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Porous crystalline conjugated macrocyclic materials (CMMs) possess high porosity, tunable structure/function and efficient charge transport ability owing to their planar macrocyclic conjugated π-electron system, which make them promising candidates for applications in energy storage. In this review, we thoroughly summarize the timely development of porous crystalline CMMs in energy storage related fields. Specifically, we summarize and discuss their structures and properties. In addition, their energy storage applications, such as lithium ion batteries, lithium sulfur batteries, sodium ion batteries, potassium ion batteries, Li-CO2 batteries, Li-O2 batteries, Zn-air batteries, supercapacitors and triboelectric nanogenerators, are also discussed. Finally, we present the existing challenges and future prospects. We hope this review will inspire the development of advanced energy storage materials based on porous crystalline CMMs.
RESUMEN
Human endogenous retroviruses (HERVs) are the remnants of ancient retroviral infections integrated into the human genome. Although most HERVs are silenced or rendered inactive by various regulatory mechanisms, they retain the potential to influence the nearby genes. We analyzed the regulatory map of 91 HERV-Ks on neighboring genes in human breast cancer and investigated the impact of HERV-Ks on the tumor microenvironment (TME) and prognosis of breast cancer. Nine RNA-seq datasets were obtained from GEO and NCBI SRA. Differentially expressed genes and HERV-Ks were analyzed using DESeq2. Validation of high-risk prognostic candidate genes using TCGA data. These included Overall survival (multivariate Cox regression model), immune infiltration analysis (TIMER), tumor mutation burden (maftools), and drug sensitivity analysis (GSCA). A total of 88 candidate genes related to breast cancer prognosis were screened, of which CD48, SLAMF7, SLAMF1, IGLL1, IGHA1, and LRRC8A were key genes. Functionally, these six key genes were significantly enriched in some immune function-related pathways, which may be associated with poor prognosis for breast cancer (p = 0.00016), and the expression levels of these genes were significantly correlated with the sensitivity of breast cancer treatment-related drugs. Mechanistically, they may influence breast cancer development by modulating the infiltration of various immune cells into the TME. We further experimentally validated these genes to confirm the results obtained from bioinformatics analysis. This study represents the first report on the regulatory potential of HERV-K in the neighboring breast cancer genome. We identified three key HERV-Ks and five neighboring genes that hold promise as novel targets for future interventions and treatments for breast cancer.
Asunto(s)
Neoplasias de la Mama , Retrovirus Endógenos , Humanos , Femenino , Neoplasias de la Mama/genética , Retrovirus Endógenos/genética , Genoma Humano , Expresión Génica , Pronóstico , Microambiente Tumoral/genética , Proteínas de la Membrana/genéticaRESUMEN
The inhomogeneous consumption of anions and direct contact between electrolyte and anode during the Zn-deposition process generate Zn-dendrites and side reactions that can aggravate the space-charge effect to hinder the practical implementation of zinc-metal batteries (ZMBs). Herein, electrospray has been applied for the scalable fabrication (>10 000â cm2 in a batch-experiment) of hetero-metallic cluster covalent-organic-frameworks (MCOF-Ti6 Cu3 ) nanosheet-coating (MNC) with integrated micro space electrostatic field for ZMBs anode protection. The MNC@Zn symmetric cell presents ultralow overpotential (≈72.8â mV) over 10 000 cycles at 1â mAh cm-2 with 20â mA cm-2 , which is superior to bare Zn and state-of-the-art porous crystalline materials. Theoretical calculations reveal that MNC with integrated micro space electrostatic field can facilitate the deposition-kinetic and homogenize the electric field of anode to significantly promote the lifespan of ZMBs.
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Anisotropically hybridized porous crystalline Li-S battery separators based on porous crystalline materials that can meet the multiple functionalities of both anodic and cathodic sides are much desired for Li-S battery yet still challenging in directional design. Here, an anisotropically hybridized separator (CPM) based on an ionic liquid-modified porphyrin-based covalent-organic framework (COF-366-OH-IL) and catalytically active metal-organic framework (Ni3 (HITP)2 ) that can integrate the lithium-polysulfides (LiPSs) adsorption/catalytic conversion and ion-conduction sites together to directionally meet the requirements of electrodes is reported. Remarkably, the-obtained separator exhibits an exceptional high Li+ transference-number (tLi+ = 0.8), ultralow polarization-voltage (<30 mV), high initial specific-capacity (921.38 mAh g-1 at 1 C), and stable cycling-performance, much superior to polypropylene and monolayer-modified separators. Moreover, theoretical calculations confirm the anisotropic effect of CPM on the anodic side (e.g., Li+ transfer, LiPSs adsorption, and anode-protection) and cathodic side (e.g., LiPSs adsorption/catalysis). This work might provide a new perspective for separator exploration.
RESUMEN
The elaborate design of powerful Li-S binders with extended-functions like polysulfides adsorption/catalysis and Li+ hopping/transferring in addition to robust adhesion-property has remained a challenge. Here, an in situ cathode-interweaving strategy based on metalloporphyrin based covalent-bonding organic polymer (M-COP, M = Mn, Ni, and Zn) binders is reported for the first time. Thus-produced functional binders possess excellent mechanical-strengths, polysulfides adsorption/catalysis, and Li+ hopping/transferring ability. Specifically, the modulus of Mn-COP can reach up to ≈54.60 GPa (≈40 times higher than poly(vinylidene fluoride)) and the relative cell delivers a high initial-capacity (1027 mAh g-1 , 1 C and 913 mAh g-1 , 2 C), and excellent cycling-stability for >1000 cycles even at 4 C. The utilization-rate of sulfur can reach up to 81.8% and the electrodes based on these powerful binders can be easily scale-up fabricated (≈20 cm in a batch-experiment). Noteworthy, Mn-COP based cell delivers excellent capacities at a high sulfur-loading (8.6 mg cm-2 ) and low E/S ratio (5.8 µL mg-1 ). In addition, theoretical calculations reveal the vital roles of metalloporphyrin and thiourea-groups in enhancing the battery-performance.
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Zn-based aqueous batteries have attracted much attention because of their high theoretical-capacity, safety, and low-cost, yet the H2 -evolution, qualification or inhibition mechanism investigations that are closely related to the dendrite-growth are rare and challenging. Herein, a series of zincophilic metal-covalent organic frameworks (e.g., Zn-AAn-COF, Zn-DAAQ-COF, and Zn-DAA-COF) have been explored as model-platforms to manipulate the H2 -evolution and Zn2+ flux. Best of them, Zn-AAn-COF based cell only produces 0.002â mmol h-1 cm-2 H2 , which is >2 orders of magnitude lower than bare Zn. Noteworthy, it affords high stability for 3000â cycles (overpotential, <79.1â mV) at 20â mA cm-2 in symmetric-cell and enhanced cycling-stability up to 6000â cycles at 2000â mA g-1 in the assembled full-battery. Besides, mechanistic characterizations show that Zn-AAn-COF can enhance the energy-barrier of H2 -evolution and homogenize the ion-distribution or electric-filed to achieve high performance.
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Breast cancer with HER2 overexpressing type links to malignant tumor growth and poor clinical outcome. Successful development of sensitive and selective nano-probe for identification of HER2-positive breast cancer cells is of great importance for breast cancer early diagnosis, subtype classification, and treatment planning. Herein, we report a HER2 antibody conjugated near infrared (NIR) emitted MnCuInS/ZnS qumtun dots (QDs) encapsulated bovine serum albumin (BSA) nano-probe for accurately targeted imaging of HER2-positive breast cancer cells. This NIR nano-probe shows good biocompatibility, low nonspecificity and cytotoxicity, high colloidal stability, and allows HER2-positive breast cancer cell identification with good selectivity. The practicality of this targeted NIR fluorescent nano-probe was proved by successful identifying HER2-positive breast cancer cells from HER2-negative breast cancer cells, which indicates that it can be efficiently applied in selective screening of HER2 overexpressing cancer cells, and provide a platform for the strategy design on the distinction of different breast cancer subtypes.
Asunto(s)
Neoplasias de la Mama/diagnóstico por imagen , Neoplasias de la Mama/tratamiento farmacológico , Colorantes Fluorescentes/farmacología , Metales Pesados/farmacología , Nanopartículas/química , Imagen Óptica , Albúmina Sérica Bovina/química , Animales , Neoplasias de la Mama/patología , Bovinos , Supervivencia Celular/efectos de los fármacos , Colorantes Fluorescentes/química , Humanos , Rayos Infrarrojos , Metales Pesados/química , Tamaño de la Partícula , Propiedades de Superficie , Células Tumorales CultivadasRESUMEN
The rotationally resolved infrared spectra of (HCOOH)2, (HCOOD)2, and HCOOH-HCOOD complexes have been measured in 7.2 µm region by using a segmented rapid-scan distributed-feedback quantum cascade laser absorption spectrometer to probe a slit supersonic jet expansion. The observed spectra are assigned to the v21 (H-C/O-H in-plane bending) fundamental band of (HCOOH)2, the v15 (H-C/O-D in-plane bending) fundamental band of HCOOH-HCOOD, and the v20 (H-C-O in-plane bending) fundamental band of (HCOOD)2. Strong local perturbations caused by the rotation-tunneling coupling between two tunneling components are observed in (HCOOH)2. The v21 fundamental band of (HCOOH)2 and the previously measured v22 fundamental and v12 + v14 combination bands [K. G. Goroya et al., J. Chem. Phys. 140, 164311 (2014)] are analyzed together, yielding a more precise tunneling splitting in the ground state, 0.011 367(92) cm-1. The band-origin of the v21 band of (HCOOH)2 is 1371.776 74(8) cm-1, and the tunneling splitting decreases to 0.000 38(18) cm-1 upon the vibrational excitation. The vibrational energy is 1386.755 49(16) cm-1 for the v15 vibrational mode of HCOOH-HCOOD and 1391.084 39(17) cm-1 for the v20 vibrational mode of (HCOOD)2. No apparent spectral splittings are resolved for HCOOH-HCOOD and (HCOOD)2 under our experimental conditions. The tunneling splitting in the ground state of HCOOH-HCOOD is estimated to be 0.001 13 cm-1 from its average linewidth.