Ratiometric Detection of Glutathione Based on Disulfide Linkage Rupture between a FRET Coumarin Donor and a Rhodamine Acceptor

Abnormal levels of glutathione, a cellular antioxidant, can lead to a variety of diseases. We have constructed a near-infrared ratiometric fluorescent probe to detect glutathione concentrations in biological samples. The probe consists of a coumarin donor, which is connected through a disulfide-tethered linker to a rhodamine acceptor. Under the excitation of the coumarin donor at 405 nm, the probe shows weak visible fluorescence of the coumarin donor at 470 nm and strong near-infrared fluorescence of the rhodamine acceptor at 652 nm due to efficient Forster resonance energy transfer (FRET) from the donor to the acceptor. Glutathione breaks the disulfide bond through reduction, which results in a dramatic increase in coumarin fluorescence and a corresponding decrease in rhodamine fluorescence. The probe possesses excellent cell permeability, biocompatibility, and good ratiometric fluorescence responses to glutathione and cysteine with a self-calibration capability. The probe was utilized to ratiometrically visualize glutathione concentration alterations in HeLa cells and Drosophila melanogaster larvae.     

Thiol-Functionalized Covalent Organic Frameworks as Thermal History Indictor for Temperature and Time History Monitoring

Various products, including foods and pharmaceuticals, are sensitive to temperature fluctuations. Thus, temperature monitoring during production, transportation, and storage is critical. Facile indicators are required to monitor temperature conditions via color changes in real time. This study aimed to prepare and apply thiol-functionalized covalent organic frameworks (COFs) as a novel indicator for monitoring thermal history and temperature abuse. The COFs underwent obvious color changes from bright yellow to purple after exposure to different temperatures for varying durations. The reaction kinetics are analyzed under isothermal conditions, which reveal that the order of reaction rates is k_−20°C < k_4°C < k_20°C < k_35°C < k_55°C. The activation energy (E_a) of the COFs is calculated using the Arrhenius equation as 50.71 kJ moL⁻¹. The COFs are capable of sensitive color changes and offer a broad temperature tracking range, thereby demonstrating their application potential for the monitoring of temperature and time exposure history during production, transportation, and storage. This excellent performance thermal history indicator also shows promise for expanding the application field of COFs.     

Enhanced photo-electrochemical activity of ZnO/Cu2S nanotube arrays photocathodes

ZnO/Cu₂S nanotube arrays are fabricated firstly by a facile and capping-agent-free method, and the photo-electrochemical performance has been studied systematically. The results show that ZnO/Cu₂S nanotube arrays achieve enhanced photo-electrochemical water splitting performance and the photocurrent densities of ZnO/Cu₂S are 7.9 times than that of ZnO at 0 V versus Ag/AgCl. The performance of the ZnO/Cu₂S nanotube arrays can be adjusted by changing the amount of Cu₂S microcrystals. The results confirm that the enhanced photo-electrochemical performance of ZnO/Cu₂S is due to the significantly improved visible light absorption, effective separation of photo-induced carriers due to the well band energy match and the formed p-n junction between ZnO and Cu₂S.     

In situ Raman spectroscopic study towards the growth and excellent HER catalysis of Ni/Ni(OH)2 heterostructure

The electrochemical water splitting to produce H₂ in high efficiency with earth-abundant-metal catalysts remains a challenge. Here, we describe a simple “cyclic voltammetry + ageing” protocol at room temperature to activate Ni electrode (AC-Ni/NF) for hydrogen evolution reaction (HER), by which Ni/Ni(OH)₂ heterostructure is formed at the surface. In situ Raman spectroscopy reveals the gradual growth of Ni/Ni(OH)₂ heterostructure during the first 30 min of the aging treatment and combined with polarization measurements, it suggests a positive relation between the Ni/Ni(OH)₂ amount and HER performance of the electrode. The obtained AC-Ni/NF catalyst, with plentiful Ni–Ni(OH)₂ interfaces, exhibits remarkable performance towards HER, with the low overpotential of only 30 mV at a H₂-evolving current density of 10 mA/cm² and 153 mV at 100 mA/cm², as well as a small Tafel slope of 46.8 mV/dec in 1 M KOH electrolyte at ambient temperature. The excellent HER performance of the AC-Ni/NF could be maintained for at least 24 h without obvious decay. Ex situ experiments and in situ electrochemical-Raman spectroscopy along with density functional theory (DFT) calculations reveal that Ni/Ni(OH)₂ heterostructure, although partially reduced, can still persist during HER catalysis and it is the Ni–Ni(OH)₂ interface reducing the energy barrier of H1 adsorption thus promoting the HER performance.     

Experimental study on the permeability and self-healing capacity of geosynthetic clay liners in heavy metal solutions

Geosynthetic clay liners (GCLs), which have a very low permeability to water and a considerably high self-healing capacity, are widely used in liner systems of landfills. In this study, a series of experimental tests were carried out under complex conditions on typical commercial GCLs from China. In particular, the effects of pH values and lead ions (Pb²⁺) were tested in addition to other factors. The swelling properties of natural bentonite encapsulated between geotextile components in the GCLs were tested first. The swelling capacity was reduced rapidly at pH values < 3 and concentrations of Pb²⁺ >40 mM. Permeability tests on GCLs with different concentrations of lead ions were then performed by using the self-developed multi-link flexible wall permeameter, and data showed that increases in lead ion concentrations greatly improved the permeability. Finally, self-healing capacity tests were conducted on needle-punched GCLs under different levels of damage. Results showed that the GCLs have a good self-healing capacity with small diameter damage holes (2 mm, close to three times the original aperture), but with a damage aperture larger than 15% of the sample area, the self-healing capacity could not prevent leakage; hence, in certain situations it will be necessary to repair the damage to meet the anti-seepage requirement.