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Efficient and precise calculations of thermal transport properties and figures of merit, alongside a deep comprehension of thermal transport mechanisms, are essential for the practical utilization of advanced thermoelectric materials. In this study, we explore the microscopic processes governing thermal transport in the distinguished crystalline material Tl 9 SbTe 6 by integrating a unified thermal transport theory with machine learning-assisted self-consistent phonon calculations. Leveraging machine learning potentials, we expedite the analysis of phonon energy shifts, higher-order scattering mechanisms, and thermal conductivity arising from various contributing factors, such as population and coherence channels. Our finding unveils an exceptionally low thermal conductivity of 0.31 W m -1 K -1 at room temperature, a result that closely correlates with experimental observations. Notably, we observe that the off-diagonal terms of heat flux operators play a significant role in shaping the overall lattice thermal conductivity of Tl 9 SbTe 6 , where the ultralow thermal conductivity resembles that of glass due to limited group velocities. Furthermore, we achieve a maximum ZT value of 3.17 in the c -axis orientation for p -type Tl 9 SbTe 6 at 600 K and an optimal ZT value of 2.26 in the a -axis and b -axis direction for n -type Tl 9 SbTe 6 at 500 K. The crystalline Tl 9 SbTe 6 not only showcases remarkable thermal insulation but also demonstrates impressive electrical properties owing to the dual-degeneracy phenomenon within its valence band. These results not only elucidate the underlying reasons for the exceptional thermoelectric performance of Tl 9 SbTe 6 but also suggest potential avenues for further experimental exploration.

The origin of life on Earth is believed to be from the ocean, which offers abundant resources in its depths. However, deep-sea operations are limited due to the lack of underwater robots and rigid grippers with sensitive force sensors. Therefore, it is crucial for deep-sea pressure sensors to be integrated with mechanical hands for manipulation. Here, a flexible stress sensor is presented that can function effectively under high water pressure in the deep ocean. Inspired by biological structures found in the abyssal zone, our sensor is designed with an internal and external pressure balance structure (hollow interlocking spherical structure). The digital light processing (DLP) three-dimensional (3D) printing technology is utilized to construct this complex structure after obtaining optimized structural parameters using finite element simulation. The sensor exhibits linear sensitivity of 0.114 kPa -1 within the range of 0-15 kPa and has an extremely short response time of 32 ms, good dynamic-static load response capability, and excellent resistance cycling stability. It shows high sensitivity of 1.74 kPa -1 even under 30 MPa static water pressures and the theoretical working pressure can exceed 110 MPa, which provides a new solution for deep-sea robots.

The optimization of electromagnetic microwave absorbing (EMA) materials for radar stealth has been a continuous endeavor. However, meeting the defense requirements across multiple-frequency bands in increasingly complex and variable environments remains challenging. Drawing inspiration from the cytoskeleton-organelle structure, we designed and prepared a hierarchical MXene/NiFe 2 O 4 /calcined melamine foam (MNC) composite. The composite exhibits efficient and adjustable microwave absorption, infrared stealth, and solar absorption performance through the synergistic interaction of the components and the spatial effect of its novel microstructure. The composite achieves a minimum reflection loss of -58.57 dB and an effective absorption bandwidth (EAB) of 7.00 GHz, both of which can vary with the thickness. MNC also offers stable infrared stealth performance for heat sources ranging from 37 to 300 °C and high solar absorptivity up to 96.2%, promoting ambient-temperature-adaptive infrared stealth through electricity-sunlight cooperative regulation. With exceptional environmental adaptability characteristics such as photothermal conversion, lightness, elasticity, and hydrophobicity, the MNC composite holds promise as a multispectrum defense material for radar, infrared, and visible light for various forms of equipment, clothing, and wearables in harsh conditions.

Antimicrobial peptides (AMPs) are expected to be an alternative promising solution to the global public health problem of antibiotic resistance due to their unique antimicrobial mechanism. However, extensive efforts are still needed to improve the shortcomings of traditional AMPs, such as rapid proteolysis, hemolysis, slow response, toxicity, etc., by exploring AMP-based new antimicrobial strategies. Here, we develop cationic peptide bundles into novel antimicrobial architectures that can rapidly kill multiple types of bacteria including drug-resistant bacteria. Remarkably, cationic peptide bundles can be used as polymerization units to cross-link with other polymers through simple two-component polymerization to produce diverse antimicrobial materials. For the proof of concept, three materials were fabricated and investigated, including an antimicrobial hydrogel that can significantly accelerate the healing of infected wounds, a multifunctional antimicrobial bioadhesive that shows promise in antimicrobial coatings for medical devices, and a photo-cross-linked antimicrobial gelatin hydrogel with broad application potential. The integration of antimicrobial units into the materials' backbone endows their biocompatibility. Cationic peptide bundles not only represent a new antimicrobial strategy but also provide a versatile and promising processing method to create diversified, multifunctional, and biocompatible antimicrobial materials.

Nanoparticles have aroused widespread interest because of their unique surface structure and nano effect, which presents novel characteristics like as sound, light, electricity, magnetism, and thermal properties. However, two critical defects have hindered their applications: (1) poor processability resulting from the high melting temperature (e.g., >1000 °C) for some inorganic nanoparticles; (2) the restriction of the nano effect caused by the easy aggregation of the nanoparticles. To solve those issues, solvent-free nanofluids (SNFs) with hard cores and flexible organic chains were successfully designed and fabricated at the beginning of the twenty-first century. The promising technology of SNFs not only solved the dispersion problem of nanomaterials but also imparted novel functionalization to nanoparticles. Up to now, many researchers have been devoted to developing diverse cores and flexible organic polymer chains to endow SNFs with particular functions, such as conductivity, fluorescence, lubricity, and so on. However, there are few review reports on the research progress in the fabrication and applications of functional SNFs. To gain a better understanding of SNFs, this paper presents an overall investigation into the development, fabrication, as well as the applications of functional SNFs.

The coupling of charge and phonon transport in solids is a long-standing issue for thermoelectric performance enhancement. Herein, two new narrow-gap semiconductors with the same chemical formula of GeSe 0.65 Te 0.35 (GST) are rationally designed and synthesized: one with a layered hexagonal structure (H-GST) and the other with a non-layered rhombohedral structure (R-GST). Thanks to the three-dimensional (3D) network structure, R-GST possesses a significantly larger weighted mobility than H-GST. Surprisingly, 3D-structured R-GST displays an extremely low lattice thermal conductivity of ∼0.5 W m -1 K -1 at 523 K, which is comparable to that of layered H-GST. The two-dimensional (2D)-like phonon transport in R-GST stems from the unique off-centering Ge atoms that induce ferroelectric instability, yielding soft polar phonons, as demonstrated by the Boson peak detected by the low-temperature specific heat and calculated phonon spectra. Furthermore, 1 mol % doping of Sb is utilized to successfully suppress the undesired phase transition of R-GST toward H-GST at elevated temperatures. Consequently, a peak ZT of 1.1 at 623 K is attained in the rhombohedral Ge 0.99 Sb 0.01 Se 0.65 Te 0.35 sample, which is 1 order of magnitude larger than that of GeSe. This work demonstrates the feasibility of exploring high-performance thermoelectric materials with decoupled charge and phonon transport in off-centering compounds.

Low-loading Pd supported on Fe 2 O 3 nanoparticles was synthesized. A common nanocatalyst system with previously reported synergistic enhancement of reactivity that is attributed to the electronic interactions between Pd and the Fe 2 O 3 support. Fe 2 O 3 -selective precoalescence overcoating with ZnO atomic layer deposition (ALD), using Zn(CH 2 CH 3 ) 2 and H 2 O as precursors, dampens competitive hydrogenation reactivity at Fe 2 O 3 -based sites. The result is enhanced efficiency at the low-loading but high reactivity Pd sites. While this increases catalyst efficiency toward most aqueous redox reactions tested, it suppresses reactivity toward polyaromatic core substrates. X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) show minimal electronic impacts for the ZnO overcoat on the Pd particles, implying a predominantly physical site blocking effect as the reason for the modified reactivity. This serves as a proof-of-concept of not only stabilizing supported nanocatalysts but also altering reactivity with ultrathin ALD overcoats. The results point to a facile ALD route for selective enhancement of reactivity for low-loading Pd-based supported nanocatalysts.

Scalable micro graphene Hall sensors (μGHSs) hold tremendous potential for highly sensitive and label-free biomagnetic sensing in physiological solutions. To enhance the performance of these devices, it is crucial to optimize frequency-dependent flicker noise to reduce the limit of detection (LOD), but it remains a great challenge due to the large contact resistance at the graphene-metal contact. Here we present a surface modification strategy employing persistent carbene on gold electrodes to reduce the contact resistivity by a factor of 25, greatly diminishing μGHS flicker noise by a factor of 1000 to 3.13 × 10 -14 V 2 /Hz while simultaneously lowering the magnetic LOD S B 1/2 to 1440 nT/Hz 1/2 at 1 kHz under a 100 μA bias current. To the best of our knowledge, this represents the lowest S B 1/2 reported for scalable μGHSs fabricated through wafer-scale photolithography. The reduction in contact noise is attributed to the π-π stacking interaction between the graphene and the benzene rings of persistent carbene, as well as the decrease in the work function of gold as confirmed by Kelvin Probe Force Microscopy. By incorporating a microcoil into the μGHS, we have demonstrated the real-time detection of superparamagnetic nanoparticles (SNPs), achieving a remarkable LOD of ∼528 μg/L. This advancement holds great potential for the label-free detection of magnetic biomarkers, e.g., ferritin, for the early diagnosis of diseases associated with iron overload, such as hereditary hemochromatosis (HHC).

Electrocatalytic sulfur reduction reaction (SRR) is emerging as an effective strategy to combat the polysulfide shuttling effect, which remains a critical factor impeding the practical application of the Li-S battery. Single-atom catalyst (SAC), one of the most studied catalytic materials, has shown considerable potential in addressing the polysulfide shuttling effect in a Li-S battery. However, the role played by transition metal vs coordination mode in electrocatalytic SRR is trial-and-error, and the general understanding that guides the synthesis of the specific SAC with desired property remains elusive. Herein, we use first-principles calculations and machine learning to screen a comprehensive data set of graphene-based SACs with different transition metals, heteroatom doping, and coordination modes. The results reveal that the type of transition metal plays the decisive role in SAC for electrocatalytic SRR, rather than the coordination mode. Specifically, the 3d transition metals exhibit admirable electrocatalytic SRR activity for all of the coordination modes. Compared with the reported N 3 C 1 and N 4 coordinated graphene-based SACs covering 3d, 4d, and 5d transition metals, the proposed para-MnO 2 C 2 and para-FeN 2 C 2 possess significant advantages on the electrocatalytic SRR, including a considerably low overpotential down to 1 mV and reduced Li 2 S decomposition energy barrier, both suggesting an accelerated conversion process among the polysulfides. This study may clarify some understanding of the role played by transition metal vs coordination mode for SAC materials with specific structure and desired catalytic properties toward electrocatalytic SRR and beyond.

Pickering emulsions stabilized by functional nanoparticles (NPs) have received considerable attention for improving the physical stability and biological function of NPs. Herein, hydrophobic polyphenols were chosen as phenolic ligands to form metal-phenolic network (MPN) coatings on NPs (e.g., silica, polystyrene) mediated by the sono-Fenton reaction. The MPN coatings modulated the surface wettability and charges of NPs and achieved emulsification behavior for preparing Pickering emulsions with pH responsiveness and oxidation resistance. A series of polyphenols, including resveratrol, rutin, naringin, and curcumin, were used to form MPN coatings on NPs, which served as stabilizers for the engineering of functionalized oil-in-water (O/W) Pickering emulsions. This work provides a new avenue for the use of hydrophobic polyphenols to modulate NP emulsifiers, which broadens the application of polyphenols for constructing Pickering emulsions with antioxidant properties.

Much of current clinical interest has focused on mRNA therapeutics for the treatment of lung-associated diseases, such as infections, genetic disorders, and cancers. However, the safe and efficient delivery of mRNA therapeutics to the lungs, especially to different pulmonary cell types, is still a formidable challenge. In this paper, we proposed a cationic lipid pair (CLP) strategy, which utilized the liver-targeted ionizable lipid and its derived quaternary ammonium lipid as the CLP to improve liver-to-lung tropism of four-component lipid nanoparticles (LNPs) for in vivo mRNA delivery. Interestingly, the structure-activity investigation identified that using liver-targeted ionizable lipids with higher mRNA delivery performance and their derived lipid counterparts is the optimal CLP design for improving lung-targeted mRNA delivery. The CLP strategy was also verified to be universal and suitable for clinically available ionizable lipids such as SM-102 and ALC-0315 to develop lung-targeted LNP delivery systems. Moreover, we demonstrated that CLP-based LNPs were safe and exhibited potent mRNA transfection in pulmonary endothelial and epithelial cells. As a result, we provided a powerful CLP strategy for shifting the mRNA delivery preference of LNPs from the liver to the lungs, exhibiting great potential for broadening the application scenario of mRNA-based therapy.

Liraglutide has been extensively applied in the treatment of type 2 diabetes mellitus (T2DM), but its 11-15 h half-life resulted in daily administration, which led to poor patient compliance. This study aimed to solve this problem by developing liraglutide-loaded microspheres with a 1 month sustained release prepared by the W 1 /O/W 2 method combined with the premix membrane emulsification technique to improve therapeutic efficacy. Remarkably, we found that the amphiphilic properties of liraglutide successfully reduced the oil-water interfacial tension, resulting in a stable primary emulsion and decreasing the level of drug leakage into the external water phase. As a result, exceptional drug loading (>8%) and encapsulation efficiency (>85%) of microspheres were achieved. Furthermore, the uniformity in microsphere size facilitated an in-depth exploration of the structural characteristics of liraglutide-loaded microspheres. The results indicated that the dimensions of the internal cavities of the microspheres were significantly influenced by the size of the inner water droplets in the primary emulsion. A denser and more uniform cavity structure decreased the initial burst release, improving the release process of liraglutide from the microspheres. To evaluate the release behavior of liraglutide from microspheres, a set of in vitro release assays and in vivo pharmacodynamics were performed. The liraglutide-loaded microspheres effectively decreased fasting blood glucose (FBG) levels and hemoglobin A1c (HbA1c) levels while enhancing the pancreatic and hepatic functions in db/db mice. In conclusion, liraglutide sustained-release microspheres showed the potential for future clinical applications in the management of T2DM and provided an effective therapeutic approach to overcoming patient compliance issues.

Stimuli-responsive micro/nanoscale photonic barcodes show great capacity for encryption and anticounterfeiting technologies due to multiple authentications, yet their application is commonly restricted by invasive stimuli. Herein, we report noninvasive light-stimulated high-security photonic barcodes based on spatially assembled photoresponsive two-dimensional (2D) 1,3,5-benzenetribenzoate (BTB)@Ln-MOF host-guest heterostructures. The photoluminescence (PL) spectra information on BTB@Ln-MOF heterostructures could be precisely controlled by the different wavelengths of ultraviolet (UV) light trigger. By using the PL properties and 2D heterostructures as cryptographic primitives, spatially resolved smart photonic barcodes based on both spectral and graphical coding are realized in BTB@Ln-MOF host-guest materials. These results will pave an avenue for the development of smart stimuli-responsive photonic barcodes for anticounterfeiting applications.

Employing transition metal catalysts (TMCs) to perform bioorthogonal activation of prodrugs and pro-fluorophores in biological systems, particularly in a conditional fashion, remains a challenge. Here, we used a mesoporous organosilica nanoscaffold (RuMSN), which localizes Ru(II) conjugates on the pore wall, enabling the biorthogonal photoreduction reactions of azide groups. Due to easily adjustable surface charges and pore diameter, this efficiently engineering RuMSN catalyst, with abundant active sites on the inner pore well, could spontaneously repel or attract substrates with different molecular sizes and charges and thus ensure selective bioorthogonal catalysis. Depending on it, engineering RuMSN nanoreactors showed fascinating application scales from conditional bioorthogonal activation of prodrugs and pro-fluorophores in either intra- or extracellular localization to performing intracellular concurrent and tandem catalysis together with natural enzymes.

Periodontitis, a complex inflammatory disease initiated by bacterial infections, presents a significant challenge in public health. The increased levels of reactive oxygen species and the subsequent exaggerated immune response associated with periodontitis often lead to alveolar bone resorption and tooth loss. Herein, we develop multifunctional metal-phenolic composites (i.e., Au@MPN-BMP2) to address the complex nature of periodontitis, where gold nanoparticles (AuNPs) are coated by metal-phenolic networks (MPNs) and bone morphogenetic protein 2 (BMP2). In this design, MPNs exhibit remarkable antibacterial and antioxidant properties, and AuNPs and BMP2 promote osteogenic differentiation of bone marrow mesenchymal stem cells under inflammatory conditions. In a rat model of periodontitis, treatment with Au@MPN-BMP2 leads to notable therapeutic outcomes, including mitigated oxidative stress, reduced progression of inflammation, and the significant prevention of inflammatory bone loss. These results highlight the multifunctionality of Au@MPN-BMP2 nanoparticles as a promising therapeutic approach for periodontitis, addressing both microbial causative factors and an overactivated immune response. We envision that the rational design of metal-phenolic composites will provide versatile nanoplatforms for tissue regeneration and potential clinical applications.

PEO-LiX solid polymer electrolyte (SPE) with the addition of Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) fillers is considered as a promising solid-state electrolyte for solid-state Li-ion batteries. However, the developments of the SPE have caused additional challenges, such as poor contact interface and SPE/Li interface stability during cycling, which always lead to potentially catastrophic battery failure. The main problem is that the real impact of LLZTO fillers on the interfacial properties between SPE and Li metal is still unclear. Herein, we combined the electrochemical measurement and in situ synchrotron-based X-ray absorption near-edge structure (XANES) imaging technology to study the role of LLZTO fillers in directing SPE/Li interface electrochemical performance. In situ XRF-XANES mapping during cycling showed that addition of an appropriate amount of LLZTO fillers (50 wt %) can improve the interfacial contact and stability between SPE and Li metal without reacting with the PEO and Li salts. Additionally, it also demonstrated the beneficial effect of LLZTO particles for suppressing the interface reactions between the Li metal and PEO-LiTFSI SPE and further inhibiting Li-metal dendrite growth. The Li|LiFePO 4 batteries deliver long cycling for over 700 cycles with a low-capacity fade rate of 0.08% per cycle at a rate of 0.3C, revealing tremendous potential in promoting the large-scale application of future solid-state Li-ion batteries.

A facilely in situ fabricated hydrogen-bonded organic framework (HOF) hydrogel film with perfect photoluminescent performance was designed for visual sensing of tetracycline antibiotics (TCs) and information security. Luminescent HOF (MA-IPA) was combined with sodium alginate (SA) through hydrogen bonding actions and electrostatic interactions, then cross-linked with Ca 2+ ions to form HOF hydrogel film (Ca@MA-IPA@SA). The HOF hydrogel film exhibited exceptional mechanical robustness along with stable blue fluorescence and ultralong green phosphorescence. After exposure to TCs, Ca 2+ was combined with TCs to generate a new green fluorescence exciplex (TC-Ca 2+ ) in hydrogel films. Due to fluorescence resonance energy transfer, the fluorescence of MA-IPA was quenched, and the fluorescent color of the HOF hydrogel film was changed from blue to green. This dichromatic fluorescent response is convenient for the visual and rapid detection of TCs. The detection limits of tetracycline (TC), oxytetracycline (OTC), and chlortetracycline (CTC) were 5.1, 7.7, and 32.7 ng mL -1 , respectively. Importantly, this hydrogel sensing platform was free of tedious operation and enabled the ultrasensitive and selective detection of TCs within 6 min. It has been successfully applied to TC detection in pork and milk samples. Based on the stable photoluminescence performance of HOF hydrogel films and fluorescent-responsive properties to TCs, two types of anticounterfeiting arrays were fabricated for information encryption and decryption. This work provides a novel approach for on-site detection of TCs and offers valuable insights into information security.

Parkinson's disease (PD) affects millions of people's lives worldwide. The main pathogenesis of PD is dopaminergic neuron necrosis and neuroinflammation mediated by activated microglia cells. In recent years, the anti-inflammatory ability and neuroprotective effects of miR-124 in PD models were well proved, but the in vivo delivery of miR-124 remains challenging. Herein, we report a protein nanosystem modified with a brain-targeting peptide ApoE that could efficiently deliver miR-124 across the blood-brain barrier (BBB). This nanosystem showed good cell viability on brain endothelial cells and microglia cells, and administration of this nanosystem significantly decreased the neuroinflammation and dopaminergic neuron loss, as well as recovered parts of neurobehavioral deficits. This ApoE peptide-based protein nanosystem holds great promise for the delivery of RNA therapeutics to the brain and for realizing neuron protection in PD treatment.

The low-temperature atomic layer deposition of metal on polymer surfaces is often challenging owing to the deficiency of functional groups and reactivity. Here, the deposition of ALD-Cu employing Cu(hfac) 2 and Et 2 Zn at a low temperature (120 °C) on polyimide (PI) substrates is improved by the utilization of an in situ ultrathin ALD-ZnO buffer layer. A conformal and continuous ALD-Cu thin film with low resistivity (6.07 μΩ cm) is fabricated on an ALD-ZnO/PI substrate. The findings demonstrate that the ALD-ZnO buffer layer provides chemisorption and a nucleation site for the initial growth of ALD-Cu. Transmission electron microscopy and energy-dispersive X-ray analysis reveal that the ALD-ZnO layer plays a buffer role in the fitness of ALD-Cu on PI substrates and its ability to elicit the formation of an ALD-ZnO nanocluster and polar surface. ALD-ZnO can be effectively utilized as a buffer layer for polymer-based ALD-metal processes, showing potential in flexible electronic applications.

Mild photothermal therapy (mPTT), which circumvents the limitations of conventional photothermal therapy, is emerging and exhibits remarkable potential in clinical applications. Nevertheless, mPTT is not able to efficiently eradicate tumors because its therapeutic efficacy is dramatically diminished by stress-induced heat shock proteins (HSP). Herein, a core-shell structured Au@Pd (AP) bimetallic nanozyme was fabricated for reactive oxygen species (ROS) augmentation-induced mPTT. The nanocatalytic AP nanozymes with photothermal conversion performance harbor multienzymatic (catalase, oxidase, and peroxidase) activities to induce ROS storm formation. The generated ROS could suppress the heat-defense response of tumor cells by cleaving HSP. Overall, our work highlights a ROS-regulating strategy to counteract hyperthermia-associated resistance in mPTT.

Herein, a dual-function strategy, in which CsPbI 2 Br is treated by CsPbBr 3 nanocrystals (NCs) via addition and surface modification to construct the "electron bridge" and gradient heterojunction, respectively, to notably improve the performance of the CsPbI 2 Br solar cells, is proposed. The "electron bridge" formed by the CsPbBr 3 NCs provides an extra transport channel for the photogenerated electrons in the CsPbI 2 Br layer, thus facilitating electron transport. Meanwhile, surface modification of CsPbI 2 Br by the CsPbBr 3 NCs forms a gradient heterojunction between the CsPbI 2 Br layer and the P3HT layer, enhancing hole extraction accordingly. In addition, the CsPbBr 3 NC treatment passivates the defects at the bulk and surface of the CsPbI 2 Br layers, thus suppressing carrier recombination. Thanks to these positive effects of the CsPbBr 3 NCs, the demonstration device with a simple configuration of ITO/SnO 2 /CsPbI 2 Br/P3HT/Ag achieves a notable power conversion efficiency of 17.03%, which is among the highest efficiencies reported for CsPbI 2 Br-based solar cells.

Sustainable energy conversion and effective biosynthesis for value-added chemicals have attracted considerable attention, but most biosynthesis systems cannot work independently without external power. In this work, a self-powered biohybrid system based on organic materials is designed and constructed successfully by integrating electroactive microorganisms with electrochemical devices. Among them, the hybrid living materials based on S. oneidensis /poly[3-(3'-N,N,N-triethylamino-1'-propyloxy)-4-methyl-2,5-thiophene chloride] (PMNT) biofilms for microbial fuel cells played a crucial role in electrocatalytic biocurrent generation by using biowaste as the only energy source. Without any external power supplies, the self-powered biohybrid systems could generate, convert, and store electrical energy for effective photosynthetic regulation and sustained chemical production. This work provides a new strategy to combine comprehensive renewable energy production with chemical manufacturing without an external power source in the future.

Nanochannel ionic diodes require extremely complex and expensive fabrication processes. Polyelectrolyte ionic diodes attracted widespread attention among ionic rectification systems due to their simplicity of development and the ability to break the size limits of the nanochannel. However, enhancement of their rectification ratio is still in the exploratory stage. In this study, chitosan (CS) hydrogels and sodium polyacrylate (PAAs) hydrogels were prepared as the substrates for the heterostructured ionic diodes. 5,10,15,20-Tetrakis(4-aminophenyl)-21H,23H-porphyrin (TAPP) was selected to regulate the rectification ratio of ionic diodes. By adding 0.05 wt % TAPP to the CS hydrogel, the rectification ratio of the ionic diode can be increased to 10, which is 4 times larger than that of the undoped ionic diode. In contrast, the rectification ratio of the ionic diodes with TAPP added in the PAAs hydrogel decreases to 2. In addition, the ionic diode composed of the TAPP-doped CS hydrogel and PAAs hydrogel has the characteristics of a high open-circuit voltage. The open-circuit voltage of the 10 mm × 10 mm × 4 mm heterojunction hydrogel reached 370 mV. The ionic diodes can be used as a self-powered power supply device.

In photothermal treatments (PTTs), normal tissues around cancerous tumors get injured by excessive heat, whereas damaged cancer cells are easily restored by stress-induced heat shock proteins (HSPs) at low temperatures. Therefore, to achieve a unique tumor microenvironment (TME), it is imperative to increase PTT efficiency and reduce normal tissue injury by adopting appropriate reactive oxygen species (ROS) and lipid peroxides (LPO) cross-linked with HSPs. In the present research, a potential strategy for mild photothermal treatments (mPTTs) was proposed by initiating localized catalytic chemical reactions in TME based on Pd nanozyme-modified hydrogenated TiO 2 (H-TiO 2 @Pd). In vitro and in vivo evaluations demonstrated that H-TiO 2 @Pd had good peroxidase-like activities (POD), glutathione oxidase-like activities (GSHOx), and photodynamic properties and also satisfactory biocompatibility for 4T1 cells. Localized catalytic chemical reactions in H-TiO 2 @Pd significantly depleted GSH to downregulate the protein expression of GPX4 and promoted the accumulation of LPO and ROS, which consumed HSP70 or inhibited its function in 4T1 cells. Hence, the as-constructed low-temperature photothermal therapeutic platform based on Pd nanozyme-modified H-TiO 2 can be a promising candidate to develop a safe and effective mPTT for cancer treatments.

Metal-organic frameworks (MOF) are promising candidates for the construction of artificial nanozymes and have found applications in many fields. However, the preparation of nanosized MOF materials with high performance and good dispersibility is still a big challenge and is in great demand as signal labels for immunoassays. In this work, hierarchically structured and highly dispersible MOF nanoparticles were facilely prepared in a one-pot method. Self-assembled micelles from PEGylated hematin were used as structured templates to mediate the formation of zeolitic imidazole framework-8 (ZIF-8) nanoparticles in aqueous solution. The encapsulation of micelles in ZIF-8 frameworks produces well-dispersed nanoparticles and generates dual-confinement effects for catalytic hematin. Owing to the hierarchical structures, the formed MOF nanozymes show enhanced peroxidase-like activity and enable persistent chemiluminescence behaviors for the luminol system. Sandwich-type chemiluminescence immunoassays for carcinoembryonic antigen (CEA) were proposed using MOF nanozymes as signal labels, and good analytical performances were achieved. The combination of self-assembly and biomineralization may open new avenues for the development of MOF nanomaterials.

Silica glass devices are widely used due to their exceptional physical and chemical properties. However, prolonged usage may result in abrasion and contamination of silica glass devices, adversely affecting the service life. One of the most effective solutions to this issue is surface modification, in which superhydrophobicity with high transmittance and mechanical robustness is highly desired. Inspired by the concept of protective armor, we proposed a novel approach for the direct integration of robust and transparent superhydrophobic structures on silica glass. In this method, microstereolithography synergistic heat treatment processes are used to create a micrometer-scale biomimetic frame on the surface of silica glass and then filled with in situ deposited nanoparticles. The superhydrophobicity of the surface can be obtained through the nanoparticles, and the biomimetic frame can protect the surface from direct contact with external objects to achieve durability. This process allows the preparation of superhydrophobic silica structures on the silica device surface at temperatures below its melting point, which prevents any damage to the devices during the heat treatment. Moreover, up to 90% transmittance does not affect the performance of silica devices. The composite structure maintains a contact angle of over 150° after multiple abrasion tests, verifying the mechanical robustness. This innovative process paves the way for forming a high mechanical robustness and excellent transmittance protective layer on silica glass devices, which expands the application field.

Layered double hydroxides (LDHs) have come to the foreground recently, considering their unique layered structure and short ion channels when they act as electrode materials for supercapacitors (SCs). However, due to their poor rate and cycle performance, they are not highly sought after in the market. Therefore, a flower-like hierarchical NiCo-LDH@C nanostructure with flake NiCo-LDH anchored on the carbon skeleton has emerged here, which is constructed by calcination and hydrothermal reaction and applying flake ZIF-67 as a precursor. In this structure, NiCo-LDH grows outward with abundant and homogeneously distributed Co nanoparticles on Co@C as nucleation sites, forming a hierarchical structure that is combined tightly with the carbon skeleton. The flower-like hierarchical nanostructures formed by the composite of metal-organic frameworks (MOFs) and LDHs have successfully enhanced the cycle and rate performance of LDH materials on the strength of strong structural stability, large specific surface area, and unique cooperative effect. The NiCo-LDH@C electrode displays superb electrochemical performance, with a specific capacitance of 2210.6 F g -1 at 1 A g -1 and 88.8% capacitance retention at 10 A g -1 . Furthermore, the asymmetric supercapacitor (ASC) constructed with NiCo-LDH@C//RGO reveals a remarkable energy density of 45.02 W h kg -1 with a power density of 799.96 W kg -1 . This project aims to propose a novel avenue to exploit NiCo-LDH electrode materials and provide theory and methodological guidance for deriving complex structures from MOF derivatives.

The use of bismuth (Bi) as an anode material in nickel-metal batteries has gained significant attention due to its highly reversible redox reaction and suitable operating conditions. However, the cycling stability and flexibility of nickel-bismuth (Ni//Bi) batteries need to be further improved. This paper employs a facile electrodeposition technique to prepare Bi nanosheets uniformly grown on a porous carbon cloth (PCC), denoted as Bi-PCC electrodes. The Bi-PCC electrode portrays a specific surface area and good wettability that enable fast charge transfer and ion transport channels. Consequently, the Bi-PCC electrode demonstrates a high specific capacity of up to 297.1 mAh g -1 at 2 A g -1 , with a capacity retention of up to 71.5% at 2-40 A g -1 and an impressive capacity retention of 79.9% after 1000 cycles at 2-40 A g -1 . More importantly, the flexible rechargeable Ni//Bi battery (denoted as Ni(OH) 2 -PCC//Bi-PCC) with Bi-PCC as the anode and Ni(OH) 2 -PCC as the cathode has excellent electrochemical performance. The Ni(OH) 2 -PCC//Bi-PCC battery boasts a remarkable capacity retention of 93.6% after 3000 cycles at 10 A g -1 . Further, the cell presents a maximum energy density of 73.1 Wh kg -1 and an impressive power density of 11.9 kW kg -1 .

Cs 2 SnI 6 powder is, for the first time, solution-prepared via the formula CsI + SnI 2 + I 2 → Cs 2 SnI 6 . The product is highly pure and air/thermal stable. It is found that N,N -dimethylformamide (DMF) and methanol induce severe Cs 2 SnI 6 deterioration with the appearance of a CsI phase in film preparation from Cs 2 SnI 6 powder, while solvents of γ-butyrolactone (GBL) and ethylene glycol methyl ether (EGME) (Film-EGME) give better results. Then, by introducing EGME solvent, in situ preparation of Cs 2 SnI 6 films (Film-1 to Film-4) is realized under solution reaction, which is found to be dominated by thermal dynamic process, i.e., highly pure/oriented Film-4 is obtained under the maximum reagent-concentration. Besides, for good reaction, the solubility of solvent should be balanced among all the reagents and products. Solid-state dye sensitized solar cells (ss-DSSCs) comprising a Cs 2 SnI 6 electrolyte are investigated. The power conversion efficiencies (PCEs) of the ss-DSSCs based on solution-casted Film-EGME and the in situ-prepared Film-4 are 1.81% and 3.30%, respectively. Particularly, with the in situ prepared Cs 2 SnI 6 films, it is found that the open circuit voltages of the ss-DSSCs are closely related to their gap states. When additive is added in Cs 2 SnI 6 electrolyte, a PCE of 6.14% is obtained in an ss-DSSC. Our work highlights the importance of solvent in film preparation and the role of Cs 2 SnI 6 gap states in device performance.

As electronic equipment develops rapidly, higher requirements are placed on electrochemical energy-storage devices. These requirements can be met by a lithium-sulfur (Li-S) battery since it has an impressive energy density of 2600 Wh kg -1 and a high theoretical specific capacity of 1675 mAh g -1 . Pitifully, the sluggish redox reaction kinetics and the shuttle effect of polysulfide seriously limit its applications. Separator modification has been proven to be an effective strategy for improving the performance of Li-S batteries. Herein, we have designed a competent three-dimensional separator. It is obtained by embedding Co 3 Se 4 nanoparticles on nitrogen-doped porous carbon (Co 3 Se 4 @N-C) by high-temperature selenization of ZIF-67, which are compounded with Ti 3 C 2 T x by electrostatic dispersion self-assembly, and the compound is used to adjust the surface properties of a polypropylene (PP) separator. Due to the synergistic effect of the superior catalytic performance of Co 3 Se 4 @N-C and the enhancement of adsorption and conductivity bestowed by Ti 3 C 2 T x , lithium-sulfur batteries perform excellently with the modified PP separator. Specifically, the battery with a Co 3 Se 4 @N-C/Ti 3 C 2 T x -modified PP separator exhibits an outstanding rate performance of 787 mAh g -1 at 4C, and stable performance is maintained after 300 cycles at 2C. The density functional theory (DFT) calculations are also performed to confirm the synergistic effect of Co 3 Se 4 @N-C and Ti 3 C 2 T x . This design integrates the merits of catalysis and adsorption and provides a new method for constructing high-performance lithium-sulfur batteries.

Metal-organic frameworks (MOFs) are promising candidates for the advanced membrane materials based on their diverse structures, modifiable pore environment, precise pore sizes, etc. Nevertheless, the use of supports and large amounts of solvents in traditional solvothermal synthesis of MOF membranes is considered inefficient, costly, and environmentally problematic, coupled with challenges in their scalable manufacturing. In this work, we report a solvent-free space-confined conversion (SFSC) approach for the fabrication of a series of free-standing MOF (ZIF-8, Zn(EtIm) 2 , and Zn 2 (BIm) 4 ) membranes. This approach excludes the employment of solvents and supports that require tedious pretreatment and, thus, makes the process more environment-friendly and highly efficient. The free-standing membranes feature a robust and unique architecture, which comprise dense surface layers and highly porous interlayer with large amounts of irregular-shaped micron-scale pore cavities, inducing satisfactory H 2 /CO 2 selectivities and exceptional H 2 permeances. The ZIF-8 membrane affords a considerable H 2 permeance of 2653.7 GPU with a competitive H 2 /CO 2 selectivity of 17.1, and the Zn(EtIm) 2 membrane exhibits a high H 2 /CO 2 selectivity of 22.1 with an excellent H 2 permeance (6268.7 GPU). The SFSC approach potentially provides a new pathway for preparing free-standing MOF membranes under solvent-free conditions, rendering it feasible for scale-up production of membrane materials for gas separation.

Bacteria-infected skin wounds caused by external injuries remain a serious challenge to the whole society. Wound healing dressings, with excellent antibacterial activities and potent regeneration capability, are increasingly needed clinically. Here, we reported a novel functional microneedle (MN) array comprising methacrylated hyaluronic acid (MeHA) embedded with pH-responsive functionalized zeolitic imidazolate framework-8 (ZIF-8) nanoparticles to treat bacteria-infected cutaneous wounds. Antibacterial activity was introduced into Zn-ZIF-8 to achieve sterilization through releasing Zn ions, as well as increased angiogenesis by dimethyloxalylglycine (DMOG) molecules that were distributed within its framework. Furthermore, biodegradable MeHA was chosen as a substrate material carrier to fabricate DMOG@ZIF-8 MN arrays. By such design, DMOG@ZIF-8 MN arrays would not only exhibit excellent antibacterial activity against pathogenic bacteria but also enhance angiogenesis within wound bed by upregulating the expression of HIF-1α, leading to a significant therapeutic efficiency on bacteria-infected cutaneous wound healing. Based on these results, we conclude that this new treatment strategy can provide a promising alternative for accelerating infected wound healing via effective antibacterial activity and ameliorative angiogenesis.

Donor-doped TiO 2 -based materials are promising thermoelectrics (TEs) due to their low cost and high stability at elevated temperatures. Herein, high-performance Nb-doped TiO 2 thick films are fabricated by facile and scalable screen-printing techniques. Enhanced TE performance has been achieved by forming high-density crystallographic shear (CS) structures. All films exhibit the same matrix rutile structure but contain different nano-sized defect structures. Typically, in films with low Nb content, high concentrations of oxygen-deficient {121} CS planes are formed, while in films with high Nb content, a high density of twin boundaries are found. Through the use of strongly reducing atmospheres, a novel Al-segregated {210} CS structure is formed in films with higher Nb content. By advanced aberration-corrected scanning transmission electron microscopy techniques, we reveal the nature of the {210} CS structure at the nano-scale. These CS structures contain abundant oxygen vacancies and are believed to enable energy-filtering effects, leading to simultaneous enhancement of both the electrical conductivity and Seebeck coefficients. The optimized films exhibit a maximum power factor of 4.3 × 10 -4 W m -1 K -2 at 673 K, the highest value for TiO 2 -based TE films at elevated temperatures. Our modulation strategy based on microstructure modification provides a novel route for atomic-level defect engineering which should guide the development of other TE materials.

Noninvasive and sensitive thermometry is crucial to human health monitoring and applications in disease diagnosis. Despite recent advances in optical temperature detection, the construction of sensitive wearable temperature sensors remains a considerable challenge. Here, a flexible and biocompatible optical temperature sensor is developed by combining plasmonic semiconductor W 18 O 49 enhanced upconversion emission (UCNPs/WO) with flexible poly(lactic acid) (PLA)-based optical fibers. The UCNPs/WO offers highly thermal-sensitive and obviously enhanced dual-wavelength emissions for ratiometric temperature sensing. The PLA polymer endows the sensor with excellent light-transmitting ability for laser excitation and emission collection and high biocompatibility. The fabricated UCNPs/WO-PLA sensor exhibits stable and rapid temperature response in the range 298-368 K, with a high relative sensitivity of 1.53% K -1 and detection limit as low as ±0.4 K. More importantly, this proposed sensor is demonstrated to possess dual function on real-time detection for physiological thermal changes and heat release, exhibiting great potential in wearable health monitoring and biotherapy applications.

Hydrogels with good flexibility and strong hydrophilicity can be candidates for excellent flexible electrolyte materials. However, the poor structural stability, uncontrollable swelling, and lower potential window of hydrogel electrolytes need to be improved. This work combined quaternized gelatin with cross-linked poly(acrylic acid-co-acrylamide) to form a semi-interpenetrating network and gelatinized in situ in a flexible porous wood skeleton. The flexible wood (FW) skeleton enhances the hydrogel and limits the swelling of the hydrogel. In addition, quaternary ammonium groups and FW act synergistically to provide the composite hydrogel electrolyte with a high ionic conductivity of 5.57 × 10 -2 S cm -1 . The composite hydrogel electrolyte can enable the flexible supercapacitor to operate safely in a potential window of 0-2 V. The optimized supercapacitor has a high specific capacitance of 286.74 F g -1 and provides an outstanding energy density of 39.09 W h kg -1 . The flexible supercapacitor shows a capacitance retention of up to 94.6% after 10,000 charge-discharge cycles, indicating dramatic cycling stability. Simultaneously, a capacitance retention of nearly 90% can be maintained by the flexible supercapacitor after 180° bends for 1000 times. A viable idea for developing high-performance hydrogel electrolytes and flexible supercapacitors is provided in this research.

Determination of trace amounts of targets or even a single molecule target has always been a challenge in the detection field. Digital measurement methods established for single molecule counting of proteins, such as single molecule arrays (Simoa) or dropcast single molecule assays (dSimoa), are not suitable for detecting small molecule, because of the limited category of small molecule antibodies and the weak signal that can be captured. To address this issue, we have developed a strategy for single molecule detection of small molecules, called small molecule detection with single molecule assays (smSimoa). In this strategy, an aptamer is used as a recognition element, and an addressable DNA Nanoflower (DNF) attached on the magnetic beads surface, which exhibit fluorescence imaging, is employed as the output signal. Accompanied by digital imaging and automated counting analysis, E2 at the attomolar level can be measured. The smSimoa breaks the barrier of small molecule detection concentration and provides a basis for high throughput detection of multiple substances with fluorescence encoded magnetic beads.

Developing piezoelectric ceramics with high piezoelectric properties and broad temperature usage ranges via low-temperature sintering is one of decisive importance for flourishing developments for emerging electromechanical applications. However, these properties are usually mutually exclusive, such as low-temperature sintering and high piezoelectricity as well as high piezoelectricity and temperature stability. Here, we report high piezoelectricity (i.e., piezoelectric constant d 33 ≈ 744 pC/N, electromechanical coupling factor k p ≈ 75%, and Curie temperature T C ≈ 201 °C) and superior temperature stability ( d 33 varies less than 10% within 25-160 °C) in Pb 0.905 Ba 0.095 (Zr 0.54 Ti 0.46 )O 3 + 1 mol % Nb 2 O 5 + 1 wt % Bi 2 O 3 + x wt % CdCO 3 (PBZTNB- x Cd) ceramics that are fabricated at a sintering temperature of as low as 960 °C, superior to those of other reported random and textured ceramics. Good piezoelectricity is attributed to the remaining rhombohedral-tetragonal (R-T) phase coexistence and the high ceramic density. Excellent temperature stability is related to the stable crystal structure and domain structure. These properties confer to the produced materials attractive characteristics for further consideration in several advanced applications, especially for piezoelectric transducer applications requiring constant structures over a broad temperature range.

Conductive hydrogels have attracted attention because of their wide application in wearable devices. However, it is still a challenge to achieve conductive hydrogels with high sensitivity and wide frequency band response for smart wearable strain sensors. Here, we report a composite hydrogel with piezoresistive and piezoelectric sensing for flexible strain sensors. The composite hydrogel consists of cross-linked chitosan quaternary ammonium salt (CHACC) as the hydrogel matrix, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) as the conductive filler, and poly(vinylidene fluoride- co -trifluoroethylene) (PVDF-TrFE) as the piezoelectric filler. A one-pot thermoforming and solution exchange method was used to synthesize the CHACC/PEDOT: PSS/PVDF-TrFE hydrogel. The hydrogel-based strain sensor exhibits very high sensitivity (GF: 19.3), fast response (response time: 63.2 ms), and wide frequency range (response frequency: 5-25 Hz), while maintaining excellent mechanical properties (elongation at break up to 293%). It can be concluded that enhanced strain-sensing properties of the hydrogel are contributed to both greater change in the relative resistance under stress and wider response to dynamic and static stimulus by adding PVDF-TrFE. This has a broad application in monitoring human motion, detecting subtle movements, and identifying object contours and a hydrogel-based array sensor. This work provides an insight into the design of composite hydrogels based on piezoelectric and piezoresistive sensing with applications for wearable sensors.

Most conventional chemotherapeutics indiscriminately kill both cancerous and healthy cells and cause toxic side effects, limiting the maximum tolerated dose and thereby compromising therapeutic efficacy. To address this challenge, here dual-targeting intelligent DNA guided missile (GM)-integrated nanospacecraft (NSC) (abbreviated as GM-NSC) is demonstrated for staged chemotherapeutic drug delivery exclusively into cancer cells and then mitochondria (not into healthy cells). GM-NSC is essentially a core/shell nanocomposite composed of gold nanoparticles (AuNPs) surrounded by a high-density multilayer DNA crown that is self-assembled from DNA tetrahedral units (DNA Tetra) in a highly ordered manner. Each tetrahedral structural unit is equipped with three functional components: a cancer cell-targeting aptamer pointing toward the outside environment, a hidden mitochondria-targeting triphenylphosphonium (TPP), and an explosive bolt (E-bolt). GM-NSC can remain intact in fetal bovine serum solution over 12 h and has 53-fold improved systemic stability. Each GM-NSC accommodates 1250 anticancer doxorubicin (Dox), achieving a 48-63-fold improved drug payload capacity. When systemically administrated into a tumor-bearing xenograft murine model, Dox-loaded GM-NSC enters into tumor sites with 18-fold improved specificity followed by autonomous separation of GMs from the NSC core and specific mitochondrial accumulation due to the explosion of E-bolt upon stimuli of endogenous miRNAs. About 80% of Dox uptaken is transferred into mitochondria and induces mitochondria-mediated apoptosis. As a result, the growth of malignant tumor is almost 100% inhibited without detectable toxicity to healthy tissues. Due to the desirable systemic stability, good biocompatibility, high cargo loading capability, satisfactory in vivo biodistribution, and therapeutic efficacy without adverse effects, intelligible GM-NSC is expected to become an alternative drug delivery system for precision cancer therapy.

Hepatic stellate cells (HSCs), as an important part of the tumor microenvironment (TME), could be activated by tumor cells as cancer-associated fibroblasts (CAFs), thereby promoting the production of extracellular matrix (ECM) and favoring the development of tumors. Therefore, blocking the "CAFs-ECM" axis is a promising pathway to improve antitumor efficacy. Based on this, we developed a multifunctional nanosized delivery system composed of hyaluronic acid-modified pH-sensitive liposomes (CTHLs) and glycyrrheic acid-modified nanomicelles (DGNs), which combines the advantages of targeted delivery, pH-sensitivity, and deep drug penetration. To mimic actual TME, a novel HSCs+BEL-7402 cocultured cell model and a m-HSCs+H22 coimplanted mice model were established. As expected, CTHLs and DGNs could target CAFs and tumor cells, respectively, and promote the drug penetration and retention in tumor regions. Notably, CTHLs+DGNs not only exhibited a superior antitumor effect in three-level tumor-bearing mice but also presented excellent antimetastasis efficiency in lung-metastatic mice. The antitumor mechanism revealed that the lipid&micelle mixed formulations effectively inhibited the activation of CAFs, reduced the deposition of ECM, and reversed the epithelial-mesenchymal transition (EMT) of tumor cells. In brief, the nanosized delivery system composed of CTHLs and DGNs could effectively improve the therapeutic effect of liver cancer by blocking the "CAFs-ECM" axis, which has a good clinical application prospect.

Metal-organic frameworks (MOFs) have many attractive features, including tunable composition, rigid structure, controllable pore size, and large specific surface area, and thus are highly applicable in molecular analysis. Depending on the MOF structure, a high number of unsaturated metal sites can be exposed to catalyze chemical reactions. In the present work, we report that using both Co(II) and Fe(III) to prepare the MIL-88(NH 2 ) MOF, we can produce the bimetallic MOF that can catalyze the conversion of 3,3',5,5″-tetramethylbenzidine (TMB) to a color product through a reaction with H 2 O 2 at a higher reaction rate than the monometallic Fe-MIL-88(NH 2 ). The Michaelis constants ( K m ) of the catalytic reaction for TMB and H 2 O 2 are 3-5 times smaller, and the catalytic constants ( k cat ) are 5-10 times higher than those of the horseradish peroxidase (HRP), supporting ultrahigh peroxidase-like activity. These values are also much more superior to those of the HRP-mimicking MOFs reported previously. Interestingly, the bimetallic MOF can be coupled with glucose oxidase (GOx) to trigger the cascade enzymatic reaction for highly sensitive detection of extracellular vesicles (EVs), a family of important biomarkers. Through conjugation to the aptamer that recognizes the marker protein on EV surface, the MOF can help isolate the EVs from biological matrices, which are subsequently labeled by GOx via antibody recognition. The cascade enzymatic reaction between MOF and GOx enables the detection of EVs at a concentration as low as 7.8 × 10 4 particles/mL. The assay can be applied to monitor EV secretion by cultured cells and also can successfully detect the different EV quantities in the sera samples collected from cancer patients and healthy controls. Overall, we prove that the bimetallic Fe/Co-MIL-88(NH 2 ) MOF, with its high peroxidase activity and high biocompatibility, is a valuable tool deployable in clinical assays to facilitate disease diagnosis and prognosis.

Deep-seated tumors of the liver, brain, and other organ systems often recur after initial surgical, chemotherapeutic, radiation, or focal treatments. Repeating these treatments is often invasive and traumatic. We propose an iron oxide nanoparticle (IONP)-enhanced precipitating hydrophobic injectable liquid (PHIL, MicroVention inc.) embolic as a localized dual treatment implant for nutrient deprivation and multiple repeatable thermal ablation. Following a single injection, multiple thermal treatments can be repeated as needed, based on monitoring of tumor growth/recurrence. Herein we show the ability to create an injectable stable PHIL-IONP solution, monitor deposition of the PHIL-IONP precipitate dispersion by μCT, and gauge the IONP distribution within the embolic by magnetic resonance imaging. Once precipitated, the implant could be heated to reach therapeutic temperatures >8 °C for thermal ablation (clinical temperature of ∼45 °C), in a model disk and a 3D tumor bed model. Heat output was not affected by physiological conditions, multiple heating sessions, or heating at intervals over a 1 month duration. Further, in ex vivo mice hind-limb tumors, we could noninvasively heat the embolic to an "ablative" temperature elevation of 17 °C (clinically 54 °C) in the first 5 min and maintain the temperature rise over +8 °C (clinically a temperature of 45 °C) for longer than 15 min.

Three-dimensional (3D) embedded printing is emerging as a potential solution for the fabrication of complex biological structures and with ultrasoft biomaterials. For the supporting medium, bulk gels can support a wide range of bioinks with higher printing resolution as well as better finishing surfaces than granular microgel baths. However, the difficulties of regulating the physical properties of existing bulk gel supporting baths limit the further development of this method. This work has developed a bulk gel supporting bath with easily regulable physical properties to facilitate soft-material fabrication. The proposed bath is composed based on the hydrophobic association between a hydrophobically modified hydroxypropylmethyl cellulose (H-HPMC) and Pluronic F-127 (PF-127). Its rheological properties can be easily regulated; in the preprinting stage by varying the relative concentration of components, during printing by changing the temperature, and postprinting by adding additives with strong hydrophobicity or hydrophilicity. This has made the supporting bath not only available for various bioinks with a range of printing windows but also easy to be removed. Also, the removal strategy is independent of printing conditions like temperature and ions, which empowers the bath to hold great potential for the embedded printing of commonly used biomaterials. The adjustable rheological properties of the bath were leveraged to characterize the embedded printing quantitatively, involving the disturbance during the printing, filament cross-sectional shape, printing resolution, continuity, and the coalescence between adjacent filaments. The match between the bioink and the bath was also explored. Furthermore, low-viscosity bioinks (with 0.008-2.4 Pa s viscosity) were patterned into various 3D complex delicate soft structures (with a 0.5-5 kPa compressive modulus). It is believed that such an easily regulable assembled bath could serve as an available tool to support the complex biological structure fabrication and open unique prospects for personalized medicine.

CsPbI 2 Br is promising in the application of perovskite solar cells (PSCs) owing to its reasonable bandgap and good thermal stability. However, the reported power conversion efficiency (PCE) of the CsPbI 2 Br solar cells is still much lower than that of the organic-inorganic hybrid PSCs, mainly due to relatively poor CsPbI 2 Br crystal quality. Herein, additive engineering to the photoactive layer of CsPbI 2 Br using the Ti 3 C 2 T x MXene nanosheets is reported. Thanks to the improved crystallinity/reduced defect density, together with the formation of the Schottky junction between the MXene nanosheets and CsPbI 2 Br, enhanced separation and transfer of the photogenerated electron-hole pairs can be achieved for optimal MXene addition. A simple device configuration of ITO/SnO 2 /Ti 3 C 2 T x -added CsPbI 2 Br/P3HT/Ag can thus deliver a significantly boosted PCE of 15.10%, i.e., a ∼16.69% relative increment compared with that (12.94%) of the control device without adding MXene. In addition, the enhanced humidity resistance is achieved for the MXene-added CsPbI 2 Br layers.

Timely restoration of blood supply following ischemia is critical to rescue damaged tissue. However, clinical efficacy is hampered by the inflammatory response after ischemia. Whether inflammation fine tunes the angiogenesis and the function of blood vessels via the heterogeneity of neutrophils remain poorly understood. Herein, the objective of this work is to incorporate the growth factors secreted by neutrophils into a porous gelatin methacrylate (GelMA) hydrogel, which subsequently is used as a novel regenerative scaffold with defined architecture for ischemia. We demonstrate that anti-inflammatory neutrophils (N 2 -polarized neutrophils) play an important role in promoting the migration of human umbilical vein endothelial cells (HUVECs) and formation of capillary-like networks in vitro . More importantly, vascular anastomosis can be achieved by modulating the neutrophils to N 2 phenotype. In addition, N 2 -polarized composite hydrogel scaffolds can regulate inflammation, maintain the survival of exogenous cells, and promote angiogenesis in vivo . Notably, the composite hydrogel scaffolds promote neovascularization during exogenous introduction of endothelial cells by anastomosis. Taken together, this study highlights N 2 -polarized neutrophils composite hydrogels can achieve vascularization rapidly by regulating inflammation and promoting vascular anastomosis. This work lays the foundation for research into the treatment of ischemia and may inspire further research into novel treatment options.

Polymer dielectrics have drawn tremendous attention worldwide due to their huge potential for pulsed power capacitors. Recent studies have demonstrated that linear/nonlinear layered composites, which can effectively balance energy density and efficiency, have huge potential for capacitive energy storage applications. However, further enhanced energy densities are strongly desired to meet the everincreasing demand for the miniaturization of electronic devices. Herein, a novel class of core-shell structured graphene@titanium dioxide nanoboxes is successfully synthesized and introduced into poly(vinylidene fluoride-hexafluoropropylene)-poly(ether imide) double-layer films. It is exciting to find that the introduction of merely 0.5 wt % nanoboxes results in a substantially enhanced energy density of 19.39 J/cm 3 , which is over 2.6 times that of the film without nanoboxes (7.44 J/cm 3 ). Meanwhile, a high breakdown strength of 655 kV/mm and a high efficiency of 83% are achieved. Furthermore, the nanocomposites also show excellent power densities and cycling stabilities. These composites with excellent comprehensive energy storage performances have huge potential for advanced pulsed power capacitors.

Enrichment and separation of specific endogenous molecules are essential for disease diagnosis and the pharmaceutical industry. Although many solid sorbents have been developed for target molecule enrichment, simultaneous separation of multitargets is still a challenge for adsorbents. In this study, we develop a multitarget selective sorbent based on a nanochannel membrane prepared by the anodization of a Ti-Cu alloy. The in situ growth of a metal-organic framework (MOF, herein using Cu-based HKUST-1) in the nanochannels enables the resulting MOF-in-nanochannel membrane to act as a nanofilter. Benefitting from the size-exclusion effect of MOFs and the distinct surface characteristics of each component in the HKUST-1/TiO 2 nanochannels, the as-proposed membranes can be simply operated as a filter and exhibit satisfactory selectivities and enrichment capacities in the separation of aromatic amino acids, histidine-rich proteins, and phosphoproteins. More importantly, the adsorbed multitargets can be further controllably released from the membrane in a sequence via a staged recovery process. The use of this system is envisioned to provide an innovative and potential design for efficient sorption media for the selective enrichment and staged separation of specific biomolecules.

The electrochemical CO 2 reduction over Cu catalysts has shown great potential in producing a wide range of valuable chemicals, but it is still plagued by a poor controllability on product distribution. Herein, we demonstrate an effective regulation of CO 2 reduction paths through a preanodization treatment of Cu foil electrodes in different electrolytes. The Cu electrode exhibits a superior C 1 and C 2+ product selectivity after being preanodized in NaClO 4 (Cu- NaClO 4 ) and Na 2 HPO 4 electrolyte (Cu- Na 2 HPO 4 ), respectively. Combined with in situ electrochemical Raman, ATR-SEIRAS, and SEM characterizations, the preferential C 1 path is due to the deposition of many Cu nanocrystals with dominant Cu(111) facets on the Cu- NaClO 4 electrode. In contrast, the preferential C 2+ path over the Cu- Na 2 HPO 4 is attributed to formation of a unique Cu nanodendritic morphology, which strengthens the *CO intermediate adsorption and induces an environment of low local H 2 O/CO 2 stoichiometric ratio, thus facilitating C-C coupling for C 2+ production. Our findings may shed light on the rational control of the CO 2 reduction path through engineering of the Cu surface structure.

Supported metal catalysts play a significant role in heterogeneous catalysis in liquid phase reaction systems, but they usually suffer from a stability problem. Encapsulation of active metal species without the compromise of catalytic performance has been considered as an effective strategy. Here, we report an ultrastable Ru-based catalyst with particle size of around 1.1 nm for selective hydrogenation reaction. The highly dispersed Ru species are covered by the in situ formed porous N-C-ZnO overlayer, which is induced through the transforming of ZIF-8 shell that derives from a ZnO substrate. The resulting Ru/ZnO@N-C-ZnO catalyst can exhibit good stability in the hydrogenation of p -chloronitrobenzene after 20 cyclic runs with 100% selectivity toward p -chloroaniline. Comparatively, the naked Ru/ZnO catalyst with larger Ru particles shows serious metal leaching issue with inferior stability and poor selectivity. It is revealed that the excellent performance of Ru/ZnO@N-C-ZnO is attributed to the porous overlayer, which strengthens the bonding of Ru nanoparticles on ZnO.

Functionalized biocarriers that can perform bio-orthogonal reactions in tumor cells may provide solutions to overcome the efflux of the chemotherapeutic agent from drug-resistant tumor cells. Herein, we report the enrichment of therapeutic drugs in tumor cells through intracellular click reaction with functionalized bacteria. Specifically, an intracellular bioactive drug enrichment template (OPV@ Escherichia coli ) is constructed by combining positively charged oligo(phenylene-vinylene)-alkyne (OPV-C≡CH) with E. coli via electrostatic interaction. After the cell uptake of OPV@ E. coli and Cu(II)-based complex, Cu(I) generated in situ can catalyze the bio-orthogonal click reaction to covalently anchor the azide-bearing molecules of cyanine 5 (Cy5-N 3 ) and paclitaxel (PTX-N 3 ) on OPV@ E. coli . These molecules and their functions were retained and enriched inside the drug-resistant tumor cells A549T, which can label cells with fluorescent probes and selectively induce the apoptosis of drug-resistant tumor cells.