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The dinuclear motif of dinuclear platinum complexes regulate and direct biochemical interactions. A molecular mechanism can change the antitumor activity of cis-(PtCl2{NH3}2) (cis-DDP) and other related complexes. A comparison of the DNA binding properties of three 1,4-butanediamine-linked dinuclear Pt complexes indicates that steric effects due to the leaving groups that are aligned cis to the diamine bridge or the occurrence of planar pyridine ligands reduce binding.

Unique structural modifications in DNA are caused by primary basic conformational aspects such as sterically obstructed planar ligands or pyridine, which can cause ordered changes. Pt-NH3 complexes reveal an empirical conformation-activity relationship which varies from that seen in DNA. The pyridine ligand augments interstrand cross-linking and DNA unwinding, which are principal aspects of biological activity. Complexes with a trans-structure are deeply affected.

We apply attenuated total internal reflection Fourier transform infrared (ATIR-FTIR) spectroscopy to directly probe active layers in organic thin film transistors (OTFTs). The OTFT studied uses the n-type organic semiconductor N-N-dioctyl-3,4,9, 10-perylene tetracarboxylic diimide (PTCDI-C8) and a polymer electrolyte gate dielectric made from poly(ethylene oxide) and LiCIO4. FTIR spectroscopy of the device shows signatures of anionic PTCDI-C8 species and broad polaron bands when the organic semiconductor layer is doped under positive gate bias (VG). There are two distinctive doping regions: a reversible and electrostatic doping region for VG ⩽ 2 V and an irreversible and electrochemical doping regime for VG > 2 V. On the basis of intensity loss of vibrational peaks attributed to neutral PTCDI-C8, we obtain a charge carrier density of 2.9 × 1014/cm2 at VG = 2 V; this charge injection density corresponds to the conversion of slightly more than one monolayer of PTCDI-C8 molecules into anions. At higher gate bias voltage, electrochemical doping involving the intercalation of Li+ into the organic semiconductor film can convert all PTCDI-C8 molecules in a 30-nm film into anionic species. For comparison, when a conventional gate dielectric (polystyrene) is used, the maximum charge carrier density achievable at VG = 200 V is ∼4.5 × 1013/cm2, which corresponds to the conversion of 18% of a monolayer of PTCDI-C8 molecules into anions. [ABSTRACT FROM AUTHOR]

In green plants, the chloroplast is responsible for light energy transition and organic assimilation. However, the molecular mechanisms underlying chloroplast development in horticultural crops remain unclear. Here, four-dimensional data-independent acquisition-based proteomic profiling identified 1,727 differentially expressed proteins between "Zhongshu 4" (ZS4) and yellowing mutant ( ym ) leaves, a considerable proportion of which were down-regulated chloroplast proteins. Functional analysis revealed that light harvesting and chlorophyll biosynthesis were correlated with ym leaf yellowing, validated by RNA sequencing. Quantitative PCR confirmed that chlorophyll a/b-binding protein 3C (CAB3C) related to light harvesting and NADPH:protochlorophyllide oxidoreductase 3 (POR3) involved in chlorophyll biosynthesis were repressed in ym leaves. Virus-induced gene silencing showed that suppressing CAB3C and POR3 decreased the net photosynthetic rate and chlorophyll content. Additionally, the F-box protein Slym1 negatively regulated the expression of CAB3C by depressing transcription factor SlFHY3 levels. Our findings offer insights into the regulatory mechanisms of chloroplast development in tomato.

Dual leucine zipper kinase (DLK), expressed primarily in neuronal cells, is a regulator of neuronal degeneration in response to cellular stress from chronic disease or neuronal injury. This makes it an attractive target for the treatment of neurodegenerative diseases such as Alzheimer's, Parkinson's, and amyotrophic lateral sclerosis, and neuronal injury, such as chemotherapy-induced peripheral neuropathy. Here, we describe the discovery of a potent, selective, brain-penetrant DLK inhibitor, KAI-11101 ( 59 ). Throughout the program's progression, medicinal chemistry challenges such as potency, hERG inhibition, CNS penetration, CYP3A time-dependent inhibition, and kinase selectivity were overcome through the implementation of cutting-edge in silico tools. KAI-11101 displayed an excellent in vitro safety profile and showed neuroprotective properties in an ex vivo axon fragmentation assay as well as dose-dependent activity in a mouse PD model.

Anionic redox has emerged as a transformative paradigm for high-energy layered transition-metal (TM) oxide cathodes, but it is usually accompanied by the formation of anionic redox-mediated oxygen vacancies (OVs) due to irreversible oxygen release. Additionally, external factor-induced OVs (defined as intrinsic OVs) also play a pivotal role in the physicochemical properties of layered TM oxides. However, an in-depth understanding of the interplay between intrinsic and anionic redox-mediated OVs and the corresponding regulation mechanism of the dynamic evolution of OVs is still missing. Herein, we disclose the strong interrelationship between these OVs and demonstrate that the presence of intrinsic OVs in the TMO 2 layers could induce weak integrity of the TM-O frameworks and unlock additional diffusion paths to trigger the generation and migration of anionic redox-mediated OVs. Accordingly, an OV stabilization strategy is proposed by deliberately introducing high-valence Nb 5+ , which could serve as an important building block in anchoring the oxygen sublattice and preventing the formation of a percolating OV migration network, thereby suppressing the formation/diffusion of anionic redox-mediated OVs. Consequently, superb structural integrity and improved electrochemical performance with reversible anionic redox chemistry are achieved. This work advances our understanding of the role of OVs for developing high-performance energy storage systems utilizing anionic redox.

Ginsenosides and lipids are both bioactive ingredients for ginseng. Targeting these two categories of components, this study was designed to develop desorption electrospray ionization-mass spectrometry imaging approaches and spatial metabolomics strategies, achieving the visualization and differentiation among different parts of Panax ginseng root (e.g., rhizome, main root, lateral root, fibrous root, and adventitious root). Potential chemical markers were identified by searching an in-house ginsenoside library and online Lipid Maps database, together with high-resolution MS 2 data analysis. Six ginsenosides and 11 lipids were diagnostic to differentiate five different parts of the P. ginseng root. Additionally, three ginsenosides and 20 lipids were identified as differential markers among the six positions of the main root of P. ginseng . High-abundance malonyl- and oleanolic acid-ginsenosides were observed in the rhizome. These results assist in understanding the accumulation of bioactive molecules all through the root of P. ginseng , which can benefit its quality control and rational use.

Doping of organic semiconductors (OSCs) has been developed as an effective means of modulating the density and transfer efficiency of charge carriers; however, realization of effective doping to tailor the chemical sensing performance of OSC-based sensors still remains not explored extensively. In addition, the application of OSCs in chemical sensors is usually limited by the poor stability and low selectivity. Herein, flexible donor-acceptor copolymer-based organic field-effect transistor (OFET) chemical sensors are designed via an electrophilic attack doping strategy. The p-dopant trityl tetrakis(pentafluorophenyl) borate (TrTPFB) can be effectively doped into the host molecular N -alkyl-diketopyrrolo-pyrroledithienylthieno[3,2- b ]thiophene (DPPDTT). It is simple to alter the doping efficiency and film thickness ( ca . 5.5-17.7 nm) by adjusting the proportion and concentration of guest-host molecules, which endows facile carrier mobility and enhanced sensing sensitivity modulation toward reducing gases at room temperature. Particularly, 1.0 mol% TrTPFB-doped DPPDTT achieved the highest response to H 2 S gas, including ultralow detection concentration (0.5 ppb), excellent selectivity, high humidity stability, and long-term storage stability. This work can provide a new strategy for the potential applications of the organic electronic sensing devices.

The efficient preparation of two-dimensional large-sized monolayer covalent organic framework (COF) nanosheets for highly permeable membranes has posed a long-standing challenge in the COF field. While the self-exfoliation of charged COFs represents a promising method for nanosheet production, its efficiency requires further enhancement. In this study, we present a novel finding that the presence of hydroxyl groups on the monomer significantly influences the self-exfoliation efficiency of charged COFs. Through precise regulation of hydroxyl group numbers on the monomers, we successfully achieved the efficient fabrication of large monolayer cationic COF nanosheets with impressive solubilities in common organic solvents. By virtue of their positive charge, COF monolayer nanosheets rapidly interacted with negatively charged monolayer graphene oxide (GO) in solution, facilitating their assembly into interlaced composite membranes through electrostatic interactions. The composite membranes benefited from the strong Coulombic attraction between the COF and GO nanosheets, leading to enhanced membrane stability, while the shielding effect of GO on the COF pores contributed to improved size sieving efficiency. This innovative strategy enabled the composite membranes to achieve highly selective separation of ReO 4 - and MoO 4 2- , with a remarkable 100% interception rate for MoO 4 2- .

Synthesis of nitrogen-centered radicals (NCRs) for radical coupling reactions is a powerful and versatile tool in the arsenal of organic synthetic chemistry. However, there are few reports on the direct synthesis of NCRs based on aqueous electrocatalysis. Herein, we present a new electrochemical primary amine oxidation reaction (ePAOR) system with R 1 R 2 -CH-NH 2 as the substrate for synthesizing NCRs and N-N coupling products. However, ePAOR on the model catalyst (NiO) suffers from low N-N coupling selectivity due to the weak adsorption energy of imine (R 1 R 2 -C═NH) intermediates. Guided by theoretical calculations, the oxygen vacancy gives NiO a strong adsorption capacity of R 1 R 2 -C═NH so that it boosts nitrogen-centered radical coupling initiated by the ePAOR on oxygen vacancy-rich NiO (V O -NiO), and the effective utilization rate of NCRs was increased from 36 to 75%. This approach is compatible with a wide range of primary amines and can be applied to N-N cross-coupling systems as well.

The conversion of CO 2 into value-added chemicals and fuels using stable, cost-effective, and eco-friendly metal-free catalysts is a promising technology to mitigate the global environmental crisis. In the Calvin cycle of natural photosynthesis, CO 2 reduction (CO 2 R) is achieved using the cofactor NADPH as the reducing agent through 2 e - /1H + or H - transfer. Consequently, inspired by NAD(P)H, a series of organohydrides with adjustable reducibility show remarkable potential for efficient metal-free CO 2 R. In this review, we first summarize the photosensitizers for NAD(P)H regeneration and list the representative photoenzyme CO 2 R system. Then, we introduce the NAD(P)H-inspired organohydrides and their applications in redox reactions. Furthermore, we discuss recent progress and breakthroughs by utilizing organohydrides as metal-free CO 2 R catalysts. Moreover, we delve into the reaction mechanisms and applications of these organohydrides, shedding light on their potential as sustainable alternatives to metal-based CO 2 R catalysts. Finally, we offer insights into the prospects and potential directions for advancing this intriguing avenue of organohydride-based catalysts for CO 2 R.

The crucial roles of proteoforms in biological processes and disease mechanisms have been increasingly recognized. However, the rate at which new proteoforms are being discovered using top-down proteomics has far outpaced the rate at which the functional significance of different proteoforms can be determined. Because of the close connection between protein folding and protein function, protein folding stability measurements on proteoforms have the potential to identify functionally significant proteoforms of a given protein. While a number of mass spectrometry-based proteomics methods for making protein folding stability measurements on the proteomic scale have been reported over the past decade, none have been interfaced with top-down proteomics. Described here is a top-down (TD) stability of proteins from the rates of oxidation (SPROX) approach for making proteoform specific folding stability measurements. This approach is validated using a mixture of three model proteins with well-characterized protein folding behavior by conventional SPROX as well as other more conventional biophysical techniques. The method is also used to evaluate the relative folding stabilities of the <30 kDa protein fraction isolated from an MCF-7 cell lysate. The relative folding stabilities of 150 proteoforms from 83 proteins were successfully characterized in the cell lysate analysis using the TD-SPROX approach.

The invasion of bacteria and inflammation impeded infected wounds heal. Here, a hyaluronan-based scaffold (HAG- g -C) was designed by cross-linking with gallic acid-modified gelatin to provide a protein microenvironment and decorated with cathelicidin-BF (CBF), a natural antimicrobial peptide, to remove bacterial infections and reverse the inflammatory environment. In vitro , HAG- g -C presented an antibacterial effect on Staphylococcus aureus and Escherichia coli . Meanwhile, it could drive the phenotypic switch of macrophage from M1 to M2 to accelerate tissue remodeling. In a mouse model of S. aureus -infected total skin defects, HAG- g -C inhibited the process of infection at the beginning of the wound and then regulated the M1 macrophage transformed to M2 phenotype on day 12. In addition, HAG- g -C induced collagen deposition, and reduced the expression of TNF-α, thereby significantly accelerating the reconstruction of infected wounds.

Myeloid differentiation primary response 88 (MyD88) plays a central role in inflammatory responses and diseases. However, only a few inhibitors of MyD88 with some limits have been reported currently. Herein, we identified a lead compound ( L7 ) through virtual screening and synthesized twenty-seven L7 derivatives. An optimal compound ( A5 ) was determined through enzyme-linked immunosorbent assay (ELISA), 2,5-diphenyl-2 H -tetrazolium bromide (MTT), and biolayer interferometry (BLI) assay. The potent isomer A5S showed a high MyD88 binding ability and exerted an anti-inflammatory effect through the NF-κB/MAPK pathway. A5S had good stability and safety, showed the highest distribution concentration in the lungs, and exhibited good therapeutic effects on LPS-induced and sepsis-induced ALI mouse models. Most importantly, A5S showed advantages in PK properties, and was identified as a promising MyD88 inhibitor with favorable drug-like properties, compared to the only approved MyD88 inhibitor, TJ-M2010-5 , which is currently undergoing a Phase I study, and our previously reported MyD88 inhibitors LM8 .

Various polarity chemicals exist in complex samples, such as plasma; nontargeted comprehensive analysis naturally requires multiple polar-extracted solvents; consequently, the polarity of the solvent plays a crucial role in the extraction efficiency of analytes from complex samples. In the present study, based on the diffusion behavior and nanoconfinement effect of solvents in the nanoconfined space, the polarity gradient solvent confinement liquid-phase nanoextraction (PGSC-NLPNE) protocol aimed to perform a one-step nontargeted analysis of a wide range of metabolites in plasma was established. The continuously wide range of extracted solvent polarities on carbon nanofibers/carbon fiber (CNFs/CF) membranes was achieved using a mixture of hexane, dichloromethane, methanol, and water as nanoconfined solvents. The polarities (Log  P ) of gradient solvents ranged from -1.38 to 3.94. Correlational analyses indicated that metabolites with Log  P values ranging from -1.90 to 3.84 were closely related according to similarity-intermiscibility theory. Coupled with a homemade modified guard column device, CNFs/CF membrane cartridge (CCMC), a PGSC-NLPNE-UHPLC-MS online protocol was established and applied in plasma untargeted analysis. By comparing metabolome coverage, reproducibility, and extraction recovery with protein precipitation and two-step liquid-liquid extraction commonly used in untargeted analysis, the PGSC-NLPNE-CCMC protocol demonstrated higher reproducibility and recovery. This protocol has shown great potential for ultrafast analysis of plasma untargeted metabolomics with broader metabolome coverage. It could be a potential tool to rapidly screen out valuable biomarkers related to diseases in the clinic.

Extracellular vesicles (EVs) hosting enzymatic activities that function as independent metabolic units are attractive natural biocatalytic platforms. However, directly using these metabolically active nanoreactors for effective biocatalytic applications remains challenging, mainly due to their constrained catalytic capabilities. Here, we construct an EV-templated nanobiohybrid system by engineering an EV surface with a photoresponsive zeolitic imidazolate framework (ZIF). The deposition of ZIF nanostructures on EVs not only contributes to improved biocatalytic stability but also enables interfacial coupling between photoexcited electrons from the ZIF and the enzymatic reaction of metabolically active EVs. Nearly 300% of biomass conversion efficiency increment could be achieved by EVs derived from macrophages. This enhanced biocatalysis, high catalytic stability, and low cytotoxicity endowed the EV@ZIF nanosystem with robust biosynthesis and antimicrobial activity. When evaluated in a mouse periodontitis model, we show that the autologous biocatalytic EV@ZIF demonstrated efficient therapeutic capability by killing bacteria and inhibiting inflammation. This nanoengineering strategy will benefit the future optimization of metabolically active EV nanoreactors as biocatalysts for a broad range of therapeutics.

Emerging evidence suggests that physiological C-terminal truncation of α-synuclein (αS) plays a critical role in regulating liquid-liquid phase separation and promoting amyloid aggregation, processes implicated in neurodegenerative diseases such as Parkinson's disease (PD). However, the molecular mechanisms through which C-terminal truncation influences αS conformation and modulates its aggregation remain poorly understood. In this study, we investigated the impact of C-terminal truncation on αS conformational dynamics by comparing full-length αS 1-140 with truncated αS 1-103 monomers using atomistic discrete molecular dynamics simulations. Our findings revealed that both αS 1-140 and αS 1-103 primarily adopted helical conformations around residues 7-32, while residues 36-95, located in the second half of the N-terminal and NAC domains, predominantly formed a dynamic β-sheet core. The C-terminus of αS 1-140 was largely unstructured and dynamically wrapped around the β-sheet core. While residues 1-95 exhibited similar secondary structure propensities in both αS 1-140 and αS 1-103 , the dynamic capping by the C-terminus in αS 1-140 slightly enhanced β-sheet formation around residues 36-95. In contrast, key aggregation-driving regions (residues 2-9, 36-42, 45-57, and 68-78) were dynamically shielded by the C-terminus in αS 1-140 , reducing their exposure and potentially preventing interpeptide interactions that drive aggregation. C-terminal truncation, on the other hand, increased the exposed surface area of these aggregation-prone regions, thereby enhancing interpeptide interactions, phase separation, and amyloid aggregation. Overall, our simulations provide valuable insights into the conformational effects of C-terminal truncation on αS and its role in promoting pathological aggregation.

Characterization of PLGA polymers used in FDA-approved drug products is critical for quality control and qualitative/quantitative (Q1/Q2) evaluation of potential generic formulations. Various techniques have been developed and used to characterize the molecular properties of PLGA polymers, such as molecular weight, molecular composition, and molecular structure. Commonly used techniques include gel permeation chromatography (GPC), nuclear magnetic resonance (NMR), semisolvent methods, and GPC-based intrinsic viscosity measurement. It is noted that the existing analytical methods may not be able to separate and quantify PLGA polymers when used as a mixture in a drug product (e.g., Durysta and Ozurdex). In particular, one assay method still lacking is quantitating the PLGA polymer with acid-end-cap (PLGA-A) in the mixture containing PLGA with ester-end-cap (PLGA-E), especially when the sample quantity is below the submilligram level. The total PLGA quantities available in Durysta and Ozurdex formulations are too small (<1 mg) to use existing assay methods to quantify the PLGA-A content. A new assay method was developed to quantitate PLGA-A in the mixture with PLGA-E. The acid end-cap was modified with pyrene methylamine (a UV dye) to enhance the signal and compared with the total PLGA quantity measured with the refractive index (RI) after a sample was run through a GPC. This GPC-UV/RI approach is based on measuring the total acid number (TAN) of PLGA-A and converting it to the PLGA-A quantity to compare with the total PLGA. Unlike conventional methods of measuring TAN, the GPC-UV/RI methods enables TAN measurements of submilligram PLGA quantities. Application of this method to Ozurdex-similar samples showed the expected acid:ester ratio of PLGAs. This new approach provides another powerful tool for characterizing PLGA polymers in FDA-approved drug products. This is especially significant considering that the PLGAs of commercial products are likely to have molecular properties different from those of the raw PLGAs before going through the manufacturing process.

The integration of lithium niobate (LiNbO 3 or LN) and silicon (Si) has emerged as a promising heterogeneous platform for microelectromechanical systems (MEMSs) and photonic integrated circuits (PICs). Particularly, the lithium niobate on silicon (LNOS) architecture leverages the superior piezo-optomechanical properties of LN, making it compatible with superconducting circuits and quantum systems. This opens an avenue for the development of advanced quantum sensors and processors. However, existing LN and Si bonding methods suffer from inherent limitations, such as low interfacial strength and the formation of thick, amorphous interlayers. In this work, we present an asymmetric surface activation strategy to address these challenges. By employing proton-exchange-enhanced chemical activation on the LN surface and oxygen plasma treatment on the Si side, we have achieved remarkable bonding strengths of up to 10 MPa at a moderate annealing temperature of 150 °C. Notably, the bonding mechanism in our approach differs from that in conventional diffusion-based processes. Here, the dehydration condensation of surface functional groups results in an exceptionally thin interfacial layer, less than 2 nm thick, without the presence of amorphous LN. This innovative fabrication method for LNOS demonstrates superior reliability, piezoelectric performance, thermal management capabilities, and optical transmission qualities, paving the way for cutting-edge photonic and quantum applications.

The cleavage of the benzene-oxygen (C aryl -O(C)) bond of the lignin β-O-4 linkage is expected to relieve condensation of the degradation product and improve the product value. Nevertheless, the electrochemical breaking of the C aryl -O(C) bond has not been achieved yet due to the high dissociation energy (∼409 kJ mol -1 ) and the easy over-reduction of aromatic compounds. Here, we report an aqueous electrochemical reduction strategy for breaking C aryl -O(C) bonds via the regulation of molecular adsorption. The density functional theory (DFT) calculations and quartz crystal microbalance (QCM) measurements reveal that the residual Cu(I) in the CuO electrocatalyst enhances the adsorption of the 2-phenoxy-1-phenylethyl alcohol (PPE) by the C aryl -O(C) bond and lowers the energy barrier of the protons attacking the oxygen atom in the β-O-4 linkage. Thus, compared to the Cu electrocatalyst (with a hydroquinone yield of 47.4% and a benzyl alcohol yield of 24.8%), the CuO nanorod exhibits a much higher yield of hydroquinone (95.3%) and benzyl alcohol (88.6%) at a potential of -0.4 V vs reversible hydrogen electrode (RHE) in an undivided cell. Moreover, the reaction pathway and the cleavage of the C aryl -O(C) bond are identified through a combination of in situ synchrotron-radiation Fourier transformed infrared spectroscopy (SR-FTIR) and DFT calculations. This effective method is utilized for poplar lignin electrolysis, yielding 10.9 wt % of guaiacylglycerol, with an outstanding selectivity of >63.0%. This work provides an efficient and mild method of cleavage of C aryl -O(C) bonds in lignin valorization.

The type-II Dirac candidate semimetal WSi 2 is a promising candidate for electronic devices, quantum computing, and topological materials research, owing its distinct electronic structure and superior mechanical properties. Here, we synthesized high-quality WSi 2 materials and systematically investigated their compressive behavior, and structural and electronic properties under high pressure using in-situ high pressure experiments, complemented by first-principles calculations. The results confirms that WSi 2 has the properties of a type-II Dirac semimetal. Our results demonstrate that WSi 2 maintains structural stability under high pressure but undergoes an electronic phase transition from a semimetal to a metal around 40 GPa. Additionally, the mechanical hardness softens discontinuously at this pressure. The structural stability of WSi 2 under high pressure is attributed to the strong hybridization of Si-3 p and W-5 d electrons, the rigid crystal lattice, and the adaptable electronic structure. The pressure-induced electronic phase transition and softening are primarily governed by the energy band reconstruction and W-5 d orbitals. This study provides valuable insights into the high-pressure behavior of type-II Dirac semimetal, highlighting their potential for advanced applications in electronic devices and topological quantum computing under extreme conditions by elucidating their structural stability and electronic phase transition mechanisms.

This work was designed for the in-depth characterization and holistic comparison of up to 12 ginseng varieties, which can benefit the development of functional foods and ensure their authenticity in the food industry. An online comprehensive two-dimensional liquid chromatography/quadrupole time-of-flight mass spectrometry (2D-LC/QTOF-MS) approach was established by configurating the XCharge C18 and HSS Cyano columns. Under the optimal conditions, we characterized a total of 1146 ginsenosides (including 876 potentially new compounds) from 12 ginseng varieties by reference to an in-house library of 573 known ginsenosides and 70 reference compounds. The online 2D-LC/QTOF-MS-based untargeted metabolomics workflows were developed, by which 126 potential ginsenoside markers were unveiled and utilized to establish the key identification points for each ginseng species. Compared with the conventional liquid chromatography/mass spectrometry metabolomics, our multidimensional chromatography approach performed better in discriminating multiple ginseng varieties. This work demonstrates a potent and practical methodology to identify easily confused functional plants.

In this research, we introduce a PdSe 2 /2H-MoTe 2 heterojunction photodetector that exhibits both broadband self-powered photodetection and linear/circular polarization detection capabilities. It has a broad spectral response range (covering 375-2200 nm) and reaches a peak sensitivity at 532 nm, exhibiting a notable responsivity of 7.3 × 10 3 A/W and a substantial specific detectivity of 8.5 × 10 12 Jones. Even in the near-infrared region of 1310 nm, it still has a high responsivity of 20 A/W. The self-powered photodetection capabilities of the PdSe 2 /2H-MoTe 2 heterojunction are equally impressive, covering a broad range from 375 to 1550 nm, with a responsivity of 243 mA/W, a specific detectivity of 6.46 × 10 10 Jones, a fill factor of 0.8, and an external quantum efficiency of 56.73%. Finally, simultaneous implementation of linear/circular polarization detection on the PdSe 2 /2H-MoTe 2 heterojunction provides a powerful solution for near-infrared full-Stokes polarization detectors with high integration, miniaturization, and portability.

Analyzing single-cell protein and mRNA levels yields invaluable insights into cellular functions and the intricacies of biologically heterogeneous systems. Current joint mRNAs and protein analysis methodologies suffer from relative quantification, low sensitivity, possible background interference, and tedious manual manipulation. Therefore, we propose DMF-Bimol that leverages addressable digital microfluidics to automate digital counting of single-cell mRNA and protein based on proximity ligation assay (PLA) and one-step RT-droplet digital PCR (RT-ddPCR). Through an engineered hydrophilic-hydrophobic interface, DMF-Bimol enables efficient single-cell isolation and lossless protein and nucleic acid processing. The closed droplet reaction system enhances the protein concentration and isolates exogenous contaminants, thereby dramatically improving the efficiency of the PLA reaction. The limit of detection of this approach achieves 3313 protein copies, marking a significant 17-fold enhancement in sensitivity over traditional benchtop PLA. This heightened sensitivity also uncovers a lower correlation between mRNA and protein levels in individual cells (Spearman r = 0.255) than bulk results, reflecting the complex relationship in heterogeneous cells. Using DMF-Bimol, we observed a significant upsurge of CD147 protein in CD138 + myeloma cells but consistent levels of CD147 mRNAs compared with normal leukocytes. This discovery indicates a possible consequence of CD147 oncogenic activation that tends to harness protein translation to bolster tumor cell survival and enhance invasiveness, highlighting the potential of DMF-Bimol in unveiling intricate dynamics in translation processes at the single-cell level.

This study introduces an innovative copper/electric dual-catalyzed approach to Ullmann coupling reactions. Our research delineates a series of chemoselective cross-couplings among various halogenated aromatics and enantioselective couplings involving halogenated aryl aldehydes. We employed a flux screening technique to refine the reaction parameters, which is rarely reported in the field of electrochemical synthesis. This advancement accelerates the determination of optimal reaction conditions and affords some inspiration for developing sustainable and ecofriendly chemical synthesis.

Tannic acid is widely regarded as one of the most promising natural polyphenolic compounds. However, current research predominantly focuses on the utilization of its phenolic hydroxyl groups, with limited exploration of the functional potential of its aromatic structure. Herein, one-dimensional nanofibers based on supramolecular self-assembly were successfully prepared through the simple alkylation reaction of tannic acid and the π-π stacking of aromatic structures. These fibers, with lengths reaching tens of micrometers and an average height of 10 nm, were clearly observed using SEM and AFM. A film with excellent electrical conductivity (σ = 37.9 μS/cm) was fabricated by vacuum filtering the organic suspension of these fibers, which was 100-fold higher than that of the TA film. Additionally, the hydrophobic and lipophilic properties of Bn-TA were further investigated through oil-water separation experiments, where the Bn-TA membrane displayed excellent separation efficiency and durability, maintaining stable performance over multiple cycles. This strategy presents opportunities for the high-value utilization of tannic acid.

The aberrant accumulation of the transactive response deoxyribonucleic acid (DNA)-binding protein of 43 kDa (TDP-43) aggregates in the cytoplasm of motor neurons is the main pathological hallmark of amyotrophic lateral sclerosis (ALS). Previous experiments reported that adenosine triphosphate (ATP), the universal energy currency for all living cells, could induce aggregation and enhance the folding of TDP-43 fibrillar aggregates. However, the significance of ATP on TDP-43 fibrillation and the mechanism behind it remain elusive. In this work, we conducted multiple atomistic molecular dynamics (MD) simulations totaling 20 μs to search the critical nucleus size of TDP-43 282-360 and investigate the impact of ATP molecules on preformed protofibrils. The results reveal that the trimer is the critical nucleus for TDP-43 282-360 fibril formation and the tetramer is the minimal stable nucleus. When ATP molecules bind to the TDP-43 282-360 trimer and tetramer, they can consolidate the TDP-43 282-360 protofibrils by increasing the content of the β-sheet structure and promoting the formation of hydrogen bonds (H-bonds). Binding site analyses show that the N-terminus of TDP-43 282-360 protofibrils is the main binding site of ATP, and R293 dominates the direct binding of ATP. Further analyses reveal that the π-π, cation-π, salt bridge, and H-bonding interactions together contribute to the binding of ATP to TDP-43 282-360 protofibrils. This study decoded the detailed stabilization mechanism of protofibrillar TDP-43 282-360 oligomers by ATP, and may provide new avenues for the development of drug design against ALS.

Glioblastoma multiforme (GBM) is a highly malignant brain tumor with a poor prognosis and limited treatment options. Drug delivery by stimuli-responsive nanocarriers holds great promise for improving the treatment modalities of GBM. At the beginning of the review, we highlighted the stimuli-active polymeric nanocarriers carrying therapies that potentially boost anti-GBM responses by employing endogenous (pH, redox, hypoxia, enzyme) or exogenous stimuli (light, ultrasonic, magnetic, temperature, radiation) as triggers for controlled drug release mainly via hydrophobic/hydrophilic transition, degradability, ionizability, etc. Modifying these nanocarriers with target ligands further enhanced their capacity to traverse the blood-brain barrier (BBB) and preferentially accumulate in glioma cells. These unique features potentially lead to more effective brain cancer treatment with minimal adverse reactions and superior therapeutic outcomes. Finally, the review summarizes the existing difficulties and future prospects in stimuli-responsive nanocarriers for treating GBM. Overall, this review offers theoretical guidelines for developing intelligent and versatile stimuli-responsive nanocarriers to facilitate precise drug delivery and treatment of GBM in clinical settings.

Peri -acenes are valuable models for zigzag-edged graphene nanoribbons, but their synthesis poses significant challenges. In this study, stable derivatives of peri -pentacene ( Peri-P ) and peri -hexacene ( Peri-H ) were synthesized. Through kinetic blocking and a synergistic captodative effect, both compounds displayed remarkable stability under ambient air and light conditions. They show significant diradical character ( y 0 ), with y 0 = 75.4% for Peri-P and y 0 = 90.7% for Peri-H , alongside narrow singlet-triplet energy gaps of -1.68 ± 0.04 and -1.28 ± 0.02 kcal/mol, respectively. The structure of Peri-H was confirmed by X-ray crystallography, with bond-length analysis and theoretical calculations indicating a dominant structure featuring five aromatic sextet rings. Their optical and electrochemical properties were also studied and compared to those of smaller peri -acenes.

After charging to a high state-of-charge (SoC), layered oxide cathodes exhibit high capacities but suffer from gliding-induced structural distortions caused by deep Li depletion within alkali metal (AM) layers, especially for high-nickel candidates. In this study, we identify the essential structure of the detrimental H3 phase formed at high SoC to be an intergrowth structure characterized by random sequences of the O3 and O1 slabs, where the O3 slabs represent Li-rich layers and the O1 slabs denote Li-depleted (or empty) layers that glide from the O3 slabs. Moreover, we adopt two doping strategies targeting different doping sites to eliminate the formation of Li-vacant O1 slabs. First, we introduce direct transition metal (TM) pillars between TMO 2 slabs achieved through dopants (e.g., Nb) positioned within AM layers, significantly improving the cycling stability. Second, we introduce indirect Li pillars achieved through dopants located at TM layers to adjust the Li-O bond strength. While this strategy can regulate the uniformity of Li at the slab level, it results in an uneven Li distribution at the particle scale, ultimately failing to enhance the electrochemical performance. Our established research strategy facilitates the realization of diverse pillars between TMO 2 slabs through doping, thereby offering guidance for stabilizing high-capacity layered oxide cathodes at high SoC.

A conserved two-gene cassette in fungi was discovered by genome mining, which encodes a UbiA family intramembrane prenyltansferase (VviA) and a haloacid dehalogenase-like hydrolase family terpene cyclase (VviB), respectively. A series of in vivo and in vitro investigations revealed that VviA exclusively uses VviB-synthesized drim-8-ene diphosphate (cyclo-farnesyl diphosphate) as the native prenyl donor to catalyze prenylation on d-mannitol, showcasing a previously unidentified function of UbiA-type prenyltransferases and a new prenylation manner in fungi.

Ni-based electrocatalysts have been predicted as highly potential candidates for hydrogen evolution reaction (HER); however, their applicability is hindered by an unfavorable d-band energy level ( E d ). Moreover, precise d-band structural engineering of Ni-based materials is deterred by appropriative synthesis methods and experimental characterization. Herein, we meticulously synthesize a special single-iodine-atom structure (I-Ni@C) and characterize the E d manipulation via resonant inelastic X-ray scattering (RIXS) spectroscopy to fill this gap. The complex catalytic mechanism has been elucidated via synchrotron radiation-based multitechniques (SRMS) including X-ray absorption fine structure (XAFS), in situ synchrotron radiation-based Fourier transform infrared (SR-FTIR) spectroscopy, and near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). In particular, RIXS is innovatively applied to reveal the precise regulation of Ni E d of I-Ni@C. Consequently, the role of such single-iodine-atom strategy is confirmed to not only facilitate the moderate E d of the Ni site for balancing the adsorption/desorption capacities of key intermediates but also act as a bridge to enhance the electronic interaction between Ni and the carbon shell for forming a localized polarized electric field conducive to H 2 O dissociation. As a result, I-Ni@C exhibits an enhanced alkaline hydrogen evolution performance with an overpotential of 78 mV at 10 mA/cm 2 and superior stability, surpassing the majority of the reported Ni-based catalysts. Overall, this study has managed to successfully tailor the d-band center of materials from the SRMS perspective, which has crucial implications for nanotechnology, chemistry, catalysis, and other fields.

Melanoma is one of the most aggressive types of cancer and is prone to metastasis, making current clinical treatment quite difficult. The usage of the first-line medication dacarbazine (DTIC) for melanoma is limited due to harsh side effects, limited water solubility, and a short half-life. To tackle these disadvantages, polylactic acid-hydroxyacetic acid copolymer nanoparticles (NPs) loaded with dacarbazine and ursolic acid (NPs) were fabricated, which were further encapsulated with a red blood cell membrane (RNPs). MTT, apoptosis assay, wound healing assay, colony formation assay, and immunohistochemistry were used to assess the antitumor effect of NPs and RNPs. Ferroptosis evaluation was implemented using GSH detection and the malondialdehyde assay. We found that RNPs exhibited stability and biosafety in vitro and in vivo and achieved superior anticancer ability against xenograft tumors compared with single agents and NPs, which indicated the synergistic and biomimetic efficacy. Furthermore, ferroptotic activity was observed in RNPs-treated tumor cells, and ferroptosis inhibition could partially rescue melanoma cells from RNPs-induced cell death. Collectively, this study evaluated the potential of RNPs as a novel biomimetic nanomedicine for synergistic melanoma therapy by eliciting ferroptosis in tumor cells with both anticancer activity and biosafety., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Sunlight-responsive minerals contribute significantly to biogeochemical cycles by activating oxygen (O 2 ) to generate reactive oxygen species (ROS). However, the role of crystal water, incorporated into minerals through hydration during rock cycles, in O 2 activation remains largely unexplored. Here, we construct tungstite models containing oxygen vacancies to elucidate the modulation of mineral-based ROS dynamics by the synergy between oxygen vacancy and crystal water. Crystal water promotes the protonation process of superoxide anion radicals to produce hydrogen peroxide (H 2 O 2 ) and alleviates its decomposition. This mineral-based H 2 O 2 photosynthesis system efficiently eliminates organic pollutants in a sequential light-dark reaction. Furthermore, this synergy effect can extend to other metal oxide minerals such as TiO 2 , SnO 2 , CuO, ZnO, and Bi 2 O 3 . Our results illuminate an overlooked pathway for modulating the protonation process by immobilized water in hydrous minerals, playing a crucial role in ROS storage and migration and pollutant dynamics in a natural environment throughout the day/night cycle.

The NLRP3 inflammasome is a multiprotein complex that is a component of the innate immune system, involved in the production of pro-inflammatory cytokines. Its abnormal activation is associated with many inflammatory diseases. In this study, we designed and synthesized a series of NLRP3 inflammasome inhibitors based on pyridazine scaffolds. Among them, P33 exhibited significant inhibitory effects against nigericin-induced IL-1β release in THP-1 cells, BMDMs, and PBMCs, with IC 50 values of 2.7, 15.3, and 2.9 nM, respectively. Mechanism studies indicated that P33 directly binds to NLRP3 protein ( K D = 17.5 nM), inhibiting NLRP3 inflammasome activation and pyroptosis by suppressing ASC oligomerization during NLRP3 assembly. Additionally, P33 displayed excellent pharmacokinetic properties, with an oral bioavailability of 62%. In vivo efficacy studies revealed that P33 significantly ameliorated LPS-induced septic shock and MSU crystal-induced peritonitis in mice. These results indicate that P33 has great potential for further development as a candidate for treating NLRP3 inflammasome-mediated diseases.

Herein, we described the rational drug design and synthesis of a series of 5-amino-4-fluoro-1 H -benzo[ d ]imidazole-6-carboxamide derivatives that inhibit MEK and RAF kinases. The detailed screening cascades revealed that 16b was a preferred compound, which might act like a "clamp" to stabilize the MEK/RAF complex, thereby effectively inhibiting MEK1, BRAF, and BRAF V600E with IC 50 values of 28, 3, and 3 nM, respectively. 16b possessed an excellent selectivity over other 312 human-related kinases at 1 μM. In vitro, 16b showed potent antiproliferative activities against MIA PaCa-2 (G12C KRAS), HCT116 (G13D KRAS), and C26 (G12D KRAS) cells with IC 50 values of 0.011, 0.079, and 0.096 μM, respectively. CoIP experiments demonstrated that 16b could induce MEK/RAF complex formation. Most importantly, in the C26 syngeneic colorectal and HCT116 mice xenograft tumor models, 16b demonstrated tumor growth inhibition of 70 and 93%, respectively, suggesting that 16b may be a promising MEK/RAF complex inhibitor and worthy of further development.

The escalating energy and environmental challenges have catalyzed a global shift toward seeking more sustainable, economical, and eco-friendly energy solutions. Water, capturing 35% of the Earth's solar energy, represents a vast reservoir of clean energy. However, current industrial capabilities harness only a fraction of the energy within the hydrological cycle. The past decade has seen rapid advancements in nanoscience and nanomaterials leading to a comprehensive exploration of liquid-solid triboelectrification as a low-carbon, efficient method for water energy harvesting. This review explores two fundamental principle models involved in liquid-solid triboelectrification. On the basis of these models, two distinct types of water energy harvesting devices, including droplet-based nanogenerators and water evaporation-induced nanogenerators, are summarized from their working principles, recent developments, materials, structures, and performance optimization techniques. Additionally, the applications of these nanogenerators in energy harvesting, self-powered sensing, and healthcare are also discussed. Ultimately, the challenges and future prospects of liquid-solid triboelectrification are further explored.

Macrophage-derived foam cells play a crucial role in plaque formation and rupture during the progression of atherosclerosis. Traditional studies have often overlooked the heterogeneity of foam cells, focusing instead on populations of cells. To address this, we have developed time-resolved, single-cell metabolomics and lipidomics approaches to explore the heterogeneity of macrophages during foam cell formation. Our dynamic metabolomic and lipidomic analyses revealed a dual regulatory axis involving inflammation and ferroptosis. Further, single-cell metabolomics and lipidomics have delineated a continuum of macrophage states, with varied susceptibilities to apoptosis and ferroptosis. Single-cell transcriptomic profiling confirmed these divergent fates, both in established cell lines and in macrophages derived from peripheral blood monocytes. This research has uncovered the complex molecular interactions that dictate these divergent cell fates, providing crucial insights into the pathogenesis of atherosclerosis.

We have successfully fabricated single-layer (SL) 1T-VSe 2 /Bi 2 Se 3 heterostructures using molecular beam epitaxy (MBE), which exhibits uniform moiré patterns on the heterostructure surface. Scanning tunneling microscopy/spectroscopy (STM/STS) reveals a notable quantum state near the Fermi energy, robust across the entire moiré lattice. This quantum state peak shifts slightly across different domain ranges, suggesting an elastic strain dependence in SL VSe 2 , confirmed by geometric phase analysis (GPA) simulations. Density functional theory (DFT) calculations indicate that the enhanced quantum state results from charge redistribution between the substrate and the epifilm with the orbitals of Se atoms in the deformed VSe 2 playing a dominant role.

Intracellular pathogens can survive inside the macrophages to protect themselves from eradication by the innate immune system and conventional antibiotics, resulting in severe bacterial infections. In this work, an antibiotic-free nanocomplex (HA/GA-Fe@NO-DON), exhibiting macrophage-targeted synergistic gas therapy (nitric oxide, NO)/chemodynamic therapy/immunotherapy, was reported. HA/GA-Fe nanoparticles were synthesized by the strong coordination interactions among carboxyl groups of hyaluronic acid (HA), polyphenol groups of gallic acid (GA), and Fe(II) ions. The hydrophobic glutathione (GSH)-responsive NO donor (NO-DON) was encapsulated in HA/GA-Fe nanoparticles to form the final nanocomplexes (HA/GA-Fe@NO-DON). HA on the nanocomplexes guides the macrophage-specific uptake and intracellular accumulation. After the uptake, HA/GA-Fe@NO-DON nanocomplexes could not only generate highly toxic hydroxyl radicals ( • OH) by the Fenton reaction and GSH depletion but also release NO when stimulated by intracellular GSH. Meanwhile, the nanocomplexes could trigger an efficient proinflammation immune response to reinforce the antibacterial activity. This work presents the development of antibiotic-free macrophage-targeted HA/GA-Fe@NO-DON nanocomplexes as an effective adjuvant nanomedicine with synergistic gas therapy/chemodynamic therapy/immunotherapy for eliminating intracellular bacterial infection.

The electrocatalytic hydrogenation (ECH) of furfural (FF) to furfuryl alcohol, which does not require additional hydrogen or high pressure, is a green and promising production route. In this study, we explore the effects of anions on FF ECH in two buffer electrolytes (KHCO 3 and phosphate-buffered saline [PBS]). Anions influence the yield of furfuryl alcohol through molecular activation and adsorption. Molecular dynamics simulations show that bicarbonate is present in the first shell layer of the FF molecule and induces strong hydrogen bonding interactions. In contrast, hydrogen phosphate is present only in the second shell layer, resulting in weak hydrogen bonding interactions. Owing to the interfacial anions and hydrogen bonding, FF molecules exhibit strong flat adsorption on the electrode surface in the KHCO 3 solution, while weak adsorption is observed in the PBS solution, as confirmed by operando synchrotron-radiation Fourier-transform infrared spectroscopy and in situ Raman spectroscopy. Density-functional theory calculations reveal that the overall anionic hydrogen bonding network promotes the activation of the carbonyl group in the FF molecule in KHCO 3 , whereas electrophilic activity is inhibited in PBS. Consequently, FF ECH demonstrates much faster kinetics in KHCO 3 , while it exhibits sluggish ECH kinetics and a severe hydrogen evolution reaction in PBS. This work introduces a new strategy to optimize the catalytic process through the modulation of the microenvironment.

In situ self-assembly in living systems is referred to as the processes that regulate assembly by stimuli-responsive reactions at target sites under physiological conditions. Due to the advantages of precisely forming well-defined nanostructures at pathological lesions, in situ-formed assemblies with tailored bioactivity are promising for the development of next-generation biomedical agents. In this Perspective, we summarize the progress of in situ self-assembly of peptides in living cells with an emphasis on the state-of-the-art strategies regulating assembly processes, establishing complexity within assembly systems, and exploiting their applications in biomedicines. We also provide our forward conceiving perspectives on the challenges in the development of in situ assembly in living cells to demonstrate its great potential in creating biomaterials for healthcare in the future.

The high incidence and heavy disease burden of prostate cancer (PC) require accurate and comprehensive assessment for appropriate disease management. Prostate-specific membrane antigen (PSMA) positron emission tomography (PET) cannot detect PSMA-negative lesions, despite its key role in PC disease management. The overexpression of gastrin-releasing peptide receptor (GRPR) in PC lesions reportedly performs as a complementary target for the diagnosis and therapy of PC. Radiopharmaceuticals derived from the natural ligands of GRPR have been developed. These radiopharmaceuticals enable the visualization and quantification of GRPR within the body, which can be used for disease assessment and therapeutic guidance. Recently developed radiopharmaceuticals exhibit improved pharmacokinetic parameters without deterioration in affinity. Several heterodimers targeting GRPR have been constructed as alternatives because of their potential to detect tumor lesions with a low diagnostic efficiency of single target detection. Moreover, some GRPR-targeted radiopharmaceuticals have entered clinical trials for the initial staging or biochemical recurrence detection of PC to guide disease stratification and therapy, indicating considerable potential in PC disease management. Herein, we comprehensively summarize the progress of radiopharmaceuticals targeting GRPR. In particular, we discuss the impact of ligands, chelators, and linkers on the distribution of radiopharmaceuticals. Furthermore, we summarize a potential design scheme to facilitate the advancement of radiopharmaceuticals and, thus, prompt clinical translation.

Prenylation of amino acids is a critical step for synthesizing building blocks of prenylated alkaloid family natural products, where the corresponding prenyltransferase that catalyzes prenylation on free l-histidine (l-His) has not yet been identified. Here, we first discovered and characterized a prenyltransferase FunA from the antifungal agent fungerin pathway that efficiently performs C4 -dimethylallylation on l-His. Crystal structure-guided engineering of the prenyl-binding pocket of FunA, a single M181A mutation, successfully converted it into a C4 -geranyltransferase. Furthermore, FunA and its variant FunA-M181A show broad substrate promiscuity toward substrates that vary in substituents of the imidazole ring. Our work furthers our knowledge of free amino acid prenyltransferase and expands the arsenal of alkylation biocatalysts for imidazole-containing small molecules.

Unlike conventional natural gas reservoirs, shale gas development involves systematic changes in methane carbon isotopes that cannot be effectively described by existing isotope fractionation models and mechanisms. Therefore, based on fundamental theories such as Rayleigh fractionation, mass transfer flow, and mass conservation, this study established isotopic fractionation equations for methane in adsorbed and free gas. By considering adsorbed and free gases as two end-members and using an isotope mixing model, a fractionation model for methane carbon isotopes during shale gas desorption was constructed. This model quantifies the isotopic fractionation effects during shale gas desorption and elucidates the mechanism of methane carbon isotope fractionation. Using on-site desorbed gas content and isotope data, parameter fitting and model calculations were conducted to characterize methane carbon isotope variations throughout the process of shale core field desorption. The results show a pattern of "initially negative and then turning positive," consistent with those of physical simulation experiments. It was clarified that differences in mixing the two end-members and isotopic fractionation play key roles in the variation of methane carbon isotopic composition in shale gas. By applying the methane carbon isotope fractionation model, the contribution of adsorbed gas during shale gas production was explored. It was found that in the early stage of development, the adsorbed gas in Well JY 1 was negligible. After nearly seven years of development, the contribution of adsorbed gas in the later stage has only reached nearly 15%, indicating that the production contribution of adsorbed gas is still less than 0.3 million cubic feet per day. The open flow of Well JY 6-2 is more conducive to the production of adsorbed gas, but the production capacity is still mainly contributed by free gas, indicating that the shale gas production capacity in the later stage in the Jiaoshiba gas field is still primarily dominated by free gas., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Molecular doping plays a crucial role in modulating the performance of polymeric semiconductor (PSC) materials and devices. Despite the development of numerous molecular dopants and doping methods over the past few decades, achieving highly efficient doping of PSCs remains challenging, primarily because of the inadequate matching of frontier energy levels between the host polymers and the dopants, which is critical for facilitating charge transfer. In this work, we introduce a novel doping method termed photoexcitation-assisted molecular doping (PE-MD), capable of transcending limitations imposed by energy level disparities through the mediation of efficient photoinduced electron transfer between polymers and dopants. This approach significantly amplifies the electrical conductivity of the PDPP4T polymer, increasing it by more than 4 orders of magnitude to a maximum value of 349.67 S cm -1 . Given that only the irradiated region experiences a substantial increase in doping level, the PE-MD process facilitates the photoresist-free and precise patterning of doped polymers at a resolution down to 1 μm. Furthermore, the enhanced electrical conductivity of the photoexcitation-assisted molecularly doped PDPP4T film promotes efficient thermoelectric conversion, yielding an impressive initial power factor of 226.1 μW m -1 K -2 and a figure-of-merit ( ZT ) of 0.18, accompanied by improved thermal and ambient stability. The PE-MD strategy not only remarkably elevates the doping level of PSCs toward efficient thermoelectric conversion but also preserves the easy processability of flexible and integrated devices., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Hard carbon (HC) is a promising anode candidate for Na-ion batteries (NIBs) because of its excellent Na-storage performance, abundance, and low cost. However, a precise understanding of its Na-storage behavior remains elusive. Herein, based on the D 2 O/H 2 SO 4 -based TMS results collected on charged/discharged state HC electrodes, detailed Na-storage mechanisms (the Na-storage states and active sites in different voltage regions), specific SEI dynamic evolution process (formation, rupture, regeneration and loss), and irreversible capacity contribution (dead Na 0 , NaH, etc.) were elucidated. Moreover, by employing the online electrochemical mass spectrometry (OEMS) to monitor the gassing behavior of HC-Na half-cell during the overdischarging process, a surprising rehydrogen evolution reaction (re-HER) process at around 0.02 V vs Na + /Na was identified, indicating the occurrence of Na-plating above 0 V vs Na + /Na. Additionally, the typical fluorine ethylene carbonate (FEC) additive was demonstrated to reduce the accumulation of dead Na 0 and inhibit the re-HER process triggered by plated Na.

Central nervous system (CNS) diseases, ranging from brain cancers to neurodegenerative disorders like dementia and acute conditions such as strokes, have been heavily burdening healthcare and have a direct impact on patient quality of life. A significant hurdle in developing effective treatments is the presence of the blood-brain barrier (BBB), a highly selective barrier that prevents most drugs from reaching the brain. The tight junctions and adherens junctions between the endothelial cells and various receptors expressed on the cells make the BBB form a nonfenestrated and highly selective structure that is crucial for brain homeostasis but complicates drug delivery. Nanotechnology offers a novel pathway to circumvent this barrier, with nanoparticles engineered to ferry drugs across the BBB, protect drugs from degradation, and deliver medications to the designated area. After years of development, nanoparticle optimization, including sizes, shapes, surface modifications, and targeting ligands, can enable nanomaterials tailored to specific brain drug delivery settings. Moreover, smart nano drug delivery systems can respond to endogenous and exogenous stimuli that control subsequent drug release. Here, we address the importance of the BBB in brain disease treatment, summarize different delivery routes for brain drug delivery, discuss the cutting-edge nanotechnology-based strategies for brain drug delivery, and further offer valuable insights into how these innovations in nanoparticle technology could revolutionize the treatment of CNS diseases, presenting a promising avenue for noninvasive, targeted therapeutic interventions.