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1.
FASEB J ; 37(3): e22824, 2023 03.
Artigo em Inglês | MEDLINE | ID: mdl-36809539

RESUMO

The present study investigated the effects of 2'-5' oligoadenylate synthetase-like (OASL) on the biological functions of stomach adenocarcinoma (STAD) cells and tumor formation in nude mice. The differential expression levels of OASL in the different cancer types from TCGA dataset were analyzed using gene expression profiling interactive analysis. Overall survival and the receiver operating characteristic were analyzed using the KM plotter and R, respectively. Furthermore, OASL expression and its effects on the biological functions of STAD cells were detected. The possible upstream transcription factors of OASL were predicted using JASPAR. The downstream signaling pathways of OASL were analyzed using GSEA. Tumor formation experiments were performed to evaluate the effect of OASL on tumor formation in nude mice. The results showed that OASL was highly expressed in STAD tissues and cell lines. OASL knockdown markedly inhibited cell viability, proliferation, migration, and invasion and accelerated STAD cell apoptosis. Conversely, OASL overexpression had the opposite effect on STAD cells. JASPAR analysis revealed that STAT1 is an upstream transcription factor of OASL. Furthermore, GSEA showed that OASL activated the mTORC1 signaling pathway in STAD. The protein expression levels of p-mTOR and p-RPS6KB1 were suppressed by OASL knockdown and promoted by OASL overexpression. The mTOR inhibitor, rapamycin, markedly reversed the effect of OASL overexpression on STAD cells. Additionally, OASL promoted tumor formation and increased tumor weight and volume in vivo. In conclusion, OASL knockdown suppressed the proliferation, migration, invasion, and tumor formation of STAD cells by inhibiting the mTOR signaling pathway.


Assuntos
2',5'-Oligoadenilato Sintetase , Adenocarcinoma , Neoplasias Gástricas , Animais , Camundongos , Adenocarcinoma/patologia , Alvo Mecanístico do Complexo 1 de Rapamicina/metabolismo , Camundongos Nus , Transdução de Sinais , Neoplasias Gástricas/genética , Serina-Treonina Quinases TOR/metabolismo , 2',5'-Oligoadenilato Sintetase/genética
2.
Drug Resist Updat ; 68: 100936, 2023 05.
Artigo em Inglês | MEDLINE | ID: mdl-36764075

RESUMO

AIMS: Long non-coding RNAs (lncRNAs), as one of the components of exosomes derived from cancer-associated fibroblasts (CAFs), exhibit a crucial role in the pathogenesis and chemoresistance of gastric cancer (GC). Herein, we investigated the role and mechanism of a novel lncRNA disheveled binding antagonist of beta catenin3 antisense1 (DACT3-AS1) and its involvement in GC. METHODS: DACT3-AS1 was identified by RNA-sequencing and verified by quantitative reverse transcription polymerase chain reaction (qRT-PCR). The functional role of DACT3-AS1 in GC was evaluated using in vitro and in vivo experiments including Transwell assay, 5-Ethynyl-2'-deoxyuridine (EdU) assay, immunoblotting, and xenograft tumor mouse model. Dual-luciferase reporter assay was performed to assess the association between genes. RESULTS: DACT3-AS1 was downregulated and involved in poor prognosis of patients with GC. The results from both in vitro and in vivo experiments showed that DACT3-AS1 suppressed cell proliferation, migration, and invasion through targeting miR-181a-5p/sirtuin 1 (SIRT1) axis. Additionally, DACT3-AS1 was transmitted from CAFs to GC cells mainly via exosomes. Exosomal DACT3-AS1 alleviated xenograft tumor growth. DACT3-AS1 conferred sensitivity of cancer cells to oxaliplatin through SIRT1-mediated ferroptosis both in vitro and in vivo. CONCLUSIONS: CAFs-derived exosomal DACT3-AS1 is a suppressive regulator in malignant transformation and oxaliplatin resistance. DACT3-AS1 could be used for diagnosis and treatment of GC.


Assuntos
Fibroblastos Associados a Câncer , Ferroptose , MicroRNAs , Neoplasias Gástricas , Humanos , Camundongos , Animais , MicroRNAs/genética , MicroRNAs/metabolismo , Oxaliplatina/farmacologia , Oxaliplatina/uso terapêutico , Neoplasias Gástricas/tratamento farmacológico , Neoplasias Gástricas/genética , Neoplasias Gástricas/metabolismo , Ferroptose/genética , Sirtuína 1/metabolismo , Fibroblastos Associados a Câncer/metabolismo , Transformação Celular Neoplásica , Proliferação de Células , Linhagem Celular Tumoral , Proteínas Adaptadoras de Transdução de Sinal/metabolismo
3.
Phys Chem Chem Phys ; 25(41): 28086-28093, 2023 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-37817676

RESUMO

The competition between E2 and SN2 reactions is essential in organic chemistry. In this paper, the reaction mechanism of F- + CH3CH2Cl is investigated utilizing direct dynamics simulations, and unravel how the collision energy (Ecoll) and the leaving group affect the competition between SN2 and E2 in the F- + CH3CH2Y (Y = Cl and Br) reactions. Simulation results for F- + CH3CH2Cl reaction show that the anti-E2 channel is dominant, but with the increase of Ecoll from 0.04 to 1.9 eV the branching ratio of the anti-E2 pathway significantly decreases by 21%, and the SN2 pathway becomes more important. A transition from indirect to direct reaction has been revealed when Ecoll is increased from 0.04 to 1.90 eV. At lower Ecoll, a large ratio of indirect events occurs via a long-lived hydrogen-bonded complex, and as the collision energy is increased, the lifetimes of the hydrogen-bonded complexes are shortened, due to an initial faster relative velocity. The simulation results of F- + CH3CH2Cl are further compared with the F- + CH3CH2Br reaction at Ecoll of 0.04 eV. Changing the leaving group from Cl to Br drastically suppresses the indirect events of anti-E2 with a branching ratio decreasing from 0.46 to 0.36 due to the mass effect, and promotes direct rebound mechanism resulting from a looser transition state geometry caused by varied electronegativity.

4.
J Phys Chem A ; 127(15): 3381-3389, 2023 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-37039624

RESUMO

The effect of nucleophiles on the gas-phase E2/SN2 competition is still not completely elucidated, despite its importance in chemistry. In the current work, the electronic structure calculations of prototypical reactions X- + CH3CH2Cl (X = OH, F, Cl, Br, and I) are performed at the MP2 level with aug-cc-pVDZ or ECP/d. The effects of nucleophiles on the competing E2 and SN2 reactions in terms of the correlation between the barrier height and reaction energy, electronegativity of X, bond length, charge distribution, and proton affinity of anionic nucleophile X- are explored and emphasized. As the nucleophile changes from OH- to I-, both SN2 and E2 reactions become more exothermic, with the reaction energy in the ranges from -51.9 to 10.8 kcal mol-1 (SN2) and -36.8 to 38.0 kcal mol-1(E2). For X- = F- and OH-, the sequence of reactivity for the four pathways is ret-SN2 < syn-E2 < anti-E2 ∼ inv-SN2. However, for X- = Cl-, Br-, and I-, the anti-E2 barrier is much higher in energy (17.1-29.4 kcal mol-1) than that of inv-SN2. Energy decomposition analysis illustrates that the anti-E2 pathway possesses the highly destabilizing characteristic distortion, resulting in a larger reaction barrier and hence becoming a more unfavorable pathway than inv-SN2. More interestingly, only ion-dipole complex exists in the entrance channel for reactions involving OH-, Cl-, Br-, and I-, and in contrast, a significant hydrogen-bonded complex formation is also revealed for X- = F-, which can further affect E2/SN2 competition and atomic-level mechanisms, especially, for the isoelectronic nucleophile F- and OH-. It has been revealed here that electronegativity of central atoms in X and ionic radii of nucleophiles are the important factors affecting the entrance channel complex.

5.
Molecules ; 28(17)2023 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-37687098

RESUMO

The competition between base-induced elimination (E2) and bimolecular nucleophilic substitution (SN2) is of significant importance in organic chemistry and is influenced by many factors. The electronic structure calculations for the gas-phase reactions of F- + RY (R = CH3, C2H5, iC3H7, tC4H9, and Y = Cl, I) are executed at the MP2 level with aug-cc-pVDZ or ECP/d basis set to investigate the α-methyl substitution effect. The variation in barrier height, reaction enthalpy, and competition of SN2/E2 as a function of methyl-substitution and leaving group ability has been emphasized. And the nature of these rules has been explored. As the degree of methyl substitution on α-carbon increases, the E2 channel becomes more competitive and dominant with R varying from C2H5, iC3H7, to tC4H9. Energy decomposition analysis offers new insights into the competition between E2 and SN2 processes, which suggests that the drop in interaction energy with an increasing degree of substitution cannot compensate for the rapid growth of preparation energy, leading to a rapid increase in the SN2 energy barrier. By altering the leaving group from Cl to I, the barriers of both SN2 and E2 monotonically decrease, and, with the increased number of substituents, they reduce more dramatically, which is attributed to the looser transition state structures with the stronger leaving group ability. Interestingly, ∆E0‡ exhibits a positive linear correlation with reaction enthalpy (∆H) and halogen electronegativity. With the added number of substituents, the differences in ∆E0‡ and ∆H between Y = Cl and I likewise exhibit good linearity.

6.
Phys Chem Chem Phys ; 24(39): 24146-24154, 2022 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-36168813

RESUMO

Direct dynamic simulations have been employed to investigate the OH- + CH3Cl reaction with the chosen B3LYP/aug-cc-pVDZ method. The calculated rate coefficient for the bimolecular nucleophilic substitution reaction (SN2), 1.0 × 10-9 cm3 mol-1 s-1 at 300 K, agrees well with the experimental result of (1.3-1.6) × 10-9 cm3 mol-1 s-1. The simulations reveal that the majority of the SN2 reactions are temporarily trapped in the hydrogen-bonded complex at Ecoll = 0.89 kcal mol-1. Importantly, the influences of the leaving group and nucleophile have been discussed by comparisons of X- + CH3Y (X = F, OH; Y = Cl, I) reactions. For the X = F- reactions, the reaction probability of SN2 increases along the increased leaving group ability Cl < I, suggesting that the thermodynamic factor plays a key role. The indirect mechanisms were found to be dominant for both reactions. In contrast, for X = OH-, the fraction of SN2 drops with the enhanced leaving group ability. In particular, a dramatic transition occurs for the dominant atomic reaction mechanisms, i.e., from complex-mediated indirect to direct, implying an interesting contest between the leaving group and the nucleophile and the importance of the dynamic factors, i.e., the dipole moment, steric hindrance, and electronegativity.

7.
Molecules ; 27(21)2022 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-36364445

RESUMO

Nonmetallic co-doping and surface hole construction are simple and efficient strategies for improving the photocatalytic activity and regulating the electronic structure of g-C3N4. Here, the g-C3N4 catalysts with B-F or B-S co-doping combined with nitrogen vacancies (Nv) are designed. Compared to the pristine g-C3N4, the direction of the excited electron orbit for the B-F-co-doped system is more matching (N2pz→C2pz), facilitating the separation of electrons and holes. Simultaneously, the introduced nitrogen vacancy can further reduce the bandgap by generating impurity states, thus improving the utilization rate of visible light. The doped S atoms can also narrow the bandgap of the B-S-Nv-co-doped g-C3N4, which originates from the p-orbital hybridization between C, N, and S atoms, and the impurity states are generated by the introduction of N vacancies. The doping of B-F-Nv and B-S-Nv exhibits a better CO2 reduction activity with a reduced barrier for the rate-determining step of around 0.2 eV compared to g-C3N4. By changing F to S, the origin of the rate-determining step varies from *CO2→*COOH to *HCHO→*OCH3, which eventually leads to different products of CH3OH and CH4, respectively.

8.
Phys Chem Chem Phys ; 23(18): 10814-10821, 2021 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-33908439

RESUMO

Proton transfer between HOCO+ and CO produces the formyl cation HCO+ and isoformyl cation HOC+ isomers initiating multiple astrochemical reaction networks. Here, the direct chemical dynamics simulations are performed to uncover the underlying atomistic dynamics of the above reaction. The simulations reproduce the measured product energy and scattering angle distributions and reveal that the reaction proceeds predominantly through a direct stripping mechanism which results in the prominent forward scattering observed in experiments. The reaction dynamics show propensity for the HCO+ product even at a collision energy larger than the threshold for HOC+ formation. This is a consequence of the larger opacity and impact parameter range for HCO+. In accordance with the revealed direct mechanistic feature, the reaction can be controlled by orienting the reactants into a reactive H-C orientation that also favors HCO+ formation. Considering the lack of equilibrated reactant complexes and the on the fly migration of the proton, the CO2-catalyzed isomerization is assumed to have insignificant impact on the isomer ratios. This work provides insights of dynamical effects besides energetics into the interesting finding of strongly suppressed formation of the metastable isoformyl cation for related proton transfer reactions in the measurements.

9.
Cell Mol Life Sci ; 77(14): 2681-2699, 2020 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31974658

RESUMO

This review provides a comprehensive overview on the biomedical applications of electrical stimulation (EStim). EStim has a wide range of direct effects on both biomolecules and cells. These effects have been exploited to facilitate proliferation and functional development of engineered tissue constructs for regenerative medicine applications. They have also been tested or used in clinics for pain mitigation, muscle rehabilitation, the treatment of motor/consciousness disorders, wound healing, and drug delivery. However, the research on fundamental mechanism of cellular response to EStim has fell behind its applications, which has hindered the full exploitation of the clinical potential of EStim. Moreover, despite the positive outcome from the in vitro and animal studies testing the efficacy of EStim, existing clinical trials failed to establish strong, conclusive supports for the therapeutic efficacy of EStim for most of the clinical applications mentioned above. Two potential directions of future research to improve the clinical utility of EStim are presented, including the optimization and standardization of the stimulation protocol and the development of more tissue-matching devices.


Assuntos
Estimulação Elétrica , Manejo da Dor , Medicina Regenerativa , Engenharia Tecidual , Animais , Proliferação de Células/efeitos da radiação , Humanos
10.
Chemistry ; 26(6): 1306-1313, 2020 Jan 27.
Artigo em Inglês | MEDLINE | ID: mdl-31691411

RESUMO

Oxygen electrocatalysis is of remarkable significance for electrochemical energy storage and conversion technologies, together with fuel cells, metal-air batteries, and water splitting devices. Substituting noble metal-based electrocatalysts by decidedly effective and low-cost metal-based oxygen electrocatalysts is imperative for the commercial application of these technologies. Herein, a novel strategy is presented to fabricate selenized and phosphorized porous cobalt-nickel oxide microcubes by using a sacrificial ZnO spherical template and the resulting microcubes are employed as an oxygen evolution reaction (OER) electrocatalyst. The selenized samples manifest desirable and robust OER performance, with comparable overpotential at 10 mA cm-2 (312 mV) as RuO2 (308 mV) and better activity when the current reaches 13.7 mA cm-2 . The phosphorized samples exhibit core-shell structure with low-crystalline oxides inside amorphous phosphides, which ensures superior activity than RuO2 with the same overpotential (at 10 mA cm-2 ) yet lower Tafel slope. Such a surface doping method possibly will provide inspiration for engineering electrocatalysts applied in water oxidation.

11.
J Environ Manage ; 233: 499-512, 2019 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-30594115

RESUMO

Due to rapid urbanization and modernization, the construction sector now generates one third of all greenhouse gas emissions in China. Using an equilibrium strategy combined with the carbon allowance allocation, this study presents a synergistic Stackelberg model based on a construction project planning framework to deal with cumulative CO2 emissions. The bi-level model simultaneously considers the sequential decision-making relationship between the authority (leader) and the enterprises' interactive objectives and constraints. Unlike previous research, this bi-level model gives a holistic analysis of the interactivity of multiple stakeholders, thereby enabling the inherent conflicts and equilibrium between environmental protection and decision makers' profits to be reconciled and balanced. To deal with the bi-level model complexity, an interactive solution method that integrates an evolutionary mechanism and improved particle swarm optimization (IPSO) is designed for solving a construction supply planning problem. The robustness and practicality of the proposed methodology are then validated in a real world case, and sensitivity analyses under different carbon emissions quotas are also given. The results indicate that the methodology can systematically reduce carbon emissions in the Chinese construction sector, and when the authority has a strict emissions reduction altitude, construction practitioners are able to attain high carbon efficiencies; therefore, the model provides valuable strategy guidance for policymakers and business executives.


Assuntos
Carbono , Conservação dos Recursos Naturais , China , Comércio
12.
Anal Chem ; 90(9): 5833-5840, 2018 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-29633611

RESUMO

In this paper, we introduce a novel microfluidic combinatorial synthesis platform, referred to as Microfluidic Print-to-Synthesis (MPS), for custom high-throughput and automated synthesis of a large number of unique peptides in a microarray format. The MPS method utilizes standard Fmoc chemistry to link amino acids on a polyethylene glycol (PEG)-functionalized microdisc array. The resulting peptide microarrays permit rapid screening for interactions with molecular targets or live cells, with low nonspecific binding. Such combinatorial peptide microarrays can be reliably prepared at a spot size of 200 µm with 1 mm center-to-center distance, dimensions that require only minimal reagent consumption (less than 30 nL per spot per coupling reaction). The MPS platform has a scalable design for extended multiplexibility, allowing for 12 different building blocks and coupling reagents to be dispensed in one microfluidic cartridge in the current format, and could be further scaled up. As proof of concept for the MPS platform, we designed and constructed a focused tetrapeptide library featuring 2560 synthetic peptide sequences, capped at the N-terminus with 4-[( N'-2-methylphenyl)ureido]phenylacetic acid. We then used live human T lymphocyte Jurkat cells as a probe to screen the peptide microarrays for their interaction with α4ß1 integrin overexpressed and activated on these cells. Unlike the one-bead-one-compound approach that requires subsequent decoding of positive beads, each spot in the MPS array is spatially addressable. Therefore, this platform is an ideal tool for rapid optimization of lead compounds found in nature or discovered from diverse combinatorial libraries, using either biochemical or cell-based assays.


Assuntos
Técnicas de Química Combinatória , Técnicas Analíticas Microfluídicas , Peptídeos/análise , Impressão , Análise Serial de Proteínas , Humanos , Células Jurkat , Tamanho da Partícula , Biblioteca de Peptídeos
13.
Adv Funct Mater ; 28(10)2018 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-32440259

RESUMO

Hydrogels have been the focus of extensive research due to their potential use in fields including biomedical, pharmaceutical, biosensors, and cosmetics. However, the general weak mechanical properties of hydrogels limit their utility. Here, we generate pristine silk fibroin (SF) hydrogels with excellent mechanical properties via a binary solvent induced conformation transition (BSICT) strategy. In this method, the conformational transition of SF is regulated by moderate binary solvent diffusion and SF/solvent interactions. ß-sheet formation serves as the physical crosslinks that connect disparate protein chains to form continuous 3D hydrogel networks, avoiding complex chemical and/or physical treatments. The Young's modulus of these new BSICT-silk fibroin hydrogels can reach up to 6.5±0.2 MPa, tens to hundreds of times higher than that of conventional hydrogels (0.01-0.1 MPa). These new materials filled the "empty soft materials space" in the elastic modulus/strain Ashby plot. More remarkably, the BSICT-SF hydrogels can be processed into different constructions through different polymer and/or metal based processing techniques, such as molding, laser cutting, and machining. Thus, these new hydrogel systems exhibit potential utility in many biomedical and engineering fields.

14.
Appl Opt ; 56(2): 193-199, 2017 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-28085850

RESUMO

Noninvasive blood glucose determination has received considerable attention in the past from both patients and scientists all over the world, and it is becoming increasingly important as a research focus. The two most difficult problems leading to no breakthrough in this area are sensitivity and specificity in determination. In order to obtain reliable measurement results of blood glucose levels, we propose a new liquid photoacoustic resonance theory that can significantly enhance the intensity of the signal and improve the sensitivity. This paper demonstrates the theory of liquid photoacoustic resonance, gives a rigorous mathematical expression, and analyzes the variation of the transducer output in the case of liquid photoacoustic resonance. A signal processing method is demonstrated at the same time under the liquid photoacoustic resonance condition. Meanwhile, the feasibility and validity are verified by experiments with different concentrations of glucose solution. The result shows that liquid photoacoustic resonance can strengthen the signal, and the resolution achieves 20 mg/dL. This method overcomes the issue of low sensitivity and the inaccurate detection in the nonresonant case, and gets accurate results. This result could provide a theoretical basis for realization of noninvasive measurement of blood glucose.


Assuntos
Glicemia/análise , Técnicas Fotoacústicas , Estudos de Viabilidade , Humanos , Matemática , Reprodutibilidade dos Testes , Análise de Frequência de Ressonância , Sensibilidade e Especificidade , Transdutores
15.
Sensors (Basel) ; 17(5)2017 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-28505131

RESUMO

Directional dithering of a laser beam potentially limits the detection accuracy of a laser triangulation displacement probe. A theoretical analysis indicates that the measurement accuracy will linearly decrease as the laser dithering angle increases. To suppress laser dithering, a scheme for reduction of the influence of laser beam directional dithering in a laser triangulation displacement probe, which consists of a collimated red laser, a laser beam pointing control setup, a receiver lens, and a charge-coupled device, is proposed in this paper. The laser beam pointing control setup is inserted into the source laser beam and the measured object and can separate the source laser beam into two symmetrical laser beams. Hence, at the angle at which the source laser beam dithers, the positional averages of the two laser spots are equal and opposite. Moreover, a virtual linear function method is used to maintain a stable average of the positions of the two spots on the imaging side. Experimental results indicate that with laser beam pointing control, the estimated standard deviation of the fitting error decreases from 0.3531 mm to 0.0100 mm , the repeatability accuracy can be lowered from ±7 mm to ±5 µ m , and the nonlinear error can be reduced from ±6 % FS (full scale) to ±0.16 % FS.

16.
J Cell Sci ; 127(Pt 15): 3233-9, 2014 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-24928904

RESUMO

The apicobasal polarity of enterocytes determines where the brush border membrane (apical membrane) will form, but how this apical membrane faces the lumen is not well understood. The electrical signal across the epithelium could serve as a coordinating cue, orienting and polarizing enterocytes. Here, we show that applying a physiological electric field to intestinal epithelial cells, to mimic the natural electric field created by the transepithelial potential difference, polarized phosphorylation of the actin-binding protein ezrin, increased expression of intestinal alkaline phosphatase (ALPI, a differentiation marker) and remodeled the actin cytoskeleton selectively on the cathode side. In addition, an applied electric field also activated ERK1/2 and LKB1 (also known as STK11), key molecules in apical membrane formation. Disruption of the tyrosine protein kinase transmembrane receptor Ror2 suppressed activation of ERK1/2 and LKB1 significantly, and subsequently inhibited apical membrane formation in enterocytes. Our findings indicate that the endogenous electric field created by the transepithelial potential difference might act as an essential coordinating signal for apical membrane formation at a tissue level, through activation of LKB1 mediated by Ror2-ERK signaling.


Assuntos
Polaridade Celular , Proteínas do Citoesqueleto/metabolismo , Eletricidade , Mucosa Intestinal/fisiologia , Receptores Órfãos Semelhantes a Receptor Tirosina Quinase/metabolismo , Quinases Proteína-Quinases Ativadas por AMP , Citoesqueleto de Actina/metabolismo , Fosfatase Alcalina/genética , Fosfatase Alcalina/metabolismo , Linhagem Celular , Polaridade Celular/genética , Humanos , Mucosa Intestinal/ultraestrutura , Sistema de Sinalização das MAP Quinases/genética , Microvilosidades/ultraestrutura , Mutação/genética , Proteínas Serina-Treonina Quinases/metabolismo , RNA Interferente Pequeno/genética , Receptores Órfãos Semelhantes a Receptor Tirosina Quinase/genética , Transgenes/genética
17.
EMBO Rep ; 14(2): 184-90, 2013 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-23328740

RESUMO

Mechanisms that guide directional migration of neuroblasts from the subventricular zone (SVZ) are not well understood. We report here that endogenous electric currents serve as a guidance cue for neuroblast migration. We identify the existence of naturally occurring electric currents (1.5±0.6 µA/cm(2), average field strength of ∼3 mV/mm) along the rostral migration path in adult mouse brain. Electric fields of similar strength direct migration of neuroblasts from the SVZ in culture and in brain slices. The purinergic receptor P2Y1 mediates this migration. The results indicate that naturally occurring electric currents serve as a new guidance mechanism for rostral neuronal migration.


Assuntos
Movimento Celular , Células-Tronco Neurais/fisiologia , Receptores Purinérgicos P2Y1/fisiologia , Animais , Ventrículos Cerebrais/citologia , Impedância Elétrica , Estimulação Elétrica , Eletrodos , Técnicas de Silenciamento de Genes , Técnicas In Vitro , Camundongos , Células-Tronco Neurais/efeitos dos fármacos , Bulbo Olfatório/citologia , Antagonistas do Receptor Purinérgico P2Y/farmacologia , RNA Interferente Pequeno/genética , Suramina/farmacologia
18.
ACS Nano ; 18(2): 1733-1743, 2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-38175544

RESUMO

The carbonaceous anodes in sodium ion batteries suffer from low initial Coulombic efficiency (ICE) and poor cyclability due to rampant solid electrolyte interface (SEI) growth. The concept of the weakly solvating electrolyte (WSE) has been popularized for SEI regulation on the anode by adjusting the cation solvation structure. Nevertheless, the effects on the solvation sheath from the electrode/electrolyte interface are ignored in most WSE applications. In this work, we extend the WSE from the bulk electrolyte to the electrolyte/carbon interface. By recycling asphalt wastes into sp2 C enriched few-layer carbon on hard carbon, a weakly solvating interface is fabricated with lower adsorption energy to electrolyte solvent molecules than a pristine anode (-0.89 vs -1.08 eV for Na/diglyme). Accordingly, more anionic groups are attracted into the solvent-weakened solvation sheath during sodiation (2.30 vs 1.96 coordination number for PF6-). The anion-mediated contact ion pairs facilitate a thin, inorganic-rich SEI layer with a homogeneous distribution, which confers a high ICE of 97.9% and a high capacity of 335.6 mA h g-1 at 1 C (89.5% retention, 1000 cycles). The full battery also manifests an energy density of 209 W h kg-1. This interfacial design is applicable in both ether- and ester-based electrolytes, which is promising in cost-effective modification for carbonaceous electrodes.

19.
Adv Mater ; 36(29): e2400976, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38740388

RESUMO

ZnSO4-based electrolytes for aqueous zinc ion batteries fail to meet practical application metrics due to hydrogen evolution reaction (HER) and dendrite growth. In this work, a highly polarized eutectic additive, glycerophosphorylcholine (GPC) is rationally designed, to regulate the electric double layer (EDL) structure for stable Zn anodes with a high depth of discharge (DOD). On one hand, GPC molecules with abundant hydroxyl groups can precisely regulate the hydrogen bond network in EDL to suppress HER. On the other hand, the enrichment of GPC at the interface is positively responsible for the negative charge density on the Zn surface, which leads to the formation of a robust ZnxPyOz-rich solid-electrolyte interphase and terminates dendrite growth in the charge-rich sites. This EDL-oriented eutectic additive engineering enables highly reversible and selectively (002)-textured Zn anodes to operate for over 1450 h at a high DOD of 45.3%. Meanwhile, a high-capacity (185.7 mAh g-1) aqueous Zn||VS2 full cell shows remarkable cycling stability over 220 cycles with an excellent capacity retention of 90.4% even at a low current density of 0.1 A g-1 (0.5 C). This work sheds light on electrolyte design and interface engineering for high-performance aqueous batteries.

20.
Adv Mater ; : e2402739, 2024 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-38762766

RESUMO

Advanced lithium-ion batteries utilize high upper cut-off voltages up to 4.8 V versus lithium metal to reach extraordinary energy densities. Such a harsh environment challenges the cathode stability and requires the construction of robust cathode electrolyte interphases at their electrochemical interface. Inspired by carbonated beverages with supersaturated CO2, here, a surface modification strategy that produces effective passivation layer of low modulus from the weakest link, is proposed CO2 bubbles preferentially nucleate and grow at rough surfaces, which in oxide cathodes, are also the local regions offering fast degradation pathway. Metal ion exchange on carbonated layer assists the construction of highly elastic interface under the guidance of packing factor. This method enables surface reconstruction at both primary and secondary particle levels for various cathodes exemplified by high-voltage LiNi0.8Co0.1Mn0.1O2 (NCM811) and LiCoO2 (LCO). Remarkably, with ultra-high upper cut-off voltage of 4.8 V versus Li+/Li, over 235 mAh g-1 discharge capacity, and over 900 W h kg-1 discharge energy at cathode level, ≈90% capacity retention can be obtained for LiNi0.8Co0.1Mn0.1O2 over 100 cycles at 0.5 C with commercial carbonate electrolytes. This carbonated beverage chemistry is promising for constructing high-quality surface passivation in many extreme-condition applications beyond battery cathodes.

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