Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative

Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip‐phen derivative, 1,3‐bis(1,10‐phenanthrolin‐2‐yloxy)‐N‐(4‐(methylthio)benzylidene)propan‐2‐amine (2CP‐Bz‐SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu^I intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H₂O₂, thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH^..     

Tetraphenylethene‐Based Conjugated Fluoranthene: A Potential Fluorescent Probe for Detection of Nitroaromatic Compounds

This study reports the synthesis and photophysical properties of a star‐shaped, novel, fluoranthene–tetraphenylethene (TFPE) conjugated luminogen, which exhibits aggregation‐induced blue‐shifted emission (AIBSE). The bulky fluoranthene units at the periphery prevent intramolecular rotation (IMR) of phenyl rings and induces a blueshift with enhanced emission. The AIBSE phenomenon was investigated by solvatochromic and temperature‐dependent emission studies. Nanoaggregates of TFPE, formed by varying the water/THF ratio, were investigated by SEM and TEM and correlated with optical properties. The TFPE conjugate was found to be a promising fluorescent probe towards the detection of nitroaromatic compounds (NACs), especially for 2,4,6‐trinitrophenol (PA) with high sensitivity and a high Stern–Volmer quenching constant. The study reveals that nanoaggregates of TFPE formed at 30 and 70 % water in THF showed unprecedented sensitivity with detection limits of 0.8 and 0.5 ppb, respectively. The nanoaggregates formed at water fractions of 30 and 70 % exhibit high Stern–Volmer constants (K_sv=79 998 and 51 120 m ^?1, respectively) towards PA. Fluorescence quenching is ascribed to photoinduced electron transfer between TFPE and NACs with a static quenching mechanism. Test strips coated with TFPE luminogen demonstrate fast and ultra‐low‐level detection of PA for real‐time field analysis.     

Regioselective Synthesis of Polycyclic and Heptagon-embedded Aromatic Compounds through a Versatile π-Extension of Aryl Halides

A versatile π-extension reaction was developed based on the three-component cross-coupling of aryl halides, 2-haloarylcarboxylic acids, and norbornadiene. The transformation is driven by the direction and subsequent decarboxylation of the carboxyl group, while norbornadiene serves as an ortho-C−H activator and ethylene synthon via a retro-Diels–Alder reaction. Comprehensive DFT calculations were performed to account for the catalytic intermediates.     

Suppression of the Charge Density Wave State in Two-Dimensional 1T-TiSe2 by Atmospheric Oxidation

Two-dimensional (2D) metallic transition-metal dichalcogenides (TMDCs), such as 1T-TiSe₂, have recently emerged as unique platforms for exploring their exciting properties of superconductivity and the charge density wave (CDW). 2D 1T-TiSe₂ undergoes rapid oxidation under ambient conditions, significantly affecting its CDW phase-transition behavior. We comprehensively investigate the oxidation process of 2D TiSe₂ by tracking the evolution of the chemical composition and atomic structure with various microscopic and spectroscopic techniques and reveal its unique selenium-assisting oxidation mechanism. Our findings facilitate a better understanding of the chemistry of ultrathin TMDCs crystals, introduce an effective method to passivate their surfaces with capping layers, and thus open a way to further explore the functionality of these materials toward devices.     

Synthesis of Symmetrical and Nonsymmetrical Bisthienylcyclopentenes

Diarylethenes possess unique structural properties, which enabled them to find widespread applications in the field of photochromism. Nowadays, bisthienylcyclopentenes (BTCs) present the most popular subfamily of these compounds, which are widely used as P‐type chromophores. This minireview summarises the main strategies for the synthesis of symmetrical and nonsymmetrical BTCs. In addition, attention is drawn to desymmetrisations achieved by monosubstitutions, which is not frequently utilised, although it can be highly advantageous. This is supported with some of the authors’ latest results.     

Why Do Cycloaddition Reactions Involving C60 Prefer [6,6] over [5,6] Bonds?

The origin of the experimentally known preference for [6,6] over [5,6] bonds in cycloaddition reactions involving C₆₀ has been computationally explored. To this end, the Diels–Alder reaction between cyclopentadiene and C₆₀ has been analysed by means of the recently introduced activation strain model of reactivity in combination with the energy decomposition analysis method. Other issues, such as the aromaticity of the corresponding transition states, have also been considered. These results indicate that the major factor controlling the observed regioselectivity is the more stabilising interaction between the deformed reactants in the [6,6] reaction pathway along the entire reaction coordinate.