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Metabolic fingerprinting provides valuable information on the physiopathological states of cells and tissues. Traditional imaging mass spectrometry and magnetic resonance imaging are unable to probe the spatial-temporal dynamics of metabolites at the subcellular level due to either lack of spatial resolution or inability to perform live cell imaging. Here we report a complementary metabolic imaging technique that is based on hyperspectral stimulated Raman scattering (hsSRS). We demonstrated the use of hsSRS imaging in quantifying two major neutral lipids: cholesteryl ester and triacylglycerol in cells and tissues. Our imaging results revealed previously unknown changes of lipid composition associated with obesity and steatohepatitis. We further used stable-isotope labeling to trace the metabolic dynamics of fatty acids in live cells and live Caenorhabditis elegans with hsSRS imaging. We found that unsaturated fatty acid has preferential uptake into lipid storage while saturated fatty acid exhibits toxicity in hepatic cells. Simultaneous metabolic fingerprinting of deuterium-labeled saturated and unsaturated fatty acids in living C. elegans revealed that there is a lack of interaction between the two, unlike previously hypothesized. Our findings provide new approaches for metabolic tracing of neutral lipids and their precursors in living cells and organisms, and could potentially serve as a general approach for metabolic fingerprinting of other metabolites.

Ammonia (NH 3 ) slip from diesel vehicle aftertreatment systems and internal combustion engines fueled by NH 3 or NH 3 /H 2 poses serious environmental problems. Ag-based catalysts are widely used for the selective catalytic oxidation of NH 3 to N 2 (NH 3 -SCO), and their performance is greatly dependent on the state of Ag, which is influenced by the anchoring sites on the support. Despite efforts to identify the direct anchoring sites of metal atoms on TiO 2 , conflicting views persist. Here, we compared the correlation between Ag dispersion and the content of hydroxyl (OH) groups or defects on TiO 2 and conducted density functional theory (DFT) calculations, and the results confirmed that the surface OH groups of TiO 2 serve as the direct anchoring sites for Ag. By modulating the OH group content through thermal induction, the optimal OH group content on TiO 2 -800 resulted in more metallic Ag nanoparticles (Ag 0 NPs) in larger sizes, leading to the development of an excellent NH 3 -SCO catalyst. Moreover, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), kinetic studies, and DFT calculations suggested that more Ag 0 NPs in larger sizes on 10Ag/TiO 2 -800 were conducive to O 2 activation and NH 3 dissociation. Our findings provide new insights for designing efficient NH 3 -SCO catalysts, and OH groups as direct anchoring sites could be extended to other metals and supports for the rational design of catalysts.

How to address the resistance of cisplatin (CDDP) has always been a clinical challenge. The resistance mechanism of platinum-based drugs is very complex, including nuclear DNA damage repair, apoptosis escape, and tumor metabolism reprogramming. Tumor cells can switch between mitochondrial oxidative phosphorylation (OXPHOS) and glycolysis and develop resistance to chemotherapy drugs through metabolic variability. In addition, due to the lack of histone protection and a relatively weak damage repair ability, mitochondrial DNA (mtDNA) is more susceptible to damage, which in turn affects mitochondrial OXPHOS and can become a potential target for platinum-based drugs. Therefore, mitochondria, as targets of anticancer drugs, have become a hot topic in tumor resistance research. This study constructed a self-assembled nanotargeted drug delivery system LND-SS-Pt-TPP/HA-CD. β-Cyclodextrin-grafted hydronic acid (HA-CD)-encapsulated prodrug nanoparticles can target CD44 on the tumor surface and further deliver the prodrug to intracellular mitochondria through a triphenylphosphine group (TPP + ). Disulfide bonds can be selectively degraded by glutathione (GSH) in mitochondria, releasing lonidamine (LND) and the cisplatin prodrug (Pt(IV)). Under the action of GSH and ascorbic acid, Pt(IV) is further reduced to cisplatin (Pt(II)). Cisplatin can cause mtDNA damage, induce mitochondrial dysfunction and mitophagy, and then affect mitochondrial OXPHOS. Meanwhile, LND can reduce the hexokinase II (HK II) level, induce destruction of mitochondria, and block energy supply by glycolysis inhibition. Ultimately, this self-assembled nano targeted delivery system can synergistically kill cisplatin-resistant lung cancer cells, which supplies an overcome cisplatin resistance choice via the disrupt mitochondria therapy.

HDAC8 plays crucial roles in biological processes, from gene regulation to cell motility, making it a highly desirable target for therapeutic intervention. HDAC8 also has deacetylase-independent activity which cannot be blocked by a conventional inhibitor. In this study, we report the discovery of YX862, a highly potent and selective hydrazide-based HDAC8-proteolysis targeting chimera (PROTAC) degrader. The selectivity is achieved through rational design of the warhead to spare HDAC3 activity from the previous HDAC3/8 dual degrader YX968. We demonstrate that the degradation of HDAC8 by YX862 increases acetylation levels of its nonhistone substrates such as SMC3 without significantly triggering histone PTM, supporting HDAC8's major role in nonhistone PTM regulation. YX862 exhibits promising on-target antiproliferative activity against DLBCL cells with higher potency than the HDAC8 selective inhibitor PCI-34051. As a selective HDAC8 degrader that avoids pan-HDAC inhibition, YX862 represents a valuable tool for exploring the biological and therapeutic potential of HDAC8.

Exploring the structure-performance relationship of high-voltage organic solar cells (OSCs) is significant for pushing material design and promoting photovoltaic performance. Herein, we chose a D-π-A type polymer composed of 4,8-bis(thiophene-2-yl)-benzo[1,2- b :4,5- b ']dithiophene (BDT-T) and benzotriazole (BTA) units as the benchmark to investigate the effect of the fluorination number and position of the polymers on the device performance of the high-voltage OSCs, with a benzotriazole-based small molecule (BTA3) as the acceptor. F00 , F20 , and F40 are the polymers with progressively increasing F atoms on the D units, while F02 , F22 , and F42 are the polymers with further attachment of F atoms to the BTA units based on the above three polymers. Fluorination positively affects the molecular planarity, dipole moment, and molecular aggregations. Our results show that V OC increases with the number of fluorine atoms, and fluorination on the D units has a greater effect on V OC than on the A unit. F42 with six fluorine atom substitutions achieves the highest V OC (1.23 V). When four F atoms are located on the D units, the short-circuit current ( J SC ) and fill factor (FF) plummet, and before that, they remain almost constant. The drop in J SC and FF in F40- and F42- based devices may be attributed to inefficient charge transfer and severe charge recombination. The F22 :BTA3 system achieves the highest power conversion efficiency of 9.5% with a V OC of 1.20 V due to the excellent balance between the photovoltaic parameters. Our study provides insights for the future application of fluorination strategies in molecular design for high-voltage organic photovoltaics.

The elimination of uranium from radioactive wastewater is crucial for the safe management and operation of environmental remediation. Here, we present a layered vanadate with high acid/base stability, [Me 2 NH 2 ]V 3 O 7 , as an excellent ion exchanger capturing uranyl from highly complex aqueous solutions. The material possesses an indirect band gap, ferromagnetic characteristic and a flower-like morphology comprising parallel nanosheets. The layered structure of [Me 2 NH 2 ]V 3 O 7 is predominantly upheld by the H-bond interaction between anionic framework [V 3 O 7 ] n n - and intercalated [Me 2 NH 2 ] + . The [Me 2 NH 2 ] + within [Me 2 NH 2 ]V 3 O 7 can be readily exchanged with UO 2 2+ . [Me 2 NH 2 ]V 3 O 7 exhibits high exchange capacity ( q m = 176.19 mg/g), fast kinetics (within 15 min), high removal efficiencies (>99%), and good selectivity against an excess of interfering ions. It also displays activity for UO 2 2+ ion exchange over a wide pH range (2.00-7.12). More importantly, [Me 2 NH 2 ]V 3 O 7 has the capability to effectively remove low-concentration uranium, yielding a residual U concentration of 13 ppb, which falls below the EPA-defined acceptable limit of 30 ppb in typical drinking water. [Me 2 NH 2 ]V 3 O 7 can also efficiently separate UO 2 2+ from Cs + or Sr 2+ achieving the highest separation factors (SF U/Cs of 589 and SF U/Sr of 227) to date. The BOMD and DFT calculations reveal that the driving force of ion exchange is dominated by the interaction between UO 2 2+ and [V 3 O 7 ] n n - , whereas the ion exchange rate is influenced by the mobility of UO 2 2+ and [Me 2 NH 2 ] + . Our experimental findings indicate that [Me 2 NH 2 ]V 3 O 7 can be considered as a promising uranium scavenger for environmental remediation. Additionally, the simulation results provide valuable mechanistic interpretations for ion exchange and serve as a reference for designing novel ion exchangers.

The hydrochemical characteristics of groundwater are of great significance for studying the source, development, and utilization of groundwater. This study investigated the characteristics of anions and cations, total dissolved solids (TDS), hydrochemical types, and hydrogen and oxygen isotopes of surface water and groundwater in the Balasu coalfield. By conducting experiments using inductively coupled plasma emission electron spectrometry, ion chromatography, acid-base titration, and gravimetric analysis, the characteristics of ion concentration and TDS in different aquifers were analyzed to determine the possible source of groundwater in C2 (number 2 coal seam in Yan'an Formation). The Piper trilinear diagram was used to determine the hydrochemical types of aquifers, and the source of groundwater was determined based on the stable isotope characteristics of hydrogen and oxygen. The changes in ion, TDS, hydrogen, and oxygen isotopes of surface water and groundwater were analyzed, and the groundwater differences between the two sets of coal seams were compared. The research results indicate that the groundwater in C2 (number 2 coal seam in Yan'an Formation) is caused by the original sedimentary water and the infiltration of Zhiluo Formation and A1 (strata at the top of the Yan'an Formation to number 2 coal seam). However, C4 (number 3 coal seam in Yan'an Formation) is hindered by the well-developed mudstone in A3 (bottom of number 2 coal seam to the top of number 3 coal seam), which hinders the infiltration of groundwater. The study emphasizes that the overlying strata can have a significant impact on the coal seam when the moisture content is high and there is a lack of overlap, thereby promoting changes in the moisture content of the coal seam. This study provides some insights into the safety of coal mines, especially in mining areas with a high coal seam moisture content., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Heparan sulfate proteoglycans (HSPGs) play a crucial role in regulating cancer growth and migration by mediating interactions with growth factors. In this study, we developed a self-assembling peptide ( S1 ) containing a sulfate group to simulate the contiguous sulfated regions (S-domains) in heparan sulfate for growth factor binding, aiming to sequester growth factors like VEGF. Spectral and structural studies as well as simulation studies suggested that S1 self-assembled into nanostructures similar to the heparan sulfate chains and effectively bound to VEGF. On cancer cell surfaces, S1 self-assemblies sequestered VEGF, leading to a reduction in VEGF levels in the medium, consequently inhibiting cancer cell growth, invasion, and angiogenesis. This study highlights the potential of self-assembling peptides to emulate extracellular matrix functions, offering insights for future cancer therapeutic strategies.

The urea-assisted water splitting not only enables a reduction in energy consumption during hydrogen production but also addresses the issue of environmental pollution caused by urea. Doping heterogeneous atoms in Ni-based electrocatalysts is considered an efficient means for regulating the electronic structure of Ni sites in catalytic processes. However, the current methodologies for synthesizing heteroatom-doped Ni-based electrocatalysts exhibit certain limitations, including intricate experimental procedures, prolonged reaction durations, and low product yield. Herein, Fe-doped NiO electrocatalysts were successfully synthesized using a rapid and facile solution combustion method, enabling the synthesis of 1.1107 g within a mere 5 min. The incorporation of iron atoms facilitates the modulation of the electronic environment around Ni atoms, generating a substantial decrease in the Gibbs free energy of intermediate species for the Fe-NiO catalyst. This modification promotes efficient cleavage of C-N bonds and consequently enhances the catalytic performance of UOR. Benefiting from the tunability of the electronic environment around the active sites and its efficient electron transfer, Fe-NiO electrocatalysts only needs 1.334 V to achieve 50 mA cm -2 during UOR. Moreover, Fe-NiO catalysts were integrated into a dual electrode urea electrolytic system, requiring only 1.43 V of cell voltage at 10 mA cm -2 .

The light-fueled microparticle oscillator, exemplifying sustained driving in a static light source, potentially holds applications in fundamental physics, cellular manipulation, fluid dynamics, and various other soft-matter systems. The challenges of photodamage due to laser focusing on particles and the control of the oscillation direction have always been two major issues for microparticle oscillators. Here, we present an optical-thermal method for achieving a 3D microparticle oscillator with a fixed direction by employing laser heating of the gold film surface. First, the microparticle oscillation without direction limitation is studied. The photothermal conversion originates from the laser heating of a gold film. The oscillation mechanism is the coordination of the forces exerted on the particles, including the thermal convective force, thermophoresis force, and gravity. Subsequently, the additional Marangoni convection force, generated by the temperature gradient on the surface of a microbubble, is utilized to control the oscillation direction of the microparticle. Finally, a dual-channel oscillation mode is achieved by utilizing two microbubbles. During the oscillation process, the microparticle is influenced by flow field forces and temperature gradient force, completely avoiding optical damage to the oscillating microparticle.

Piezoelectric-photocatalysis is distinguished by its piezoelectricity as an external force that induces deformation within the catalyst to engender a polarized electric field compared to conventional photocatalysis. Herein, the piezoelectric photocatalyst BiOBr has been expertly synthesized via a plasma process and applied for piezoelectric-photocatalysis removal of uranium(VI) for the first time. The abundant surface oxygen vacancies (OVs) could induce a dipole moment and built-in electric field, which endows BiOBr with excellent separation and transport efficiency of photogenerated charges to actuate more charges to participate in the piezoelectric-photocatalytic reduction process. Consequently, under visible light and ultrasound (150 W and 40 kHz), the removal rate constant of OVs-BiOBr-30 (0.0306 min -1 ) was 2.4, 30.6, and 6 times higher than those of BiOBr (0.01273 min -1 ), ultrasound, or photocatalysis, respectively. The piezoelectric-photocatalytic synergy is also universal for BiOX (X = Cl, Br, or I) to accelerate the reduction rate of uranium(VI). This work highlights the role of piezoelectric-photocatalysis in the treatment of uranium-containing wastewater, which is of great significance for resource conservation and environmental remediation.

Conventional ocean wave observation instruments are powered by batteries, limiting the continuous observation time. Besides, the waste of batteries brings environmental contaminations. Triboelectric nanogenerators (TENGs) can reveal ocean wave information through their electrical output, taking the triboelectric charge as the information carrier. However, charge amplification is necessary, consuming additional energy. Herein, taking the photons rather than electrons as the information carrier, we developed a fully self-powered natural light-enabled sensing system for ocean wave monitoring by coupling two rotary-freestanding sliding TENGs (RFS-TENGs) and a polymer network liquid crystal (PNLC)-triggered optical system. The natural light is modulated by the PNLC driven by ocean wave-induced friction. With the assistance of a one-way bearing, the rise and fall of the wave will trigger different RFS-TENGs to power the PNLC in different voltage drops, leading to different transmitted natural light intensities. The wave height information can be obtained through the number of pulse signals with the same trough light intensity, while the wave period can be obtained through the duration between the same two sets of pulse signals. The effectiveness of the developed sensing paradigm in practical applications was verified by flume-based experiments, with the highest accuracies of 90.7% in wave height and 99.8% in wave period.

Lipid nanoparticles (LNPs), a nonviral nucleic acid delivery system, have shown vast potential for vaccine development and disease treatment. LNPs assist mRNA to cross physiological barriers such as cell membranes and endosomes/lysosomes, promoting the intracellular presentation of mRNA. However, the endosome escape efficiency and biosafety of currently commercialized LNPs are still unsatisfactory, resulting in underutilization of mRNA. Herein, we report that fluorinated modification of the 1,2-distearoyl- sn -glycero-3-phosphoethanolamine-poly(ethylene glycol)-2000 (PEG-DSPE), termed as FPD, in the LNPs can improve the delivery efficiency of mRNA. FPD accounts for only 1.5% of lipids in LNPs but could mediate a 5-fold and nearly 2-fold enhancement of mRNA expression efficiency in B16F10 tumor cells and primary dendritic cells, respectively. Mechanism studies reveal that FPD promotes the cellular internalization of LNPs as well as endosome escape. In vivo studies substantiate that FPD can augment overall mRNA expression at least 3-fold, either by intravenous or intraperitoneal injection, compared to LNPs prepared with nonfluorinated PEG-lipids at a relatively low mRNA dose. Besides, with the introduction of FPD, mRNA expression in the spleen augmented compared to that of the DMG-PEG commercial formulations. Benefiting from a prudent dosage of fluorine, the fluorinated LNPs display favorable biosafety profiles at cellular and zoological levels.

This investigation probes the intricate interplay of catalyst dynamics and reaction pathways during the oxygen evolution reaction (OER), highlighting the significance of atomic-level and local ligand structure insights in crafting highly active electrocatalysts. Leveraging a tailored ion exchange reaction followed by electrochemical dynamic reconstruction, we engineered a novel catalytic structure featuring single Ir atoms anchored to NiOOH (Ir 1 @NiOOH). This novel approach involved the strategic replacement of Fe with Ir, facilitating the transition of selenide precatalysts into active (oxy)hydroxides. This elemental substitution promoted an upward shift in the O 2p band and intensified the metal-oxygen covalency, thereby altering the OER mechanism toward enhanced activity. The shift from a single-metal site mechanism (SMSM) in NiOOH to a dual-metal-site mechanism (DMSM) in Ir 1 @NiOOH was substantiated by in situ differential electrochemical mass spectrometry (DEMS) and supported by theoretical insights. Remarkably, the Ir 1 @NiOOH electrode exhibited exceptional electrocatalytic performance, achieving overpotentials as low as 142 and 308 mV at current densities of 10 and 1000 mA cm -2 , respectively, setting a new benchmark for the electrocatalysis of OER.

Supported platinum nanoparticle catalysts are known to convert polyolefins to high-quality liquid hydrocarbons using hydrogen under relatively mild conditions. To date, few studies using platinum grafted onto various metal oxide (M x O y ) supports have been undertaken to understand the role of the acidity of the oxide support in the carbon-carbon bond cleavage of polyethylene under consistent catalytic conditions. Specifically, two Pt/M x O y catalysts (M x O y = SrTiO 3 and SiO 2 -Al 2 O 3 ; Al = 3.0 wt %, target Pt loading 2 wt % Pt ∼1.5 nm), under identical catalytic polyethylene hydrogenolysis conditions ( T = 300 °C, P(H 2 ) = 170 psi, t = 24 h; M w = ∼3,800 g/mol, M n = ∼1,100 g/mol, Đ = 3.45, N branch/100C = 1.0), yielded a narrow distribution of hydrocarbons with molecular weights in the range of lubricants ( M w = < 600 g/mol; M n < 400 g/mol; Đ = 1.5). While Pt/SrTiO 3 formed saturated hydrocarbons with negligible branching, Pt/SiO 2 -Al 2 O 3 formed partially unsaturated hydrocarbons (<1 mol % alkenes and ∼4 mol % alkyl aromatics) with increased branch density ( N branch/100C = 5.5). Further investigations suggest evidence for a competitive hydrocracking mechanism occurring alongside hydrogenolysis, stemming from the increased acidity of Pt/SiO 2 -Al 2 O 3 compared to Pt/SrTiO 3 . Additionally, the products of these polymer deconstruction reactions were found to be independent of the polyethylene feedstock, allowing the potential to upcycle polyethylenes with various properties into a value-added product.

Photoelectrochemical (PEC) water splitting in acidic media holds promise as an efficient approach to renewable hydrogen production. However, the development of highly active and stable photoanodes under acidic conditions remains a significant challenge. Herein, we demonstrate the remarkable water oxidation performance of Ru single atom decorated hematite (Fe 2 O 3 ) photoanodes, resulting in a high photocurrent of 1.42 mA cm -2 at 1.23 V RHE under acidic conditions. Comprehensive experimental and theoretical investigations shed light on the mechanisms underlying the superior activity of the Ru-decorated photoanode. The presence of single Ru atoms enhances the separation and transfer of photogenerated carriers, facilitating efficient water oxidation kinetics on the Fe 2 O 3 surface. This is achieved by creating additional energy levels within the Fe 2 O 3 bandgap and optimizing the free adsorption energy of intermediates. These modifications effectively lower the energy barrier of the rate-determining step for water splitting, thereby promoting efficient PEC hydrogen production.

Understanding the mechanism of adipogenesis is an important basis for improving meat quality traits of livestock. Alternative polyadenylation (APA) is a vital mechanism to regulate the expression of eukaryotic genes. However, how the individual APA functions in adipogenesis remains elusive. This study was intended to investigate the effect of malic enzyme 1 (ME1) APA on adipogenesis. Here, intracellular lipid droplets were stained using Oil red O. 3' RACE was used to verify APA events of the ME1 gene. Interactions between ME1 3' untranslated region (3' UTR)-APA isoforms and miRNAs, as well as differential expression of isoforms, were examined using dual-luciferase reporter and molecular experiments. The mechanism of ME1 APA on adipogenesis was explored by gain and loss of function assays. In this study, two ME1 isoforms with different 3' UTR lengths were detected during adipogenesis. Moreover, the ME1 isoform with a short 3' UTR was significantly upregulated compared with the one with a long 3' UTR. Mechanistically, only the long ME1 isoform was targeted by miR-153-3p to attenuate adipogenesis, while the short one escaped the regulation of miR-153-3p to accelerate adipogenesis. Our results reveal a novel mechanism of ME1 APA in regulating adipogenesis.

Current ocean wave observation is achieved by separate battery-powered sensing and signal transmission modules. Owing to the limited electrical supply and information channel space, the long-time span observation is restricted and only wave height and period information rather than the whole wave profile are sent back to the receiver. In this work, a self-powered ocean wave observation system was achieved by a developed polymer network liquid crystal (PNLC)-based smart reflector powered by a tailored triboelectric nanogenerator embedded with one-way overrunning clutches. The off-shore smart reflector modulated the on-shore emitted laser light, where ocean wave motion information can be revealed from the remotely detected reflected laser light without cable connections. The ocean wave rise and fall are distinguished by the developed one-way overrunning clutch, which selects the TENG to power the PNLC. Through the developed paradigm, ocean wave sensing and signal transmission can be achieved simultaneously, which is fully self-powered and free-of-cable. The flume-based self-powered ocean observation was performed with demonstrated wave height and period sensing accuracies of 92.66 and 97.32%, respectively.

Inflammatory bowel disease (IBD) is one of the main factors leading to colitis-associated colorectal cancer (CAC). Therefore, it is critical to develop an effective treatment for IBD to prevent secondary colorectal carcinogenesis. M2 macrophages play crucial roles in the resolution phase of intestinal inflammation. However, traditional drugs rarely target intestinal M2 macrophages, and they are not easily cleared. Gold nanoclusters are known for their in vivo safety and intrinsic biomedical activities. In this study, a glutathione-protected gold nanocluster is synthesized and evaluated, namely, GA. Interestingly, GA specifically accumulates in the colon during IBD. Furthermore, GA not only promotes M2 differentiation of IL-4-treated peritoneal macrophages but also reprograms macrophage polarization from M1 to M2 in a pro-inflammatory environment. Mechanistically, this regulatory effect is exerted through activating the antioxidant Nrf2 signaling pathway, but not traditional STAT6. When applied in IBD mice, we found that GA elevates M2 macrophages and alleviates IBD in an Nrf2-dependent manner, evidenced by the abolished therapeutic effect upon Nrf2 inhibitor treatment. Most importantly, GA administration significantly suppresses AOM/DSS-induced CAC, without causing obvious tissue damage, providing critical evidence for the potential application of gold nanoclusters as nanomedicine for the treatment of IBD and CAC.

Luminescent supramolecular metallacycles have attracted great interest as a new promising class of sensing substrates. In this work, two tetraphenylethene (TPE)-based diimidazole and dipyrazole ligands with the aggregation-induced emission (AIE) feature were designed for the construction of supramolecular tetragonal metallacycles 1 - 4 with two 90° mononuclear [(bpy)M] 2+ or dinuclear [(bpy) 2 M 2 ] 4+ acceptors (bpy = 2,2'-dipyridine; M = Pd, Pt), in which the fluorescence can be quenched to an "off" state due to the ligand-to-metal charge transfer (LMCT). Metallacycle 1 was utilized as a fluorescence sensor for phosphate (PO 4 3- ) detection in aqueous solution by means of disassembly, leading to the release of the ligand. Additionally, the metallacycle can be regenerated through self-assembly via the introduction of Pd(II) acceptors. PO 4 3- was detected using TPE-based metallacycles over a wide concentration range, with a detection limit as low as 2.1 × 10 -8 M. Furthermore, sensor 1 also presented the semiquantitative visual detection ability for PO 4 3- in the test paper mode via fluorescence changes. The aforementioned studies not only enhance the current research on fluorescent materials but also offer a strategy for the creation of stimuli-responsive supramolecular coordination complexes.

The Stokes shift is negligible in bulk perovskites but large in two-dimensional (2D) CsPbBr 3 perovskites. The issue has attracted a lot of discussion, but it remains controversial. Here, we report the temperature-dependent absorption and photoluminescence (PL) spectra of CsPbBr 3 perovskite nanoplatelets (NPLs). We observe a temperature-dependent Stokes shift changing from 26 to 41 meV. This phenomenon was attributed to the exciton fine structure according to the great difference in peak width. The triple bright exciton levels all participate in the absorption process and result in a wide absorption peak, while only the lowest exciton level contributes to photon emission and exhibits a relatively narrow PL peak. The PL decay curves also present the characterization of bright and dark exciton couplings at low temperatures. The splitting of triple bright excitons is induced by the morphology anisotropy of the 2D structure, so the large Stokes shift is proposed to be an intrinsic property of 2D perovskites.

Wearable electrochemical sensors provide means to detect molecular-level information from the biochemical markers in biofluids for physiological health evaluation. However, a high-density array is often required for multiplexed detection of multiple markers in complex biofluids, which is challenging with low-cost fabrication methods. This work reports the low-cost direct laser writing of porous graphene foam as a flexible electrochemical sensor to detect biomarkers and electrolytes in sweat. The resulting electrochemical sensor exhibits high sensitivity and low limit of detection for various biomarkers (e.g., the sensitivity of 6.49/6.87/0.94/0.16 μA μM -1 cm -2 and detection limit of 0.28/0.26/1.43/11.3 μM to uric acid/dopamine/tyrosine/ascorbic acid) in sweat. The results from this work open up opportunities for noninvasive continuous monitoring of gout, hydration status, and drug intake/overdose.

Metal-organic gels (MOGs) are a category of metal-organic smart soft materials with large specific surface areas, loose porous structures, and open metal active sites. In this work, trimetallic Fe(III)Co(II)Ni(II)-based MOGs (FeCoNi-MOGs) were synthesized at room temperature via a simple and mild one-step procedure. Fe 3+ , Co 2+ , and Ni 2+ were the three central metal ions in it, while 1,3,5-benzenetricarboxylic acid (H 3 BTC) served as the ligand. The solvent enclosed in it was then removed by freeze-drying to get the corresponding metal-organic xerogels (MOXs). The as-prepared FeCoNi-MOXs have excellent peroxidase-like activity and can significantly enhance luminol/H 2 O 2 chemiluminescence (CL) by more than 3000 times, which is very effective compared with other reported MOXs. Based on the inhibitory effect of dopamine on the CL of the FeCoNi-MOXs/luminol/H 2 O 2 system, a simple, rapid, sensitive, and selective CL method for dopamine detection was established with a linear range of 5-1000 nM and a limit of detection of 2.9 nM (LOD, S/N = 3). Furthermore, it has been effectively used for the quantitative measurement of dopamine in dopamine injections and human serum samples, with a recovery rate of 99.5-109.1%. This research brings up prospects for the application of MOXs with peroxidase-like activity in CL.

Uranium-bearing wastewaters exert a great threat to the ecological environment due to its high radiotoxicity level. The designing and fabrication of novel adsorption materials can be promoted for radionuclide elimination from wastewater. In this work, results from density functional theory and Born-Oppenheimer molecular dynamics simulations are reported for the uranyl adsorption behavior on the MoS 2 /Mo 2 CT x heterostructure in the gas phase and in an aqueous environment. Uranyl ions prefer to be adsorbed at deprotonated O sites on the Mo 2 COH surface and S sites on the MoS 2 side of the heterojunctions, resulting in the formation of bidentate configurations. In addition to coordination interaction, H-bond and van der Waals interactions can also play an important role in binding configurations. More importantly, the oxidation state U(VI) can be reduced to U(V) and then to U(IV) caused by the strong reducibility of the Mo 2 COH surface at room temperature, whereas the uranyl complex can move freely on the MoS 2 surface. However, the coordination number of U with respect to H 2 O in the first hydration shell on the Mo 2 COH surface remains unchanged and is found to be 3, which is similar to that on the MoS 2 surface. This work provides novel nanosorbents for the removal of uranyl from wastewater. The present viewpoint provides valuable mechanistic interpretations for uranyl adsorption and will give a supplement to the experimental research.

With the development of nuclear magnetic resonance (NMR) spectrometers and probes, two-dimensional quantitative nuclear magnetic resonance (2D qNMR) technology with a high signal resolution and great application potential has become increasingly accessible for the quantitation of complex mixtures. However, the requirement that the relaxation recovery time be equal to at least five times T (longitudinal relaxation time) makes it difficult for 2D qNMR to simultaneously achieve high quantitative accuracy and high data acquisition efficiency. By comprehensively using relaxation optimization and nonuniform sampling, we successfully established an optimized 2D qNMR strategy for HSQC experiments at the half-hour level and then accurately quantified the diester-type C 1 (longitudinal relaxation time) makes it difficult for 2D qNMR to simultaneously achieve high quantitative accuracy and high data acquisition efficiency. By comprehensively using relaxation optimization and nonuniform sampling, we successfully established an optimized 2D qNMR strategy for HSQC experiments at the half-hour level and then accurately quantified the diester-type C 19 -diterpenoid alkaloids in Aconitum carmichaelii . The optimized strategy had the advantages of high efficiency, high accuracy, good reproducibility, and low cost and thus could serve as a reference to optimize 2D qNMR experiments for quantitative analysis of natural products, metabolites, and other complex mixtures.

Lightweight, compact, integrated, and miniaturized energy devices are under high pursuit for portable and wearable electronics. However, improving the energy density per area still remains a long-standing challenge. Herein, we report the design and fabrication of a solid-state zinc-air microbattery (ZAmB) by a facile 3D direct printing technique. The interdigital electrodes, gel electrolyte, and encapsulation frame are all printed with a customized design by optimzing the composition of the printing inks to obtain the best battery performance. Multiple layers of interdigital electrodes are sequentially printed with a fine overlap to achieve an ultrahigh thickness of 2.5 mm for a remarkably increased specific areal energy of up to 77.2 mWh cm -2 . To meet the practical powering requirements for different output voltages and currents, battery modules consisting of individual ZAmBs connected in series or parallel or a combination of the two are printed with a facile integration to external loads. Powering of LEDs, digital watch, and a miniature rotary motor and even charging of a smartphone by the printed ZAmB modules are successfully demonstrated. The versatile 3D direct printing technique enables the fabricated ZAmBs with an adjustable form factor and integration capability with other electronics, paving the way for exploring new energy systems with diverse structures and extended functionalities.

Novel bismuth selenite iodate oxide BiSeIO 6 was synthesized in a mild hydrothermal condition. BiSeIO 6 was crystallized in the polar space group Pna 2 1 of an orthorhombic system. The crystal structure features a three-dimensional framework composed of three types of lone pair cations with distorted BiO 7 polyhedra, SeO 3 pyramids, and IO 3 pyramids in one structure. Interestingly, BiSeIO 6 exhibits a strong and phase-matchable second-harmonic generation (SHG) of ∼6 times that of KH 2 PO 4 (KDP). Dipole moment analysis shows that all three local acentric groups of BiO 7 , SeO 3 , and IO 3 cooperatively contribute to the large macroscopic polarization and thereby strong SHG efficiency of BiSeIO 6 . In addition, BiSeIO 6 has a broad transparency range from 0.35 to 11 μm, indicating its promising nonlinear optical applications from visible to mid-infrared bands.

Metal-organic polyhedra featuring non-Archimedean/Platonic architectures with multiple kinds of vertices have aroused great attention for their fascinating structures and properties but are yet challenging to achieve. Here, we report a combinatorial strategy to make such nonclassic polyhedral cages by combining kinetically labile metal ions with non-planar organic linkers instead of the usual only inert metal centers and planar ligands. This facilitates the synthesis of an enantiopure twisted tetra(3-pyridyl)-based TADDOL (TADDOL = tetraaryl-1,3-dioxolane-4,5-dimethanol) ligand ( L ) capable of binding Ni(II) ions to produce a regular convex cage, Ni 6 L 8 , with two mixed metal/organic vertices and three rarely reported concave cages Ni 14 L 8 , Ni 18 L 12 , and Ni 24 L 16 with three or four mixed vertices. Each of the cages has an amphiphilic cavity decorated with chiral dihydroxyl functionalities and packs into a three-dimensional structure. The enantioselective adsorption and separation performances of the cages are strongly dependent on their pore structure features. Particularly, Ni 14 L 8 and Ni 18 L 12 with wide openings can be solid adsorbents for the adsorptive and solid-phase extractive separation of a variety of racemic spirodiols with up to 98% ee, whereas Ni 6 L 8 and Ni 24 L 16 with smaller pore apertures cannot adsorb the racemates. The combination of single-crystal X-ray diffraction analysis of the host-guest adduct and GCMC simulation indicates that the enantiospecific recognition capabilities originate from the well-organized chiral inner sphere as well as multiple interactions within the chiral microenvironment. This work therefore provides an attractive strategy for the rational design of polyhedral cages, showing geometrically fascinating structures with properties different from those of classic assemblies.

Nature's blueprint provides the fundamental principles for expanding the use of abundant metals in catalysis; however, mimicking both the structure and function of copper enzymes simultaneously in one artificial system for selective C-H bond oxidation faces marked challenges. Herein, we report a new approach to the assembly of artificial monooxygenases utilizing a binuclear Cu 2 S 2 Cl 2 cluster to duplicate the identical structure and catalysis of the Cu A enzyme. The designed monooxygenase Cu-Cl-bpyc facilitates well-defined redox potential that initially activated O 2 via photoinduced electron transfer, and generated an active chlorine radical via formed copper(II) center. The chlorine radical abstracts a hydrogen atom selectively from C(sp in situ formed copper(II) center. The chlorine radical abstracts a hydrogen atom selectively from C(sp 3 species interacted with the mimic to form mixed-valence species, giving the desired oxidization products with inherent product selectivity of copper monooxygenases and recovering the catalyst directly. This enzymatic protocol exhibits excellent recyclability, good functional group tolerance, and broad substrate scope, including some biological and pharmacologically relevant targets. Mechanistic studies indicate that the C-H bond cleavage was the rate-determining step and the cuprous interactions were essential to stabilize the active oxygen species. The well-defined structural characters and the fine-modified catalytic properties open a new avenue to develop robust artificial enzymes with uniform and precise active sites and high catalytic performances.2 •- species interacted with the mimic to form mixed-valence species, giving the desired oxidization products with inherent product selectivity of copper monooxygenases and recovering the catalyst directly. This enzymatic protocol exhibits excellent recyclability, good functional group tolerance, and broad substrate scope, including some biological and pharmacologically relevant targets. Mechanistic studies indicate that the C-H bond cleavage was the rate-determining step and the cuprous interactions were essential to stabilize the active oxygen species. The well-defined structural characters and the fine-modified catalytic properties open a new avenue to develop robust artificial enzymes with uniform and precise active sites and high catalytic performances.

Activated B cell-like diffuse large B-cell lymphoma (ABC-DLBCL) is the most aggressive form of DLBCL, with a significantly inferior prognosis due to resistance to the standard R-CHOP immunochemotherapy. Survival of ABC-DLBCL cells addicted to the constitutive activations of both canonical and noncanonical NF-κB signaling makes them attractive therapeutic targets. However, a pharmaceutical approach simultaneously targeting the canonical and noncanonical NF-κB pathway in the ABC-DLBCL cell is still lacking. Peptide-conjugated gold nanoclusters (AuNCs) have emerged unique intrinsic biomedical activities and possess a great potential in cancer theranostics. Here, we demonstrated a Au 25 nanocluster conjugated by cell-penetrating peptides that can selectively repress the growth of ABC-DLBCL cells by inducing efficient apoptosis, more efficiently than glutathione (GSH)-conjugated AuNCs. The mechanism study showed that the cell-penetrating peptides enhanced the cellular internalization efficiency of AuNCs, and the selective repression in ABC-DLBCL cells is due to the inhibition of inherent constitutive canonical and noncanonical NF-κB activities by AuNCs. Several NF-κB target genes involved in chemotherapy resistance in ABC-DLBCL cells, including anti-apoptotic Bcl-2 family members and DNA damage repair proteins, were effectively down-regulated by the AuNC. The emerged novel activity of AuNCs in targeting both arms of NF-κB signaling in ABC-DLBCL cells may provide a promising candidate and a new insight into the rational design of peptide-conjugated Au nanomedicine for molecular targeting treatment of refractory lymphomas.

Lithium (Li) metal is a candidate anode for the next generation of high-energy density secondary batteries. Unfortunately, Li metal anodes (LMAs) are extremely reactive with electrolytes to accumulate uncontrolled dendrites and to generate unwanted parasitic electrochemical reactions. Much attention has been focused on carbon materials to address these issues. Ulteriorly, the failure mechanism investigation of lithiophilic sites on carbon materials has been not taken seriously. Herein, we design a new type of sesame ball-like carbon sphere (AgNPs@CS, an average diameter of ∼700 nm) with uniformly interfacial anchored silver nanoparticles (AgNPs), which is used as the dendrite-free Li metal anode host. This anchored structure significantly enhances reversible and chemical affinity of Li, effectively inhibiting "dead Li". In addition, the protective effect of the carbon layer can avoid the damage of lithiophilic AgNPs in the carbon matrix. With a plating/striping capacity of 2 mA h cm -2 , the AgNPs@CS electrode can be cycled over 2400 h at 0.5 mA cm -2 . When the stripping voltage increases to 1 V, the AgNPs@CS electrode also enables excellent cycling stability to achieve over 260 cycles (1 mA cm -2 , 1 mA h cm -2 ) and 130 cycles (2 mA cm -2 , 1 mA h cm -2 ). This material by electrochemical characterization highlights the efficacy of this facile method for developing dendrite-free LMAs.

As an emerging porous crystal polymer, covalent organic frameworks (COFs) possess unique characteristics, such as high porosity, excellent stability, diverse topologies, designable open channels, and functional tunability. However, limited by the solid powder form, most COFs display low active site utilization and weak binding force with the current collector. In this pioneering research, we integrate redox-active COFs onto carbon fiber surfaces (AC-COFs) via strong covalent bridging. The 2,6-diaminoanthraquinone (DAAQ) pillars embedded on the carbon fiber surface are the key to precisely controlling the growth direction of COFs. The obtained tentacle-like array vertically supported on the surface of the carbon fiber can effectively induce charge transfer and prevent COFs from aggregating/collapsing. The strong covalent coupling and increase of accessible active sites contributed to the high specific capacitance of AC-COFs electrode (1034 mF cm -2 ). In addition, the COF-based flexible electrode retains an initial capacitance of 98% after 20000 charge-discharge cycles. The flexible all-solid-state symmetric supercapacitor is assembled by PVA/H 2 SO 4 gel electrolyte with an areal capacitance of 715 mF cm -2 . Besides, a red LED can be easily powered by three-bending AC-COFs//AC-COFs devices. The innovative synthesis strategy opens up new opportunities to develop high-performance flexible energy storage devices based on COFs.

Silicon (Si) is considered a promising anode material for rechargeable lithium-ion batteries (LIBs) due to its high theoretical capacity, low working potential, and safety features. However, the practical use of Si-based anodes is hampered by their huge volume expansion during the process of lithiation/delithiation, and they have relatively low intrinsic electronic conductivity, therefore seriously restricting their application in energy storage. Here, we propose a facile approach to directly transform siliceous biomass (bamboo leaves) into a porous carbon skeleton-wrapped Si nanodot architecture through a partial oxidization strategy and magnesium thermal reaction to obtain a high Si nanodot component composite (denoted as Si/C-O). With the synergistic effect of the porous carbon skeleton structure and uniformly dispersed Si nanodots, the Si/C-O composite anode with a stable structure that can avoid pulverization and accommodate volume expansion during cycling is fabricated. As expected, the biomass-converted Si/C-O anode not only presents a high Si component (59.7 wt %) by TGA but also exhibits an excellent capacity of 1013 mAh g -1 at 0.5 A g -1 and robust cycling stability with a capacity retention of 526 mAh g -1 after 650 cycles. Moreover, the Si/C-O anode demonstrates considerable performance in practical LIBs when assembled with a commercial LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode. This work provides an effective strategy and long-term insights into the utilization of porous Si-based materials converted by biomass to design and synthesize high-performance LIB materials.

Perovskite light-emitting diodes (PeLEDs) have become a hot research topic in recent years and can now achieve an external quantum efficiency (EQE) of over 22% for green and red devices. However, the efficiency of blue PeLEDs, which are essential for display applications, lags far behind their green and red counterparts. The interface of the PeLEDs has a critical influence on the carrier transport and exciton recombination dynamics, and interface engineering is considered to be an effective strategy to improve the device performance. Herein, quaternary ammonium-based ionic liquids serve as an interfacial modification layer to significantly improve the device efficiency and stability. The interaction of quaternary ammonium cations with Pb(Br/Cl) 6 octahedra promotes nucleation sites, which significantly improves the morphology of perovskite films and reduces the formation of defects in films. In addition, ion migration is also effectively suppressed in the device. As a result, with tributylmethylammonium bromide (TMAB) used as the interface layer, the EQE of the device is successfully increased from 3.5 to 6.7%, and the operational stability with a half-lifetime ( T 50 ) is increased by over 12 times. Our work provides a new class of interface modification materials toward high-performance blue PeLEDs.

Epidermal growth factor receptor tyrosine kinase inhibitors (EGFR-TKIs) are the most important chemotherapeutics for non-small-cell lung cancer (NSCLC) therapy. The resistance to EGFR-TKIs is one of the biggest obstacles to NSCLC outcome. In this study, taking advantage of phospho- and proximal proteomic techniques, we analyzed the network rearrangement in cell lines responding to AZD9291 treatment and found that cell-cell adhesion was dramatically enhanced in AZD9291-resistant cells. Further analysis revealed that protein tyrosine kinase 7 (PTK7) expression was significantly elevated. Knockdown or overexpression assays showed that PTK7 played a critical role in improving cell adhesion, which enhanced drug resistance. Because PTK7 is a membrane-localized pseudokinase, the proximal labeling probe BirA* was fused to reveal PTK7-interacting proteins. We found that PTK7 interacted with and stabilized NDRG1, which is located predominantly adjacent to adherens junctions. Downregulation of PTK7 or NDRG1 eliminated the resistance of H1975-resistant (H1975-R) and PC9-resistant (PC9-R) cells to AZD9291, suggesting that the PTK7-NDRG1 axis might be a potential target to eliminate the EGFR-TKI resistance during NSCLC therapy.

Tunable metasurfaces promise to enable adaptive optical systems with complex functionalities. Among possible realizations, a recent platform combining microelectromechanical systems (MEMS) with gap-surface plasmon (GSP) metasurfaces offers high modulation efficiency, broadband operation, and fast response. We compare tunable metasurfaces operating in GSP and Fabry-Pérot (FP) regions by investigating polarization-independent blazed gratings both numerically and experimentally. Peak efficiency is calculated to be ∼75% in both cases (∼40% in measurements), while the operation bandwidth is found larger when operating in the GSP region. Advantages of operating in the FP region include relaxed assembly requirements and operation tolerances. Additionally, simulation and experimental results show that coupling between neighboring unit cells increases for larger air gaps, resulting in deteriorated efficiency. We believe the presented analysis provides important guidelines for designing tunable metasurfaces for diverse applications in miniaturized adaptive optical systems.

As a most promising formaldehyde-free crosslinking agent for the antiwrinkle treatment of cotton fabrics, 1,2,3,4-butanetetracarboxylic acid (BTCA) has been explored for many years to replace the traditional N -methylol resin. However, the current methodology for preparing antiwrinkle cotton fabrics with BTCA mainly highlights the troublesome problem of higher curing temperature. In this research, a novel strategy with the aid of dimethyl sulfone (MSM) was developed to decrease the curing temperature of BTCA for fabricating antiwrinkle cotton fabrics, which is an eco-friendly additive with low price and wonderful biocompatibility. Temperature-dependent Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and computational simulations were employed to analyze the mechanism of MSM in the overall reaction between BTCA and cellulose. Based on the strong hydrogen-bond acceptor property of MSM, the noncovalent interactions in the crosslinking system could be easily interrupted, which facilitates the BTCA diffusion in amorphous regions of cellulose, anhydride formation, and the thermal vibration of cellulose chains during the processing. Physically and chemically speaking, both reactivities of grafting and crosslinking reactions of BTCA are significantly increased with the assistance of MSM, consequently reducing the curing temperature, which will hopefully help achieve the industrial-scale application of BTCA in antiwrinkle treatment., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

A novel theranostic co-prodrug SCB has been designed by combining a co-prodrug from CDDO-Me and SAHA with a biotin-coupled near-infrared (NIR) probe hemicyanine via redox-responsive linker thiolactate to enhance the tumor theranostic efficacy and reduce the toxic side effects using both active and passive targeting strategies. SCB displayed reactive oxygen species (ROS)- and glutathione (GSH)-dependent release of NIR fluorescence and two parent drugs. Furthermore, the administration of SCB caused selective illumination of the tumor tissues for >24 h, thereby guiding precise removal of a tumor from intraoperative mice. Importantly, SCB exhibited highly efficient tumor inhibition, exerted selective combination therapy through prodrug mode, and minimized the adverse effects. Finally, SCB induced mitochondrial depolarization, DNA damage, and cell apoptosis through ROS generation and downregulation of HDAC6 protein, as verified by H2AX, Bax, cleaved-PARP, and Mcl-1 proteins. Thus, we suggest that SCB can provide a new platform for both precise diagnosis-guided tumor removal and selective combination therapy with high safety.

Colloidal systems are abundant in technology, in biomedical settings, and in our daily life. The so-called "colloidal atoms" paradigm exploits interparticle interactions to self-assemble colloidal analogs of atomic and molecular crystals, liquid crystal glasses, and other types of condensed matter from nanometer- or micrometer-sized colloidal building blocks. Nematic colloids, which comprise colloidal particles dispersed within an anisotropic nematic fluid host medium, provide a particularly rich variety of physical behaviors at the mesoscale, not only matching but even exceeding the diversity of structural and phase behavior in conventional atomic and molecular systems. This feature article, using primarily examples of works from our own group, highlights recent developments in the design, fabrication, and self-assembly of nematic colloidal particles, including the capabilities of preprogramming their behavior by controlling the particle's surface boundary conditions for liquid crystal molecules at the colloidal surfaces as well as by defining the shape and topology of the colloidal particles. Recent progress in defining particle-induced defects, elastic multipoles, self-assembly, and dynamics is discussed along with open issues and challenges within this research field.

Selectively anchoring active centers on the external surface for forming highly exposed acid sites is a highly desirable but challenging task in zeolite catalyst synthesis. Herein, a defect-guided etching-regrowth strategy is rationally designed for facilely positioning Sn Lewis acid sites on the outer surface of the Sn-B-Beta while fabricating a bifunctional hierarchical structure. The synthesis was conducted by hydrothermal treatment of the as-made B-Beta (uncalcined), which has intrinsic defects of the BEA structure, with Sn source and basic organic structure directing agent (SDA). Under a moderate SDA concentration, with blocked micropore channels, such SDA-triggered etching-regrowth will proceed along the defect defined pathway, which ensures Sn selectively anchored on the external surface. Moreover, this methodology has exclusively introduced tetrahedrally coordinated framework Sn with open Sn sites as the predominated species. Mono- and disaccharide isomerizations in ethanol over different Sn-Beta catalysts proved the prominent advantages of the hierarchical structure with highly exposed and synergetic acid sites.

Hydraulic fracturing plays an important role in the commercial development of unconventional oil and gas, which is directly related to the production of oil and gas wells. An accurate evaluation is critical for hydraulic fracturing, but it is urgent to propose a quantitative assessment of hydraulic fracturing fracture propagation for realizing hydraulic fracturing fracture propagation and multiposition permeability measurement under an in situ stress environment. Herein, a true triaxial stress loading and permeability testing device was designed and fabricated, and a permeability evaluation model was established under various states, which can realize the accurate measurement of multiple faces and the total permeability of tight specimens before and after hydraulic fracturing. It can directly measure permeability under the conditions of the true triaxial fracture propagation experiment. The comparative experimental result shows that the new technique can quantitatively evaluate the fracture propagation experiment of true triaxial hydraulic fracturing. The overall permeability and the directional permeability of the five faces were obtained, and the fracture propagation was evaluated by comparing the change in permeability. The test permeability error rate is within ±10%. Furthermore, a more refined evaluation of hydraulic fracturing fracture propagation can be carried out based on the fracture observation and AE event results. The research results provide a new strategy for a more quantitative and refined evaluation of fracture propagation and help to optimize the parameters of hydraulic fracturing., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Because of its advantages such as abundant resources, low cost, simple synthesis, and high electrochemical stability, cobalt phosphide (CoP) is considered as a promising candidate for electrocatalytic hydrogen evolution reaction. Through element doping, the morphology and electronic structure of the catalyst can be tuned, resulting in both the increase of the active site number and the improvement of the intrinsic activity of each site. Herein, we designed and fabricated Mn-doped CoP nanowires with a length of 3 μm, a diameter of 50 nm, and the pores between the grains of 10 nm. As a highly efficient electrocatalyst for alkaline hydrogen evolution, the Mn 10 -doped CoP/NF (doping amount is about 10 atom %) electrode presented overpotentials of 60 mV @ 10 mA cm -2 and 112 mV @ 100 mA cm -2 , improved by 35 and 23%, respectively, compared with CoP/NF. Characterizations indicate that Mn doping increases the electrochemical active area, reduces the impedance, and tunes the electronic structure of the material. Density functional theory calculations also revealed that an appropriate amount of Mn dopant at a suitable location can both react as an active site itself and boost the activity of the surrounding Co sites, delivering favorable H* adsorption and rapid reaction kinetics. This result may not only promote the development of hydrogen evolution reaction catalysts but also encourage explorations of the relationship between the property and fine doping structure.

Triboelectric nanogenerators (TENGs) have shown huge application potential in the fields of micro-nano energy harvesting and multifunctional sensing. However, the damage of triboelectric material is one of the challenges for their practical applications. Herein, we fabricated a flexible TENG employing self-healing hydrogel and fluorinated ethylene propylene film as triboelectric materials for mechanical energy harvesting and pressure monitoring. The prepared hydrogel not only has excellent flexibility, transparency, and self-healing property but also exhibits good mechanical property without plastic deformation and damage under a large stretchable strain of 200%. The output electric signals of TENGs are as high as 33.0 V and 3 μA under a contact frequency of 0.40 Hz and a pressure of 2.9 N, respectively, which can charge a capacitor of 0.22 μF to 24.3 V within 300 s. Note that the voltage retention rate of TENGs after self-healing is up to 88.0%. Moreover, hydrogel-based TENGs can act as a wearable pressure sensor for monitoring human motion, exhibiting a high sensitivity of 105.9 mV/N or 1.73 nA/N under a contact frequency of 0.40 Hz. This research provides a reference roadmap for designing TENGs and self-powered pressure sensors with flexibility, self-healing, and robustness., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The surge in air pollution and respiratory diseases across the globe has spurred significant interest in the development of flexible gas sensors prepared by low-cost and scalable fabrication methods. However, the limited breathability in the commonly used substrate materials reduces the exchange of air and moisture to result in irritation and a low level of comfort. This study presents the design and demonstration of a breathable, flexible, and highly sensitive NO 2 gas sensor based on the silver (Ag)-decorated laser-induced graphene (LIG) foam. The scalable laser direct writing transforms the self-assembled block copolymer and resin mixture with different mass ratios into highly porous LIG with varying pore sizes. Decoration of Ag nanoparticles on the porous LIG further increases the specific surface area and conductivity to result in a highly sensitive and selective composite to detect nitrogen oxides. The as-fabricated Ag/LIG gas sensor on a flexible polyethylene substrate exhibits a large response of -12‰, a fast response/recovery of 40/291 s, and a low detection limit of a few parts per billion at room temperature. Integrating the Ag/LIG composite on diverse fabric substrates further results in breathable gas sensors and intelligent clothing, which allows permeation of air and moisture to provide long-term practical use with an improved level of comfort.

Tyrosine kinases (TKs) are prominent targets in cancer therapies, and more than 30 TK inhibitors have been approved for treatments in tumors with abnormal TK. Disappointingly, an incomplete response can occur with the long-term use of TK inhibitors, known as cancer drug resistance, which can be caused by kinome reprogramming. Hence, monitoring the status of TKs is crucial for revealing the underlying drug resistance mechanism. Here, we describe a TK activity-representing peptide library-based multiple reaction monitoring (TARPL-MRM) strategy for directly inferring TK activities. The strategy facilitated the assay of 87 human TKs through target quantification of 301 phosphorylation sites. Using this strategy, we demonstrated the heterogeneity of TK activity in different non-small cell lung cancer (NSCLC) cell lines and assessed the response of TK activities to the EGFR inhibitor AZD9291 in NSCLC cells. We found that the acquired resistance of H1975 cells to AZD9291 requires SRC activity, and inhibition of SRC plays potential roles in overcoming this resistance. In summary, our work reveals that this strategy has the potential to become a powerful tool for TK studies, clinical diagnostics, and the discovery of new therapeutic targets.

Herein, we report the development of the photocatalytic C-H functionalization of methane, ethane, and heavier gaseous alkanes with good yields and selectivity, broad scope (57 examples), mild conditions, and low cost. Kinetics and density functional theory calculations were investigated for the key photoinduced ligand-to-metal charge transfer and hydrogen atom transfer processes to reveal the detailed mechanism of iron photocatalysis. This work may bring novel ideas for feedstock upgrading and catalyst design.

By adjusting the structure of vanadium oxides, their electrochemical performances as cathode materials for aqueous rechargeable zinc-ion batteries (ARZIBs) can be improved effectively. Due to the layered structure and high specific capacity of V 2 O 5 , many guests (like metal ions and conducting polymers) intercalated and regulated the structure to enhance its electrochemical properties. Polypyrrole (PPy) has attracted people's attention due to its good conductive ability. However, the intercalation of PPy into a lamellar structure of hydrated V 2 O 5 (VOH) has rarely been achieved as a cathode material for ARZIBs. Herein, we developed a pyridinesulfonic acid (PSA)-assisted approach to intercalate PPy into the interplanar spacing of VOH under acidic conditions, and the sample is denoted as VOH-PPy (PSA). The presence of protic acid can improve the electrical conductivity of the polymer and enhance the oxidation of VOH, making the polymerization of pyrrole easier. Furthermore, the nitrogen-containing groups in PSA can interact with vanadium to further expand the layer space of VOH, and the sulfonic groups can facilitate the polymerization of pyrrole. The addition of the PSA results in an ultralarge interlayer spacing of 15.8 Å. VOH-PPy (PSA) delivers an excellent specific capacity of up to 422 mAh·g -1 at 0.1 A·g -1 and a stable cycle performance of 165 mAh·g -1 after 5000 cycles at 10 A·g -1 . This work not only realizes PPy expanding the lamellar structure of VOH but also provides feasibility for improving the electrochemical properties of VOH as a cathode material for ARZIBs by intercalating conductive polymers.

Cuprous clusters are well known for their important fluorescent properties and tunable redox behavior, but the coordinated protecting groups restrict their application in photocatalysis, in particular, the inner-sphere activation of substrates. By modifying fluorescent cuprous clusters with terminal iodides into two-dimensional coordination sheets, we report a photocatalytic regulator to synergistically combine electron transfer and energy transfer for the oxidative coupling of benzoquinone and terminal alkynes. Under visible light irradiation, the well-modified excited state of the cuprous clusters in the coordination sheets reduces benzoquinones to generate aoxy radicals through electron transfer and activates oxygen through energy transfer. The aoxy radicals interact with copper-coordinated phenylacetylene to form an active intermediate, which is further oxidized by the in situ formed active oxygen species and aryl ketones are obtained. The warranted potential of the excited coordination sheets enables the reductive activation of thianthrenium salts as radical precursors, facilitating radical capture and further C-N coupling via an inner-sphere activation mechanism. The new catalytic approach optimizes the redox properties and excited-state lifetime, shortens the electron transfer steps, and promotes the potential collision of a low concentration of active species in tandem catalytic cycles, thus paving a new way to develop ecologically benign, cost-effective, multipurpose, and flexible catalytic systems.