU's service life. The findings of this work provide a general strategy for overcoming traditional trade-offs in preparing SMPUs with both high strength and good durability.

Molten salt mediated single-step synthesis of reusable nanostructured CaTiO3 for the removal and recovery of Sr2+: A potential adsorbent for the contaminated water bodies.

The facile synthesis approach for the adsorbent preparation and recyclability during decontamination of radioactive pollutants is a significant concern in water treatment. The objective of this study is to, synthesis via solid-state reaction of the nanostructured CaTiO3 for the removal and recovery of strontium (Sr2+) from the various water sources. The influence of the adsorption-dependent parameters including, initial concentration, adsorbent dose, pH, contact time and co-existing ions interference were investigated. The prepared adsorbent was characterized by different analytical techniques like FT-IR, SEM with EDAX, TEM, TGA-DTG, Powder XRD and BET surface analysis. The kinetic models were also used, and according to the kinetic models, a pseudo-second-order kinetic model (R2 = 0.999) was better fitted to the adsorption of Sr2+ ions onto CaTiO3 rather than pseudo-first-order kinetics, which could properly represent the observed adsorption of Sr2+. For the isotherm study, the results are best fitted to the Langmuir isotherm model (R2 = 0.98) with a maximum adsorption capacity of 102.04 mg/g. The common ions (Na+, Mg2+, Ca2+, and K+) and Sr2+ having a concentration of 1:2, 1:3, and 1:4, where 82.8, 79.5, and 68.2 % removal was achieved of Sr2+ in each respective matrix. In addition, the adsorption and corresponding recovery and removal for the different Sr2+spiked matrices in deionized water, tap water, well water, lake water, and seawater were investigated with 97, 65.6, 76.5, 73.9 and 17.8 % removal respectively. Also, the CaTiO3 showed excellent recyclability with minimal loss even after 5 consecutive recyclability cycles and >90% removal of strontium achieved. Hence, prepared nanostructured CaTiO3 could be considered a promising adsorbent for the removal and recovery of Sr2+ions from contaminated water bodies.

A novel and sustainable composite of L@PSAC for superior removal of pharmaceuticals from different water matrices: Production, characterization, and application.

This study endeavors to develop cost-effective environmentally friendly technology for removing harmful residual pharmaceuticals from water and wastewater by utilizing the effective adsorption of pistachio shell (PS) biochar and the degradation potency of laccase immobilized on the biochar (L@PSAC). The carbonatization and activation of the shells were optimized regarding temperature, time, and NH4NO3/PS ratio. This step yielded an optimum PS biochar (PSAC) with the highest porosity and surface area treated at 700 °C for 3 h using an NH4NO3/PS ratio of 3% wt. The immobilization of laccase onto PSAC (L@PSAC) was at its best level at pH 5, 60 U/g, and 30 °C. The optimum L@PSAC maintained a high level of enzyme activity over two months. Almost a complete removal (>99%) of diclofenac, carbamazepine, and ciprofloxacin in Milli-Q (MQ) water and wastewater was achieved. Adsorption was responsible for >80% of the removal and the rest was facilitated by laccase degradation. L@PSAC maintained effective removal of pharmaceuticals of ≥60% for up to six treatment cycles underscoring the promising application of this material for wastewater treatment. These results indicate that activated carbon derived from the pistachio shell could potentially be utilized as a carrier and adsorbent to efficiently remove pharmaceutical compounds. This enzymatic physical elimination approach has the potential to be used on a large-scale.

Macro-manufacturing robust and stable metal-organic framework beads for antibiotics removal from wastewater.

Metal-organic frameworks (MOFs) have shown great prospects in wastewater remediation. However, the easy aggregation, difficult separation and inferior reusability greatly limit their large-scale application. Herein, we proposed a facile, green and low-cost strategy to construct robust and stable MOF-based hydrogel beads (Fe-BTC-HBs) in a gram scale, and employed them to remove antibiotics from wastewater. As a result, the Fe-BTC-HBs demonstrated outstanding adsorption capacity for both ofloxacin (OFL) and tetracycline (TC) (281.17 mg/g for OFL and 223.60 mg/g for TC) under a near-neutral environment. The main adsorption mechanisms of OFL and TC were hydrogen bonding and π-π stacking interaction. Owing to its macroscopic granule and stable structure, Fe-BTC-HBs can be separated rapidly from wastewater after capturing antibiotics, and more than 85% adsorption capacity still remained after six cycles, while the powdered Fe-BTC only showed less than 6% recovery efficiency with massive weight loss (around 92%). In real industrial effluent, the adsorption performance of Fe-BTC-HBs toward two antibiotics exhibited negligible decreases (2.9% for OFL and 2.2% for TC) compared with that in corresponding solutions. Furthermore, Fe-BTC-HBs also had appealing economic and environmental benefit. Overall, the macro-manufactured MOF beads have the promising potential for the large-scale wastewater treatment.

Peroxymonosulfate activation by walnut shell activated carbon supported nano zero-valent iron for the degradation of tetracycline: Performance, degradation pathway and mechanism.

In this study, activated carbon (WS-AC) was prepared from walnut shell. Nano-zero-valent iron (nZVI) was loaded on walnut shell activated carbon by liquid phase reduction method and used as catalyst (WS-AC/nZVI) to activate peroxymonosulfate (PMS) to efficiently degrade tetracycline (TC) in solution. The composite material with a mass ratio of WS-AC to nZVI of 1:1 has the highest catalytic performance for activating PMS to degrade TC. The results showed that under the conditions of TC concentration of 100 ppm, PMS dosage of 0.2 mM and WS-AC/nZVI dosage of 0.1 g/L, the removal efficiency of TC could reach 81%. Based on quenching experiments and electron spin resonance (EPR), it was verified that •OH, SO4•- and 1O2 bound on the catalyst surface were the main reactive oxygen species during the reaction. The intermediate products of TC were identified by liquid chromatography-mass spectrometry (HPLC-MS) and DFT calculation, and the possible degradation pathway of TC was proposed. The catalyst still maintained high removal efficiency of TC after four cycles of experiments, and the minimal iron loss on the surface of the catalyst indicated that it had good stability. The efficient and stable WS-AC/nZVI activated PMS showed great potential in the degradation of antibiotics.

Unraveling the synergism mechanistic insight of O-vacancy and interfacial charge transfer in WO3-x decorated on Ag2CO3/BiOBr for photocatalysis of water pollutants: Based on experimental and density functional theory (DFT) studies.

Photocatalysis has been widely used as one of the most promising approaches to remove various pollutants in liquid or gas phases during the last decade. The main emphasis of the study is on the synergy of vacancy engineering and heterojunction formation, two widely used modifying approaches, to significantly alter photocatalytic performance. The vacancy-induced Ag2CO3/BiOBr/WO3-x heterojunction system has been fabricated using a co-precipitation technique to efficiently abate methylene blue (MB) dye and doxycycline (DC) antibiotic. The as-fabricated Ag2CO3/BiOBr/WO3-x heterojunction system displayed improved optoelectronic characteristic features because of the rational combination of dual charge transferal route and defect modulation. The Ag2CO3/BiOBr/WO3-x system possessed 97% and 74% photodegradation efficacy for MB and DC, respectively, with better charge isolation and migration efficacy. The ternary photocatalyst possessed a multi-fold increase in the reaction rate for both MB and DC, i.e., 0.021 and 0.0078 min-1, respectively, compared to pristine counterparts. Additionally, more insightful deductions about the photodegradation routes were made possible by the structural investigations of MB and DC using density functional theory (DFT) simulations. This study advances the understanding of the mechanisms forming visible light active dual Z-scheme heterojunction for effective environmental remediation.

Activity and recyclability enhancement of pH-dependent Fe0@BC-mediated heterogeneous sodium percarbonate (SPC)-reducing agents (RA) system.

Dyes pose great threats to the aquatic environment and human health. Fe0-based Fenton-like systems have been widely employed for the degradation of organic dyes. However, the regulation of degradability and recyclability was still unclear. In this study, Rhodamine B (RhB) was served as the model pollutant, hydroxylamine hydrochloride was selected as the RA, the natural photocatalysis system demonstrated stable operation. RA, as performance enhancement agent, was firstly reported in micro/nano-Zero-Valent Iron@Biochar (m/nZVI@BC) based SPC-RA system. Carrier size-fractionated m/nZVI@BC was fabricated by one-step carbothermal method. As a result, RA synergistically interacted with SPC, and the reaction time reduced from 15 min to 4 min. In the 0.010 g m/nZVI@BC-mediated SPC-RA system, over 95% of RhB (100 mg·L-1, 1041.667 mg·g-1) was successfully degraded. The maximum degradation ability could still exceed 1g·g-1 via 5 times repeated applications. Meanwhile, the loss of degradability, caused by halving SPC concentration could be compensated by RA dosage measurement. The entire degradation process was predominantly dominated by free radicals (•OH> 1O2> •O2-> •CO3-). Reactive oxidizing species (ROSs) were primarily excited by α-Fe0, Fe3C and N sites of biochar (BC). Light and BC carrier dedicated slight influence. These discoveries shed a light on the activity and recyclability regulation of catalytic material, aligning with the principles of green chemistry and cleaner production. This study demonstrates a novel approach to efficient management of solid waste disposal, reuse of waste biomass, advanced treatment of dye-containing wastewater, pollution control in aquatic environments.

Novel soy protein isolate/sodium alginate-based functional aerogel for efficient uptake of organic dye from effluents.

In response to the increasing global concern regarding water pollution, there is a growing demand for the development of novel adsorbents capable of effectively eliminating hazardous organic pollutants from effluents. In this study, we present a functional soy protein isolate (SPI)/sodium alginate (ALG)/polyethyleneimine (PEI) aerogel prepared via a facile chemical crosslinking process as a novel adsorbent with excellent capabilities for removing toxic methyl blue (MB) dye from effluents. Thanks to the synergistic dense oxygen and nitrogen-containing functional groups in the networks, the ALG/SPI/PEI (ASP) aerogel displayed high adsorption capacity for MB (106.3 mg/g) complying the adsorption kinetics and isotherm with the pseudo-second-order and Langmuir models, respectively. Remarkably, the MB adsorption capability of the ASP aerogel surpasses that of its pristine counterpart and outperforms recently reported adsorbents. Moreover, the aerogel maintained >80% of initial adsorption capability in the fourth regenerative cycle, indicating excellent reusability. The superior MB adsorbability coupled with high-efficiency regenerability in this study reveal the significant potential of ASP aerogel in efficiently eliminating organic dye from wastewater.

Synthesis of a novel magnetic calcium-rich biochar nanocomposite for efficient removal of phosphate from aqueous solution.

Phosphorus (P) scarcity and eutrophication have triggered the development of new materials for P recovery. In this work, a novel magnetic calcium-rich biochar nanocomposite (MCRB) was prepared through co-precipitation of crab shell derived biochar, Fe2+ and Fe3+. Characteristics of the material demonstrated that the MCRB was rich in calcite and that the Fe3O4 NPs with a diameter range of 18-22 nanometers were uniformly adhered on the biochar surface by strong ether linking (C-O-Fe). Batch tests demonstrated that the removal of P was pH dependent with an optimal pH of 3-7. The MCRB exhibited a superior P removal performance, with a maximum removal capacity of 105.6 mg g-1, which was even higher than the majority lanthanum containing compounds. Study of the removal mechanisms revealed that the P removal by MCRB involved the formation of hydroxyapatite (HAP-Ca5(PO4)3OH), electrostatic attraction and ligand exchange. The recyclability test demonstrated that a certain level (approximately 60%) was still maintained even after the six adsorption-desorption process, suggesting that MCRB is a promising material for P removal from wastewater.

Synthesis of bis(2-aminoethyl)amine functionalized mesoporous silica (SBA-15) adsorbent for selective adsorption of Pb2+ ions from wastewater.

Rapid growth in the industry has released large quantities of contaminants, particularly metal discharges into the environment. Heavy metal poisoning in water bodies has become a major problem due to its toxicity to living organisms. In this study, we developed a 3-chloropropyl triethoxysilane incorporated mesoporous silica nanoparticle (SBA-15) based adsorbent utilizing the sol-gel process and Pluronic 123 (P123) as a structure-directing surfactant. Furthermore, the produced SBA-15 NPs were functionalized with bis(2-aminoethyl)amine (BDA) using the surface grafting approach. The physical and chemical properties of the prepared SBA-15@BDA NPs were determined using a variety of instruments, including small-angle X-ray diffraction (SAXS), Fourier-transform infrared (FTIR), scanning electron microscope (SEM), N2 adsorption-desorption, thermogravimetric, particle size distribution, and zeta potential analysis. The MSN has a large surface area of up to 574 m2/g, a pore volume of 0.57 cm3/g, and a well-ordered mesoporous nanostructure with an average pore size of 3.6 nm. The produced SBA-15@BDA NPs were used to adsorb selectively to lead (Pd2+) ions from an aqueous solution. The adsorption study was performed under various conditions, including the influence of solution pH, adsorbent dose, adsorption kinetics, adsorption selectivity in the presence of competing metal ions, and reusability. The results of the kinetic study demonstrated that SBA-15@BDA NPs absorb selectively Pb2+ ions via chemisorption. The SBA-15@BDA NPs show Pb2+ ions with a maximum adsorption capacity of ~ 88% and an adsorbed quantity of approximately ~ 112 mg/g from the studied aqueous solution. The adsorption mechanism relies on coordination bonding between Pb2+ ions and surface-functionalized amine groups on SBA-15@BDA NPs. Furthermore, the proposed SBA-15@BDA NPs adsorbent demonstrated excellent reusability over five cycles without significantly reducing adsorption performance. As a consequence, SBA-15@BDA NPs might serve as an effective adsorbent for the selective removal of Pb2+ ions from aqueous effluent.

Achieving Exceptional Thermal and Hydrolytic Resistance in Chemically Circular Polyesters via In-Chain 1,3-Cyclobutane Rings.

Polyesters, a highly promising class of circular polymers for achieving a closed-loop sustainable plastic economy, inherently exhibit material stability defects, especially in thermal and hydrolytic instability. Here, we introduce a class of polyesters, P(4R-BL) (R=Ph, Bu), featuring conformationally rigid 1,3-cyclobutane rings in the backbone. These polyesters not only exhibit superior thermostability (Td,5%=376-380 °C) but also demonstrate exceptional hydrolytic resistance with good integrity even after 1 year in basic and acidic aqueous solutions, distinguishing themselves from typical counterparts. Tailoring the flexibility of the side group R enables the controlled thermal and mechanical performance of P(4Ph-BL) and P(4Bu-BL) to rival durable syndiotactic polystyrene (SPS) and low-density polyethylene (LDPE), respectively. Significantly, despite their high stability, both polyesters can be effectively depolymerized into pristine monomers, establishing a circular life cycle.

Ultrastable, Superrobust, and Recyclable Supramolecular Polymer Networks.

Supramolecular polymer networks (SPNs), crosslinked by noncovalent bonds, have emerged as reorganizable and recyclable polymeric materials with unique functionality. However, poor stability is an imperative challenge faced by SPNs, because SPNs are susceptible to heat, water, and/or solvents due to the dynamic and reversible nature of noncovalent bonds. Herein, the design of a noncovalent cooperative network (NCoN) to simultaneously stabilize and reinforce SPNs is reported, resulting in an ultrastable, superrobust, and recyclable SPN. The NCoN is constructed by multiplying the H-bonding sites and tuning the conformation/geometry of the H-bonding segment to optimize the multivalence cooperativity of H-bonds. The rationally designed H-bonding segment with high conformational compliance favors the formation of tightly packed H-bond arrays comprising higher-density and stronger H-bonds. Consequently, the H-bonded crosslinks in the NCoN display a covalent crosslinking effect but retain on-demand dynamics and reversibility. The resultant ultrastable SPN not only displays remarkable resistance to heat up to 120 °C, water soaking, and a broad spectrum of solvents, but also possesses a superhigh true stress at break (1.1 GPa) and an ultrahigh toughness (406 MJ m-3 ). Despite the covalent-network-like stability, the SPN is recyclable through activating its reversibility in a high-polarity solvent heated to a threshold temperature.

Torsional Strain Enabled Ring-Opening Polymerization towards Axially Chiral Semiaromatic Polyesters with Chemical Recyclability.

The development of new chemically recyclable polymers via monomer design would provide a transformative strategy to address the energy crisis and plastic pollution problem. Biaryl-fused cyclic esters were targeted to generate axially chiral polymers, which would impart new material performance. To overcome the non-polymerizability of the biaryl-fused monomer DBO, a cyclic ester Me-DBO installed with dimethyl substitution was prepared to enable its polymerizability via enhancing torsional strain. Impressively, Me-DBO readily went through well-controlled ring-opening polymerization, producing polymer P(Me-DBO) with high glass transition temperature (Tg >100 °C). Intriguingly, mixing these complementary enantiopure polymers containing axial chirality promoted a transformation from amorphous to crystalline material, affording a semicrystalline stereocomplex with a melting transition temperature more than 300 °C. P(Me-DBO) were capable of depolymerizing back to Me-DBO in high efficiency, highlighting an excellent recyclability.

Dynamic Covalent Bonds Enabled Carbon Fiber Reinforced Polymers Recyclability and Material Circularity.

Due to their remarkable features of lightweight, high strength, stiffness, high-temperature resistance, and corrosion resistance, carbon fiber reinforced polymers (CFRPs) are extensively used in sports equipment, vehicles, aircraft, windmill blades, and other sectors. The urging need to develop a resource-saving and environmentally responsible society requires the recycling of CFRPs. Traditional CFRPs, on the other hand, are difficult to recycle due to the permanent covalent crosslinking of polymer matrices. The combination of covalent adaptable networks (CANs) with carbon fibers (CFs) marks a new development path for closed-loop recyclable CFRPs and polymer resins. This review summarizes the most recent developments of closed-loop recyclable CFRPs from the unique paradigm of dynamic crosslinking polymers, CANs. These sophisticated materials with diverse functions, oriented towards CFs recycling and resin sustainability, are further categorized into several active domains of dynamic covalent bonds, including ester bonds, imine bonds, disulfide bonds, boronic ester bonds, and acetal linkages, etc. Finally, the possible strategies for the future design of recyclable CFPRs by combining dynamic covalent chemistry innovation with materials interface science are proposed.