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Keywords: Impact resistance; Molecular granular materials; Relaxation dynamics; Sub-nanoscale particle; Topological interaction EN Impact resistance Molecular granular materials Relaxation dynamics Sub-nanoscale particle Topological interaction 1 1 1 05/18/23 20230516 NES 230516 B Recent advances in b molecular granular materials (MGMs) which are assembled from molecular cluster (MC) units have been systematically reviewed from both molecular mechanisms and application aspects. Impact resistance, Molecular granular materials, Relaxation dynamics, Sub-nanoscale particle, Topological interaction The hierarchical structural dynamics endow MGMs with unique mechanical properties including tunable viscoelasticity and impact-resistant capacity. [Extracted from the article]

Herein, a rational design of "cobalt/cobalt oxide/cobalt molybdate/nickel foam" multi-hierarchical tandem type electrocatalyst was achieved, where in situ reduced Co and CoO nanoparticles were dispersed uniformly and stabilized by CoMoO 3 cuboids. This novel tandem type structure enables strong hydroxyl adsorption on CoO and moderated hydrogen adsorption on Co and therefore promotes the dissociation of water and the recombination of hydrogen intermediates into molecular hydrogen, respectively, and both act synergistically to catalyze the HER reaction. As a result, the current densities were up to 1.3 A cm−2 at only 173 mV overpotential in 1.0 M KOH and 379 mV in 1.0 M PBS solution, respectively. The high rate H 2 production of 4.35 ml min−1 at − 1.18 V (vs. SCE) and the outstanding performance of 10 A lasting for more than 800 h in a MEA electrolyzer both indicate the prospect for the usage in practical. [Display omitted] • The special multi-hierarchical tandem type electrocatalyst Co/CoO/CoMoO 3 was designed. • Co/CoO/CoMoO 3 exhibited low overpotentials to reach 1.3 A cm−2 in alkaline and neutral media, with excellent long-term stability of 400 h. • DFT calculation and methanol probe demonstrate that the CoO is more qualified to adsorb OH* while Co to adsorb H* to promote the water dissociation and hydrogen generation. [ABSTRACT FROM AUTHOR]

Fe incorporated Ni-based electrocatalysts have emerged as one of the most active oxygen-evolving catalysts under alkaline conditions and deciphering the effect of iron incorporation in enhancing the activity is challenging but critical for the catalyst design. Herein, the as-prepared nanocube Ni-based catalysts underwent a reconstruction process and transformed from γ-NiOOH to β-NiOOH structure by iron incorporation under the applied bias, which was confirmed by in-situ Raman measurement. According to the methanol oxidation current response difference, the hydroxyl adsorption intensity was proposed to be regulated by iron incorporation and the rate-determining step would be the formation of *OOH for Fe-doped β-NiOOH, which was further supported by DFT calculation. This work reveals the effect of iron-doped on the phase structure transform and the regulation of intermediate species elaborately and offers new insight on the understanding of the activity origins for NiFe-based catalysts. [Display omitted] • Potential-induced reconstruction process from γ-NiOOH to β-NiOOH structure by iron incorporation under applied bias. • The Fe-doped β-NiOOH exhibited an overpotential of 247 mV at 10 mA·cm−2 and a Tafel slope of 40.15 mV·dec−1. • The surface coverage of *OH varies in the trend: NiOOH > Fe-doped β-NiOOH > FeOOH. [ABSTRACT FROM AUTHOR]

Transition metal dichalcogenides (TMDs) have recently attracted substantial attention due to their potential application in the catalysis of the hydrogen evolution reaction (HER). In this study, triangular WSe2 and W(SexS1−x)2 nanoflakes uniformly dispersed on the surface of electrospun carbon nanofiber mats were synthesized in a chemical vapor deposition (CVD) system. The morphology and structure of these products were systematically characterized, revealing that WSe2 nanoflakes are configured in the 2H phase with high crystallinity, and the W(SexS1−x)2 nanoflakes are configured in the alloy form without any obvious phase separation. The hybrid catalyst mats were directly used as hydrogen evolution cathodes to investigate their HER activity. Excellent HER performances, including low overpotential, high current density and long-term stability, were achieved by optimizing the content of the initial W precursor and the appropriate substitution of selenium with sulfur, which resulted from the appropriate cover density and thickness of the WSe2 nanoflakes and the defective structure of the W(SexS1−x)2 nanoflakes. [ABSTRACT FROM AUTHOR]

Non-neurogenic cell types, such as cortical astroglia and fibroblasts, can be directly converted into neurons by the overexpression of defined transcription factors. Normally, the cellular phenotype of such differentiated cells is remarkably stable and resists direct cell transdifferentiation. Here we show that the Ink4a/Arf (also known as Cdkn2a) locus is a developmental barrier to direct neuronal transdifferentiation induced by transcription factor overexpression. With serial passage in vitro, wild-type postnatal cortical astroglia become progressively resistant to Dlx2-induced neuronal transdifferentiation. In contrast, the neurogenic competence of Ink4a/Arfdeficient astroglia is both greatly increased and does not diminish through serial cell culture passage. Electrophysiological analysis further demonstrates the neuronal identity of cells induced from Ink4a/Arf-null astroglia, and short hairpin RNA-mediated acute knockdown of p16Ink4a and p19Arf p16Ink4a and p19Arf indicates that these gene products function postnatally as a barrier to cellular transdifferentiation. Finally, we found that mouse fibroblasts deficient for Ink4a/Arf also exhibit greatly enhanced transcription factorinduced neuronal induction. These data indicate that Ink4a/Arf is a potent barrier to direct neuronal transdifferentiation and further suggest that this locus functions normally in the progressive developmental restriction of postnatal astrocytes. [ABSTRACT FROM AUTHOR]

Preterm birth is the second most common cause of death in children under 5 years of age. The etiology of preterm birth has not yet been elucidated. Although maternal exposure to endocrine disrupting chemicals (EDCs) may increase the risk for preterm birth, associations have not been confirmed. We performed a meta-analysis to elucidate the relationships between maternal exposure to EDCs and preterm birth. A systematic search of PubMed, Ovid-EMBASE, and the Cochrane Library (CENTRAL) for relevant published studies providing quantitative data on the association between maternal EDC exposure and preterm birth in humans was conducted in July 2021. To calculate the overall estimates, we pooled the adjusted regression coefficients with 95% confidence intervals (CIs) from each study by the inverse variance method. A total of 59 studies were included. The pooled results indicated that maternal exposure to metals (OR, 1.23; 95% CI, 1.17 to 1.29) and phthalates (OR, 1.31; 95% CI, 1.21 to 1.42) was related to an increased risk for preterm birth. Specifically, maternal exposure to lead, cadmium, chromium, copper and manganese appeared to be correlated with an elevated risk for preterm birth. Additionally, maternal exposure to monoethyl phthalate (MEP), mono-2-ethyl-5-carboxypentyl phthalate (MECPP), monobenzyl phthalate (MBzP), and di (2-ethylhexyl) phthalate (DEHP) was also associated with preterm birth. In conclusion, maternal exposure to metals and phthalates may increase the risk for preterm birth based on current evidence. [Display omitted] • Associations between maternal EDC exposure and preterm birth have not been clarified. • Maternal EDC exposure may be associated with an increased risk for preterm birth. • Maternal exposure to phthalates and metals may increase the risk for preterm birth. [ABSTRACT FROM AUTHOR]

[Display omitted] • Electrochemical activation was employed to prepare Pt/PtTe x heterojunctions. • CV method and DFT calculation both reveal the change of intermediates adsorption. • Pt/PtTe x interface structure reduces H* adsorption and enhances OH* adsorption. • Pt/PtTe x NRs show significantly improved acidic and alkaline HER activity. Increasing OH* adsorption to promote water dissociation while reducing H* adsorption to accelerate hydrogen generation kinetics is an effective solution to further improve the HER activity of Pt-based catalysts. Herein, we have successfully constructed a Pt/PtTe x heterogeneous catalysis interface by electrochemical activation of PtTe 2 nanorods (NRs). The reduction of H* adsorption and significant increase of OH* adsorption was observed on Pt/PtTe x heterojunction via cyclic voltammetry method. Theoretical calculations indicate that Gibbs free energy change (ΔG) of H* is closer to 0.00 eV and ΔG of OH* decreased from 1.36 eV of Pt (111) to −0.40 eV of Pt/PtTe x , which reinforces the experimental results. The rational modulation of adsorbed intermediates endows Pt/PtTe x NRs with exceptionally lower Tafel slopes of 16 and 23 mV dec−1 in 0.5 M H 2 SO 4 and 1.0 M KOH electrolytes, which is among the best reported HER electrocatalysts. [ABSTRACT FROM AUTHOR]

Glutathione S-transferases (GSTs) are members of a protein superfamily with diverse physiological functions, including cellular detoxification and protection against oxidative damage. However, there is limited research on GSTs responding to cadmium (Cd) stress. This study classified 46 GST genes in Dendrobium officinale (D. officinale) into nine groups using model construction and domain annotation. Evolutionary analysis revealed nine subfamilies with diverse physical and chemical properties. Prediction of subcellular localization revealed that half of the GST members were located in the cytoplasm. According to the expression analysis of GST family genes responding to Cd stress, DoGST5 responded significantly to Cd stress. Transient expression of DoGST5-GFP in tobacco leaves revealed that DoGST5 was localized in the cytoplasm. DoGST5 overexpression in Arabidopsis enhanced Cd tolerance by reducing Cd-induced H2O2 and O2− levels. These findings demonstrate that DoGST5 plays a critical role in enhancing Cd tolerance by balancing reactive oxygen species (ROS) levels, offering potential applications for improving plant adaptability to heavy metal stress. [ABSTRACT FROM AUTHOR]

High‐quality epitaxial graphene is prepared on semi‐insulated 4H‐SiC (0001) by ultra‐high vacuum thermal decomposition method and used in graphene/SiC/graphene ultraviolet‐visible dual‐band photodetectors. The dual‐band detector exhibits an extremely low dark current (5.2 × 10−14 A) and a peak responsivity of 1.17 A W−1 corresponding to an external quantum efficiency of 518%. A high detectivity of 3.14 × 1014 Jones is achieved under 280 nm light illumination at 30 V, while a high response speed is obtained with a rise time of 25.17 ns and a decay time of 540.10 ns. The detector shows a responsivity of 1.4 × 10−5 A W−1 and a detectivity of 6.5 × 109 Jones under 430 nm light illumination. The dual‐band detector equipped with SiC grating and asymmetrical graphene electrodes is demonstrated for high‐performance optoelectronic logic "AND" gate with high detectivity at 280 and 430 nm. [ABSTRACT FROM AUTHOR]

[Display omitted] • Plasmon-enhanced fluorescence-Raman scattering (PEF-SERS) sensors are reviewed. • Signal enhancement mechanisms for fluorescence/Raman probes are explained. • Construction strategies for plasmonic enhancement substrates are highlighted. • Several signal readout modes and advanced practical applications are overviewed. • The present challenges and perspectives are proposed. Plasmonic nanomaterials could improve various optical performance including fluorescence emission, Raman scattering, infrared absorption, etc. Among them, plasmon-enhanced fluorescence (PEF) can realize high-sensitivity sensing and super-resolution imaging quickly, but with inferior multiplexed detection capability. Surface-enhanced Raman scattering (SERS) can offer fingerprint-like spectra for multiplexing, but its imaging speed and resolution are limited. The PEF-SERS integrated sensors could congregate their individual strengths while overcoming inherent weaknesses. Specifically, they can use fluorescence signals to rapidly screen out "suspicious" locations within numerous samples or a broad area, and then conduct multi-peak SERS measurements there to gather more detailed information. Besides, cross-verification of PEF and SERS results is possible to realize self-correction. Hence, many existing issues could be addressed including sensitivity, accuracy, speed, and multiplexing. Attracted by these superior advantages, we review here the interaction between plasmonic nanomaterials and fluorescence/Raman probes to explain enhancement mechanisms, the construction strategies for plasmonic substrates with better PEF-SERS performance, different modes for transforming analyte's information into measurable optical signals, as well as the main application in substance research, disease diagnosis, cell imaging, drug delivery. We believe, a deeper understanding of the state-of-arts of multifunctional plasmonic platforms could provide a generic guideline for their future development and practical application. [ABSTRACT FROM AUTHOR]

[Display omitted] Adavosertib (ADA) is a WEE1 inhibitor that exhibits a synthetic lethal effect on p53-mutated gallbladder cancer (GBC). However, drug resistance due to DNA damage response compensation pathways and high toxicity limits further applications. Herein, estrone-targeted ADA-encapsulated metal–organic frameworks (ADA@MOF-EPL) for GBC synthetic lethal treatment by inducing conditional factors are developed. The high expression of estrogen receptors in GBC enables ADA@MOF-EPL to quickly enter and accumulate near the cell nucleus through estrone-mediated endocytosis and release ADA to inhibit WEE1 upon entering the acidic tumor microenvironment. Ultrasound irradiation induces ADA@MOF-EPL to generate reactive oxygen species (ROS), which leads to a further increase in DNA damage, resulting in a higher sensitivity of p53-mutated cancer cells to WEE1 inhibitor and promoting cell death via conditional synthetic lethality. The conditional factor induced by ADA@MOF-EPL further enhances the antitumor efficacy while significantly reducing systemic toxicity. Moreover, ADA@MOF-EPL demonstrates similar antitumor abilities in other p53-mutated solid tumors, revealing its potential as a broad-spectrum antitumor drug. [ABSTRACT FROM AUTHOR]

The ability to differentiate stimuli that predict fear is critical for survival; however, the underlying molecular and circuit mechanisms remain poorly understood. We combined transgenic mice, in vivo transsynaptic circuit-dissecting anatomical approaches, optogenetics, pharmacological methods, and electrophysiological recording to investigate the involvement of specific extended amygdala circuits in different fear memory. We identified the projections from central lateral amygdala (CeL) protein kinase C δ (PKCδ)–positive neurons and somatostatin (SST)-positive neurons to GABAergic (gamma-aminobutyric acidergic) and glutamatergic neurons in the ventral part of the bed nucleus of stria terminalis (vBNST). Prolonged optogenetic activation or inhibition of the PKCδCeL-vBNST pathway specifically reduced context fear memory, whereas the SSTCeL-vBNST pathway mainly reduced tone fear memory. Intriguingly, optogenetic manipulation of vBNST neurons that received the projection from PKCδCeL neurons exerted bidirectional regulation of context fear, whereas manipulation of vBNST neurons that received the projection from SSTCeL neurons could bidirectionally regulate both context and tone fear memory. We subsequently demonstrated the presence of δ and κ opioid receptor protein expression within the CeL-vBNST circuits, potentially accounting for the discrepancy between prolonged activation of GABAergic circuits and inhibition of downstream vBNST neurons. Finally, administration of an opioid receptor antagonist cocktail on the PKCδCeL-vBNST or SSTCeL-vBNST pathway successfully restored context or tone fear memory reduction induced by prolonged activation of the circuits. Together, these findings establish a functional role for distinct CeL-vBNST circuits in the differential regulation and appropriate maintenance of fear. [ABSTRACT FROM AUTHOR]

Cost‐effective, non‐fluorinated polymer proton exchange membranes (PEMs) are highly desirable in emerging hydrogen fuel cells (FCs) technology; however, their low proton conductivities and poor chemical and dimension stabilities hinder their further development as alternatives to commercial Nafion®. Here, we report the inorganic‐organic hybridization strategy by facilely complexing commercial polymers, polyvinyl butyral (PVB), with inorganic molecular nanoparticles, H3PW12O40 (PW) via supramolecular interaction. The strong affinity among them endows the obtained nanocomposites amphiphilicity and further lead to phase separation for bi‐continuous structures with both inter‐connected proton transportation channels and robust polymer scaffold, enabling high proton conductivities, mechanical/dimension stability and barrier performance, and the H2/O2 FCs equipped with the composite PEM show promising power densities and long‐term stability. Interestingly, the hybrid PEM can be fabricated continuously in large scale at challenging ~10 μm thickness via typical tape casting technique originated from their facile complexing strategy and the hybrids' excellent mechanical properties. This work not only provides potential material systems for commercial PEMs, but also raises interest for the research on hybrid composites for PEMs. [ABSTRACT FROM AUTHOR]

Exogenous variables, unrelated to the recommendation system itself, can significantly enhance its performance. Therefore, integrating these time-evolving exogenous variables into a time series and conducting time series predictions can maximize the potential of recommendation systems. We refer to this task as Time Series Prediction Empowering Recommendations (TSPER). However, as a subtask within the recommendation system, TSPER faces unique challenges such as computational and data constraints, system evolution, and the need for performance and interpretability. To meet these unique needs, we propose a lightweight Multi-Layer Perceptron architecture with joint Time-Frequency information, named Light All-MLP with joint TimE-frEquency information (LAMEE). LAMEE utilizes a lightweight MLP architecture to achieve computing efficiency and adaptive online learning. Moreover, various strategies have been employed to improve the model, ensuring stable performance and model interpretability. Across multiple time series datasets potentially related to recommendation systems, LAMEE balances performance, efficiency, and interpretability, overall surpassing existing complex methods. [ABSTRACT FROM AUTHOR]

Summary In the developing human neocortex, progenitor cells generate diverse cell types prenatally. Progenitor cells and newborn neurons respond to signaling cues, including neurotransmitters. While single-cell RNA sequencing has revealed cellular diversity, physiological heterogeneity has yet to be mapped onto these developing and diverse cell types. By combining measurements of intracellular Ca2+ elevations in response to neurotransmitter receptor agonists and RNA sequencing of the same single cells, we show that Ca2+ responses are cell-type-specific and change dynamically with lineage progression. Physiological response properties predict molecular cell identity and additionally reveal diversity not captured by single-cell transcriptomics. We find that the serotonin receptor HTR2A selectively activates radial glia cells in the developing human, but not mouse, neocortex, and inhibiting HTR2A receptors in human radial glia disrupts the radial glial scaffold. We show highly specific neurotransmitter signaling during neurogenesis in the developing human neocortex and highlight evolutionarily divergent mechanisms of physiological signaling. Graphical Abstract Highlights • Multimodal analysis differentiates cells beyond transcriptomic classification • Single-cell analysis links stimulus-induced calcium elevations to transcriptomes • Cell-type-specific responses to neurotransmitters are associated with maturation • Serotonergic signaling in human radial glia promotes radial fiber formation Mayer et al. develop a microfluidics-based approach that links calcium imaging and single-cell transcriptomics to study cellular responses to neurotransmitters in the developing human neocortex. They reveal dynamically changing response profiles as progenitor cells differentiate to diverse types of neurons. [ABSTRACT FROM AUTHOR]

Invertase is the key enzyme involved in several crucial biological processes by hydrolyzing sucrose for production of glucose and fructose. Invertase plays important roles in the fields of food, pharmacy, cosmetics, biofuels, and agriculture. Detection of invertase activity is urgently necessary for scientific research and industrial processes. Herein, a continuous fluorometric method was developed for real-time detection of invertase activity. 8-Isoquinolinylboronic acid responded to fructose by formation of a fluorescent complex in turn-on manner, and served as a fluorescent sensor to selectively recognize fructose in ternary enzymatic mixture containing sucrose and glucose. The limit of detection (LOD) for fructose was 0.07 mM. Progress curve for fructose production was established by directly and continuously monitoring the fluorescence for invertase reaction with sucrose as substrate. Initial velocity was obtained to characterize invertase activity. LOD for invertase assay was 0.10 U·mL−1. Km and υmax for invertase were determined as 7.70 mM and 0.86 mM·min−1, respectively. Copper ion was demonstrated to inhibit the invertase activity with IC50 of 33.61 mM. Applicability in high-throughput screening for inhibitor was demonstrated. The proposed method allows for real-time, simple, and rapidly monitoring the invertase activity. It has a broad range of potential applications for kinetics and screening inhibitor. [ABSTRACT FROM AUTHOR]

Supplemental Digital Content is Available in the Text. An ACVR1 activating mutation causes heat and mechanical pain hypersensitivity and induces sensory neuron hyperexcitability in humans. Altered bone morphogenetic protein (BMP) signaling is associated with many musculoskeletal diseases. However, it remains unknown whether BMP dysfunction has direct contribution to debilitating pain reported in many of these disorders. Here, we identified a novel neuropathic pain phenotype in patients with fibrodysplasia ossificans progressiva (FOP), a rare autosomal-dominant musculoskeletal disorder characterized by progressive heterotopic ossification. Ninety-seven percent of these patients carry an R206H gain-of-function point mutation in the BMP type I receptor ACVR1 (ACVR1R206H), which causes neofunction to Activin A and constitutively activates signaling through phosphorylated SMAD1/5/8. Although patients with FOP can harbor pathological lesions in the peripheral and central nervous system, their etiology and clinical impact are unclear. Quantitative sensory testing of patients with FOP revealed significant heat and mechanical pain hypersensitivity. Although there was no major effect of ACVR1R206H on differentiation and maturation of nociceptive sensory neurons (iSNs) derived from FOP induced pluripotent stem cells, both intracellular and extracellular electrophysiology analyses of the ACVR1R206H iSNs displayed ACVR1-dependent hyperexcitability, a hallmark of neuropathic pain. Consistent with this phenotype, we recorded enhanced responses of ACVR1R206H iSNs to TRPV1 and TRPA1 agonists. Thus, activated ACVR1 signaling can modulate pain processing in humans and may represent a potential target for pain management in FOP and related BMP pathway diseases. [ABSTRACT FROM AUTHOR]

Delicate construction of sophisticated bimetallic nanostructures provides a favorable way to boost the efficiency of bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which is critical to the fabrication of rechargeable Zn-air batteries. Herein, hetero-structured Cu/Co 93 Cu 7 nanoparticles confined inside N-doped carbon nanocages (denoted as Cu/Co 93 Cu 7 @NC NCs) are fabricated through a facile "MOF-in situ-reduction and in situ-growth-MOF" strategy. Benefiting from the unique hollow architecture and superior intrinsic activity of the optimized interfaces, the as-prepared catalyst displays an appealing electrocatalytic performance including a positive half-wave potential (E 1/2) of 0.88 V for ORR and a low OER overpotential of 262 mV at 10 mA cm−2. Theoretical calculations further disclose the key role of the rationally designed Co/Cu/N-doped carbon heterostructures, which significantly reduces the energy barrier for *OOH formation and eventually promotes the ORR. Rechargeable Zn-air batteries assembled with the Cu/Co 93 Cu 7 @NC NCs exhibit a large specific capacity of 884.9 mAh g Zn −1 and a maximum power density of 225.9 mW cm−2. Moreover, the assembled batteries are stable for 1000 h during the long-term charge and discharge cycling, demonstrating the great promise for practical applications. [Display omitted] • An efficient Cu/Co 93 Cu 7 @NC NCs catalyst is designed for ORR and OER. • The hollow architecture enhances the electrocatalytic kinetics. • DFT verifies that N–C, Cu and Co cooperatively improve the intrinsic activity. • The as-assembled Zn-air batteries exhibit excellent activity and durability. [ABSTRACT FROM AUTHOR]

Surfactants occupy a prominent place in the domestic and industrial fields. Amino acid surfactants have attracted attention as alternatives to petrochemical-based surfactants owing to their good biocompatibility and biodegradability. Conventional amino acid surfactants with structures having only acyl linkages lack multifunctionality. Therefore, novel amino acid surfactants must be developed to achieve this feature. Inspired by melanogenesis, the biomimetic synthesis of melanin-like amino acid surfactants with structures similar to that of melanin was conceived. Natural polyphenols with catechol moieties serve as building blocks for hydrophobic moieties. As a proof-of-concept, caffeic acid phenethyl ester was oxidized to o- quinone using periodate resin. Melanin-like amino acid surfactants were synthesized by conjugating amino acids to o -quinones via Michael addition and Schiff base reactions. The structure was confirmed by mass spectrometry. Melanin-like amino acid surfactants have outstanding surface activity with a low critical micelle concentration and excellent capacity for foaming, emulsifying, dispersing, wetting, and solubilizing. Melanin-like amino acid surfactants exhibit low skin irritation, as well as high tolerance to ions and pH. The utilization of polyphenols introduces multifunctionality, affording antioxidant, antibacterial and whitening activities. This study proposes a modular strategy for fabricating new and multifunctional amino acid surfactants that mimic melanin by simply replacing the o -quinone building block. This biomimetic synthesis route is a sustainable process for the green production of amino acid surfactants. This new generation of amino acid surfactants will contribute to meeting the increasing demand for multifunctional surfactants in both academia and industry. [Display omitted] • Novel structure similar with melanin by N-quinonyl linkage. • Biomimetic synthesis route by Michael addition inspired from melanogenesis. • Multifunctionality from natural polyphenols, antioxidant and antibacterial activity. • Modular toolbox by changing the o-quinone building block. • Superior performance on foaming, emulsifying, solubilizing, and dispersing capacity. [ABSTRACT FROM AUTHOR]

A bifunctional Co 2 (OH) 3 Cl/FeOOH electrode used in a 10*10 cm2 membrane electrode assembly for a cyclohexanone production rate of 3.44 g/h and electricity saved about 0.24 kWh/m3 (H 2). The carbon free-radical reaction pathways for cyclohexanol electrooxidation on CoII/CoIII redox active species was elaborately elucidated. [Display omitted] • A voltage of 1.46 V at 10 mA·cm−2 was required for H 2 and CXO product. • In-situ measurements and DFT calculations elucidated the synergistic effect. • Carbon free-radical pathway for CXL oxidation on CoII/CoIII redox active species. • A CXO yield was 3.44 g/h and electricity saved about 0.24 kWh/ m3 (H 2) in MEA. Replacing oxygen evolution reaction with the more thermodynamically favorable organics oxidation reaction is crucial to reduce the required voltage of overall water splitting. Herein, Co 2 (OH) 3 Cl/FeOOH nanosheets are served as both cathode and anode for the concurrent high purity hydrogen generation and high value-added cyclohexanone productions. Thanks to the wondrous synergistic effect between Co 2 (OH) 3 Cl and FeOOH, for Co 2 (OH) 3 Cl acted as the optimal catalytic sites for cyclohexanol oxidization and FeOOH accelerated the reaction rates by reducing the charge transfer resistance, the two-electrode configuration only required a voltage as low as 1.46 V at 10 mA·cm−2 for cathode H 2 and anode cyclohexanone. Moreover, by further scaling up the configuration into the 10*10 cm2 anion membrane electrode assembly reactor, a cyclohexanone production rate of 3.44 g/h and the electricity saved about 0.24 kWh/ m3 (H 2) were achieved. In addition, the reaction pathways, the C–H bond cleaves first, and then the intermediate carbon free radical is dehydrogenated to generate cyclohexanone on CoII/CoIII redox, was elucidated elaborately. This work offers an approach to actuate effective transformation of organics with high selectivity and industrial practicability under ambient conditions powered by renewable energy. [ABSTRACT FROM AUTHOR]

The electron-rich interface of Cu-Co heterostructure nanoparticle an realize the effective separation of photogenerated charge and hole, accelerate the transfer of photogenerated charges, which is a stable and efficient cocatalyst for photocatalytic hydrogen evolution reaction. [Display omitted] • Carbon-coated Cu-Co alloy nanoparticles (CuCo@C) nanoparticles are fabricated. • The bimetallic CuCo has a heterogeneous structure with abundant Cu-Co interfaces. • A large number of photogenerated electrons can be collected at the Cu-Co interface. • The CuCo@C is a high-performance cocatalyst for photocatalytic H 2 evolution. Heterogeneous nano-metal structures are widely used in the field of photocatalysis as an efficient cocatalyst, but the structure–activity relationship has not been elucidated clearly. In this work, a classical CuCo@C nanoparticle with a core of bimetallic CuCo and a carbon shell was used as a cocatalyst to explore and reveal the mechanism of interfacial effect for enhanced photocatalytic hydrogen evolution. It was found that the bimetallic CuCo had a heterogeneous structure with abundant Cu-Co interfaces. The desirable visible-light-driven photocatalytic hydrogen evolution rate of CuCo@C/g-C 3 N 4 was much higher than that of Cu@C/g-C 3 N 4 , Co@C/g-C 3 N 4 , and superior to that of the control group loaded with 1 wt% Pt (Pt/g-C 3 N 4). According to the experimental characterizations and density functional theory calculations, electrons were enriched at the Cu-Co interface, which can promote the electron-hole pairs separation and accelerate charge transfer of the g-C 3 N 4 host photocatalysts. On the other hand, the surface carbon layer and Cu-Co interface modulated the H adsorption free energy on the CuCo@C, which was favorable for hydrogen evolution. It is conceivable that further investigating and tuning different metal interfaces will facilitate the large-scale application of bimetallic cocatalysts. [ABSTRACT FROM AUTHOR]

Promoting the self-reconstruction of NiFe-based catalysts represents a promising approach to facilitate seawater splitting, albeit with significant challenges. Herein, the redox cycle of Ni species is subtly regulated by decorating NiFe hydroxides with vanadium. Both experimental and theoretical studies demonstrate that the incorporation of V boosts the self-reconstruction of NiFe hydroxides and allows a superior OER performance on account of diminished propensity for chlorine adsorption and optimized binding energy of oxygen-containing intermediates. Consequently, the NiFeV/NF catalyst delivers 2.0 A cm−2 at an ultralow overpotential of 369 mV in 1.0 M KOH and exhibits exceptional stability for 720 h at 20 A in an alkaline membrane electrode assembly (MEA) electrolyzer. In alkaline seawater, it achieves prolonged stability, surpassing 240 h at 500 mA cm−2 with OER selectivity of 99 %. This work significantly advances the field of seawater electrolysis powered by marine renewables, paving the way for on-site hydrogen production. [Display omitted] • The redox cycle of Ni species is subtly regulated by decorating NiFe hydroxides with vanadium. • The incorporation of V diminishes the propensity of Cl− adsorption and optimizes the absorption of oxygen-containing species. • The NiFeV/NF delivers 2.0 A cm−2 at an overpotential of 369 mV and exhibits exceptional stability for 720 h at 20 A. • Deciphering the contributions of Cl* and OH* to the activity of seawater oxidation. [ABSTRACT FROM AUTHOR]

Marine algal toxin contamination is a major threat to human health. Thus, it is crucial to develop rapid and on-site techniques for detecting algal toxins. In this work, we developed colorimetric cloth and paper hybrid microfluidic devices (μCPADs) for rapid detection of gonyautoxin (GTX1/4) combined with molecularly imprinted polymers. In addition, the metal-organic frameworks (MOFs) composites were applied for this approach by their unique features. Guanosine serves as a dummy template for surface imprinting and has certain structural advantages in recognizing gonyautoxin. MOF@MIPs composites were able to perform a catalytic color reaction using hydrogen peroxide-tetramethylbenzidine for the detection of GTX1/4. The cloth-based sensing substrates were assembled on origami μPADs to form user-friendly, miniaturized colorimetric μCPADs. Combined with a smartphone, the proposed colorimetric μCPADs successfully achieved a low limit of detection of 0.65 μg/L within the range of 1–200 μg/L for rapid visual detection of GTX1/4. Moreover, the GTX1/4 of real shellfish and seawater samples were satisfactorily detected to indicate the application prospect of the μCPADs. The proposed method shows good potential in the low-cost, stable establishment of assays for the rapid detection of environmental biotoxins. [Display omitted] • We propose a colorimetric strategy using the imprinted MOFs on cloth and μPADs. • The cloth-based substrates support long-term stirring and soaking for fabrication. • The μCPADs show high sensitivity and selectivity for detecting gonyautoxin 1/4. • The μCPADs can achieve rapid visual detection of gonyautoxin 1/4 by a smartphone. [ABSTRACT FROM AUTHOR]

This study aimed to investigate the effect of dissolution medium on dissolutions of pH dependent nanocrystals and solubilizer related nanocrystals by using sink conditions and non-sink conditions. Indomethacin and meloxicam were tested in different pH buffers. It is difficult to recognize the dissolution difference in sink conditions between two different particle sizes (a difference of around 100 nm) due to the fast action of pH and size. Effects of quercetin size and polysorbate (solubilizer in the media) on dissolution were statistically investigated. Dissolution could be divided into two-phases under non-sink conditions. Phase I: a fast dissolution phase (smaller particle sizes led to higher dissolution values); Phase II: residual nanocrystals further slowly dissolved to achieve an equilibrium if polysorbate was high concentration (smaller particle sizes led to faster achievement of saturation solubility). Effect of size on dissolution would become insignificant, when polysorbate was high in non-sink conditions or in sink conditions. [Display omitted] • Dissolution pH dependent drug in PBS sink conditions significantly improved. • Polysorbate 80 as solubilizer altered the dissolution of quercetin nanocrystals. • Quercetin nanocrystals dissolved fast at first phase due to size and polysorbate. • Quercetin slowly dissolved in second phase get equilibrium if high polysorbate. • Effect of size on dissolution insignificant if sink conditions for all selected APIs. [ABSTRACT FROM AUTHOR]

Di(2-ethylhexyl) phthalate (DEHP) is a widely-used plasticizer and has long been recognized as an endocrine-disrupting chemical with male reproductive toxicities. DEHP exposure at the prepubertal stage may lead to extensive testicular injury. However, the underlying mechanisms remain to be elucidated. In the present study, we gavaged male C57BL/6 mice with different concentrations of DEHP (0, 250, and 500 mg/kg-bw·d) from postnatal day 22–35, and exposed TM3 Leydig cells with 0, 100, 200, 300, and 400 μM of MEHP (bioactive metabolite of DEHP) for 12–48 h. RNA sequencing was performed both in testicular tissue and TM3 cells. The results showed that DEHP disrupts testicular development and reduces serum testosterone levels in male prepubertal mice. Bioinformatic analysis and experimental verification have revealed that DEHP/MEHP induces cell cycle arrest in TM3 cells and increases apoptosis both in vivo and in vitro. Furthermore, the p53 signaling pathway was found to be activated upon DEHP/MEHP treatment. The inhibition of p53 by pifithrin-α significantly reduced MEHP-induced injuries in TM3 cells. Cumulatively, these findings revealed the involvement of the p53 signaling pathway in DEHP-induced prepubertal testicular injury by promoting cell apoptosis and inhibiting cell proliferation of Leydig cells. ga1 • Prepubertal DEHP exposure induces testicular maldevelopment and testicular dysfunction. • DEHP enhances apoptosis and activates the p53 signaling pathway in prepubertal testes. • MEHP promotes cell apoptosis and inhibits cell proliferation in immature Leydig cells. • Activation of p53 signaling pathway is involved in MEHP induced Leydig cell injury. [ABSTRACT FROM AUTHOR]

Self-assembled functional nanomaterials with electromagnetic hot spots are crucial and highly desirable in surface-enhanced Raman scattering (SERS). Due to its versatile biological scaffold, the M13 phage has been employed to produce novel nano-building blocks and devices. In this study, we propose a novel M13 phage-based SERS nanocarrier, that utilizes the pVIII capsid in M13 to conjugate Au@Ag core-shell nanorod (Au@AgNR) with linker carboxy-PEG-thiol (M13-Au@AgNR) and the pIII capsid to specifically target Escherichia coli (E. coli). The M13-Au@AgNR@DTTC (3,3′- diethylthiocarbocyanine iodide) SERS probe was used to detect E. coli in a concentration range of 6 to 6 × 105 cfu/mL, achieving a limit of detection (LOD) of 0.5 cfu/mL. The proposed SERS platform was also tested in real samples, showing good recoveries (92%–114.3%) and a relative standard deviation (RSD) of 1.2%–4.7%. Furthermore, the system demonstrated high antibacterial efficiency against E. coli , approximately 90%, as measured by the standard plate-count method. The investigation provides an effective strategy for in vitro bacteria detection and inactivation. [ABSTRACT FROM AUTHOR]

[Display omitted] • Defect-riched Pd 3 Pb bimetallic aerogels were prepared for the first time. • Pd 3 Pb bimetallic aerogels have excellent oxygen reduction reaction performance. • They effectively regulate the competitive adsorption of O 2 with CH 3 OH and CO. Palladium (Pd) plays a vital role in oxygen reduction reaction (ORR) for direct methanol fuel cells due to its excellent activity, but it still suffers from CO poisoning and low CH 3 OH tolerance. Herein, for the first time, the Pd 3 Pb bimetallic aerogels (BMAs) were synthesized by ionic liquid assisted strategy for boosting ORR performance. The Pd 3 Pb BMAs possess excellent ORR activity and anti-poisoning property in 0.1 M KOH and maintain their original ORR activity after 10,000 cycles even in poisoning circumstances, outperforming Pd metallic aerogels and the commercial Pd/C. Mechanism studies show that the strong interaction between Pd and Pb, as well as the abundant unsaturated sites of the Pd 3 Pb BMAs are beneficial to optimizing the adsorption and dissociation of intermediates during ORR, while suppressing the adsorption of CO and CH 3 OH. This work demonstrates a novel route to the rational development of excellent active and anti-poisoned ORR electrocatalysts based upon BMAs. [ABSTRACT FROM AUTHOR]

Achieving large current density is crucial to the practical application of large-scale hydrogen production by water splitting, but it is hindered by sluggish and unstable catalysts. Herein, a Pt-induced NiFe layered double hydroxide (Pt-NiFe LDH) nanosheet is synthesized for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). It affords 10 mA cm–2 at overpotentials of only 198 mV and 36 mV for OER and HER, respectively. Impressively, an alkali-electrolyzer (Pt-NiFe LDH || Pt-NiFe LDH) exhibits a stable cell voltage of 1.887 V to deliver a current density of 1000 mA cm–2 over 3000 h. The introduction of Pt modulates the electronic structure on the surface of NiFe LDH by charging redistribution at the interface and decreasing the Gibbs free energy change (ΔG) for the potential determining step (from *O to *OOH) during OER. This work provides a facile strategy for developing catalysts for large current density water splitting. [Display omitted] • The Pt-NiFe LDH obtains excellent HER/OER activity in alkaline medium. • The homemade alkaline electrolyzer operated at 1000 mA cm−2 for over 3000 h. • The density functional theory (DFT) reveals that the introduction of Pt clusters on NiFe LDH reduces the energy barrier of OER. [ABSTRACT FROM AUTHOR]

Di(2-ethylhexyl) phthalate (DEHP) early exposure leads to immature testicular injury, and we aimed to utilize single-cell RNA (scRNA) sequencing to comprehensively assess the toxic effect of DEHP on testicular development. Therefore, we gavaged pregnant C57BL/6 mice with 750 mg/kg body weight DEHP from gestational day 13.5 to delivery and performed scRNA sequencing of neonatal testes at postnatal day 5.5. The results revealed the gene expression dynamics in testicular cells. DEHP disrupted the developmental trajectory of germ cells and the balance between the self-renewal and differentiation of spermatogonial stem cells. Additionally, DEHP caused an abnormal developmental trajectory, cytoskeletal damage and cell cycle arrest in Sertoli cells; disrupted the metabolism of testosterone in Leydig cells; and disturbed the developmental trajectory in peritubular myoid cells. Elevated oxidative stress and excessive apoptosis mediated by p53 were observed in almost all testicular cells. The intercellular interactions among four cell types were altered, and biological processes related to glial cell line-derived neurotrophic factor (GDNF), transforming growth factor-β (TGF-β), NOTCH, platelet-derived growth factor (PDGF) and WNT signaling pathways were enriched after DEHP treatment. These findings systematically describe the damaging effects of DEHP on the immature testes and provide substantial novel insights into the reproductive toxicity of DEHP. [Display omitted] [ABSTRACT FROM AUTHOR]

Di-(2-ethylhexyl) phthalate (DEHP) is an extensively used plasticizer and has been shown to cause reproductive dysfunction in humans and model animals. However, the exact mechanisms of testicular injury induced by DEHP exposure have not been fully clarified. Using gas chromatography-mass spectrometry, we found that mono-2-ethylhexyl ester (MEHP, a major biometabolite of DEHP) and DEHP concentrations were elevated in mouse serum after DEHP exposure. Using RNA-seq, we found that ferroptosis and HIF-1 signaling pathways might be involved in testicular injury due to prepubertal DEHP exposure. Subsequent Western blotting, ferrous iron and MDA measurements, and immunofluorescence of testicular sections verified the RNA-seq findings. Consistently, based on the RNA-seq findings, we found that ferroptosis and HIF-1 signaling pathways might play crucial roles in Leydig and Sertoli cell injury due to MEHP exposure in vitro. Further experiments also confirmed ferroptosis in Leydig and Sertoli cells. Using Western blotting, cellular immunofluorescence and ChIP-qPCR, we found that MEHP exposure caused HIF-1α accumulation and stabilization, resulted in HIF-1α translocation into the nucleus, and induced HIF-1α/ Hmox1 binding in Leydig and Sertoli cells. To clarify whether HIF-1α plays a pivotal role in MEHP-induced ferroptosis, we knocked out Hif-1α using the CRISPR/Cas9 technique. We found that Hif-1α knockout rescued MEHP-induced ferroptosis. In summary, our findings certified that prepubertal DEHP exposure led to ferroptosis in mouse testes via the HIF-1α/HO-1 signaling pathway. [Display omitted] • DEHP exposure triggers ferroptosis in mouse testes. • HIF-1α regulates Hmox1 transcription by binding to the Hmox1 promoter region. • Hif-1α knockout rescues MEHP-induced ferroptosis in Leydig and Sertoli cells. [ABSTRACT FROM AUTHOR]

[Display omitted] • Residual stress and microstructure of an additively manufactured plate was studied. • Significant mesoscopic variations in the residual stresses were revealed. • The mesoscopic residual strain and microstructures are reckoned together. Localised fluctuation in residual stress distribution for direct energy deposited 316L stainless steel thin plate was revealed through high-energy synchrotron X-ray diffraction. The macroscopic residual stress levels are changed steadily across the article according to the characteristic cooling rates, as implied by the measured dendrite arm lengths. Localised fluctuations of residual stress in the length scale, between 500 and 600 µm, coincides well with the morphological variations of the solidification microstructure that formed during direct energy deposition. Computations indicate a greater propensity for related mesoscopic thermal gradient fluctuations along the solidification front of the moving melt pool. Novel perspectives on residual stress across multiple length-scales and its relevance to the formation of solidification microstructure in metal additive manufacturing is analysed by considering the experimental results. [ABSTRACT FROM AUTHOR]

The high-speed impact-resistanct materials are of great significance while their development is hindered by the intrinsic tradeoff between mechanical strength and energy dissipation capability. Herein, the new chemical system of molecular granular material (MGM) is developed for the design of impact-resistant materials from the supramolecular complexation of sub-nm molecular clusters (MCs) and hyper-branched polyelectrolytes. Their hierarchical aggregation provides the origin of the decoupling of mechanical strengths and structural relaxation dynamics. The MCs' intrinsic fast dynamics afford excellent high-speed impact-resistance, up to 5600 s -1 impact in a typical split-Hopkinson pressure bar test while only tiny boundary cracks can be observed even under 7200 s -1 impact. The high loadings of MCs and their hierarchical aggregates provide high-density sacrificial bonding for the effective dissipation of the impact energy, enabling the protection of fragile devices from the direct impact of over 200 m s -1 bullet. Moreover, the MGMs can be conveniently processed into protective coatings or films with promising recyclability due to the supramolecular interaction feature. The research not only reveals the unique relaxation dynamics and mechanical properties of MGMs in comparison with polymers and colloids, but also develops new chemical systems for the fabrication of high-speed impact-resistant materials., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

The practical application of electrochemical CO2 reduction reaction (CO2RR) is hindered by the competing CO production, hydrogen evolution reaction (HER), and the lack of pH-universal catalysts. Here, Te-modified Bi nanorods (Te-Bi NRs) were synthesized through in situ reconstruction of Bi2Te4O11 NRs under the CO2RR condition. Our study illustrates that the complex reconstruction process of Bi2Te4O11 NRs during CO2RR could be decoupled into three distinct steps, i.e., the destruction of Bi2Te4O11, the formation of Te/Bi phases, and the dissolution of Te. The thus-obtained Te-Bi NRs exhibit remarkably high performance in CO2RR towards formate production, showing high activity, selectivity, and stability across all pH conditions (acidic, neutral, and alkaline). In a flow cell reactor under neutral, alkaline, or acidic conditions, the catalysts achieved HCOOH Faradaic efficiencies of up to 94.3%, 96.4%, and 91.0%, respectively, at a high current density of 300 mA cm-2. DFT calculations, along with operando spectral measurements, reveal that Te manipulates the Bi sites to an electron-deficient state, enhancing the adsorption strength of the *OCHO intermediate, and significantly suppressing the competing HER and CO production. This study highlights the substantial influence of catalyst reconstruction under operational conditions and offers insights into designing highly active and stable electrocatalysts towards CO2RR., (© 2024 Wiley‐VCH GmbH.)

2,3-Indole-fused 1,4-diazocines represent a new family of indole alkaloid compounds and are difficult to access by the reported protocols. Herein, we report a copper-catalyzed decarboxylative cyclization of cyclic propargylic carbamates with imidazolidines via sequential C-N/C-N/C-C bond formation to deliver a series of 2,3-indole-fused 1,4-diazocines, with a broad substrate scope and mild conditions.

Electrochemically converting carbon dioxide (CO 2 ) into valuable fuels and renewable chemical feedstocks is considered a highly promising approach to achieve carbon neutrality. In this work, a robust interfacial built-in electric field (BEF) has been successfully designed and created in Bi/Bi 2 Te 3 nanowires (NWs). The Bi/Bi 2 Te 3 NWs consistently maintain over 90% Faradaic efficiency (FE) within a wide potential range (-0.8 to -1.2 V), with HCOOH selectivity reaching 97.2% at -1.0 V. Moreover, the FE HCOOH of Bi/Bi 2 Te 3 NWs can still reach 94.3% at a current density of 100 mA cm -2 when it is used as a cathode electrocatalyst in a flow-cell system. Detailed in situ experiments confirm that the presence of interfacial BEF between Bi and Bi/Bi 2 Te 3 promotes the formation of *OHCO intermediates, thus facilitating the production of HCOOH species. DFT calculations show that Bi/Bi 2 Te 3 NWs increase the formation energies of H* and *COOH while reducing the energy barrier for *OCHO formation, thus achieving a bidirectional optimization of intermediate adsorption. This work provides a feasible scheme for exploring electrocatalytic reaction intermediates by using the BEF strategy.

Advances in surface-enhanced Raman scattering (SERS) detection have helped to overcome the limitations of traditional in vitro diagnostic methods, such as fluorescence and chemiluminescence, owing to its high sensitivity and multiplex detection capability. However, for the implementation of SERS detection technology in disease diagnosis, a SERS-based assay platform capable of analyzing clinical samples is essential. Moreover, infectious diseases like COVID-19 require the development of point-of-care (POC) diagnostic technologies that can rapidly and accurately determine infection status. As an effective assay platform, SERS-based bioassays utilize SERS nanotags labeled with protein or DNA receptors on Au or Ag nanoparticles, serving as highly sensitive optical probes. Additionally, a microdevice is necessary as an interface between the target biomolecules and SERS nanotags. This review aims to introduce various microdevices developed for SERS detection, available for POC diagnostics, including LFA strips, microfluidic chips, and microarray chips. Furthermore, the article presents research findings reported in the last 20 years for the SERS-based bioassay of various diseases, such as cancer, cardiovascular diseases, and infectious diseases. Finally, the prospects of SERS bioassays are discussed concerning the integration of SERS-based microdevices and portable Raman readers into POC systems, along with the utilization of artificial intelligence technology.

Background: Psoriasis is a chronic dermatological condition characterized by a complex pathogenesis that impacts approximately 3% of adults in the United States and brings enormous social burdens. For many diseases, the systemic immune-inflammatory index (SII), defined as neutrophils × platelets/lymphocytes, has been recognized as a prognostic indicator. Therefore, we conducted a cross-sectional study to assess the association between SII and psoriasis among outpatient US adults., Methods: In this cross-sectional study, we used data on the US adults 20 to 59 years of age from the National Health and Nutrition Examination Survey (NHANES) spanning 2003-2006 and 2009-2014. Sample-weighted logistic regression and stratified analysis of subgroups were used., Results: Among the 16,831 adults, there were 8,801 women and 8,030 men, with a psoriasis prevalence rate of 3.0%. A fully adjusted model revealed a positive association between a SII higher than 479.15 × 10 9 /L and a high risk of psoriasis. According to subgroup analysis and interaction testing (p for interaction > 0.05), age, sex, alcohol drinking status, marital status, and body mass index (BMI) were not significantly correlated with this positive association., Conclusion: Our findings suggested that SII higher than 479.15 × 10 9 /L was positively associated with a high risk of psoriasis among outpatient US adults. To the best of our knowledge, this is the first cross-sectional study using NHANES data focused on the risk of higher SII on psoriasis among outpatient US adults. The outcomes of this cross-sectional serve to supplement previous research, indicating a need for larger-scale prospective cohorts for further validation., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Ding, Li, Lin, Xie, Jing, Chen, Chen and Lu.)