Luminescent Perovskite-Cross-Linked Polymer with Low Shrinkage and Excellent Stability.

When organic cross-linked polymers are combined with metal halide perovskite nanocrystals (PNCs) for realizing luminescent perovskite-polymer display materials, the stability of PNCs is enhanced and their shrinkage is suppressed. This work presents a feasible strategy for preparing CsPbBr3 nanocrystals (NCs) within a polydicyclopentadiene (PDCPD) thermosetting cross-linked resin matrix simultaneously via a one-step reaction. The obtained PDCPD@PNCs composite exhibits narrow peak half-widths (15-20 nm), high light transmittance (80%), low curing volume shrinkage (1.4%), tunable tensile properties, excellent stability, and a photoluminescence quantum yield (PLQY) of 44.3%. The composite material exhibits long-term stability in water, acid, and base solutions for over 90 days, with the PL intensity being maintained at over 90%. Furthermore, the composite is highly resistant to polar organic solvents owing to the insolubility imparted by cross-linking. White LEDs (WLED) fabricated using the as-prepared composite demonstrate excellent potential as light sources in optical devices.

Dynamic Thermosetting Resins with Synergistic Enhanced Strength and Toughness through Combination with Rigid and Soft Microdomains.

Preparation of materials that possess highly strong and tough properties simultaneously is a great challenge. Thermosetting resins as a type of widely used polymeric materials without synergistic strength and toughness limit their applications in some special fields. In this report, an effective strategy to prepare thermosetting resins with synergistic strength and toughness, is presented. In this method, the soft and rigid microspheres with dynamic hemiaminal bonds are fabricated first, followed by hot-pressing to crosslink at the interfaces. Specifically, the rigid or soft microspheres are prepared via precipitation polymerization. After hot-pressing, the resulting rigid-soft blending materials exhibit superior strength and toughness, simultaneously. As compared with the precursor rigid or soft materials, the toughness of the rigid-soft blending films (RSBFs) is improved to 240% and 2100%, respectively, while the strength is comparable to the rigid precursor. As compared with the traditional crushing, blending, and hot-pressing of rigid or soft materials to get the nonuniform materials, the strength and toughness of the RSBFs are improved to 168% and 255%, respectively. This approach holds significant promise for the fabrication of polymer thermosets with a unique combination of strength and toughness.

IMD-Net: Interpretable multi-scale detection network for infrared dim and small objects.

This study proposed an interpretable multi-scale infrared small object detection network (IMD-Net) design method to improve the precision of infrared small object detection and contour segmentation in complex backgrounds. To this end, a multi-scale object enhancement module was constructed, which converted artificially designed features into network structures. The network structure was used to enhance actual objects and extract shallow detail and deep semantic features of images. Next, a global object response, channel attention, and multilayer feature fusion modules were introduced, combining context and channel information and aggregated information, selected data, and decoded objects. Finally, the multiple loss constraint module was constructed, which effectively constrained the network output using multiple losses and solved the problems of high false alarms and high missed detections. Experimental results showed that the proposed network model outperformed local energy factor (LEF), self-regularized weighted sparse model (SRWS), asymmetric contextual modulation (ACM), and other state of the art methods in the intersection-over-union (IoU) and Fmeasure values by 10.8% and 11.3%, respectively. The proposed method performed best on the currently available datasets, achieving accurate detection and effective segmentation of dim and small objects in various infrared complex background images.

Relief of Residual Stress in Bulk Thermosets in the Glassy State by Local Bond Exchange.

The covalently cross-linked network gives thermosets superior thermal, mechanical, and electrical properties, which, however, squarely makes the large residual stress that is inevitably induced during preparation hardly relieved in the glassy state. In this work, an incredible reduction in residual stress is successfully achieved in bulk thermosets in the glassy state through introducing highly dynamic thiocarbamate bonds by "click" reactions of thiols and isocyanates. Due to the excellent dynamic behaviors of thiocarbamate bonds, local network rearrangement is achieved through thermal stimulation, while the strong 3D cross-linked network is well maintained. Ultimately, a decrease by 44% in residual stress is detected by simply annealing samples at 30 °C below glass transition temperature (Tg), during which they could well maintain more than 98.4% of the storage modulus. After the annealing, more uniform residual stress distribution is also observed, showing a 32% decline in sample standard deviation. However, the residual stress of epoxy resin, a typical thermoset as a reference, changes little even after annealing at Tg. The results prove it a feasible strategy to reduce residual stress in bulk thermosets in the glassy state by introducing proper dynamic covalent bonds.

Dynamic Cross-Linked Polyethylene Networks with High Energy Storage and Electrical Damage Self-Healability.

Dielectric polymers that exhibit high energy density Ue, low dielectric loss, and thermal resistance are ideal materials for next-generation electrical equipment. The most widely utilized approach to improving Ue involves augmenting the polarization through increasing the dielectric constant εr or the breakdown strength Eb. However, as a conflicting parameter, the dielectric loss also increases inevitably at the same time. In addition, due to the long-term work under a strong electric field or high potential, dielectric materials often produce electrical damage (electrical tree), which is one of the main factors affecting the reliability and service life of electrical equipment. To address these problems, we herein develop dynamic cross-linked polyethylene materials (PE-MA-Epo) by polyethylene-graft-maleic anhydride (PE-MA) and polar epoxy monomers, which showed high εr (>7), low dielectric loss (<0.02), high Ue (5.16 J/cm3 at 425 MV/m), and outstanding discharge efficiency (97%). The performances of the materials are adequate to rival biaxially oriented polypropylene (BOPP) films. Moreover, the excellent self-healing capability of PE-MA-Epo enables the total recovery of εr and tan δ after electrical tree healing. After two cycles of electrical breakdown healing, Eb remained at 80%, which improves the durability and reliability of dielectric polymers. Therefore, PE-MA-Epo shows great potential for applications in advanced electronic power devices.

Molecular Clogging Organogels with Excellent Solvent Maintenance, Adjustable Modulus, and Advanced Mechanics for Impact Protection.

Inspired by mechanically interlocking supramolecular materials, exploiting the size difference between the bulky solvent and the cross-linked network mesh, a molecular clogging (MC) effect is developed to effectively inhibit solvent migration in organogels. A bulky solvent (branched citrate ester, BCE) with a molecular size above 1.4 nm is designed and synthesized. Series of MC-Gels are prepared by in situ polymerization of crosslinked polyurea with BCE as the gel solvent. The MC-Gels are colorless, transparent, and highly homogeneous, show significantly improved stability than gels prepared with small molecule solvents. As solvent migration is strongly inhibited by molecular clogging, the solvent content of the gels can be precisely controlled, resulting in a series of MC-Gels with continuously adjustable mechanics. In particular, the modulus of MC-Gel can be regulated from 1.3 GPa to 30 kPa, with a variation of 43 000 times. The molecular clogging effect also provides MC-Gels with unique high damping (maximum damping factor of 1.9), impact resistant mechanics (high impact toughness up to 40.68 MJ m-3 ). By applying shatter protection to items including eggs and ceramic armor plates, the potential of MC-Gels as high strength, high damping soft materials for a wide range of applications is well demonstrated.

Thioaminal Covalent Adaptable Networks via Thiol-Aldehyde-Amine Multicomponent Polymerization.

Multicomponent polymerization (MCP) has the advantages of high efficiency, mild reaction conditions, and high yield and has been widely used to synthesize multifunctional polymers. In this report, we develop novel covalent adaptable networks (CANs) with dynamic thioaminal covalent bonds via a simple one-pot thiol-aldehyde-amine MCP. The dynamic behaviors of the thioaminal group are demonstrated. The obtained thioaminal CANs show the tensile strength of as high as 45 MPa via MCP of pentaerythritol tetra(3-mercaptopropionate), the mixture of formaldehyde and benzaldehyde, and 4,4'-methylenedianiline. Moreover, the CANs exhibit reprocessability, recyclability, and reconfigurable shape memory behaviors. Thus, the thiol-aldehyde-amine MCP represents a simple and efficient strategy for the preparation of versatile thioaminal CANs.

Tough and Thermostable Polybutylene Terephthalate (PBT)/Vitrimer Blend with Enhanced Interfacial Compatibility.

Polymer blending is an efficient way to obtain extraordinary polymeric materials. However, once permanently cross-linked thermosets are involved in blending, there are challenges in designing and optimizing the structures and interfacial compatibility of blends. Vitrimer with dynamic covalent polymer networks provides an innovative opportunity for blending thermoplastics and thermosets. Herein, a reactive blending strategy is proposed to develop thermoplastic-thermoset blend with enhanced compatibility on the basis of dynamic covalent chemistry. Specifically, polybutylene terephthalate (PBT) and polymerized epoxy vitrimer can be directly melt blended to obtain tough and thermostable blends with desirable microstructures and interfacial interaction. Bond exchange facilitates the grafting of PBT and epoxy vitrimer chains, thus enhancing the interfacial compatibility and thermal stability of blends. The obtained blend balances the strength and stretchability of PBT and epoxy vitrimer, resulting in enhanced toughness. This work offers a new way of designing and fabricating new polymeric materials by blending thermoplastics and thermosets. It also suggests a facile direction towards upcycling thermoplastics and thermosets.

Digital micelles of encoded polymeric amphiphiles for direct sequence reading and ex vivo label-free quantification.

Identification and quantification of synthetic polymers in complex biological milieu are crucial for delivery, sensing and scaffolding functions, but conventional techniques based on imaging probe labellings only afford qualitative results. Here we report modular construction of precise sequence-defined amphiphilic polymers that self-assemble into digital micelles with contour lengths strictly regulated by oligourethane sequences. Direct sequence reading is accomplished with matrix-assisted laser desorption/ionization (MALDI) tandem mass spectrometry, facilitated by high-affinity binding of alkali metal ions with poly(ethylene glycol) dendrons and selective cleavage of benzyl-carbamate linkages. A mixture of four types of digital micelles could be identified, sequence-decoded and quantified by MALDI and MALDI imaging at cellular, organ and tissue slice levels upon in vivo administration, enabling direct comparison of biological properties for each type of digital micelle in the same animal. The concept of digital micelles and encoded amphiphiles capable of direct sequencing and high-throughput label-free quantification could be exploited for next-generation precision nanomedicine designs (such as digital lipids) and protein corona studies.

Polythiourethane Covalent Adaptable Networks for Strong and Reworkable Adhesives and Fully Recyclable Carbon Fiber-Reinforced Composites.

The development of adhesives with superior optical and mechanical performance, solvent resistance, and reworkability is gaining increasing attention in recent years. However, traditional materials do not possess reprocessability and healing characteristics for sustainable development. Here, a superior dynamic polythiourethane (PTU) adhesive with high reprocessability was developed by introducing covalent adaptable networks (CANs). Specifically, dynamic thiocarbamate bonds (TCB) were used to prepare PTU CANs, which showed dramatically enhanced malleability and recyclability. The Young's modulus of the material was 2.0 GPa and the tensile strength was 62.7 MPa. The reprocessing temperature of CANs was reduced to 80 °C while more than 90% of their mechanical properties were retained, even after being reprocessed several times. Moreover, the highly transparent and water-resistant PTU CANs featured an excellent bonding property and reworkability for various materials including glass, with a lap shear strength of 2.9 MPa, metal (5.1 MPa), and wood (6.3 MPa), compared with commercially available adhesives. Additionally, carbon fiber-reinforced composites constructed with PTU CANs were capable of being fully recycled and reused. Importantly, laminated glass with a toughened PTU-PU elastomer interface exhibited an outstanding impact fatigue-resistance behavior, sustaining thousands of impacts. These features demonstrate that PTU CANs show great potential as sustainable materials.

H-Bonding Supramolecular Hydrogels with Promising Mechanical Strength and Shape Memory Properties for Postoperative Antiadhesion Application.

Development of a physical barrier with mechanical properties similar to human smooth muscle and an on-demand degradation profile is crucial for the clinical prevention of postoperative adhesion. Herein, a series of supramolecular hydrogels (PMI hydrogels) composed of poly(ethylene glycol) (PEG), methylenediphenyl 4, 4-diisocyanate (MDI), and imidazolidinyl urea (IU, hydrogen bonding reinforced factor) with biodegradability and high toughness are reported to serve as physical barriers for abdominal adhesion prevention. The tensile fracture strength and strain of the PMI hydrogels could be adjusted in the ranges of 0.6-2.3 MPa and 100-440%, respectively, and their Young's moduli (0.2-1.6 MPa) are close to that of human soft tissues like smooth muscle and skin tissue as well as they have outstanding shape memory properties. The PMI hydrogels show good cell and tissue biocompatibility, and the in vivo retention time is in accord with the needs for the postoperative antiadhesion physical barriers. Through an abdominal defect model on mice, this study shows that the PMI hydrogel can completely prevent tissue adhesion compared to the commercialized Seprafilm with high safety. Owing to the promising mechanical properties and good biocompatibility, the PMI hydrogels may be extended for various biomedical applications and the development of advanced flexible electronic devices.

Extremely Tough, Puncture-Resistant, Transparent, and Photoluminescent Polyurethane Elastomers for Crack Self-Diagnose and Healing Tracking.

Ensuring material performance reliability and lifetime is crucial for practical operations. Small cracks on the material surface are often detrimental to its safe operation. This study describes the development of a hydrogen bond-rich puncture-resistant polyurethane elastomer with supertoughness. The as-prepared polyurethane transparent films feature high tensile break strength (57.4 MPa) and great toughness (228 MJ m-3). Additionally, a facile, low-cost, crack self-diagnostic approach through photoluminescence using a small luminous pen is reported. The materials efficiently achieved self-healing at 90 °C after the crack formation. The change of fluorescence intensity on the crack can be used to track the self-healing process. Therefore, this work provides a guideline for the material design of supertough, puncture-resistant, transparent, and healable elastomers and a crack self-diagnosis and healing approach.

A Series Three-Dimensional Ln4Cr4 (Ln = Gd, Tb, Er) Heterometallic Cluster-Based Coordination Polymers Containing Interesting Nanotubes Exhibiting High Magnetic Entropy.

A series of novel 3D 3d-4f heterometallic cluster-based coordination polymers, [Ln4Cr4(µ3-O)4(µ4-O)4(NA)8(H2O)12]·xH2O (Ln = 1-Gd, 2-Tb, 3-Er; HNA = nicotinic acid; x = 13 (1-Gd), 11.33 (2-Tb), 15 (3-Er)), have been successfully synthesized by hydrothermal method using nicotinic acid as bridging ligand. The single-crystal X-ray diffraction (SCXRD) analysis indicated that the basic unit of Ln4Cr4 shows a butterfly-shaped structure. Furthermore, each Ln4Cr4 cluster connects with other four Ln4Cr4 clusters by bridging NA- ligands to form a 3D structure containing interesting 1D honeycomb-shaped coordination nanotubes. The variable temperature magnetic susceptibility measurements of compound 1 revealed that the existence of antiferromagnetic (AF) coupling between the metal ions in the Gd4Cr4 clusters. Field-dependent isothermal magnetization studies displayed that the magnetic entropy change (-ΔSm) value of 1-Gd reached 22.05 J K-1 kg-1.

Catalyst-Free One-Step Preparation of Self-Crosslinked pH-Responsive Vesicles.

The fabrication of block copolymer (BCP) vesicles with controlled membrane permeability and promising stability remains a considerable challenge. Herein, a new type of pH-responsive and self-crosslinked vesicle based on a hydrolytically hindered urea bond is reported. This kind of vesicle is formed by the self-assembly of a pH-responsive and hydrolytically self-crosslinkable copolymer poly(ethylene glycol)-block-poly[2-(3-(tert-butyl)-3-ethylureido)ethyl methacrylate-co-2-(diethylamino)ethyl methacrylate] (PEG-b-P(TBEU-co-DEA)). The BCP can be easily synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-(3-(tert-butyl)-3-ethylureido)ethyl methacrylate (TBEU) and 2-(diethylamino)ethyl methacrylate (DEA) using PEG-based macro-chain transfer agent. The copolymer could self-assemble into stable vesicles by the hydrophobic interaction and in situ cross-linking between amines and isocyanates after the hydrolysis of the hindered urea bonds without any catalyst. Dynamic light scattering (DLS) studies show that the vesicles exhibit enhanced stability against the dilution of organic solvent, and the size can be adjusted through the change of pH values. Moreover, the alkaline phosphatase-loaded vesicles can act as nano-reactor and enable free diffusion of small molecules into the vesicles, followed by the significantly improved fluorescence intensity of phosphate-caged fluorescein. This self-crosslinking and pH-sensitive vesicles may serve as a smart platform in controlled drug delivery and molecular reactor.

Exploring the Magnetic Interaction of Asymmetric Structures Based on Chiral VIII8 Clusters.

Polyoxovanadates (III) are important class of polyoxometalates in molecular magnetism field, and particularly the systems which contain vanadium(III) centers. To date, only very few highly reduced vanadium polynuclear complexes were reported, which remains a significant challenge to synthesize novel polyoxovanadates, owing to the characteristics of easily oxidized vanadium(III). Herein, two unprecedented petaloid chiral octanuclear polyoxovanadates, l- and d-[H2N(CH3)2]12.5(H3N(CH2)2NH3)(H3O)1.5(VIIIµ2-OH)8(SO4)16·2H2O (L-, D-V8), have been successfully obtained by solvothermal method without any chiral auxiliary. Both L- and D-V8 compounds contain the motif eight-membered ring (Vµ2-O)8(SO4)16 constituted of three different chiral entangled loops with the V atoms as nodes. Bond valence calculation (BVC) analysis indicates that all the V ions existed in L, D-V8 are +3 value. The magnetic behavior of compounds indicated ferromagnetic coupling between vanadium(III) ions. To our knowledge, it is the first chiral highly reduced polyoxovanadates that exhibit excellent ferromagnetism.

Polyoxometalate-Based Well-Defined Rodlike Structural Multifunctional Materials: Synthesis, Structure, and Properties.

The unpredictability of the polyoxometalate (POM) coordination model and the diversity of organic ligands provide more possibilities for the exploration and fabrication of various novel POM-based materials. In this work, a series of POM-based lanthanide (Ln)-Schiff base nanoclusters, [Ln(H2O)2(DAPSC)]2[Ln(H2O)3(DAPSC)]2[(SiW12O40)]3·15H2O (Ln = Sm, 1; Eu, 2; Tb, 3), have been successfully isolated by the reaction of classical Keggin POMs, a Ln3+ ion, and a Schiff-base ligand [2,6-diacetylpyridine bis(semicarbazone), abbreviated as DAPSC]. Both the hindrance effect of the organic ligand and charge balance endow the cluster with fascinating structural features of discrete and linear arrangement. The title compounds with dimensions of ca. 4 × 1 × 1 nm3 are first trimeric polyoxometalate-based nanosized compounds, constructed by saturated POM anions (SiW12O404-, denoted as SiW12). Moreover, the properties (stability, electrochemistry, third-order nonlinear optics, and magnetism) of the compounds have also been studied.

Exploring the Performance Improvement of Magnetocaloric Effect Based Gd-Exclusive Cluster Gd60.

Despite wide potential applications of Gd-clusters in magnetocaloric effect (MCE) owing to f7 electron configuration of Gd(III), the structural improvement in order to enhance MCE remains difficult. A new approach of the situ hydrolysis of acetonitrile is reported, and the slow release of small ligand CH3COO- is realized in the design and synthesis of high-nuclearity lanthanide clusters. A large lanthanide-exclusive cluster complex, [Gd60(CO3)8(CH3COO)12(µ2-OH)24(µ3-OH)96(H2O)56](NO3)15Br12(dmp)5·30CH3OH·20Hdmp (1-Gd60), was isolated under solvothermal conditions. To the best our knowledge, cluster 1 possesses the high metal/ligand ratio (magnetic density) and the largest magnetic entropy change (- Δ Smmax = 48.0 J kg-1 K-1 at 2 K for Δ H = 7 T) among previously reported high-nuclearity lanthanide clusters.

Two Pairs of Chiral "Tower-Like" Ln4 Cr4 (Ln=Gd, Dy) Clusters: Syntheses, Structure, and Magnetocaloric Effect.

Two pairs of novel chiral chromium lanthanide compounds, formulated as l- and d-[Gd4 Cr4 (IN)10 (µ3 -OH)4 (µ4 -O)4 (H2 O)12 ]⋅[IN]2 ⋅8 H2 O (1 and 3), and l- and d-[Dy4 Cr4 (IN)11 (µ3 -OH)4 (µ4 -O)4 (H2 O)8 ]⋅[IN]⋅1.5 H2 O (2 and 4) (HIN=isonicotinic acid) have been successfully synthesized and characterized. Structural analysis reveals that four Ln3+ ions and four Cr3+ ions connect with each other and yield a "tower-like" [Ln4 Cr4 ] skeleton. Apart from the above featuring an aesthetically charming structure, circular dichroism (CD) spectra confirm that compounds 1 and 3, 2 and 4 are enantiomers. To the best of our knowledge, these are the largest chiral chromium lanthanide compounds. In addition, magnetic interaction shows that Gd (the mixture of 1 and 3) exhibits significant cryogenic magnetocaloric effect (MCE) with -ΔSm =18.08 J kg-1 K-1 (34.69 mJ cm-3 K-1 ). Also, the observed second-harmonic generation efficiencies of [Gd4 Cr4 (IN)10 (µ3 -OH)4 (µ4 -O)4 (H2 O)12 ]⋅[IN]2 ⋅8 H2 O and [Dy4 Cr4 (IN)11 (µ3 -OH)4 (µ4 -O)4 (H2 O)8 ]⋅[IN]⋅1.5 H2 O are 0.3 and 0.4 times that of urea, respectively.

Three new high-nuclear transition-metal-substituted heteropolytungstates: syntheses, crystal structures, magnetic studies and NLO properties.

Three new nickel-cluster-substituted polyoxometalates (POMs), [Ni6(H2O)9(µ3-OH)3(HSiW9O34)]2·12H2O (1), [Ni(en)(H2O)3][Ni6(H2O)3(en)2L(µ3-OH)3(HSiW9O34)]2·9H2O (2) (en = ethylenediamine; L = C7H5O2 = benzoic acid) and [Ni6(L')6(CH3COO)(H2O)3(µ3-OH)3(HPW9O34)]2·9H2O (3) (L' = C5NH5 = pyridine) were successfully isolated under hydro-/solvothermal conditions. 1-3 were structurally characterized by single-crystal XRD, elemental analyses, PXRD, IR, and TGA. Compound 1 mainly consists of a pair of {Ni6SiW9} fragments and some water molecules. Interestingly, the whole structure can be regarded as the connection of {Ni6SiW9} and another unit rotated 180° through Ni-O-W bonds, forming a dimeric structure {Ni6SiW9}2. Compounds 2 and 3 also have an {Ni6XW9}2 (X = Si, P) dimer, but there is a big difference in the connection between {Ni6SiW9} units. On this basis, mono-dentate conjugated organic ligands (benzoic acid (L) and pyridine (L')) were successfully introduced. It is noteworthy that pyridine molecules were first integrated into {Ni6SiW9}-based clusters and 3 features the highest number of organic ligands (six pyridines per Ni6) in the reported {Ni6XW9}-based clusters. The introduction of organic ligands to compounds 2 and 3 can bring about better third-order nonlinear optical properties. Magnetic research indicated the existence of ferromagnetic interactions in 2-3.

A Series of Lanthanide Compounds Constructed from Ln8 Rings Exhibiting Large Magnetocaloric Effect and Interesting Luminescence.

A series of lanthanide compounds, [Ln8(CH2OHCH2OH)8(SO4)12]· m(C2H7N)· nH2O (Ln = Gd (1), Sm (2), Tb (3), La (5), m = 2, n = 2; Ln = Eu (4), m = 0, n = 8), which contain Ln8 rings by sulfate and glycol as the ligand have been synthesized and characterized. Besides, small organic amine and l-tartaric acid act as dual templating roles during the synthetic process. Magnetic investigation of compound 1 reveals the existence of weak antiferromagnetic interactions between GdIII ions and the data of magnetic entropy change (-Δ Sm) is 36.86 J K-1 kg-1 (108.55 mJ cm-3 K-1) for Δ H = 7 T at 2.0 K, which is comparatively large among GdIII based compounds. Additionally, because of the excellent luminescence properties of SmIII, TbIII, and EuIII, compounds 2-4 were investigated.