Tetrazine-Linked Covalent Organic Frameworks With Acid Sensing and Photocatalytic Activity.

The first synthesis and comprehensive characterization of two vinyl tetrazine-linked covalent organic frameworks (COF), TA-COF-1 and TA-COF-2, are reported. These materials exhibit high crystallinity and high specific surface areas of 1323 and 1114 m2 g-1. The COFs demonstrate favorable band positions and narrow band gaps suitable for light-driven applications. These advantages enable TA-COFs to act as reusable metal-free photocatalysts in the arylboronic acids oxidation and light-induced coupling of benzylamines. In addition, these TA-COFs show acid sensing capabilities, exhibiting visible and reversible color changes upon exposure to HCl solution, HCl vapor, and NH3 vapor. Further, the TA-COFs outperform a wide range of previously reported COF photocathodes. The tetrazine linker in the COF skeleton represents a significant advancement in the field of COF synthesis, enhancing the separation efficiency of charge carriers during the photoreaction and contributing to their photocathodic properties. TA-COFs can also degrade 5-nitro-1,2,4-triazol-3-one (NTO), an insensitive explosive present in industrial wastewater, in 20 min in a sunlight-driven photocatalytic process; thus, revealing dual functionality of the protonated TA-COFs as both photodegradation and Brønsted acid catalysts. This pioneering work opens new avenues for harnessing the potential of the tetrazine linker in COF-based materials, facilitating advances in catalysis, sensing, and other related fields.

First-Principles Investigations of Novel Guanidine-Based Dyes.

In the pursuit of finding efficient D-π-A organic dyes as photosensitizers for dye-sensitized solar cells (DSSCs), first-principles calculations of guanidine-based dyes [A1-A18] were executed using density functional theory (DFT). The various electronic and optical properties of guanidine-based organic dyes with different D-π-A structural modifications were investigated. The structural modification of guanidine-based dyes largely affects the properties of molecules, such as excitation energies, the oscillator strength dipole moment, the transition dipole moment, and light-harvesting efficiencies. The energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) is responsible for the reduction and injection of electrons. Modification of the guanidine subunit by different structural modifications gave a range of HOMO-LUMO energy gaps. Chemical and optical characteristics of the dyes indicated prominent charge transfer and light-harvesting efficiencies. The wide electronic absorption spectra of these guanidine-based dyes computed by TD-DFT-B3LYP with 6-31G, 6-311G, and cc-PVDZ basis sets have been observed in the visible region of spectra due to the presence of chromophore groups of dye molecules. Better anchorage of dyes to the surface of TiO2 semiconductors helps in charge-transfer phenomena, and the results suggested that -COOH, -CN, and -NO2 proved to be proficient anchoring groups, making dyes very encouraging candidates for DSSCs. Molecular electrostatic potential explained the electrostatic potential of organic dyes, and IR spectrum and conformational analyses ensured the suitability of organic dyes for the fabrication of DSSCs.

Nanoparticles Based Sensors for Cyanide Ion Sensing, Basic Principle, Mechanism and Applications.

Rapidly detecting potentially toxic ions such as cyanide is paramount to maintaining a sustainable and environmentally friendly ecosystem for living organisms. In recent years, molecular sensors have been developed to detect cyanide ions, which provide a naked-eye or fluorometric response, making them an ideal choice for cyanide sensing. Nanosensors, on the other hand, have become increasingly popular over the last two decades due water solubility, quick reaction times, environmental friendliness, and straightforward synthesis. Researchers have designed many nanosensors and successfully utilized them for the detection of cyanide ions in various environmental samples. The majority of these sensors use gold and silver-based nanosensors because cyanide ions have a high affinity for these metals ions and coordinate through covalent bonds. These metal nanoparticles are typically combined or coated with fluorescent materials, which quench their fluorescence. However, adding cyanide ions etches out the metal nanoparticles, restoring their fluorescence/color. This principle has been followed by most nanosensors used for cyanide ion sensing. In this review, different nanosensors and their sensing mechanisms are discussed in relation to cyanide ions. The primary purpose is to compare the sensing abilities of these sensors, mainly their sensitivity, advantages, application and to find out research gaps for future work. In this review paper, the development made in nanosensors in the last thirteen years (2010-2023) was discussed and the nanosensors for cyanide ions were compared with molecular sensors while the nanosensors with the excellent limit of detection were highlighted.