Photocatalytic Hantzsch Ester-Mediated Pinacol-Type Coupling of Aldehydes and Ketones.

We have developed a photocatalyst-free reaction system that uses Hantzsch esters as photoreducing agents to promote the coupling of carbonyl compounds to 1,2-diols. The system fully utilizes the single electron transfer and proton donor roles of Hantzsch esters. The system shows a wide range of substrate application. Aromatic ketones, aliphatic ketones, and aldehydes can be applied to the catalytic system. Both self-coupling and cross-coupling can achieve ideal results.

Poly(ionic liquid)s: A Promising Matrix for Thermal Interface Materials.

The swift progression of high-density chiplet packaging, propelled by the artificial intelligence revolution, has precipitated a critical need for high-performance chip-scale thermal interface materials (TIMs). The elevated thermal resistance, limited interfacial adhesion, and mechanical flexibility intrinsic to silicone systems present a substantial challenge in meeting reliability standards amidst chip warpage. This particular matter underscores a significant performance bottleneck within existing high-end TIMs. In this study, we present poly(ionic liquid)s (PILs) as an innovative matrix for TIMs. Our findings highlight the unique properties of PILs, showcasing a low elastic modulus (60 kPa), exceptional flexibility and stretchability (>3800%), high adhesion to diverse substrates (up to 4.10 MPa), favorable filler compatibility, remarkable thermal stability, and prompt self-healing capabilities coupled with recyclability. The collective findings suggest that the PIL serves as an ideal matrix for heat transfer. As a proof of concept, PIL blended with liquid metal was straightforwardly combined to produce a TIM, exhibiting exceptional performance within practical encapsulated structures. The PIL-based TIM demonstrates substantial elongation at break (>350%), coupled with sustained high adhesion strength (up to 1.70 MPa), and exhibits favorable thermal conductivity in package testing. This study presents an innovative TIM matrix with the potential to enhance existing TIM systems, delivering significant performance benefits compared to silicones. Besides elucidating their multifaceted characteristics, this study forecasts an expanded range of applications for PILs, along with laying the groundwork for advancing next-generation TIMs.

Observation of heat pumping effect by radiative shuttling.

Heat shuttling phenomenon is characterized by the presence of a non-zero heat flow between two bodies without net thermal bias on average. It was initially predicted in the context of nonlinear heat conduction within atomic lattices coupled to two time-oscillating thermostats. Recent theoretical works revealed an analog of this effect for heat exchanges mediated by thermal photons between two solids having a temperature dependent emissivity. In this paper, we present the experimental proof of this effect using systems made with composite materials based on phase change materials. By periodically modulating the temperature of one of two solids we report that the system akin to heat pumping with a controllable heat flow direction. Additionally, we demonstrate the effectiveness of a simultaneous modulation of two temperatures to control both the strength and direction of heat shuttling by exploiting the phase delay between these temperatures. These results show that this effect is promising for an active thermal management of solid-state technology, to cool down solids, to insulate them from their background or to amplify heat exchanges.

Therapeutic potential of mesenchymal stem cell-derived exosomes in skeletal diseases.

Skeletal diseases impose a considerable burden on society. The clinical and tissue-engineering therapies applied to alleviate such diseases frequently result in complications and are inadequately effective. Research has shifted from conventional therapies based on mesenchymal stem cells (MSCs) to exosomes derived from MSCs. Exosomes are natural nanocarriers of endogenous DNA, RNA, proteins, and lipids and have a low immune clearance rate and good barrier penetration and allow targeted delivery of therapeutics. MSC-derived exosomes (MSC-exosomes) have the characteristics of both MSCs and exosomes, and so they can have both immunosuppressive and tissue-regenerative effects. Despite advances in our knowledge of MSC-exosomes, their regulatory mechanisms and functionalities are unclear. Here we review the therapeutic potential of MSC-exosomes for skeletal diseases.

Thermally Conductive Elastomer Composites with High Toughness, Softness, and Resilience Enabled by Regulating Interfacial Structure and Dynamics.

The emerging applications of thermally conductive elastomer composites in modern electronic devices for heat dissipation require them to maintain both high toughness and resilience under thermomechanical stresses. However, such a combination of thermal conductivity and desired mechanical characteristics is extremely challenging to achieve in elastomer composites. Here this long-standing mismatch is resolved via regulating interfacial structure and dynamics response. This regulation is realized both by tuning the molecular weight of the dangling chains in the polymer networks and by silane grafting of the fillers, thereby creating a broad dynamic-gradient interfacial region comprising of entanglements. These entanglements can provide the slipping topological constraint that allows for tension equalization between and along the chains, while also tightening into rigid knots to prevent chain disentanglement upon stretching. Combined with ultrahigh loading of aluminum-fillers (90 wt%), this design provides a low Young's modulus (350.0 kPa), high fracture toughness (831.5 J m-2), excellent resilience (79%) and enhanced thermal conductivity (3.20 W m-1 k-1). This work presents a generalizable preparation strategy toward engineering soft, tough, and resilient high-filled elastomer composites, suitable for complex environments, such as automotive electronics, and wearable devices.

Design of Soft/Hard Interface with High Adhesion Energy and Low Interfacial Thermal Resistance via Regulation of Interfacial Hydrogen Bonding Interaction.

Adhesion ability and interfacial thermal transfer capacity at soft/hard interfaces are of critical importance to a wide variety of applications, ranging from electronic packaging and soft electronics to batteries. However, these two properties are difficult to obtain simultaneously due to their conflicting nature at soft/hard interfaces. Herein, we report a polyurethane/silicon interface with both high adhesion energy (13535 J m-2) and low thermal interfacial resistance (0.89 × 10-6 m2 K W-1) by regulating hydrogen interactions at the interface. This is achieved by introducing a soybean-oil-based epoxy cross-linker, which can destroy the hydrogen bonds in polyurethane networks and meanwhile can promote the formation of hydrogen bonds at the polyurethane/silicon interface. This study provides a comprehensive understanding of enhancing adhesion energy and reducing interfacial thermal resistance at soft/hard interfaces, which offers a promising perspective to tailor interfacial properties in various material systems.

Deterministic Areal Enhancement of Interlayer Exciton Emission by a Plasmonic Lattice on Mirror.

The emergence of interlayer excitons (IX) in atomically thin heterostructures of transition metal dichalcogenides (TMDCs) has drawn great attention due to their unique and exotic optical and optoelectronic properties. Because of the spatially indirect nature of IX, its oscillator strength is 2 orders of magnitude smaller than that of the intralayer excitons, resulting in a relatively low photoluminescence (PL) efficiency. Here, we achieve the PL enhancement of IX by more than 2 orders of magnitude across the entire heterostructure area with a plasmonic lattice on mirror (PLoM) structure. The significant PL enhancement mainly arises from resonant coupling between the amplified electric field strength within the PLoM gap and the out-of-plane dipole moment of IX excitons, increasing the emission efficiency by a factor of around 47.5 through the Purcell effect. This mechanism is further verified by detuning the PLoM resonance frequency with respect to the IX emission energy, which is consistent with our theoretical model. Moreover, our simulation results reveal that the PLoM structure greatly alters the far-field radiation of the IX excitons preferentially to the surface normal direction, which increases the collection efficiency by a factor of around 10. Our work provides a reliable and universal method to enhance and manipulate the emission properties of the out-of-plane excitons in a deterministic way and holds great promise for boosting the development of photoelectronic devices based on the IX excitons.

CircZFR promotes colorectal cancer progression via stabilizing BCLAF1 and regulating the miR-3127-5p/RTKN2 axis.

Aberrant expression of circular RNAs (circRNAs) is frequently linked to colorectal cancer (CRC). Here, we identified circZFR as a promising biomarker for CRC diagnosis and prognosis. CircZFR was upregulated in CRC tissues and serum exosomes and its level was linked to cancer incidence, advanced-stages, and metastasis. In both in vitro and in vivo settings, circZFR promoted the growth and spread while suppressing apoptosis of CRC. Exosomes with circZFR overexpression promoted the proliferation and migration of cocultured CRC cells. Mechanistically, epithelial splicing regulatory protein 1 (ESRP1) in CRC cells may enhance the production of circZFR. BCL2-associated transcription factor 1 (BCLAF1) bound to circZFR, which prevented its ubiquitinated degradation. Additionally, circZFR sponged miR-3127-5p to boost rhotekin 2 (RTKN2) expression. Our TCP1-CD-QDs nanocarrier was able to carry and deliver circZFR siRNA (si-circZFR) to the vasculature of CRC tissues and cells, which inhibited the growth of tumors in patient-derived xenograft (PDX) models. Taken together, our results show that circZFR is an oncogenic circRNA, which promotes the development and spread of CRC in a BCLAF1 and miR-3127-5p-dependent manner. CircZFR is a possible serum biopsy marker for the diagnosis and a desirable target for further treatment of CRC.

Emerging 2D Ferroelectric Devices for In-Sensor and In-Memory Computing.

The quantity of sensor nodes within current computing systems is rapidly increasing in tandem with the sensing data. The presence of a bottleneck in data transmission between the sensors, computing, and memory units obstructs the system's efficiency and speed. To minimize the latency of data transmission between units, novel in-memory and in-sensor computing architectures are proposed as alternatives to the conventional von Neumann architecture, aiming for data-intensive sensing and computing applications. The integration of 2D materials and 2D ferroelectric materials has been expected to build these novel sensing and computing architectures due to the dangling-bond-free surface, ultra-fast polarization flipping, and ultra-low power consumption of the 2D ferroelectrics. Here, the recent progress of 2D ferroelectric devices for in-sensing and in-memory neuromorphic computing is reviewed. Experimental and theoretical progresses on 2D ferroelectric devices, including passive ferroelectrics-integrated 2D devices and active ferroelectrics-integrated 2D devices, are reviewed followed by the integration of perception, memory, and computing application. Notably, 2D ferroelectric devices have been used to simulate synaptic weights, neuronal model functions, and neural networks for image processing. As an emerging device configuration, 2D ferroelectric devices have the potential to expand into the sensor-memory and computing integration application field, leading to new possibilities for modern electronics.

Regulating Surface-Passivator Binding Priority for Efficient Perovskite Light-Emitting Diodes.

Suppressing trap-assisted nonradiative losses through passivators is a prerequisite for efficient perovskite light-emitting diodes (PeLEDs). However, the complex bonding between passivators and perovskites severely suppresses the passivation process, which still lacks comprehensive understanding. Herein, the number, category, and degree of bonds between different functional groups and the perovskite are quantitatively assessed to study the passivation dynamics. Functional groups with high electrostatic potential and large steric hindrance prioritize strong bonding with organic cations and halides on the perfect surface, leading to suppressed coordination with bulky defects. By modulating the binding priorities and coordination capacity, hindrance from the intense interaction with perfect perovskite is significantly reduced, leading to a more direct passivation process. Consequently, the near-infrared PeLED without external light out-coupling demonstrates a record external quantum efficiency of 24.3% at a current density of 42 mA cm-2. In addition, the device exhibits a record-level-cycle ON/OFF switching of 20 000 and ultralong half-lifetime of 1126.3 h under 5 mA cm-2. An in-depth understanding of the passivators can offer new insights into the development of high-performance PeLEDs.

Room-temperature low-threshold avalanche effect in stepwise van-der-Waals homojunction photodiodes.

Avalanche or carrier-multiplication effect, based on impact ionization processes in semiconductors, has a great potential for enhancing the performance of photodetector and solar cells. However, in practical applications, it suffers from high threshold energy, reducing the advantages of carrier multiplication. Here, we report on a low-threshold avalanche effect in a stepwise WSe2 structure, in which the combination of weak electron-phonon scattering and high electric fields leads to a low-loss carrier acceleration and multiplication. Owing to this effect, the room-temperature threshold energy approaches the fundamental limit, Ethre ≈ Eg, where Eg is the bandgap of the semiconductor. Our findings offer an alternative perspective on the design and fabrication of future avalanche and hot-carrier photovoltaic devices.

ZIF-8-Encapsulated Pexidartinib Delivery via Targeted Peptide-Modified M1 Macrophages Attenuates MDSC-Mediated Immunosuppression in Osteosarcoma.

Adoptive cellular therapy is a promising strategy for cancer treatment. However, the effectiveness of this therapy is limited by its intricate and immunosuppressive tumor microenvironment. In this study, a targeted therapeutic strategy for macrophage loading of drugs is presented to enhance anti-tumor efficacy of macrophages. K7M2-target peptide (KTP) is used to modify macrophages to enhance their affinity for tumors. Pexidartinib-loaded ZIF-8 nanoparticles (P@ZIF-8) are loaded into macrophages to synergistically alleviate the immunosuppressive tumor microenvironment synergistically. Thus, the M1 macrophages decorated with KTP carried P@ZIF-8 and are named P@ZIF/M1-KTP. The tumor volumes in the P@ZIF/M1-KTP group are significantly smaller than those in the other groups, indicating that P@ZIF/M1-KTP exhibited enhanced anti-tumor efficacy. Mechanistically, an increased ratio of CD4+ T cells and a decreased ratio of MDSCs in the tumor tissues after treatment with P@ZIF/M1-KTP indicated that it can alleviate the immunosuppressive tumor microenvironment. RNA-seq further confirms the enhanced immune cell function. Consequently, P@ZIF/M1-KTP has great potential as a novel adoptive cellular therapeutic strategy for tumors.

Engineered MgO nanoparticles for cartilage-bone synergistic therapy.

The emerging therapeutic strategies for osteoarthritis (OA) are shifting toward comprehensive approaches that target periarticular tissues, involving both cartilage and subchondral bone. This shift drives the development of single-component therapeutics capable of acting on multiple tissues and cells. Magnesium, an element essential for maintaining skeletal health, shows promise in treating OA. However, the precise effects of magnesium on cartilage and subchondral bone are not yet clear. Here, we investigated the therapeutic effect of Mg2+ on OA, unveiling its protective effects on both cartilage and bone at the cellular and animal levels. The beneficial effect on the cartilage-bone interaction is primarily mediated by the PI3K/AKT pathway. In addition, we developed poly(lactic-co-glycolic acid) (PLGA) microspheres loaded with nano-magnesium oxide modified with stearic acid (SA), MgO&SA@PLGA, for intra-articular injection. These microspheres demonstrated remarkable efficacy in alleviating OA in rat models, highlighting their translational potential in clinical applications.

Charge Injection and Auger Recombination Modulation for Efficient and Stable Quasi-2D Perovskite Light-Emitting Diodes.

The inefficient charge transport and large exciton binding energy of quasi-2D perovskites pose challenges to the emission efficiency and roll-off issues for perovskite light-emitting diodes (PeLEDs) despite excellent stability compared to 3D counterparts. Herein, alkyldiammonium cations with different molecular sizes, namely 1,4-butanediamine (BDA), 1,6-hexanediamine (HDA) and 1,8-octanediamine (ODA), are employed into quasi-2D perovskites, to simultaneously modulate the injection efficiency and recombination dynamics. The size increase of the bulky cation leads to increased excitonic recombination and also larger Auger recombination rate. Besides, the larger size assists the formation of randomly distributed 2D perovskite nanoplates, which results in less efficient injection and deteriorates the electroluminescent performance. Moderate exciton binding energy, suppressed 2D phases and balanced carrier injection of HDA-based PeLEDs contribute to a peak external quantum efficiency of 21.9%, among the highest in quasi-2D perovskite based near-infrared devices. Besides, the HDA-PeLED shows an ultralong operational half-lifetime T50 up to 479 h at 20 mA cm‒2, and sustains the initial performance after a record-level 30 000 cycles of ON-OFF switching, attributed to the suppressed migration of iodide anions into adjacent layers and the electrochemical reaction in HDA-PeLEDs. This work provides a potential direction of cation design for efficient and stable quasi-2D-PeLEDs.

Thread-structural microneedles loaded with engineered exosomes for annulus fibrosus repair by regulating mitophagy recovery and extracellular matrix homeostasis.

Low back pain is among the most grave public health concerns worldwide and the major clinical manifestation of intervertebral disc degeneration (IVDD). The destruction of annulus fibrosus (AF) is the primary cause of IVDD. A sustainable and stable treatment system for IVDD is lacking because of the special organizational structure and low nutrient supply of AF. We here found that IVDD results in the impaired mitochondrial function of AF tissue, and mitochondrial autophagy (mitophagy) plays a protective role in this process. We therefore reported a thread-structural microneedle (T-MN) matching the ring structure of AF. Based on the adsorption effect of laminin, our T-MN could load with bone marrow mesenchymal stem cell-derived exosomes to envelope the regulating mitophagy microRNA (miRNA 378), named as T-MN@EXO@miR-378. In general, we offered in situ locking in the defect site of AF to prevent nucleus pulposus leakage and promoted AF repair. The design of the thread structure was aimed at bionically matching the layered AF structure, thereby providing stronger adhesion. The T-MN@EXO@miR-378 effectively attached to AF and slowly released therapeutic engineered exosomes, and prevented IVDD progression by restoring mitophagy, promoting AF cell proliferation and migration, and inhibiting the pathological remodeling of the extracellular matrix. This functional system can be used as an excellent tool for sustained drug release and has a certain prospect in substituting the conventional treatment of IVDD.

Multicomponent chitosan complex/polyvinyl alcohol blended film with full-band UV-shielding performance and excellent antioxidant property for active food packaging.

Utilizing renewable natural resources to construct multifunctional packaging materials is critical to achieving sustainable development in the food packaging industry. In this study, we crafted transparent films with comprehensive UV-shielding and antioxidant properties by blending a multicomponent chitosan complex with polyvinyl alcohol (PVA), subsequently applied to preserve peanut butter. The multicomponent chitosan complex, synthesized from chitosan, ferulic acid (FA), and 5-oxo-3,5-dihydro-2H-thiazolo [3,2-a] pyridine-7-carboxylic acid (TPCA) through direct heating in water, served as the foundation. This chitosan complex was seamlessly blended with PVA, resulting in the creation of a transparent film through the solvent casting method. A meticulous investigation into the chemical structure and physicochemical properties of the blended films was conducted. The FA and TPCA components exhibited robust ultraviolet absorption properties, conferring virtually complete full-band ultraviolet shielding ability to the blend film. Additionally, FA endowed the blended film with significant antioxidant activity. The effectiveness of the chitosan complex/PVA blended film in preserving peanut butter from oxidative spoilage was demonstrated, showcasing its robustness in food preservation. Our research underscores the significance of creating advanced packaging materials from sustainable sources.

2D Dual Gate Field-Effect Transistor Enabled Versatile Functions.

Advanced computing technologies such as distributed computing and the Internet of Things require highly integrated and multifunctional electronic devices. Beyond the Si technology, 2D-materials-based dual-gate transistors are expected to meet these demands due to the ultra-thin body and the dangling-bond-free surface. In this work, a molybdenum disulfide (MoS2 ) asymmetric-dual-gate field-effect transistor (ADGFET) with an In2 Se3 top gate and a global bottom gate is designed. The independently controlled double gates enable the device to achieve an on/off ratio of 106 with a low subthreshold swing of 94.3 mV dec-1 while presenting a logic function. The coupling effect between the double gates allows the top gate to work as a charge-trapping layer, realizing nonvolatile memory (105 on/off ratio with retention time over 104 s) and six-level memory states. Additionally, ADGFET displays a tunable photodetection with the responsivity reaching the highest value of 857 A W-1 , benefiting from the interface coupling between the double gates. Meanwhile, the photo-memory property of ADGFET is also verified by using the varying exposure dosages-dependent illumination. The multifunctional applications demonstrate that the ADGFET provides an alternative way to integrate logic, memory, and sensing into one device architecture.

An On-Demand Collaborative Innate-Adaptive Immune Response to Infection Treatment.

Deep tissue infection is a common clinical issue and therapeutic difficulty caused by the disruption of the host antibacterial immune function, resulting in treatment failure and infection relapse. Intracellular pathogens are refractory to elimination and can manipulate host cell biology even after appropriate treatment, resulting in a locoregional immunosuppressive state that leads to an inadequate response to conventional anti-infective therapies. Here, a novel antibacterial strategy involving autogenous immunity using a biomimetic nanoparticle (NP)-based regulating system is reported to induce in situ collaborative innate-adaptive immune responses. It is observed that a macrophage membrane coating facilitates NP enrichment at the infection site, followed by active NP accumulation in macrophages in a mannose-dependent manner. These NP-armed macrophages exhibit considerably improved innate capabilities, including more efficient intracellular ROS generation and pro-inflammatory factor secretion, M1 phenotype promotion, and effective eradication of invasive bacteria. Furthermore, the reprogrammed macrophages direct T cell activation at infectious sites, resulting in a robust adaptive antimicrobial immune response to ultimately achieve bacterial clearance and prevent infection relapse. Overall, these results provide a conceptual framework for a novel macrophage-based strategy for infection treatment via the regulation of autogenous immunity.

Correlating Young's Modulus with High Thermal Conductivity in Organic Conjugated Small Molecules.

Attaining elevated thermal conductivity in organic materials stands as a coveted objective, particularly within electronic packaging, thermal interface materials, and organic matrix heat exchangers. These applications have reignited interest in researching thermally conductive organic materials. The understanding of thermal transport mechanisms in these organic materials is currently constrained. This study concentrates on N, N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8), an organic conjugated crystal. A correlation between elevated thermal conductivity and augmented Young's modulus is substantiated through meticulous experimentation. Achievement via employing the physical vapor transport method, capitalizing on the robust C═C covalent linkages running through the organic matrix chain, bolstered by π-π stacking and noncovalent affiliations that intertwine the chains. The coexistence of these dynamic interactions, alongside the perpendicular alignment of PTCDI-C8 molecules, is confirmed through structural analysis. PTCDI-C8 thin film exhibits an out-of-plane thermal conductivity of 3.1 ± 0.1 W m-1 K-1, as determined by time-domain thermoreflectance. This outpaces conventional organic materials by an order of magnitude. Nanoindentation tests and molecular dynamics simulations elucidate how molecular orientation and intermolecular forces within PTCDI-C8 molecules drive the film's high Young's modulus, contributing to its elevated thermal conductivity. This study's progress offers theoretical guidance for designing high thermal conductivity organic materials, expanding their applications and performance potential.

Monolayer Organic Crystals for Ultrahigh Performance Molecular Diodes.

Molecular diodes are of considerable interest for the increasing technical demands of device miniaturization. However, the molecular diode performance remains contact-limited, which represents a major challenge for the advancement of rectification ratio and conductance. Here, it is demonstrated that high-quality ultrathin organic semiconductors can be grown on several classes of metal substrates via solution-shearing epitaxy, with a well-controlled number of layers and monolayer single crystal over 1 mm. The crystals are atomically smooth and pinhole-free, providing a native interface for high-performance monolayer molecular diodes. As a result, the monolayer molecular diodes show record-high rectification ratio up to 5 × 108 , ideality factor close to unity, aggressive unit conductance over 103 S cm-2 , ultrahigh breakdown electric field, excellent electrical stability, and well-defined contact interface. Large-area monolayer molecular diode arrays with 100% yield and excellent uniformity in the diode metrics are further fabricated. These results suggest that monolayer molecular crystals have great potential to build reliable, high-performance molecular diodes and deeply understand their intrinsic electronic behavior.