Recent Progress in Modular Electrochemical Synthesis of Hydrogen and High-Value-added Chemicals based on Solid Redox Mediator.

Electrochemical synthesis of H2 and high-value-added chemicals is an efficient and cost-effective approach that can be powered using renewable electricity. Compared to a conventional electrochemical production system, the modular electrochemical production system (MEPS) based on a solid redox mediator (SRM) can separate the anodic and cathodic reactions in time and space. The MEPS can avoid the use of membranes and formation of useless products, as well as eliminate the mutual dependence of production rates at anode and cathode. The SRM can temporarily store or release electrons and ions to pair with cathodic and anodic reactions, respectively, in MEPS. Designing of SRMs with large charge capacity and good cyclability is of great significance for constructing a high-performance MEPS. This work summarizes the design principles, recent advances in MEPS based on SRM, and application in redox flow cells. Moreover, structure design strategies as well as in situ characterization techniques and theoretical calculations for SRM is also proposed. It is expected to promote the vigorous development of MEPS based on SRM. Finally, the challenges and perspectives of MEPS based on SRM are discussed.

Mechanistic insights into photoinduced energy and charge transfer dynamics between magnesium-centered tetrapyrroles and carbon nanotubes.

Functionalizing single-walled carbon nanotubes (SWNTs) with light-harvesting molecules is a facile way to construct donor-acceptor nanoarchitectures with intriguing optoelectronic properties. Magnesium-centered bacteriochlorin (MgBC), chlorin (MgC), and porphyrin (MgP) are a series of tetrapyrrole macrocycles comprising a central metal and four coordinated aromatic or antiaromatic five-membered rings linked by methine units, which show excellent visible light absorption. To delineate the effects of the aromaticity of coordinated rings on the optoelectronic properties of the nanocomposites, the photoinduced energy and charge transfer dynamics between Mg-centered tetrapyrroles and SWNTs are explored. The results show that excited energy transfer (EET) can occur within MgP@SWNT ascribed to the stabilization of the highest occupied molecular orbital (HOMO) in MgP with the increase of aromatic coordinated rings, while only electron transfer can take place in MgBC@SWNT and MgC@SWNT. Non-adiabatic dynamics simulations demonstrate that electron and hole transfer from MgP to SWNT is asynchronous. The electron transfer is ultrafast with a timescale of ca. 50 fs. By contrast, the hole transfer is significantly suppressed, although it can be accelerated to some extent when using a lower excitation energy of 2.2 eV as opposed to 3.1 eV. Further analysis reveals that the large energy gaps between charge-donor and charge-acceptor states play a crucial role in regulating photoexcited state relaxation dynamics. Our theoretical insights elucidate the structure-functionality interrelations between Mg-centered tetrapyrroles and SWNTs and provide a comprehensive understanding of the underlying charge transfer mechanism within MgP@SWNT nanocomposites, which paves the way for the forthcoming development of SWNT-based photo-related functional materials with targeted applications.

MFF-Net: Multiscale feature fusion semantic segmentation network for intracranial surgical instruments.

BACKGROUND: In robot-assisted surgery, automatic segmentation of surgical instrument images is crucial for surgical safety. The proposed method addresses challenges in the craniotomy environment, such as occlusion and illumination, through an efficient surgical instrument segmentation network. METHODS: The network uses YOLOv8 as the target detection framework and integrates a semantic segmentation head to achieve detection and segmentation capabilities. A concatenation of multi-channel feature maps is designed to enhance model generalisation by fusing deep and shallow features. The innovative GBC2f module ensures the lightweight of the network and the ability to capture global information. RESULTS: Experimental validation of the intracranial glioma surgical instrument dataset shows excellent performance: 94.9% MPA score, 89.9% MIoU value, and 126.6 FPS. CONCLUSIONS: According to the experimental results, the segmentation model proposed in this study has significant advantages over other state-of-the-art models. This provides a valuable reference for the further development of intelligent surgical robots.

An intramolecular vibrationally excited intermolecular potential energy surface and predicted 2OH overtone spectroscopy of H2O-Kr.

A new five-dimensional potential energy surface (PES) for H2O-Kr which explicitly includes the intramolecular 2OH overtone state of the H2O monomer is presented. The intermolecular potential energies were evaluated using explicitly correlated coupled cluster theory [CCSD(T)-F12] with a large basis set. Four vibrationally averaged analytical intermolecular PESs for H2O-Kr with H2O molecules in its |00+〉, |02+〉, |02-〉, and |11+〉 states are obtained by fitting to the multi-dimensional Morse/Long-Range potential function form. Each vibrationally averaged PES fitted to 578 points has root-mean-square (RMS) deviations smaller than 0.14 cm-1 and requires only 58 parameters. The combined radial discrete variable representation/angular finite basis representation method and the Lanczos algorithm were employed to calculate the rovibrational energy levels for |00+〉, |02+〉, |02-〉, and |11+〉 states of the H2O-Kr complexes. The calculated |02-〉Πf/e(101) ← |00+〉Σe(000) and |02+〉Πf/e(110) ← |00+〉Σe(101) infrared transitions are in excellent agreement with the experimental values with RMS discrepancies being only 0.007 and 0.016 cm-1, respectively. These analytical PESs can be used to provide reliable theoretical guidance for future infrared overtone spectroscopy of H2O-Kr.

InstrumentNet: An integrated model for real-time segmentation of intracranial surgical instruments.

In robot-assisted surgery, precise surgical instrument segmentation technology can provide accurate location and pose data for surgeons, helping them perform a series of surgical operations efficiently and safely. However, there are still some interfering factors, such as surgical instruments being covered by tissue, multiple surgical instruments interlacing with each other, and instrument shaking during surgery. To better address these issues, an effective surgical instrument segmentation network called InstrumentNet is proposed, which adopts YOLOv7 as the object detection framework to achieve a real-time detection solution. Specifically, a multiscale feature fusion network is constructed, which aims to avoid problems such as feature redundancy and feature loss and enhance the generalization ability. Furthermore, an adaptive feature-weighted fusion mechanism is introduced to regulate network learning and convergence. Finally, a semantic segmentation head is introduced to integrate the detection and segmentation functions, and a multitask learning loss function is specifically designed to optimize the surgical instrument segmentation performance. The proposed segmentation model is validated on a dataset of intracranial surgical instruments provided by seven experts from Beijing Tiantan Hospital and achieved an mAP score of 93.5 %, Dice score of 82.49 %, and MIoU score of 85.48 %, demonstrating its universality and superiority. The experimental results demonstrate that the proposed model achieves good segmentation performance on surgical instruments compared to other advanced models and can provide a reference for developing intelligent medical robots.

High-Entropy Laminates with High Ion Conductivities for High-Power All-Solid-State Lithium Metal Batteries.

Solid-state electrolytes (SSEs) are crucial to high-energy-density lithium metal batteries, but they commonly suffer from slow Li+ transfer kinetics and low mechanical strength, severely hampering the application for all-solid-state batteries. Here, we develop a two-dimensional (2D) high-entropy lithium-ion conductor, lithium-containing transition-metal phosphorus sulfide, HE-LixMPS3 (Lix(Fe1/5Co1/5Ni1/5Mn1/5Zn1/5)PS3) with five transition-metal atoms and lithium ions (Li+) dispersed into [P2S6]2- framework layers, exhibiting high lattice distortions and a large amount of cation vacancies. Such unique features enable to efficiently accelerate the migration of Li+ in 2D [P2S6]2- interlamination, delivering a high ionic conductivity of 5 × 10-4 S cm-1 at room temperature. Moreover, the HE-LixMPS3 laminate can be employed as a building block to construct an ultrathin SSE film (∼10 µm) based on strong C-S bonding between HE-LixMPS3 and nitrile-butadiene rubber. The SSE film delivers a strong mechanical robustness (6.0 MPa, 310% elongation) and a high ionic conductivity of 4 × 10-4 S cm-1, showing a long cycle stability of 800 h in lithium symmetric cells. Coupled with LiFePO4 cathode and lithium anode, the all-solid-state battery presents a high Coulombic efficiency of 99.8% within 2000 cycles at 5.0 C.

High buffering capacity cobalt-doped nickel hydroxide electrode as redox mediator for flexible hydrogen evolution by two-step water electrolysis.

Two-step water electrolysis has been proposed to tackle the ticklish H2/O2 mixture problems in conventional alkaline water electrolysis recently. However, low buffering capacity of pure nickel hydroxide electrode as redox mediator limited practical application of two-step water electrolysis system. A high-capacity redox mediator (RM) is urgently needed to permit consecutive operation of two-step cycles and high-efficiency hydrogen evolution. Consequently, a high mass-loading cobalt-doped nickel hydroxide/active carbon cloth (NiCo-LDH/ACC) RM is synthesized via a facile electrochemical method. The proper Co doping can apparently enhance the conductivity and simultaneously remain the high-capacity of the electrode. Density functional theory results further confirms more negative values in redox potential of NiCo-LDH/ACC than Ni(OH)2/ACC on account of the charge redistribution induced by Co doping, which can prevent the parasitic O2 evolution on RM electrode during decoupled H2 evolution step. As a result, the NiCo-LDH/ACC combined the superiorities of high-capacity Ni(OH)2/ACC and high-conductivity Co(OH)2/ACC, and the NiCo-LDH/ACC with 4:1 ratio of Ni to Co presented a large specific capacitance of 33.52F/cm2 for reversible charge-discharge and high buffering capacity with two-step H2/O2 evolution duration of 1740 s at 10 mA/cm2. The necessary input voltage (2.00 V) of the whole water electrolysis was broken into two smaller ones, 1.41 and 0.38 V, for H2 and O2 production, respectively. NiCo-LDH/ACC provided a favorable electrode material for the practical application of two-step water electrolysis system.

Ultralow-Dielectric-Constant Atomic Layers of Amorphous Carbon Nitride Topologically Derived from MXene.

Low-dielectric-constant materials such as silicon dioxide serving as interconnect insulators in current integrated circuit face a great challenge due to their relatively high dielectric constant of ≈4, twice that of the recommended value by the International Roadmap for Devices and Systems, causing severe parasitic capacitance and associated response delay. Here, novel atomic layers of amorphous carbon nitride (a-CN) are prepared via a topological conversion of MXene-Ti3 CNTx under bromine vapor. Remarkably, the assembled a-CN film exhibits an ultralow dielectric constant of 1.69 at 100 kHz, much lower than the previously reported dielectric materials such as amorphous carbon (2.2) and fluorinated-doped SiO2 (3.6), ascribed to the low density of 0.55 g cm-3 and high sp3 C level of 35.7%. Moreover, the a-CN film has a breakdown strength of 5.6 MV cm-1 , showing great potential in integrated circuit application.

Photo- or Electrochemical Cyclization of Dienes with Diselenides to Access Seleno-Benzo[b]azepines.

A cascade selenylation/cyclization of dienes with diselenides has been realized under visible-light irradiation or electrolysis conditions. Employing O2 or electricity as a "green" oxidant, this protocol provides a green and efficient method for an array of biologically important seleno-benzo[b]azepine derivatives in moderate to good yields. The direct sunlight irradiation and gram-scale reaction render the approach practical and attractive.

Visible-Light-Promoted Selective Sulfonylation and Selenylation of Dienes to Access Sulfonyl-/Seleno-benzazepine Derivatives.

A novel visible-light-promoted selective sulfonylation and selenylation of dienes with selenosulfonates has been developed. This technology provides mild access to a wide range of sulfonyl benzo[b]azepinones and seleno-benzo[b]azepines. Preliminary mechanistic studies suggest that the sulfonylation involves a sulfonyl radical engaged cascade process, and the selenylation is accomplished through a sequential oxidation/electrophilic cyclization process. The large-scale operation and late-stage modification experiment reveal the promising utility of this protocol.

Metal-Bonded Atomic Layers of Transition Metal Carbides (MXenes).

Although 2D transition metal carbides and nitrides (MXenes) have fantastic physical and chemical properties as well as wide applications, it remains challenging to produce stable MXenes due to their rapid structural degradation. Here, unique metal-bonded atomic layers of transition metal carbides with high stabilities are produced via a simple topological reaction between chlorine-terminated MXenes and selected metals, where the metals enable them to not only remove partially Cl terminations, but also bond with adjacent atomic MXene slabs, driven by the symmetry of MAX phases. The films constructed from Al-bonded Ti3 C2 Clx atomic layers show high oxidation resistance up to 400 °C and low sheet resistance of 9.3 Ω sq-1 . Coupled to the multilayer structure, the Al-bonded Ti3 C2 Clx film displays a significantly improved electromagnetic interference (EMI) shielding capability with a total shielding effectiveness value of 39 dB at a low thickness of 3.1 µm, outperforming pure Ti3 C2 Clx film.

Three-dimensional ordered macroporous molybdenum doped NiCoP honeycomb electrode for two-step water electrolysis.

Two-step alkaline water electrolysis is considered a safe and efficient method for producing hydrogen from renewable energy. Reversal of the current polarity in a bifunctional electrocatalyst used as a gas evolution electrode (GEE) in two-step water electrolysis can generate H2/O2 at different times and in different spaces. The design of a bifunctional electrocatalyst with high durability and excellent activity is imperative to achieving continuous, safe, and pure H2 generation via two-step alkaline water electrolysis. Here, we present for the first time a novel 3D Mo-doped NiCo phosphide honeycomb electrocatalyst that was grown on nickel foam (3D Mo-NiCoP/NF) and fabricated using polystyrene as a template. The electrocatalyst exhibited extremely low overpotentials in both the hydrogen evolution reaction (HER; 117 mV at 10 mA/cm2) and the oxygen evolution reaction (OER; 344 mV at 100 mA/cm2). As a bifunctional electrocatalyst for two-step alkaline water electrolysis, the device had a 1.784 V cell voltage at 10 mA/cm2, 95% decoupling efficiency, and ∼83% energy conversion efficiency. Taken together, the use of 3D Mo-NiCoP/NF as a GEE reduced the complexity and lowered the cost of the electrolyzer. The latter could be used to construct highly competitive water-splitting systems for continuous H2 production and green energy harvesting.

ROS generation and p-38 activation contribute to montmorillonite-induced corneal toxicity in vitro and in vivo.

BACKGROUND: Montmorillonite (Mt) and its derivatives are now widely used in industrial and biomedical fields. Therefore, safety assessments of these materials are critical to protect human health after exposure; however, studies on the ocular toxicity of Mt are lacking. In particular, varying physicochemical characteristics of Mt may greatly alter their toxicological potential. To explore the effects of such characteristics on the eyes, five types of Mt were investigated in vitro and in vivo for the first time, and their underlying mechanisms studied. RESULTS: The different types of Mt caused cytotoxicity in human HCEC-B4G12 corneal cells based on analyses of ATP content, lactate dehydrogenase (LDH) leakage, cell morphology, and the distribution of Mt in cells. Among the five Mt types, Na-Mt exhibited the highest cytotoxicity. Notably, Na-Mt and chitosan-modified acidic Na-Mt (C-H-Na-Mt) induced ocular toxicity in vivo, as demonstrated by increases corneal injury area and the number of apoptotic cells. Na-Mt and C-H-Na-Mt also induced reactive oxygen species (ROS) generation in vitro and in vivo, as indicated by 2',7'-dichlorofluorescin diacetate and dihydroethidium staining. In addition, Na-Mt activated the mitogen-activated protein kinase signaling pathway. The pretreatment of HCEC-B4G12 cells with N-acetylcysteine, an ROS scavenger, attenuated the Na-Mt-induced cytotoxicity and suppressed p38 activation, while inhibiting p38 activation with a p38-specific inhibitor decreased Na-Mt-induced cytotoxicity. CONCLUSIONS: The results indicate that Mt induces corneal toxicity in vitro and in vivo. The physicochemical properties of Mt greatly affect its toxicological potential. Furthermore, ROS generation and p38 activation contribute at least in part to Na-Mt-induced toxicity.

Nanoparticles loaded with pharmacologically active plant-derived natural products: Biomedical applications and toxicity.

Pharmacologically active natural products have played a significant role in the history of drug development. They have acted as sources of therapeutic drugs for various diseases such as cancer and infectious diseases. However, most natural products suffer from poor water solubility and low bioavailability, limiting their clinical applications. The rapid development of nanotechnology has opened up new directions for applying natural products and numerous studies have explored the biomedical applications of nanomaterials loaded with natural products. This review covers the recent research on applying plant-derived natural products (PDNPs) nanomaterials, including nanomedicines loaded with flavonoids, non-flavonoid polyphenols, alkaloids, and quinones, especially their use in treating various diseases. Furthermore, some drugs derived from natural products can be toxic to the body, so the toxicity of them is discussed. This comprehensive review includes fundamental discoveries and exploratory advances in natural product-loaded nanomaterials that may be helpful for future clinical development.

Phase-Changeable Dynamic Conformal Electrode/electrolyte Interlayer enabling Pressure-Independent Solid-State Lithium Metal Batteries.

Lithium-metal-based solid-state batteries (Li-SSBs) are one of the most promising energy storage devices due to their high energy densities. However, under insufficient pressure constraints (

MXene Derivatives for Energy Storage and Conversions.

Associated with the rapid development of 2D transition metal carbides, nitrides, and carbonitrides (MXenes), MXene derivatives have been recently exploited and exhibited unique physical/chemical properties, holding promising applications in the areas of energy storage and conversions. This review provides a comprehensive summarization of the latest research and progress on MXene derivatives, including termination-tailored MXenes, single-atom implanted MXenes, intercalated MXenes, van der Waals atomic layers, and non-van der Waals heterostructures. The intrinsic relationship between structure, properties, and corresponding applications for MXene derivatives are then emphasized. Finally, the essential challenges are addressed and perspectives for the MXene derivatives are also discussed.

Triel Bond Formed by Malondialdehyde and Its Influence on the Intramolecular H-Bond and Proton Transfer.

Malondialdehyde (MDA) engages in a triel bond (TrB) with TrX3 (Tr = B and Al; X = H, F, Cl, and Br) in three modes, in which the hydroxyl O, carbonyl O, and central carbon atoms of MDA act as the electron donors, respectively. A H···X secondary interaction coexists with the TrB in the former two types of complexes. The carbonyl O forms a stronger TrB than the hydroxyl O, and both of them are better electron donors than the central carbon atom. The TrB formed by the hydroxyl O enhances the intramolecular H-bond in MDA and thus promotes proton transfer in MDA-BX3 (X = Cl and Br) and MDA-AlX3 (X = halogen), while a weakening H-bond and the inhibition of proton transfer are caused by the TrB formed by the carbonyl O. The TrB formed by the central carbon atom imposes little influence on the H-bond. The BH2 substitution on the central C-H bond can also realise the proton transfer in the triel-bonded complexes between the hydroxyl O and TrH3 (Tr = B and Al).

A Highly Durable Rubber-Derived Lithium-Conducting Elastomer for Lithium Metal Batteries.

Elastomers offer attractive advantages over classical solid-state electrolytes in terms of ensuring stable interfacial contact and maintaining fatigue durability, but the low ionic conductivity obstructs their practical applications in long-life lithium metal batteries. In this work, rubber-derived lithium-conducting elastomer has been developed via sulfur vulcanization of nitrile butadiene rubber with a polymerizable ionic liquid to provide both high resilience and dramatically improved ionic conductivity. Owing to the chemically crosslinked network between rubber chains and ionic liquid fragments generated during vulcanization, the elastic lithium-conductor achieves high resilience of 0.92 MJ m-3 , superior cyclic durability of 1000 cycles at 50% strain, and high room-temperature ionic conductivity of 2.7 × 10-4  S cm-1 . Consequently, the corresponding solid-state lithium/LiFePO4 battery exhibits a high capacity of ≈146 mAh g-1 with a high capacity retention of 94.3% for up to 300 cycles.

Elucidation of the Mechanisms and Effective Substances of Paeoniae Radix Rubra Against Toxic Heat and Blood Stasis Syndrome With a Stage-Oriented Strategy.

In the clinical practice of traditional Chinese medicine, toxic heat and blood stasis syndrome (THBSS) is a common syndrome observed in various critical diseases. Paeoniae Radix Rubra (PRR) has known therapeutic effects on THBSS. However, its pharmacodynamic mechanisms and effective substances in the treatment of THBSS still need further elucidation. Our previous study indicated that THBSS had three stages of progression, and the abnormal biochemical indices of each stage were different. Therefore, this study aimed to elucidate the pharmacodynamic mechanisms and effective substances of PRR for the treatment of THBSS with a stage-oriented strategy. Specifically, research was performed separately in two stable stages of THBSS: the excessive heat and little blood stasis (EHLBS) and blood stasis (BS) stages. THBSS model rats, at different time periods after syndrome initiation (first 5 h for EHLBS and 24 h later for BS), were used to conduct the two-stage investigation. Targeted metabonomics analysis was performed to elucidate the pharmacodynamic mechanisms of PRR in the treatment of EHLBS or BS. Based on the relationship between the individual differences in blood drug concentrations and pharmacodynamic effects, partial least squares regression analysis was employed to screen for the effective substances from the original constituents and metabolites of PRR. We found that PRR could upregulate primary bile acid biosynthesis, glycerophospholipid metabolism, ether lipid metabolism, and five amino acid metabolic pathways (e.g., arginine and proline metabolism) to treat EHLBS. Meanwhile, PRR alleviated BS by upregulating primary bile acid biosynthesis and downregulating glycerophospholipid metabolism. But PRR had no obvious effects on ether lipid metabolism and amino acid metabolism in this stage. In total, 17 and 9 potential effective substances were found in the EHLBS and BS stages, respectively, among which there were only five common compounds between the two stages. To our knowledge, sixteen compounds were regarded as potential effective substances of PRR for the first time. Therefore, the pharmacodynamic mechanisms and effective substances of PRR in the treatment of EHLBS and BS were partly different. Overall, this stage-oriented strategy provides a new way to study the pharmacodynamic mechanisms and effective substances of traditional Chinese drugs.

Mechanistic study of silica nanoparticles on the size-dependent retinal toxicity in vitro and in vivo.

BACKGROUND: Silica nanoparticles (SiO2 NPs) are extensively applied in the biomedical field. The increasing medical application of SiO2 NPs has raised concerns about their safety. However, studies on SiO2 NP-induced retinal toxicity are lacking. METHODS: We investigated the retinal toxicity of SiO2 NPs with different sizes (15 and 50 nm) in vitro and in vivo along with the underlying mechanisms. The cytotoxicity of SiO2 NPs with different sizes was assessed in R28 human retinal precursor cells by determining the ATP content and LDH release. The cell morphologies and nanoparticle distributions in the cells were analyzed by phase-contrast microscopy and transmission electron microscopy, respectively. The mitochondrial membrane potential was examined by confocal laser scanning microscopy. The retinal toxicity induced by SiO2 NPs in vivo was examined by immunohistochemical analysis. To further investigate the mechanism of retinal toxicity induced by SiO2 NPs, reactive oxygen species (ROS) generation, glial cell activation and inflammation were monitored. RESULTS: The 15-nm SiO2 NPs were found to have higher cytotoxicity than the larger NPs. Notably, the 15-nm SiO2 NPs induced retinal toxicity in vivo, as demonstrated by increased cell death in the retina, TUNEL-stained retinal cells, retinal ganglion cell degeneration, glial cell activation, and inflammation. In addition, The SiO2 NPs caused oxidative stress, as demonstrated by the increase in the ROS indicator H2DCF-DA. Furthermore, the pretreatment of R28 cells with N-acetylcysteine, an ROS scavenger, attenuated the ROS production and cytotoxicity induced by SiO2 NPs. CONCLUSIONS: These results provide evidence that SiO2 NPs induce size-dependent retinal toxicity and suggest that glial cell activation and ROS generation contribute to this toxicity.