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1.
Phys Chem Chem Phys ; 2024 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-39037012

RESUMO

Two-dimensional (2D) materials have drawn tremendous interest as promising materials for photoelectric devices due to their extraordinary properties. As an outstanding 2D photoelectric material, Bi2O2Se (BOS) has exhibited good performance and great potential in photoelectric applications. In this report, we have constructed a photoelectric heterojunction based on BOS and CuInP2S6 (CIPS) nanosheets to achieve enhanced photoelectric performance. With modulation of the ferroelectric-polarization-induced built-in electric field in CIPS, the photogenerated carriers in BOS are effectively separated to form a stable current that is independent of the applied voltage, so that the photoelectric performance of the heterojunction is significantly improved. The photoresponsivity (R), external quantum efficiency (EQE), and normalized detectivity (D*) are calculated and analyzed to evaluate the photodetection performance of the heterojunction. Results demonstrate excellent photoelectric performance of BOS/CIPS heterojunction under irradiation of light from ultraviolet (365 nm), visible (405/550/650 nm) to near-infrared (980 nm). R, EQE, and D* are up to 338.94 A W-1, 7.65 × 104%, and 3.99 × 1010 Jones, respectively, under the condition of 550 nm and 0.24 W m-2. Meanwhile, the measured rise and fall times of the heterojunction reach 2.74 and 4.82 ms, respectively, indicating its fast photoelectric response. This work provides an effective approach to enhance the photoelectric response and stability of BOS via the ferroelectric-polarization-induced built-in electric field of CIPS.

2.
Langmuir ; 38(9): 2961-2971, 2022 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-35220714

RESUMO

While the dynamic properties of ionic liquids (ILs) in nanoconfinement play a crucial role in the performance of IL-based electrochemical and mechanical devices, experimental work mostly falls short at reporting "solid-like" versus "liquid-like" behavior of confined ILs. The present work is the first to conduct frequency-sweep oscillatory-shear rheology on IL nanofilms, reconciling the solid-versus-liquid debate and revealing the importance of shear rate in the behavior. We disentangle and analyze the viscoelasticity of nanoconfined ILs and shed light on their relaxation mechanisms. Furthermore, a master curve describes the scaling of the dynamic behavior of four (non-hydrogen-bonding) ILs under nanoconfinement and reveals the role of the compressibility of the flow units.

3.
Environ Res ; 208: 112651, 2022 05 15.
Artigo em Inglês | MEDLINE | ID: mdl-35007541

RESUMO

In this work, a new type of UiO-66 incorporated polysulfone (PSf) ultrafiltration (UF) membranes was fabricated to enhance antifouling properties and heavy metal ions removal efficiency. The UF membranes incorporating different loadings of the UiO-66 filler were prepared via the classical phase inversion process. These membranes unveiled enhanced hydrophilicity, porosity, water uptake, zeta potential, mechanical strength, permeability, and HA removal ratios due to the incorporation of hydrophilic UiO-66 fillers. Particularly, HA rejection ratios were observed to be approximately 93% for all the modified membranes, which was attributed to electrostatic repulsion interactions between the hydrophilic groups of HA and UiO-66. Moreover, the antifouling abilities of the modified membranes were evaluated and found to be much better with a high flux recovery ratio (FRR) of about 88% when compared to the blank PSf membrane (only around 34%). Moreover, the UiO-66 incorporated membranes were highly-effective in the removal of contaminants like heavy metal ions (Sr2+, Pb2+, Cd2+, and Cr6+) and HA at the same time. Overall, the PSf UF membranes incorporating UiO-66 opened up a new avenue to enhance the membrane hydrophilicity, permeability, antifouling properties as well as heavy metal ions removal abilities.


Assuntos
Estruturas Metalorgânicas , Metais Pesados , Íons , Membranas Artificiais , Ácidos Ftálicos , Ultrafiltração
4.
Nano Lett ; 21(5): 2304-2309, 2021 03 10.
Artigo em Inglês | MEDLINE | ID: mdl-33616411

RESUMO

Water-in-salt (WIS) electrolytes composed of 21 m LiTFSI have recently emerged as a safe and environmentally friendly alternative to conventional organic electrolytes in Li-ion batteries. Several studies have emphasized the relation between the high conductivity of WIS electrolytes and their nanoscale structure. Combining force measurements with a surface forces apparatus and atomic force microscopy, this study describes the nanoheterogeneity of LiTFSI solutions as a function of concentration and distance from a negatively charged (mica) surface. We report various nanostructures coexisting in the WIS electrolyte, whose size increases with concentration and is influenced by the proximity of the mica surface. Two key concentration thresholds are identified, beyond which a transition of behavior is observed. The careful scrutinization on the concentration-dependent nanostructures lays groundwork for designing novel electrolytes in future energy storage devices.

5.
Langmuir ; 37(33): 9996-10005, 2021 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-34375532

RESUMO

Graphene has unique mechanical, electronic, and optical properties that make it of interest for an array of applications. These properties can be modulated by controlling the architecture of graphene and its interactions with surfaces. Self-assembled monolayers (SAMs) can tailor graphene-surface interactions; however, spatially controlling these interactions remains a challenge. Here, we blend colloidal lithography with varying SAM chemistries to create patterned architectures that modify the properties of graphene based on its chemical interactions with the substrate and to study how these interactions are spatially arrayed. The patterned systems and their resulting structural, nanomechanical, and optical properties have been characterized using atomic force microscopy, Raman and infrared spectroscopies, scattering-type scanning near-field optical microscopy, and X-ray photoelectron spectroscopy.

6.
J Environ Manage ; 288: 112247, 2021 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-33765573

RESUMO

This study aims to reveal the biodegradation and interaction mechanism of cyclotetramethylenete-tranitramine (HMX) by a newly isolated bacteria. In this study, a bacterial strain (Bacillus aryabhattai) with high efficiency for HMX degradation was used as the test organism to analyze the changes in growth status, cell function, and mineral metabolism following exposure to different stress concentrations (0 and 5 mg L-1) of HMX. Non-targeted metabonomics was used to reveal the metabolic response of this strain to HMX stress. The results showed that when the HMX concentration was 5 mg L-1, the removal rate of HMX within 24 h of inoculation with Bacillus aryabhatta was as high as 90.5%, the OD600 turbidity was 1.024, and the BOD5 was 225 mg L-1. Scanning electron microscope (SEM) images showed that the morphology of bacteria was not obvious Variety, Fourier transform infrared spectroscopy (FTIR) showed that the cell surface -OH functional groups drifted, and ICP-MS showed that the cell mineral element metabolism was disturbed. Non-targeted metabonomics showed that HMX induced the differential expression of 254 metabolites (133 upregulated and 221 downregulated). The main differentially expressed metabolites during HMX stress were lipids and lipid-like molecules, and the most significantly affected metabolic pathway was purine metabolism. At the same time, the primary metabolic network of bacteria was disordered. These results confirmed that Bacillus aryabhattai has a high tolerance to HMX and can efficiently degrade HMX. The degradation mechanism involves the extracellular decomposition of HMX and transformation of the degradation products into intracellular purines, amino sugars, and nucleoside sugars that then participate in cell metabolism.


Assuntos
Bacillus , Azocinas , Biodegradação Ambiental
7.
Soft Matter ; 15(47): 9609-9613, 2019 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-31750504

RESUMO

We report the structural transition of a phosphonium ionic liquid-based microemulsion from the bulk to nanoconfined between atomically flat micas. Upon the nanoconfinement, we observed a firmly surface-adsorbed ionic liquid film that stabilizes the nanoconfined microemulsion. Further confinement (<11 nm) induces rearrangements in the microemulsion culminating into two well-ordered layers with slow dynamics.

8.
Langmuir ; 33(36): 8982-8992, 2017 09 12.
Artigo em Inglês | MEDLINE | ID: mdl-28771012

RESUMO

Recognizing the significance of surface interactions for ion rejection and membrane fouling in nanofiltration, we revise the theories of DLVO (named after Derjaguin, Landau, Verwey, and Overbeek) and non-DLVO forces in the context of polyamide active layers. Using an atomic force microscope, surface forces between polyamide active layers and a micrometer-large and smooth silica colloid were measured in electrolyte solutions of representative monovalent and divalent ions. While the analysis of DLVO forces, accounting for surface roughness, provides how surface charge of the active layer changes with electrolyte concentration, scrutiny of non-DLVO hydration forces gives molecular insight into the composition of the membrane-solution interface. Importantly, we report an expansion of the diffuse layer at high ionic strength, consistent with the recent development of the electrical double layer theory, but in contrast to the widely accepted phenomenon of aggregation in the secondary minimum. Further, the enhanced repulsion acting on modified membranes via polyelectrolyte adsorption can be quantitatively predicted by DLVO and non-DLVO forces. This work serves to solve past misunderstandings about the interaction forces acting on nanofiltration membranes, and it provides guidance for future work on the relation between surface properties and rejection mechanisms and fouling.

9.
Inorg Chem ; 56(3): 1757-1769, 2017 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-28079368

RESUMO

Recently, N,N-trans Re(O)(LN-O)2X (LN-O = monoanionic N-O chelates; X = Cl or Br prior to being replaced by solvents or alkoxides) complexes have been found to be superior to the corresponding N,N-cis isomers in the catalytic reduction of perchlorate via oxygen atom transfer. However, reported methods for Re(O)(LN-O)2X synthesis often yield only the N,N-cis complex or a mixture of trans and cis isomers. This study reports a geometry-inspired ligand design rationale that selectively yields N,N-trans Re(O)(LN-O)2Cl complexes. Analysis of the crystal structures revealed that the dihedral angles (DAs) between the two LN-O ligands of N,N-cis Re(O)(LN-O)2Cl complexes are less than 90°, whereas the DAs in most N,N-trans complexes are greater than 90°. Variably sized alkyl groups (-Me, -CH2Ph, and -CH2Cy) were then introduced to the 2-(2'-hydroxyphenyl)-2-oxazoline (Hhoz) ligand to increase steric hindrance in the N,N-cis structure, and it was found that substituents as small as -Me completely eliminate the formation of N,N-cis isomers. The generality of the relationship between N,N-trans/cis isomerism and DAs is further established from a literature survey of 56 crystal structures of Re(O)(LN-O)2X, Re(O)(LO-N-N-O)X, and Tc(O)(LN-O)2X congeners. Density functional theory calculations support the general strategy of introducing ligand steric hindrance to favor synthesis of N,N-trans Re(O)(LN-O)2X and Tc(O)(LN-O)2X complexes. This study demonstrates the promise of applying rational ligand design for isomeric control of metal complex structures, providing a path forward for innovations in a number of catalytic, environmental, and biomedical applications.

10.
Inorg Chem ; 55(5): 2597-611, 2016 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-26894635

RESUMO

This study develops synthetic strategies for N,N-trans and N,N-cis Re(O)(LO-N)2Cl complexes and investigates the effects of the coordination spheres and ligand structures on ancillary ligand exchange dynamics and catalytic perchlorate reduction activities of the corresponding [Re(O)(LO-N)2](+) cations. The 2-(2'-hydroxyphenyl)-2-oxazoline (Hhoz) and 2-(2'-hydroxyphenyl)-2-thiazoline (Hhtz) ligands are used to prepare homoleptic N,N-trans and N,N-cis isomers of both Re(O)(hoz)2Cl and Re(O)(htz)2Cl and one heteroleptic N,N-trans Re(O)(hoz)(htz)Cl. Selection of hoz/htz ligands determines the preferred isomeric coordination sphere, and the use of substituted pyridine bases with varying degrees of steric hindrance during complex synthesis controls the rate of isomer interconversion. The five corresponding [Re(O)(LO-N)2](+) cations exhibit a wide range of solvent exchange rates (1.4 to 24,000 s(-1) at 25 °C) and different LO-N movement patterns, as influenced by the coordination sphere of Re (trans/cis), the noncoordinating heteroatom on LO-N ligands (O/S), and the combination of the two LO-N ligands (homoleptic/heteroleptic). Ligand exchange dynamics also correlate with the activity of catalytic reduction of aqueous ClO4(-) by H2 when the Re(O)(LO-N)2Cl complexes are immobilized onto Pd/C. Findings from this study provide novel synthetic strategies and mechanistic insights for innovations in catalytic, environmental, and biomedical research.


Assuntos
Quelantes/química , Percloratos/química , Rênio/química , Catálise , Isomerismo , Ligantes , Espectroscopia de Prótons por Ressonância Magnética
11.
Environ Sci Technol ; 50(11): 5874-81, 2016 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-27182602

RESUMO

Rapid reduction of aqueous ClO4(-) to Cl(-) by H2 has been realized by a heterogeneous Re(hoz)2-Pd/C catalyst integrating Re(O)(hoz)2Cl complex (hoz = oxazolinyl-phenolato bidentate ligand) and Pd nanoparticles on carbon support, but ClOx(-) intermediates formed during reactions with concentrated ClO4(-) promote irreversible Re complex decomposition and catalyst deactivation. The original catalyst design mimics the microbial ClO4(-) reductase, which integrates Mo(MGD)2 complex (MGD = molybdopterin guanine dinucleotide) for oxygen atom transfer (OAT). Perchlorate-reducing microorganisms employ a separate enzyme, chlorite dismutase, to prevent accumulation of the destructive ClO2(-) intermediate. The structural intricacy of MGD ligand and the two-enzyme mechanism for microbial ClO4(-) reduction inspired us to improve catalyst stability by rationally tuning Re ligand structure and adding a ClOx(-) scavenger. Two new Re complexes, Re(O)(htz)2Cl and Re(O)(hoz)(htz)Cl (htz = thiazolinyl-phenolato bidentate ligand), significantly mitigate Re complex decomposition by slightly lowering the OAT activity when immobilized in Pd/C. Further stability enhancement is then obtained by switching the nanoparticles from Pd to Rh, which exhibits high reactivity with ClOx(-) intermediates and thus prevents their deactivating reaction with the Re complex. Compared to Re(hoz)2-Pd/C, the new Re(hoz)(htz)-Rh/C catalyst exhibits similar ClO4(-) reduction activity but superior stability, evidenced by a decrease of Re leaching from 37% to 0.25% and stability of surface Re speciation following the treatment of a concentrated "challenge" solution containing 1000 ppm of ClO4(-). This work demonstrates the pivotal roles of coordination chemistry control and tuning of individual catalyst components for achieving both high activity and stability in environmental catalyst applications.


Assuntos
Percloratos/química , Rênio/química , Catálise , Ligantes , Oxirredução
12.
Water Res ; 250: 121013, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38118252

RESUMO

The ecological risk of tritiated wastewater into the environment has attracted much attention. Assessing the ecological risk of tritium-containing pollution is crucial by studying low-activity tritium exposure's environmental and biological effects on freshwater micro-environment and the enrichment potential of organically bound tritium (OBT) in microalgae and aquatic plants. The impact of tritium-contaminated wastewater on the microenvironment of freshwater systems was analyzed using microcosm experiments to simulate tritium pollution in freshwater systems. Low activity tritium pollution (105 Bq/L) induced differences in microbial abundance, with Proteobacteria, Bacteroidota, and Desulfobacterota occupying important ecological niches in the water system. Low activity tritium (105-107 Bq/L) did not affect the growth of microalgae and aquatic plants, but OBT was significantly enriched in microalgae and two aquatic plants (Pistia stratiotes, Spirodela polyrrhiza), with the enrichment coefficients of 2.08-3.39 and 1.71-2.13, respectively. At the transcriptional level, low-activity tritium (105 Bq/L) has the risk of interfering with gene expression in aquatic plants. Four dominant cyanobacterial strains (Leptolyngbya sp., Synechococcus elongatus, Nostoc sp., and Anabaena sp.) were isolated and demonstrated good environmental adaptability to tritium pollution. Environmental factors can modify the tritium accumulation potential in cyanobacteria and microalgae, theoretically enhancing food chain transfer.


Assuntos
Microalgas , Trítio/análise , Águas Residuárias , Poluição Ambiental/análise , Água Doce/análise
13.
Dev Cell ; 59(14): 1809-1823.e6, 2024 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-38723629

RESUMO

In mice, skin-resident type 2 innate lymphoid cells (ILC2s) exhibit some ILC3-like characteristics. However, the underlying mechanism remains elusive. Here, we observed lower expression of the ILC2 master regulator GATA3 specifically in cutaneous ILC2s (cILC2s) compared with canonical ILC2s, in line with its functionally divergent role in transcriptional control in cILC2s. Decreased levels of GATA3 enabled the expansion of RORγt fate-mapped (RORγtfm+) cILC2s after postnatal days, displaying certain similarities to ILC3s. Single-cell trajectory analysis showed a sequential promotion of the RORγtfm+ cILC2 divergency by RORγt and GATA3. Notably, during hair follicle recycling, these RORγtfm+ cILC2s accumulated around the hair follicle dermal papilla (DP) region to facilitate the process. Mechanistically, we found that GATA3-mediated integrin α3ß1 upregulation on RORγtfm+ cILC2s was required for their positioning around the DP. Overall, our study demonstrates a distinct regulatory role of GATA3 in cILC2s, particularly in promoting the divergence of RORγtfm+ cILC2s to facilitate hair follicle recycling.


Assuntos
Fator de Transcrição GATA3 , Folículo Piloso , Imunidade Inata , Linfócitos , Pele , Animais , Fator de Transcrição GATA3/metabolismo , Fator de Transcrição GATA3/genética , Folículo Piloso/metabolismo , Camundongos , Linfócitos/metabolismo , Linfócitos/imunologia , Pele/metabolismo , Camundongos Endogâmicos C57BL , Membro 3 do Grupo F da Subfamília 1 de Receptores Nucleares/metabolismo , Membro 3 do Grupo F da Subfamília 1 de Receptores Nucleares/genética , Diferenciação Celular
14.
ACS Appl Mater Interfaces ; 15(38): 45485-45497, 2023 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-37721996

RESUMO

Ionic liquids (ILs) are organic molten salts with low-temperature melting points that hold promise as next-generation environmentally friendly boundary lubricants. This work examines the relationship between tribological and rheological behavior of thin films of five imidazolium ILs using a surface force apparatus to elucidate lubrication mechanisms. When confined to films of a few nanometers, the rheological properties change drastically as a function of the number of confined ion layers; not only the viscosity increases by several orders of magnitude but ILs can also undergo a transition from Newtonian to viscoelastic fluid and to an elastic solid. This behavior can be justified by the confinement-induced formation of supramolecular clusters with long relaxation times. The quantized friction coefficient is explained from the perspective of the strain relaxation via diffusion of these supramolecular clusters, where higher friction correlates with longer relaxation times. A deviation from this behavior is observed only for 1-ethyl-3-methylimidazolium ethylsulfate ([C2C1Im][EtSO4]), characterized by strong hydrogen bonding; this is hypothesized to restrict the reorganization of the confined IL into clusters and hinder (visco)elastic behavior, which is consistent with the smallest friction coefficient measured for this IL. We also investigate the contrasting influence of traces of water on the thin-film rheology and tribology of a hydrophobic IL, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [C2C1Im][FAP], and a hydrophilic IL, [C2C1Im][EtSO4]. [C2C1Im][EtSO4] remains Newtonian under both dry and humid conditions and provides the best lubrication, while [C2C1Im][FAP], characterized by a prominent solid-like behavior under both conditions, is a poor lubricant. The results of this study may inspire molecular designs to enable efficient IL lubrication.

15.
Nat Commun ; 14(1): 7109, 2023 11 04.
Artigo em Inglês | MEDLINE | ID: mdl-37925507

RESUMO

Tissue-resident Natural Killer (trNK) cells are crucial components of local immunity that activate rapidly upon infection. However, under steady state conditions, their responses are tightly controlled to prevent unwanted tissue damage. The mechanisms governing their differentiation and activation are not fully understood. Here, we characterise uterine trNK cells longitudinally during pregnancy by single cell RNA sequencing and find that the combined expression pattern of 4-1BB and CD55 defines their three distinct stages of differentiation in mice. Mechanistically, an IL-21R-STAT3 axis is essential for initiating the trNK cell differentiation. The fully differentiated trNK cells demonstrate enhanced functionality, which is necessary for remodelling spiral arteries in the decidua. We identify an apoptotic program that is specific to the terminal differentiation stage, which may preclude tissue damage by these highly activated trNK cells. In summary, uterine trNK cells become intensely active and effective during pregnancy, but tightly controlled via a differentiation program that also limits potential harm, suggesting an intricate mechanism for harnessing trNK cells in maintaining pregnancy.


Assuntos
Células Matadoras Naturais , Receptores de Interleucina-21 , Fator de Transcrição STAT3 , Útero , Animais , Feminino , Camundongos , Gravidez , Diferenciação Celular , Fatores de Transcrição/metabolismo , Útero/metabolismo , Receptores de Interleucina-21/metabolismo , Fator de Transcrição STAT3/metabolismo , Transdução de Sinais
16.
J Colloid Interface Sci ; 651: 558-566, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37562298

RESUMO

The development of a low-cost, high-capacity, and insertion-type anode is key for promoting "rocking chair" zinc-ion batteries. Herein, commercial Bi2O3 (BiO) particles are transformed into Bi2O2Se@Bi4O8Se (BiOSe) nanosheets through a simple selenylation process. The change in morphology from commercial BiO particle to BiOSe nanosheet leads to an increased specific surface area of the material. The enhanced electronic/ionic conductivity results in its excellent electrochemical kinetics. Ex situ XRD and XPS tests prove the intercalation-type mechanism of BiO and BiOSe as well as the superior electrochemical reversibility of BiOSe compared to BiO. Furthermore, the H+/Zn2+ co-insertion mechanism of BiOSe is revealed. This makes BiOSe to have low discharge plateaus of 0.38/0.68 V, a high reversible capacity of 182 mA h g-1 at 0.1 A g-1, and a long cyclic life of 500 cycles at 1 A g-1. Besides, the BiOSe//MnO2 "rocking chair" zinc-ion battery offers a high capacity of ≈90 mA h g-1 at 0.2 A g-1. This work provides a reference for turning commercial material into high-performance anode for "rocking chair" zinc-ion batteries.

17.
iScience ; 26(7): 107187, 2023 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-37404378

RESUMO

Tissue-residential natural killer (trNK) cells act as pioneering responders during infectious challenges. However, their discrimination with conventional NK (cNK) cells is still an issue. Through an integrative transcriptome comparison of the two NK subgroups from different tissues, we have defined two genesets capable of efficiently distinguishing them. Based on the two genesets, a fundamental difference between the activation of trNK and cNK is identified and further confirmed. Mechanistically, we have discovered a particular role of chromatin landscape in regulating the trNK activation. In addition, IL-21R and IL-18R are respectively highly expressed by trNK and cNK, indicating a role of cytokine milieu in determining their differential activation. Indeed, IL-21 is particularly critical in accessorily promoting trNK activation using a bunch of bifunctional transcription factors. Together, this study sheds light on the bona fide difference between trNK and cNK, which will further expand our knowledge about their distinct functionalities during immune responses.

18.
J Colloid Interface Sci ; 645: 483-492, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37156157

RESUMO

Developing insertion-type anode is key to advancing "rocking chair" zinc-ion batteries, though there are few reported insertion-type anodes. Herein, the Bi2O2CO3 is a high-potential anode, with a special layered structure. A one-step hydrothermal method was used to prepare Ni-doped Bi2O2CO3 nanosheet, and also a free-standing electrode consisting of Ni-Bi2O2CO3 and CNTs was designed. Both cross-linked CNTs conductive networks and Ni doping improve charge transfer. Ex situ tests (XRD, XPS, TEM, etc.) reveal the H+/Zn2+ co-insertion mechanism of Bi2O2CO3 and that Ni doping improves its electrochemical reversibility and structural stability. Therefore, this optimized electrode offers a high specific capacity of 159 mAh g-1 at 100 mA g-1, a suitable average discharge voltage of ≈0.400 V, and a long-term cycling stability of 2200 cycles at 700 mA g-1. Besides, the Ni-Bi2O2CO3//MnO2 "rocking chair" zinc-ion battery (based on the total mass of cathode and anode) delivers a high capacity of ≈100 mAh g-1 at 50.0 mA g-1. This work provides a reference for designing high-performance anode in zinc-ion batteries.

19.
ACS Nano ; 17(10): 9347-9360, 2023 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-37163519

RESUMO

The performance of electrochemical devices using ionic liquids (ILs) as electrolytes can be impaired by water uptake. This work investigates the influence of water on the behavior of hydrophilic and hydrophobic ILs─with ethylsulfate and tris(perfluoroalkyl)trifluorophosphate or bis(trifluoromethyl sulfonyl)imide (TFSI) anions, respectively─on electrified graphene, a promising electrode material. The results show that water uptake slightly reduces the IL electrochemical stability and significantly influences graphene's potential of zero charge, which is justified by the extent of anion depletion from the surface. Experiments confirm the dominant contribution of graphene's quantum capacitance (CQ) to the total interfacial capacitance (Cint) near the PZC, as expected from theory. Combining theory and experiments reveals that the hydrophilic IL efficiently screens surface charge and exhibits the largest double layer capacitance (CIL ∼ 80 µF cm-2), so that CQ governs the charge stored. The hydrophobic ILs are less efficient in charge screening and thus exhibit a smaller capacitance (CIL ∼ 6-9 µF cm-2), which governs Cint already at small potentials. An increase in the total interfacial capacitance is observed at positive voltages for humid TFSI-ILs relative to dry ones, consistent with the presence of a satellite peak. Short-range surface forces reveal the change of the interfacial layering with potential and water uptake owing to reorientation of counterions, counterion binding, co-ion repulsion, and water enrichment. These results are consistent with the charge being mainly stored in a ∼2 nm-thick double layer, which implies that ILs behave as highly concentrated electrolytes. This knowledge will advance the design of IL-graphene-based electrochemical devices.

20.
Cells ; 11(11)2022 05 27.
Artigo em Inglês | MEDLINE | ID: mdl-35681462

RESUMO

Sjögren's syndrome (SjS), characterized by keratoconjunctivitis sicca and dry mouth, is a common autoimmune disease, especially in middle-aged women. The immunopathogenesis of SjS is caused by the sequential infiltration of T and B cells into exocrine glands, including salivary and lacrimal glands. Effector cytokines produced by these immunocytes, such as interferons (IFNs), IL-17, IL-22, IL-21, IL-4, TNF-α, BAFF and APRIL, play critical roles in promoting autoimmune responses and inducing tissue damages. Epigenetic regulations, including DNA methylation, histone modification and non-coding RNAs, have recently been comprehensively studied during the activation of various immunocytes. The deficiency of key epigenetic enzymes usually leads to aberrant immune activation. Epigenetic modifications in T and B cells are usually found to be altered during the immunopathogenesis of SjS, and they are closely correlated with autoimmune responses. In particular, the important role of methylation in activating IFN pathways during SjS progression has been revealed. Thus, according to the involvement of epigenetic regulations in SjS, target therapies to reverse the altered epigenetic modifications in auto-responsive T and B cells are worthy of being considered as a potential therapeutic strategy for SjS.


Assuntos
Aparelho Lacrimal , Síndrome de Sjogren , Citocinas/metabolismo , Epigênese Genética , Glândulas Exócrinas , Feminino , Humanos , Aparelho Lacrimal/metabolismo , Pessoa de Meia-Idade , Síndrome de Sjogren/genética , Síndrome de Sjogren/terapia
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