Thibault Terencio

Bromide contamination in water sources is a growing health concern because it can generate carcinogenic disinfection byproducts during conventional water treatment. However, the selective removal of bromide from reverse osmosis (RO) permeate remains challenging. Herein, we report a benzothiazole‐functionalized covalent organic framework (COF) designed as a chalcogen‐bond donor, where σ‐holes along the C─S bond axes preferentially interact with the softer, more polarizable Br ⁻ over Cl ⁻ . Two COFs, mesoporous BTzTp (∼2.45 nm) and microporous TTzTp (∼1.13 nm), were investigated to assess the role of pore accessibility while preserving identical recognition sites. The BTzTp@rGO composite exhibited a specific capacitance of 47 F g ^{− 1} and a maximum bromide adsorption capacity of 36.7 mg‐Br ⁻ g ^{− 1} at pH 4. Notably, it maintained ∼99% capacitance retention after 50 cycles, representing the highest cycling stability reported for a bromide‐selective HCDI electrode, together with excellent selectivity (α _Br/Cl = 10). Density functional theory calculations reveal that selectivity originates from strong chalcogen bonding, evidenced by near‐linear C─S···Br ⁻ geometries (178°–179°), normalized contacts of 0.84, HOMO delocalization across the S···Br ⁻ interface, and greater charge transfer to Br ⁻ (0.222 e) than Cl ⁻ (0.154 e). This work demonstrates a viable strategy for highly selective and stable bromide removal in energy‐efficient water purification systems.

Bromide contamination in water sources is a growing health concern because it can generate carcinogenic disinfection byproducts during conventional water treatment. However, the selective removal of bromide from reverse osmosis (RO) permeate remains challenging. Herein, we report a benzothiazole‐functionalized covalent organic framework (COF) designed as a chalcogen‐bond donor, where σ‐holes along the C─S bond axes preferentially interact with the softer, more polarizable Br ⁻ over Cl ⁻ . Two COFs, mesoporous BTzTp (∼2.45 nm) and microporous TTzTp (∼1.13 nm), were investigated to assess the role of pore accessibility while preserving identical recognition sites. The BTzTp@rGO composite exhibited a specific capacitance of 47 F g ^{− 1} and a maximum bromide adsorption capacity of 36.7 mg‐Br ⁻ g ^{− 1} at pH 4. Notably, it maintained ∼99% capacitance retention after 50 cycles, representing the highest cycling stability reported for a bromide‐selective HCDI electrode, together with excellent selectivity (α _Br/Cl = 10). Density functional theory calculations reveal that selectivity originates from strong chalcogen bonding, evidenced by near‐linear C─S···Br ⁻ geometries (178°–179°), normalized contacts of 0.84, HOMO delocalization across the S···Br ⁻ interface, and greater charge transfer to Br ⁻ (0.222 e) than Cl ⁻ (0.154 e). This work demonstrates a viable strategy for highly selective and stable bromide removal in energy‐efficient water purification systems.

Coffee husk-derived activated carbon prepared by H₃PO₄ chemical activation was investigated for the removal of imatinib mesylate from aqueous solutions. Structural and chemical characterization using N₂ physisorption, SEM, FTIR, Raman spectroscopy, and thermogravimetric analysis revealed a porous carbon matrix containing oxygenated functional groups and a defective turbostratic structure. The adsorption behavior was evaluated through batch experiments by examining the effects of pH, adsorbent dosage, particle size, contact time, and initial drug concentration. Under optimized conditions (300 µm particle size, 0.6 g adsorbent dosage, and pH 6), imatinib mesylate removal reached 97.9%, with equilibrium achieved within 60 min. The adsorption kinetics followed the pseudo-second-order model (R² = 0.946–0.984), while equilibrium data were best described by the Sips isotherm model (R² > 0.99), indicating adsorption on a heterogeneous surface. Density functional theory calculations confirmed the contribution of oxygen-containing groups, with carboxyl-functionalized carbon exhibiting the strongest interaction with imatinib mesylate (−105.3 kJ mol⁻¹). These findings highlight the potential of coffee husk-derived activated carbon as a sustainable adsorbent for pharmaceutical contaminant removal.

Nitrogen gas is one of the most abundant resources on Earth, serving as a fundamental component in both biological and industrial processes. Nevertheless, this simple molecule can only be activated by a limited group of microorganisms in nature. Significant efforts have been devoted to replicating this biological activity using metalorganic approaches. However, it is becoming increasingly evident that non-covalent interactions, particularly ionic interactions, can further enhance catalytic reactions. In this work, the effect of alkali and alkaline-earth cations on dinitrogen activation was assessed using Density Functional Theory (DFT) at distances ranging from 2 to 10 Å. This analysis revealed three distinct activity regimes. In Case I, the polarization of the N₂ molecule is the primary driving force; in Case II, the polarization effect is less pronounced; and in Case III, electrostatic interactions dominate, enhancing electron delocalization within the N₂–Mⁿ⁺ system. Among the various cations, those belonging to group II-A are particularly noteworthy due to their high ionic potential and polarizing power, with Mg²⁺ standing out for its superior activity at an N₂–Mg²⁺ distance of 2.7 Å. Consequently, these theoretical insights can serve as a guiding strategy for designing efficient N₂-activating complexes that integrate covalent and non-covalent interactions synergistically.

Previous computational and experimental studies showed that charges located at the surroundings of hydrogen bonds can exert two opposite effects on them: rupture or strengthening of the hydrogen bond. This work aims to generalize the effect of charges in different hydrogen-bonded systems and to propose a coherent explanation of this effect. For these purposes, 19 systems with intra- and intermolecular hydrogen bonds were studied computationally with DFT. The FT-IR spectra of the systems were simulated, and two energy components of the hydrogen bond were studied separately to determine their variation upon the presence of a charge: charge transfer and molecular overlap. It was determined that either the breaking or strengthening of the hydrogen bond can be favored one over the other, for instance, depending on the heteroatom involved in the hydrogen bond. In addition, it is showed that the strengthening of the hydrogen bond by the presence of a charge is directly related to the decrease in charge transfer between the monomers, which is explained by an increase in molecular overlapping, suggesting a more covalent character of the interaction. The understanding of how hydrogen bonds are affected by charges is important, as it is a key towards a strategy to manipulate hydrogen bonds at convenience.

Cysteine‐based perfluoroaromatic (hexafluorobenzene (HFB) and decafluorobiphenyl (DFBP)) were synthesized and established as a chemoselective and available core to construct molecular systems ranging from small molecules to biomolecules with interesting properties. The DFBP was found more effective than HFB for the monoalkylation of decorated thiol molecules. As proof of concept of the potential application of perfluorinated derivatives as non‐cleavable linkers, some antibody‐perfluorinated conjugates were prepared via thiol through two different strategies, i) using thiol from reduced cystamine coupling to carboxylic acids from mAb by amide bond, and ii) using thiols from reduction of mAb disulfide bond. Conjugates cell binding analysis demonstrated that the bioconjugation does not affect the macromolecular entity. Besides, some molecular properties of synthesized compounds are evaluated through spectroscopic characterization (FTIR and ¹⁹F NMR chemical shifts) and theoretical calculations. The comparison of calculated and experimental ¹⁹F NMR shifts and IR wavenumbers give excellent correlations, asserting as powerful tools in structurally identifying HFB and DFBP derivatives. Moreover, molecular docking was also developed to predict cysteine‐based perfluorated derivatives’ affinity against topoisomerase Il and cyclooxygenase 2 (COX‐2). The results suggested that mainly cysteine‐based DFBP derivatives could be potential topoisomerase II α and COX‐2 binders, becoming potential anticancer agents and candidates for anti‐inflammatory treatment.

In recent years, both chitosan and ZnO nanostructures have been identified as potential antibacterial substances; however, the potential applications of chitosan adsorbed on ZnO nanowires have not been explored and could offer exciting new perspectives for both materials, for example, in biocompatible electronic circuits. In this work, we investigate the effect of chitosan on the electronic properties of triangular ZnO nanowires (ZnO NWs) from a theoretical perspective. All calculations were performed using density functional theory within the generalized gradient approximation. We considered six different positions of the chitosan molecule (CS) on the nanowire surface. We varied the amine position of CS, viewing it parallel, perpendicular, and at a 45° angle with respect to the NW axis. Our results show that all configurations are chemically stable; moreover, the interaction of the NW surface with the OH radical of CS creates flat states within the band gap energy of the ZnO NWs that might resemble p-doping. In addition, these states induce changes in the band gap energy of the ZnO NWs. All NWs show high chemical stability regardless of the CS position; hence, the adsorption results of all NW assemblies appear to be chemically favorable.

A series of cysteine-based perfluoroaromatic (hexafluorobenzene (I) and decafluorobiphenyl (II) were synthesized and established as a chemoselective and available core to simple or more complex systems since small molecules to biomolecules with interesting properties. As proof of concept of the potential application of perfluorinated derivatives as non-cleavable linkers, some antibody-perfluorinated conjugates were prepared via thiol, demonstrating that the bioconjugation process doesn’t affect to the macromolecular entity. Besides, some molecular properties of synthesized compounds are evaluated using a combination of spectroscopic characterization (FT-IR and 19F-NMR chemical shifts) and theoretical calculations. Moreover, molecular Docking was also developed to predict cysteine-based hexafluorobenzene and decafluorobiphenyl derivatives’ affinity against topoisomerase Il and cyclooxygenase 2 (COX-2). The results suggested that mainly cysteine-based decafluorobiphenyl derivatives could be potential topoisomerase II α and COX-2 inhibitors, becoming potential anticancer agents and candidates for anti-inflammatory treatment.