Search Results (9)

Industrial hemp (Cannabis sativa L.) was investigated as a sustainable biosorbent for removing Congo Red (CR) and Remazol Brilliant Blue R (RBBR) from wastewater. The unmodified hemp biosorbent exhibited moderate but practically relevant sorption capacities (4.47 mg/g for CR; 2.44 mg/g for RBBR), outperforming several agricultural waste materials. Kinetic studies revealed rapid uptake, with CR following pseudo-first-order kinetics (t₁/₂ < 15 min) and RBBR fitting the Elovich model, indicating heterogeneous surface interactions. Equilibrium data showed CR adsorption was best described by the Temkin isotherm (R² = 0.983), while RBBR followed the Langmuir model (R² = 0.998), reflecting their distinct binding mechanisms. Thermodynamic analysis confirmed spontaneous (ΔG° < 0), exothermic (ΔH° ≈ −2 kJ/mol), and entropy-driven processes for both dyes. Molecular docking elucidated the structural basis for performance differences: CR’s stronger binding (−7.5 kcal/mol) involved weak noncovalent interaction arising from partial overlap between the π-electron cloud of an aromatic ring and σ-bonds C-C or C-H (π-σ stacking) and hydrogen bonds with cellulose, whereas RBBR’s weaker affinity (−5.4 kcal/mol) relied on weak intermolecular interaction between a hydrogen atom (from a C-H bond) and the π-electron system of an aromatic ring (C-H∙∙∙π interactions). This work establishes industrial hemp as an eco-friendly alternative for dye removal, combining renewable sourcing with multi-mechanism adsorption capabilities suitable for small-scale water treatment applications. Full article

We studied the boron-based composite cluster B₈Al₃⁺ doped with Al atoms. The global minimum structure of the B₈Al₃⁺ cluster is a three-layer structure, consisting of three parts: an Al₂ unit, a B₈ ring and an isolated Al atom. Charge calculations analysis shows that the cluster can be expressed as [Al]⁺[B₈]²⁻[Al₂]²⁺, has 6π/6σ double aromaticity and follows the (4n+2) Hückel rule. Born–Oppenheimer molecular dynamics (BOMD) simulation shows that the B₈Al₃⁺ cluster has dynamic fluxionality properties. Remarkably, at the single-point coupled cluster singles, doubles and triples (CCSD(T)) level, the energy barrier for intramolecular rotation is merely 0.19 kcal mol⁻¹. [B₈]²⁻ molecular wheels have magical 6π/6σ double aromaticity properties, providing a continuous cloud of delocalized electrons, which is a key factor in the dynamic fluxionality of the cluster. The B₈Al₃⁺ cluster provides a new example of dynamic structural fluxionality in molecular systems. Full article

A systematic theoretical study on the molecular electronic structure of graphene and its oxides, including their interactions with molecular species of different polarity, was carried out. The influence of the O/C atomic ratio in the graphene oxides was also evaluated. Quantum chemical and COSMO-based statistical-thermodynamic calculations were performed. Geometry optimizations demonstrated that graphene sheets are structurally distorted by oxygen substitution, although they show high resistance to deformation. Furthermore, under axial O-C bonding, proton-donor and proton-acceptor centers are created on the graphene oxide surface, which could acquire an amphoteric character. In low-oxidized graphene oxides, H-bonding centers coexist with neutral highly polarizable π electron clouds. Deep graphene oxidation is also related to the formation of a quasi-two-dimensional H-bond network. These two phenomena are responsible for the exceptional adsorption and catalytic properties and the potential proton conductivity of graphene oxides. The current calculations demonstrated that the interactions of polar molecular species with deep-oxidized graphene derivatives are thermodynamically favorable, but not with low-oxidized ones. The capacity of the quantum chemical and COSMO-RS calculations to model all these issues opens the possibility of selecting or designing graphene-based materials with optimized properties for specific applications. Also, they are valuable in selecting/designing solvents with good exfoliant properties with respect to certain graphene derivatives. Full article

Attention has been paid to the application of biochar in the remediation of heavy metal contamination in soils. In this study, two modification methods, bleaching and activation, were used to enhance the biochar sorption of Cu(II) and Pb(II). Multiple techniques, including XPS, FTIR and ¹³C NMR, were applied to investigate the properties of bleached and activated biochars. Combined with density functional theory (DFT) calculations, structural changes in the biochars and the main mechanism of Cu(II) and Pb(II) sorption were discussed after modification. The bleached biochar without non-condensed aromatic C possessed many oxygen-containing groups due to oxidation. In contrast, activation increased the specific surface area (SSA) and removed the carboxyl groups. Both modifications had an excellent effect on sorption by high-temperature biochars, especially the bleaching treatment. The bleached and activated biochars exhibited superior Pb(II) sorption compared with Cu(II) due to the larger electron cloud configuration of Pb(II). The significantly positive correlation of the K_d values with the COOH/C=O content indicated that the oxygen-containing groups were responsible for Cu(II) and Pb(II) sorption. The DFT calculation demonstrated a higher energy for the cation–π interaction than for the complexation for Cu(II) sorption, whereas the opposite case was observed for Pb(II) sorption. The complexation and cation–π interaction were the main mechanisms of Cu(II) and Pb(II) sorption. This study provides important guidance for the application of modified biochars in the sorption of heavy metals in the environment. Full article

In the era of antibiotic resistance, there is an urgent need for efficient antibiotic therapies to fight bacterial infections. Cationic antimicrobial peptides (CAMP) are promising lead compounds given their membrane-targeted mechanism of action, and high affinity towards the anionic composition of bacterial membranes. We present a new CAMP, W-BP100, derived from the highly active BP100, holding an additional tryptophan at the N-terminus. W-BP100 showed a broader antibacterial activity, demonstrating a potent activity against Gram-positive strains. Revealing a high partition constant towards anionic over zwitterionic large unilamellar vesicles and inducing membrane saturation at a high peptide/lipid ratio, W-BP100 has a preferential location for hydrophobic environments. Contrary to BP100, almost no aggregation of anionic vesicles is observed around saturation conditions and at higher concentrations no aggregation is observed. With these results, it is possible to state that with the incorporation of a single tryptophan to the N-terminus, a highly active peptide was obtained due to the π–electron system of tryptophan, resulting in negatively charged clouds, that participate in cation–π interactions with lysine residues. Furthermore, we propose that W-BP100 action can be achieved by electrostatic interactions followed by peptide translocation. Full article

The chalcogen bond (ChB) is a noncovalent interaction based on electrophilic features of regions of electron charge density depletion (σ-holes) located on bound atoms of group VI. The σ-holes of sulfur and heavy chalcogen atoms (Se, Te) (donors) can interact through their positive electrostatic potential (V) with nucleophilic partners such as lone pairs, π-clouds, and anions (acceptors). In the last few years, promising applications of ChBs in catalysis, crystal engineering, molecular biology, and supramolecular chemistry have been reported. Recently, we explored the high-performance liquid chromatography (HPLC) enantioseparation of fluorinated 3-arylthio-4,4′-bipyridines containing sulfur atoms as ChB donors. Following this study, herein we describe the comparative enantioseparation of three 5,5′-dibromo-2,2′-dichloro-3-selanyl-4,4′-bipyridines on polysaccharide-based chiral stationary phases (CSPs) aiming to understand function and potentialities of selenium σ-holes in the enantiodiscrimination process. The impact of the chalcogen substituent on enantioseparation was explored by using sulfur and non-chalcogen derivatives as reference substances for comparison. Our investigation also focused on the function of the perfluorinated aromatic ring as a π-hole donor recognition site. Thermodynamic quantities associated with the enantioseparation were derived from van’t Hoff plots and local electron charge density of specific molecular regions of the interacting partners were inspected in terms of calculated V. On this basis, by correlating theoretical data and experimental results, the participation of ChBs and π-hole bonds in the enantiodiscrimination process was reasonably confirmed. Full article

In this work, a different polymer chain structure was synthesized to study π-π interactions between polymer and reduced graphene oxide (RGO). Polymers with different chain structures were obtained from free radical copolymerization of styrene with 4-cyanostyrene (containing substituted phenyl rings) and 2-vinylnaphthalene (containing naphthalene rings). In this work, the polystyrene, poly(styrene-co-4-cyanostyrene) and poly(styrene-co-2-vinylnaphthalene) were named as PS, PSCN and PSNP, respectively. RGO was prepared through modified Hummers’ method and further thermal reduction, and nanocomposites were prepared by solution blending. Thus, different π-π interactions were formed between polymers and RGO. Raman and thermal gravimetric analysis (TGA) were used to characterize the interfacial interaction, showing that the trend of the interfacial interaction should be in the order of RGO/PSCN, RGO/PS, and RGO/PSNP. The differential scanning calorimetry (DSC) measurement showed that, compared with polymer matrix, the glass transition temperature (T_g) of RGO/PS, RGO/PSCN and RGO/PSNP nanocomposites with the addition of 4.0 wt% RGO are increased by 14.3 °C, 25.2 °C and 4.4 °C, respectively. Compared with π-π interaction only formed through aromatic rings, substituent groups changed the densities of electron clouds on the phenyl rings. This change resulted in the formation of donor-acceptor interaction and reinforcement of the π-π interaction at the interface, which leads to increased value of T_g. This comparative study can be useful for selecting appropriate interaction groups, as well as suitable monomers, to prepare high performance nanocomposites. Full article

Real-time monitoring of chemical reactions is still challenging as well as important to study reaction mechanisms and reaction kinetics. Herein, we demonstrated the real-time monitoring of o-phenylenediamine (OPD) oxidation on the surface of gold nanoparticles by surface-enhanced Raman spectroscopy (SERS). The oxidation mechanism and the reaction kinetics were investigated on the basis of the SERS spectrum variation and the related density functionalized theory calculation. It was shown that the oxidation of OPD in the presence of copper ions was a two-step process of the deprotonation of the amino group on the aromatic rings and the rearrangement of the electron cloud to a π-conjugated system, which may open a new door to comprehensively understand the reaction process. Full article

At 25.0 °C the specific rates of solvolysis for allyl and vinyl chloroformates have been determined in a wide mix of pure and aqueous organic mixtures. In all the solvents studied, vinyl chloroformate was found to react significantly faster than allyl chloroformate. Multiple correlation analyses of these rates are completed using the extended (two-term) Grunwald-Winstein equation with incorporation of literature values for solvent nucleophilicity (N_T) and solvent ionizing power (Y_Cl). Both substrates were found to solvolyze by similar dual bimolecular carbonyl-addition and unimolecular ionization channels, each heavily dependent upon the solvents nucleophilicity and ionizing ability. Full article