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1.
Heliyon ; 10(16): e36103, 2024 Aug 30.
Article in English | MEDLINE | ID: mdl-39253271

ABSTRACT

Background: Hashimoto's thyroiditis (HT) is a thyroid autoimmune disease characterized by lymphocytic infiltration and thyroid destruction. Prunella vulgaris (PV) is a traditional Chinese herbal medicine with documented clinical efficacy in treating HT. We previously reported an immunoregulatory effect of PV in thyrocytes; however, the bioactive components of PV remained unclear. This study aimed to elucidate key components of PV for treating HT and their acting mechanisms. Methods: Network pharmacology was used to predict key PV components for HT. The predicted components were tested to determine whether they could exert an immunoregulatory effect of PV in human thyrocytes. Limited proteolysis-mass spectrometry (Lip-MS) was used to explore interacting proteins with PV components in human thyrocytes. Microscale thermophoresis binding assay was used to evaluate the affinity of PV components with the target protein. Results: Eleven PV components with 192 component targets and 3415 HT-related genes were gathered from public databases. With network pharmacology, a 'component-target-disease' network was established wherein four flavonoids including quercetin, luteolin, kaempferol, morin, and a phytosterol, ß-sitosterol were predicted as key components in PV for HT. In stimulated primary human thyrocytes or Nthy-ori-31 cells, key components inhibited gene expressions of inflammatory cytokines including tumor necrosis factor α (TNF-α), interleukin-6 (IL-6), and interferon-ß (IFN-ß), cellular apoptosis, and activation of nuclear factor κB (NF-κB) and interferon regulatory factor 3 (IRF-3). Heat shock protein 90 alpha, class A, member 1 (HSP90AA1), was identified to interact with flavonoids in PV by Lip-MS. Morin had the highest affinity with HSP90AA1 (KD = 122.74 µM), followed by kaempferol (KD = 168.53 µM), luteolin (KD = 293.94 µM), and quercetin (KD = 356.86 µM). Conclusion: Quercetin, luteolin, kaempferol, morin, and ß-sitosterol reproduced an anti-inflammatory and anti-apoptosis effect of PV in stimulated human thyrocytes, which potentially contributed to the treatment efficacy of PV in HT.

2.
J Hazard Mater ; 479: 135766, 2024 Nov 05.
Article in English | MEDLINE | ID: mdl-39244984

ABSTRACT

Nanoplastics (NPs) pose great challenges to soil-groundwater systems. This study investigated the transport and retention of self-synthesized 0.5-µm polystyrene NPs with different shapes using column experiments. The regular NPs were with spherical shapes, while the irregular NPs were with toroid-like shapes. The toroid-like shapes were the irregular shapes (with low aspect ratio) which have not been studied yet. The explorations were carried out in both 5-25 mM NaNO3 and 1-10 mM Ca(NO3)2 solutions. Both breakthrough curves (BTCs) and retained profiles (RPs) were monitored. Our findings uncovered a clear disparity in the transport of irregular and regular NPs, with irregular particles exhibiting lower transport ability compared to the regular ones. For example, the average breakthrough plateaus of the regular and irregular NPs were ∼0.9 and ∼0.5, respectively, in 10 mM NaNO3. In-depth theoretical analysis indicated that the lower XDLVO interaction energy barrier between the irregular NPs and quartz sand was one factor, and the greater margination of irregular NPs on quartz sand, as verified by the numerical simulation, was another factor leading to the decreased transport and increased retention of the irregular NPs. The obtained results highlighted the significance of considering particle shape in future modelling and predicting the fate of NPs in real environmental circumstances.

3.
Chemosphere ; 364: 143263, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39236924

ABSTRACT

Swine wastewater application can introduce antibiotics, antibiotic resistance genes (ARGs) into environments. Herein, the full-scale transmission of antibiotics, ARGs and their potential carriers from an intensive swine feedlot to its surroundings were explored. Results showed that lincomycin and doxycycline hydrochloride were dominant antibiotics in this ecosystem. Lincomycin concentration were strongly associated with soil bacterial communities. According to the risk quotient (RQ), lincomycin was identified as posing higher ecological risk in aquatic environments. ARGs and mobile genetic elements (MGEs) abundance in wastewater were reduced after anaerobic treatment. Notably, ARGs composition of environmental samples were clustered into two groups based on if they were directly affected by the wastewater. However, there were no remarkable difference of ARGs abundance among environmental samples. The total abundance of ARGs was positively related to that of MGEs. Pathogens Escherichia coli and Enterococcus revealed strong connection with qnrS, tet and sul. Overall, this study highlights the importance of responsible antibiotics use in livestock production and appropriate treatment technology before agricultural application and discharge.


Subject(s)
Anti-Bacterial Agents , Drug Resistance, Microbial , Wastewater , Wastewater/microbiology , Wastewater/chemistry , Animals , Swine , Anti-Bacterial Agents/pharmacology , Drug Resistance, Microbial/genetics , Genes, Bacterial , Escherichia coli/genetics , Escherichia coli/drug effects , Drug Resistance, Bacterial/genetics , Bacteria/genetics , Bacteria/drug effects , Soil Microbiology , Water Pollutants, Chemical/analysis , Enterococcus/genetics , Enterococcus/drug effects
4.
J Hazard Mater ; 478: 135564, 2024 Oct 05.
Article in English | MEDLINE | ID: mdl-39173392

ABSTRACT

Environmental plastic fragments have been verified as byproducts of large plastic and its secondary pollutants including micro and nanoplastics. There are few quantitative studies available, but their contours have values for the weathering mechanisms. We used geometric descriptors, fractal dimensions, and Fourier descriptors to characterize field and artificial polyethylene and polypropylene samples as a means of investigating the contour characteristics. It provides a methodological framework for contour classification. Unsupervised classification was performed using self-organizing neural networks with size-invariance parameters. We revealed the isometric phenomenon of plastic fragments during fragmentation, i.e., that the degree of contour rounding and complexity increase and decrease, respectively, with decreasing fragment size. With an average error rate of 8.9 %, we can distinguish artificial samples from field samples. It was also validated by the difference in Carbonyl Index between groups. We propose a two-stage process for plastic fragmentation and give three types of contour features which were key in the description of fragmented contours, i.e., size, complexity, and rounding. Our work will improve the accuracy of characterizations regarding the weathering and fragmentation processes of certain kinds of plastic fragments. The contour parameters also have the potential to be applied in more realistic scenarios and varied polymers.

5.
Biomimetics (Basel) ; 9(8)2024 Aug 02.
Article in English | MEDLINE | ID: mdl-39194448

ABSTRACT

Microneedles (MNs), characterized by their micron-sized sharp tips, can painlessly penetrate the skin and have shown significant potential in disease treatment and biosensing. With the development of artificial intelligence (AI), the design and application of MNs have experienced substantial innovation aided by machine learning (ML). This review begins with a brief introduction to the concept of ML and its current stage of development. Subsequently, the design principles and fabrication methods of MNs are explored, demonstrating the critical role of ML in optimizing their design and preparation. Integration between ML and the applications of MNs in therapy and sensing were further discussed. Finally, we outline the challenges and prospects of machine learning-assisted MN technology, aiming to advance its practical application and development in the field of smart diagnosis and treatment.

6.
Angew Chem Int Ed Engl ; : e202413949, 2024 Aug 16.
Article in English | MEDLINE | ID: mdl-39148491

ABSTRACT

Herein, we report a synergistic photoredox/palladium catalytic system for the efficient enantioconvergent synthesis of axially chiral esters from racemic heterobiaryl (pseudo)halides (bromides/triflates) with CO2 and alkyl bromides under mild conditions. A wide range of axially chiral esters were obtained in good to high yields with excellent enantioselectivities. Detailed mechanistic studies unveiled that the ratio of photocatalyst and palladium catalyst exhibited significant impact on the chemo- and enantioselectivities of the reaction. Kinetic studies and control experiments supported the proposed mechanism involving cascade asymmetric carboxylation followed by SN2 substitution. The achievement of high enantioselectivity relies not only on the choice of synergistic metallaphotoredox catalysts but also on the utilization of alkyl bromides, which trap the generated chiral carboxylic anions in situ, thus preventing their immediate racemization.

7.
Nano Lett ; 24(33): 10313-10321, 2024 Aug 21.
Article in English | MEDLINE | ID: mdl-39115248

ABSTRACT

Lightweight porous ceramics with a unique combination of superior mechanical strength and damage tolerance are in significant demand in many fields such as energy absorption, aerospace vehicles, and chemical engineering; however, it is difficult to meet these mechanical requirements with conventional porous ceramics. Here, we report a graded structure design strategy to fabricate porous ceramic nanowire networks that simultaneously possess excellent mechanical strength and energy absorption capacity. Our optimized graded nanowire networks show a compressive strength of up to 35.6 MPa at a low density of 540 mg·cm-3, giving rise to a high specific compressive strength of 65.7 kN·m·kg-1 and a high energy absorption capacity of 17.1 kJ·kg-1, owing to a homogeneous distribution of stress upon loading. These values are top performance compared to other porous ceramics, giving our materials significant potential in various engineering fields.

8.
Proc Natl Acad Sci U S A ; 121(33): e2401109121, 2024 Aug 13.
Article in English | MEDLINE | ID: mdl-39116136

ABSTRACT

Na5YSi4O12 (NYSO) is demonstrated as a promising electrolyte with high ionic conductivity and low activation energy for practical use in solid Na-ion batteries. Solid-state NMR was employed to identify the six types of coordination of Na+ ions and migration pathway, which is vital to master working mechanism and enhance performance. The assignment of each sodium site is clearly determined from high-quality 23Na NMR spectra by the aid of Density Functional Theory calculation. Well-resolved 23Na exchangespectroscopy and electrochemical tracer exchange spectra provide the first experimental evidence to show the existence of ionic exchange between sodium at Na5 and Na6 sites, revealing that Na transport route is possibly along three-dimensional chain of open channel-Na4-open channel. Variable-temperature NMR relaxometry is developed to evaluate Na jump rates and self-diffusion coefficient to probe the sodium-ion dynamics in NYSO. Furthermore, NYSO works well as a dual ion conductor in Na and Li metal batteries with Na3V2(PO4)3 and LiFePO4 as cathodes, respectively.

9.
Nat Commun ; 15(1): 7248, 2024 Aug 23.
Article in English | MEDLINE | ID: mdl-39179590

ABSTRACT

Atropisomeric biaryls bearing carbonyl groups have attracted increasing attention due to their prevalence in diverse bioactive molecules and crucial role as efficient organo-catalysts or ligands in asymmetric transformations. However, their preparation often involves tedious multiple steps, and the direct synthesis via asymmetric carbonylation has scarcely been investigated. Herein, we report an efficient palladium-catalyzed enantioconvergent aminocarbonylation of racemic heterobiaryl triflates with amines via dynamic kinetic asymmetric transformation (DyKAT). This protocol features a broad substrate scope and excellent compatibility for rapid construction of axially chiral amides in good to high yields with excellent enantioselectivities. Detailed mechanistic investigations discover that the base can impede the intramolecular hydrogen bond-assisted axis rotation of the products, thus allowing for the success to achieve high enantioselectivity. Moreover, the achieved axially chiral heterobiaryl amides can be directly utilized as N,N,N-pincer ligands in copper-catalyzed enantioselective formation of C(sp3)-N and C(sp3)-P bonds.

10.
Microbiome ; 12(1): 149, 2024 Aug 10.
Article in English | MEDLINE | ID: mdl-39123272

ABSTRACT

BACKGROUND: Gemmatimonadota bacteria are widely distributed in nature, but their metabolic potential and ecological roles in marine environments are poorly understood. RESULTS: Here, we obtained 495 metagenome-assembled genomes (MAGs), and associated viruses, from coastal to deep-sea sediments around the world. We used this expanded genomic catalog to compare the protein composition and update the phylogeny of these bacteria. The marine Gemmatimonadota are phylogenetically different from those previously reported from terrestrial environments. Functional analyses of these genomes revealed these marine genotypes are capable of degradation of complex organic carbon, denitrification, sulfate reduction, and oxidizing sulfide and sulfite. Interestingly, there is widespread genetic potential for secondary metabolite biosynthesis across Gemmatimonadota, which may represent an unexplored source of novel natural products. Furthermore, viruses associated with Gemmatimonadota have the potential to "hijack" and manipulate host metabolism, including the assembly of the lipopolysaccharide in their hosts. CONCLUSIONS: This expanded genomic diversity advances our understanding of these globally distributed bacteria across a variety of ecosystems and reveals genetic distinctions between those in terrestrial and marine communities. Video Abstract.


Subject(s)
Metagenome , Phylogeny , Genome, Bacterial , Geologic Sediments/microbiology , Genomics , Seawater/microbiology , Aquatic Organisms/genetics , Secondary Metabolism , Metagenomics
11.
Front Endocrinol (Lausanne) ; 15: 1424957, 2024.
Article in English | MEDLINE | ID: mdl-39045270

ABSTRACT

Introduction: We aimed to comprehensively investigate the causal relationship between 731 immune cell traits and autoimmune thyroiditis (AIT) and to identify and quantify the role of 1400 metabolic traits as potential mediators in between. Methods: Using summary-level data from genome-wide association studies (GWAS) we performed a two-sample bidirectional Mendelian randomization (MR) analysis of genetically predicted AIT and 731 immune cell traits. Furthermore, we used a two-step MR analysis to quantify the proportion of the total effects (that the immune cells exerted on the risk of AIT) mediated by potential metabolites. Results: We identified 24 immune cell traits (with odds ratio (OR) ranging from 1.3166 6 to 0.6323) and 10 metabolic traits (with OR ranging from 1.7954 to 0.6158) to be causally associated with AIT, respectively. Five immune cell traits (including CD38 on IgD+ CD24-, CD28 on CD28+ CD45RA+ CD8br, HLA DR+ CD4+ AC, TD CD4+ %CD4+, and CD8 on EM CD8br) were found to be associated with the risk of AIT, which were partially mediated by metabolites (including glycolithocholate sulfate, 5alpha-androstan-3alpha,17beta-diol disulfate, arachidonoylcholine, X-15486, and kynurenine). The proportion of genetically predicted AIT mediated by the identified metabolites could range from 5.58% to 17.7%. Discussion: Our study identified causal associations between AIT and immune cells which were partially mediated by metabolites, thus providing guidance for future clinical and basic research.


Subject(s)
Genome-Wide Association Study , Mendelian Randomization Analysis , Thyroiditis, Autoimmune , Humans , Thyroiditis, Autoimmune/genetics , Thyroiditis, Autoimmune/immunology , Thyroiditis, Autoimmune/metabolism , Polymorphism, Single Nucleotide , Genetic Predisposition to Disease
12.
Molecules ; 29(13)2024 Jul 04.
Article in English | MEDLINE | ID: mdl-38999143

ABSTRACT

OBJECTIVE: To elucidate the chemical profile of Xanthocerais lignum's extracts of different polarities and their impact on rheumatoid arthritis (RA), we identified anti-RA markers and predicted their action mechanisms. METHODS: A collagen-induced arthritis rat model was established, and UPLC-Q-Exactive Orbitrap MS technology was employed to analyze and identify the chemical constituents within the alcohol extract of Xanthocerais lignum and its various extraction fractions, as well as their translocation into the bloodstream. Serum spectrum-effect correlation analysis was utilized to elucidate the pharmacodynamic material basis of Xanthocerais lignum against RA and to screen for Q-Markers. Finally, the potential anti-RA mechanisms of the Q-Markers were predicted through compound-target interaction data and validated using molecular docking techniques. RESULTS: We identified 71 compounds, with flavan-3-ols and flavanones as key components. Of these, 36 were detected in the bloodstream, including 17 original and 19 metabolized forms. Proanthocyanidin A2, dihydroquercetin, catechin, and epicatechin (plus glucuronides) showed potential anti-RA activity. These compounds, acting as Q-Markers, may modulate ERK, NF-κB, HIF-1α, and VEGF in the HIF-1 pathway. CONCLUSIONS: This research clarifies Xanthocerais lignum's pharmacodynamic material basis against RA, identifies 4 Q-Markers, and offers insights into their mechanisms, aiding quality assessment and lead compound development for RA treatment.


Subject(s)
Arthritis, Rheumatoid , Biomarkers , Molecular Docking Simulation , Plant Extracts , Animals , Arthritis, Rheumatoid/drug therapy , Arthritis, Rheumatoid/blood , Arthritis, Rheumatoid/metabolism , Rats , Biomarkers/blood , Plant Extracts/chemistry , Plant Extracts/pharmacology , Arthritis, Experimental/drug therapy , Arthritis, Experimental/blood , Arthritis, Experimental/metabolism , Male , Disease Models, Animal , Hypoxia-Inducible Factor 1, alpha Subunit/metabolism , Antirheumatic Agents/pharmacology , Antirheumatic Agents/chemistry , Antirheumatic Agents/therapeutic use , Vascular Endothelial Growth Factor A/blood , Vascular Endothelial Growth Factor A/metabolism
13.
Anal Chem ; 96(28): 11525-11532, 2024 07 16.
Article in English | MEDLINE | ID: mdl-38966896

ABSTRACT

The urgent need for field detection of uranium in seawater is 2-fold: to provide prompt guidance for uranium extraction and to prevent human exposure to nuclear radiation. However, current methods for this purpose are largely hindered by bulky instrumentation, high costs of developed materials, and severe matrix interferences, which limit their further application in the field. Herein, we demonstrated a portable and label-free strategy for the field detection of uranyl in seawater based on the efficient photocleavage of DNA. Further experiments confirmed the generation of ultraviolet (UV) light-induced reactive oxygen species (ROS), such as O2•- and •OH, which fragmented oligomeric DNA in the presence of uranyl and UV light. Detailed studies showed that DNA significantly enhances uranyl absorption in the UV-visible region, leading to the generation of more ROS. A fluorescence system for the selective detection of uranyl in seawater was established by immobilizing two complementary oligonucleotides with the fluorescent dye SYBR Green I. The strategy of UV-induced photocleavage offers high selectivity, excellent interference immunity, and high sensitivity for uranyl, with a detection limit of 6.8 nM. Additionally, the fluorescence can be visually detected using a 3D-printed miniaturized device integrated with a smartphone. This method has been successfully applied to the on-site detection of uranyl in seawater in 18 Chinese coastal cities and along the coast of Hainan Island within 3 min for a single sample. The sample testing and field analysis results indicate that this strategy has promising potential for real-time monitoring of trace uranyl in China's coastal waters. It is expected to be utilized for the rapid assessment of nuclear contamination and nuclear engineering construction.


Subject(s)
DNA , Seawater , Ultraviolet Rays , Uranium , Seawater/analysis , Seawater/chemistry , DNA/analysis , China , Uranium/analysis , Fluorescent Dyes/chemistry , Reactive Oxygen Species/analysis , Limit of Detection , Photochemical Processes , Diamines , Benzothiazoles/chemistry , Organic Chemicals/analysis , Organic Chemicals/chemistry , Quinolines
14.
mBio ; 15(8): e0099624, 2024 Aug 14.
Article in English | MEDLINE | ID: mdl-38980036

ABSTRACT

Regulator of G-protein signaling (RGS) proteins exhibit GTPase-accelerating protein activities to govern G-protein function. In the rice blast fungus Magnaporthe oryzae, there is a family of at least eight RGS and RGS-like proteins (MoRgs1 to MoRgs8), each exhibiting distinct or shared functions in the growth, appressorium formation, and pathogenicity. MoRgs3 recently emerged as one of the crucial regulators that senses intracellular oxidation during appressorium formation. To explore this unique regulatory mechanism of MoRgs3, we identified the nucleoside diphosphate kinase MoNdk1 that interacts with MoRgs3. MoNdk1 phosphorylates MoRgs3 under induced intracellular reactive oxygen species levels, and MoRgs3 phosphorylation is required for appressorium formation and pathogenicity. In addition, we showed that MoRgs3 phosphorylation determines its interaction with MoCrn1, a coronin-like actin-binding protein homolog, which regulates MoRgs3 internalization. Finally, we provided evidence demonstrating that MoRgs3 functions in MoMagA-mediated cAMP signaling to regulate normal appressorium induction. By revealing a novel signal perception mechanism, our studies highlighted the complexity of regulation during the appressorium function and pathogenicity of the blast fungus. IMPORTANCE: We report that MoRgs3 becomes phosphorylated in an oxidative intracellular environment during the appressorium formation stage. We found that this phosphorylation is carried out by MoNdk1, a nucleoside diphosphate kinase. In addition, this phosphorylation leads to a higher binding affinity between MoRgs3 and MoCrn1, a coronin-like actin-binding protein that was implicated in the endocytic transport of several other RGS proteins of Magnaporthe oryzae. We further found that the internalization of MoRgs3 is indispensable for its GTPase-activating protein function toward the Gα subunit MoMagA. Importantly, we characterized how such cellular regulatory events coincide with cAMP signaling-regulated appressorium formation and pathogenicity in the blast fungus. Our studies uncovered a novel intracellular reactive oxygen species signal-transducing mechanism in a model pathogenic fungus with important basic and applied implications.


Subject(s)
Cyclic AMP , Fungal Proteins , Plant Diseases , Reactive Oxygen Species , Signal Transduction , Reactive Oxygen Species/metabolism , Cyclic AMP/metabolism , Fungal Proteins/metabolism , Fungal Proteins/genetics , Phosphorylation , Plant Diseases/microbiology , Oryza/microbiology , RGS Proteins/metabolism , RGS Proteins/genetics , Gene Expression Regulation, Fungal , Nucleoside-Diphosphate Kinase/metabolism , Nucleoside-Diphosphate Kinase/genetics , Ascomycota/genetics , Ascomycota/metabolism , Ascomycota/pathogenicity , Virulence
15.
mBio ; 15(8): e0099224, 2024 Aug 14.
Article in English | MEDLINE | ID: mdl-38980039

ABSTRACT

The microbial communities of marine seep sediments contain unexplored physiological and phylogenetic diversity. Here, we examined 30 bacterial metagenome-assembled genomes (MAGs) from cold seeps in the South China Sea, the Indian Ocean, the Scotian Basin, and the Gulf of Mexico, as well as from deep-sea hydrothermal sediments in the Guaymas Basin, Gulf of California. Phylogenetic analyses of these MAGs indicate that they form a distinct phylum-level bacterial lineage, which we propose as a new phylum, Candidatus Effluviviacota, in reference to its preferential occurrence at diverse seep areas. Based on tightly clustered high-quality MAGs, we propose two new genus-level candidatus taxa, Candidatus Effluvivivax and Candidatus Effluvibates. Genomic content analyses indicate that Candidatus Effluviviacota are chemoheterotrophs that harbor the Embden-Meyerhof-Parnas glycolysis pathway. They gain energy by fermenting organic substrates. Additionally, they display potential capabilities for the degradation of cellulose, hemicellulose, starch, xylan, and various peptides. Extracellular anaerobic respiration appears to rely on metals as electron acceptors, with electron transfer primarily mediated by multiheme cytochromes and by a flavin-based extracellular electron transfer (EET) mechanism that involves NADH-quinone oxidoreductase-demethylmenaquinone-synthesizing enzymes, uncharacterized membrane proteins, and flavin-binding proteins, also known as the NUO-DMK-EET-FMN complex. The heterogeneity within the Ca. Effluviviacota phylum suggests varying roles in energy metabolism among different genera. While NUO-DMK-EET-FMN electron transfer has been reported predominantly in Gram-positive bacteria, it is now identified in Ca. Effluviviacota as well. We detected the presence of genes associated with bacterial microcompartments in Ca. Effluviviacota, which can promote specific metabolic processes and protect the cytosol from toxic intermediates. IMPORTANCE: The newly discovered bacterial phylum Candidatus Effluviviacota is widespread across diverse seepage ecosystems, marine environments, and freshwater environments, with a notable preference for cold seeps. While maintaining an average abundance of approximately 1% in the global gene catalog of cold seep habitats, it has not hitherto been characterized. The metabolic versatility of Ca. Effluviviacota in anaerobic carbon, hydrogen, and metal cycling aligns with its prevalence in anoxic niches, with a preference for cold seep environments. Variations in metabolic potential between Ca. Effluvivivax and Ca. Effluvibates may contribute to shaping their respective habitat distributions.


Subject(s)
Bacteria , Genome, Bacterial , Geologic Sediments , Metagenome , Microbiota , Phylogeny , Bacteria/genetics , Bacteria/classification , Bacteria/isolation & purification , Bacteria/metabolism , Microbiota/genetics , Geologic Sediments/microbiology , Seawater/microbiology , Metagenomics
16.
J Am Chem Soc ; 146(29): 20059-20068, 2024 Jul 24.
Article in English | MEDLINE | ID: mdl-38994646

ABSTRACT

Ultrasmall metallic nanoclusters (NCs) protected by surface ligands represent the most promising catalytic materials; yet understanding the structure and catalytic activity of these NCs remains a challenge due to dynamic evolution of their active sites under reaction conditions. Herein, we employed a single-nanoparticle collision electrochemistry method for real-time monitoring of the dynamic electrocatalytic activity of a single fully ligand-protected Au25(PPh3)10(SC2H4Ph)5Cl22+ nanocluster (Au252+ NC) at a cavity carbon nanoelectrode toward the oxygen reduction reaction (ORR). Our experimental results and computational simulations indicated that the reversible depassivation and passivation of ligands on the surface of the Au252+ NC, combined with the dynamic conformation evolution of the Au259+ core, led to a characteristic current signal that involves "ON-OFF" switches and "ON" fluctuations during the ORR process of a single Au252+ NC. Our findings reinvent the new perception and comprehension of the structure-activity correlation of NCs at the atomic level.

17.
ACS Nano ; 18(24): 15950-15957, 2024 Jun 18.
Article in English | MEDLINE | ID: mdl-38847327

ABSTRACT

Resilient ceramic aerogels with a unique combination of lightweight, good high-temperature stability, high specific area, and thermal insulation properties are known for their promising applications in various fields. However, the mechanical properties of traditional ceramic aerogels are often constrained by insufficient interlocking of the building blocks. Here, we report a strategy to largely increase the interlocking degree of the building blocks by depositing a pyrolytic carbon (PyC) coating onto Si3N4 nanowires. The results show that the mechanical performances of the Si3N4 nanowire aerogels are intricately linked to the microstructure of the PyC nodes. The compression resilience of the Si3N4@PyC nanowire aerogels increases with an increase of the interlayer cross-linking in PyC. Additionally, benefiting from the excellent high-temperature stability of PyC, the Si3N4@PyC nanowire aerogels demonstrate significantly superior in situ resilience up to 1400 °C. The integrated mechanical and high-temperature properties of the Si3N4@PyC nanowire aerogels make them highly appealing for applications in harsh conditions. The facile method of manipulating the microstructure of the nodes may offer a perspective for tailoring the mechanical properties of ceramic aerogels.

18.
Front Psychiatry ; 15: 1377257, 2024.
Article in English | MEDLINE | ID: mdl-38863608

ABSTRACT

Background: Negative symptoms and cognitive impairments are highly frequent in schizophrenia spectrum disorders (SSD), associated with adverse functional outcomes and quality of life. Repetitive transcranial magnetic stimulation (rTMS) has been considered a promising therapeutic option in SSD. However, placebo effects of rTMS on these symptoms remained unclear. Objective: To investigate placebo effects of rTMS on alleviating negative symptoms and cognitive impairment in patients with SSD and to explore potential moderators. Methods: We systematically searched five electronic databases up to 15 July 2023. Randomized, double-blind, sham-controlled trials investigating effects of rTMS on negative symptoms or cognition in patients with SSD were included. The pooled placebo effect sizes, represented by Hedges' g, were estimated using the random-effects model. Potential moderators were explored through subgroup analysis and meta-regression. Results: Forty-four randomized controlled trials with 961 patients (mean age 37.53 years; 28.1% female) in the sham group were included. Significant low-to-moderate pooled placebo effect sizes were observed for negative symptoms (g=0.44, p<0.001), memory (g=0.31, p=0.010), executive function (g=0.35, p<0.001), working memory (g=0.26, p=0.004), and processing speed (g=0.36, p=0.004). Subgroup analysis indicated that placebo effects were affected by sham stimulation methods, rTMS targeting approaches, and stimulation frequency. Conclusions: Placebo effects of rTMS on negative symptoms and cognition in patients with SSD are significant in a small-to-moderate magnitude, which might be mediated by rTMS parameters. Our findings will provide new insights for practitioners to further optimize and establish standardized rTMS protocols for future RCTs tackling cardinal symptoms in SSD. Systematic Review Registration: https://www.crd.york.ac.uk/prospero/, identifier CRD42023390138.

19.
Environ Sci Technol ; 58(24): 10776-10785, 2024 Jun 18.
Article in English | MEDLINE | ID: mdl-38838101

ABSTRACT

Rivers have been recognized as the primary conveyors of microplastics to the oceans, and seaward transport flux of riverine microplastics is an issue of global attention. However, there is a significant discrepancy in how microplastic concentration is expressed in field occurrence investigations (number concentration) and in mass flux (mass concentration). Of urgent need is to establish efficient conversion models to correlate these two important paradigms. Here, we first established an abundant environmental microplastic dataset and then employed a deep neural residual network (ResNet50) to successfully separate microplastics into fiber, fragment, and pellet shapes with 92.67% accuracy. We also used the circularity (C) parameter to represent the surface shape alteration of pellet-shaped microplastics, which always have a more uneven surface than other shapes. Furthermore, we added thickness information to two-dimensional images, which has been ignored by most prior research because labor-intensive processes were required. Eventually, a set of accurate models for microplastic mass conversion was developed, with absolute estimation errors of 7.1, 3.1, 0.2, and 0.9% for pellet (0.50 ≤ C < 0.75), pellet (0.75 ≤ C ≤ 1.00), fiber, and fragment microplastics, respectively; environmental samples have validated that this set is significantly faster (saves ∼2 h/100 MPs) and less biased (7-fold lower estimation errors) compared to previous empirical models.


Subject(s)
Environmental Monitoring , Microplastics , Water Pollutants, Chemical , Rivers/chemistry
20.
Biology (Basel) ; 13(6)2024 May 28.
Article in English | MEDLINE | ID: mdl-38927267

ABSTRACT

Exosomes are 30-150 nm small extracellular vesicles (sEVs) which are highly stable and encapsulated by a phospholipid bilayer. Exosomes contain proteins, lipids, RNAs (mRNAs, microRNAs/miRNAs, long non-coding RNAs/lncRNAs), and DNA of their parent cell. In pathological conditions, the composition of exosomes is altered, making exosomes a potential source of biomarkers for disease diagnosis. Exosomes can cross the blood-brain barrier (BBB), which is an advantage for using exosomes in the diagnosis of central nervous system (CNS) diseases. Neuropsychiatric diseases belong to the CNS diseases, and many potential diagnostic markers have been identified for neuropsychiatric diseases. Here, we review the potential diagnostic markers of exosomes in neuropsychiatric diseases and discuss the potential application of exosomal biomarkers in the early and accurate diagnosis of these diseases. Additionally, we outline the limitations and future directions of exosomes in the diagnosis of neuropsychiatric diseases.

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