Self-evolutionary recycling of flame-retardant polyurethane foam enabled by controllable catalytic cleavage.

Polyurethane (PU) foams, pivotal in modern life, face challenges suh as fire hazards and environmental waste burdens. The current reliance of PU on potentially ecotoxic halogen-/phosphorus-based flame retardants impedes large-scale material recycling. Here, our demonstrated controllable catalytic cracking strategy, using cesium salts, enables self-evolving recycling of flame-retardant PU. The incorporation of cesium citrates facilitates efficient urethane bond cleavage at low temperatures (160 °C), promoting effective recycling, while encouraging pyrolytic rearrangement of isocyanates into char at high temperatures (300 °C) for enhanced PU fire safety. Even in the absence of halogen/phosphorus components, this foam exhibits a substantial increase in ignition time (+258.8%) and a significant reduction in total smoke release (-79%). This flame-retardant foam can be easily recycled into high-quality polyol under mild conditions, 60 °C lower than that for the pure foam. Notably, the trace amounts of cesium gathered in recycled polyols stimulate the regenerated PU to undergo self-evolution, improving both flame-retardancy and mechanical properties. Our controllable catalytic cracking strategy paves the way for the self-evolutionary recycling of high-performance firefighting materials.

Biomimetic Nanoporous Transparent Universal Fire-Resistant Coatings.

The inherent flammability of most polymeric materials poses a significant fire hazard, leading to substantial property damage and loss of life. A universal flame-retardant protective coating is considered as a promising strategy to mitigate such risks; however, simultaneously achieving high transparency of the coatings remains a great challenge. Here, inspired by the moth eye effect, we designed a nanoporous structure into a protective coating that leverages a hydrophilic-hydrophobic interactive assembly facilitated by phosphoric acid protonated amino siloxane. The coating demonstrates robust adhesion to a diverse range of substrates, including but not limited to fabrics, foams, paper, and wood. As expected, its moth-eye-inspired nanoporous structure conferred a high visible light transparency of >97% and water vapor transmittance of 96%. The synergistic effect among phosphorus (P), nitrogen (N), and silicon (Si) largely enhanced the char-forming ability and restricted the decomposition of the coated substrates, which successfully endowed the coating with high fire-fighting performance. More importantly, for both flexible and rigid substrates, the coated samples all possessed great mechanical properties. This work provides a new insight for the design of protective coatings, particularly focusing on achieving high transparency.

Electrocatalytic Coenhancement of Bimetallic Polyphthalocyanine-Anchored Ru Nanoclusters Enabling Efficient Overall Water Splitting at Ampere-Level Current Densities.

Efficient electrocatalysts capable of operating continuously at industrial ampere-level current densities are crucial for large-scale applications of electrocatalytic water decomposition for hydrogen production. However, long-term industrial overall water splitting using a single electrocatalyst remains a major challenge. Here, bimetallic polyphthalocyanine (FeCoPPc)-anchored Ru nanoclusters, an innovative electrocatalyst comprising the hydrogen evolution reaction (HER) active Ru and the oxygen evolution reaction (OER) active FeCoPPc, engineered for efficient overall water splitting are demonstrated. By density functional theory calculations and systematic experiments, the electrocatalytic coenhancement effect resulting from unique charge redistribution, which synergistically boosts the HER activity of Ru and the OER activity of FeCoPPc by optimizing the adsorption energy of intermediates, is unveiled. As a result, even at a large current density of 2.0 A cm-2 , the catalyst exhibits low overpotentials of 220 and 308 mV, respectively, for HER and OER. It exhibits excellent stability, requiring only 1.88 V of cell voltage to achieve a current density of 2.0 A cm-2 in a 6.0 m KOH electrolyte at 70 °C, with a remarkable operational stability of over 100 h. This work provides a new electrocatalytic coenhancement strategy for the design and synthesis of electrocatalyst, paving the way for industrial-scale overall water splitting applications.

Controllable proton-reservoir ordered gel towards reversible switching and reliable electromagnetic interference shielding.

Smart and dynamic electromagnetic interference (EMI) shielding materials possess a remarkable capacity to modify their EMI shielding abilities, rendering them invaluable in various civil and military applications. However, the present response mechanism of switch-type EMI shielding materials is slightly restricted, as it primarily depends on continuous pressure induction, thereby resulting in concerns regarding their durability and reliability. Herein, for the first time, we demonstrate a novel method for achieving solvent-responsive, reversible switching, and robust EMI shielding capabilities using a controlled proton-reservoir ordered gel. The gel contains polyaniline (PANI) and sodium alginate (SA). Initially, SA acts as a proton reservoir for PANI in an aqueous system, enhancing the doping level of PANI and improving its electrical conductivity. Additionally, PANI and SA chains respond to diverse polar solvents, such as water, acetonitrile, ethanol, n-hexane, and air, inducing distinct conformations that affect the degree of PANI conjugation and electron migration along the chains. This process is reversible and non-destructive to the polymer chain, ensuring the effective and uncompromised performance of the EMI shielding switch. We can achieve precise and reversible tuning (on/off) of EMI shielding with different effectiveness levels by manipulating the solvents within the framework. This work opens a new solvent-stimuli avenue for the development of EMI shielding materials with reliable and intelligent on/off switching capabilities.

A One-Step Self-Flowering Method toward Programmable Ultrathin Porous Carbon-Based Materials for Microwave Absorption and Hydrogen Evolution.

Ultrathin 2D porous carbon-based materials offer numerous fascinating electrical, catalytic, and mechanical properties, which hold great promise in various applications. However, it remains a formidable challenge to fabricate these materials with tunable morphology and composition by a simple synthesis strategy. Here, a facile one-step self-flowering method without purification and harsh conditions is reported for large-scale fabrication of high-quality ultrathin (≈1.5 nm) N-doped porous carbon nanosheets (NPC) and their composites. It is demonstrated that the layered tannic/oxamide (TA/oxamide) hybrid is spontaneously blown, exfoliated, bloomed, in situ pore-formed, and aromatized during pyrolysis to form flower-like aggregated NPC. This universal one-step self-flowering system is compatible with various precursors to construct multiscale NPC-based composites (Ru@NPC, ZnO@NPC, MoS2 @NPC, Co@NPC, rGO@NPC, etc.). Notably, the programmable architecture enables NPC-based materials with excellent multifunctional performances, such as microwave absorption and hydrogen evolution. This work provides a facile, universal, scalable, and eco-friendly avenue to fabricate functional ultrathin porous carbon-based materials with programmability.

Fully recyclable multifunctional adhesive with high durability, transparency, flame retardancy, and harsh-environment resistance.

Recyclable/reversible adhesives have attracted growing attention for sustainability and intelligence but suffer from low adhesion strength and poor durability in complex conditions. Here, we demonstrate an aromatic siloxane adhesive that exploits stimuli-responsive reversible assembly driven by π-π stacking, allowing for elimination and activation of interfacial interactions via infiltration-volatilization of ethanol. The robust cohesive energy from water-insensitive siloxane assembly enables durable strong adhesion (3.5 MPa shear strength on glasses) on diverse surfaces. Long-term adhesion performances are realized in underwater, salt, and acid/alkali solutions (pH 1-14) and at low/high temperatures (-10-90°C). With reversible assembly/disassembly, the adhesive is closed-loop recycled (~100%) and reused over 100 times without adhesion loss. Furthermore, the adhesive has unique combinations of high transparency (~98% in the visible light region of 400-800 nm) and flame retardancy. The experiments and theoretical calculations reveal the corresponding mechanism at the molecular level. This π-π stacking-driven siloxane assembly strategy opens up an avenue for high-performance adhesives with circular life and multifunctional integration.

Bromodomain and extra-terminal inhibitors emerge as potential therapeutic avenues for gastrointestinal cancers.

Gastrointestinal (GI) cancers, including colorectal cancer, pancreatic cancer, liver cancer and gastric cancer, are severe social burdens due to high incidence and mortality rates. Bromodomain and extra-terminal (BET) proteins are epigenetic readers consisting of four conserved members (BRD2, BRD3, BRD4 and BRDT). BET family perform pivotal roles in tumorigenesis through transcriptional regulation, thereby emerging as potential therapeutic targets. BET inhibitors, disrupting the interaction between BET proteins and acetylated lysines, have been reported to suppress tumor initiation and progression in most of GI cancers. In this review, we will demonstrate how BET proteins participate in the GI cancers progression and highlight the therapeutic potential of targeting BET proteins for GI cancers treatment.

Gastric cancer: An epigenetic view.

Gastric cancer (GC) poses a serious threat worldwide with unfavorable prognosis mainly due to late diagnosis and limited therapies. Therefore, precise molecular classification and search for potential targets are required for diagnosis and treatment, as GC is complicated and heterogeneous in nature. Accumulating evidence indicates that epigenetics plays a vital role in gastric carcinogenesis and progression, including histone modifications, DNA methylation and non-coding RNAs. Epigenetic biomarkers and drugs are currently under intensive evaluations to ensure efficient clinical utility in GC. In this review, key epigenetic alterations and related functions and mechanisms are summarized in GC. We focus on integration of existing epigenetic findings in GC for the bench-to-bedside translation of some pivotal epigenetic alterations into clinical practice and also describe the vacant field waiting for investigation.

Precision Aliphatic Polyesters via Cross-Metathesis Polymerization.

Cross-metathesis (CM), a carbon-carbon bond transformation that features exceptional selectivity, reactivity and tolerance to functionalities, has been extensively investigated in organic chemistry. On the other hand, the use of CM in polymer synthesis is also growing in both scope and breadth, thus offering a wealth of opportunities for introducing a vast range of functionalities into polymer backbone so as to manipulate properties and expand applications. In this review, we propose the concept of "cross-metathesis polymerization" (CMP) referring to polymer synthesis via repetitive CM reaction and summarize emerging strategies for the precision synthesis of aliphatic polyesters via CMP based on the high CM tendency between acrylates and α- olefins. Due to the carbon-carbon bond-forming step-growth polymerization nature, CMP brings a new concept to polyester synthesis. This remarkable polymerization method possesses unique advantages such as mild condition, full conversion, fast kinetics, almost quantitative yield and extraordinary tolerance to functionalities. In particular, CMP provides the ability to regulate macromolecular architectures including linear, block, cyclic, star, graft, dendron, hyperbranched and dendrimer topologies. Ultimately, advanced polymeric materials with outstanding performances can be facially constructed based on these sophisticated macromolecular architectures.

Precision Aliphatic Polyesters via Segmer Assembly Polymerization.

Precise structure-property relation of a biodegradable polymer (e.g., aliphatic polyester) is anticipated only if monomer units and chiral centers are arranged in a defined primary sequence as a biomacromolecule. An emerging synthetic methodology, namely segmer assembly polymerization (SAP), is introduced in this paper to reveal the latest progress in polyester synthesis. Almost any periodic polyester envisioned can be synthesized via SAP using a programed linear or cyclic monomer. In this context, the macroscopic properties of a biodegradable polymer are fundamentally determined by microstructural information through a bottom-up approach. It can be highlighted that SAP ideally combines the precision of organic synthesis and the high efficiency of a polymerization reaction. Previously reported strategies including nucleophilic displacement, polyesterification, cross-metathesis polymerization (CMP), ring-opening polymerization (ROP), ring-opening metathesis polymerization (ROMP) and entropy-driven ring-opening metathesis polymerization (ED-ROMP) are critically reviewed in this paper to shed light on precision synthesis of aliphatic polyesters via SAP. Emerging yet challenging, SAP is a paradigm which reflects the convergence of organic and polymer chemistries and is also an efficient pathway to microstructural control. The current status, future challenges and promising trends in this realm are analyzed and discussed in this overview of the state-of-the-art.

Hyperbranched Aliphatic Polyester via Cross-Metathesis Polymerization: Synthesis and Postpolymerization Modification.

A novel postpolymerization modification methodology is demonstrated to achieve selective functionalization of hyperbranched polymer (HBP). Terminal and internal acrylates of HBP derived from cross-metathesis polymerization (CMP) are functionalized in a chemoselective fashion using the thiol-Michael chemistries. Model reactions between different thiols (benzyl mercaptan and methyl thioglycolate) and acrylates (n-hexyl acrylate and ethyl trans-2-decenoate) by using dimethylphenylphosphine or amylamine as the catalyst are investigated to optimize the modification protocol for HBP. High-molecular-weight HBP P0 is generated through CMP of AB2 monomer 2, a compound containing one α-olefin and two acrylate metathetically polymerizable groups. CMP kinetics is monitored by NMR and gel permeation chromatography (GPC). Accordingly, microstructural analysis is conducted in detail, and CMP procedure is optimized. Postpolymerization modification of HBP P0 is performed via two distinguished strategies, namely one-step complete modification and sequential modification, to generate terminally and/or internally functionalized HBPs P1-P3 in a chemoselective fashion by using phosphine-initiated and/or base-catalyzed thiol-Michael chemistries. Finally, thermal stability and glass transition behaviors of HBPs P0-P3 are studied by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively.

Precision Aliphatic Polyesters with Alternating Microstructures via Cross-Metathesis Polymerization: An Event of Sequence Control.

Sequence-regulated polymerization is realized upon sequential cross-metathesis polymerization (CMP) and exhaustive hydrogenation to afford precision aliphatic polyesters with alternating sequences. This strategy is particularly suitable for the arrangement of well-known monomer units including glycolic acid, lactic acid, and caprolactic acid on polymer chain in a predetermined sequence. First of all, structurally asymmetric monomers bearing acrylate and α-olefin terminuses are generated in an efficient and straightforward fashion. Subsequently, cross-metathesis (co)polymerization of M1 and M2 using the Hoveyda-Grubbs second-generation catalyst (HG-II) furnishes P1-P3, respectively. Finally, hydrogenation yields the desired saturated polyesters HP1-HP3. It is noteworthy that the ε-caprolactone-derived unit is generated in situ rather than introduced to tailor-made monomers prior to CMP. NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) results verify the microstructural periodicity of these precision polyesters. Differential scanning calorimetry (DSC) results reflect that polyesters without methyl side groups exhibit crystallinity, and unsaturated polyester samples show higher glass transition temperatures than their hydrogenated counterparts owing to structural rigidity.

[Study on the Estimation Algorithm of the Temperature Based on Mid-Wave Infrared Remote Sensing].

Since objects above absolute zero agree with the Plank law, the objects' temperature is reflected by the infrared radiation. With fast response and high resolution, temperature estimation based on mid-wave infrared remote sensing could realize the temperature measurement for small, high-speed and touch-free objects. A new optical system for infrared (IR) image-spectrum integration remote sensing was used to acquire infrared emission spectra from different temperatures of metal. With this basis, we extracted four appropriate spectral features which were the center of gravity position, peak position, the value of wavelength λ1 and the value of wavelength λ2 from the training samples. The relationship between temperature and these features was studied. A multiple linear regression model was established to estimate the temperatures from the spectra. The experimental results showed that, the method could distinguish hot objects with obvious temperature differences. The absolute error was less than 30 ℃ in the experimental temperature range. The accuracy was 98% in the range that the measurement error was less than 20 ℃, which was better than the 2% precision of the general system with the complex strict emissivity, atmospheric transmittance, environmental equivalent radiation temperature and some other parameters. This method could measure the temperature of the remote objects in a simple and effective way, and so could expand the application field of temperature estimation based on infrared remote sensing.

An update on the role of miRNA-155 in pathogenic microbial infections.

MicroRNAs (miRNAs) are evolutionarily conserved and naturally abundant molecules of single-stranded, non-coding RNA from ∼17 to 25 nucleotides long. MiRNAs act at post-transcriptional level either to suppress gene translation or to induce mRNA degradation, according to the degree of complementarity with their target sequences. MiR-155 is a typical representative of the miRNA family that plays a crucial role in cell differentiation and organism development. A number of studies have shown that miR-155 can not only regulate cell proliferation, apoptosis and lymphoma progression, but also plays an important part in various other physiological and pathological processes. For instance, it is involved in hematopoietic cell differentiation, cardiovascular disease, inflammation and immune responses. In recent years, the role of miR-155 in infectious diseases has attracted considerable attention. This review will highlight the participation of miR-155 in the responses to infections caused by different pathogens.