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1.
Nano Lett ; 24(32): 9839-9845, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39087826

RESUMO

Hard carbon (HC) is a promising anode candidate for Na-ion batteries (NIBs) because of its excellent Na-storage performance, abundance, and low cost. However, a precise understanding of its Na-storage behavior remains elusive. Herein, based on the D2O/H2SO4-based TMS results collected on charged/discharged state HC electrodes, detailed Na-storage mechanisms (the Na-storage states and active sites in different voltage regions), specific SEI dynamic evolution process (formation, rupture, regeneration and loss), and irreversible capacity contribution (dead Na0, NaH, etc.) were elucidated. Moreover, by employing the online electrochemical mass spectrometry (OEMS) to monitor the gassing behavior of HC-Na half-cell during the overdischarging process, a surprising rehydrogen evolution reaction (re-HER) process at around 0.02 V vs Na+/Na was identified, indicating the occurrence of Na-plating above 0 V vs Na+/Na. Additionally, the typical fluorine ethylene carbonate (FEC) additive was demonstrated to reduce the accumulation of dead Na0 and inhibit the re-HER process triggered by plated Na.

2.
J Cell Biochem ; 125(3): e30522, 2024 03.
Artigo em Inglês | MEDLINE | ID: mdl-38224175

RESUMO

Understanding the connection between senescence phenotypes and mitochondrial dysfunction is crucial in aging and premature aging diseases. Loss of mitochondrial function leads to a decline in T cell function, which plays a significant role in this process. However, more research is required to determine if improving mitochondrial homeostasis alleviates senescence phenotypes. Our research has shown an association between NAD+ and senescent T cells through the cGAS-STING pathway, which can lead to an inflammatory phenotype. Further research is needed to fully understand the role of NAD+ in T-cell aging and how it can be utilized to improve mitochondrial homeostasis and alleviate senescence phenotypes. We demonstrate here that mitochondrial dysfunction and cellular senescence with a senescence-associated secretory phenotype (SASP) occur in senescent T cells and tumor-bearing mice. Senescence is mediated by a stimulator of interferon genes (STING) and involves ectopic cytoplasmic DNA. We further show that boosting intracellular NAD+ levels with nicotinamide mononucleotide (NMN) prevents senescence and SASP by promoting mitophagy. NMN treatment also suppresses senescence and neuroinflammation and improves the survival cycle of mice. Encouraging mitophagy may be a useful strategy to prevent CD8+ T cells from senescence due to mitochondrial dysfunction. Additionally, supplementing with NMN to increase NAD+ levels could enhance survival rates in mice while also reducing senescence and inflammation, and enhancing mitophagy as a potential therapeutic intervention.


Assuntos
Doenças Mitocondriais , NAD , Camundongos , Animais , NAD/metabolismo , Linfócitos T CD8-Positivos/metabolismo , Mitocôndrias/metabolismo , Senescência Celular/fisiologia , Homeostase , Doenças Mitocondriais/metabolismo , Suplementos Nutricionais
3.
J Am Chem Soc ; 146(25): 17103-17113, 2024 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-38869216

RESUMO

Understanding the interfacial hydrogen evolution reaction (HER) is crucial to regulate the electrochemical behavior in aqueous zinc batteries. However, the mechanism of HER related to solvation chemistry remains elusive, especially the time-dependent dynamic evolution of the hydrogen bond (H-bond) under an electric field. Herein, we combine in situ spectroscopy with molecular dynamics simulation to unravel the dynamic evolution of the interfacial solvation structure. We find two critical change processes involving Zn-electroplating/stripping, including the initial electric double layer establishment to form an H2O-rich interface (abrupt change) and the subsequent dynamic evolution of an H-bond (gradual change). Moreover, the number of H-bonds increases, and their strength weakens in comparison with the bulk electrolyte under bias potential during Zn2+ desolvation, forming a diluted interface, resulting in massive hydrogen production. On the contrary, a concentrated interface (H-bond number decreases and strength enhances) is formed and produces a small amount of hydrogen during Zn2+ solvation. The insights on the above results contribute to deciphering the H-bond evolution with competition/corrosion HER during Zn-electroplating/stripping and clarifying the essence of electrochemical window widened and HER suppression by high concentration. This work presents a new strategy for aqueous electrolyte regulation by benchmarking the abrupt change of the interfacial state under an electric field as a zinc performance-enhancement criterion.

4.
J Am Chem Soc ; 146(7): 4557-4569, 2024 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-38345667

RESUMO

Intelligent utilization of the anionic redox reaction (ARR) in Li-rich cathodes is an advanced strategy for the practical implementation of next-generation high-energy-density rechargeable batteries. However, due to the intrinsic complexity of ARR (e.g., nucleophilic attacks), the instability of the cathode-electrolyte interphase (CEI) on a Li-rich cathode presents more challenges than typical high-voltage cathodes. Here, we manipulate CEI interfacial engineering by introducing an all-fluorinated electrolyte and exploiting its interaction with the nucleophilic attack to construct a gradient CEI containing a pair of fluorinated layers on a Li-rich cathode, delivering enhanced interfacial stability. Negative/detrimental nucleophilic electrolyte decomposition has been efficiently evolved to further reinforce CEI fabrication, resulting in the construction of LiF-based indurated outer shield and fluorinated polymer-based flexible inner sheaths. Gradient interphase engineering dramatically improved the capacity retention of the Li-rich cathode from 43 to 71% after 800 cycles and achieved superior cycling stability in anode-free and pouch-type full cells (98.8% capacity retention, 220 cycles), respectively.

5.
Small ; 20(25): e2310341, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38225705

RESUMO

The safety, low cost, and high power density of aqueous Zn-based devices (AZDs) appeal to large-scale energy storage. Yet, the presence of hydrogen evolution reaction (HER) and chemical corrosion in the AZDs leads to local OH- concentration increasement and the formation of ZnxSOy(OH)z•nH2O (ZHS) by-products at the Zn/electrolyte interface, causing instability and irreversibility of the Zn-anodes. Here, a strategy is proposed to regulate OH- by introducing a bio-sourced/renewable polypeptide (ɛ-PL) as a pH regulator in electrolyte. The consumption of OH- species is evaluated through in vitro titration and cell in vivo in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy at a macroscopic and molecular level. The introduction of ɛ-PL is found to significantly suppress the formation of ZHS and associated side reactions, and reduce the local coordinated H2O of the Zn2+ solvation shell, widening electrochemical stable window and suppressing OH- generation during HER. As a result, the inclusion of ɛ-PL improves the cycle time of Zn/Zn symmetrical cells from 15 to 225 h and enhances the cycle time of aqueous Zn- I2 cells to 1650 h compared to those with pristine electrolytes. This work highlights the potential of kinetical OH- regulation for by-product and dendrite-free AZDs.

6.
Small ; : e2406110, 2024 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-39113670

RESUMO

In this study, state-of-the-art on-line pyrolysis MS (OP-MS) equipped with temperature-controlled cold trap and on-line pyrolysis GC/MS (OP-GC/MS) injected through high-vacuum negative-pressure gas sampling (HVNPGS) programming are originally designed/constructed to identify/quantify the dynamic change of common permanent gases and micromolecule organics from the anode/cathode-electrolyte reactions during thermal runaway (TR) process, and corresponding TR mechanisms are further perfected/complemented. On LiCx anode side, solid electrolyte interphase (SEI) would undergo continuous decomposition and regeneration, and the R-H+ (e.g., HF, ROH, etc.) species derived from electrolyte decomposition would continue to react with Li/LiCx to generate H2. Up to above 200 °C, the O2 would release from the charged NCM cathode and organic radicals would be consumed/oxidized by evolved O2 to form COx, H2O, and more corrosive HF. On the contrary, charged LFP cathode does not present obvious O2 evolution during heating process and the unreacted flammable/toxic organic species would exit in the form of high temperature/high-pressure (HT/HP) vapors within batteries, indicating higher potential safety risks. Additionally, the in depth understanding of the TR mechanism outlined above provides a clear direction for the design/modification of thermostable electrodes and non-flammable electrolytes for safer batteries.

7.
Microb Pathog ; 187: 106515, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38160987

RESUMO

In this study, a low molecular weight poly-d-mannose (LMWM) was separated from a mixed polysaccharide synthesized previously. Monosaccharide composition, Fourier-Transform infrared spectroscopy (FT-IR), periodate oxidation and smith degradation were determined. After safety evaluation, the inhibition of LMWM on the different biofilm formation stages of Salmonella enterica serovar Typhimurium (S. Typhimurium) was tested in vitro. Furthermore, the effect of LMWM on the adhesion of S. Typhimurium to Caco-2 cells and cell surface hydrophobicity (CSH) were observed. Results indicated that LMWM was a homopolysaccharide without cytotoxicity and hemolysis, containing both α-mannose and ß-mannose. It showed obvious anti-biofilm activity on S. Typhimurium and mainly activated on the initial adhesion and formation stage, even better than the commercial S. cerevisiae mannan (CM). LMWM inhibited the adhesion of S. Typhimurium on Caco-2 cells with the inhibition rate of 61.04 % at 2 mg/ml. Meanwhile, LMWM decreased the hydrophobicity of S. Typhimurium cell surface. In conclusion, the inhibitory effect on S. Typhimurium biofilm was not caused by bacteriostatic or bactericidal activity of LMWM. The specific anti-adhesion and the decrease of bacterial CSH by LMWM may closely relate to anti-biofilm mechanism. This study provides some supports for the application of LMWM as antibiotics alternative on S. Typhimurium in the future.


Assuntos
Manose , Salmonella typhimurium , Humanos , Manose/metabolismo , Manose/farmacologia , Células CACO-2 , Peso Molecular , Saccharomyces cerevisiae , Espectroscopia de Infravermelho com Transformada de Fourier , Biofilmes
8.
Phys Rev Lett ; 132(8): 083601, 2024 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-38457704

RESUMO

Quantum non-Gaussianity, a more potent and highly useful form of nonclassicality, excludes all convex mixtures of Gaussian states and Gaussian parametric processes generating them. Here, for the first time, we conclusively test quantum non-Gaussian coincidences of entangled photon pairs with the Clauser-Horne-Shimony-Holt-Bell factor S=2.328±0.004 from a single quantum dot with a depth up to 0.94±0.02 dB. Such deterministically generated photon pairs fundamentally overcome parametric processes by reducing crucial multiphoton errors. For the quantum non-Gaussian depth of the unheralded (heralded) single-photon state, we achieve the value of 8.08±0.05 dB (19.06±0.29 dB). Our Letter experimentally certifies the exclusive quantum non-Gaussianity properties highly relevant for optical sensing, communication, and computation.

9.
Phys Rev Lett ; 132(16): 160801, 2024 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-38701444

RESUMO

A solid-state approach for quantum networks is advantageous, as it allows the integration of nanophotonics to enhance the photon emission and the utilization of weakly coupled nuclear spins for long-lived storage. Silicon carbide, specifically point defects within it, shows great promise in this regard due to the easy of availability and well-established nanofabrication techniques. Despite of remarkable progresses made, achieving spin-photon entanglement remains a crucial aspect to be realized. In this Letter, we experimentally generate entanglement between a silicon vacancy defect in silicon carbide and a scattered single photon in the zero-phonon line. The spin state is measured by detecting photons scattered in the phonon sideband. The photonic qubit is encoded in the time-bin degree of freedom and measured using an unbalanced Mach-Zehnder interferometer. Photonic correlations not only reveal the quality of the entanglement but also verify the deterministic nature of the entanglement creation process. By harnessing two pairs of such spin-photon entanglement, it becomes straightforward to entangle remote quantum nodes at long distance.

10.
Inorg Chem ; 63(4): 2060-2071, 2024 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-38232754

RESUMO

The synthesis of two versatile fluorescent metal-organic frameworks (MOFs), [Eu(4-NCP)(1,4-bdc)]n·0.5H2O (1) and [Eu(4-NCP)(4,4'-bpdc)]n·0.75H2O (2) (HNCP = 2-(4-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline, 1,4-H2bdc = benzene-1,4-dicarboxylic acid, 4,4'-H2bpdc = 4,4'-biphenyldicarboxylic acid), was carried out using a hydrothermal method. These MOFs were characterized through various advanced technologies to determine their structural information. The results indicate that both MOFs exhibited 3D network structures with specific topologies. Furthermore, these MOFs demonstrated exceptional thermal stabilities and adsorption capabilities. Additionally, complex 2 was utilized for studying the fluorescence sensing properties of various micronutrients including metal ions, nitro aromatic compounds, and biological small molecules. Notably, complex 2 showed promising potential as a multifunctional sensor for selectively detecting Fe3+, nitrobenzene, and ascorbic acid in aqueous solutions through fluorescence quenching with low limits of detection (LODs ∼ 10-7 M) and high quenching constants (Ksv ∼ 103 M-1). Moreover, the detection mechanism of complex 2 was further investigated by using experimental methods and DFT calculations.

11.
Acta Pharmacol Sin ; 2024 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-39030309

RESUMO

Recombinant human type 5 adenovirus (H101) is an oncolytic virus used to treat nasopharyngeal carcinoma. Owing to the deletion of the E1B-55kD and E3 regions, H101 is believed to selectively inhibit nasopharyngeal carcinoma. Whether H101 inhibits other type of tumors via different mechanisms remains unclear. In this study we investigated the effects of H101 on melanomas. We established B16F10 melanoma xenograft mouse model, and treated the mice with H101 (1 × 108 TCID50) via intratumoral injection for five consecutive days. We found that H101 treatment significantly inhibited B16F10 melanoma growth in the mice. H101 treatment significantly increased the infiltration of CD8+ T cells and reduced the proportion of M2-type macrophages. We demonstrated that H101 exhibited low cytotoxicity against B16F10 cells, but the endothelial cells were more sensitive to H101 treatment. H101 induced endothelial cell pyroptosis in a caspase-1/GSDMD-dependent manner. Furthermore, we showed that the combination of H101 with the immune checkpoint inhibitor PD-L1 antibody (10 mg/kg, i.p., every three days for three times) exerted synergic suppression on B16F10 tumor growth in the mice. This study demonstrates that, in addition to oncolysis, H101 inhibits melanoma growth by promoting anti-tumor immunity and inducing pyroptosis of vascular endothelial cells.

12.
Environ Res ; 251(Pt 1): 118614, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38462084

RESUMO

Organophosphate esters (OPEs) have been widely used as flame retardants and plasticizers in consumer and industrial products. They have been found to have numerous exposure hazards. Recently, several OPEs have been detected in surface waters around the world, which may pose potential ecological risks to freshwater organisms. In this study, the concentration, spatial variation, and ecological risk of 15 OPEs in the Beiyun and Yongding rivers were unprecedentedly investigated by the ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and risk quotient (RQ) method. The result showed that triethyl phosphate (TEP), tri (2-chloroisopropyl) phosphate (TCPP) were the most abundant OPEs with average concentrations of 55.53 ng/L and 42.29 ng/L, respectively. The concentrations of OPEs in the Beiyun River are higher than in the Yongding River, and their levels were higher in densely populated and industrial areas. The risk assessment showed that there was insignificant from OPEs to freshwater organisms in these rivers (RQs <0.1). The risk was higher downstream than upstream, which was related to human-intensive industrial activities downstream in the Yongding River. The ecological risk of OPEs in surface waters worldwide was estimated by joint probability curves (JPCs), and the result showed that there was a moderate risk for tri (2-chloroethyl) phosphate (TCEP), a low risk for trimethyl phosphate (TMP), and insignificant for other OPEs. In addition, the QSAR-ICE-SSD model was used to calculate the hazardous concentration for 5% (HC5). This result validated the feasibility and accuracy of this model in predicting acute data of OPEs and reducing biological experiments on the toxicity of OPEs. These results revealed the ecological risk of OPEs and provided the scientific basis for environmental managers.


Assuntos
Monitoramento Ambiental , Organofosfatos , Rios , Poluentes Químicos da Água , Medição de Risco , Poluentes Químicos da Água/análise , Organofosfatos/análise , Rios/química , Ésteres/análise , China , Espectrometria de Massas em Tandem , Retardadores de Chama/análise , Cidades
13.
Mikrochim Acta ; 191(7): 377, 2024 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-38850342

RESUMO

A novel molecularly imprinted ratiometric fluorescent sensor CQDs@MIP/FITC@SiO2 for the detection of p-nitroaniline (p-NA) was constructed through the mixture of CQDs@MIP and FITC@SiO2 in the ratio of 1:1 (VCQDs@MIP:VFITC@SiO2). The polymers of CQDs@MIP and FITC@SiO2 were prepared by sol-gel method and reversed-phase microemulsion method, respectively. CQDs@MIP was used as the auxiliary response signal and FITC@SiO2 was used as the reference enhancement signal. The signal was measured at excitation/emission wavelengths of 365/438, 512 nm. The sensor showed good linearity in the concentration range 0.14-40.00 µM (R2 = 0.998) with a detection limit of 0.042 µM for p-NA. The color change of "blue-cyan-green" could be observed by the naked eye under 365 nm UV light, thus realizing the visual detection of p-NA. The sensor presented comparable results compared with high-performance liquid chromatography (HPLC) method for the detection of p-NA in hair dye paste and aqueous samples with recoveries of 96.8-103.7% and 95.8-104.4%, respectively. It was demonstrated that the constructed sensor possesses the advantages of simplicity, excellent selectivity, superior sensitivity, and outstanding stability.

14.
J Oral Rehabil ; 51(4): 639-647, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38100233

RESUMO

BACKGROUND: Sleep disorders are associated with temporomandibular disorders (TMDs). Limited studies have focused on excessive daytime sleepiness (EDS) and its impact on jaw functions in TMD patients. OBJECTIVE: The aim of the present investigation was to identify the impact of EDS on pain and jaw function in TMD patients. METHODS: A total of 338 TMD patients (50 males and 288 females) was included. The Epworth Sleepiness Scale (ESS) was used to classify patients into EDS group (score ≥ 10) and non-EDS group (score < 10). The Jaw Functional Limitation Scale 8-item (JFLS-8) was used to assess the severity of jaw dysfunction. Pain intensity was evaluated using the Visual Analogue Scale (VAS). Anxiety and depression were evaluated using the Generalised Anxiety Disorder 7-item (GAD-7) and the Patient Health Questionnaire 9-item (PHQ-9). All included patients were diagnosed with pain-related TMD (PT), intra-articular TMD (IT) or combined TMD (CT). RESULTS: Compared with non-EDS patients, EDS patients exhibited more severe jaw dysfunction, greater pain intensity and higher PHQ-9 scores (p < .05). Multivariate analyses showed that EDS (B = 3.69), female gender (B = 3.69), and elevated GAD-7 score (B = 0.73) were significantly associated with an increased score on the JFLS-8 (p < .05). Moreover, bivariate logistic regression analysis indicated a significant relationship between EDS and PT (OR = 2.70, p = .007). CONCLUSION: The presence of EDS was more closely related to PT, but the causal relationship between them needs to be further confirmed. More concern and intervention to alleviate poor sleep quality might be highlighted during the treatment of TMD, especially PT subtype.


Assuntos
Transtornos do Sono-Vigília , Transtornos da Articulação Temporomandibular , Masculino , Humanos , Feminino , Medição da Dor , Ansiedade , Dor , Transtornos da Articulação Temporomandibular/complicações
15.
J Oral Rehabil ; 51(7): 1166-1174, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38514933

RESUMO

OBJECTIVE: The objective of the study was to investigate the relationship between types of disc displacement (DD) diagnosed by magnetic resonance imaging (MRI), and the risk (presence or absence) and severity of condylar erosion (CE) graded using cone-beam computed tomography (CBCT) in adult Temporomandibular disorders (TMD) patients. METHODS: A total of 353 TMD patients (283 females, 70 males) underwent MRI scans to categorise DD as normal (NA), anterior displacement with reduction (ADDR), or anterior displacement without reduction (ADDNR). CE severity was graded on a scale of 0-3 (absence, mild, moderate or severe) using CBCT. To establish the plausibility and cut-off points for CE diagnosis, the severity of CE was then further divided into three classifications: Grade 0 versus 1 + 2 + 3; Grades 0 + 1 versus 2 + 3; Grades 0 + 1 + 2 versus 3. Logistic regression analysis was performed, adjusting for age, gender and joint correlation. RESULTS: ADDNR significantly increased the risk of CE compared with NA (OR = 10.04, 95% CI: [6.41, 15.73]) and showed a significant increase in CE severity across all classifications (ORs = 10.04-18.95). The effects of ADDNR were significant in both genders (p < .001) and had a greater impact in females. ADDR was predominantly associated with mild CE. CONCLUSIONS: ADDNR significantly increased the risk and severity of CE independent of gender when compared to NA, whereas ADDR was mainly associated with mild CE. Slight cortical discontinuity may represent a subclinical diagnosis requiring further investigation.


Assuntos
Tomografia Computadorizada de Feixe Cônico , Luxações Articulares , Imageamento por Ressonância Magnética , Côndilo Mandibular , Disco da Articulação Temporomandibular , Transtornos da Articulação Temporomandibular , Humanos , Feminino , Masculino , Transtornos da Articulação Temporomandibular/diagnóstico por imagem , Transtornos da Articulação Temporomandibular/fisiopatologia , Transtornos da Articulação Temporomandibular/patologia , Adulto , Luxações Articulares/diagnóstico por imagem , Luxações Articulares/patologia , Disco da Articulação Temporomandibular/diagnóstico por imagem , Disco da Articulação Temporomandibular/patologia , Côndilo Mandibular/diagnóstico por imagem , Côndilo Mandibular/patologia , Pessoa de Meia-Idade , Índice de Gravidade de Doença , Adulto Jovem , Fatores de Risco
16.
J Sci Food Agric ; 104(2): 611-619, 2024 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-37437092

RESUMO

BACKGROUND: Peeling of crayfish is a very important process in production. Crayfish peeling by machine can increase production efficiency and enhance safety in the production process. The tight muscle-shell attachment causes difficulty in peeling freshly caught crayfish. However, few studies have explored the changes in crayfish quality under favorable shell-loosening treatments. RESULTS: In this study, the shell-loosening properties of crayfish and changes in crayfish quality, microstructure and protein fluorescent features were investigated after high hydrostatic pressure (HHP) treatment. New methods were established to measure the peeling performance of crayfish, which are peelability and meat yield rate (MYR). The normalization of peelability and MYR were verified by different weights of crayfish tails and different treatments. The peeling effect of HHP-treated crayfish was evaluated by a new quantitative measurement method, and MYR was calculated. The results showed that all the HHP treatments reduced crayfish peeling work and increased MYR. The HHP treatment provided better crayfish quality in terms of texture and color and enlarged the shell-loosening gap. Among all HHP treatments, 200 MPa treatment exhibited lower peeling work, higher MYR and an expansion of the shell-loosening gap, reaching up to 573.8 µm. At the same time, 200 MPa treatment could maintain crayfish quality. CONCLUSION: The findings outlined above suggest that high pressure is a promising method for loosening crayfish shells. 200 MPa is an optimal HHP treatment condition for crayfish peeling, exhibiting a promising application in industrial processing. © 2023 Society of Chemical Industry.


Assuntos
Astacoidea , Microbiologia de Alimentos , Animais , Pressão Hidrostática , Manipulação de Alimentos/métodos , Alimentos Marinhos/análise
17.
Angew Chem Int Ed Engl ; 63(17): e202400254, 2024 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-38441399

RESUMO

Acting as a passive protective layer, solid-electrolyte interphase (SEI) plays a crucial role in maintaining the stability of the Li-metal anode. Derived from the reductive decomposition of electrolytes (e.g., anion and solvent), the SEI construction presents as an interfacial process accompanied by the dynamic de-solvation process during Li-metal plating. However, typical electrolyte engineering and related SEI modification strategies always ignore the dynamic evolution of electrolyte configuration at the Li/electrolyte interface, which essentially determines the SEI architecture. Herein, by employing advanced electrochemical in situ FT-IR and MRI technologies, we directly visualize the dynamic variations of solvation environments involving Li+-solvent/anion. Remarkably, a weakened Li+-solvent interaction and anion-lean interfacial electrolyte configuration have been synchronously revealed, which is difficult for the fabrication of anion-derived SEI layer. Moreover, as a simple electrochemical regulation strategy, pulse protocol was introduced to effectively restore the interfacial anion concentration, resulting in an enhanced LiF-rich SEI layer and improved Li-metal plating/stripping reversibility.

18.
Angew Chem Int Ed Engl ; : e202412214, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39141606

RESUMO

Electrolyte engineering is crucial for improving cathode electrolyte interphase (CEI) to enhance the performance of lithium-ion batteries, especially at high charging cut-off voltages. However, typical electrolyte modification strategies always focus on the solvation structure in the bulk region, but consistently neglect the dynamic evolution of electrolyte solvation configuration at the cathode-electrolyte interface, which directly influences the CEI construction. Herein, we reveal an anti-synergy effect between Li+-solvation and interfacial electric field by visualizing the dynamic evolution of electrolyte solvation configuration at the cathode-electrolyte interface, which determines the concentration of interfacial solvated-Li+. The Li+ solvation in the charging process facilitates the construction of a concentrated (Li+-solvent/anion-rich) interface and anion-derived CEI, while the repulsive force derived from interfacial electric field induces the formation of a diluted (solvent-rich) interface and solvent-derived CEI. Modifying the electrochemical protocols and electrolyte formulation, we regulate the "inflection voltage" arising from the anti-synergy effect and prolong the lifetime of the concentrated interface, which further improves the functionality of CEI architecture.

19.
Angew Chem Int Ed Engl ; 63(6): e202316790, 2024 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-38116869

RESUMO

Electrolyte engineering is a fascinating choice to improve the performance of Li-rich layered oxide cathodes (LRLO) for high-energy lithium-ion batteries. However, many existing electrolyte designs and adjustment principles tend to overlook the unique challenges posed by LRLO, particularly the nucleophilic attack. Here, we introduce an electrolyte modification by locally replacing carbonate solvents in traditional electrolytes with a fluoro-ether. By benefit of the decomposition of fluoro-ether under nucleophilic O-related attacks, which delivers an excellent passivation layer with LiF and polymers, possessing rigidity and flexibility on the LRLO surface. More importantly, the fluoro-ether acts as "sutures", ensuring the integrity and stability of both interfacial and bulk structures, which contributed to suppressing severe polarization and enhancing the cycling capacity retention from 39 % to 78 % after 300 cycles for the 4.8 V-class LRLO. This key electrolyte strategy with comprehensive analysis, provides new insights into addressing nucleophilic challenge for high-energy anionic redox related cathode systems.

20.
Rev Cardiovasc Med ; 23(7): 230, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-39076896

RESUMO

Background: Homeostasis of thyroid hormones has significant effects on the cardiovascular system. The aim of this study was to investigate the association between free triiodothyronine (FT3) and adverse cardiovascular events in patients with acute coronary syndrome (ACS) who were undergoing percutaneous coronary intervention (PCI). Methods: A total of 1701 patients with ACS undergoing PCI were included in this study. All patients were divided into three groups according to the tertiles of FT3 level: the lowest tertile (FT3 < 4.51 pmol/L), the middle tertile (4.51 pmol/L ≤ FT3 < 4.89 pmol/L) and the highest tertile group (FT3 ≥ 4.89 pmol/L). The primary study endpoint was a composite of major adverse cardiovascular events (MACE), which included all-cause death, ischemic stroke, myocardial infarction, or unplanned repeat revascularization. Results: During a median follow-up period of 927 days, 349 patients had at least one event. Compared with patients with the highest tertile, those with the lowest tertile had a significantly higher incidence of MACE, all-cause death, MI, ischemic stroke and repeat revascularization (all p values < 0.05). In the multivariate Cox regression analysis, the middle tertile had similar risk of MACE (HR = 0.986, 95% CI 0.728-1.336, p = 0.929) as the highest tertile, but the patients with the lowest tertile had a 92.9% higher risk of MACE (HR = 1.929, 95% CI 1.467-2.535, p < 0.001). There was a non-linear relationship between FT3 and MACE and unplanned repeat revascularization (all p values for non-linear association < 0.001). Adding the tertiles of FT3 level into the baseline model yielded a significant improvement in discrimination for predicting MACE ( Δ AUC = 0.013, p = 0.025). Conclusions: A significantly reduced FT3 level was independently associated with a worse prognosis in patients with ACS undergoing PCI.

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