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We resolved the O:H-O bond transition from the mode of ordinary water to its hydration in terms of its phonon stiffness (vibration frequency shift Δω), order of fluctuation (line width), and number fraction (phonon abundance), fx(C) = Nhyd/Ntotal. The fx(C) follows fH(C) = 0, fLi(C) ∝ fOH(C) ∝ C, and fBr(C) ∝ 1 - exp(-C/C0) toward saturation with C being the solute concentration. The invariant dfx(C)/dC suggests that the solute forms a constantly sized hydration droplet without responding to interference of other ions because its hydrating H2O dipoles fully screen its electric field. However, the number inadequacy of the highly ordered hydration H2O dipoles partially screens the large Br-. The Br- then interacts repulsively with other Br- anions, which weakens its electric field and the fBr(C) approaches saturation at higher solute concentration. The consistency in the concentration trend of the fLiBr(C), the Jones-Dole viscosity η(C), and the surface stress of LiBr solution clarifies their common origin of ionic polarization. The resultant energy of the solvent H-O exothermic elongation by O: ⇔ :O repulsion and the solute H-O endothermic contraction by bond-order deficiency heats up the LiOH solution. An estimation of at least 0.15 eV (160% of the O:H cohesive energy of 0.1 eV) suggests that the H-O elongation is the main source heating up the solution, while the molecular motion, structure fluctuation, or even evaporation dissipates energy caped at 0.1 eV. [ABSTRACT FROM AUTHOR]

The mesenchymal-epithelial transition factor (c-Met) is a receptor tyrosine kinase linked to the proliferation, survival, invasion, and metastasis of several types of cancers, including colorectal cancer (CRC), particularly when aberrantly activated. Our study strategically designs peptides derived from interactions between c-Met and the antibody Onartuzumab. By utilizing a cyclic strategy, we achieved significantly enhanced peptide stability and affinity. Our in vitro assessments confirmed that the cyclic peptide HYNIC-cycOn exhibited a higher affinity ( K D = 83.5 nM) and greater specificity compared with its linear counterpart. Through in vivo experiments, [ 99m Tc]Tc-HYNIC-cycOn displayed exceptional tumor-targeting capabilities and minimal absorption in nontumor cells, as confirmed by single-photon emission computed tomography. Notably, the ratios of tumor to muscle and tumor to intestine, 1 h postinjection, were 4.78 ± 0.86 and 3.24 ± 0.47, respectively. Comparable ratios were observed in orthotopic CRC models, recording 4.94 ± 0.32 and 3.88 ± 0.41, respectively. In summary, [ 99m Tc]Tc-HYNIC-cycOn shows substantial promise as a candidate for clinical applications. We show that [ 99m Tc]Tc-HYNIC-cycOn can effectively target and visualize c-Met-expressing tumors in vivo , providing a promising approach for enhancing diagnostic accuracy when detecting c-Met in CRC.

Hydrogen sulfide (H 2 S), a toxic gas abundant in natural gas fields and refineries, is currently being removed mainly via the Claus process. However, the emission of sulfur-containing pollutants is hard to be prevented and the hydrogen element is combined to water. Herein, we report an electron-mediated off-field electrocatalysis approach (OFEC) for complete splitting of H 2 S into H 2 and S under ambient conditions. Fe(III)/Fe(II) and V(II)/V(III) redox mediators are used to fulfill the cycles for H 2 S oxidation and H 2 production, respectively. Fe(III) effectively removes H 2 S with almost 100% conversion during its oxidation process. The H + ions are reduced by V(II) on a nonprecious metal catalyst, tungsten carbide. The mediators are regenerated in an electrolyzer at a cell voltage of 1.05 V, close to the theoretical potential difference (1.02 V) between Fe(III)/Fe(II) and V(II)/V(III). In a laboratory bench-scale plant, the energy consumption for the production of H 2 from H 2 S is estimated to be 2.8 kWh Nm -3 H 2 using Fe(III)/Fe(II) and V(II)/V(III) mediators and further reduced to about 0.5 kWh Nm -3 H 2 when employing well-designed heteropolyacid/quinone mediators. OFEC presents a cost-effective approach for the simultaneous production of H 2 and elemental sulfur from H 2 S, along with the complete removal of H 2 S from industrial processes. It also provides a practical platform for electrochemical reactions involving solid precipitation and organic synthesis.

Reducing iridium (Ir) catalyst loading for acidic oxygen evolution reaction (OER) is a critical strategy for large-scale hydrogen production via proton exchange membrane (PEM) water electrolysis. However, simultaneously achieving high activity, long-term stability, and reduced material cost remains challenging. To address this challenge, we develop a framework by combining density functional theory (DFT) prediction using model surfaces and proof-of-concept experimental verification using thin films and nanoparticles. DFT results predict that oxidized Ir monolayers over titanium nitride (IrO x /TiN) should display higher OER activity than IrO x while reducing Ir loading. This prediction is verified by depositing Ir monolayers over TiN thin films via physical vapor deposition. The promising thin film results are then extended to commercially viable powder IrO x /TiN catalysts, which demonstrate a lower overpotential and higher mass activity than commercial IrO 2 and long-term stability of 250 h to maintain a current density of 10 mA cm -2 . The superior OER performance of IrO x /TiN is further confirmed using a proton exchange membrane water electrolyzer (PEMWE), which shows a lower cell voltage than commercial IrO 2 to achieve a current density of 1 A cm -2 . Both DFT and in situ X-ray absorption spectroscopy reveal that the high OER performance of IrO x /TiN strongly depends on the IrO x -TiN interaction via direct Ir-Ti bonding. This study highlights the importance of close interaction between theoretical prediction based on mechanistic understanding and experimental verification based on thin film model catalysts to facilitate the development of more practical powder IrO x /TiN catalysts with high activity and stability for acidic OER.

Bladder cancer (BCa) is the predominant malignancy of the urinary system. Herein, a comprehensive urine proteomic feature was initially established for the noninvasive diagnosis and recurrence monitoring of bladder cancer. 279 cases (63 primary BCa, 87 nontumor controls (NT), 73 relapsed BCa (BCR), and 56 nonrelapsed BCa (BCNR)) were collected to screen urinary protein biomarkers. 4761 and 3668 proteins were qualified and quantified by DDA and sequential window acquisition of all theoretical mass spectra (SWATH-MS) analysis in two discovery sets, respectively. Upregulated proteins were validated by multiple reaction monitoring (MRM) in two independent combined sets. Using the multi-support vector machine-recursive feature elimination (mSVM-RFE) algorithm, a model comprising 13 proteins exhibited good performance between BCa and NT with an AUC of 0.821 (95% CI: 0.675-0.967), 90.9% sensitivity (95% CI: 72.7-100%), and 73.3% specificity (95% CI: 53.3-93.3%) in the diagnosis test set. Meanwhile, an 11-marker classifier significantly distinguished BCR from BCNR with 75.0% sensitivity (95% CI: 50.0-100%), 81.8% specificity (95% CI: 54.5-100%), and an AUC of 0.784 (95% CI: 0.609-0.959) in the test cohort for relapse surveillance. Notably, six proteins (SPR, AK1, CD2AP, ADGRF1, GMPS, and C8A) of 24 markers were newly reported. This paper reveals novel urinary protein biomarkers for BCa and offers new theoretical insights into the pathogenesis of bladder cancer (data identifier PXD044896).

Polydopamine (PDA)-derived melanin-like materials exhibit significant photothermal conversion owing to their broad-spectrum light absorption. However, their low near-infrared (NIR) absorption and inadequate hydrophilicity compromise their utilization of solar energy. Herein, we developed metal-loaded poly(norepinephrine) nanoparticles (PNE NPs) by predoping metal ions (Fe 3+ , Mn 3+ , Co 2+ , Ca 2+ , Ga 3+ , and Mg 2+ ) with norepinephrine, a neuron-derived biomimetic molecule, to address the limitations of PDA. The chelation between catechol and metal ions induces a ligand-to-metal charge transfer (LMCT) through the formation of donor-acceptor pairs, modulating the light absorption behavior and reducing the band gap. Under 1 sun illumination, the Fe-loaded PNE coated wood evaporator achieved a high seawater evaporation rate and efficiency of 1.75 kg m -2 h -1 and 92.4%, respectively, owing to the superior hydrophilicity and photothermal performance of PNE. Therefore, this study offers a comprehensive exploration of the role of metal ions in enhancing the photothermal properties of synthetic melanins.

Polycarboxylate superplasticizers (PCEs) are indispensable functional ingredients in modern construction, and their usage is extensive. Herein, a polyether macromonomer (VPEG) with high reactivity was used to prepare VAPCEs with different interfacial adsorption properties (acid-ether ratio) at low temperatures and reacted in 30 min. The effects of various VAPCEs on the fluidity, rheology, and strength of cement were investigated with a w/c (water/cement) ratio of 0.35. Results showed that VAPCE-3 (acid-ether ratio is 3) exhibited the best dispersion, and the fluidity of cement slurry with VAPCE-3 (280 mm) is 278.38% higher than that of the control sample (74 mm). The reason is summarized as VAPCE-3 having good adsorption performance on the surface of cement particles and having a large steric hindrance between particles. The compressive strength of cement with VAPCE-3 was enhanced by 8.29% compared with pure cement in 3 days of curing age due to its densification on microstructure and lowest R orientation index of calcium hydroxide. With the amount of acrylic acid in VAPCE increasing, the flexural strength enhanced because a more cross-linking network was formed with Ca 2+ in cement with the increase of COO - content in VAPCEs.

Adenoviral E1A binding protein 300 kDa (p300) and its closely related paralog CREB binding protein (CBP) are promising therapeutic targets for human cancer. Here, we report the first discovery of novel potent small-molecule PROTAC degraders of p300/CBP against hepatocellular carcinoma (HCC), one of the most common solid tumors. Based upon the clinical p300/CBP bromodomain inhibitor CCS1477, a conformational restriction strategy was used to optimize the linker to generate a series of PROTACs, culminating in the identification of QC-182. This compound effectively induces p300/CBP degradation in the SK-HEP-1 HCC cells in a dose-, time-, and ubiquitin-proteasome system-dependent manner. QC-182 significantly downregulates p300/CBP-associated transcriptome in HCC cells, leading to more potent cell growth inhibition compared to the parental inhibitors and the reported degrader dCBP-1. Notably, QC-182 potently depletes p300/CBP proteins in mouse SK-HEP-1 xenograft tumor tissue. QC-182 is a promising lead compound toward the development of p300/CBP-targeted HCC therapy.

Electron delocalization has an important impact on the physical properties of condensed materials. However, the L-electron delocalization in inorganic, especially nitrogen, compounds needs exploitation to improve the energy efficiency, safety, and environmental sustainability of high-energy-density materials (HEDMs). This Letter presents an intriguing N 8 molecule, ingeniously utilizing nitrogen's L-electron delocalization. The molecule, exhibiting a unique lollipop-shaped conformation, can fold at various angles with very low energy barriers, self-assembling into environmentally stable, all-nitrogen crystals. These crystals demonstrate unparalleled stability, high energy density, low mechanical sensitivity, and optimal electronic thermal conductivity, outperforming existing HEDMs. The remarkable properties of these designed materials are attributed to two distinct delocalized systems within nitrogen's L-shell: π- and lone pair σ-electrons, which not only stabilize the molecular structure but also facilitate interconnected 3D networks of intermolecular nonbonding interactions. This work might pave the way to the experimental synthesis of environmentally stable all-nitrogen solids.

Electrochemical glycerol oxidation (EGO) emerges as a promising route to valorize glycerol, an underutilized byproduct from biodiesel production, into value-added chemicals. This study employed three types of gold (Au) nanocrystals with controlled shapes to elucidate the facet-dependent electrocatalytic behavior in EGO. Octahedral, rhombic dodecahedral, and cubic Au nanocrystals with {111}, {110}, and {100} facets, respectively, were precisely synthesized with uniform size and shape. Rhombic dodecahedra exhibited the lowest onset potential for EGO due to facile AuOH formation, while octahedra showed enhanced electrochemical activity for glycerol oxidation and resistance to poisoning. In-situ FTIR analysis revealed that Au {111} surfaces selectively favored C 2 products, whereas Au {100} surfaces promoted C 3 product formation, highlighting the significant effect of facet orientation on EGO performance and informing catalyst design., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Co-published by University of Science and Technology of China and American Chemical Society.)

The tribological behavior of carboxylic acids, especially oleic acid, in boundary lubrication conditions is a subject of interest. This study presents the results of four-ball tribological tests conducted under varying contact pressures and sliding speeds. The findings reveal a critical turning speed within a confined zone, which causes a significant change in the frictional performances of oleic acid, leading to the formation of an ultralow wear tribofilm. This tribofilm, predominantly composed of oxyhydrogen compounds and hydrocarbons with more than five carbon atoms, is generated by the molecular action of oleic acid. Reactive nonequilibrium molecular dynamics simulations demonstrate that the shear speed-dependent decomposition modes of oleic acid and the transformation of the lubrication slip interface are the fundamental processes underlying the formation of this ultralow-wear boundary tribofilm.

Ferroptosis has attracted significant attention as a new mechanism of cell death. Sorafenib (SRF) is widely considered a prototypical ferroptosis-inducing drug, particularly for liver cancer treatment. However, the low solubility and hydrophobic nature of SRF, along with the absence of synergistic therapeutic strategies, still limit its application in cancer treatment. Herein, we report a dual therapeutic method incorporating photothermal therapy and ferroptosis by using Fe-doped mesoporous polydopamine nanoparticles (Fe-mPDA@SRF-TPP) as a carrier for loading SRF and targeting triphenylphosphine (TPP). SRF molecules are efficiently encapsulated within the polydopamine nanospheres with a high loading ratio (80%) attributed to the porosity of Fe-mPDA, and the inherent biocompatibility and hydrophilicity of Fe-mPDA@SRF-TPP facilitate the transport of SRF to the target cancer cells. Under the external stimuli of acidic environment (pH 5.0), glutathione (GSH), and laser irradiation, Fe-mPDA@SRF-TPP shows sustained release of SRF and Fe ions with the ratio of 72 and 50% within 48 h. Fe-mPDA@SRF-TPP nanoparticles induce intracellular GSH depletion, inhibit glutathione peroxidase 4 (GPX4) activity, and generate hydroxyl radicals, all of which are essential components of the therapeutic ferroptosis process for killing MDA-MB-231 cancer cells. Additionally, the excellent near-infrared (NIR) light absorption of Fe-mPDA@SRF-TPP nanoparticles demonstrates their capability for photothermal therapy and further enhances the therapeutic efficiency. Therefore, this nanosystem provides a multifunctional therapeutic platform that overcomes the therapeutic limitations associated with standalone ferroptosis and enhances the therapeutic efficacy of SRF for breast cancer.

CoSb 3 -based filled skutterudites (SKDs) are among the most promising materials for power generation. However, the poor interfacial stability and mechanical strength severely limit their practical application when joined with Cu electrodes. In this study, we propose multiphase Ti-based alloy barrier layers for CoSb 3 -based thermoelectric junctions to prevent the continuous brittle TiCoSb phase formation. Following the principles of coefficient of thermal expansion matching, we designed three types of Ti 80 -x Nb x Co 20 ( x = 0, 5, and 10, at.%) barrier layers with the thin intermetallic compound (IMC) layers (<20 μm). Transmission electron microscopy analysis revealed that the interfacial microstructure of the Ti 75 Nb 5 Co 20 /Ce-SKD junction comprises Ti 5 Sb 3 , Ti 5 CoSb 3 , TiCoSb, and TiSb 2 phases, as well as unreacted TiCo, Ti 2 Co, and Ti(Nb) ss phases, demonstrating a uniform staggered distribution state. After aging tests, the IMC thickness increased gradually from 7 to 12 μm, and the interfacial contact resistivity increased from 7.59 to 15.46 μΩ·cm 2 . A Cu layer was chosen as a buffer during the brazing process to prevent the formation of cracks and holes. After aging for 360 h at 823 K, the shear strength of the brazed joints remained at ∼21 MPa. Our results demonstrate that the Cu/CuSnP/Cu/Ti 75 Nb 5 Co 20 /Ce-SKD brazed joint exhibits excellent interfacial stability and satisfactory mechanical strength.

Glycosylation of proteins is an essential feature of extracellular vesicles (EVs). However, while the glycosylation heterogeneity focusing on specific EV subtypes and proteins will better reveal the functions of EVs, the determination of their specific glycans remains highly challenging. Herein, we report a method of protein-specific glycan recognition using DNA-encoded affinity ligands to label proteins and glycans. Manipulating the sequences of DNA tags and employing a DNA logic gate to trigger a spatial proximity-induced DNA replacement reaction enabled the release of glycan-representative DNA strands for the quantitative detection of multiple glycoforms. After size-dependent isolation of EV subgroups and decoding of three typical glycoforms on the epithelial growth factor receptor (EGFR), we found that the different EV subgroups of the EGFR glycoprotein varied with respect to glycan types and abundance. The distinctive glycoforms of the EV subgroups could interfere with the EGFR-related EV functions. Furthermore, the sialylation of small EVs possessed the potential as a cancer biomarker. This method provides new insights into the role of protein-specific glycoforms in EV functions.

Atherosclerosis conditions are often assessed in the clinic by measuring blood viscosity, blood flow, and blood lesion levels. In alignment with precision medicine, it is essential to develop convenient and noninvasive approaches for atherosclerosis diagnostics. Herein, an integrated electrochemical sensor was successfully demonstrated for simultaneously detecting cholesterol, transferrin, and K + in sweat, all biomarker indicators of atherosclerosis. The sensing substrate was based on carbon quantum dots integrated within multiwalled carbon nanotubes, creating a hybrid framework with low electron transfer resistance and highly efficient electron transfer rate, yielding a highly electrochemical active platform for ultrasensitive detection of trace sweat biomarkers. To ensure specificity to corresponding targets, the sensing mechanisms were based on molecular recognition reactions of cholesterol and β-cyclodextrin, transferrin and molecular cavities, and K + and ion-selective permeation membrane. Moreover, the integrated nonenzymatic sensor exhibited excellent long-term stability. Furthermore, the practical utility of the sensor was successfully demonstrated by the simultaneous detection of three atherosclerosis biomarkers in sweat from volunteers who underwent predesigned daily activities. The sensor shows promise for convenient indexing of atherosclerosis conditions in a noninvasive way.

Molybdenum-based nanomaterials have shown promise for anticancer treatment due to their strong photothermal and redox-activated capabilities. Herein, we have fabricated cerium-doped MoO x (Ce-MoO v ) with tunable Mo/Ce molar ratios by a one-pot method and investigated their effect on chemodynamic therapy (CDT) and photothermal therapy (PTT). It is found that Ce-MoO v can self-assemble into nanoclusters in acidic conditions and the increasing Ce amount will generate oxygen vacancy defects and induce the valence change of Mo 6+ /Mo 5+ and Ce 4+ /Ce 3+ , which leads to strong near-infrared absorption with high photothermal conversion efficiency of 71.31 and 49.86% for 808 and 1064 nm. Other than photothermal conversion, the materials demonstrate pH-/glutathione (GSH)-activated photoacoustic (PA) imaging capability in vitro . In addition, Ce-MoO v acts as a CDT reagent capable of converting endogenous H 2 O 2 to two types of reactive oxygen species ( • OH, 1 O 2 ) while depleting GSH. Ce-MoO v demonstrates an excellent therapeutic effect against HCT116 cells and effectively reduces the intracellular GSH level and significantly increases the number of reactive radicals under 1064 nm laser irradiation as compared with the no-laser group in vitro . This work provides a new paradigm using lanthanide-doped polymetallic oxides for pH-/GSH-responsive photothermal/chemodynamic therapy with PA imaging ability.

Hydrogen production from ammonia borane (AB) is usually governed by water activation, which is not only energy-intensive but also requires expensive and complicated catalysts. We here propose an integrated photocatalytic-photothermal system that dramatically improves water activation and lowers the transport resistance of H 2 by means of intermediate state water evaporation. This system is constructed by covering nanocomposites (Cu 3 P-carbon dots-Cu) upon vertically aligned acetate fibers (VAAFs). As a result of superior hydration effect of VAAFs and local photothermal heating for rapid water evaporation, its hydrogen production efficiency from AB hydrolysis reaches over 10 times the particulate suspension system under solar irradiation. Mechanism analysis reveals that the rapid vaporization of intermediate water promotes the cleavages of O-H bonds in bound water and the adsorption reaction of AB and water molecules at active sites. Therefore, this work provides a novel approach to optimize catalytic reaction in thermodynamics and kinetics for the hydrolysis of AB.

Si-based rechargeable lithium-ion batteries (LIBs) have generated interest as silicon has remarkably high theoretical specific capacity. It is projected that LIBs will meet the increasing need for extensive energy storage systems, electric vehicles, and portable electronics with high energy densities. However, the Si-based LIB has a substantial problem due to the volume cycle variations brought on by Si, which result in severe capacity loss. Making Si-based anodes-enabled high-performance LIBs that are easy to utilize requires an understanding of the fading mechanism. Due to its distinct advantage in morphological changes from microscale to nanoscale, even approaching atomic resolution, electron microscopy is one of the most popular methods. Based on operando electron microscopy characterization, the general comprehension of the fading mechanism and the morphology evolution of Si-based LIBs are debated in this review. The current advancements in compositional and structural interpretation for Si-based LIBs using advanced electron microscopy characterization methods are outlined. The future development trends in pertinent silicon materials characterization methods are also highlighted, along with numerous potential research avenues for Si-based LIBs design and characterization.

A continuous humidity and solar-light dual responsive intelligent solid Mg-moisture battery (SMB) with a graphdiyne nanosheets array was fabricated. The integrated battery works based on a new concept of chemical bond conversion on the surface of the graphdiyne nanosheets array that is grown in situ on a 3D melamine sponge (GDY/MS). The unique structure, excellent catalytic, and semiconductor performance of GDY endows the GDY/MS with some outstanding characteristics on trapping and transferring water molecules, catalyzing HER, and utilizing solar energy, making the GDY/MS a new generation cathode for a high-performance intelligent SMB. The performance of the GDY/MS-based smart SMB (GSMB) can be continuously tuned by humidity and solar-light. The GSMB shows a significant positive correlation between open circuit potential (OCP) and humidity, while the natural band gap of GDY makes it further act as a photoelectrode to capture light and generate photoelectrons. The GSMB can be applied as a self-power humidity monitor with an ultrafast response time of <0.24 s, a recovery time of <0.16 s, and a sensitive (36,600%) respiratory sensing performance. This simple and efficient battery-made strategy represents the future development direction of self-power supply equipment, intelligent electronic devices, and intelligent battery integration.

Nelumbo nucifera Gaertn. is an important aquatic vegetable, and its dried stamen (Nelumbinis stamen, NS) is a valuable nutraceutical usually used as a herbal tea. Here, we used ultrahigh-performance liquid chromatography (UPLC)-quadrupole time-of-flight mass spectrometry and high-performance liquid chromatography (HPLC) to chemically profile NS and quantify their main constituent flavonoids, respectively. In total, 44 components were identified, including organic acids, flavonoids, monoterpene glycosides, and fatty acids. Experimental mice were induced with fatigue by exposure to chronic restraint stress (CRS) for 8 h daily for 15 days and then treated with an aqueous extract of NS (0.5 and 1 g/kg) via gavage. NS significantly mitigated CRS-induced skeletal muscle dysfunction and fatigue in mice possibly by lowering serum corticosterone levels and restoring Sestrin2 expression in the gastrocnemius to regulate metabolism, preserve mitochondrial homeostasis, and promote antioxidant capacity. These results demonstrate that NS can be used as a nutraceutical or supplement for controlling stress-induced muscle dysfunction and fatigue.

Single-atom nanozymes (SAzymes), with individually isolated metal atom as active sites, have shown tremendous potential as enzyme-based drugs for enzymatic therapy. However, using SAzymes in tumor theranostics remains challenging because of deficient enzymatic activity and insufficient endogenous H 2 O 2 . We develop an external-field-enhanced catalysis by an atom-level engineered FeN 4 -centered nanozyme (FeN 4 -SAzyme) for radio-enzymatic therapy. This FeN 4 -SAzyme exhibits peroxidase-like activity capable of catalyzing H 2 O 2 into hydroxyl radicals and converting single-site Fe II species to Fe III for subsequent glutathione oxidase-like activity. Density functional theory calculations are used to rationalize the origin of the single-site self-cascade enzymatic activity. Importantly, using X-rays can improve the overall single-site cascade enzymatic reaction process via promoting the conversion frequency of Fe II /Fe III . As a H 2 O 2 producer, natural glucose oxidase is further decorated onto the surface of FeN 4 -SAzyme to yield the final construct GOD@FeN 4 -SAzyme. The resulting GOD@FeN 4 -SAzyme not only supplies in situ H 2 O 2 to continuously produce highly toxic hydroxyl radicals but also induces the localized deposition of radiation dose, subsequently inducing intensive apoptosis and ferroptosis in vitro. Such a synergistic effect of radiotherapy and self-cascade enzymatic therapy allows for improved tumor growth inhibition with minimal side effects in vivo. Collectively, this work demonstrates the introduction of external fields to enhance enzyme-like performance of nanozymes without changing their properties and highlights a robust therapeutic capable of self-supplying H 2 O 2 and amplifying self-cascade reactions to address the limitations of enzymatic treatment.

Pancreatic ductal adenocarcinoma is characterized by increased generation of reactive oxygen species that can cause lethal oxidative stress. Here, we evaluated the combined inhibition of the glutathione and thioredoxin antioxidant systems in preclinical models of pancreatic ductal adenocarcinoma, using buthionine sulfoximine (BSO) that targets glutathione synthesis, and auranofin that targets thioredoxin recycling. BSO potentiated the cytotoxicity of auranofin and induced lethal oxidative stress in primary pancreatic cancer cells. As assessed by the cellular thermal shift assay, auranofin engaged with thioredoxin reductase 1 in primary cells at concentrations known to induce cell death. Moreover, we used imaging mass cytometry to map the biodistribution of atomic gold in patient-derived xenografts treated with auranofin, and the drug was readily detectable throughout the epithelial and stromal compartments after treatment with a clinically relevant dose. In conclusion, combinatorial treatment with BSO and auranofin could serve as a potential therapeutic strategy in pancreatic ductal adenocarcinoma., Competing Interests: The authors declare the following competing financial interest(s): A.D.S. has received research funding from Takeda Pharmaceuticals, BMS, and Medivir AB, and consulting fees/honorarium from Astra Zeneca, Takeda, Novartis, Jazz, and Otsuka Pharmaceuticals. A.D.S. is also named on a patent application for the use of DNT cells to treat AML., (© 2022 American Chemical Society.)

Single-atom catalysts (SACs) of non-precious transition metals (TMs) often show unique electrochemical performance, including the electrochemical carbon dioxide reduction reaction (CO 2 RR). However, the inhomogeneity in their structures makes it difficult to directly compare SACs of different TM for their CO 2 RR activity, selectivity, and reaction mechanisms. In this study, the comparison of isolated TMs (Fe, Co, Ni, Cu, and Zn) is systematically investigated using a series of crystalline molecular catalysts, namely TM-coordinated phthalocyanines (TM-Pcs), to directly compare the intrinsic role of the TMs with identical local coordination environments on the CO 2 RR performance. The combined experimental measurements, in situ characterization, and density functional theory calculations of TM-Pc catalysts reveal a TM-dependent CO 2 RR activity and selectivity, with the free energy difference of Δ G (*HOCO) - Δ G (*CO) being identified as a descriptor for predicting the CO 2 RR performance.

In this paper, the 2D all-carbon graphdiyne, which possesses superior 2D strength and high mixed conductivities for both electrons and ions, is used to protect nickel cobalt oxide nanostructures with multidimensions. The in situ grown graphdiyne seamlessly wraps on nanostructures to form 3D interpenetrating networks, leading to significant improvement in the conductivity and avoidance of the structural degradation. The assembled hybrid asymmetric supercapacitor showed a high specific capacitance of 200.9 F g -1 at 1 A g -1 with an energy density of 62.8 Wh kg -1 and a power density of 747.9 W kg -1 . The device also showed a preeminent rate capability (86.4% capacitance retention, while the current density was increased from 1 to 20 A g -1 ) and an ultrastable long-term cycling performance (the capacitance retention is about 97.7% after 10 000 cycles at a high current density of 20 A g -1 ).

Despite being a low-abundance amino acid, cysteine plays an essential role in regulating protein function and serves as a satisfactory target of post-translational modifications and drug developments. To comprehensively assess reactive-cysteine-containing proteins, the development of chemical proteomic probes to label cysteine residues in human cells is an important objective. Cysteine modification using sulfonium-based probes is a novel method to identify reactive cysteine residues in proteins. Herein, we reported a set of "cysteine-reactive sulfonium-based (C-Sul)" probes to label the reactive cysteine sites in cellular proteins. Notably, water-soluble C-Sul probes have a significantly enhanced stability and cellular uptakes, displaying a high specificity toward reactive cysteines and compatibility with quantitative proteomic profiling. In comparison to the conventional iodoacetamide-based probe, C-Sul particularly has no inhibitory effects on cell viability, enabling its application in proteomic profiling of reactive cysteine residues under biorelevant conditions. We propose C-Sul probes as optimal tools of cysteine profiling for further broadly basic research.

Indium doping of cadmium sulfide (CdS) by chemical bath deposition (CBD) can be an efficient strategy to boost the CIGSSe efficiency. However, limited by the extremely low solubility of In 2 S 3 , it is difficult to increase the In doping contents and inhibit the band energy-level regulation for CdS through the traditional CBD process. In this work, we perform a novel CBD method to prepare an indium-doped CdS (In:CdS) buffer, in which the indium source is sequentially slowly added in the growing aqueous solution. In this process, the In ion concentration involved in the real-time deposition is significantly reduced. Thus, compact and uniform In:CdS with higher indium doping content is obtained. Indium doping can elevate the CdS conduction band edge and construct a more favorable spike band alignment with a CIGSSe absorber. Moreover, it introduces efficient carrier transport and reduced interface defect density. As a result, improved CIGSSe heterojunction quality is realized by utilizing In:CdS. Also, the solution-processed CIGSSe device with In:CdS as a buffer yields a high efficiency of 16.4%, with a high V OC of 670 mV and an FF of 75.3%.

Polydopamine (PDA) has been widely used in biomedical applications including imaging contrast agents, antioxidants, UV protection, and photothermal therapy due to its biocompatibility, metal-ion chelation, free-radical scavenging, and wideband absorption, but its low photothermal efficiency still needs to be improved. In this study, we chelated near-infrared (NIR) sensitive carbon quantum dots on the surface of polydopamine (PDA-PEI@N,S-CQDs) to increase its near-infrared absorption. Surprisingly, although only 4% (w/w) of carbon quantum dots was conjugated on the PDA surface, it still increased the photothermal efficiency by 30%. Moreover, PDA-PEI@N,S-CQDs could also be used as the drug carrier for loading 60% (w/w) of the DOX and achieved stimuli-responsive drug release under lysosomal pH (pH 5.0) and 808 nm laser illumination. For in vitro therapeutic experiment, PDA-PEI@N,S-CQDs showed the remarkable therapeutic performance under 808 nm laser irradiation for killing 90% of cancer cells compared with 50% by pure PDA nanoparticles, and the efficacy was even higher after loading DOX owing to the synergistic effect by photothermal therapy and chemotherapy. This intelligent and effective therapeutic nanosystem based on PDA-PEI@N,S-CQDs showed enhanced photothermal behavior after chelating carbon dots and promoted the future development of a nanoplatform for stimuli-responsive photothermal/chemo therapy.

The electrochemical carbon dioxide reduction reaction (CO 2 RR) using copper (Cu)-based catalysts has received significant attention mainly because Cu is an element capable of producing hydrocarbons and oxygenates. One possible way to control the CO 2 RR performance at the electrode interface is by modifying catalysts with specific functional groups of different polymeric binders, which are necessary components in the process of electrode fabrication. However, the modification effect of the key functional groups on the CO 2 RR activity and selectivity is poorly understood over Cu-based catalysts. In this work, the role of functional groups ( e.g. , -COOH and -CF 2 groups) in hydrophilic and hydrophobic polymeric binders on the CO 2 RR of Cu-based catalysts is investigated using a combination of electrochemical measurements, in situ characterization, and density functional theory (DFT) calculations. DFT results reveal that functional groups influence the binding energies of key intermediates involved in both CO 2 RR and the competing hydrogen evolution reaction, consistent with experimental observation of binder-dependent product distributions among formic acid, CO, CH 4 , and H 2 . This study provides a fundamental understanding that the selection of desired polymeric binders is a useful strategy for tuning the CO 2 RR activity and selectivity., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Ultrasmall nanoparticles (USNPs) with sizes below 10 nm have shown great potentials in medical applications owing to their outstanding physical, chemical, optical, and biological properties. However, they suffer from a rapid renal clearance and biodegradation rate in the biological environment due to the small size. Liposomes are one of the most promising delivery nanocarriers for loading USNPs because of their excellent biocompatibility and lipid bilayer structure. Encapsulation of USNPs into liposomes in an efficient and controllable manner remains a challenge. In this study, we achieved a high loading of graphene quantum dots (GQDs, ∼4 nm), a typical USNP, into the aqueous core of liposomes (45.68 ± 1.44%), which was controllable by the pressure. The GQDs-loaded liposomes (GQDs-LPs) exhibited a very good aqueous stability for over a month. Furthermore, indocyanine green (ICG), an efficient near-infrared (NIR) photothermal agent, was introduced in the GQDs-LP system that could convert NIR laser energy into thermal energy and break down the liposomes, causing the release of GQDs in 6 min. Moreover, this NIR light-controlled release system (GQDs-ICG-LPs) also exhibited a good photothermal therapeutic performance in vitro , and 75% of cancer cells were killed at a concentration of 200 μg/mL. Overall, the successful development of the NIR light-controlled release system has laid a solid foundation for the future biomedical application of USNPs-loaded liposomes.

Nanozymes have emerged as a fascinating nanomaterial with enzyme-like characteristics for addressing the limitations of natural enzymes. Nevertheless, how to improve the relatively low catalytic activity still remains challenging. Herein, a facile recrystallizing salt template-assisted chemical vapor deposition method was utilized to synthesize MoSe 2 /PCN heterostructures. This heterostructure displays remarkably enhanced light boosting peroxidase-like activities. Notably, the maximal reaction velocity of this heterostructure attains 17.81 and 86.89 μM min -1 [for o -phenylenediamine (OPD) and 3,3'5,5'-tetramethylbenzidine (TMB), respectively]. Moreover, various characterization means were performed to explore the mechanism deeply. It is worth mentioning that the photoinduced electrons generated by the heterostructure directly react with H 2 O 2 to yield plentiful • OH for the effective oxidation of OPD and TMB. Therefore, this work offers a promising approach for improving peroxidase-like activity by light stimulation and actuating the development of enzyme-based applications.

Surface functionalization with atoms serves as an important strategy to modulate the catalytic activities of low-dimensional nanomaterials. Herein, we developed a facile hydrogen incorporation strategy for improving the catalytic activities of SnS 2 nanosheets toward CO 2 electroreduction. Compared with SnS 2 nanosheets, the hydrogen-incorporated SnS 2 (denoted as H-SnS 2 ) nanosheets exhibited high current density and Faradaic efficiency (FE) for formate. At -0.9 V vs RHE, H-SnS 2 nanosheets displayed a maximum FE of 93% for carbonaceous product, which rivals the activities of most Sn-based catalysts in CO 2 electroreduction. Mechanistic studies disclosed that the incorporation of surface hydrogen induced the electron injection into the structures of H-SnS 2 nanosheets, which largely facilitates the process of CO 2 activation. Density functional theory (DFT) calculations further revealed that hydrogen incorporation decreased the energy barrier for the formation of HCOO* intermediates, thus contributing to the CO 2 -to-formate conversion on H-SnS 2 nanosheets.

Lithium/fluorinated carbon (Li/CF x ) primary batteries have essential applications in consumer electronics and medical and high-power military devices. However, their application is limited due to the difficulty in achieving simultaneous high power density and high energy density in the CF x cathode. The tradeoff between conductivity and fluorine content is the decisive factor. Herein, by rational design, 3D porous fluorinated graphene microspheres (FGS- x ) with both high conductivity and a high F/C ratio are successfully synthesized for the first time. FGS- x possesses an F/C ratio as high as 1.03, a nanosheet structure with hierarchical pores, abundant C═C bonds, few inactive C-F 2 bonds, and electrochemically active C-F bonds. The beneficial features that can increase discharge capacity, shorten the diffusion length for both ions and electrons, enhance the Li + intercalation kinetics, and accommodate the volume change are demonstrated. The Li/FGS-1.03 coin cell delivers an unprecedented power density of 71,180.9 W/kg at an ultrahigh rate of 50 C (43.25 A/g), coupled with a high energy density of 830.7 Wh/kg. Remarkably, the Li/FGS-1.03 pouch cell exhibits a record cell-level power density of 12,451.2 W/kg at 20 C. The in-depth investigation by the ex situ method on structural evolution at different discharge depths reveals that the excellent performance benefits from the structural stability and the uniform formation of LiF. The FGS-1.03 cathode also has excellent performance in extreme operating temperatures (0 to 100 °C) and high active material mass loading (4.3 mg/cm 2 ). These results indicate that the engineered fluorinated graphene developed here has great potential in applications requiring both high power density and high energy density.

Halide perovskites are potential humidity-detection materials due to their sensitivity to water, but the instability of traditional lead-based halide perovskites and the toxicity of Pb hinder further application in humidity sensing. Here, lead-free Cs 3 Cu 2 Br 5 perovskite microcrystals passivated by surface ligands (OLA and OAm) are used to prepare an environmentally friendly humidity sensor. The humidity sensing performance of the prepared sensors was tested, and the effect of surface ligands of perovskites on the performance of humidity sensors was analyzed. The results show that the impedance variations of the manufactured humidity sensors at 12 to 95% relative humidity are 10 6 Ω (OLA) and 10 5 Ω (OAm), respectively. Besides, the sensors demonstrated excellent repeatability, low hysteresis, and considerable stability at different RH values. Furthermore, the analysis of the different ligands attests that short-chain OLA is more conducive to the formation of porous films with stronger water absorption capacity, further improving the responsiveness of the sensor. By contrast, and long-chain OAm is more conducive to the formation of dense films, improving the response ability at low humidity. Additionally, the more hydrophilic OLA contributes to greater responsiveness, while the more hydrophobic OAm helps to shorten the response and recovery time.

A light-responsive optical switching material is reported, which was obtained by incorporating carbon dots (CDs) into thermochromic hydroxypropylmethyl cellulose (HPMC). The ultrasmall size of CDs guarantees the considerable transparency of CDs/HPMC. Under illumination, CDs/HPMC shows rapid and reversible optical switching between transparent and opaque states due to the remarkable photothermal effect of CDs. Moreover, the interaction between CDs and HPMC enhances the light absorption and boosts the nonradiative recombination of photoexcited charge carriers that further promote the photothermal conversion of CDs, and also ensures the structural stability of the composite. The obtained CDs/HPMC with good reversibility and high sensitivity which can dynamically switch their transparency in response to weather conditions exhibits excellent solar modulation ability.

Cajaninstilbene acid (CSA), an active stilbene isolated from the leaves of pigeon pea ( Cajanus cajan ), exhibits several bioactivities. To develop CSA as a potential nutraceutical and provide pharmacokinetic foundations for its further in vivo bioactivity studies, this study aims to explore its absorption, metabolism, and excretion systematically. Human colon adenocarcinoma (Caco-2) cell monolayers were utilized to investigate the CSA transport mechanism. CSA metabolites were identified in rat biological samples and quantified to explore their excretion routes. CSA exhibited a high permeability and was transported across Caco-2 monolayers mainly by passive transport via the transcellular process. Four new CSA metabolites were found in vivo , namely, CSA-2- COO -glucuronide, 6,12-dihydroxy CSA, 3-hydroxy-5-methoxystilbene-3- O -glucuronide, and 6-hydroxy CSA-3- O -glucuronide, in addition to our previously reported metabolite CSA-3- O -glucuronide. These metabolites were mainly excreted in bile. Our results indicate that metabolism but not absorption is the major barrier limiting the oral bioavailability of CSA.

Multidrug resistance (MDR) is the main obstacle in cancer chemotherapy. ATP-binding cassette (ABC) transporters can transport a wide range of antitumor drugs out of cells, which is the most common reason in the development of resistance to drugs. Currently, various therapeutic strategies are used to reverse MDR, among which CRISPR/Cas9 gene editing technique is expected to be an effective way. Here, we reviewed the research progress of reversing ABC-mediated drug resistance by CRISPR/Cas9 system.

This paper reports on the hydrothermal synthesis of a novel 2D material, magnesium silicate hydroxide/carbon (MSH/C) core-shell nanoplate, in a graphite-MgO-SiO 2 -NaOH system at 300 °C and 12 MPa for 48 h. Its significant potentials as an antiwear additive in lubricant oil were subsequently demonstrated. The 2D nanoplates consist of an MSH core and a 1-6 nm thick sp 2 -hybridized carbon shell with a layer spacing of 0.34 nm. In typical four-ball tests at a maximum Hertzian pressure of 3.4 GPa, the MSH/C core-shell nanoplates nearly eliminated wear, whether suspended in poly alpha-olefin oil or fully formulated lubricating oil, and the corresponding volume wear rates were reduced by 96.33% and 72%, respectively. The excellent antiwear performance was ascribed to the formation of a tribofilm consisting of diffusedly distributed Fe 3 O 4 nanocrystals and carbon- and/or SiO x -containing amorphous structures.

The mixed-valent tetramanganese Mn III 3 Mn IV (Mn 4 ) cubane clusters have been at the forefront of molecular magnetism and biomimetic catalysis research for decades. Incorporating robust polyoxometalates to Mn 4 cubanes significantly improves their stability and aqueous solubility, while providing a great platform for studying their deposition onto selected surfaces during device fabrication. In this work, we discovered that the terminal carboxylate ligands in these polyoxometalate-based [Mn III 3 Mn IV O 4 ] magnetic clusters can be partially or completely replaced by inorganic phosphate/polyphosphate groups. This replacement leads to oligomeric aggregates of the Mn 4 clusters. The magnetic data of the monomeric and oligomeric Mn 4 clusters suggested that the introduction of inorganic phosphate bridges may not alter the S = 9/2 ground state of individual Mn 4 clusters, although different magnetic behaviors, especially at low temperatures, were observed primarily because of intercluster interactions.

Probing and understanding the intrinsic active sites of electrocatalysts is crucial to unravel the underlying mechanism of CO 2 electroreduction and provide a prospective for the rational design of high-performance electrocatalysts. However, their structure-activity relationships are not straightforward because electrocatalysts might reconstruct under realistic working conditions. Herein, we employ in-situ measurements to unveil the intrinsic origin of the InN nanosheets which served as an efficient electrocatalyst for CO 2 reduction with a high faradaic efficiency of 95% for carbonaceous product. During the CO 2 electroreduction, InN nanosheets reconstructed to form the In-rich surface. Density functional theory calculations revealed that the reconstruction of InN led to the redistribution of surface charge that significantly promoted the adsorption of HCOO* intermediates and thus benefited the formation of formate toward CO 2 electroreduction. This work establishes a fundamental understanding on the mechanism associated with self-reconstruction of heterogeneous catalysts toward CO 2 electroreduction.

Current pulmonary arterial hypertension (PAH) therapeutic strategies mainly focus on vascular relaxation with less emphasis on vascular remodeling, which results in poor prognosis. Hence, dual pathway regulators with vasodilation effect via soluble guanylate cyclase (sGC) stimulation and vascular remodeling regulation effect by AMP-activated protein kinase (AMPK) inhibition provide more advantages and potentialities. Herein, we designed and synthesized a series of novel pyrazolo[3,4- b ] pyridine derivatives based on sGC stimulator and AMPK inhibitor scaffolds. In vitro , 2 exhibited moderate vasodilation activity and higher proliferation and migration suppressive effects compared to riociguat. In vivo , 2 significantly decreased right ventricular systolic pressure (RVSP), attenuated pulmonary artery medial thickness (PAMT), and right ventricular hypertrophy (RVH) in hypoxia-induced PAH rat models (i.g.). Given the unique advantages of significant vascular remodeling inhibition and moderate vascular relaxation based on the dual pathway regulation, we proposed 2 as a promising lead for anti-PAH drug discovery.

Cu(In,Ga)Se 2 (CIGS) is considered a promising photovoltaics material due to its excellent properties and high efficiency. However, the complicated deep defects (such as In Cu or Ga Cu ) in the CIGS layer hamper the development of polycrystalline CIGS solar cells. Numerous efforts have been employed to passivate these defects which distributed in the grain boundary and the CIGS/CdS interface. In this work, we implemented an effective Ag substituting approach to passivate bulk defects in CIGS absorber. The composition and phase characterizations revealed that Ag was successfully incorporated in the CIGS lattice. The substituting of Ag could boost the crystallization without obviously changing the band gap. The C-V and EIS results demonstrated that the device showed enlarged W d and beneficial carrier transport dynamics after Ag incorporation. The DLTS result revealed that the deep In Cu defect density was dramatically decreased after Ag substituting for Cu. A champion Ag-substituted CIGS device exhibited a remarkable efficiency of 15.82%, with improved V OC of 630 mV, J SC of 34.44 mA/cm 2 , and FF of 72.90%. Comparing with the efficiency of an unsubstituted CIGS device (12.18%), a Ag-substituted CIGS device exhibited 30% enhancement.