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1.
Nano Lett ; 24(23): 6881-6888, 2024 Jun 12.
Article in English | MEDLINE | ID: mdl-38813995

ABSTRACT

Aqueous zinc-ion batteries hold promise for sustainable energy storage, yet challenges in finding high-performance cathode materials persist. Polyoxovanadates (POVs) are emerging as potential candidates due to their structural diversity and robust redox activity. Despite their potential, issues like dissolution in electrolytes, structural degradation, and byproduct accumulation persist. This work introduces a POV-based hydrophobic two-dimensional (2D) layered superstructure that addresses these challenges. The hydrophobic nature minimizes POV dissolution, enhancing structural stability and inhibiting phase transitions during cycling. The 2D arrangement ensures a larger surface area and improved electronic conductivity, resulting in faster kinetics and higher specific capacity. The superstructure demonstrates improved cycle life and an increased operating voltage, marking a significant advancement in POV-based cathode materials for aqueous zinc-ion batteries.

2.
Small ; : e2401379, 2024 Mar 24.
Article in English | MEDLINE | ID: mdl-38522026

ABSTRACT

Phase transitions of Mn-based cathode materials associated with the charge and discharge process play a crucial role on the rate capability and cycle life of zinc ion batteries. Herein, a microscopic electrochemical failure mechanism of Zn-MnO2 batteries during the phase transitions from δ-MnO2 to λ-ZnMn2O4 is presented via systematic first-principle investigation. The initial insertion of Zn2+ intensifies the rearrangement of Mn. This is completed by the electrostatic repulsion and co-migration between guest and host ions, leading to the formation of λ-ZnMn2O4. The Mn relocation barrier for the λ-ZnMn2O4 formation path with 1.09 eV is significantly lower than the δ-MnO2 re-formation path with 2.14 eV, indicating the irreversibility of the layered-to-spinel transition. Together with the phase transition, the rearrangement of Mn elevates the Zn2+ migration barrier from 0.31 to 2.28 eV, resulting in poor rate performance. With the increase of charge-discharge cycles, irreversible and inactive λ-ZnMn2O4 products accumulate on the electrode, causing continuous capacity decay of the Zn-MnO2 battery.

3.
Small Methods ; : e2301731, 2024 Mar 01.
Article in English | MEDLINE | ID: mdl-38426647

ABSTRACT

Ensuring effective and controlled zinc ion transportation is crucial for functionality of the solid electrolyte interphase (SEI) and overall performance in zinc-based battery systems. Herein the first-ever demonstration of incorporate cation-π interactions are provided in the SEI to effectively facilitate uniform zinc ion flux. The artificial SEI design involves the immobilization of 4-amino-p-terphenyl (TPA), a strong amphiphilic cation-π interaction donor, as a monolayer onto a conductive poly(3,4-ethylenedioxythiophene) (PEDOT) matrix, which enable the establishment of a robust network of cation-π interactions. Through a carefully-designed interfacial polymerization process, a high-quality, large-area, robust is achieved, thin polymeric TPA/PEDOT (TP) film for the use of artificial SEI. Consequently, this interphase exhibits exceptional cycling stability with low overpotential and enables high reversibility of Zn plating/stripping. Symmetrical cells with TP/Zn electrodes can be cycled for more than 3200 hours at 1 mA cm-2 and 1 mAh cm-2 . And the asymmetric cells can cycle 3000 cycles stably with a high Coulomb efficiency of 99.78%. Also, under the extreme conditions of lean electrolyte and low N/P ratio, the battery with TP protective layer can still achieve ultra-stable cycle.

4.
Nature ; 623(7987): 499-501, 2023 Nov.
Article in English | MEDLINE | ID: mdl-37938777

ABSTRACT

The majority of massive disk galaxies in the local Universe show a stellar barred structure in their central regions, including our Milky Way1,2. Bars are supposed to develop in dynamically cold stellar disks at low redshift, as the strong gas turbulence typical of disk galaxies at high redshift suppresses or delays bar formation3,4. Moreover, simulations predict bars to be almost absent beyond z = 1.5 in the progenitors of Milky Way-like galaxies5,6. Here we report observations of ceers-2112, a barred spiral galaxy at redshift zphot ≈ 3, which was already mature when the Universe was only 2 Gyr old. The stellar mass (M★ = 3.9 × 109 M⊙) and barred morphology mean that ceers-2112 can be considered a progenitor of the Milky Way7-9, in terms of both structure and mass-assembly history in the first 2 Gyr of the Universe, and was the closest in mass in the first 4 Gyr. We infer that baryons in galaxies could have already dominated over dark matter at z ≈ 3, that high-redshift bars could form in approximately 400 Myr and that dynamically cold stellar disks could have been in place by redshift z = 4-5 (more than 12 Gyrs ago)10,11.

5.
Addict Biol ; 28(9): e13323, 2023 09.
Article in English | MEDLINE | ID: mdl-37644896

ABSTRACT

Chronic exposure to methamphetamine (METH) causes severe and persistent cognitive impairment. The present study aimed to investigate the role of dynorphin/κ opioid receptor (KOR) system in the development of METH-induced cognitive impairment. We found that mice showed significant cognitive impairment in the novel object recognition test (NOR) following daily injections of METH (10 mg/kg) for seven consecutive days. Systemic blockade of KOR prevented METH-induced cognitive impairment by pretreatment of the selective KOR antagonist norBNI (10 mg/kg, i.p.) or KOR deletion. Then, significant increased dynorphin and KOR mRNA were observed exclusively in prelimbic cortex (PL) other than infralimbic cortex. Finally, microinjection with norBNI into PL also improved cognitive memory in METH-treated mice using NOR and spontaneous alternation behaviour test. Our results demonstrated that dynorphin/KOR system activation in PL may be a possible mechanism for METH-induced cognitive impairment and shed light on KOR antagonists as a potential neuroprotective agent against the cognitive deficits induced by drug abuse.


Subject(s)
Cognition Disorders , Cognitive Dysfunction , Methamphetamine , Animals , Mice , Dynorphins , Receptors, Opioid, kappa , Cognitive Dysfunction/chemically induced , Cognitive Dysfunction/prevention & control , Methamphetamine/pharmacology , Narcotic Antagonists
6.
J Phys Chem Lett ; 14(30): 6749-6756, 2023 Aug 03.
Article in English | MEDLINE | ID: mdl-37471689

ABSTRACT

Transition metal phthalocyanines are potential soluble redox mediators for Li-O2 batteries. In this work, effective strategies to control the redox potentials and activities of iron phthalocyanine (FePc) based redox mediators are designed by the introduction of electron-withdrawing or electron-donating groups. Substituted electron-donating groups can shift the oxidation potential of FePc to a higher energy level, consequently reducing the charging voltage of Li-O2 batteries. Especially, oxygen radical anion (-O-) modified FePc (FePc-O-) shows the most significant improvement to the oxygen reduction and evolution reactions of Li-O2 batteries. Electronic analysis indicates that -O- substitution can break the symmetry of electronic structures of FePc which further tunes the reduction of O2 and the oxidation of Li2O2. Detailed reaction mechanisms of (FePc-O-)-mediated Li-O2 batteries are proposed based on first-principles molecular dynamics simulations and thermodynamic free energy calculations.

7.
Small ; 19(29): e2302105, 2023 Jul.
Article in English | MEDLINE | ID: mdl-37189230

ABSTRACT

The practical applications of aqueous zinc ion batteries are hindered by the formation of dendrites on the anode, the narrow electrochemical window of electrolyte, and the instability of the cathode. To address all these challenges simultaneously, a multi-functional electrolyte additive of 1-phenylethylamine hydrochloride (PEA) is developed for aqueous zinc ion batteries based on polyaniline (PANI) cathode. Experiments and theoretical calculations confirm that the PEA additive can regulate the solvation sheath of Zn2+ and form a protective layer on the surface of the Zn metal anode. This broadens the electrochemical stability window of the aqueous electrolyte and enables uniform deposition of Zn. On the cathode side, the Cl- anions from PEA enter the PANI chain during charge and release fewer water molecules surrounding the oxidized PANI, thus suppressing harmful side reactions. When used in a Zn||PANI battery, this cathode/anode compatible electrolyte exhibits excellent rate performance and long cycle life, making it highly attractive for practical applications.

8.
Nano Lett ; 23(1): 42-50, 2023 01 11.
Article in English | MEDLINE | ID: mdl-36562792

ABSTRACT

Dendrite growth and side reactions of Zn metal anodes remain unresolved obstacles for practical application of aqueous Zn ion batteries. Herein, a two-dimensional (2D) organic-inorganic heterostructure with controlled thickness was constructed as a protective layer for a Zn metal anode. The reduction of uniformly distributed polyoxometalate in the layer causes a negative charge density gradient, which can accelerate zinc ion transfer, homogenize zinc deposition, and shield sulfates at the electrode interface, while the exposed hydrophobic alkyl chain of the layer can isolate the direct contact of water with the Zn anode. As a result of the synergetic effect, this 2D organic-inorganic heterostructure enables high Zn plating/stripping reversibility, with high average Coulombic efficiencies of 99.97% for 3700 cycles at 2 mA cm-2. Under high Zn utilization conditions, a high areal-capacity full cell with hundreds of cycles was demonstrated.


Subject(s)
Metals , Zinc , Electric Power Supplies , Electrodes , Water
10.
ACS Appl Mater Interfaces ; 14(14): 16928-16938, 2022 Apr 13.
Article in English | MEDLINE | ID: mdl-35353496

ABSTRACT

Developing atomic-scale synthesis control is a prerequisite for understanding and engineering the exotic physics inherent to transition-metal oxide heterostructures. Thus, far, however, the number of materials systems explored has been extremely limited, particularly with regard to the crystalline substrate, which is routinely SrTiO3. Here, we investigate the growth of a rare-earth nickelate─LaNiO3─on (LaAlO3)(Sr2AlTaO6) (LSAT) (001) by oxide molecular beam epitaxy (MBE). Whereas the LSAT substrates are smooth, they do not exhibit the single surface termination usually assumed necessary for control over the interface structure. Performing both nonresonant and resonant anomalous in situ synchrotron surface X-ray scattering during MBE growth, we show that reproducible heterostructures can be achieved regardless of both the mixed surface termination and the layer-by-layer deposition sequence. The rearrangement of the layers occurs dynamically during growth, resulting in the fabrication of high-quality LaNiO3/LSAT heterostructures with a sharp and consistent interfacial structure. This is due to the thermodynamics of the deposition window as well as the nature of the chemical species at interfaces─here, the flexible charge state of nickel at the oxide surface. This has important implications regarding the use of a wider variety of substrates for fundamental studies on complex oxide synthesis.

11.
Emerg Microbes Infect ; 11(1): 1058-1071, 2022 Dec.
Article in English | MEDLINE | ID: mdl-35311493

ABSTRACT

Safe, efficacious, and deployable vaccines are urgently needed to control COVID-19 in the large-scale vaccination campaigns. We report here the preclinical studies of an approved protein subunit vaccine against COVID-19, ZF2001, which contains tandem-repeat dimeric receptor-binding domain (RBD) protein with alum-based adjuvant. We assessed vaccine immunogenicity and efficacy in both mice and non-human primates (NHPs). ZF2001 induced high levels of RBD-binding and SARS-CoV-2 neutralizing antibody in both mice and non-human primates, and elicited balanced TH1/TH2 cellular responses in NHPs. Two doses of ZF2001 protected Ad-hACE2-transduced mice against SARS-CoV-2 infection, as detected by reduced viral RNA and relieved lung injuries. In NHPs, vaccination of either 25 µg or 50 µg ZF2001 prevented infection with SARS-CoV-2 in lung, trachea, and bronchi, with milder lung lesions. No evidence of disease enhancement was observed in both animal models. ZF2001 has been approved for emergency use in China, Uzbekistan, Indonesia, and Columbia. The high safety, immunogenicity, and protection efficacy in both mice and NHPs found in this preclinical study was consistent with the results in human clinical trials.


Subject(s)
COVID-19 Vaccines , COVID-19 , Animals , Antibodies, Neutralizing , Antibodies, Viral , COVID-19/prevention & control , Carrier Proteins , Humans , Immunogenicity, Vaccine , Mice , Mice, Inbred BALB C , Primates , SARS-CoV-2 , Spike Glycoprotein, Coronavirus/genetics , Vaccines, Subunit
12.
ACS Appl Mater Interfaces ; 13(44): 52508-52518, 2021 Nov 10.
Article in English | MEDLINE | ID: mdl-34699189

ABSTRACT

MXenes have been used as substrate materials for single-atom catalysts (SACs) due to their unique two-dimensional (2D) structure, high surface area, and high electronic conductivity. Oxygen is the primary terminating group of MXenes; however, all of the reported Pt SACs till now are fabricated with F-terminated MXenes. According to the first-principles calculations of this work, the failure of using O-terminated MXenes as substrates is due to the low charge density around Pt and C, which weakens the catalytic activity of Pt. By adjusting the electronic structure of M2C using a second submetal with a lower work function than M, 18 potential bifunctional Pt SACs are constructed based on O-terminated bimetal MXenes. After further consideration of some important practical application factors such as overpotential, solvation effect, and reaction barriers, only four of them, i.e., Cr2Nb2C3O2-VO-Pt, Cr2Ta2C3O2-VO-Pt, Cr2NbC2O2-VO-Pt, and Cr2TaC2O2-VO-Pt, are screened as bifunctional oxygen reduction reaction/oxygen evolution reaction (ORR/OER) catalysts. All of these screened SACs are originated from Cr-based MXenes, implying the significance of Cr-based MXenes in designing bifunctional Pt SACs.

13.
Cell ; 182(3): 722-733.e11, 2020 08 06.
Article in English | MEDLINE | ID: mdl-32645327

ABSTRACT

Vaccines are urgently needed to control the ongoing pandemic COVID-19 and previously emerging MERS/SARS caused by coronavirus (CoV) infections. The CoV spike receptor-binding domain (RBD) is an attractive vaccine target but is undermined by limited immunogenicity. We describe a dimeric form of MERS-CoV RBD that overcomes this limitation. The RBD-dimer significantly increased neutralizing antibody (NAb) titers compared to conventional monomeric form and protected mice against MERS-CoV infection. Crystal structure showed RBD-dimer fully exposed dual receptor-binding motifs, the major target for NAbs. Structure-guided design further yielded a stable version of RBD-dimer as a tandem repeat single-chain (RBD-sc-dimer) which retained the vaccine potency. We generalized this strategy to design vaccines against COVID-19 and SARS, achieving 10- to 100-fold enhancement of NAb titers. RBD-sc-dimers in pilot scale production yielded high yields, supporting their scalability for further clinical development. The framework of immunogen design can be universally applied to other beta-CoV vaccines to counter emerging threats.


Subject(s)
Betacoronavirus/immunology , Coronavirus Infections/prevention & control , Middle East Respiratory Syndrome Coronavirus/immunology , Pandemics/prevention & control , Pneumonia, Viral/prevention & control , Severe acute respiratory syndrome-related coronavirus/immunology , Universal Design , Angiotensin-Converting Enzyme 2 , Animals , Antibodies, Neutralizing/immunology , Antibodies, Viral/immunology , Betacoronavirus/chemistry , COVID-19 , COVID-19 Vaccines , Cell Line, Tumor , Chlorocebus aethiops , Coronavirus Infections/virology , HEK293 Cells , Humans , Mice , Mice, Inbred BALB C , Middle East Respiratory Syndrome Coronavirus/chemistry , Peptidyl-Dipeptidase A/genetics , Peptidyl-Dipeptidase A/metabolism , Pneumonia, Viral/virology , Protein Binding , Protein Interaction Domains and Motifs/immunology , Receptors, Virus/metabolism , Severe acute respiratory syndrome-related coronavirus/chemistry , SARS-CoV-2 , Sf9 Cells , Specific Pathogen-Free Organisms , Spodoptera , Transfection , Vaccination/methods , Vero Cells , Viral Vaccines
14.
Small ; 16(11): e1906946, 2020 03.
Article in English | MEDLINE | ID: mdl-32068965

ABSTRACT

Prussian blue (PB) and its analogues are recognized as promising cathodes for rechargeable batteries intended for application in low-cost and large-scale electric energy storage. With respect to PB cathodes, however, their intrinsic crystal regularity, vacancies, and coordinated water will lead to low specific capacity and poor rate performance, impeding their application. Herein, nanocubic porous Nax FeFe(CN)6 coated with polydopamine (PDA) as a coupling layer to improve its electrochemical performance is reported, inspired by the excellent adhesive property of PDA. As a cathode for sodium-ion batteries, the Nax FeFe(CN)6 electrode coupled with PDA delivers a reversible capacity of 93.8 mA h g-1 after 500 cycles at 0.2 A g-1 , and a discharge capacity of 72.6 mA h g-1 at 5.0 A g-1 . The sodium storage mechanism of this Nax FeFe(CN)6 coupled with PDA is revealed via in situ Raman spectroscopy. The first-principles computational results indicate that FeII sites in PB prefer to couple with the robust PDA layer to stabilize the PB structure. Moreover, the sodium-ion migration in the PB structure is enhanced after coating with PDA, thus improving the sodium storage properties. Both experiments and computational simulations present guidelines for the rational design of nanomaterials as electrodes for energy storage devices.

15.
Antiviral Res ; 97(3): 227-31, 2013 Mar.
Article in English | MEDLINE | ID: mdl-23295353

ABSTRACT

A suicidal DNA vaccine based on a Semliki Forest virus (SFV) replicon was evaluated for the development of a vaccine against rabbit hemorrhagic disease virus (RHDV). The VP60 gene of RHDV was cloned and inserted into pSCA1, an SFV DNA-based replicon vector. The resultant plasmid, pSCA/VP60, was transfected into BHK-21 cells, and the antigenicity of the expressed protein was confirmed using indirect immunofluorescence and a western blot assay. In addition, immunogenicity was studied in rabbits. Fifteen rabbits were injected intramuscularly twice with pSCA/VP60 at 2-week intervals. They were challenged with an RHDV isolate 2weeks after the second immunization. In all cases, anti-RHDV antibodies were detected by ELISA. Additionally, the lymphocyte proliferation response was tested by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide method, and neutralizing antibodies were measured by microneutralization tests. Our results showed that RHDV-specific antibodies and an RHDV-specific cell-mediated immune response were strongly induced in rabbits. Furthermore, all of the rabbits were protected against challenge with wild type RHDV. In conclusion, we demonstrated that the suicidal DNA vaccine is a promising vaccine candidate that facilitates the prevention of rabbit hemorrhagic disease caused by RHDV.


Subject(s)
Caliciviridae Infections/veterinary , Genes, Transgenic, Suicide , Hemorrhagic Disease Virus, Rabbit/immunology , Rabbits/immunology , Vaccines, DNA/immunology , Viral Structural Proteins/immunology , Viral Vaccines/immunology , Animals , Antibodies, Viral/immunology , Caliciviridae Infections/immunology , Caliciviridae Infections/prevention & control , Caliciviridae Infections/virology , Hemorrhagic Disease Virus, Rabbit/genetics , Immunization , Rabbits/virology , Vaccines, DNA/administration & dosage , Vaccines, DNA/genetics , Viral Structural Proteins/genetics , Viral Vaccines/administration & dosage , Viral Vaccines/genetics
16.
Guang Pu Xue Yu Guang Pu Fen Xi ; 30(8): 2299-302, 2010 Aug.
Article in Chinese | MEDLINE | ID: mdl-20939362

ABSTRACT

Studied with X-ray fluorescence spectrum analytic (XRF), powder X-ray diffraction (PXRD) and Fourier transform infrared spectroscopy (FTIR) for five different species of Salvia miltiorrhiza bge grew in Anguo, the intrinsic components and microstructures were determined and comprehensive characterization was carried out. The figure of comprehensive characterization can describe characteristics of intrinsic components from elements, crystal and amorphous active component, it can give an intuitive description for the same components and subtle differences in the intrinsic components of Salvia miltiorrhiza bge, which are different idioplasmatic and same species. It is the ideal method because of the simple preparation of sample, rapid and fine accurate measurement with reproducibility and objectivity, so that it can be used for breeding of fine varieties of Chinese medicinal materials, Chinese medicinal materials GAP guidance of growing conditions, medicinal origin characteristics, the intrinsic composition and microstructure characterization, quality control and authenticity of the identification.


Subject(s)
Drugs, Chinese Herbal/chemistry , Salvia miltiorrhiza/chemistry , Powders , Quality Control , Reproducibility of Results , Salvia miltiorrhiza/classification , Spectroscopy, Fourier Transform Infrared , X-Ray Diffraction
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