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The development of electrochemiluminescence (ECL) emitters of different colors with high ECL efficiency (ΦECL) is appealing yet challenging for ultrasensitive multiplexed bioassays. Herein, we report the synthesis of highly efficient polymeric carbon nitride (CN) films with fine-tuned ECL emission from blue to green (410, 450, 470, and 525 nm) using the precursor crystallization method. More importantly, naked eye-observable and significantly enhanced ECL emission was achieved, and the cathodic ΦECL values were ca. 112, 394, 353, and 251 times those of the aqueous Ru(bpy)3Cl2/K2S2O8 reference. Mechanism studies showed that the density of surface-trapped electrons, the associated nonradiative decay pathways, and electron-hole recombination kinetics were crucial factors for the high ΦECL of CN. Based on high ΦECL and different colors of ECL emission, the wavelength-resolved multiplexing ECL biosensor was constructed to simultaneously detect miRNA-21 and miRNA-141 with superior low detection limits of 0.13 fM and 25.17 aM, respectively. This work provides a facile method to synthesize wavelength-resolved ECL emitters based on metal-free CN polymers with high ΦECL for multiplexed bioassays.
Asunto(s)
Técnicas Biosensibles , MicroARNs , Mediciones Luminiscentes/métodos , Técnicas Electroquímicas/métodos , Fotometría , Técnicas Biosensibles/métodos , PolímerosRESUMEN
Using first-principles calculation based on density functional theory, the effects of B, Al and B-Al doping on the structural stability and electrochemical properties of silicene were systematically studied, and their potential as anode materials for lithium ion batteries was evaluated. The calculated results of formation energy indicate that the doped system has good stability. The charge density difference and density of states show that doping can improve the conductivity of silicene, and enhance the interaction with Li. Moreover, on the surface of B, Al and B-Al doped silicene, the diffusion barriers of the most easily migrated path for Li ions are 0.22 eV, 0.19 eV, and 0.21 eV, respectively, suggesting that all doped systems have good Li ion migration rates. And the open circuit voltage is between 0.40 V and 0.54 V, which is relatively stable and low. Therefore, B, Al and B-Al doping can effectively regulate the structural stability and electrochemical performance of silicene, which provides a theoretical basis for the experimental preparation of excellent silicene anode materials.
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The structural stability and electrochemical performance of intrinsic and B doped T-graphene nanotubes with different tube lengths are systematically studied by using first-principles calculations within the framework of density functional theory (DFT). The results show that with the increase of tube length, the adsorption energy of both intrinsic and B doped T-graphene nanotubes exhibits regular oscillations, and B doping is beneficial for elevating the adsorption ability of T-graphene nanotubes. The density of states show that intrinsic T-graphene nanotubes are zero band gap semiconductors, and the orbitals' electronic states cross the Fermi level to form a p-type semiconductor, indicating that B doping greatly improves the conductivity of the system. The results of migration behavior demonstrate that B doping can effectively reduce the diffusion barrier of lithium ions on their surface, especially in B doped T-graphene nanotubes with a tube length of N = 1, resulting in more effective migration behavior and excellent rate performance. These findings provide a theoretical basis for the development and application of negative electrode materials for lithium-ion batteries.
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The first-principles method of density functional theory (DFT) is used to study the structural stability and electrochemical properties of B doped graphene with concentrations of 3.125%, 6.25% and 18.75% respectively, and their lithium storage mechanism and characteristics are further studied. The results show that the doped systems all have negative adsorption energy, indicating that the structures can exist stably, and the adsorption energy of lithium ions on graphene decreases with the increase of B doping concentration. Among them, the B6C26 structure has the lowest adsorption energy and can adsorb more lithium ions. The density of states indicates that doping with B can increase the conductivity of graphene greatly. Subsequently, the CI-NEB method to search for the transition state of the doped structure is used, showing that the B6C26 structure has the lowest diffusion barrier and good rate performance. Therefore, these findings provide a certain research foundation for the development and application of lithium-ion battery anode materials.
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Herein, the feasibility of Fe substitution by Ga, Ge and As in Li2FeSiO4 in modulating its structural, mechanical, electrochemical, capacity and electronic properties was systematically studied via first-principles calculations based on density functional theory within the generalized gradient approximation with Hubbard corrections (GGA+U). The calculated results show that Ga, Ge and As doping can effectively reduce the range of the cell volume change during Li+ removal, improving the Li+ detachment ability and cycle stability of the system. Meanwhile, the calculated mechanical properties including modulus ratio, B/G, and Poisson ratio, ν, indicate that the doped systems of Ga, Ge and As exhibit excellent mechanical properties. In addition, besides the increase in theoretical average deintercalation voltage induced by the Ga dopant when more than one Li+ ion is removed in the formula unit, the doping of Ga, Ge and As all reduce the theoretical average deintercalation voltage in the process of Li+ extraction. Especially in the case of doping of Ge, when 0.5 Li+ is removed from LiFe0.5Ge0.5SiO4, the theoretical average deintercalation voltage only increases by 0.19 V compared with the case of the removal of one Li+ in Li2Fe0.5Ge0.5SiO4, which causes the cathode material to have a longer and more stable discharge platform. Moreover, in the process of Li+ removal, the doping of Ga, Ge and As can effectively participate in the charge compensation of the system, and Ge and As can provide further charge, increasing the capacity of the Li2FeSiO4 cathode material considerably.
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Lead (Pb) induces male infertility in vertebrates. Whether lead is related to reproductive abnormalities in aquatic invertebrates remains uncertain. In this work, effects of Pb on the sperm quality and oxidative stress of the freshwater crab Sinopotamon henanense were investigated after 3, 5 and 7d exposure to different Pb concentrations (0, 3.675, 7.35, 14.7, 29.4 and 58.8mg/L). Sperm quality indices including sperm plasma-membrane integrity and acrosomal-membrane integrity were measured by flow cytometry. DNA integrity was measured by fluorescence microscopy. The results showed that Pb levels in sperm increased significantly upon Pb exposure in most treated groups, sperm plasma-membrane integrity, acrosomal-membrane integrity, and DNA integrity were reduced at higher concentrations after 5 d and 7d. Oxidative stress of sperm induced by Pb was reflected in significant up-regulation of reactive oxygen species (ROS) levels after 3, 5 and 7d. A significant reduction of the total antioxidant capacity levels occurred after exposure to 14.7mg/L Pb and above at 7d compared to the control. The results of oxidative damage to lipids, proteins and DNA of sperm showed that malondialdehyde, protein carbonylation and DNA-protein crosslinks were increased in a concentration- and time-dependent manner. Our findings document that Pb can induce harmful effects on several reproductive endpoints in a freshwater crab.
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Braquiuros/efectos de los fármacos , Braquiuros/metabolismo , Plomo/toxicidad , Estrés Oxidativo/efectos de los fármacos , Espermatozoides/efectos de los fármacos , Acrosoma/efectos de los fármacos , Animales , Membrana Celular/efectos de los fármacos , ADN/efectos de los fármacos , ADN/metabolismo , Relación Dosis-Respuesta a Droga , Agua Dulce , Masculino , Malondialdehído/metabolismo , Carbonilación Proteica , Especies Reactivas de Oxígeno/metabolismo , Regulación hacia ArribaRESUMEN
Lead (Pb) is one of the most toxic environmental pollutants and known to exert multiple toxic effects including gonadotoxic and spermiotoxic effects. In order to understand toxic mechanisms of lead (Pb) on the testes and the accessory glands of crabs, we investigated Pb accumulation in testes and accessory glands and the survival rate of sperms of freshwater crab, Sinopotamon henanense. The tissue damaging effects of Pb was also investigated by histopathological examination and analyses of antioxidant enzymes as well as lipid peroxidation. Crabs were exposed to different Pb concentrations (0, 3.675, 7.35, 14.7, 29.4 and 58.8 mg/L) for 3, 5 and 7 days. The results showed that Pb levels in testes and accessory glands increased significantly following Pb exposure for 5 and 7 days in almost all treated groups, and survival rate of sperm decreased with increasing Pb concentrations at 5 and 7 days. Morphological changes identified histologically were discovered in testes, including a disordered arrangement of germ cells, a decreased number of sperm in the lumina of the seminiferous tubules, extensive necrosis in the germinal layer of the seminiferous tubules, etc. At the same time, histological abnormalities were discovered in accessory glands, the wall cells were separated from the basement membrane, and wall cells were missing partly. The activities of SOD, GPx and CAT in testes showed no statistically significant changes compared to the control for 3 days, and initially increased and subsequently decreased with increasing Pb concentrations at 5 and 7 days. The antioxidant enzyme activities in accessory glands initially increased and subsequently decreased with increasing Pb concentrations and Pb exposure. This was accompanied with an increase in malondialdehyde (MDA) content in a concentration-dependent manner. These results showed that acute Pb exposure led to a reduction of survival rate of sperm and harmful effects at the cellular level of crab testes and accessory glands, which are most likely linked to Pb-induced oxidative stress.
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Antioxidantes/metabolismo , Braquiuros/efectos de los fármacos , Plomo/toxicidad , Espermatozoides/efectos de los fármacos , Testículo/efectos de los fármacos , Animales , Braquiuros/metabolismo , Catalasa/metabolismo , Agua Dulce , Glutatión Peroxidasa/metabolismo , Plomo/metabolismo , Peroxidación de Lípido/efectos de los fármacos , Masculino , Malondialdehído/metabolismo , Estrés Oxidativo , Superóxido Dismutasa/metabolismo , Testículo/enzimología , Pruebas de ToxicidadRESUMEN
Highly efficient interconversion of different types of energy plays a crucial role in both science and technology. Among them, electrochemiluminescence, an emission of light excited by electrochemical reactions, has drawn attention as a powerful tool for bioassays. Nonetheless, the large differences in timescale among diverse charge-transfer pathways from picoseconds to seconds significantly limit the electrochemiluminescence efficiency and hamper their broad applications. Here, we report a timescale coordination strategy to improve the electrochemiluminescence efficiency of carbon nitrides by engineering shallow electron trap states via Au-N bond functionalization. Quantitative electrochemiluminescence kinetics measurements and theoretic calculations jointly disclose that Au-N bonds endow shallow electron trap states, which coordinate the timescale of the fast electron transfer in the bulk emitter and the slow redox reaction of co-reagent at diffusion layers. The shallow electron trap states ultimately accelerate the rate and kinetics of emissive electron-hole recombination, setting a new cathodic electrochemiluminescence efficiency record of carbon nitrides, and empowering a visual electrochemiluminescence sensor for nitrite ion, a typical environmental contaminant, with superior detection range and limit.
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The toxicity of several waterborne heavy metals to aquatic organisms is associated with oxidative damages due to the formation of reactive oxygen species (ROS). In the present work, the reproductive toxicity of the heavy metal cadmium was tested with the sperm of freshwater crab. The crabs were exposed to sublethal concentrations of 0, 7.25, 14.5, 29, 58 and 116 mg/L of Cd²âº for 3, 5 and 7 d. Cd²âº accumulation, ROS formation, and the total antioxidant capacity (TAC) in Sinopotamon henanense sperm were measured. Biomarkers of oxidative damage to lipid (Malondialdehyde, MDA), proteins (protein carbonyl derivates, PCO) and DNA (DNA-protein crosslinks, DPC) were investigated to address Cd²âº effects on crucial macromolecules of the S. henanense sperm. Transmission electron microscopy (TEM) was applied to assess ultrastructural changes induced by 29 and 116 mg/L Cd²âº exposure for 7 d. The results showed that sperm Cd²âº levels were significantly increased at 3, 5 and 7 d starting from the 14.5 mg L⻹ Cd²âº-treated groups. Meanwhile, ROS levels were significantly increased over the experimental period. In terms of TAC, statistically significant changes were observed only at day 7 with the Cd²âº concentrations of 14.5, 29, 58 and 116 mg/L. This resulted in an increase of MDA content (5 d and 7 d), PCO content (Cd²âº: 58 and 116 mg/L, 7 d), and DPC levels (Cd²âº: 116 mg/L, 3 d and 7 d), by 26.32%, 37.47%, 22.04%, respectively, in the 116 mg/L Cd²âº group at day seven. For ultrastructural observations, the sperm membrane became wrinkled and partly dissolved, the nuclear envelope turned wrinkled and the chromatin condensed, the acrosome was incomplete with a damaged acrosomal membrane in crabs treated with 29 mg/L Cd²âº for 7 d. After treatment with 116 mg/L Cd²âº for 7 d, the sperm membrane was almost dissolved, the chromatin in the nucleus was more heavily condensed, chromatin irregularities and serious acrosome damage were observed.
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Braquiuros/efectos de los fármacos , Cadmio/toxicidad , Espermatozoides/efectos de los fármacos , Contaminantes Químicos del Agua/toxicidad , Animales , Antioxidantes/metabolismo , Braquiuros/metabolismo , Braquiuros/ultraestructura , Cadmio/metabolismo , Agua Dulce , Masculino , Malondialdehído/metabolismo , Especies Reactivas de Oxígeno/metabolismo , Espermatozoides/metabolismo , Espermatozoides/ultraestructuraRESUMEN
Accumulating evidences demonstrated that early postnatal maternal separation induced remarkable social and memory defects in the adult rodents. Early-life stress induced long-lasting functional adaptation of neuroendocrine hypothalamic-pituitary-adrenal axis, including neuropeptide corticotrophin-releasing hormone (CRH) in the brain. In the present study, a significantly increased hippocampal CRH was observed in the adult rats with postnatal maternal separation, and blockade of CRHR1 signaling significantly attenuated the hippocampal synaptic dysfunction and memory defects in the modeled rats. Postnatal maternal separation enduringly increased histone H3 acetylation and decreased cytosine methylation in Crh promoter region, resulting from the functional adaptation of several transcriptional factors, in the hippocampal CA1 of the modeled rats. Enriched environment reversed the epigenetic upregulation of CRH, and ameliorated the hippocampal synaptic dysfunction and memory defects in the adult rats with postnatal maternal separation. This study provided novel insights into the epigenetic mechanism underlying postnatal maternal separation-induced memory deficiency, and suggested environment enrichment as a potential approach for the treatment of this disorder.
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Hormona Liberadora de Corticotropina/genética , Epigénesis Genética , Privación Materna , Trastornos de la Memoria/genética , Regulación hacia Arriba , Acetilación/efectos de los fármacos , Animales , Animales Recién Nacidos , Hormona Liberadora de Corticotropina/metabolismo , Estimulación Eléctrica , Epigénesis Genética/efectos de los fármacos , Hipocampo/efectos de los fármacos , Hipocampo/fisiopatología , Histonas/metabolismo , Potenciación a Largo Plazo/efectos de los fármacos , Aprendizaje por Laberinto/efectos de los fármacos , Trastornos de la Memoria/fisiopatología , Proteína 2 de Unión a Metil-CpG/metabolismo , Plasticidad Neuronal/efectos de los fármacos , Fosforilación/efectos de los fármacos , Regiones Promotoras Genéticas/genética , Pirimidinas/farmacología , Pirroles/farmacología , ARN Mensajero/genética , ARN Mensajero/metabolismo , Ratas Sprague-Dawley , Receptores de Hormona Liberadora de Corticotropina/metabolismo , Regulación hacia Arriba/efectos de los fármacosRESUMEN
The ground state equilibrium bond length, harmonic vibrational frequency, and dissociation energy of AlX (X=3d,4d,5d elements and Lu) dimers are investigated by density functional method B3LYP. The present results are in good agreement with the available experimental and other theoretical values except the dissociation energy of AlCr. The present calculations show that the late transition metal can combine strongly with aluminum compared with the former transition metal. The present calculation also indicates that it is more reasonable to replace La with Lu in the Periodic Table and that the bonding strengths of zinc, cadmium, and mercury with aluminum are very weak.