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Electroactive organic electrode materials exhibit remarkable potential in aqueous zinc ion batteries (AZIBs) due to their abundant availability, customizable structures, sustainability, and high reversibility. However, the research on AZIBs has predominantly concentrated on unraveling the storage mechanism of zinc cations, often neglecting the significance of anions in this regard. Herein, bipolar poly(thionine) is synthesized by a simple and efficient polymerization reaction, and the kinetics of different anions are investigated using poly(thionine) as the cathode of AZIBs. Notably, poly(thionine) is a bipolar organic polymer electrode material and exhibits enhanced stability in aqueous solutions compared to thionine monomers. Kinetic analysis reveals that ClO4 - exhibits the fastest kinetics among SO4 2-, Cl-, and OTF-, demonstrating excellent rate performance (109 mAh g-1 @ 0.5 A g-1 and 92 mAh g-1 @ 20 A g-1). Mechanism studies reveal that the poly(thionine) cathode facilitates the co-storage of both anions and cations in Zn(ClO4)2. Furthermore, the lower electrostatic potential of ClO4 - influences the strength of hydrogen bonding with water molecules, thereby enhancing the overall kinetics in aqueous electrolytes. This work provides an effective strategy for synthesizing high-quality organic materials and offers new insights into the kinetic behavior of anions in AZIBs.
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Accurate classification of tumor cells is of importance for cancer diagnosis and further therapy. In this study, we develop multimolecular marker-activated transmembrane DNA computing systems (MTD). Employing the cell membrane as a native gate, the MTD system enables direct signal output following simple spatial events of "transmembrane" and "in-cell target encounter", bypassing the need of multistep signal conversion. The MTD system comprises two intelligent nanorobots capable of independently sensing three molecular markers (MUC1, EpCAM, and miR-21), resulting in comprehensive analysis. Our AND-AND logic-gated system (MTDAND-AND) demonstrates exceptional specificity, allowing targeted release of drug-DNA specifically in MCF-7 cells. Furthermore, the transformed OR-AND logic-gated system (MTDOR-AND) exhibits broader adaptability, facilitating the release of drug-DNA in three positive cancer cell lines (MCF-7, HeLa, and HepG2). Importantly, MTDAND-AND and MTDOR-AND, while possessing distinct personalized therapeutic potential, share the ability of outputting three imaging signals without any intermediate conversion steps. This feature ensures precise classification cross diverse cells (MCF-7, HeLa, HepG2, and MCF-10A), even in mixed populations. This study provides a straightforward yet effective solution to augment the versatility and precision of DNA computing systems, advancing their potential applications in biomedical diagnostic and therapeutic research.
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ADN , Molécula de Adhesión Celular Epitelial , MicroARNs , Humanos , Molécula de Adhesión Celular Epitelial/metabolismo , ADN/química , MicroARNs/análisis , MicroARNs/metabolismo , Mucina-1/metabolismo , Mucina-1/análisis , Computadores Moleculares , Células MCF-7 , Biomarcadores de Tumor/metabolismo , Biomarcadores de Tumor/análisis , Membrana Celular/metabolismo , Membrana Celular/química , Células Hep G2RESUMEN
Self-charging zinc batteries that combine energy harvesting technology with batteries are candidates for reliable self-charging power systems. However, the lack of rational materials design results in unsatisfactory self-charging performance. Here, a covalent organic framework containing pyrene-4,5,9,10-tetraone groups (COF-PTO) is reported as a cathode material for aqueous self-charging zinc batteries. The ordered channel structure of the COF-PTO provides excellent capacity retention of 98% after 18 000 cycles at 10 A g-1 and ultra-fast ion transfer. To visually assess the self-charging performance, two parameters, namely self-charging efficiency (self-charging discharge capacity/galvanostatic discharge capacity, η) and average self-charging rate (total discharge capacity after cyclic self-charging/total cyclic self-charging time, ν), are proposed for performance evaluation. COF-PTO achieves an impressive η of 96.9% and an ν of 30 mAh g-1 self-charge capacity per hour in 100 self-charging cycles, surpassing the previous reports. Mechanism studies reveal the co-insertion of Zn2+ and H+ double ions in COF-PTO of self-charging zinc batteries. In addition, the CâN and CâO (on the benzene) in COF-PTO are ortho structures to each other, which can easily form metal heterocycles with Zn ions, thereby driving the forward progress of the self-charging reaction and enhancing the self-charging performance.
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Background: Psoriatic patients tend to develop metabolic syndrome (MS). MS accelerates psoriasis, but the exact molecular mechanisms are poorly understood.Objectives: We aim to investigate the impact of leptin on keratinocyte insulin sensitivity and explore its underlying molecular mechanism, which might play a role in the pathogenesis of this disease.Methods: ELISA and immunohistochemistry were applied respectively to detect the level of leptin in serum and in lesion of psoriatic patients with and without MS. The HaCaT cell line was cultured and western-blot assay was performed to assess the change of insulin sensibility. q-PCR and western-blot assay were applied to detect the SOCS3 expressions. Knockdown of SOCS3 were generated in HaCaT cell line by siRNA. Leptin and insulin were treated for 6 days and K10 expression was evaluated by western-blot assay.Results: Patients with MS had higher level of leptin in serum and lesions than their counterparts without MS. Serum levels of leptin was negatively correlated to PASI decline index in psoriatic patients. Long-term treatment of leptin induced insulin resistance in HaCaT cell line, as indicated by elevated expression of p-IRS-1 (ser636) and lower p-PKB (ser473). Leptin treatment up-regulated the mRNA and protein expression of SOCS3. Knockdown of SOCS3 blocked the effect of leptin-induced insulin resistance. Leptin treatment attenuated insulin-elicited K10 expression.Conclusions: Leptin induces insulin resistance by upregulating SOCS3 and give rise to differentiation disorder of keratinocyte. Insulin resistance may serve as a target for anti-psoriatic therapies.
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Resistencia a la Insulina , Insulinas , Síndrome Metabólico , Psoriasis , Humanos , Leptina , Psoriasis/inducido químicamente , Queratinocitos , Insulinas/efectos adversos , Insulinas/metabolismoRESUMEN
Background: Psoriasis is a frequent form of chronic inflammation in dermatology that is unmistakably linked to the metabolic syndrome (MetS) and its elements. This study was to explore the current status and new developments in the global research, and the holistic landscape of this field more intuitively through bibliometric analysis of scientific output and activity. Methods: Publications regarding psoriasis and MetS were searched and chosen from the database of the Web of Science Core Collection. Excel 2019, VOSviewer, and CiteSpace software were utilized to conduct bibliometric analysis. Results: There were 1096 publications included. The scientific outputs in this field had increased from 2004 to 2022, and the expansion could continue in the following years. The United States contributed the most publications (241, 21.99%) and had the most citation frequency (13,489 times). The University of California System was the most productive affiliation. Girolomoni G., Armstrong A.W., Gisondi P. and Gelfand J.M. were key and influential researchers. Journal of the European Academy of Dermatology and Venereology published the greatest number of articles (65 articles). By analyzing keyword frequency and clustering, we have identified the following areas of research interest and frontiers: prevalence, risk, association, gene expression, waist circumference, adipose tissue inflammation, vascular inflammation, cardiovascular disease, psoriatic arthritis, and fibrosis. Conclusion: This bibliometric analysis elucidates research domain of psoriasis and MetS, portraying present hotspots and future emerging trends. This field has generated significant interest and displays potential for further growth. The United States has made distinguished contributions, and currently dominates this field.
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Aqueous iron batteries are appealing candidates for large-scale energy storage due to their safety and low-cost aspects. However, the development of aqueous Fe batteries is hindered by their inadequate long-term cycling stability. Here, we propose the synthesis and application as positive electrode active material of cross-linked polyaniline (C-PANI). We use melamine as the crosslinker to improve the electronical conductivity and electrochemical stability of the C-PANI. Indeed, when the C-PANI is tested in combination with a Fe metal negative electrode and 1 M iron trifluoromethanesulfonate (Fe(TOF)2) electrolyte solution, the coin cell can deliver a specific capacity of about 110 mAh g-1 and an average discharge voltage of 0.55 V after 39,000 cycles at 25 A g-1 with a test temperature of 28 °C ± 1 °C. Furthermore, mechanistic studies suggest that Fe2+ ions are bonded to TOF- anions to form positively charged complexes Fe(TOF)+, which are stored with protons in the C-PANI electrode structures. Finally, we also demonstrate the use of C-PANI in combination with a polymeric hydrogel electrolyte to produce a flexible reflective electrochromic lab-scale iron battery prototype.
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Gaseous impurities contained in hydrogen (H2) profoundly affect the performance of hydrogen proton-exchange membrane fuel cells. We demonstrate the utility of cavity-enhanced Raman spectroscopy as a unique approach for detection of gaseous impurities. A dense-pattern multipass cavity which is composed of four spherical mirrors placed in a Z-shaped configuration is used to enhance the Raman signal by extending the laser-gas interaction length. A total of 85 spots are identified on the 2-inch-diameter front (or rear) mirror, which indicates that 510 beams exist in the cavity. Detection limits of the impurity gases, including oxygen (O2), nitrogen (N2), carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), ammonia (NH3), and hydrogen sulfide (H2S), reach sub-ppm- and ppb-levels at a total pressure of 0.1 and 2.5 MPa, respectively. This satisfies the detection requirements according to the maximum allowable concentration for these gases. Our cavity-enhanced Raman spectroscopy (CERS) apparatus can simultaneously measure multiple gases with high sensitivity and selectivity with no sample destruction. It has excellent application prospects in gaseous impurity analysis for the quality assessment of gaseous energy.
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The introduction of inorganic crystallites into a solid-electrolyte interphase (SEI) is an effective strategy for improving the reversibility of the Zn metal anode (ZMA). However, the structure-performance relationship of the SEI is not fully understood because the existing forms of its inorganic and organic components in their pristine states are not resolved. Here, a highly effective SEI is constructed for ZMA using a bisolvent electrolyte and resolved its composition/structure by cryogenic transmission electron microscopy. This highly fluorinated SEI with amorphous inorganic ZnFx uniformly distributed in the organic matrix is largely different from the common mosaic and multilayer SEIs with crystalline inorganics. It features improved structural integrity, mechanical toughness, and Zn2+ ion conductivity. Consequently, the ZMA exhibits excellent reversibility with an enhanced plating/stripping Coulombic efficiency of 99.8%. The ZMA-based full cell achieves a high Zn utilization ratio of 54% at a practical areal capacity of 3.2 mAh cm-2 and stable cycling over 1800 h during which the accumulated capacity reached 5600 mAh cm-2 . This research highlights the detailed structure and composition of amorphous SEIs for highly reversible metal anodes.
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Aqueous rechargeable batteries are prospective candidates for large-scale grid energy storage. However, traditional anode materials applied lack acid-alkali co-tolerance. Herein, we report a covalent organic framework containing pyrazine (C=N) and phenylimino (-NH-) groups (HPP-COF) as a long-cycle and high-rate anode for both acidic and alkaline batteries. The HPP-COF's robust covalent linkage and the hydrogen bond network between -NH- and water molecules collectively improve the acid-alkaline co-tolerance. More importantly, the hydrogen bond network promotes the rapid transport of H+ /OH- by the Grotthuss mechanism. As a result, the HPP-COF delivers a superior capacity and cycle stability (66.6â mAh g-1 @ 30â A g-1 , over 40000 cycles in 1â M H2 SO4 electrolyte; 91.7â mAh g-1 @ 100â A g-1 , over 30000 cycles @ 30â A g-1 in 1â M NaOH electrolyte). The work opens a new direction for the structural design and application of COF materials in acidic and alkaline batteries.
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Accurate quantification of low-abundance protein Cystatin-C (CysC) in serum by liquid chromatography tandem mass spectrometry (LC-MS/MS) method is very difficult. After sample processing and tryptic digestion, the matrix of CysC surrogate peptides is very complexity, and the concentrations of them are very low, so solid-phase extraction (SPE) must be used to make the surrogate peptides purification and enrichment. In this paper, we used C18 reversed-phase SPE (RP-SPE) and mixed-mode SPE as SPE cartridges. We quantitatively assessed and compared the CysC surrogate peptides recoveries and matrix effects by different SPE cartridges. The sequence of CysC surrogate peptide is ALDFAVGEYNK, and sequence-specific subions y6 (VGEYNK+, m/z 709.3) and y9 (DFAVGEYNK+, m/z 1042.4) were selected for quantification of CysC, because the two fragment ions showed the highest sensitivity. In neat solution, the highest recoveries were similarly for y9 and y6 when used RP-SPE and mixed-mode SPE. However, in serum matrix, the recoveries were significantly higher when used mixed-mode SPE than RP-SPE, which was caused by matrix effects. Results showed that both RP-SPE and mixed-mode SPE were resulted in ion enhancement for CysC surrogate peptides quantification by LC-MS/MS, but mixed-mode SPE reduced more matrix effects. So mixed-mode SPE was more suitable SPE type for purification and enrichment of CysC surrogate peptides.
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Péptidos , Espectrometría de Masas en Tándem , Cromatografía Líquida de Alta Presión/métodos , Cromatografía Liquida/métodos , Péptidos/química , Extracción en Fase Sólida/métodos , Espectrometría de Masas en Tándem/métodos , Cistatina C/químicaRESUMEN
Objective: Rapid identification is critical for ischemic stroke due to the very narrow therapeutic time window. The objective of this study was to construct a diagnostic model for the rapid identification of ischemic stroke. Methods: A mixture population constituted of patients with ischemic stroke (n = 481), patients with hemorrhagic stroke (n = 116), and healthy individuals from communities (n = 2498) were randomly resampled into training (n = 1547, mean age: 55 years, 44% males) and testing (n = 1548, mean age: 54 years, 43% males) samples. Serum corin was assayed using commercial ELISA kits. Potential risk factors including age, sex, education level, cigarette smoking, alcohol consumption, obesity, blood pressure, lipids, glucose, and medical history were obtained as candidate predictors. The diagnostic model of ischemic stroke was developed using a backward stepwise logistic regression model in the training sample and validated in the testing sample. Results: The final diagnostic model included age, sex, cigarette smoking, family history of stroke, history of hypertension, systolic blood pressure, total cholesterol, high-density lipoprotein cholesterol, fasting glucose, and serum corin. The diagnostic model exhibited good discrimination in both training (AUC: 0.910, 95% CI: 0.884-0.936) and testing (AUC: 0.907, 95% CI: 0.881-0.934) samples. Calibration curves showed good concordance between the observed and predicted probability of ischemic stroke in both samples (all P>0.05). Conclusion: We developed a simple diagnostic model with routinely available variables to assist rapid identification of ischemic stroke. The effectiveness and efficiency of this model warranted further investigation.
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Lattice distortion and structure collapse are two intrinsic issues of intercalative-type electrodes derived from repeated ion shuttling. In contrast, rechargeable iodine batteries (RIBs) based on the conversion reaction of iodine stand out for high reversibility and satisfying voltage output characteristics no matter when dealing with both monovalent and multivalent ions. Foreseeable performance superiorities lead to an influx of considerable focus and thus a renaissance in RIBs. This review provides a comprehensive overview of the fundamental chemistry of RIBs from the perspectives of physicochemical properties, conversion mechanism, and existing issues. Furthermore, we refine the optimization strategies for high-performance RIBs, focusing on physical adsorption and chemical interaction strengthening, electrolytes regulation, and nanoscale-iodine design. Then the pros and cons of tremendous RIBs are compared and specified. Ultimately, we conclude with remaining challenges and perspectives to our best knowledge, which may inspire the construction of next-generation RIBs.
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We report a dense-pattern multi-pass cavity (MPC) based on four spherical mirrors placed in a Z-shaped cavity configuration for improving the Raman signals from gases. The folding structure of the cavity causes dense patterns of spots, and at least 420 beams are reflected in the cavity. Raman spectra of ambient air, methane, and ethylene are recorded to demonstrate the performance of our apparatus. At atmospheric pressure, ppm-level detection limits of the gases are achieved with 10 s of exposure time. The Raman signal intensities of the gases show excellent linearity with the gases' partial pressures, which means that high-accuracy detection is also feasible.
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The development of cost-effective non-noble metal electrocatalysts is critical for the research of renewable energy. Transition metal cobalt metaphosphate-based materials have the potential to replace the noble metal Pt. Hence, in this work, we synthesize three-dimensional graphene-supported cobalt metaphosphate (Co(PO3)2-3D RGO) for the first time through the one-step hydrothermal synthesis method at low temperature with the aid of PH3 phosphating. In a 0.5 mol L-1 H2SO4 solution, the obtained electrocatalyst exhibits excellent electrochemical activity for the hydrogen evolution reaction (HER) with a small overpotential of 176 mV at a current density of 10 mA cm-2 and a Tafel slope of 63 mV dec-1. Additionally, in a 1 mol L-1 KOH solution, the electrocatalyst also shows outstanding HER activity with a small overpotential of 158 mV at a current density of 10 mA cm-2 and a Tafel slope of 88 mV dec-1. Co(PO3)2-3D RGO can maintain its catalytic activity for at least ten hours whether in acid or alkali. This work not only demonstrates an excellent electrocatalyst for the hydrogen evolution reaction, but also provides an extremely convenient preparation technology, which provides a new strategy for the development and utilization of high-performance electrocatalysts.
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Magnesium ion batteries have potential for large-scale energy storage. However, the high charge density of Mg2+ ions establishes a strong intercalation energy barrier in host materials, causing sluggish diffusion kinetics and structural degradation. Here, we report that the kinetic and dissolution issues connected to cathode materials can be resolved simultaneously using a tetraethylene glycol dimethyl ether (TEGDME)-water hybrid electrolyte. The lubricating and shielding effect of water solvent could boost the swift transport of Mg2+, contributing to a high diffusion coefficient within the sodium vanadate (NaV8O20·nH2O) cathode. Meanwhile, the organic TEGDME component can coordinate with water to diminish its activity, thus providing the hybrid electrolyte with a broad electrochemical window of 3.9 V. More importantly, the TEGDME preferentially amassed at the interface, leading to a robust cathode electrolyte interface layer that suppresses the dissolution of vanadium species. Consequently, the NaV8O20·nH2O cathode achieved a specific capacity of 351 mAh g-1 at 0.3 A g-1 and a long cycle life of 1000 cycles in this hybrid electrolyte. A mechanism study revealed the reversible interaction of Mg2+ during cycles. This organic water hybrid electrolyte is effective for overcoming the difficulty of multivalent ion storage.
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An ionic-liquid-based Zn salt electrolyte is demonstrated to be an effective route to solve both the side-reaction of the hydrogen evolution reaction (HER) and Zn-dendrite growth in Zn-ion batteries. The developed electrolyte enables hydrogen-free, dendrite-free Zn plating/stripping over 1500 h cycle (3000 cycles) at 2 mA cm-2 with nearly 100% coulombic efficiency. Meanwhile, the oxygen-induced corrosion and passivation are also effectively suppressed. These features bring Zn-ion batteries an unprecedented long lifespan over 40 000 cycles at 4 A g-1 and high voltage of 2.05 V with a cobalt hexacyanoferrate cathode. Furthermore, a 28.6 µm thick solid polymer electrolyte of a poly(vinylidene fluoride-hexafluoropropylene) film filled with poly(ethylene oxide)/ionic-liquid-based Zn salt is constructed to build an all-solid-state Zn-ion battery. The all-solid-state Zn-ion batteries show excellent cycling performance of 30 000 cycles at 2 A g-1 at room temperature and withstand high temperature up to 70 °C, low temperature to -20 °C, as well as abuse test of bending deformation up to 150° for 100 cycles and eight times cutting. This is the first demonstration of an all-solid-state Zn-ion battery based on a newly developed electrolyte, which meanwhile solves the deep-seated hydrogen evolution and dendrite growth problem in traditional Zn-ion batteries.
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Nonbattery behavior related phase transition of electrodes is usually not favorable for any batteries because it results in performance degradation at all times. Here, we demonstrate a zinc hybrid-ion battery (ZHIB) with an unusual capacity enhancement even within 18â¯000 cycles by employing V2CTX MXene as the cathode, enormously differing from all reported counterparts with capacity degradation initiated within hundreds of cycles. The dominated mechanisms are determined to be MXene delamination and an unexpected phase transition during cycling. Both the original cathode and secondary derivative contribute to capacity simultaneously, resulting in the unusual capacity enhancement. Consequently, the specific capacity of 508 mAh g-1 (highest for all reported aqueous zinc-ion batteries) and high energy density of 386.2 Wh kg-1 are realized. Also, the quasi-solid-state batteries fabricated can output stably at -20 °C and in bending, twisting, stabbing, and cutting conditions. Our work brings an effective approach, that is, utilizing "unstable" electrode materials, which should usually be avoided, to achieve continuously enhanced performance of a battery. The idea to use both original and secondary materials for energy storage may be developed to be a general method to achieve extraordinary cycling stability of batteries.
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Multiple stretchability has never been demonstrated as supercapacitors because the hydrogel used cannot fully recover after being heavily deformed. Now, a highly reversibly stretchable all-polymer supercapacitor was fabricated using a developed double network hydrogel (DN hydrogel) as electrolyte and pure polypyrrole (PPy) as electrode. The DN hydrogel provides excellent mechanical properties, which can be stretched up to 500 % many times and then restore almost 100 % of the original length. To fabricate the fully recoverable stretchable supercapacitor, we annealed a free-standing pure conducting polymer film as electrode so that the electrodes induced retardance is minimized. The as-fabricated DN hydrogel/pure conducting polymer supercapacitors can be perfectly recovered from 100 % strain with almost no residual deformation left and the electrochemical performance can be maintained even after 1000 stretches (but not bending).
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While α-MnO2 has been intensively studied for zinc batteries, δ-MnO2 is usually believed to be more suitable for ion storage with its layered structure. Unfortunately, the extraordinary Zn ion storage performance that δ-MnO2 should exhibit has not yet been achieved due to the frustrating structural degradation during charge-discharge cycles. Here, we found the Na ion and water molecules pre-intercalation can effectively activate stable Zn ion storage of δ-MnO2. Our results reveal that the resulted Zn//pre-intercalated δ-MnO2 battery delivers an extraordinarily high-rate performance, with a high capacity of 278 mAh g-1 at 1 C and up to 20 C, and a high capacity of 106 mAh g-1 can still be measured. The capacity retention is as high as 98% after charged-discharged up to 10,000 cycles benefiting from smooth Zn ion diffusion in the pre-intercalated structure. Further in situ/ex situ characterization confirms the superfast Zn ion diffusion in the pre-intercalated structure at room temperature. In addition, utilizing the well-chosen electrode material and modified polyurethane shell, we fabricated a quasi-solid-state healable Zn-δ-MnO2, which can be self-healed after multiple catastrophic damages, emphasizing the advanced features of aqueous Zn ion battery for wearable applications.