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Chiral architectures, one of the key structural features of natural systems ranging from the nanoscale to macroscale, are an infinite source of inspiration for functional materials. Researchers have been, and still are, strongly pursuing the goal of constructing such structures with renewable and sustainable building blocks via simple and efficient strategies. With the merits of high sustainability, renewability, and the ability to self-assemble into chiral nematic structures in aqueous suspensions that can be preserved in the solid state, polysaccharide nanocrystals (PNs) including cellulose nanocrystals (CNCs) and chitin nanocrystals (ChNCs) offer opportunities to reach the target. We herein provide a comprehensive review that focuses on the development of CNCs and ChNCs for the use in advanced functional materials. First, the introduction of CNCs and ChNCs, and cellulose- and chitin-formed chiral nematic organizations in the natural world, are given. Then, the self-assembly process of such PNs and the factors influencing this process are comprehensively discussed. After that, we showcased the emerging applications of the self-assembled chiral nematic structures of CNCs and ChNCs. Finally, this review concludes with perspectives on the challenges and opportunities in this field.

X-ray photoelectron spectroscopy (XPS) is a powerful characterization technique that unveils subtle chemical environment differences via core-electron binding energy (CEBE) analysis. We extend the development of real-space pseudopotential methods to calculating 1s, 2s, and 2p 3/2 CEBEs of third-row elements (S, P, and Si) within the framework of Kohn-Sham density-functional theory (KS-DFT). The new approach systematically prevents variational collapse and simplifies core-excited orbital selection within dense energy level distributions. However, careful error cancellation analysis is required to achieve accuracy comparable to all-electron methods and experiments. Combined with real-space KS-DFT implementation, this development enables large-scale simulations with both Dirichlet boundary conditions and periodic boundary conditions.

A photoredox-catalyzed sequential decarboxylative/defluorinative aminoalkylation of CF 3 -alkenes with N -arylglycines is described. This metal-free and redox-neutral protocol provided efficient access to the monofluoroalkenyl-1,5-diamines in good yields with excellent functional group compatibility. Mechanistic studies revealed that the reaction proceeds via a radical pathway with the gem -difluoroalkenyl amine as an intermediate.

High-entropy alloys (HEAs), characterized as compositionally complex solid solutions with five or more metal elements, have emerged as a novel class of catalytic materials with unique attributes. Because of the remarkable diversity of multielement sites or site ensembles stabilized by configurational entropy, human exploration of the multidimensional design space of HEAs presents a formidable challenge, necessitating an efficient, computational and data-driven strategy over traditional trial-and-error experimentation or physics-based modeling. Leveraging deep learning interatomic potentials for large-scale molecular simulations and pretrained machine learning models of surface reactivity, our approach effectively rationalizes the enhanced activity of a previously synthesized PdCuPtNiCo HEA nanoparticle system for electrochemical oxygen reduction, as corroborated by experimental observations. We contend that this framework deepens our fundamental understanding of the surface reactivity of high-entropy materials and fosters the accelerated development and synthesis of monodisperse HEA nanoparticles as a versatile material platform for catalyzing sustainable chemical and energy transformations., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Soap bubbles exhibit abundant fascinating phenomena throughout the entire life of evolution with different fundamental physics governing them. Nevertheless, the complicated dynamics of small objects in soap films are still unrevealed. Here, we report the first observation of spontaneous particle ordering in a complicated galaxy of soap films without any external energy. The balance of interfacial tension at two liquid-gas interfaces is theoretically predicted to govern belted wetted particles (BWPs) traveling along a specified path spontaneously. Such spontaneous particle path-finding is found to depend on the particle size and hydrophilic properties. Spontaneous particle sorting is directly realized via these discrete and distinctive paths for different particles. The deformation of the soap membrane facilitates 1D/2D particle organization along the path. This observation represents the discovery of a new spontaneous order phenomenon in soap film systems and provides a new energy-free approach for particle separation and soft colloidal crystal assembly.

Persistent foot odor and itchiness are common symptoms of tinea pedis, significantly disrupting the daily life of those affected. The cuticular barrier at the site of the tinea pedis is thickened, which impedes the effective penetration of antifungal agents. Additionally, fungi can migrate from the skin surface to deeper tissues, posing challenges in the current clinical treatment for tinea pedis. To effectively treat tinea pedis, we developed a platform of bilayer gelatin methacrylate (GelMA) microneedles (MNs) loaded with salicylic acid (SA) and FK13-a1 (SA/FK13-a1@GelMA MNs). SA/FK13-a1@GelMA MNs exhibit pH- and matrix metalloproteinase (MMP)-responsive properties for efficient drug delivery. The MNs are designed to deliver salicylic acid (SA) deep into the stratum corneum, softening the cuticle and creating microchannels. This process enables the antibacterial peptide FK13-a1 to penetrate through the stratum corneum barrier, facilitating intradermal diffusion and exerting antifungal and anti-inflammatory effects. In severe cases of tinea pedis, heightened local pH levels and MMP activity further accelerate drug release. Our research demonstrates that SA/FK13-a1@GelMA MNs are highly effective against Trichophyton mentagrophytes , Trichophyton rubrum , and Candida albicans . They also reduced stratum corneum thickness, fungal burden, and inflammation in a guinea pig model of tinea pedis induced by T. mentagrophytes . Furthermore, it was discovered that SA/FK13-a1@GelMA MNs exhibit excellent biocompatibility. These findings suggest that SA/FK13-a1@GelMA MNs have significant potential for the clinical treatment of tinea pedis as well as other fungal skin disorders.

The present work describes a preclinical trial ( in silico , in vivo and in vitro ) protocol to assess the biomechanical performance and osteogenic capability of 3D-printed polymeric scaffolds implants used to repair partial defects in a sheep mandible. The protocol spans multiple steps of the medical device development pipeline, including initial concept design of the scaffold implant, digital twin in silico finite element modeling, manufacturing of the device prototype, in vivo device implantation, and in vitro laboratory mechanical testing. First, a patient-specific one-body scaffold implant used for reconstructing a critical-sized defect along the lower border of the sheep mandible ramus was designed using on computed-tomographic (CT) imagery and computer-aided design software. Next, the biomechanical performance of the implant was predicted numerically by simulating physiological load conditions in a digital twin in silico finite element model of the sheep mandible. This allowed for possible redesigning of the implant prior to commencing in vivo experimentation. Then, two types of polymeric biomaterials were used to manufacture the mandibular scaffold implants: poly ether ether ketone (PEEK) and poly ether ketone (PEK) printed with fused deposition modeling (FDM) and selective laser sintering (SLS), respectively. Then, after being implanted for 13 weeks in vivo, the implant and surrounding bone tissue was harvested and microCT scanned to visualize and quantify neo-tissue formation in the porous space of the scaffold. Finally, the implant and local bone tissue was assessed by in vitro laboratory mechanical testing to quantify the osteointegration. The protocol consists of six component procedures: (i) scaffold design and finite element analysis to predict its biomechanical response, (ii) scaffold fabrication with FDM and SLS 3D printing, (iii) surface treatment of the scaffold with plasma immersion ion implantation (PIII) techniques, (iv) ovine mandibular implantation, (v) postoperative sheep recovery, euthanasia, and harvesting of the scaffold and surrounding host bone, microCT scanning, and (vi) in vitro laboratory mechanical tests of the harvested scaffolds. The results of microCT imagery and 3-point mechanical bend testing demonstrate that PIII-SLS-PEK is a promising biomaterial for the manufacturing of scaffold implants to enhance the bone-scaffold contact and bone ingrowth in porous scaffold implants. MicroCT images of the harvested implant and surrounding bone tissue showed encouraging new bone growth at the scaffold-bone interface and inside the porous network of the lattice structure of the SLS-PEK scaffolds.

Bi 2 Te 3 -based thermoelectric (TE) materials are the state-of-the-art compounds for commercial applications near room temperature. Nevertheless, the application of the n-type Bi 2 Te 2.7 Se 0.3 (BTS) is restricted by the comparatively low figure of merit (ZT) and intrinsic embrittlement. Here, we show that through dispersion of amorphous Si 3 N 4 ( a -Si 3 N 4 ) nanoparticles both 14% increase in power factor (at 300 K) and 48% decrease in lattice thermal conductivity are simultaneously realized. The increased power factor comes from enhanced thermopower and reduced electrical resistivity while the reduced lattice thermal conductivity originates mainly from scattering of middle- and low-frequency phonons at the incorporated a -Si 3 N 4 nanoparticles. As a result, a large ZT max = 1.19 (at 373 K) and an average ZT ave ∼ 1.12 (300-473 K) with better mechanical properties are achieved for the BTS/0.25 wt % Si 3 N 4 sample. Present results demonstrate that the incorporation of a -Si 3 N 4 is a promising way to improve TE performance.

N-type Bi 2 Te 2.7 Se 0.3 (BTS) alloy has relatively low thermoelectric performance as compared to its p-type counterpart, which restricts its widespread applications. Herein, we designed and prepared a novel composite system, which consists of an n-type BTS matrix incorporated with both inorganic and organic nanoinclusions. The results indicate that the thermopower of the composite samples can be enhanced by more than 19% upon incorporating inorganic nanophase AgBi 3 S 5 (ABS) due to the energy-dependent carrier scattering, which ensures a high power factor. On the other hand, further incorporation of organic nanophase polypyrrole (PPy) can drastically reduce its lattice thermal conductivity owing to the strong scattering of mid- and low-frequency phonons at these nanoinclusions. As a result, high figures of merit ZT max = 1.3 at 348 K and ZT ave = 1.17 (300-500 K) are achieved with improved mechanical properties in BTS-based composites incorporated with 1.5 wt % ABS and 0.5 wt % PPy, demonstrating that the incorporation of both inorganic and organic nanoinclusions is an effective way to improve its thermoelectric performance.

A sustainable, cyanide-free synthesis of alkyl nitriles via the aerobic oxidative deconstruction of unstrained cycloalkanones with ammonium salts has been developed. Using inexpensive and stable ammonium salts as the nitrogen source, a variety of alkyl nitriles containing a distal carbonyl group were obtained in good yields under visible-light-promoted iron catalysis. This protocol is characterized by mild conditions, abundant and environmentally benign materials, and high atom and step economy with minimal waste generation. The primary mechanism study revealed that 1 O 2 is likely to be involved in this reaction.

The process of reconstructing an arterial graft is a complex and dynamic process that is subject to the influence of various mechanical factors, including tissue regeneration and blood pressure. The attainment of favorable remodeling outcomes is contingent upon the biocompatibility and biomechanical properties of the arterial graft. A promising strategy involves the emulation of the three-layer structure of the native artery, wherein the inner layer is composed of polycaprolactone (PCL) fibers aligned with blood flow, exhibiting excellent biocompatibility that fosters endothelial cell growth and effectively prevents platelet adhesion. The middle layer, consisting of PCL and polyurethane (PU), offers mechanical support and stability by forming a contractile smooth muscle ring and antiexpansion PU network. The outer layer, composed of PCL fibers with an irregular arrangement, promotes the growth of nerves and pericytes for long-term vascular function. Prioritizing the reconstruction of the inner and outer layers establishes a stable environment for intermediate smooth muscle growth. Our three-layer arterial graft is designed to provide the blood vessel with mechanical support and stability through nondegradable PU, while the incorporation of degradable PCL generates potential spaces for tissue ingrowth, thereby transforming our graft into a living implant., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Lung cancer poses a significant threat to human health. Surgical intervention is the preferred treatment modality for lung cancer, but a large number of patients are deprived of the opportunity for surgery for various reasons and are compelled to undergo radiotherapy and chemotherapy, which entail systemic adverse reactions. In recent years, with the advancement of nanomedicine, chemodynamic therapy (CDT) based on free radicals has been extensively investigated. In this study, we fabricated copper-citrate-chitosan composite nanoparticles (CuCC NPs) by encapsulating copper-citrate complexes with natural chitosan polymers, resulting in a substantial reduction in the biotoxicity of copper ions. The CuCC NPs selectively accumulated in tumor tissues through the enhanced permeability and retention effect (EPR) and gradually degraded within the acidic and glutathione (GSH)-rich microenvironment of the tumor, thereby releasing the loaded copper ions. Through CDT, the copper ions converted the overexpressed hydrogen peroxide (H 2 O 2 ) in the tumor tissue into hydroxyl radicals (•OH), leading to the eradication of tumor cells. In animal experiments, CuCC NPs exhibited remarkable efficacy in CDT. Further histopathological and hematological analyses demonstrated that CuCC NPs could induce substantial apoptosis in tumor tissues while maintaining an extremely high level of safety., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Transition-metal dichalcogenide WSe 2 has attracted increasing interest due to its large thermopower ( S ), low-cost, and environment-friendly constituents. However, its thermoelectric figure of merit, ZT , of WSe 2 is limited due to its large lattice thermal conductivity (κ L ) and low electrical conductivity. In view of WSe 2 and MoS 2 having the same crystal structure, here we designed and prepared Nb-doped quarternary mixed crystal (MC) Nb 0.05 W 0.95- x Mo x (Se 1- x S x ) 2 (0 ≤ x ≤ 0.095). The results indicate that the κ L of the MC can reach as low as 0.12 W m K -1 at 850 K, being 93% smaller than that of WSe 2 . Our analysis reveals that its low κ L originates chiefly from intense scattering of both high-frequency phonons from point defects (mainly alloying elements) and mid/low-frequency phonons from MoS 2 inclusions residual within MC. In addition, the alloying of WSe 2 with MoS 2 causes a 5-fold increase in cation vacancies (V W ‴' ), leading to a large increase in hole concentration and electrical conductivity, which gives rise to a ∼7.5 times increase in power factor (reaching 4.2 μ W cm -1 K -2 at 850 K). As a result, a record high ZT max = 0.63 is achieved at 850 K for the MC sample with x = 0.076, which is 20 times larger than that of WSe 2 , demonstrating that MC Nb 0.05 W 0.95- x Mo x (Se 1- x S x ) 2 is a promising thermoelectric material.

Imatinib (IMA) is a common chemotherapy drug for the treatment of leukemia and can potentially lead to drug resistance and toxicity during the course of treatment. Monitoring IMA concentrations in body fluids is necessary to optimize therapeutic schedules and avoid overdosage. In this paper, a novel ultrasensitive electrochemical sensor based on CuMOF and SWCNTs@AuNPs was developed to determine this antileukemic drug. Herein, AuNPs were supported on carboxylic single-walled carbon nanotubes (SWCNT-COOH), and then poly(diallyldimethylammonium chloride) (PDDA) was used as a dispersant to overcome the internal van der Waals interactions among the CNTs, further increasing the AuNP loading. Moreover, the morphology, structure, composition, and electrochemical properties of the CuMOF-SWCNTs@AuNPs composite film were characterized using SEM, TEM, FT-IR, UV-vis, XRD, XPS, CV, and EIS. Due to the advantage of the superior electrocatalytic and conductive properties of SWCNTs@AuNPs and their preferable adsorptivity and affinity to IMA of CuMOF, the fabricated glassy carbon electrode significantly improved the determination performance via their synergetic amplified effect. Under optimal conditions, a wide linear response was exhibited in the range from 0.05 to 20.0 μM and the low detection limit of 5.2 nM. In addition, our prepared sensor has been applied to the analysis of IMA in blood serum samples with acceptable results. Therefore, our CuMOF-SWCNTs@AuNPs-based electrochemical sensor possessed prominent sensing responses for IMA, which could be used as a prospective approach in clinical application., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Nanoscale composite lignin colloids were prepared on a large scale with a process of assembly-mediated internal cross-linking in a good solvent, thus possessing absolutely nanoscale dimensions, excellent robustness, and less aggregation. The therefore prime UV resistance and various natural visible colors contribute to the preservation and beautification of skin.

Propiconazole (PRO) has been widely used in the treatment of fungal infection in fruits, vegetables, cereals, and seeds. In this study, a newly established chiral liquid chromatography tandem mass spectrometry method was applied to the systemic stereoselectivity evaluation of PRO enantiomers, including toxicokinetics, tissue distributions, cytotoxicity, accumulation, and degradation. Our results showed that both trans (+)-2 S ,4 S -PRO and cis (-)-2 S ,4 R -PRO had lower C max and AUC 0-∞ and higher CLz/F values in plasma and lower accumulation concentrations in the liver, heart, and brain. In cytotoxic assays, cis (-)-2 S ,4 R -PRO exhibited the lowest cytotoxicity in PC12 neuronal, N9 microglia, SH-SY5Y neuroblastoma, and MRC5 lung fibroblast cell lines. Moreover, the Eisenia fetida incubation experiment revealed that the accumulations of both trans (+)-2 S ,4 S -PRO and cis (-)-2 S ,4 R -PRO were higher than those of their antipodes in E. fetida . In summary, our findings first suggested that the application of cis (-)-2 S ,4 R -PRO for agriculture would hugely reduce the environmental risk.

Brain inflammation is regarded as one of the leading causes that aggravates secondary brain injury and hinders the prognosis of ischemic stroke. After ischemic stroke, high quantities of peripheral neutrophils are recruited to brain lesions and release neutrophil extracellular traps (NETs), leading to the aggravation of blood-brain barrier (BBB) damage, activation of microglia, and ultimate neuronal death. Herein, a smart multifunctional delivery system has been developed to regulate immune disorders in the ischemic brain. Briefly, Cl-amidine, an inhibitor of peptidylarginine deiminase 4 (PAD4), is encapsulated into self-assembled liposomal nanocarriers (C-Lipo/CA) that are modified by reactive oxygen species (ROS)-responsive polymers and fibrin-binding peptide to achieve targeting ischemic lesions and stimuli-responsive release of a drug. In the mouse model of cerebral artery occlusion/reperfusion (MCAO), C-Lipo/CA can suppress the NETs release process (NETosis) and further inhibit the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway in an ischemic brain. In addition, MCAO mice treated with C-Lipo/CA significantly mitigated ischemic and reperfusion injury, with a reduction in the area of cerebral infarction to 12.1%, compared with the saline group of about 46.7%. These results demonstrated that C-Lipo/CA, which integrated microglia regulation, BBB protection, and neuron survival, exerts a potential therapy strategy to maximize ameliorating the mortality of ischemic stroke.

The search for highly active and selective catalysts with high precious metal atom utilization efficiency has attracted increasing interest in both the fundamental synthesis of materials and important industrial reactions. Here, we report the synthesis of Pd-Cu nanocubes with a Cu core and an ordered B2 intermetallic CuPd shell with controllable atomic layers on the surface (denoted as Cu/B2 CuPd), which can efficiently and robustly catalyze the selective hydrogenation of acetylene (C 2 H 2 ) to ethylene (C 2 H 4 ) under mild conditions. The optimized Cu/B2 CuPd with a Pd loading of 9.5 at. % exhibited outstanding performance in the C 2 H 2 semi-hydrogenation with 100% C 2 H 2 conversion and 95.2% C 2 H 4 selectivity at 90 °C. We attributed this outstanding performance to the core/shell structure with a high surface density of active Pd sites isolated by Cu in the B2 intermetallic matrix, representing a structural motif of single-atom alloys (SAAs) on the surface. The combined experimental and computational studies further revealed that the electronic states of Pd and Cu are modulated by SAAs from the synergistic effect between Pd and Cu, leading to enhanced performance compared with pristine Pd and Cu catalysts. This study provides a new synthetic methodology for making single-atom catalysts with high precious metal atom utilization efficiency, enabling simultaneous tuning of both geometric and electronic structures of Pd active sites for enhanced catalysis.

The construction of material prediction models using machine learning algorithms can aid in the polyimide structural design and screening of materials as well as accelerate the development of new materials. There is a lack of research on predicting the optical properties of polyimide materials and the interpretation of the structural features. Here, we collected 652 polyimide molecular structures and used seven popular machine learning algorithms to predict the glass transition temperature and cut-off wavelength of polyimide materials and extract key feature information of repeating unit structures. The results showed that the root mean square error of the glass transition temperature prediction model was 33.92 °C, and the correlation coefficient was 0.861. The root mean square error of the cut-off wavelength prediction model was 17.18 nm, and the correlation coefficient was 0.837. The elasticity of the molecular structure was also found to be the key factor affecting glass transition temperature, and the presence and location of heterogeneous atoms had a significant effect on the cut-off wavelengths. Finally, eight polyimide materials were synthesized to test the accuracy of the prediction models, and the experimental characterization values agreed with the predicted values. The results would contribute to the development of polyimide structural design and materials preparation for flexible display.

n-Type Bi 2 Te 2.7 Se 0.3 (BTS) is the state-of-the-art thermoelectric material near room temperature. However, the figure of merit ZT of commercial BTS ingots is still limited and further improvement is imperative for their wide applications. Here, the results show that through dispersion of the Ag 2 Te nanophase in BTS, one can not only elevate its power factor (PF) by as high as 14% (at 300 K) but also reduce its thermal conductivity κ tot to as small as ∼29% (at 300 K). Experimental evidences show that the improved PF comes from both increased electron mobility via inhibited Te vacancies and enhanced thermopower due to energy filtering effect, while the reduction of κ tot originates from the drop of both electronic thermal conductivity largely owing to the reduced number of vacancy V Te ·· and intensified phonon scattering chiefly from the dispersed Ag 2 Te nanophase. Consequently, the largest ZT max = 1.31 (at 350 K) and average ZT ave = 1.16 (300-500 K) are achieved for the Bi 2 Te 2.7 Se 0.3 -0.3 wt % Ag 2 Te composite sample, leading to a projected conversion efficiency η = 8.3% (300-500 K). The present results demonstrate that incorporation of nanophase Ag 2 Te is an effective approach to boosting the thermoelectric performance of BTS.

An array of redox-neutral alkylation/cyclization cascade reactions of N -functionalized acrylamides with cycloalkyl hydroperoxides were achieved via the alkoxyl radical-triggered C-C bond cleavage. Through adjusting the radical acceptors on the N atom, a variety of keto-alkylated chain-containing azaheterocycles, including indolo[2,1- a ]isoquinolin-6(5 H )-ones, quinoline-2,4-diones, and pyrido[4,3,2- gh ]phenanthridines were constructed by a one-pot procedure with good yields and excellent functional group tolerance.

In clinical practice, the incidence and mortality of non-small cell lung cancer are increasing year by year, which is a serious threat to the health of patients. Once the optimal surgical window is missed, the toxic side effects of chemotherapy have to be confronted. With the rapid development of nanotechnology in recent years, medical science and health have been greatly impacted. Therefore, in this manuscript, we design and prepare chemotherapeutic drug vinorelbine (VRL)-loaded polydopamine (PDA) shell-coated Fe 3 O 4 superparticles, and further graft the targeted ligand RGD onto their surface. Because of the introduction of the PDA shell, the toxicity of the prepared Fe 3 O 4 @PDA/VRL-RGD SPs is greatly reduced. At the same time, due to the existence of Fe 3 O 4 , the Fe 3 O 4 @PDA/VRL-RGD SPs also have MRI contrast capability. Under the dual-targeting effect of RGD peptide and external magnetic field, Fe 3 O 4 @PDA/VRL-RGD SPs can accumulate into tumors effectively. The accumulated superparticles in the tumor sites can not only effectively identify and mark the location and boundary of the tumor under MRI, guideing the application of near-infrared laser, but also release the loaded VRL under the stimulation of the acidic microenvironment of the tumor to play the role of chemotherapy. On further combination with photothermal therapy under laser irradiation, A549 tumors are completely eliminated without recurrence. Our proposed RGD/magnetic field dual-targeting strategy can effectively improve the bioavailability of nanomaterials and contribute to better imaging and therapeutic effects, which has a promising application prospect in the future., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Current understanding of the intrinsic point defects and potential extrinsic dopants in p-type Cu 2 SnSe 3 is limited, which hinders further improvement of its thermoelectric performance. Here, we show that the dominant intrinsic defects in Cu 2 SnSe 3 are Cu Sn and V Cu under different chemical conditions, respectively. The presence of V Cu will damage the hole conduction network and reduce hole mobility. Besides, we find that the substitution of Al, Ga, In, Cd, Zn, Fe, and Mn for Sn can inhibit the formation of V Cu ; introducing Cu Sn , Fe Sn , Mn Sn , and Ni Cu defects can significantly enhance electronic density of states near the Fermi level due to the contribution of 3d orbitals. Therefore, increasing the Cu content and/or introducing the above beneficial dopants appropriately are expected to cause enhancement of carrier mobility and/or thermopower of Cu 2 SnSe 3 . Furthermore, introducing Ag Cu , Al Sn , Zn Sn , Ge Sn , and Mn Sn defects can induce large mass and strain field fluctuations, lowering lattice thermal conductivity remarkably. Present results not only deepen one's insights into point defects in Cu 2 SnSe 3 but also provide us with a guide to improve its thermoelectric properties.

The ε-LiVOPO 4 cathode for Li-ion batteries has attracted wide attention with its multivalent electronic states and improved discharge capacity of over 300 mAh/g. Oxygen loss stands as a potential cause for structural degradations of the ε-LiVOPO 4 cathode and its derivatives but has been barely studied. Through in situ environmental transmission electron microscopy, we probe lattice oxygen loss and the associated structural degradations by spatially and temporally resolving the atomic-scale structural dynamics and phase transformation pathways in ε-LiVOPO 4 . We demonstrate that the mild oxygen loss at 400 °C induces a topotactic phase transformation of ε-LiVOPO 4 → α-Li 3 V 2 (PO 4 ) 3 in the particle surface via a nucleation and growth mechanism, leading to the formation of a core-shell configuration. The phase transformation can be reversed by switching to an oxidizing environment, in which the α-Li 3 V 2 (PO 4 ) 3 is reoxidized to ε-LiVOPO 4 . By contrast, oxygen loss at higher temperatures of 500 and 600 °C results in a high concentration of oxygen vacancies that subsequently induces irreversible structural damages including lattice amorphization and formation of nanocavities. This work illustrates the fundamental mechanisms governing the structural failure of oxide cathodes and underlines possible strategies to overcome such issues by exploiting environmental constraints.

The large amount of reactive oxygen species (ROS) produced by high glucose metabolism in diabetic patients not only induces inflammation but also damages blood vessels, finally resulting in low limb temperature, and the high glucose environment in diabetic patients also makes them susceptible to bacterial infection. Therefore, diabetic foot ulcer (DFU) usually presents as a nonhealing wound. To efficaciously prevent and treat DFU, we proposed a near-infrared (NIR) responsive microneedle (MN) patch hierarchical microparticle (HMP)-ZnO-MN-vascular endothelial growth factor and basic fibroblast growth factor (H-Z-MN-VEGF&bFGF), which could deliver drugs to the limbs painlessly, accurately, and controllably under NIR irradiation. Therein, the hair-derived HMPs exhibited the capacity of scavenging ROS, thereby preventing damage to the blood vessels. Meanwhile, zinc oxide (ZnO) nanoparticles endowed the MN patch with excellent antibacterial activity which could be further enhanced with the photothermal effect of HMPs under NIR irradiation. Moreover, vascular endothelial growth factor and basic fibroblast growth factor could promote the angiogenesis. A series of experiments proved that the MN patch exhibited broad-spectrum antibacterial and anti-inflammatory capacities. In vivo , it obviously increased the temperature of fingertips in diabetic rats as well as promoted collagen deposition and angiogenesis during wound healing. In conclusion, this therapeutic platform provides a promising method for the prevention and treatment of DFU.

The local coordination structure of metal sites essentially determines the performance of supported metal catalysts. Using a surface defect enrichment strategy, we successfully fabricated Pt atomic single-layer (Pt ASL ) structures with 100% metal dispersion and precisely controlled local coordination environment (embedded vs adsorbed) derived from Pt single-atoms (Pt 1 ) on ceria-alumina supports. The local coordination environment of Pt 1 not only governs its catalytic activity but also determines the Pt 1 structure evolution upon reduction activation. For CO oxidation, the highest turnover frequency can be achieved on the embedded Pt ASL in the CeO 2 lattice, which is 3.5 times of that on the adsorbed Pt ASL on the CeO 2 surface and 10-70 times of that on Pt 1 . The favorable CO adsorption on embedded Pt ASL and improved activation/reactivity of lattice oxygen within CeO 2 effectively facilitate the CO oxidation. This work provides new insights for the precise control of the local coordination structure of active metal sites for achieving 100% atomic utilization efficiency and optimal intrinsic catalytic activity for targeted reactions simultaneously.

Benefiting from the stimuli-responsive property and powerful loading capacity, functionalized hydrogels are favorable for the fabrication of sensing devices. Herein, we design aggregation-induced emission (AIE)-active hydrogel discs by embedding gold nanoclusters@zeolite-like imidazole framework (AuNCs@ZIF) composites in double-network hydrogels to build a sensitive pesticide biosensor. The hydrogel discs integrate an AIE effect of AuNCs, a stimuli-responsive property of ZIF, and a porous network structure of the hydrogel, which enhances the sensing sensitivity via boosting the stable fluorescent signal and antifouling performance. In conjunction with a homemade device, the fluorescence images of hydrogel discs could be transduced into data information for accurate quantification of chlorpyrifos pesticide with a detection limit of 0.2 ng/mL. The dynamic degradation of chlorpyrifos in Chinese cabbage is demonstrated to confirm the practical application of hydrogel discs. Such AIE-active hydrogel discs could be a plant health sensor for the on-site quantification of pesticide residues on crops, holding great promise for precision agriculture.

Organic Lewis bases [2,2'-bipyridine (BPY), 4-hydroxy-1,5-naphthyridine-3-carbonitrile (DQCN), and thenoyltrifluoroacetone (TTFA)] with bi-coordination sites of N and O were employed as perovskite surface defect passivants to address the efficiency and stability issues of perovskite solar cells (PSCs), with typical phenethylammonium iodide (PEAI) and piperazinium iodide (PI) passivants as reference. The surface properties of the perovskite films before and after passivation were characterized by Fourier-transform infrared, ultraviolet-visible, photoluminescence (PL), and time-resolved PL spectroscopy, X-ray diffraction, ultraviolet photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy. The characterizations reveal that BPY, DQCN, or TTFA forms coordination bonds with exposed "Pb 2+ ", leading to a slight decrease in the highest occupied molecular orbital or lowest unoccupied molecular orbital energy level and bandgap. These passivants (especially TTFA) can passivate the perovskite surface defects to inhibit non-radiative recombination while having almost no influence on the grain size and surface morphology. Utilizing the passivated perovskite as the light absorption layer, solar cells with an inverted configuration of indium tin oxide/NiO x /passivated MAPbCl x I 3- x /C 60 /BCP/Ag have been fabricated, and power conversion efficiencies of 19.22, 17.85, 16.49, 16.31, and 17.88% have been achieved from PEAI, PI, BPY, DQCN, and TTFA, respectively. All the device performance based on passivated perovskite is superior to that of the control (15.75%) owing to the reduced carrier recombination. The device from TTFA exhibits almost comparable efficiency to that of PEAI and PI controls, indicating that TTFA has an equal excellent passivation effect to state-of-the-art PEAI and PI. Furthermore, the devices based on BPY, DQCN, and TTFA show superior long-term stability with an efficiency loss of only 13.2, 16.7, and 12.9%, respectively, after being stored for 40 days in a ∼12% humidity, low-oxygen level environment, which is 45.4, 38.8, and 44.4% for the control, PEAI, and PI devices, respectively, primarily due to the improved hydrophobicity of the perovskite surface. Our results demonstrate that it is feasible to achieve high-efficiency and long-term-stable perovskite solar cells via selecting the appropriate molecules to passivate perovskite surface defects., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Glioma is the most lethal brain tumor with a poor prognosis, and a combination of multiple therapeutic strategies is critical for postoperative glioma treatment. Herein, a multifunctional hybrid hydrogel system (designated as CP&CL@RNP PTX -Gel) was developed for local treatment of postoperative glioma. The system was composed of self-illuminating chlorin e6 (Ce6) conjugated with luminol molecule (CL)-loaded glioma-targeting paclitaxel prodrug nanoparticles and copper peroxide nanodots (CP NDs) coembedded into a three-dimensional thermosensitive hydroxypropyl chitin hydrogel frame. After injection of CP&CL@RNP PTX -Gel into the cavity of postoperative glioma, the solution could be cross-linked into the gel as a drug reservoir under body temperature stimulation. Then, the sustained-released CP NDs decomposed into Cu 2+ and H 2 O 2 in the acidic microenvironment of the glioma cells to exert chemodynamic therapy (CDT). Meanwhile, Cu 2+ could catalyze the self-luminescence of CL to induce photodynamic therapy (PDT) without external excitation light. Moreover, paclitaxel prodrug nanoparticles degraded into paclitaxel to restrain residual glioma cells in response to intracellular reduced glutathione (GSH). The in vitro and in vivo results showed that CP&CL@RNP PTX -Gel had great potential as a multifunctional hybrid hydrogel system with remarkable therapeutic effects for postoperative glioma treatment via a combination of chemotherapy, CDT, and PDT.

Transition metal nitrides (TMN x ) often exhibit high catalytic activity in many important reactions. Due to their low stability in a reaction environment, it remains as a crucial issue to reveal surface active structures in catalytic reactions, particularly for the cases containing both oxidative and reductive gases. Herein, MoN and Mo 2 N nanosheets have been constructed on Al 2 O 3 (0001) and Au foil surfaces, and in situ surface characterizations are performed on the model catalysts in ambient-pressure CO 2 , H 2 , and CO 2 + H 2 gases. In situ Raman spectroscopy and quasi in situ X-ray photoelectron spectroscopy (XPS) analysis indicate that MoO 3 and defective MoO 3- x overlayers form on both MoN and Mo 2 N surfaces in CO 2 , and the surface oxidation occurs under a milder condition on Mo 2 N than on MoN. Further, a hydrogenated Mo oxide (H z MoO 3- y ) overlayer forms in a CO 2 + H 2 atmosphere, as confirmed using quasi in situ XPS and time-of-flight secondary ion mass spectroscopy. The surface analysis over the model nitride catalysts suggests that O and/or H atoms may be incorporated into surface layers to form the active structure in many O and H-containing reactions.

Encapsulation of metal nanoparticles by support-derived materials known as the classical strong metal-support interaction (SMSI) often happens upon thermal treatment of supported metal catalysts at high temperatures (≥500 °C) and consequently lowers the catalytic performance due to blockage of metal active sites. Here, we show that this SMSI state can be constructed in a Ru-MoO 3 catalyst using CO 2 hydrogenation reaction gas and at a low temperature of 250 °C, which favors the selective CO 2 hydrogenation to CO. During the reaction, Ru nanoparticles facilitate reduction of MoO 3 to generate active MoO 3- x overlayers with oxygen vacancies, which migrate onto Ru nanoparticles' surface and form the encapsulated structure, that is, Ru@MoO 3- x . The formed SMSI state changes 100% CH 4 selectivity on fresh Ru particle surfaces to above 99.0% CO selectivity with excellent activity and long-term catalytic stability. The encapsulating oxide layers can be removed via O 2 treatment, switching back completely to the methanation. This work suggests that the encapsulation of metal nanocatalysts can be dynamically generated in real reactions, which helps to gain the target products with high activity.

Microsurgery and biopsies on individual cells in a cellular microenvironment are of great importance to better understand the fundamental cellular processes at subcellular and even single-molecular levels. However, it is still a big challenge for in situ surgery without interfering with neighboring living cells. Here, we report a thermoplasmonics combined optical trapping (TOT) technique for in situ single-cell surgery and intracellular organelle manipulation, without interfering with neighboring cells. A selective single-cell perforation was demonstrated via a localized thermoplasmonic effect, which facilitated further targeted gene delivery. Such a perforation was reversible, and the damaged membrane was capable of being repaired. Remarkably, a targeted extraction and precise manipulation of intracellular organelles were realized via the optical trapping. This TOT technique represents a new way for single-cell microsurgery, gene delivery, and intracellular organelle manipulation, and it provides a new insight for a deeper understanding of cellular processes as well as to reveal underlying causes of diseases associated with organelle malfunctions at a subcellular level.

Tumor-associated neutrophil extracellular traps (NETs) play a critical role in promoting tumor growth and assisting tumor metastasis. Herein, a smart nanocarrier (designated as mP-NPs-DNase/PTX) based on regulating tumor-associated NETs has been developed, which consists of a paclitaxel (PTX) prodrug nanoparticle core and a poly-l-lysine (PLL) conjugated with the matrix metalloproteinase 9 (MMP-9)-cleavable Tat-peptide-coupled deoxyribonuclease I (DNase I) shell. After accumulating at the site of the tumor tissue, the nanocarrier can release DNase I in response to MMP-9 to degrade the structure of NETs. Then, the remaining moiety can uptake the tumor cells via the mediation of exposed cell penetrating peptide, and the PTX prodrug nanoparticles will lyse in response to the high intracellular concentration of reduced glutathione to release PTX to exert a cytotoxic effect of tumor cells. Through in vitro and in vivo evaluations, it has been proven that mP-NPs-DNase/PTX could serve as potential NET-regulated nanocarrier for enhanced inhibition of malignant tumor growth and distant metastasis.

Immunoregulation represents a booming field of biomaterial design. The unique physical and chemical properties of biomaterials offer tremendous opportunities for development. Each of their parameters exerts immunogenic effects at the immune system, cellular, and molecular levels. Herein, the perspective summarizes the interaction of biomaterials with immune cells and the underlying mechanisms to control immunoregulation in a top-down manner, providing solid inspiration for biomedical applications of immunologically effective biomaterials.

Understanding the nature of chemical bonding and its variation in strength across physically tunable factors is important for the development of novel catalytic materials. One way to speed up this process is to employ machine learning (ML) algorithms with online data repositories curated from high-throughput experiments or quantum-chemical simulations. Despite the reasonable predictive performance of ML models for predicting reactivity properties of solid surfaces, the ever-growing complexity of modern algorithms, e.g., deep learning, makes them black boxes with little to no explanation. In this Perspective, we discuss recent advances of interpretable ML for opening up these black boxes from the standpoints of feature engineering, algorithm development, and post hoc analysis. We underline the pivotal role of interpretability as the foundation of next-generation ML algorithms and emerging AI platforms for driving discoveries across scientific disciplines.

Coalfield fire area reburning is one of the serious disasters in fire prevention and safety production. In this study, a synchronous thermal analyzer was used to conduct isothermal pyrolysis of jet coal at different temperatures, and the reaction characteristic parameters of different pyrolysis residual structures were analyzed. FTIR was used to measure group contents in raw coal and different pyrolysis residues. Programmed oxidation thermogravimetric experiments were carried out on the residues to obtain their oxidation characteristic parameters. The results demonstrated that the reaction characteristic parameters of the residual structures changed at 450 °C. The pyrolysis reaction mainly affected the variation of hydroxyl, aliphatic hydrocarbon, and aromatic hydrocarbon groups. The increase in pyrolysis temperature resulted in the decline in hydroxyl and aliphatic hydrocarbon groups as well as the increase in the aromatic hydrocarbon group. After pyrolysis, the ignition point temperature of the coal sample decreased, which causes the coal more likely to spontaneously ignite. It indicated that the pyrolysis residue at 450 °C is most likely to reburn. Compared with raw coal, the maximum combustion intensity of the pyrolysis residue was greatly increased, which reached the peak at 500 °C., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

As an eco-friendly thermoelectric material, Cu 2 SnSe 3 has recently drawn much attention. However, its high electrical resistivity ρ and low thermopower S prohibit its thermoelectric performance. Herein, we show that a widened band gap and the increased density of states are achieved via S alloying, resulting in 1.6 times enhancement of S (from 170 to 277 μV/K). Moreover, doping In at the Sn site can cause a 19-fold decrease of ρ and a 2.2 times enhancement of S (at room temperature) due to both multivalence bands' participation in electrical transport and the further enhancement of the density of states effective mass, which allows a sharp increase in the power factor. As a result, PF = 9.3 μW cm -1 K -2 was achieved at ∼800 K for the Cu 2 Sn 0.82 In 0.18 Se 2.7 S 0.3 sample. Besides, as large as 44% reduction of lattice thermal conductivity is obtained via intensified phonon scattering by In-doping-induced formation of multidimensional defects, such as Sn vacancies, dislocations, twin boundaries, and CuInSe 2 nanoprecipitates. Consequently, a record high figure of merit of ZT = 1.51 at 858 K is acquired for Cu 2 Sn 0.82 In 0.18 Se 2.7 S 0.3 , which is 4.7-fold larger than that of pristine Cu 2 SnSe 3 .

A visible light-driven, copper-catalyzed aerobic oxidative cleavage of cycloalkanones has been presented. A variety of cycloalkanones with varying ring sizes and various α-substituents reacted well to give the distal keto acids or dicarboxylic acids with moderate to good yields.

It is crucial for thermoelectric (TE) devices to obtain both p-type and n-type materials and control charge carrier density. However, n-type thermoelectric materials are quite deficient and have lower thermoelectric properties. We report one oxygen-rich polymer named polyethylene glycol (PEG) for converting p-type single-walled carbon nanotubes (SWCNTs) to air-stable n-type thermoelectric materials. When pristine SWCNTs were doped with 2 mg·mL -1 PEG in an ethanol solution, the optimal Seebeck coefficient of PEG/SWCNT composites reached -50.8 μV·K -1 . The result of ultraviolet photoelectron spectroscopy demonstrated that the lone pair of oxygen atoms in the PEG chain has electron transferability to SWCNTs. According to the hard and soft acid and base theory, sodium hydroxide (NaOH) was further introduced to improve air stability and thermoelectric performance of doped SWCNTs. As a result, PEG/NaOH/SWCNT composites achieved the highest power factor of 173.8 μW·m -1 ·K -2 at 300 K. Meanwhile, their final changes in electrical conductivity and the Seebeck coefficient are less than 8% in the investigation of air stability over two months. Inspired by this finding, we fabricated the TE generator composed of the pristine p-type SWCNTs and n-type PEG/NaOH/SWCNT composites. The maximum output power of this robust TE device reached 5.3 μW at a temperature gradient of 76 K, which is superior to many reported TE devices. Moreover, the experimental procedure is attractive as a sustainable process for materials preparation. Our study has indicated that the oxygen-rich polymer-functionalized SWCNTs have huge potential for developing air-stable n-type carbon-based thermoelectric materials.

A dual-response (near-infrared, alternating magnetic field) multifunctional nanoplatform was developed based on urokinase plasminogen activators (uPA)-loaded metal-organic-framework (MOF)-derived carbon nanomaterials (referred to uPA@CFs below) for thrombolytic therapy. uPA loaded in mesoporous CFs could be released under the action of near-infrared (NIR)-mediated photothermy to achieve superficial thrombolysis. More importantly, with the assistance of alternating magnetic field (AMF), this system could also precisely heat the thrombosis in the deep tissue area. Quantitative experiments proved that the thrombolytic efficiency of this dual-response system at deep venous thrombosis was nearly 6 times than that of NIR alone. This is the first application that MOF-derived carbon nanomaterials in the field of targeted thrombolysis. To our delight, the MOF-derived carbon nanomaterials (CFs) not only maintained the drug-carrying capacity, but also endowed CFs with reliable magnetic targeting ability. More encouragingly, the CFs also showed extraordinary angiogenic performance, thus opening up the prospect of its clinical application.

The strong metal-support interaction (SMSI) is one of the most important concepts in heterogeneous catalysis, which has been widely investigated between metals and active oxides triggered by reductive atmospheres. Here, we report the oxidative strong metal-support interaction (O-SMSI) effect between Pt nanoparticles (NPs) and inert hexagonal boron nitride (h-BN) sheets, in which Pt NPs are encapsulated by oxidized boron (BO x ) overlayers derived from the h-BN support under oxidative conditions. De-encapsulation of Pt NPs has been achieved by washing in water, and the residual ultrathin BO x overlayers work synergistically with surface Pt sites for enhancing CO oxidation reaction. The O-SMSI effect is also present in other h-BN-supported metal catalysts such as Au, Rh, Ru, and Ir within different oxidative atmospheres including O 2 and CO 2 , which is determined by metal-boron interaction and O affinity of metals.

ConspectusAzulene, an isomer of naphthalene, is a molecule of historical interest for its unusual photophysical properties, including a beautiful blue color derived from the narrow HOMO-LUMO energy gap and anti-Kasha fluorescence from S 2 to S 0 . More recently, it has attracted increasing attention for its novel electronic structure, including an electron-rich five-membered ring and an electron-deficient seven-membered ring with a dipole moment of 1.08 D resulting from resonance delocalization, its different reactivities at odd and even positions, and its stimuli-responsive behavior. As a key building block, azulene has been used in various fields because of its unique physicochemical properties. Recent studies have demonstrated the great potential of azulene for constructing advanced organic materials. However, exploring azulene-based materials has long been hindered by challenges in molecular design and synthesis. Most of the reported azulene-based materials have the azulene unit incorporated through the five-membered ring or seven-membered ring. Creating azulene-based novel building blocks for optoelectronics and using 2,6-connected azulene units to construct conjugated polymers that can adequately utilize the "donor-acceptor" structure of azulene remained underexplored before our contributions. Besides, for most azulene-fused polycyclic aromatic hydrocarbons (PAHs) and heteroaromatics, the azulene substructures were created during later synthesis stages, and the use of azulene derivatives as starting materials to design and synthesize PAHs and heteroaromatics intelligently is still limited.In this Account, we summarize our efforts on the design, synthesis, and applications of azulene-based π-functional materials. Our studies start with the creation of novel π-conjugated structures based on azulene. The design strategy, synthesis, and optoelectronic performance of the first class of azulene-based aromatic diimides, 2,2'-biazulene-1,1',3,3'-tetracarboxylic diimide (BAzDI) and its π-extended and π-bridged derivatives, are presented. Notably, antiparallel stacking between adjacent azulene units derived from azulene's dipole was observed in single crystals of BAzDI and its derivatives. Besides, we developed an azulene-fused isoindigo analogue, azulenoisoindigo, which combines the merits of both isoindigo and azulene, including reversible redox behavior and reversible proton responsiveness. Then we discuss our contributions to the design and synthesis of 2,6-azulene-based conjugated polymers. By incorporation of 2,6-connected azulene units into the polymeric backbone, two conjugated polymers with high organic field-effect transistor (OFET) performance were developed. Two 2,6-azulene-based polymers with proton responsiveness and high electrical conductivity upon protonation were also provided. We also discuss our recent studies on azulene-based heteroaromatics. Two azulene-fused BN-heteroaromatics were designed and synthesized, and they exhibited a selective response to fluoride ion and unexpected deboronization upon the addition of trifluoroacetic acid. An unexpected synthesis of azulene-pyridine-fused heteroaromatics (Az-Py) by reductive cyclization of 1-nitroazulenes and the OFET performance of Az-Py-1 are included. Afterward, we discuss several examples of azulene-capped organic conjugated molecules. The molecules capped with the five-membered ring of azulene favor hole transport, whereas the ones capped with the seven-membered ring favor electron transport.

Islet transplantation is currently a promising treatment for type 1 diabetes mellitus. However, the foreign body reaction and retrieval difficulty often lead to transplantation failure and hinder the clinical application. To address these two challenges, we propose a balanced charged sodium alginate-polyethyleneimine-melanin (SA-PEI-Melanin) threadlike hydrogel with immune shielding and retrievable properties. The attractiveness of this study lies in that the introduction of melanin can stimulate insulin secretion, especially under near-infrared (NIR) irradiation. After demonstrating a good immune-shielding effect, we performed an in vivo transplantation experiment. The results showed that the blood glucose level in the SA-PEI-Melanin group was stably controlled below the diabetic blood glucose criterion, and this blood glucose level could be further adjusted after NIR irradiation. In addition, the evaluation after retrieving the SA-PEI-Melanin hydrogel indicated that the islets still maintained a normal physiological function, further proving its excellent immunological protection. This study provides a new approach for the accurate regulation of blood glucose in patients with type 1 diabetes mellitus and contributes to developing a promising transplant system to reconcile real-time and precise light-defined insulin secretion regulation.

Injecting nitrogen into goaf has been widely adopted for preventing fire hazards in coal mines. In this paper, the coupling relation between different locations of negative pressure of cross-cut drainage and nitrogen injection was investigated. The minefield data collection was carried out by an in situ beam tube system on the intake airway and return airway of the mine goaf. The validated Computational Fluid Dynamics (CFD) model that was secondarily modified by on-site collected data was applied for further research. It is demonstrated that the area of the spontaneous combustion zone generally shows a sharp decline first, then tends to stabilize, and finally has a slight drop and rise with the increasing nitrogen injection time. It is obvious that the location of the negative pressure of cross-cut exerts a significant influence on the optimal nitrogen injection location and time. When the cross-cut is located in the center of the air leakage zone, spontaneous combustion zone, and asphyxiation zone of goaf, the optimal nitrogen injection location and time correspond to the P 2 (25 m, 1200 min), P 3 (30 m, 120 min), and P 4 (35m, 1800 min), respectively. According to the simulation result, the specific relation between the optimal nitrogen injection point N ( x ) and the distance from the working distance of the cross-cut ( x ) by Newton interpolation polynomial analysis was figured out and verified that N ( x ) = 24.70808 + 0.293356 x - 0.001436 x 2 . It is hoped that the result can provide scientific guidance for coal mine fire prevention and control with nitrogen injection., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

Bioinspired and biohybrid micromotors represent a revolution in microrobotic research and are playing an increasingly important role in biomedical applications. In particular, biological micromotors that are multifunctional and can perform complex tasks are in great demand. Here, we report living and multifunctional micromotors based on single cells (green microalgae: Chlamydomonas reinhardtii ) that are controlled by optical force. The micromotor's locomotion can be carefully controlled in a variety of biological media including cell culture medium, saliva, human serum, plasma, blood, and bone marrow fluid. It exhibits the capabilities to perform multiple tasks, in particular, indirect manipulation of biological targets and disruption of biological aggregates including in vitro blood clots. These micromotors can also act as elements in reconfigurable motor arrays where they efficiently work collaboratively and synchronously. This work provides new possibilities for many in vitro biomedical applications including target manipulation, cargo delivery and release, and biological aggregate removal.

To achieve high thermoelectric conversion efficiency in Bi 0.4 Sb 1.6 Te 3 (BST) alloy is vital for its applications in low-grade energy harvesting. Here, we show that 56% increase in the power factor (PF) (from 16 to 25 μW cm -1 K -2 ) and 32% reduction of lattice thermal conductivity κ L (from 0.56 to 0.38 W m -1 K -1 ) as well as an approximately four-fold decrease in bipolar-effect contribution κ b (from 0.48 to 0.12 W m -1 K -1 ) can be achieved at 512 K through the incorporation of 0.2 vol % PbSe nanoparticles in the BST matrix. Analyses indicate that the remarkable increase in PF for the composite samples can be mainly attributed to strong electron scattering at the large interface barriers, inhibiting effectively the electron contribution to the total thermopower at elevated temperatures, while the large drop of κ L and κ b originates from enhanced phonon scattering by PbSe nanoinclusions as well as phase boundaries (among BST and PbSe nanophase) and suppression of electron transport, respectively. As a result, a maximum figure of merit (ZT) of 1.56 (at 400 K) and an average ZT (ZT ave ) of 1.44 in the temperature range of 300-512 K are reached. Correspondingly, a record projected conversion efficiency η = 11% is achieved at the cold side 300 K and hot side 512 K in the BST-based composite incorporated with 0.2 vol % PbSe nanoinclusions.

In order to further understand the mechanism of coal self-heating in the initial stage, the aldehyde group was analyzed by using the quantum chemistry methods. The charge distribution, structural parameters, and molecular orbital were analyzed to determine the active sites existing in the structure of aldehyde group. Then, a chemical reaction model including five elementary reaction sequences was established. In elementary reaction E1, the hydrogen of the aldehyde group is captured by hydroxyl to form the aldehyde radical, which provides the reactant and accumulates heat for the subsequent reaction. In elementary reaction E2, the aldehyde radical further reacts to form a carbon-free radical (R · ) and CO, which is the main source for CO generation during coal spontaneous combustion. In elementary reaction E3, the aldehyde radical is oxidized to a carboxyl radical, providing the reactant for elementary reaction E4, which is directly related to CO 2 generation during coal spontaneous combustion. The thermodynamic parameters of the elementary reactions were further analyzed and confirmed by quantum chemistry methods. The results are helpful for further understanding the pathways of CO generation in the initial stage of coal spontaneous combustion, which provides theoretical support for prediction of coal spontaneous combustion., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Hydrogen economy is one of the most promising candidates to replace the current energy system on depleting fossil fuels. As a clean and sustainable way to produce hydrogen, electrocatalytic water splitting attracts ever-increasing interest from the research community. Although the wide application of platinum group metal (PGM) catalysts is limited because of the scarcity and high cost toward hydrogen evolution reaction (HER), the non-PGM electrocatalysts usually suffer from unsatisfactory activity and poor durability. In this work, we report an active and durable V-doped Ni 5 P 4 electrocatalyst that can be used for all-pH HER. Particularly, V-Ni 5 P 4 has an HER activity that is comparable to that of Pt in preferred alkaline media, with overpotentials as low as 13 mV and 295 mV at current densities of 10 and 1000 mA cm -2 , respectively. The low-cost V-Ni 5 P 4 that enables ultrahigh current density (i.e., at the level of A cm -2 ) would be of great interest to the hydrogen production industry.