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1.
Chem Sci ; 2024 Aug 13.
Article in English | MEDLINE | ID: mdl-39246352

ABSTRACT

Dialkyldiazirines have emerged as a photo-reactive group of choice for interactome mapping in live cell experiments. Upon irradiation, 'linear' dialkyldiazirines produce dialkylcarbenes which are susceptible to both intramolecular reactions and unimolecular elimination processes, as well as diazoalkanes, which also participate in intermolecular labeling. Cyclobutylidene has a nonclassical bonding structure and is stable enough to be captured in bimolecular reactions. Cyclobutanediazirines have more recently been studied as photoaffinity probes based on cyclobutylidene, but the mechanism, especially with respect to the role of putative diazo intermediates, was not fully understood. Here, we show that photolysis (365 nm) of cyclobutanediazirines can produce cyclobutylidene intermediates as evidenced by formation of their expected bimolecular and unimolecular products, including methylenecyclopropane derivatives. Unlike linear diazirines, cyclobutanediazirine photolysis in the presence of tetramethylethylene produces a [2 + 1] cycloaddition adduct. By contrast, linear diazirines produce diazo compounds upon low temperature photolysis in THF, whereas diazo compounds are not detected in similar photolyses of cyclobutanediazirines. Diazocyclobutane, prepared by independent synthesis, is labile, reactive toward water and capable of protein alkylation. The rate of diazocyclobutane decomposition is not affected by 365 nm light, suggesting that the photochemical conversion of diazocyclobutane to cyclobutylidene is not an important pathway. Finally, chemical proteomic studies revealed that a likely consequence of this primary conversion to a highly reactive carbene is a marked decrease in labeling by cyclobutanediazirine-based probes relative to linear diazirine counterparts both at the individual protein and proteome-wide levels. Collectively, these observations are consistent with a mechanistic picture for cyclobutanediazirine photolysis that involves carbene chemistry with minimal formation of diazo intermediates, and contrasts with the photolyses of linear diazirines where alkylation by diazo intermediates plays a more significant role.

2.
Environ Pollut ; 361: 124915, 2024 Sep 07.
Article in English | MEDLINE | ID: mdl-39245204

ABSTRACT

Chinese traditional smoked pork was contaminated with polycyclic aromatic hydrocarbons (PAHs) and chlorinated and brominated PAHs (ClPAHs and BrPAHs; XPAHs) during the smoking process. Therefore, our study investigated the concentrations, enrichment characteristics, and health risks associated with PAHs, as well as ClPAHs and BrPAHs in Chinese traditional smoked pork. The total concentrations of PAHs, ClPAHs and BrPAHs in traditional smoked pork ranged from 90.0 to 79200 ng/g fat weight (fw), 23.6-2340 pg/g fw and 0.550-200 pg/g fw, respectively, which were significantly higher than their levels found in raw pork. Additionally, the concentrations of PAHs and XPAHs in the surface of smoked pork were higher than those in the inner parts. High-ring PAHs exhibited a greater enrichment compared to low-ring PAHs, and BrPAHs exhibited greater enrichment ability than ClPAHs in smoked pork. Furthermore, the ability of individual congeners to migrate from the surface to the inner parts of the smoked pork were varied. When the smoking fuels were similar, a longer smoking time resulted in higher concentrations of PAHs and XPAHs in smoked pork, while casing effectively reduced their concentrations. The correlation between XPAH and parent PAH concentrations indicated that chlorination of PAHs was one of the primary formation mechanisms of some monochlorinated PAHs. Over half of the smoked pork samples posed a potential carcinogenic risk, particularly the surface samples. It is recommended to remove the surface parts when consuming smoked pork and to improve traditional smoking methods to mitigate the health risks.

3.
Environ Res ; 262(Pt 2): 119807, 2024 Sep 01.
Article in English | MEDLINE | ID: mdl-39222731

ABSTRACT

Dechlorane plus (DP) has been detected in a variety of environmental media and in human. Measurement of DPs in hair, urine, and house dust across different habitats allows for the assessment of short-term spatial changes in human exposure to DPs, as well as their excretion in urine. This offers a significant reference point for further research on the behavior of persistent pollutants within organisms. We measured and analyzed the concentrations of DP in the hair and urine of 32 students from a university in Beijing during school and home phases, and in indoor dust from dormitories and some home environments. The results indicated that the concentrations of DP in three types of samples were higher during the home phase compared to the school phase. We compared the fanti values and identified selective enrichment of syn-DP in hair, along with selective excretion of syn-DP in urine. Utilizing molecular docking technique, we simulated the binding effect between DP and the Megalin protein. The results demonstrated that the binding energy of anti-DP to Megalin was higher than that of syn-DP, suggesting that anti-DP has a greater propensity to bind to Megalin and be reabsorbed. This results in higher levels of syn-DP excretion in urine. Finally, we categorized students based on their participation in the organic exposure experiment and their BMI. The results indicated that the concentrations of DP in hair and urine were higher in the exposed group compared to the non-exposed group during the school year. After excluding the effect of exposure, habitat changes were more likely to affect the accumulation and excretion of DP in normal-weight students (BMI ≤24 kg/m2, n = 28), while overweight students (BMI >24 kg/m2, n = 4) were less affected by the effect of habitat because of their higher body fat percentage and their greater ability to accumulate DP.

4.
Heliyon ; 10(16): e35905, 2024 Aug 30.
Article in English | MEDLINE | ID: mdl-39253195

ABSTRACT

Background: Secreted frizzled-related protein 5 (SFRP5) is a novel adipokine that has been found to be closely associated with metabolic and cardiovascular diseases. We investigated serum SFRP5 levels during the acute phase and their predictive value for the prognosis of acute aortic dissection (AAD). Methods: In total, 152 AAD patients and 164 controls were enrolled in this study. Serum SFRP5 levels were measured using an enzyme-linked immunosorbent assay (ELISA). AAD patients were divided into high-SFRP5 and low-SFRP5 groups based on the optimal cutoff value and followed up for prognosis. The primary endpoint was all-cause mortality, and the secondary endpoint focused on AAD-related events (including AAD-related mortality and unplanned reoperations). Results: Serum SFRP5 levels were significantly higher in AAD patients than in non-AAD controls, regardless of whether they had Stanford type A or B AD. Multivariate logistic regression analysis revealed an independent association between SFRP5 and the presence of AAD (adjusted OR 1.267, 95 % CI 1.152-1.394; p < 0.001). The receiver operating characteristic curve demonstrated that the optimal cutoff value for SFRP5 to predict the presence of AAD was 10.26 ng/mL (AUC 0.7241, sensitivity 49.34 %, specificity 87.20 %). Notably, serum SFRP5 levels of patients in the death group were significantly higher than those in the survival group. Compared with patients in the low-SFRP5 group, those in the high-SFRP5 group exhibited a significantly increased risk of all-cause mortality (HR 9.540, 95 % CI 2.803-32.473; p < 0.001) and AAD-related events (HR 6.915, 95 % CI 2.361-20.254; p < 0.001) during the follow-up period. Conclusion: Serum SFRP5 levels were significantly elevated in the acute phase of AAD, and high serum SFRP5 levels were independently associated with poor AAD prognosis. These results suggest that serum SFRP5 level during the acute phase may be an effective biomarker and therapeutic target for the prognosis of AAD.

5.
Int Immunopharmacol ; 140: 112858, 2024 Oct 25.
Article in English | MEDLINE | ID: mdl-39111145

ABSTRACT

OBJECTIVE: The aim of this study was to investigate whether ASA VI controls osteoarthritis (OA) by regulating mitochondrial function. METHODS: Primary chondrocytes were isolated and cultured from rat knee joints. The chondrocytes were treated with ASA VI and interleukin-1ß (IL-1ß) to simulate the inflammatory environment of OA. Cell viability, apoptosis, inflammatory cytokine levels, and extracellular matrix (ECM) component levels were assessed. Mitochondrial function, including ATP levels, mitochondrial membrane potential, reactive oxygen species (ROS) levels, and mitochondrial DNA content, was evaluated. The expression of Sirtuin 3 (Sirt3), a key regulator of mitochondrial homeostasis, was examined. Additionally, a rat OA model was established by destabilizing the medial meniscus, and the effects of ASA VI on cartilage degeneration were assessed. RESULTS: ASA VI treatment improved cell viability, reduced apoptosis, and decreased IL-6 and TNF-α levels in IL-1ß-induced chondrocytes. ASA VI also upregulated Collagen II and Aggrecan expression, while downregulating ADAMTS5 and MMP-13 expression. Furthermore, ASA VI mitigated IL-1ß-induced mitochondrial dysfunction by increasing ATP levels, restoring mitochondrial membrane potential, reducing ROS production, and preserving mitochondrial DNA content. These effects were accompanied by the activation of Sirt3. In the rat OA model, ASA VI treatment increased Sirt3 expression and alleviated cartilage degeneration. CONCLUSION: ASA VI exerts chondroprotective and anti-inflammatory effects on IL-1ß-induced chondrocytes by improving mitochondrial function through Sirt3 activation. ASA VI also attenuates cartilage degeneration in a rat OA model. These findings suggest that ASA VI may be a potential therapeutic agent for the treatment of osteoarthritis by targeting mitochondrial dysfunction.


Subject(s)
Chondrocytes , Homeostasis , Mitochondria , Osteoarthritis , Saponins , Sirtuin 3 , Animals , Male , Mice , Rats , Anti-Inflammatory Agents/pharmacology , Anti-Inflammatory Agents/therapeutic use , Apoptosis/drug effects , Cartilage, Articular/pathology , Cartilage, Articular/metabolism , Cartilage, Articular/drug effects , Cell Survival/drug effects , Cells, Cultured , Chondrocytes/drug effects , Chondrocytes/metabolism , Cytokines/metabolism , Disease Models, Animal , Interleukin-1beta/metabolism , Membrane Potential, Mitochondrial/drug effects , Mitochondria/metabolism , Mitochondria/drug effects , Osteoarthritis/drug therapy , Osteoarthritis/metabolism , Osteoarthritis/pathology , Rats, Sprague-Dawley , Reactive Oxygen Species/metabolism , Sirtuin 3/metabolism , Sirtuin 3/genetics , Saponins/pharmacology
6.
Chemosphere ; 363: 142953, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39089337

ABSTRACT

In this study, we have utilized theoretical calculations to predict the reaction active sites of naproxen when reacting with radicals and to further study the thermodynamics and kinetics of the reactions with ·OH and SO4-·. The evidence, derived from the average local ionization energy and electrostatic potential, points to the naphthalene ring as the preferred site of attack, especially for the C2, C6, C9, and C10 sites. The changes in Gibbs free energy and enthalpy of the reactions initiated by ·OH and SO4-· ranged between -19.6 kcal/mol - 26.3 kcal/mol and -22.3 kcal/mol -18.5 kcal/mol, respectively. More in-depth investigation revealed that RA2 pathway for ·OH exhibited the lowest free energy of activation, suggesting this reaction is more inclined to proceed. The second-order rate constant results indicate the ·OH attacking reaction is faster than reactions initiated by SO4·-, yet controlled by diffusion. The consistency between theoretical findings and experimental data underscores the validity of this computational method for our study.


Subject(s)
Hydroxyl Radical , Naproxen , Sulfates , Thermodynamics , Naproxen/chemistry , Kinetics , Hydroxyl Radical/chemistry , Sulfates/chemistry , Water/chemistry , Models, Chemical
7.
Int J Mol Sci ; 25(15)2024 Jul 23.
Article in English | MEDLINE | ID: mdl-39125585

ABSTRACT

Acute respiratory distress syndrome (ARDS) occurs as an acute onset condition, and patients present with diffuse alveolar damage, refractory hypoxemia, and non-cardiac pulmonary edema. ARDS progresses through an initial exudative phase, an inflammatory phase, and a final fibrotic phase. Pirfenidone, a powerful anti-fibrotic agent, is known as an agent that inhibits the progression of fibrosis in idiopathic pulmonary fibrosis. In this study, we studied the treatment efficiency of pirfenidone on lipopolysaccharide (LPS) and bleomycin-induced ARDS using rats. The ARDS rat model was created by the intratracheal administration of 3 mg/kg LPS of and 3 mg/kg of bleomycin dissolved in 0.2 mL of normal saline. The pirfenidone treatment group was administered 100 or 200 mg/kg of pirfenidone dissolved in 0.5 mL distilled water orally 10 times every 2 days for 20 days. The administration of LPS and bleomycin intratracheally increased lung injury scores and significantly produced pro-inflammatory cytokines. ARDS induction increased the expressions of transforming growth factor (TGF)-ß1/Smad-2 signaling factors. Additionally, matrix metalloproteinase (MMP)-9/tissue inhibitor of metalloproteinase (TIMP)-1 imbalance occurred, resulting in enhanced fibrosis-related factors. Treatment with pirfenidone strongly suppressed the expressions of TGF-ß1/Smad-2 signaling factors and improved the imbalance of MMP-9/TIMP-1 compared to the untreated group. These effects led to a decrease in fibrosis factors and pro-inflammatory cytokines, promoting the recovery of damaged lung tissue. These results of this study showed that pirfenidone administration suppressed inflammation and fibrosis in the ARDS animal model. Therefore, pirfenidone can be considered a new early treatment for ARDS.


Subject(s)
Bleomycin , Lipopolysaccharides , Pyridones , Respiratory Distress Syndrome , Signal Transduction , Animals , Pyridones/pharmacology , Pyridones/therapeutic use , Respiratory Distress Syndrome/drug therapy , Respiratory Distress Syndrome/metabolism , Respiratory Distress Syndrome/pathology , Respiratory Distress Syndrome/chemically induced , Signal Transduction/drug effects , Rats , Male , Bleomycin/adverse effects , Tissue Inhibitor of Metalloproteinase-1/metabolism , Smad2 Protein/metabolism , Rats, Sprague-Dawley , Inflammation/drug therapy , Inflammation/metabolism , Inflammation/pathology , Disease Models, Animal , Matrix Metalloproteinase 9/metabolism , Transforming Growth Factor beta1/metabolism , Transforming Growth Factor beta/metabolism , Lung/pathology , Lung/drug effects , Lung/metabolism , Smad Proteins/metabolism
8.
Proc Natl Acad Sci U S A ; 121(36): e2406925121, 2024 Sep 03.
Article in English | MEDLINE | ID: mdl-39196627

ABSTRACT

Endosymbionts provide essential nutrients for hosts, promoting growth, development, and reproduction. However, the molecular regulation of nutrient transport from endosymbiont to host is not well understood. Here, we used bioinformatic analysis, RNA-Sequencing, luciferase assays, RNA immunoprecipitation, and in situ hybridization to show that a bacteriocyte-distributed MRP4 gene (multidrug resistance-associated protein 4) is negatively regulated by a host (aphid)-specific microRNA (miR-3024). Targeted metabolomics, microbiome analysis, vitamin B6 (VB6) supplements, 3D modeling/molecular docking, in vitro binding assays (voltage clamp recording and microscale thermophoresis), and functional complementation of Escherichia coli were jointly used to show that the miR-3024/MRP4 axis controls endosymbiont (Serratia)-produced VB6 transport to the host. The supplementation of miR-3024 increased the mortality of aphids, but partial rescue was achieved by providing an external source of VB6. The use of miR-3024 as part of a sustainable aphid pest-control strategy was evaluated by safety assessments in nontarget organisms (pollinators, predators, and entomopathogenic fungi) using virus-induced gene silencing assays and the expression of miR-3024 in transgenic tobacco. The supplementation of miR-3024 suppresses MRP4 expression, restricting the number of membrane channels, inhibiting VB6 transport, and ultimately killing the host. Under aphids facing stress conditions, the endosymbiont titer is decreased, and the VB6 production is also down-regulated, while the aphid's autonomous inhibition of miR-3024 enhances the expression of MRP4 and then increases the VB6 transport which finally ensures the VB6 homeostasis. The results confirm that miR-3024 regulates nutrient transport in the endosymbiont-host system and is a suitable target for sustainable pest control.


Subject(s)
Aphids , Homeostasis , MicroRNAs , Symbiosis , MicroRNAs/genetics , MicroRNAs/metabolism , Animals , Aphids/microbiology , Aphids/metabolism , Vitamin B 6/metabolism , Multidrug Resistance-Associated Proteins/metabolism , Multidrug Resistance-Associated Proteins/genetics , Nutrients/metabolism , Escherichia coli/metabolism , Escherichia coli/genetics
9.
Int J Biol Macromol ; 278(Pt 3): 134819, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39154672

ABSTRACT

Treatment of multiple bacterial infected wounds by eliminating bacteria and promoting tissue regeneration remains a clinical challenge. Herein, dual-network hydrogels (CS-GA/A-ß-CD) with snap-structure were designed to achieve curcumin immobilization, using gallic acid-grafted chitosan (CS-GA) and aldehyde-ß-cyclodextrin (A-ß-CD) crosslinked. A-ß-CD were able to achieve rapid dissolution (≥222.35 mg/mL H2O), and helped CS-GA/A-ß-CD achieve rapid gelation (≤66.23 s). By adjusting the ratio of aldehyde groups of A-ß-CD, mechanical properties and drug release can be controlled. CS-GA/A-ß-CD/Cur exhibited excellent antimicrobial properties against S. aureus, E. coli, and P. aeruginosa. In vivo experiments demonstrated that CS-GA/A-ß-CD/Cur achieved acute bacterial infection wound healing after 20th days, proving its great potential for wound dressing.


Subject(s)
Anti-Bacterial Agents , Chitosan , Hydrogels , Wound Healing , Wound Infection , beta-Cyclodextrins , Chitosan/chemistry , Hydrogels/chemistry , Hydrogels/pharmacology , beta-Cyclodextrins/chemistry , Animals , Wound Healing/drug effects , Wound Infection/drug therapy , Wound Infection/microbiology , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Polyphenols/chemistry , Polyphenols/pharmacology , Drug Liberation , Mice , Staphylococcus aureus/drug effects , Aldehydes/chemistry , Escherichia coli/drug effects , Curcumin/chemistry , Curcumin/pharmacology , Bandages
10.
Intensive Care Med ; 50(8): 1298-1309, 2024 Aug.
Article in English | MEDLINE | ID: mdl-39088076

ABSTRACT

PURPOSE: Awake prone positioning has been reported to reduce endotracheal intubation in patients with coronavirus disease 2019 (COVID-19)-related acute hypoxemic respiratory failure (AHRF). However, it is still unclear whether using the awake prone positioning for longer periods can further improve outcomes. METHODS: In this randomized, open-label clinical trial conducted at 12 hospitals in China, non-intubated patients with COVID-19-related AHRF were randomly assigned to prolonged awake prone positioning (target > 12 h daily for 7 days) or standard care with a shorter period of awake prone positioning. The primary outcome was endotracheal intubation within 28 days after randomization. The key secondary outcomes included mortality and adverse events. RESULTS: In total, 409 patients were enrolled and randomly assigned to prolonged awake prone positioning (n = 205) or standard care (n = 204). In the first 7 days after randomization, the median duration of prone positioning was 12 h/d (interquartile range [IQR] 12-14 h/d) in the prolonged awake prone positioning group vs. 5 h/d (IQR 2-8 h/d) in the standard care group. In the intention-to-treat analysis, intubation occurred in 35 (17%) patients assigned to prolonged awake prone positioning and in 56 (27%) patients assigned to standard care (relative risk 0.62 [95% confidence interval (CI) 0.42-0.9]). The hazard ratio (HR) for intubation was 0.56 (0.37-0.86), and for mortality was 0.63 (0.42-0.96) for prolonged awake prone positioning versus standard care, within 28 days. The incidence of pre-specified adverse events was low and similar in both groups. CONCLUSION: Prolonged awake prone positioning of patients with COVID-19-related AHRF reduces the intubation rate without significant harm. These results support prolonged awake prone positioning of patients with COVID-19-related AHRF.


Subject(s)
COVID-19 , Intubation, Intratracheal , Patient Positioning , Respiratory Insufficiency , Humans , COVID-19/complications , COVID-19/therapy , Prone Position , Male , Female , Middle Aged , Patient Positioning/methods , Intubation, Intratracheal/methods , Intubation, Intratracheal/statistics & numerical data , Aged , Respiratory Insufficiency/therapy , Respiratory Insufficiency/etiology , Wakefulness , China/epidemiology , Time Factors , SARS-CoV-2
11.
Chem Commun (Camb) ; 60(69): 9246-9249, 2024 Aug 22.
Article in English | MEDLINE | ID: mdl-39115146

ABSTRACT

K can reversibly intercalate into graphite by forming KC8 (279 mA h g-1, ≈0.2 V) in conventional carbonate electrolytes, but the large ionic radius of K+ (1.38 Å) easily results in structural degradation and rapid capacity decay. Here, commercial graphite particles are directly electrospun into network-like carbon fibers, thus forming a flexible Gr@CNF membrane. This hybrid electrode configuration can efficiently withstand the volume expansion during K+ insertion. K||Gr@CNF half-cells can stably operate for over 800 cycles (running time of 170 days at C/3) and achieve fast K+-intercalation kinetics at 5C. The fabricated Gr@CNF||AC K-ion hybrid capacitor delivers a high energy density of 119.3 W h kg-1 at 2717.82 W kg-1, corresponding to a fast-charge time of 3.2 min.

12.
Prog Lipid Res ; 95: 101289, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38986846

ABSTRACT

Atherosclerosis is a causative factor associated with cardiovascular disease (CVD). Over the past few decades, extensive research has been carried out on the relationship between the n-6/n-3 fatty acid ratio of ingested lipids and the progression of atherosclerosis. However, there are still many uncertainties regarding the precise nature of this relationship, which has led to challenges in providing sound dietary advice to the general public. There is therefore a pressing need to review our current understanding of the relationship between the dietary n-6/n-3 fatty acid ratio and atherosclerosis, and to summarize the underlying factors contributing to the current uncertainties. Initially, this article reviews the association between the n-6/n-3 fatty acid ratio and CVDs in different countries. A summary of the current understanding of the molecular mechanisms of n-6/n-3 fatty acid ratio on atherosclerosis is then given, including inflammatory responses, lipid metabolism, low-density lipoprotein cholesterol oxidation, and vascular function. Possible reasons behind the current controversies on the relationship between the n-6/n-3 fatty acid ratio and atherosclerosis are then provided, including the precise molecular structures of the fatty acids, diet-gene interactions, the role of fat-soluble phytochemicals, and the impact of other nutritional factors. An important objective of this article is to highlight areas where further research is needed to clarify the role of n-6/n-3 fatty acid ratio on atherosclerosis.


Subject(s)
Atherosclerosis , Fatty Acids, Omega-3 , Fatty Acids, Omega-6 , Humans , Atherosclerosis/metabolism , Fatty Acids, Omega-3/metabolism , Fatty Acids, Omega-6/metabolism , Animals , Risk Factors
13.
J Control Release ; 373: 105-116, 2024 Sep.
Article in English | MEDLINE | ID: mdl-38992622

ABSTRACT

Nanomedicines hold promise for the treatment of various diseases. However, treating cancer metastasis remains highly challenging. In this study, we synthesized gold nanorods (AuNRs) containing (α-GC), an immune stimulator, for the treatment of primary cancer, metastasis, and recurrence of the cancer. Therefore, the AuNR were coated with lipid bilayers loaded with α-GC (α-LA). Upon irradiation with 808 nm light, α-LA showed a temperature increase. Intra-tumoral injection of α-LA in mice and local irradiation of the 4T1 breast cancer tumor effectively eliminated tumor growth. We found that the presence of α-GC in α-LA activated dendritic cells and T cells in the spleen, which completely blocked the development of lung metastasis. In mice injected with α-LA for primary breast cancer treatment, we observed antigen-specific T cell responses and increased cytotoxicity against 4T1 cells. We conclude that α-LA is promising for the treatment of both primary breast cancer and its metastasis.


Subject(s)
Breast Neoplasms , Gold , Immunotherapy , Lung Neoplasms , Mice, Inbred BALB C , Nanotubes , Phototherapy , Animals , Gold/chemistry , Gold/administration & dosage , Nanotubes/chemistry , Female , Cell Line, Tumor , Breast Neoplasms/pathology , Breast Neoplasms/therapy , Breast Neoplasms/immunology , Immunotherapy/methods , Phototherapy/methods , Lung Neoplasms/secondary , Lung Neoplasms/therapy , Lung Neoplasms/immunology , Lung Neoplasms/pathology , Mice , T-Lymphocytes/immunology , T-Lymphocytes/drug effects
14.
J Colloid Interface Sci ; 675: 806-814, 2024 Dec.
Article in English | MEDLINE | ID: mdl-39002231

ABSTRACT

Metal-organic compounds have attracted significant attention for lithium-ion battery (LIB) anodes. However, their practical application is severely hindered by the poor structural stability and sluggish Li+ reaction kinetics. Herein, we proposed a new type of metal-organic compound, metal alkoxides, for high-performance LIBs. A series of metal-alkoxide/graphene composites with different transition metal centers and alkoxide anions are prepared to investigate the structural stability, Li-storage ability, and Li+ diffusion kinetics. The results reveal that the metal centers and alkoxide anions have significant influence on the structural stability, molar mass, and electronic structures, which are highly related to the Li-storage performance. Among them, Co-EG/rGO (EG represents the ethylene glycol anion) delivers the best performance involving high specific capacity (975 mAh g-1 at 0.2 A g-1), excellent rate capability (400.8 mAh g-1 at 10 A g-1), and stable cycling performance (86.8 % capacity retention after 600 cycles) due to its stable structure, smaller molar mass, and favorable electronic structure. Moreover, the Li-storage mechanism and solid electrolyte interphase (SEI) evolution of the Co-EG/rGO electrode are studied in detail through multiple ex-situ/in-situ characterizations. This work provides a new type of metal alkoxide anode material for high-rate and long-life LIBs toward practical energy applications.

15.
Adv Mater ; 36(36): e2406794, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39032124

ABSTRACT

The large size of K+ ions (1.38 Å) sets a challenge in achieving high kinetics and long lifespan of potassium storage devices. Here, a fibrous ZrO2 membrane is utilized as a reactive template to construct a dual-carbon K-ion capacitor. Unlike graphite, ZrO2-catalyzed graphitic carbon presents a relatively disordered layer arrangement with an expanded interlayer spacing of 0.378 nm to accommodate K+ insertion/extraction. Pyridine-derived nitrogen sites can locally store K-ions without disrupting the formation of stage-1 graphite intercalation compounds (GICs). Consequently, N-doped hollow graphitic carbon fiber achieves a K+-storage capacity (primarily below 1 V), which is 1.5 time that of commercial graphite. Potassium-ion hybrid capacitors are assembled using the hollow carbon fiber electrodes and the ZrO2 nanofiber membrane as the separator. The capacitor exhibits a high power of 40 000 W kg-1, full charge in 8.5 s, 93% capacity retention after 5000 cycles at 2 A g-1, and a low self-discharge rate of 8.6 mV h-1. The scalability and high performance of the lattice-expanded tubular carbon electrodes underscores may advance the practical potassium-ion capacitors.

16.
J Colloid Interface Sci ; 675: 52-63, 2024 Dec.
Article in English | MEDLINE | ID: mdl-38964124

ABSTRACT

Construction of hierarchical architecture with suitable band alignment for graphitic carbon nitride (g-C3N4) played a pivotal role in enhancing the efficiency of photocatalysts. In this study, a novel attapulgite-intercalated g-C3N4/ZnIn2S4 nanocomposite material (ZIS/CN/ATP, abbreviated as ZCA) was successfully synthesized using the freeze-drying technique, thermal polymerization, and a simple low-temperature hydrothermal method. Attapulgite (ATP) was intercalated into g-C3N4 to effectively regulate its interlayer structure. The results reveal a substantial enlargement of its internal space, thereby facilitating the provision of additional active sites for improved dispersibility of ZnIn2S4. Notably, the optimized photocatalyst, comprising a mass ratio of ATP, g-C3N4, and ZnIn2S4 at 1:1:2.5 respectively, achieves an outstanding hydrogen evolution rate of 3906.15 µmol g-1h-1, without the need for a Pt co-catalyst. This rate surpasses that of pristine g-C3N4 by a factor of 475 and ZnIn2S4 by a factor of 5, representing a significant improvement in performance. This significant enhancement can be primarily attributed to the higher specific surface area, richer active sites, broadened light response range, and efficient interfacial charge transfer channels of the ZCA composite photocatalyst. Furthermore, the Z-scheme photocatalytic mechanism for the sandwich-like layered structure heterojunction was thoroughly investigated using diverse characterization techniques. This work offers new insights for enhancing photocatalytic performance through the expanded utilization of natural minerals, paving the way for future advancements in this field.

17.
ACS Appl Mater Interfaces ; 16(28): 36343-36353, 2024 Jul 17.
Article in English | MEDLINE | ID: mdl-38965043

ABSTRACT

Solid oxide electrolysis cells (SOECs) show significant promise in converting CO2 to valuable fuels and chemicals, yet exploiting efficient electrode materials poses a great challenge. Perovskite oxides, known for their stability as SOEC electrodes, require improvements in electrocatalytic activity and conductivity. Herein, vanadium(V) cation is newly introduced into the B-site of Sr2Fe1.5Mo0.5O6-δ perovskite to promote its electrochemical performance. The substitution of variable valence V5+ for Mo6+ along with the creation of oxygen vacancies contribute to improved electronic conductivity and enhanced electrocatalytic activity for CO2 reduction. Notably, the Sr2Fe1.5Mo0.4V0.1O6-δ based symmetrical SOEC achieves a current density of 1.56 A cm-2 at 1.5 V and 800 °C, maintaining outstanding durability over 300 h. Theoretical analysis unveils that V-doping facilitates the formation of oxygen vacancies, resulting in high intrinsic electrocatalytic activity for CO2 reduction. These findings present a viable and facile strategy for advancing electrocatalysts in CO2 conversion technologies.

18.
Huan Jing Ke Xue ; 45(7): 4361-4374, 2024 Jul 08.
Article in Chinese | MEDLINE | ID: mdl-39022980

ABSTRACT

In order to systematically understand the urban environmental benefit improvement of municipal solid waste (MSW) classification, based on the disposal data of MSW before and after the MSW classification in Suzhou from 2017 to 2021, the environmental impact potential (EIP) of the MSW collection-transportation-disposal process was calculated, and the environmental benefits of the MSW integrated management in Suzhou to 2035 were predicted. After the MSW classification in Suzhou at the end of 2019, the EIP (in terms of PET2000, the same below) of the per unit weight of MSW was reduced by 18.38% from 2.34×10-13 t-1 in 2017 to 1.91×10-13 t-1 in 2021. The environmental benefits of the MSW integrated management could be improved by classification. Based on the Suzhou MSW removal and transportation situation in 2021, different classification and disposal scenarios were established to calculate. It was found that after the classification effect showed gradient improvement, and the disposal capacity matched accordingly, the environmental benefits of MSW were further improved. Under the planning disposal capacity scenario of "zero waste to landfill", the EIP and the total carbon emissions of per unit weight of MSW should be reduced by 23.96% and 30.73%, respectively, compared with the actual situation in 2021. Based on the linear model of population and economic development level of Suzhou, it is expected that the annual production of MSW in Suzhou will be increased to 6.965 million tons in 2035. Under the background of continuous improvement of MSW classification and continuous optimization of city appearance and environment in Suzhou, based on the status quo of terminal disposal capacity in Suzhou, the EIP of per unit weight of MSW after improving the efficiency of classification by 2035 was predicted to be 1.54×10-13 t-1, the total EIP would be 1.05×10-6, and the total carbon emissions would increase to 3.80 million tons. Under the ideal scenario of expanding the scale of waste disposal, "zero landfill" of raw MSW, and full resource utilization of food waste, the EIP of per unit weight of MSW in 2035 was predicted to be 1.28×10-13 t-1, and the total EIP and the total carbon emissions would be 8.69×10-7 and 3.23 million tons, respectively, which was approximately 5.65% and 1.23% less than the actual scenario in 2021, respectively. The EIP and carbon emissions of MSW integrated management could be controlled better by the coordinated promotion of classified collection and transportation and quality disposal.

19.
J Colloid Interface Sci ; 677(Pt A): 90-98, 2024 Jul 27.
Article in English | MEDLINE | ID: mdl-39083895

ABSTRACT

The recombination of photogenerated electron-hole pairs of the photoanode seriously impairs the application of bismuth vanadate (BiVO4) in photoelectrochemical water splitting. To address this issue, we prepared a Yb:BiVO4/Co3O4/FeOOH composite photoanode by employing drop-casting and soaking methods to attach Co3O4/FeOOH cocatalysts to the surface of ytterbium-doped BiVO4. The prepared Yb:BiVO4/Co3O4/FeOOH photoanode demonstrates a high photocurrent density of 4.89 mA cm-2 at 1.23 V versus the reversible hydrogen electrode (RHE), which is 5.1 times that of bare BiVO4 (0.95 mA cm-2). Detailed characterization and testing demonstrated that Yb doping narrows the band gap and significantly enhances the carrier density. Furthermore, Co3O4 serves as a hole transfer layer to expedite hole migration and diminish recombination, while FeOOH offers additional active sites and minimizes surface trap states, thus boosting stability. The synergistic effects of Yb doping and Co3O4/FeOOH cocatalyst significantly improved the reaction kinetics and overall performance of PEC water oxidation. This work provides a strategy for designing efficient photoanodes for PEC water oxidation.

20.
Dalton Trans ; 53(29): 12291-12300, 2024 Jul 23.
Article in English | MEDLINE | ID: mdl-38984478

ABSTRACT

Photocatalytic ammonia production holds immense promise as an environmentally sustainable approach to nitrogen fixation. In this study, In2O3/In2S3-ZnCdS ternary heterostructures were successfully constructed through an innovative in situ anion exchange process, coupled with a low-temperature hydrothermal method for ZnCdS (ZCS) incorporation. The resulting In2O3/In2S3-ZCS photocatalyst was proved to be highly efficient in converting N2 to NH3 under mild conditions, eliminating the need for sacrificial agents or precious metal catalysts. Notably, the NH4+ yield of In2O3/In2S3-0.5ZCS reached a significant level of 71.2 µmol g-1 h-1, which was 10.47 times higher than that of In2O3 (6.8 µmol g-1 h-1) and 3.22 times higher than that of In2O3/In2S3 (22.1 µmol g-1 h-1). This outstanding performance can be attributed to the ternary heterojunction configuration, which significantly extends the lifetime of photogenerated carriers and enhances the spatial separation of electrons and holes. The synergistic interplay between CdZnS, In2S3, and In2O3 in the heterojunction facilitates electron transport, thereby boosting the rate of the photocatalytic nitrogen fixation reaction. Our study not only validates the efficacy of ternary heterojunctions in photocatalytic nitrogen fixation but also offers valuable insights for the design and construction of such catalysts for future applications.

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