Search Results (164)

Four novel crystalline architectures based on benzo[c]cinnolininium trifluoromethanesulonate salts, [C₁₂H₉N₂]⁺[CF₃SO₃]⁻, have been isolated as single-crystals, and their structures have been determined by X-ray diffraction analysis. The formation of the new salts results from reactions involving the dimeric hydroxo di-n-butylstannane trifluoromethanesulfonato complex [n-Bu₂Sn(OH)(H₂O)(CF₃SO₃)]₂ (1) and benzo[c]cinnoline (C₁₂H₈N₂, BCC). Organic salts I, II, III, and IV were crystallized through slow evaporation at room temperature from a mixture of toluene/dichloromethane. The cystallographic structures of I, II, and IV exhibit the presence of monoprotonated benzo[c]cinnolinium cations in interactions with a free benzo[c]cinnoline molecule through N–H···N hydrogen bonding, while for salt III, the monoprotonated cation directly interacts with the CF₃SO₃⁻ anion via an N–H···O interaction. For all four salts, aromatic π-π interactions involving rings of various components (free benzo[c]cinnoline molecule, benzo[c]cinnolinium cation, toluene molecule), combined with weak C–H···O and C–H···F interactions implying the trifluoromethanesulfonate anion, promote the solid-state self-assembly of supramolecular stacks. In parallel to the formation of benzo[c]cinnolinium based-salts, organotin(IV) 1 was converted into a distannoxane compound, ²_∞{[n-Bu₂(μ-OH)SnOSn(μ-η²-O₃SCF₃)n-Bu₂]₂[n-Bu₂(η¹-O₃SCF₃)SnOSn(μ-OH)n-Bu₂]₂} (3), which was also isolated as a single crystal and whose crystallographic structure was previously established by us. Full article

Two-dimensional (2D) crystals which present unconventional stoichiometries on graphene surfaces in ambient conditions, such as Na₂Cl, Na₃Cl, and CaCl, have attracted significant attention in recent years due to their electronic structures and abnormal cation–anion ratios, which differ from those of conventional three-dimensional crystals. This unconventional crystallization is attributed to the cation–π interaction between ions and the π-conjugated system of the graphene surface. Consequently, their physical and chemical properties—including their electrical, optical, magnetic, and mechanical characteristics—often differ markedly from those of conventional crystals. This review summarizes the recent progress made in the fabrication and analysis of the structures, distinctive features, and applications of these 2D unconventional stoichiometry crystals on graphene surfaces in ambient conditions. Their special properties, including their piezoelectricity, metallicity, heterojunction, and room-temperature ferromagnetism, are given particularly close attention. Finally, some significant prospects and further developments in this exciting interdisciplinary field are proposed. Full article

Nowadays, nitrate ions and azo dyes are a significant source of water pollution due to their high toxicity, persistence, and potential to be carcinogenic. Both contaminants are the result of anthropogenic sources, such as sewage or industrial wastewater discharge; the first one results also as a consequence of the intensive use of fertilizers. In this work we report the use of a new quaternized pentablock copolymer (PTBr) for the removal of nitrate ions and methyl orange (MO) dye from water by adsorption processes. Morphological, chemical, and thermal properties of the pentablock copolymer were investigated, respectively, by scanning electron microscopy (SEM), Attenuated Total Reflectance Infrared Spectroscopy (ATR-FTIR) (FT-IR), and X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC) analyses. Anionic removal ability and adsorption rate in water solutions containing either a single contaminant species or a mix of the two contaminants were studied by UV–VIS absorbance spectroscopy as a function of time and initial concentration. The presence of imidazole groups confers on PTBr a positive charge and a hydrophilic character that are responsible for an effective removal of anions from water. PTBr film reports an adsorption efficiency of 10.15 mg/g for nitrate removal and this value is in line with others reported in the literature. In the case of the simultaneous presence of nitrate and MO, it is found that nitrate ions removal is slightly affected by the presence of the dye, since both contaminants compete for electrostatic interaction with imidazole groups. On the contrary, the dye removal does not show significant change with or without the presence of nitrate ions, probably due to other kinds of interaction that it can establish with the polymer surface (π-π interaction). The adsorption process and the related mechanisms are described using kinetic and isothermal models. Despite a certain reduction in the adsorption efficiency for one of the investigated contaminants, the results confirm the possibility of using the quaternized pentablock copolymer for the co-adsorption of both inorganic and organic anions. Full article

High-performance water-based inkjet inks are critical for advancing inkjet printing technology. The performance of water-based inkjet inks depends largely on the dispersion stability of organic pigments. This imposes higher demands on the performance of polymeric dispersants. However, the relatively weak interaction between polymeric dispersants and organic pigments limits their performance in water-based inkjet inks. Consequently, it is crucial to seek dispersants that exhibit stronger interactions with pigments, alongside high performance, and universality. In this work, five types of polymeric nanoparticles (PNPs) with anion-π groups were synthesized via a simple emulsion polymerization method. Compared to traditional polymeric dispersants, anion-π type PNPs exhibited significant advantages including low viscosity, solvent resistance, and high temperature resistance. Stronger interactions, including salt-bridge hydrogen bondings (H-bonds) and π–π interactions, between these PNPs and different types of organic pigments were demonstrated by FTIR, UV-Vis, and XPS spectral tests. In particular, PNPs-5, bearing -PhSO₃⁻ groups, exhibited the strongest interaction with the organic pigments. The water-based inkjet inks, formulated with PNPs-5 serving as a dispersant, exhibited remarkable dispersion stability and outstanding weatherability. This work rationally constructs a strategy for preparing universally applicable polymeric dispersants to enhance the dispersion of pigments in water-based inkjet inks, thereby presenting a broader perspective for applications in the field of inkjet printing. Full article

Graphene materials and their derivatives have shown promising capabilities in removing anionic and cationic dyes from wastewater. The present study aims at the synthesis of graphene-based material with a high specific surface area and evaluates its use as an adsorbent for removing toluidine blue and methyl violet from aqueous solutions. The physicochemical characterization of the adsorbent before and after dye adsorption is made by XRD, Raman spectroscopy, SEM, TEM, nitrogen physisorption, TG-DTA, and XPS. The influence of the solution’s pH, contact time, dye concentration, and temperature on the adsorption efficiency is investigated. The adsorbent demonstrated high adsorption capacity towards toluidine blue (265.2 mg.g⁻¹) and methyl violet (200.4 mg.g⁻¹) dyes from water. The adsorption process for both dyes follows the Langmuir model and involves physical rather than chemical interactions. Kinetic parameters were also determined. The adsorption of the studied cationic dyes can be attributed to a combination of mechanisms, including electrostatic interactions, hydrogen bonding, and π-π interactions between the dye molecules and the aromatic structure of reduced graphene oxide. The findings in the present work highlight the possibilities for enhancing graphene-based materials’ adsorption capabilities. Full article

The interaction of sodium phytate hydrate C₆H₁₈O₂₄P₆·xNa·yH₂O (phytNa) with Cu(OAc)₂·H₂O and 1,10-phenanthroline (phen) led to the anionic tetranuclear complex [Cu₄(H₂O)₄(phen)₄(phyt)]·2Na⁺·2NH₄⁺·32H₂O (1), the structure of the latter was determined by X-ray diffraction analysis. The phytate 1 is completely deprotonated; six phosphate⁻ fragments (with atoms P1–P6) are characterized by different spatial arrangements relative to the cyclohexane ring (1a5e conformation), which determines two different types of coordination to the complexing agents—P1 and P3, P4, and P6 have monodentate, while P2 and P5 are bidentately bound to Cu²⁺ cations. The molecular structure of the anion complex is stabilized by a set of strong intramolecular hydrogen bonds involving coordinated water molecules. Aromatic systems of phen ligands chelating copper ions participate in strong intramolecular and intermolecular π-π interactions, further contributing to their association. At the supramolecular level, endless stacks are formed, in the voids of which sodium and ammonium cations and water molecules are present. The stability of 1 in the presence of human serum albumin (HSA) was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. Continuous wave (CW) EPR spectra in water/glycerol frozen solution clearly indicate a presence of an exchange-coupled Cu(II)-Cu(II) dimeric unit, as well as a Cu(II) monomer-like signal arising from spins sufficiently distant from each other, with comparable contributions of two types of signals. In the presence of albumin at a 1:1 ratio (1 to albumin), the EPR spectrum changes significantly, primarily due to the reduced contribution of the S = 1 fraction showing dipole–dipole splitting. The biological activity of 1 in vitro against the non-pathogenic (model for Mycobacterium tuberculosis) strain of Mycolicibacterium smegmatis is comparable to the first-line drug for tuberculosis treatment, rifampicin. Full article

Inspired by the reported crystal structure of compound 1, we aimed to synthesize and determine the structure of compound 2, where two imidazolium (H₂im⁺) ions serve as diamagnetic countercations. Here, we report the thermal stabilities, FT–IR, visible, and RSE spectra, as well as the magnetic properties of both compounds. In these structures, µ-EDTA acts as a pentadentate chelator for both terminal Cu centers within the centrosymmetric linear trinuclear anion. The Cu(µ-EDTA) chelates bind to the central Cu(Him)₄ unit in subtly different ways: in compound 1, µ-EDTA has a free acetate arm and binds the central Cu(II) center through a syn,anti-carboxylate group. In contrast, in compound 2, the non-chelating acetate arm serves as a monodentate O-donor to the central Cu(II) atom, increasing the Cu(terminal)···Cu(central) distance from 6.08 Å in 1 to 6.80 Å in 2. Additionally, pairs of H₂im⁺ ions in compound 2 display antiparallel π-stacking interactions. We conclude that the H₂im⁺ counterions in compound 2 enable the magnetic isolation of the nearly identical trinuclear anion present in both compounds. DFT calculations further support the role of different interactions in stabilizing each crystal structure. In compound 2, dominant contributions from N–H···O hydrogen bonds and π-stacking interactions are accompanied by other, less conventional interactions, such as multiple C–H···O contacts and an O···CO(π-hole) interaction within the trinuclear anion. Full article

Our recent study demonstrated that fulvic and humic acids are the major contributors to the adsorption of phenoxyalkanoic acid herbicides in soils. At very low pH, the neutral forms of these herbicides are bound directly to fulvic and humic acids, whereas at higher pH, their anionic forms are adsorbed mainly via bridges created by Al³⁺ species. The number of active sorption sites associated with Al³⁺ species complexed with fulvic acids is pH-dependent, whereas the number of corresponding sites in humic acids is pH-independent. Based on the results of the FTIR analysis, research into adsorption thermodynamics, and molecular modeling, an attempt was made in the present study to explain the adsorption mechanisms of six phenoxyalkanoic herbicides used currently in the European Union on the surfaces of the above fractions of humic substances. The obtained values of standard enthalpy (${\Delta H}^0$) for the adsorption of the anionic forms of phenoxyalkanoic herbicides on fulvic or humic acids complexed with Al³⁺ were in the range of physical adsorption, i.e., from −8.4 kJ/mol to −2.9 kJ/mol for the former, and from −5.3 kJ/mol to −2.4 kJ/mol for the latter. The study demonstrated that the neutral forms of phenoxyalkanoic herbicides were bound to humic substances mainly via H-bonds, π-π stacking interactions, and hydrophobic interactions. Al³⁺ species were complexed with fulvic and humic acids to form outer-sphere complexes. Ternary outer-sphere complexes were also created between the anionic forms of phenoxyalkanoic acid herbicides and positively charged Al³⁺ species complexed with fulvic acids. The mechanisms of adsorption on humic acids involved a ligand exchange between a loosely bound hydroxyl group of hydrolyzed Al³⁺ complexed with this adsorbent and the anionic form of the herbicide. However, in this case, adsorption took place only in the presence of sufficiently strong hydrophobic and π-π stacking interactions supported by H-bonds. These findings elucidate why phenoxyalkanoic herbicides are mobile in the soil profile and are often rapidly degraded in soils. Full article

To investigate the halogen substitution effect on the anionic spin crossover (SCO) complexes, azobisphenolate ligands with 5,5′-dihalogen substituents from fluorine to iodine were synthesized, and their anionic Fe^III complexes 1F, 1Cl, 1Br, and 1I were isolated. The temperature dependence of magnetic susceptibility and crystal structure revealed that 1F, 1Cl, and 1Br are all isostructural and exhibit SCO with the rotational motion of the cation and ligands, whereas 1I shows incomplete SCO. Note that 1Cl and 1Br showed irreversible and reversible cooperative SCO transitions, respectively. Short intermolecular contacts between the Fe^III complex anions were found despite Coulomb repulsions for all the complexes. The topological analysis of the electron density distributions revealed the existence of X···X halogen bonds, C–H···X, C–H···N, and C–H···O hydrogen bonds, and C–H···π interactions are evident. The dimensionality of intermolecular interactions is suggested to be responsible for the cooperative SCO transitions in 1Cl and 1Br, whereas the disorder due to the freezing of ligand rotations in 1Cl is revealed to inhibit the SCO cooperativity. Full article

In the present work, we reported the synthesis and characterization [single crystal X-ray diffraction technique, spectroscopic, etc.] of two new Ni(II) and Zn(II) coordination compounds, viz. [Ni(2,6-PDC)₂]₂[Ni(en)₂(H₂O)₂]₂[Ni(en)(H₂O)₄]·4H₂O (1) and [Zn(2,6-PDC)(Hdmpz)₂] (2) (where 2,6-PDC = 2,6-pyridinedicarboxylate, en = ethylene-1,2-diamine, and Hdmpz = 3,5-dimethyl pyrazole). Compound 1 is found to crystallize as a multicomponent Ni(II) compound with five discrete complex moieties, whereas compound 2 is isolated as a mononuclear Zn(II) compound. A deep analysis of the crystal structure of 1 unfolds unusual dual enclathration of guest complex cationic moieties within the supramolecular host cavity stabilized by anion–π, π-stacking, N–H⋯O, C–H⋯O, and O–H⋯O hydrogen bonding interactions. Again, the crystal structure of compound 2 is stabilized by the presence of unconventional C–H⋯π(chelate ring) interactions along with C–H⋯O, C–H⋯N hydrogen bonding, π-stacking, and C–H⋯π(pyridyl) interactions. These non-covalent interactions were further studied theoretically using density functional theory (DFT) calculations, molecular electrostatic potential (MEP) surfaces, non-covalent interaction (NCI) plot index, and quantum theory of atoms in molecules (QTAIM) computational tools. The computational study displays that π-stacking or H bonds greatly tune the directionality of compound 1, although non-directional electrostatic forces dominate energetically. For compound 2, a combined QTAIM/NCI plot analysis confirms the presence of unconventional C–H⋯π(chelate ring) interactions along with other weak interactions obtained from the crystal structure analysis. Further, the individual energy contributions of these weak yet significant non-covalent interactions have also been determined computationally. Full article

The crystalline sponge method has proven invaluable in the preparation and analysis of supramolecular host/guest complexes if the host can be obtained in a suitable crystalline form, allowing the analysis of guest binding modes inside host cavities which can inform other studies into processes such as catalysis. Here, we report the structures of a set of ten host/guest complexes using an octanuclear coordination cage host with a range of small-molecule neutral organic guests including four aromatic aldehydes and ketones, three cyclic lactams, and three epoxides. In all cases, the cavity-bound guests are anchored by a collection of CH•••O hydrogen-bonding interactions between an O atom on the guest and a convergent set of CH protons at a pocket on the cage interior surface. Depending on guest size and the presence of solvent molecules as additional guests, there may be one or two cavity-bound guests, with small aromatic guests forming π-stacked pairs. Some guests (the lactams) participate in additional NH•••F H-bonding interactions with surface-bound fluoroborate anions, which indicate the type of anion/guest interactions thought to be responsible for solution-phase catalytic reactions of bound guests. Full article

The enantioselective mechanism of the esterase QeH against the two enantiomers of quizalofop–ethyl (QE) has been primitively studied using computational and experimental approaches. However, it is still unclear how the esterase QeH adjusts its conformation to adapt to substrate binding and promote enzyme–substrate interactions in the catalytic kinetics. The equilibrium processes of enzyme–substrate interactions and catalytic dynamics were reproduced by performing independent molecular dynamics (MD) runs on the QeH-(R)/(S)-QE complexes with a newly developed residue-specific force field (RSFF2C). Our results indicated that the benzene ring of the (R)-QE structure can simultaneously form anion–π and cation–π interactions with the side-chain group of Glu328 and Arg384 in the binding cavity of the QeH-(R)-QE complex, resulting in (R)-QE being closer to its catalytic triplet system (Ser78-Lys81-Tyr189) with the distances measured for the hydroxyl oxygen atom of the catalytic Ser78 of QeH and the carbonyl carbon atom of (R)-QE of 7.39 Å, compared to the 8.87 Å for (S)-QE, whereas the (S)-QE structure can only form an anion–π interaction with the side chain of Glu328 in the QeH-(S)-QE complex, being less close to its catalytic site. The computational alanine scanning mutation (CAS) calculations further demonstrated that the π–π stacking interaction between the indole ring of Trp351 and the benzene ring of (R)/(S)-QE contributed a lot to the binding stability of the enzyme–substrate (QeH-(R)/(S)-QE). These results facilitate the understanding of their catalytic processes and provide new theoretical guidance for the directional design of other key enzymes for the initial degradation of aryloxyphenoxypropionate (AOPP) herbicides with higher catalytic efficiencies. Full article

Using a co-precipitation technique, the anionic form of sulisobenzone (benzophenone-4) sunscreen ingredient was incorporated into the interlayer space of CaFe-hydrocalumite for the first time. Using detailed post-synthetic millings of the photoprotective nanocomposite obtained, we aimed to study the mechanochemical effects on complex, hybridized layered double hydroxides (LDHs). Various physicochemical properties of the ground and the intact LDHs were compared by powder X-ray diffractometry, N₂ adsorption-desorption, UV–Vis diffuse reflectance, infrared and Raman spectroscopy, scanning electron microscopy and thermogravimetric measurements. The data showed significant structural and morphological deformations, surface and textural changes and multifarious thermal behavior. The most interesting development was the change in the optical properties of organic LDHs; the milling significantly improved the UV light blocking ability, especially around 320 nm. Spectroscopic results verified that this could be explained by a modification in interaction between the LDH layers and the sulisobenzone anions, through modulated π–π conjugation and light absorption of benzene rings. In addition to the vibrating mill often used in the laboratory, the photoprotection reinforcement can also be induced by the drum mill grinding system commonly applied in industry. Full article

We describe the antioxidant capability of scavenging the superoxide radical of several tea and yerba mate samples using rotating ring–disk electrochemistry (RRDE). We directly measured superoxide concentrations and detected their decrease upon the addition of an antioxidant to the electrochemical cell. We studied two varieties of yerba mate, two varieties of black tea from Bangladesh, a sample of Pu-erh tea from China, and two components, caffeic acid and chlorogenic acid. All of these plant infusions and components showed strong antioxidant activities, virtually annihilating the available superoxide concentration. Using density functional theory (DFT) calculations, we describe a mechanism of superoxide scavenging via caffeic and chlorogenic acids. Superoxide can initially interact at two sites in these acids: the H4 catechol hydrogen (a) or the acidic proton of the acid (b). For (a), caffeic acid needs an additional π–π superoxide radical, which transfers electron density to the ring and forms a HO₂⁻ anion. A second caffeic acid proton and HO₂⁻ anion forms H₂O₂. Chlorogenic acid acts differently, as the initial approach of superoxide to the catechol moiety (a) is enough to form the HO₂⁻ anion. After an additional acidic proton of chlorogenic acid is given to HO₂⁻, three well-separated compounds arise: (1) a carboxylate moiety, (2) H₂O₂, and a (3) chlorogenic acid semiquinone. The latter can capture a second superoxide in a π–π manner, which remains trapped due to the aromatic ring, as for caffeic acid. With enough of both acids and superoxide radicals, the final products are equivalent: H₂O₂ plus a complex of the type [X-acid–η–O₂], X = caffeic, chlorogenic. Chlorogenic acid (b) is described by the following reaction: 2 O₂^•− + 2 chlorogenic acid → 2 chlorogenic carboxylate + O₂ + H₂O₂, and so, it acts as a non-enzymatic superoxide dismutase (SOD) mimic, as shown via the product formation of O₂ plus H₂O₂, which is limited due to chlorogenic acid consumption. Caffeic acid (b) differs from chlorogenic acid, as there is no acidic proton capture via superoxide. In this case, approaching a second superoxide to the H4 polyphenol moiety forms a HO₂⁻ anion and, later, an H₂O₂ molecule upon the transfer of a second caffeic acid proton. Full article

A series of novel salts based on aromatic polyamines and 2,3-pyrazinedicarboxylic acid, such as C₁₀H₁₂N₆O₅ (1), C₁₀H₉ClN₆O₄ (2), C₁₁H₁₀N₈O₄ (3), and C₁₄H₁₇N₁₆O_5.5 (4) or 3,4-thiophenedicarboxylic acid, such as C₁₀H₁₀N₄O₄S (5), C₁₀H₉ClN₄O₄S (6), and C₁₀H₁₀N₄O₄S₂ (7), were synthesized and characterized by single-crystal X-ray diffraction. All compounds crystallize in a monoclinic space group. The structure was subjected to complex Hirshfeld surface analysis, molecular electrostatic potential, enrichment ratio, and energy framework calculations. The influence of different cations on the packing of 3-carboxypyrazine-2-carboxylate and 4-carboxythiophene-3-carboxylate anions in the crystal lattice was studied. O^…H/H^…O interactions are the main contributor in all crystals. In addition, in a series of pyrazine-containing structures, N(C)^…H/H^…N(C) interactions have relevance, while in a series of thiophene-based compounds, C^…H/H^…C and S^…H(O)/H(O)^…S. In addition, Cl-based interactions are observed in compound 2. According to the enrichment ratio calculations, O^…H/H^…O and C^…C are the most preferable interactions in all structures. The energy frameworks are dominated by the dispersive contribution, only in compound 3 is the electrostatic term dominant. The analyzed structures reveal intra- and intermolecular recurrent supramolecular synthons. In both series of crystals, the robust H-bonded centrosymmetric dimer R²₂(8) as homo- or as heterosynthon (in compounds 2, 3, 6, and 7) and the intramolecular synthon S(7) generated by O-H^…O interactions (in compounds 2, 6, and 7) are present. The supramolecular patterns formed by π^…π (C^…C) and C-O(Cl,S)^…C are also noticeable. Notably, a dual synthon linking the supramolecular chain via π^…π interactions and the homosynthon R²₂(8) via N-H^…N interactions is visible in both series of new salts. A library of H-bonding motifs at diverse levels of supramolecular architecture is provided. We extended the analysis of intramolecular H-bonding motifs to similar structures deposited in the Cambridge Structural Database. Another important feature is the existence of an intramolecular O^…H^…O bridge between two neighboring carboxylic groups as substituents in anions in compounds 3 and 5. In this context, we performed quantum theory of atoms-in-molecule calculations to reveal more details. Full article