Coping with the critical challenge of imidacloprid (IMI) contamination in sewage treatment and farmland drainage purification, this study presents a pioneering development of an advanced modified graphitic white melon seed shells biochar (Fe/Zn@WBC). The Fe/Zn@WBC demonstrates a substantial enhancement in adsorption efficiency for IMI, achieving a remarkable removal rate of 87.69% within 30 min and a significantly higher initial adsorption rate parameter h = 4.176 mg g-1·min-1. This significant improvement outperforms WBC (12.22%, h = 0.115 mg g-1·min-1) and highlights the influence of optimized adsorption conditions at 900 °C and the graphitization degree resulting from Fe/Zn bimetallic oxide modification. Characterization analysis and batch sorption experiments including kinetics, isotherms, thermodynamics and pH factors illustrate that chemical adsorption is the main type of adsorption mechanism responsible for this superior ability to remove IMI through pore filling, hydrogen bonding, hydrophobic interaction, electrostatics interaction, π-π interactions as well as complexation processes. Furthermore, we demonstrate exceptional stability of Fe/Zn@WBC across a broad pH range (pH = 3-11), co-existing ions presence along with humic acid under various real water conditions while maintaining high removal efficiency. This study presents an advanced biochar adsorbent, Fe/Zn@WBC, with efficient adsorption capacity and easy preparation. Through three regeneration cycles via pyrolysis method, it demonstrates excellent pyrolysis regeneration capabilities with an average removal efficiency of 92.02%. The magnetic properties enable rapid separation facilitated by magnetic analysis. By elucidating the efficacy and mechanistic foundations of Fe/Zn@WBC, this research significantly contributes to the field of environmental remediation by providing a scalable solution for IMI removal and enhancing scientific understanding of bimetallic oxides-hydrophilic organic pollutant interactions.

Protein lattices that shift the structure and shape anisotropy in response to environmental cues are closely coupled to potential functionality. However, to design and construct shape-anisotropic protein arrays from the same building blocks in response to different external stimuli remains challenging. Here, by a combination of the multiple, symmetric interaction sites on the outer surface of protein nanocages and the tunable features of phenylalanine-phenylalanine interactions, a protein engineering approach is reported to construct a variety of superstructures with shape anisotropy, including 3D cubic, 2D hexagonal layered, and 1D rod-like crystalline protein nanocage arrays by using one single protein building block. Notably, the assembly of these crystalline protein arrays is reversible, which can be tuned by external stimuli (pH and ionic strength). The anisotropic morphologies of the fabricated macroscopic crystals can be correlated with the Å-to-nm scale protein arrangement details by crystallographic elucidation. These results enhance the understanding of the freedom offered by an object\'s symmetry and inter-object π-π stacking interactions for protein building blocks to assemble into direction- and shape-anisotropic biomaterials.

This article presents two groups of V-shaped π-scaffolds that consist of two N-heteroacene units fused with either a rigid or flexible eight-membered ring. These rigid and flexible N-heteroacene dimers were synthesized through the condensation of tetraphenylenetetraone with the corresponding diamine and the Pd-catalyzed cross-coupling of tetrabromodibenzo[a,e]cyclooctatetraene with the corresponding diamine, respectively. A comparison of electronic structures and properties of the two groups of V-shaped N-heteroacene dimers shows subtle difference between the rigid and flexible eight-membered ring linkers in forming extended π-systems. X-ray crystallography of these V-shaped molecules has revealed interesting π-π interaction modes, which are dependent on the central connecting units and substituting groups. These π-π interactions between the V-shaped π-scaffolds have enabled the molecules to function as organic semiconductors in solution-processed field effect transistors.

Anthraquinones are widely distributed in higher plants and possess broad biological activities. The conventional separation procedures for isolating anthraquinones from the plant crude extracts require multiple extraction, concentration, and column chromatography steps. In this study, we synthesized three alizarin (AZ)-modified Fe3O4 nanoparticles (Fe3O4@AZ, Fe3O4@SiO2-AZ, and Fe3O4@SiO2-PEI-AZ) by thermal solubilization method. Fe3O4@SiO2-PEI-AZ showed strong magnetic responsiveness, high methanol/water dispersion, good recyclability, and high loading capacity for anthraquinones. To evaluate the feasibility of using Fe3O4@SiO2-PEI-AZ for separating various aromatic compounds, we employed molecular dynamics simulations to predict the adsorption/desorption effects of PEI-AZ for various aromatic compounds in different methanol concentrations. The results showed that the anthraquinones could be efficiently separated from the monocyclic and bicyclic aromatic compounds by adjusting the methanol/water ratio. The Fe3O4@SiO2-PEI-AZ nanoparticles were then used to separate the anthraquinones from the rhubarb extract. At 5% methanol, all the anthraquinones were adsorbed by the nanoparticles, thus allowing their separation from other components in the crude extract. Compared with the conventional separation methods, this adsorption method has the advantages of high adsorption specificity, simple operation, and solvent saving. This method sheds light on the future application of functionalized Fe3O4 magnetic nanoparticles to selectively separate desired components from complex plant and microbial crude extracts.

We employ a molecular torsion balance displaying bifurcated conformational isomerism to quantitatively evaluate the non-covalent interactions between the fullerene surface and substituted arene moieties containing elements with high atomic numbers, as well as the thermodynamic processes involved in the folding equilibrium using nuclear magnetic resonance spectroscopy. The interaction between fullerene and haloaryl groups was stronger in cases where the introduced halogen had a higher atomic number, indicating that dispersion forces play a significant role in the interaction between fullerenes and 4-haloaryl groups. The dispersion term also significantly contributed to the interaction between fullerene and the 4-mercaptophenyl group. Moreover, the addition of an appropriate base to the 4-mercaptophenyl-appended torsion balance formed the corresponding thiophenolate anion, resulting in a large negative change in the folding free energy in CDCl3 . Detailed analysis suggested that the observed attractive anionic arene-fullerene interactions predominantly originated from solvation effects.

Thermal oxidation is efficient for enhancing the photocatalysis performance of graphitic carbon nitride (g-C3N4), while its effect on adsorption performance has not been fully studied, which is crucial to the application of g-C3N4 as adsorbents and photocatalysts. In this study, thermal oxidation was used to prepare sheet-like g-C3N4 (TCN), and its application for adsorption of humic acids (HA) and fulvic acids (FA) was evaluated. The results showed that thermal oxidation clearly affected the properties of TCN. After thermal oxidation, the adsorption performance of TCN was enhanced significantly, and the adsorption amount of HA increased from 63.23 (the bulk g-C3N4) to 145.35 mg/g [TCN prepared at 600 °C (TCN-600)]. Based on fitting results using the Sips model, the maximum adsorption amounts of TCN-600 for HA and FA were 327.88 and 213.58 mg/g, respectively. The adsorption for HA and FA was markedly affected by pH, alkaline, and alkaline earth metals due to electrostatic interactions. The major adsorption mechanisms included electrostatic interactions, π-π interactions, hydrogen bonding, along with a special pH-dependent conformation (for HA). These findings implied that TCN prepared from environmental-friendly thermal oxidation showed promising prospects for humic substances (HSs) adsorption in natural water and wastewater.

The unique properties and environmental implications of biochar nanoparticles (BNPs) have attracted increasing attention. The abundant functional groups and aromatic structures in BNPs may promote the aggregation of BNPs, but the mechanism and implications of this aggregation process remain unclear. Thus, this study investigated the aggregation of BNPs and the sorption of bisphenol A (BPA) on BNPs by combining experimental investigations with molecular dynamics simulations. As the concentration of BNP increased from 100 mg/L to 500 mg/L, the particle size increased from approximately 200 nm to 500 nm, and the exposed surface area ratio in the aqueous phase decreased from 0.46 to 0.05, which confirmed the aggregation of BNPs. The sorption of BPA on BNPs decreased with increasing BNP concentration in both the experiments and molecular dynamics simulations because of BNP aggregation. According to a detailed analysis of the BPA molecules adsorbed on BNP aggregates, the sorption mechanisms were hydrogen bonding, hydrophobic effect, and π-π interactions, which were driven by aromatic rings and O- and N-containing functional groups. The aggregation of BNPs embedded some functional groups in the aggregates and thus inhibited sorption. Interestingly, the steady configuration of the BNP aggregates in the molecular dynamics simulations (2000 ps relaxation) also determined the apparent BPA sorption. BPA molecules were adsorbed in the V-shaped interlayers of the BNP aggregates that acted as semi-closed pores, but could not be adsorbed in the parallel interlayers because of their small layer spacing. This study can provide theoretical guidance for the application of BNPs in pollution control and remediation.

The nature and strength of the noncovalent intermolecular interactions on the surface of fullerenes must be understood for the application of these molecules in pharmaceuticals and materials chemistry. Consequently, experimental and theoretical evaluations of such weak interactions have been conducted in parallel. Nevertheless, the nature of these interactions remains a topic of ongoing debate. In this context, this concept article summarizes recent advances in experimental and theoretical efforts aimed at characterizing the nature and strength of non-covalent interactions on fullerene surfaces. Specifically, this article summarizes recent studies conducted on host-guest chemistry based on various macrocycles and on catalyst chemistry based on conjugated molecular catalysts composed of fullerenes and amines. In addition, conformational isomerism analyses performed using fullerene-based molecular torsion balances and state-of-the-art computational chemistry are reviewed. These studies have enabled a comprehensive evaluation of the contributions of electrostatic, dispersion, and polar interactions on the surface of fullerenes.

In this paper, two chelate resins prepared by a simple procedure were used for the removal of Cd2+, Ni2+, Cu2+, and Pb2+ (M2+) from aqueous solutions. Amberlite IRA 402 strongly basic anion exchange resin in Cl− form (IRA 402 (Cl−) together with Amberlite XAD7HP acrylic ester co-polymer (XAD7HP) were functionalized with chelating agent Direct red 23 (DR 23). The chelate resins (IRA 402-DR 23 and XAD7HP-DR 23) were obtained in batch mode. The influence of interaction time, pH and the initial concentration of DR 23 solution was investigated using UV-Vis spectrometry. The time necessary to reach equilibrium was 90 min for both resins. A negligible effect of adsorption capacity (Qe) was obtained when the DR 23 solution was adjusted at a pH of 2 and 7.9. The Qe of the XAD7HP resin (27 mg DR 23/g) is greater than for IRA 402 (Cl−) (21 mg DR 23/g). The efficiency of chelating resins was checked via M2+ removal determined by the atomic adsorption spectrometry method (AAS). The M2+ removal by the IRA 402-DR 23 and XAD7HP-DR 23 showed that the latter is more efficient for this propose. As a consequence, for divalent ions, the chelated resins followed the selectivity sequence: Cd2+ > Cu2+ > Ni2+ > Pb2+. Additionally, Cd2+, Cu2+ and Ni2+ removal was fitted very well with the Freundlich model in terms of height correlation coefficient (R2), while Pb2+ was best fitted with Langmuir model for IRA 402-DR 23, the Cu2+ removal is described by the Langmuir model, and Cd2+, Ni2+ and Pb2+ removal was found to be in concordance with the Freundlich model for XAD7HP-DR 23. The M2+ elution from the chelate resins was carried out using 2 M HCl. The greater M2+ recovery from chelating resins mass confirmed their sustainability. The chelate resins used before and after M2+ removal by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) analysis were evaluated.

In this study, generalized predictive models were developed to estimate KOA of four kinds of aromatic pollutants based on the calculated solvation free energy and taking the dimer effect into account. Uncorrected log KOA values, which were directly estimated from the calculated solvation free energy of individual molecules, underestimated experimental values, and the deviation increased with increasing log KOA. Dimers were found to greatly affect the apparent KOA values of these aromatic pollutants, which were driven by π-π interactions. London dispersion and exchange-repulsion terms were identified to be dominant components of the underlying π-π interactions. It is interesting to find that the π-π interactions of polybrominated diphenyl ethers correlate with not only the molecular polarizability but also the size of opposing aromatic surfaces, which leads to a different trend of π-π interactions from other aromatic pollutants. A universal quantitative structure-activity relationship model was developed to estimate the proportion of dimers based on five molecular structural descriptors relevant to the π-π interactions. After calibration with the dimer effect, estimations of log KOA were consistent with experimental values. Therefore, the dimer effect should be taken into consideration when investigating the partition behavior of aromatic pollutants, and the solvation free energy model could be an alternative method for the prediction of KOA.