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[Display omitted] • Halloysite and histidine were combined as a bio-based heterogeneous acidic catalyst for converting fructose to HMF. • DFT calculations revealed that histidine-based ionic liquid with halloysite outperform other amino acids catalytically. • NCI plots highlighted the crucial role of hydrogen bonds, favoring histidine over tryptophan due to its higher contribution. • Chemical functionalization of Halloysite with IL significantly improved the catalyst's acidity and catalytic performance. • The catalyst demonstrated high activity under mild conditions and was highly recyclable. In an effort to design a bio-based catalyst with enough acidic strength to promote the conversion of fructose to 5-hydroxymethylfurfural, a series of halloysite clay-supported acidic ionic liquids were considered as potential candidates. The catalysts could be synthesized from reaction of Cl-functionalized halloysite with histidine, histamine, adenine and tryptophan, followed by treatment with chlorosulfuric acid. Predictive computational studies were performed and approved the superior activity of the histidine-based catalyst. In addition, the computational studies aimed to identify the optimal catalyst using Density Functional Theory (DFT) calculations and other characterization techniques, particularly non covalent interactions plots. Aknowledged by computational results, histidine based catalyst was prepared, characterized and its catalytic activity and recyclability were appraised for the synthesis of 5-hydroxymethylfurfural from fructose as a bio-based starting material. The reaction conditions were optimized and it was revealed that using 30 wt% catalyst, the desired product could be achieved at 100 °C within 1 h. Notably, the catalyst exhibited high recyclability and efficiently promoted the reaction of other mono-saccharides as well. [ABSTRACT FROM AUTHOR]

[Display omitted] • Adsorption of VOC molecules, carbon dioxide, and water were investigated. • Pure and Lithium-decorated bismuthene proves to be effective as a VOC sensor. • All VOCs biomarkers and interfering gases are absorbed within acceptable range. To meet the crucial need for VOC detection, we propose a nanosensor based on bismuthene, employing density functional theory calculations. This nano-sensor aims to detect specific volatile organic compounds (VOCs) present in human breath, including acetone (C 3 H 6 O), ethanol (C 2 H 6 O), methanol (CH 3 OH), formaldehyde (CH 2 O), and toluene (C 7 H 8), which serve as potential biomarkers for identifying physiological disorders. Additionally, we investigate how carbon dioxide (CO 2) and water vapor (H 2 O), common in exhaled breath, interact with bismuthene as likely interfering species. Notably, toluene exhibited higher adsorption energy with pure and Li-decorated bismuthene. The favorable adsorption and desorption performance of bismuthene with molecules such as formaldehyde, methanol, and acetone at near-ambient temperatures suggest its suitability as a VOCs sensor with simple operational conditions. The density of states, charge analysis, adsorption properties, sensitivity, conductivity, selectivity, and recovery time have been calculated and discussed. Our results highlight Bismuthene's potential as an efficient nano-sensor for detecting VOCs associated with pulmonary malignancies. [ABSTRACT FROM AUTHOR]

[Display omitted] • Homolysis of C-Cl bonds in the first triplet state induced the dechlorination. • Hydrated electron enhanced the dechlorination of pentachlorophenolate. • Reduction of phenoxyl radical by HS−/S2− generated pentachlorophenolate and HS/S −. • Nucleophilic substitution of HS/S − played a decisive role in the dechlorination. Pentachlorophenol (PCP), a highly toxic and persistent agrochemical, is urgent to be dechlorinated for the disintoxication and degradation. Thus, this study aimed to investigate the dechlorination of PCP through ultraviolet (UV) photolysis in the presence of hydrogen sulfide (H 2 S) in the water, using density functional theory calculations. The theoretical results suggest that 78.2 and 87.6 kcal·mol−1 were required for the dechlorination of PCP and pentachlorophenolate (PCP−) by the homolysis of C-Cl bonds under UV irradiation. The UV photolysis of PCP− could eject hydrated electron (e aq −) and pentachlorophenoxyl radical (PR) in the water. The absorption of e aq − by PCP− enhanced the dechlorination by releasing Cl−. Additionally, the dechlorination could also occur through the nucleophilic reactions of OH−, HS− and S2− with PR, which might be responsible for the enhancement of dechlorination from pH 6.2 to 7.7, and their respective forward energy barriers were 0.5, 6.6 and 21.7 kcal·mol−1 at the para -position. Furthermore, the dechlorination of major quinoid metabolite of PCP (tetrachloro- p -benzoquinone) and its monohydroxylated product under the UV irradiation was facilitated by the nucleophilic attacks on the first triplet states, with the forward energy barriers of 20.4 and 21.7 kcal·mol−1, respectively. Based on the findings in this work, the nucleophilicity of additives may play a dominant role in the dechlorination of PCP, and the combination of H 2 S and PCP may be helpful for not only the dechlorination of PCP but also the elimination of H 2 S. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ifosfamide adsorption onto the Pt- and Au-decorated and trapped B 12 N 12 fullerenes are evaluated using DFT and TDDFT calculations. • Adsorption mechanism of Ifosfamide chemisorbed onto Pt- and Au-trapped B 12 N 12 fullerenes are chemisorption. • Pt- and Au-decorated B 12 N 12 fullerenes are electronically and optically sensitive to Ifosfamide drug. Using density functional theory (DFT) calculations, the loading of Ifosfamide (IFO) via it's the phosphoryl (P = O) group onto the surface of Pt@B 12 N 12 , Au@B 12 N 12 , B 12 PtN 12 , and B 12 AuN 12 fullerene like-cages in vacuum and water environments were studied for the analysis. We observed that the trapping of Pt and Au atoms within the B 12 N 12 fullerene-like cages enhances the binding energy during interaction with IFO, compared to when Pt and Au atoms are decorated onto the B 12 N 12 in both vacuum and water phases. The polarity of the IFO/B 12 AuN 12 complex (18.43 Debye) is enhanced compared to the IFO/Au@B 12 N 12 complex (16.67 Debye), which is significant for effective in vivo drug delivery. These changes contributed to a slight enhancement in binding energy observed with the trapping of Pt and Au atoms into the fullerene in a water environment compared to the vacuum environment. Quantum molecular descriptor analysis indicates that the decline in hardness and electrophilicity leads to a decrease in the energy gap, which in turn enhances the polarizability of the electron cloud. The theoretical infrared (IR) spectrum indicates that the vibrational frequency of the P = O group in the drug changes upon interacting with the Pt@B 12 N 12 , Au@B 12 N 12 , B 12 PtN 12 , and B 12 AuN 12 fullerene-like cages, and this change is consistent with the experimental data. The electronic characteristics of Pt@B 12 N 12 as a biosensor are highly responsive to the presence of IFO molecules compared to Au@B 12 N 12 , resulting in a significant change in the energy gap of the fullerene-like cage after the adsorption process: 50.26 % in the water phase and 114 % in the vacuum phase. These findings suggest that Pt@B 12 N 12 functions as a good electrophile and has the capacity for enhanced drug adsorption and sensitivity. [ABSTRACT FROM AUTHOR]

[Display omitted] • The ionic liquid [HOEmim][NTf 2 ] can strengthen the extraction performance of TBP for Co2+. • The extraction efficiency of TBP/kerosene/[HOEmim][NTf 2 ] system for Co2+ is up to 99.6 %. • DFT calculations and FT-IR analysis indicate that Co2+ mainly binds to P=O in TBP. • A theoretical basis for removing Co2+ from waste water based on ionic liquids was laid. • ABSTRACT In order to achieve effective removal of radioactive Co(II) from the primary circuit wastewater of nuclear power plants and promote the safe use of nuclear energy, an efficient and eco-friendly method using ionic liquid as a co-extractant was proposed. The effects of ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C 2 mim][NTf 2 ]) or 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([HOEmim][NTf 2 ]) as co-extractants on the extraction of Co(II) using tributyl phosphate (TBP) as an extractant were investigated in this work. The results reveal that the optimal extraction conditions for Co(II) are as follows: V TBP : V kerosene : V [HOEmim][NTf2] = 18:1:1, R(O/A) = 1, pH=4. Under these conditions, the extraction efficiency of Co(II) (E Co) reaches 99.6 %, with a distribution ratio (D Co) of 257. Notably, a single TBP or ionic liquid exhibits minimal ability to extract Co2+, while adding only 5 % (v/v) ionic liquid based on TBP/kerosene system can increase D Co by 104 times. The slope method and FT-IR analysis demonstrate that the TBP/kerosene/[HOEmim][NTf 2 ]/ system extracted Co2+ by a cation exchange mechanism. In addition, density functional theory (DFT) calculations were employed to explain the influence of different ionic liquid systems on the E Co , and further elucidate the extraction mechanism of Co2+. The striping results indicate that 92.2 % of Co2+ is stripped with 1.0 mol L−1 HNO 3. The extraction efficiency of Co(II) from the TBP/kerosene/[HOEmim][NTf 2 ] system remained at 98 % after 6 cycles. Therefore, the extraction system exhibits great practical potential in removing Co(II) from contaminated water. This work not only proposes an extraction system with excellent reusability and stability, but also lays a theoretical foundation for the ionic liquid-based cobalt extraction process. [ABSTRACT FROM AUTHOR]

[Display omitted] • The hydrophobic deep eutectic solvents was composed of amide (hydrogen bond acceptor) and lactic acid (hydrogen bond donor). • The density and acidity were correlated with hydrogen bond acceptors' alkyl chain and hydrogen bond donors' content. • Milliequivalents calculation was found to be more accurate than pH measurement when describing the acidity. • Density Functional Theory calculation was applied to investigate the intermolecular interaction. • Fourier-transform infrared spectroscopy proved the existence of hydrogen bond. Hydrophobic deep eutectic solvents (HDESs) were considered as a kind of green media and were widely used for extraction, synthesis and catalytic reactions. Exploring the physicochemical property and intermolecular interaction was of great significance. In this work, we synthesized a series of HDESs using amide as hydrogen bond acceptor (HBA) and lactic acid as hydrogen bond donor (HBD). The density, acidity and intermolecular interactions of HDESs were investigated from experimental and theoretical viewpoints. Firstly, density results indicated that the increase of HBD content as well as the decrease of HBA alkyl chain could increase the density of HDESs. Secondly, acidity was found to be more accurate using milliequivalents calculation than pH measurement. The increase of HBD content as well as the decrease of HBA alkyl chain could also enhance the acidity of HDESs. In addition, the intermolecular hydrogen bond was investigated by multiple theoretical approaches, including electrostatic potential distribution map, the length of molecular bond, independent gradient model based on Hirshfeld partition and topology analysis of atoms. Ultimately, Fourier-transform infrared spectroscopy (FT-IR) was further applied to prove the existence of hydrogen bond. We believe this work would be valuable for understanding the nature of HDESs and providing guides for practical applications of HDESs. [ABSTRACT FROM AUTHOR]

[Display omitted] • Demonstration of method for the separation of uranium from sulfuric acid medium. • First reports on the recovery of U(VI) from analytical waste contains sulfuric acid along with phosphoric acid by DalHPs. • First investigations on the extraction mechanism of U(VI)-DalHPs complexes. • EXAFS studies insights that the three ligands are coordinated to uranyl sulfate moiety. The structural effects of the carbon chain on the extraction of uranium have been examined by dialkylhydrogen phosphonates (DalHPs). The extraction of uranium by 0.55 M solutions of DalHPs in n -dodecane (n -DD) was investigated as a function of aqueous phase sulfuric and phosphoric acid concentration (0.1–6 M), and the obtained results were compared with 0.55 M solution of tri-n-butyl phosphate (TBP) in n -DD system under similar experimental conditions. The batch distribution data for the extraction of uranium from sulfuric acid and phosphoric acid medium indicated that DalHPs showed dual extraction behavior, i.e., cation exchange at lower acidities and solvation at higher acidities. The extraction of uranium from the sulfuric acid medium was found to be higher than that from the phosphoric acid medium. The extracted U-DalHPs complexes were characterized by extended X-ray absorption fine structure (EXAFS) and the local atomic structure was discerned. The coordination number of uranium was derived from the EXAFS fitting data for various sulfuric acid concentrations. Density functional theory (DFT) computations were performed to understand the electronic structure and binding affinity of U-DalHPs. An acid-dependent extraction mechanism was derived computationally to understand the complexation of U-DalHPs. The trends observed in the distribution ratios of uranium, and the coordination number deduced from EXAFS fitting was found to be in good agreement with the DFT computations. These investigations have opened up new avenues for use of DalHPs for the extraction/recovery of heavy metal ions from sulfuric acid medium. [ABSTRACT FROM AUTHOR]

• It has been demonstrated that compounds based on camphor have the potential to be antimalarial medicines using DFT and molecular docking investigations. • Using the B3LYP/6-31G level of theory, DFT simulations were first performed on all 15 compounds to investigate molecular geometry and other molecular properties. • The DFT-optimized compounds have been molecularly docked with two distinct proteins involved in the transmission of malaria, using Discover Studio and Autodock Vina software. • This research opens up a line of inquiry for the experimental study of these heterocyclic compounds based on camphor with antimalarial properties. Nowadays, camphor-based heterocycles have attained the greater focus of the scientific community due to their specific and target-oriented medicinal properties. Based on the literature, it has been observed that the novel camphor-based heterocycles may act as prominent scaffolds to cure one of the potential diseases called malaria, which was caused by Plasmodium falciparum. In this regard, some novel camphor-based heterocycles have been designed to test their efficacy towards their antimalarial activity. First, using Spartan-14 software, Density Functional Theory investigations were conducted on the suggested heterocycles to ascertain their geometry and their associated chemical properties. All optimized camphor-based heterocycles have been docked against the proteins (PDB: 1LF3 & 3BPF) with Discovery Studio software and Autodock Vina and has been observed that the binding energies of the compounds CBH 1–15 with both the proteins have shown better results which are in the range of −6.0 to −8.6 kcal/mol. Based on docking examinations, the compounds with 1lF3 protein in CBH-10, CBH-11, and CBH-1/CBH-6 had the highest binding energies of −8.6, −8.3, and −8.2; for the compounds in CBH-11, CBH-10, and CBH-1/CBH-3 /CBH-6 CBH-13, the highest binding energies were −7.8, −7.7, and −7.6. In addition, the ADMET properties of all the compounds have been determined and observed that these compounds might be used as potential antimalarial agents. [ABSTRACT FROM AUTHOR]

• Design and evaluate novel drug candidates targeting Alzheimer's Disease from Donepezil derivatives. • Fluorinated Donepezil derivatives enhance pharmacokinetic properties. • The findings suggest that the meta -F, 3,5-F, and 2,4,6-F derivatives exhibit promising multitarget anti-AD activities, making them attractive candidates. Alzheimer's disease (AD) is the most common type of dementia, yet its precise etiology remains elusive. AD is a multifaceted disorder involved in the hydrolysis of the neurotransmitter acetylcholine and amyloid-beta (Aβ) accumulation in the Alzheimer's brain. Despite FDA-approved single-target drugs showing potential, therapeutic efficacy in AD treatment remains deficient, urging the development of multifunctional drugs. In this study, we design fluorinated derivatives from a widely prescribed therapeutic candidate, donepezil. Employing a computational approach integrating molecular docking, molecular dynamics (MD) simulations, and density functional theory analysis, we modified the benzene moiety of donepezil with fluorine-based functional groups to enhance pharmacokinetic properties and anti-amyloid activity. Evaluation of mono, di-, and tri-fluorinated derivatives revealed adherence to Lipinski's rule of five and blood–brain barrier penetration. Docking scores for all the fluorinated derivatives are varied within −10.8 to −11.7 kcal/mol, indicating binding affinity of fluorinated derivatives to acetylcholinesterase. The fluorinated derivatives display halogen bonding interactions with His 440 of catalytic site of enzyme. Among the mono-, di-, and tri-fluorinated derivatives, the meta -F (−25.2 ± 2.9 kcal/mol), 3,5-F (−36.6 ± 2.5 kcal/mol) and 2,4,6-F (−39.3 ± 2.1 kcal/mol) derivative, respectively, show strong binding affinity towards the AChE. These fluorinated derivatives are further assessed against both Aβ42 protofibrils and the full-length fibrils, demonstrating a strong binding affinity. The impact of fluorinated derivatives on secondary structural transformation is greater in the pentamer Aβ42 protofibrils compared to Aβ fibrils, suggesting inhibition of toxic amyloid beta-sheet conformations in the Aβ42 protofibrils. Quantum chemical analysis highlighted the heightened structural chemical stability of novel lead fluorinated compounds, suggesting promising anti-AD potential. Overall, meta -F, 3,5-F, and 2,4,6-F derivatives might be a potential multitarget candidates for anti-AD activities, suggesting the need for continued drug design efforts in this direction. [ABSTRACT FROM AUTHOR]

[Display omitted] • Single vacancy defect and stone–wales defect can improve the mechanical properties of pristine graphene modified asphalt. • The defects can modulate the electrostatic potential of pristine graphene to adsorb the non-polar aromatic molecule in the asphalt matrix. • Defective graphene as a new synergist presents another promising solution for modified asphalt. Pristine graphene is a desirable candidate to improve the pavement performances of modified asphalt due to its superior two-dimensional (2D) nano properties. However, the influences of defects unavoidably existing in pristine graphene nanosheet on the reinforcing effect of modified asphalt remain unclear. Herein, the single-vacancy defect and Stone-Wales defect on the interfacial interactions between pristine graphene and asphalt molecules are comprehensively explored by molecular dynamics (MD) simulations and density functional theory (DFT) calculations for the first time. MD simulations show that the graphene with single vacancy defect or Stone-Wales defect can selectively adsorb polar and non-polar molecules in asphalt to enhance the densification of pristine graphene modified asphalt, thus improving the mechanical properties of them. DFT calculations further reveal that defects produce localized polarization of electrostatic potential by altering the charge distribution of pristine graphene, which endows pristine graphene with a unique amphipathic property in asphalt matrix via a new dipole–dipole interactions, thus enhancing thermodynamic stability of the original colloidal structures of asphalt. This in-depth understanding of defective graphene modified asphalt on aromatic scale provides a new insight on the selection of graphene-based modifier to design durable asphalt pavement materials. [ABSTRACT FROM AUTHOR]

[Display omitted] • Quantum chemistry was conducted to examine the polarity and chemical reactivity of HiMA molecules in ROS aging. • Molecular dynamics simulation was used to study the intermolecular interaction between SBS and asphalt molecules in ROS aging. • Multifield microscopy was employed to analyze the microstructural characteristics of HiMA components during ROS aging. • ROS aging leads to a significant increase in the polarity of asphaltene and resin molecules. • SBS and saturates have good resistance to ROS oxidation. • The adsorption capacity of SBS to asphaltene becomes stronger after ROS aging. The objective of this study is to investigate the intermolecular interactions between polymers and asphalt components due to the oxidation of reactive oxygen species (ROS). Quantum chemistry (QC) and molecular dynamics (MD) were employed to simulate the molecular properties and intermolecular interactions between SBS and asphalt components during ROS aging. Multifield optical microscopy was utilized to analyze the microstructural characteristics and validate intermolecular interactions of SBS and asphalt components during ROS aging. The results show that asphaltenes have the most uneven electrostatic potential (ESP) distribution, followed by resins and aromatics, while saturates exhibit the most uniform ESP distribution. ROS aging leads to a more uneven ESP distribution and a higher polarity for HiMA molecules, especially for asphaltenes and resins with increased formation of polar functional groups. SBS and saturates exhibit small energy gaps and electronic softness, indicating good resistance to ROS oxidation, whereas asphaltenes and resins are prone to free radical oxidation reactions with ROS. The potential ROS oxidation site of asphaltenes and resins are mainly distributed in benzene ring regions and heteroatoms, while that of SBS are primarily located at the polybutadiene chains. The interactions between SBS and asphalt components are primarily driven by van der Waals forces. However, the hydrogen bonding appears after ROS aging, enhancing the intermolecular interactions. The interaction energies of SBS-asphaltenes and SBS-resins are significantly enhanced, and the intermolecular distances are shortened as ROS aging progresses. Multifield microscopy observation reveals that the development of bee structures in polymer regions is significantly faster than that in asphalt regions, indicating a significantly enhanced adsorption of asphaltenes by polymers after ROS aging. This is attributed to the uneven charge distribution, increased polarity, and enhanced reactivity of asphaltenes and SBS due to ROS aging. This study contributes to a molecular-atomic-level understanding of the intermolecular interactions between polymers and asphalt components during ROS aging. [ABSTRACT FROM AUTHOR]

• First attempt to explore the U extraction mechanisms of TiAP coexisted with HDiAP. • UO 2 (NO 3) 2 (Ligand) 2 and UO 2 (DiAP) 2 (Ligand) 2 are the main extracted U species. • Electrostatic attraction dominates the interaction between U and extractants. • The HDiAP can enhance the U extraction but resist the U stripping. Exploring the extraction behavior and mechanism of extractants in the presence of the radiolysis products was helpful to the design and subsequent utilization of those potential spent fuel extractants. In this work, Di- iso -amyl phosphate (HDiAP), a major acidic radiolysis product of Tri- iso -amyl phosphate (TiAP), was employed to study its effects on uranium (U(VI)) extraction behavior and mechanisms of 36 % TiAP/n-Dodecane (36 % TiAP/nDD) system by using extraction experiments, density functional theory calculations (DFT) and molecular dynamic simulations (MD). The results demonstrated that the presence of HDiAP improved U(VI) extraction but inhibited U(VI) stripping. The extracted U(VI) species analysis identified the UO 2 (NO 3) 2 (L) 2 and UO 2 (DiAP) 2 (L) 2 (L = TiAP/HDiAP) as the primary extracted U(VI) complexes. The DFT calculations revealed a higher tendency and a more exothermic process for the formation of U(VI)–HDiAP complexes than U(VI)–TiAP complexes. The MD simulations showed that HDiAP will be closer to the interface than TiAP, which is beneficial to its interaction with U(VI). The electrostatic force dominated the interaction between U(VI) and ligands, and its strength follows the order of U–DiAP− > U–TiAP > U–HDiAP. The presence of DiAP− was the main reason that impeded the U(VI) stripping. This work reveals the U(VI) extraction behavior and mechanism of the 36 % TiAP/nDD system in the presence of HDiAP, providing new insights into the effects of radiolysis products on the U(VI) extraction by potential fuel reprocessing extractants. [ABSTRACT FROM AUTHOR]

[Display omitted] • Global reactive parameters, structural and topological studies provides the clear insight of the compound. • Chemical reactivity of the 2-(Carboxymethyl)benzoic acid is analyzed by MEP study in different solvent phases. • Enhanced NLO parameters provide favourable nonlinear optical applications. • Molecular docking studies verify the title compound's potent anticancer activity and its bioactive characteristics. Nowadays density functional theory (DFT) is one of the best methods to explore the vibrational modes and structure of the biological system. Quantum mechanical calculations are performed using gas phase and different solvents (DMSO, methanol and water). The derived global reactive parameters, structural and topological study provides the clear insight of the 2-(Carboxymethyl) benzoic acid. Depth studies of DFT proves the existence of hydrogen bonds between donor and acceptor in the compound, which is supportive for the biological applications. In this paper, different experimental and computational simulated FT-IR, FT-Raman, UV–Vis spectral studies are used to explicate vibration assignments of the 2-(Carboxymethyl) benzoic acid. Experimentally observed vibrational frequency is compared with theoretically simulated spectrum. B3LYP method with 6–311++G (d, p) basis set is used in DFT to optimize the 2-(Carboxymethyl)benzoic acid structure. The most stable lower energy conformer is identified using potential energy surface (PES) analysis using Gaussian 16 W software. ESP, HOMO-LUMO, NBO, and QTAIM calculations have evinced an adequate electronic characterization of 2-(Carboxymethyl) benzoic acid. Further, van der Waals and steric interactions among 2-(Carboxymethyl) benzoic acid have been discussed with the help of RDG study. Hirshfeld surface studies establish the existing various interaction among molecules and total packing arrangement of the crystal structure. Due to the high biological activity score, 2-(Carboxymethyl) benzoic acid is a good therapeutic candidate. Lipophilicity analysis of 2-(Carboxymethyl)benzoic acid clearly explicates the bioactivity properties and its effective drug applications. Further, molecular docking investigates that the compound can be used as anticancer medication. The detailed DFT study of the 2-(Carboxymethyl) benzoic acid justified its biological applications of the present communication. The calculated NLO parameters of 2-(Carboxymethyl)benzoic acid evidenced for good efficacy in diverse filed application has been discussed. [ABSTRACT FROM AUTHOR]

[Display omitted] • B 9 N 9 nanoring was examined as nitrobenzene (NB) sensor using DFT. • The pristine B 9 N 9 can serve as an electronic and φ-type sensor for NB molecule. • The pristine B 9 N 9 nanoring can be utilized as an effective NB sensor. • The Sc decorated B 9 N 9 nanoring can be used for NB removal from the environment. Nitrobenzene (NB), an aromatic organic compound widely used in various industries, has several environmental risks. Due to its risks, reliable sensing mechanisms are crucial. In the present work, we investigated the potential of the pristine and Sc decorated B 9 N 9 nanoring as a sensor for detection of the toxic NB molecule using density functional theory (DFT). We have analyzed the structural parameters, adsorption energy (E ad), highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), HOMO-LUMO gap, density of states (DOS) spectra, Mulliken charge transfer, dipole moment, IR spectra, non-covalent interactions (NCI) iso-surfaces, recovery time (τ) and work function (φ) before and after the adsorption of NB onto pristine and Sc decorated B 9 N 9 nanorings. Our analysis revealed that the NB interacted optimally with the pristine B 9 N 9 nanoring, as evidenced by changes in electronic properties and E ad value of −0.58 eV. However, the Sc decorated B 9 N 9 nanoring indicated a strong interaction with NB with E ad of −4.09 eV at a proximal distance of 2.12 Å. Furthermore, our study demonstrated that the pristine B 9 N 9 nanoring could be used as both an "electronic sensor" and "φ-type sensor". Additionally, to esteem rapid recovery for practical feasibility, we calculated τ for both the pristine and Sc decorated B 9 N 9 nanoring. The short τ of the pristine nanoring indicates its suitability as NB sensor. In contrast, the longer τ of the Sc decorated nanoring suggests its applicability for NB storage or its removal from the surroundings. Overall, our findings underscore the potential of pristine B 9 N 9 nanoring as effective NB sensor and removal. We hope that our study will assist experimentalists to develope a reliable B 9 N 9 nanoring based sensor for the detection of NB molecules. [ABSTRACT FROM AUTHOR]

• Waste and natural materials for corrosion inhibition of steel are reviewed in this work. • Their experimental as well as computational investigations are explained. • Their popularity and working mechanisms are discussed in detail. • The challenges in their application and future strategy to overcome them are explained. • This review comprises analysis of 110 works (1987-2023), which provides a broader overview. Inhibitors have been proven successful and effective in controlling corrosion rates. However, their cost and harmful side effects are bothering them. Hence, natural materials (NMs) are in high demand for many years. NMs are considered a rich source of various active molecules that can build a protective layer to shield metals in corrosive environments. Based on the reported results, the NMs are found to be highly efficient (>95 % in some cases). The reason is adsorption of their phytochemicals on metals and blockage of corrosive molecules to the surface. Theoretical approaches like density functional theory (DFT) calculations and Monte Carlo (MC) as well as molecular dynamics (MD) simulations, are also used for accessing and comparing their performance. To achieve more economic and environment-friendly inhibition, waste natural materials (WNMs) have also been widely investigated. All the investigations advocated that they are very useful and could be a good replacement for synthetic inhibitors for various applications. However, there are some associated challenges, too. Their degradation at high temperatures, the inability of long-term protection, high concentrations in some cases, a reduced life cycle, the need for dedicated purification, efficient synthesis procedures, and more scientific selection are the few major challenges. This review provides a view of the NMs and WNMs that have been used for corrosion protection in various applications in the last twenty years and discusses their utilities, challenges, and future scopes, with additional details based on the analysis. [ABSTRACT FROM AUTHOR]

[Display omitted] • The in-situ conversion of hydrogen bonds into static electricity on the simulated biomembrane surface was investigated using SECM. • The number of hydrogen bonds at different pH was characterized by voltammetry and Approaching curves. • The intensity of in-situ conversion can be controlled by changing applied potential. • The key sites of weak interactions were visualized based on theoretical calculations. • Explored the influence of ion pairs on conversion intensity. In order to deeply understand the mechanism of biological function, it is significance to study conversion of weak interactions at the biomembrane surface. In this paper, the 3-mercaptopropionic acid self-assembled monolayer (3-MPA SAM) was constructed as a simplified model to simulate biomembrane, in which ferrocene carboxylic acid (FcCOOH) is adsorbed on the membrane surface through hydrogen bonds. Under positive potential induction, the in-situ conversion of hydrogen bonds into static electricity was investigated using scanning electrochemical microscopy (SECM). The conversion mechanism was the positive potential promoting the dissociation of carboxylic acids (COO−) on the membrane surface, followed by electrostatic attraction with the oxidation products (Fc+COOH). The study also found a positive correlation between conversion rate and potential value. Based on density functional theory (DFT), relevant information such as molecular structure, electrostatic potential and binding energy were obtained, and key sites of weak interactions were visualized using a reduced density gradient (RDG). The universality and competitiveness of conversion have been confirmed in different environments. This work provided some reference for revealing the properties and variations of weak interaction conversion at the biomembrane surface. [ABSTRACT FROM AUTHOR]

[Display omitted] • The modified D201 resin can be directly used in high-acid actual leach solution. • The removal rate of rhenium reached 97.46 %, demonstrating excellent selectivity. • D201 resin exhibits a maximum adsorption capacity of 92.16 mg/g for rhenium. • ReO 4 − first combines with the protonated –CHN+H 2 CH 2 Cl on the resin surface. • DFT calculations indicate that ReO 4 − is most prone to ion exchange with Cl−. Recovering rhenium from highly acidic rhenium-containing leach solutions is challenging for most resins, particularly in multiplexed systems. Herein, we introduce a scheme for selectively obtaining rhenium from a multielement solution containing high concentrations of sulfuric acid using modified D201 resin. Considering the dosage of resin and parameters such as pH and adsorption temperature, the adsorption efficiencies under optimal conditions for rhenium, molybdenum, iron, and cerium were 97.46 %, 0.38 %, 0.94 %, and 1.10 %, respectively. The selective recovery mechanism of rhenium was investigated by fitting the experimental data to kinetic and adsorption isotherm models. The pseudo-second-order and Langmuir models better fit results corresponding to the experimental data, which indicates monolayer chemisorption of ReO 4 − formed on the resin surface. Meanwhile, various characterizations such as SEM-EDS, FTIR, XPS, etc., indicate that ReO 4 − initially combines with the protonated −CHN+H 2 CH 2 Cl on the modified resin surface and then undergoes ion exchange reaction with doped Cl−. Furthermore, because of the diverse forms and similar properties of molybdenum and rhenium ions in acidic solutions, a theoretical model based on density functional theory was used to simulate the selective adsorption process in leach solution with a pH of 1.7. The simulation results demonstrate a highest occupied molecular orbital–lowest unoccupied molecular orbital energy gap, observed in the following order: Δ EMoO 2 2+ = Δ EReO 4 − < Δ EMoO 4 2− < Δ EMo 7 O 24 6− , which implies that MoO 2 2+ and ReO 4 − were most likely to transition from their ground states to excited states and react with the electron donor and acceptor groups, respectively. Compared with MoO 4 2−, ReO 4 − is more likely to react with the electron acceptor group and provides the corresponding methods and a theoretical reference for selective separation of rhenium in multielement solutions. [ABSTRACT FROM AUTHOR]

[Display omitted] • A series of new biphenyl benzoate embedded chalcone mesogens have been synthesized. • New mesogens exhibited polymorphism with wide range of N, SmA and SmC mesophase. • Structure-property relationship investigations revealed the significant influence of mesogenic core as well as other structural variables. • DFT simulations carried out by and FMO and MEP delve into the molecular surroundings and quantum chemical behaviour of these compounds. The construction of multifunctional molecular self-assembly is one of the fascinating areas of current research. Herein we reported a series of biphenyl benzoate derived mesogenic material EBPCH-(2 – 16), containing ester-imine and chalcone as connecting units. Compounds were substituted by decyloxy chain at one end while the other end has been systematically varied from C2-C16. By using various spectroscopic techniques, and elemental analysis, the structures of the biphenyl benzoates were determined; the results are consistent with the suggested structure. The mesomorphism of new molecules has been studied by differential scanning calorimetry and polarizing optical microscopy. Initial members of the series up to C8 exhibited enantiotropic Smectic-A (SmA) as well as nematic mesophase with good thermal stability, whereas compounds above C10 up to C16 revealed only smectogenic behaviour with enantiotropic SmA as well as SmC mesophase. Apart from these findings, additional variables like the alkyloxy groups in the molecules and the polarity and polarizability of the linking units may also have an impact on these mesogens. Further, the structure–property relationship was carried out by thorough investigations and comparison with structurally related literature on the target compounds' mesomorphism. In addition, Density functional theory simulations verify the potential conformer of biphenyl benzoates, whereas studies conducted by frontier molecular orbitals and molecular electrostatic potential delve into the molecular surroundings and quantum chemical behaviour of these compounds. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hirshfeld surface analysis was firstly used to analysis the mechanism of DES and active substances. • Quantum chemistry and MD were used to analyze the mechanism of DES extraction of flavonoids and polyphenols. • Three active substances and six DESs were selected to analyze the selectivity during extraction. • HBD of hydroxyl group and short carbon chain showed advantages on the extraction of active substances. • Ethanolamine with both amino and hydroxyl groups had the best extraction effect. Choline chloride-based deep eutectic solvents (DES) have been demonstrated as promising green solvents for the extraction of flavonoids and polyphenols. This study investigates the interaction between six different hydrogen bond donors (HBD) choline chloride-based DES and three types of polyphenolic flavonoid substrates. Density functional theory (DFT) and molecular dynamics (MD) simulations suggest that Cl− dominates the interaction primarily through electrostatic forces. The extraction effect of alcohol DES on rutin was optimized obviously, and the maximum interaction could reach 737.6 kJ/mol. Acid DES has a better extraction effect on anthocyanins, with a maximum interaction of 376.4 kJ/mol. With the increase of the carbon chain of HBA and the increase of the number of functional groups, the interaction between DES and the active substance decreases. As HBD, ethanolamine with both hydroxyl and amino groups showed the best effect in the extraction process of DES, forming the maximum interaction energy of 1575.8 kJ/mol. Additionally, multivariate analysis is employed to establish the relationship between different variables and interaction energy. This study provides micro-theoretical support for the extraction of flavonoids and polyphenols. [ABSTRACT FROM AUTHOR]

• The polarization and vibrational spectrum of [Emim][NTf 2 ] on graphene surface under the EEFs are systematically investigated using DFT. • Analyzing geometrical configuration and stability of functional groups within the graphene-[Emim][NTf 2 ] system as applied EEF increases. • Analyzing the shift values of different vibrational peaks as applied EEF increases. • Revealing underlying mechanism of vibrational frequency shifts depending on EEF intensity. • Confirming exchange energy for the cis and trans isomers to be responsible for the distinct shifts of different vibrational peaks. Ionic liquids, emerging as innovative solvents for energy harvesting, necessitate a comprehensive understanding of their structural characteristics at the graphene-ionic liquid interface. This work delves into the effects of external electric fields (EEFs) on the polarization and vibrational spectrum of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][NTf 2 ]) on a graphene surface, employing density functional theory calculations. The analysis reveals that the geometrical configuration and stability of functional groups within the graphene-[Emim][NTf 2 ] system are influenced by both the direction and intensity of the applied EEF. Notably, the threshold EEF strength required for dissociation varies based on the structural configuration of the anion. The electronic energy, dipole moment, and polarization rate under varying EEF conditions have been quantitatively assessed, providing insights into their EEF-dependent behaviors. Utilizing the independent gradient model approach, the inter-ion interactions, such as hydrogen bonding and van der Waals forces, under the influence of EEFs were analyzed, and how these interactions evolve with changes in the direction and intensity of the EEFs were also explored. Furthermore, the vibrational spectrum of [Emim][NTf 2 ] on the graphene surface, spanning a range of 10–3500 cm−1, was meticulously calculated to systematically investigate the impact of the EEF on the vibrational spectra of the graphene-[Emim][NTf 2 ] system. A key finding of this work is the distinct shifts in the vibrational peaks of the cis and trans isomers of [NTf 2 ]− on the graphene surface, which can be attributed to differences in their exchange energies. Specifically, the exchange energy for the cis isomer of [NTf 2 ]− is measured at 107.43 kJ∙mol−1, in contrast to 98.51 kJ∙mol−1 for the trans isomer. [ABSTRACT FROM AUTHOR]

[Display omitted] • Decyl-bishydroxamic acid (DCBHA) was synthesized and innovatively used as a collector for fluorite-calcite flotation separation. • DCBHA exhibited superior selectivity compared to BHA and OHA, yielded a concentrate grade of up to 70.99% with a recovery of 76.24%. at optimal conditions. • EDDA chemisorbed on bastnaesite surface by forming a five-element ring. • Revealed the disparities in adsorption mechanisms of DCBHA across various morphologies on mineral surfaces. The surface characteristics of fluorite and calcite exhibit a close analogy, posing a formidable challenge to flotation separation. Hence, the development of a highly efficient reagent for fluorite holds paramount significance and value in addressing the challenging separation of fluorite and calcium-bearing minerals. In this study, a novel collector, decyl-bishydroxamic acid (DCBHA), has been ingeniously designed and synthesized to effectively separate fluorite and calcite. Conducting micro-flotation experiments encompassing single minerals and artificially mixed minerals, we systematically investigate the flotation performance of DCBHA in fluorite flotation systems. It was observed that DCBHA exhibited commendable collective and selective ability compared to BHA and OHA, yielded a concentrate grade of up to 70.99% with a recovery of 76.24%. at optimal conditions. The zeta potential, AFM, FTIR and XPS examinations indicated the selective chemical adsorption of DCBHA on the metallic sites of the fluorite surface. The incorporation of a second hydroxamic acid group concurrently enhanced the collecting capacity and selectivity of the reagent. The mechanism of interaction between the novel collector DCBHA and mineral surfaces was investigated through Density Functional Theory (DFT), revealing that DCBHA exhibited a "bidentate" adsorption pattern upon losing a proton H, forming bonds with the mineral surface. Furthermore, the adsorption affinity of DCBHA to fluorite surpassed that to calcite, providing advantageous support for experimental findings. [ABSTRACT FROM AUTHOR]

[Display omitted] • Design and synthesis of new terpyridine analogue (i.e. 6′-oxo-1′,6′-dihydro-[4,2′:4′,4′'-terpyridine]-5′-carbonitrile) via one pot synthesis. • The designed molecule exhibited enhanced photophysical properties and also showed the aggregation induced emission property. • DFT calculation has been carried out for the designed molecule and the theoretical results are compared with experimental results for deeper understanding. • The molecule is proved to be p-type in nature, via computational hole reorganization energy value and from electrochemical studies. • The electrochemical studies as achieved the specific capacitance of 39.2 F g−1 at 1 A g−1 current density, which suggests that this molecule can be used for energy storage application. A new 6′-oxo-1′,6′-dihydro-[4,2′:4′,4′'-terpyridine]-5′-carbonitrile (Terpyridine analogue) has been designed and synthesized via one-pot synthesis. Thermal studies showed that the compound is stable up to 346.42 ℃ and the degradation starts to occur above this temperature. The compound displayed the behaviour of a bluish-green emitter in its solution state with a relative quantum yield of 20.45 %. Also, the compound exhibited aggregation induced emission properties in DMSO/water mixtures. Further, its variable temperature dependence photoluminescence study in DMSO solvent showed that its emission intensity decreases while heating and the emission intensity increases while cooling the solution. The compound showed the p -type behaviour and utilized as an electrode which exhibited the maximum specific capacitance of 39.2 F g−1 at a current density of 1 A g−1 through galvanostatic charge–discharge analysis. Finally, its experimental results were correlated to the theoretical results. [ABSTRACT FROM AUTHOR]

[Display omitted] • N H 4 + inhibit the phase transition of vaterite by changing the reaction system's properties. • N H 4 + can replace water molecules on the surface of vaterite. • N H 4 + retard the phase transformation mainly through preventing the dissolution process. Vaterite calcium carbonate (CaCO 3) possesses unique advantages compared to calcite; however, some critical issues need to be addressed, such as vaterite stability. Numerous studies have indicated that N H 4 + can promote vaterite formation and prevent its transformation. However, as vaterite is an instantaneous microscopic process that is easy to transform, directly revealing the role of N H 4 + in stabilizing vaterite remains challenging in experiments. This research aims to reveal the role of N H 4 + in stabilizing vaterite and retarding phase transformations. Vaterite stabilization was investigated at different N H 4 + concentrations and characterized by XRD and SEM. The reaction system's pH, electrical conductivity, and surface tension changes were analyzed in the presence of N H 4 +. Computational and experimental studies were utilized to determine the role of N H 4 + in the stabilization of vaterite. Results revealed that N H 4 + can significantly increase the existence time of vaterite in the water solution. The density functional theory (DFT) indicated that the adsorption energy of N H 4 + and vaterite (1 1 0), (1 1 2), and (1 1 4) is obviously higher than that of H 2 O molecules. The molecular dynamics (MD) simulation research shows that N H 4 + can replace water molecules on the crystalline surface of vaterite and mainly interact with carbonate ions on the surface of vaterite. The mechanism analysis shows that the inhibitory effect of N H 4 + on the phase transformation of vaterite is primarily caused by preventing the dissolution process. This study systematically explains the role of N H 4 + in the stability of vaterite and further reveals that N H 4 + can not only promote the formation of vaterite but also play a decisive role in inhibiting its phase transition. [ABSTRACT FROM AUTHOR]

[Display omitted] • Strong interactions occur between HBC and BCNU.adsorption process and electronic. • The electronic properties of HBC are not sensitive to the presence of BCNU Detection. • The geometry of the nanographenes remains unchanged after the drug molecule. • BNHBC seems to be a suitable option for carrying and revealing BCNU drug. We conducted research on the adsorption of carmustine (BCNU) on the surface of pristine, N-doped, and BN-doped Hexa- peri -hexabenzocoronene (HBC) nanographene using density functional theory calculations. We used the B3LYP functional in conjunction with 6-31+G(d) and 6-311+G(d,p) basis sets to perform geometrical optimization calculations, vibrational frequencies, and natural bond orbitals (NBO) analysis. The dispersion correction term of Grimme-D3 was incorporated to account for the dispersion interactions. We found that the geometry of the nanographenes remains unchanged after the drug molecule adsorption. The calculated adsorption energies (E ads) were −17.1 kcal.mol−1 for HBC-BCNU, −17.0 kcal.mol−1 for NHBC-BCNU, and −17.9 kcal.mol−1 for BNHBC-BCNU when using the 6-31+G(d) basis set. The corresponding values calculated employing the 6-311+G(d,p) basis set were −17.9, −17.3, and −19.1 kcal.mol−1, respectively. Analysis of frontier molecular orbitals (HOMO and LUMO) showed that the electronic properties of NHBC were significantly affected by the presence of BCNU. We used NBO analysis to investigate the distribution of partial atomic charges in different systems. Finally, using the transition state equation and the smaller basis set, we found that the required time for BCNU to release from HBC, NHBC, and BNHBC is approximately 3.3, 1.8, and 13.0 s, respectively. The obtained values are 13.0, 4.6, and 96.0 s, respectively, for the higher level of calculations. The recovery time for all nanographenes is within a reasonable range, while NHBC exhibits the highest sensitivity for drug detection. [ABSTRACT FROM AUTHOR]

[Display omitted] • Analysis of HOMO, LUMO, and ESP confirmed the adsorption capability of Carbon Nano CNCs toward GB and GA, indicating their potential as carriers for targeted nerve agents. • The inner region (P1) of CNCs exhibits superior adsorption efficacy than the outer one. • A greater affinity is evidenced at a higher concentration of adsorbent/adsorbate ratio. • The interaction nature (van der Waals forces.) was proved via the Non-Covalent Interaction (NCI) plots. • MC and MD simulations provided molecular insights into adsorption of nerve agents. Carbon NanoCones (CNCs), distinguished by their conical shape and large surface area, are evaluated for their potential application in nerve gas [tabun (GA) and sarin (GB)] adsorption. Density Functional Theory (DFT) calculations, Molecular Dynamics (MD), and Monte Carlo (MC) simulations are employed to investigate this phenomenon comprehensively. The study findings indicate that tabun (GA) and sarin (GB) undergo spontaneous adsorption, characterized by significant negative energy values. Density Functional Theory (DFT) calculations indicate electron donation tendencies of nerve agents to CNC surfaces. Computational analysis shows higher adsorption efficiency in the inner portion (P1) of CNCs. Molecular Dynamics (MD) and Monte Carlo (MC) simulations confirm planar adsorption configurations parallel to CNC surfaces. The DFT calculations show that GA has a far greater adsorption energy on a Carbon Nanocone compared to GB (−44.96 kcal/mol for GA, whereas GB has an adsorption energy of −35.95 kcal/mol). Furthermore, the analysis reveals significant differences between Sarin and Tabun nerve agents. Sarin exhibits higher global hardness, indicating increased stability, while Tabun shows higher overall softness, suggesting greater reactivity. Despite similar electronegativities, Sarin's greater ionization energy and electron affinity imply enhanced stability and reactivity. Differences in HOMO and LUMO energies highlight unique reactivity profiles, with Sarin being more susceptible to nucleophilic attacks and Tabun to electrophilic attack. Sarin's larger energy gap between HOMO and LUMO orbitals signifies its superior stability under electronic disturbances. [ABSTRACT FROM AUTHOR]

Ferulic acid (FA) possesses diverse biological properties and is extensively utilized in pharmaceuticals, cosmetics, and the food industry due to its non-toxic nature. However, environmental factors such as temperature and solvent polarity play a significant role in influencing the thermodynamic and photophysical properties of drugs, particularly during the drug optimization and design phases. This study investigates the impact of temperature and solvent polarity on the thermodynamic and optical properties of FA using density functional theory (DFT) with the B3LYP functional approach and the 6-311++G(d, p) basis set under various solvent and gas conditions. Additionally, vertical UV-vis absorption and emission spectra of FA in different solvent polarities and gas phases were analyzed using time-dependent density-functional theory (TDDFT) with the B3LYP method and the 6-31++G(d, p) basis set. Applying Koopman's theory, the chemical activity of FA was assessed based on the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) values. The findings indicate that an increase in temperature within the range of 100–1000 K leads to elevated enthalpy, heat capacity, and entropy due to molecular vibrational activity, resulting in FA degradation and instability. Furthermore, thermodynamic parameters, HOMO and LUMO values, and the chemical activity of FA were also influenced by different solvent polarities. The absorption and emission spectra of FA exhibited a red shift due to interactions with solvents and solutes. Overall, this study analyzed the significance of environmental factors such as temperature and solvent polarity in pharmaceutical design and optimization processes to enhance drug efficacy and stability. • The influence of temperature and solvent polarity on the thermodynamic properties of ferulic acid was investigated. • The significance of solvent polarity on the photophysical properties and chemical reactivity of ferulic acid was explored. • The effect of solvent polarity on the ultraviolet-visible absorption and emission spectra of ferulic acid was analyzed. [ABSTRACT FROM AUTHOR]

• N-oleoyl sarcosine (N-OSS) was firstly tested as spodumene collector. • N-OSS could effectively separate spodumene from albite at low temperature. • N-OSS preferentially adsorbed on Ca-activated spodumene compared with albite. • O atoms of N-OSS strongly bonded with Ca and Al atoms on Ca-activated spodumene. • N-OSS weakly interacted with a single Ca active site on Ca-activated albite. In this study, N-OSS was explored as an efficient collector in the flotation of spodumene from albite. The flotation behaviors were examined by micro-flotation tests and the interaction mechanisms were comprehensively uncovered from atomical scale. It indicated N-OSS could effectively collect spodumene from albite at low temperature and N-OSS was more inclined to adsorb on spodumene surface than that on albite surface, thus significantly expanding the hydrophobicity difference. X-ray photoelectron spectroscopy (XPS) analysis suggested that N-OSS chemically interacted with both Ca and Al active sites on Ca-activated spodumene surface. Whereas, it weakly adsorbed on Ca-activated albite. Density functional theory (DFT) calculations reconfirmed that the adsorption of N-OSS on Ca-activated spodumene surface was more favorable than that on albite surface. The strong adsorption on spodumene was due to the hybridization reaction between the O 2p orbitals of C-O and C=O groups of N-OSS with Ca 4s orbitals as well as Al 3s orbitals on spodumene surface. Nevertheless, N-OSS weakly interacted with Ca atoms on Ca-activated albite due to steric hindrance. N-OSS exhibited selective collecting ability at low temperature in the flotation of spodumene from albite compared with conventional collector, which has promising prospects in the low-temperature flotation of spodumene from albite. [ABSTRACT FROM AUTHOR]

[Display omitted] • Successful adsorption of various hazardous gases, including methane, carbon dioxide, hydrogen, ammonia, and sulfur dioxide, onto kekulene surfaces. • Enthalpy calculations confirm the spontaneous nature of gas adsorption onto kekulene surfaces. • Frontier molecular orbitals reveals distinctive electronic characteristics of kekulene-gas complexes. • The study highlights the potential of kekulene as a selective adsorbent for toxic gases, particularly sulfur dioxide (SO 2). A Density Functional Theory were used to investigate the interactions between kekulene and various noxious gases, including methane(CH 4), carbon dioxide (CO 2), hydrogen(H 2), ammonia(NH 3), and sulfur dioxide(SO 2). The adsorption energies and bond distances were computed, indicating successful molecular interactions with kekulene, particularly notable in the exothermic nature of the adsorption process. Enthalpy calculations further confirmed the exothermic nature of the reactions, suggesting spontaneous adsorption. The analysis of frontier molecular orbitals revealed distinctive electronic characteristics, with HOMO-LUMO plots indicating a significant energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Chemical descriptors derived from these calculations provided insights into the reactivity and polarizability of the compounds. Furthermore, the molecular electrostatic potential (MEP) surface maps illustrated the electrostatic potential distribution, aiding in predicting the molecule's reactivity. Overall, the study highlights the potential of kekulene as a selective adsorbent for toxic gas (SO 2), offering valuable insights into its chemical and electronic properties for various applications, particularly in environmental and industrial settings. [ABSTRACT FROM AUTHOR]

The adsorption behavior of small thiol-protected gold cluster Au 12 (SCH 3) 9 + to temozolomide has been investigated under different environmental conditions. [Display omitted] • The adsorption behavior of small thiol-protected gold cluster Au 12 (SCH 3) 9 + to temozolomide has been investigated using density functional theory. • The newly generated Au–O and Au−N bonds in TMZ-Au 12 (SCH 3) 9 + exhibit ionic characteristics. • The change in solvent is beneficial for adjusting the interaction strength and mode between TMZ and Au 12 (SCH 3) 9 +. The adsorption behavior of a thiol-protected gold cluster Au 12 (SCH 3) 9 + to temozolomide (TMZ) has been investigated at the M06-2X-D3/6-311G(d, p)&LanL2dz//B3LYP-D3(BJ)/6-31G(d,p)&LanL2dz. Results show that TMZ prefers to combine with the central Au atom in the Au cluster via its O and N atoms, forming ionic Au–O and Au–N bonds, respectively. The calculated adsorption energies of TMZ on Au 12 (SCH 3) 9 + are − 44.43, −12.27, −43.59, and −10.01 kcal·mol−1 in the gas phase, water, acetic acid, and dimethyl sulfoxide, respectively. The interaction strength and mode between the TMZ drug and Au 12 (SCH 3) 9 + vary with different solution environments. Therefore, the solvent could influence the interaction of TMZ-Au 12 (SCH 3) 9 + complexes. Such a property of TMZ–Au 12 (SCH 3) 9 + could be applied to drug-delivery processes, which might contribute to improving the efficiency of this drug and reducing its toxic and side effects. Based on the natural population analysis and QTAIM analysis, noticeable charge transfer from TMZ to the Au cluster was observed, increasing the dipole moments of TMZ–Au 12 (SCH 3) 9 + complexes. We believe that this work could extend the applications of small Au-based clusters, especially thiol-protected gold clusters in drug-delivery processes. [ABSTRACT FROM AUTHOR]

The microscopic H-bonds interactions and clusters of Brønsted acidic ionic liquids had been investigated by DFT calculations and FTIR experiments. [Display omitted] Brønsted acidic ionic liquids (BAILs) are clean and versatile replacements for traditional homogeneous acid catalysts and have attracted much attention as efficient catalysts for the synthesis of valuable chemicals. It's critically important to understand the structural properties of BAILs from the molecular level. In this work, we studied a series of −SO 3 H functionalized acidic ionic liquids by density functional theory (DFT) calculations, and the most stable geometries were obtained by global semiempirical quantum mechanical search. The most stable structures of cations are formed when more intramolecular H-bonds exist. For BAILs clusters, intramolecular and intermolecular H-bonds coexist and play a critical role in the stability of the system. The interaction energy decreases with increasing alkyl chain length. When the alkyl chain was replaced by −SO 3 H groups, the interaction energy increased due to more H-bonds formed with the anions. The quasi-3D network is formed in the BAILs clusters and the electrostatic interaction plays a critical role in stabilizing the ion clusters. This work helps to understand the microcosmic interactions of BAILs in-depth and design them in a "task-specific" way. [ABSTRACT FROM AUTHOR]

• The effects of twelve organic solvents on the reaction selectivity of m-xylene nitration were investigated. • Thermal safety parameters of m-xylene nitration were calculated to evaluate process hazards. • Solubility of m-xylene under twelve organic solvents was analyzed by MPI. • Interaction energy and visualization analysis between HNO 3 and solvents were studied. • The promoting effects of acetic and propionic anhydrides on NO 2 + production were revealed theoretically. Selection of appropriate solvents is of great significance for achieving efficient and safe m-xylene nitration. In this study, the exothermic behavior of m-xylene nitration under twelve organic solvents were studied by reaction calorimetry. The process hazards were assessed by calculation of thermal safety parameters. The reaction selectivity was quantified. The anhydrides exhibited the prominent promotion as water absorbent and active reagent in nitration, followed by selected aliphatic hydrocarbons, chlorinated hydrocarbons. While acetic acid, propionic acid and ethyl acetate had negative effects. The maximum yield of 95.6 % was achieved in nitric acid-acetic anhydride (HNO 3 -Ac 2 O) system. The thermal weight loss of the products appeared at around 150−230 °C by thermogravimetry experiments. The activation energy was determined to be 192.9 kJ/mol through adiabatic kinetic calculations. Furthermore, the solvent effects were analyzed by calculating the solvent polarity and its interaction energy with HNO 3. The different action mechanisms of Ac 2 O and Pc 2 O on NO 2 + generation were revealed. The density functional theory calculations were in agreement with the experimental results. These findings can provide guidance for understanding of the solvent effect on the reaction hazards and selectivity of m-xylene nitration, and provide experimental and theoretical basis for solvent screening for the nitration of similar aromatic compounds. [ABSTRACT FROM AUTHOR]

[Display omitted] • Four phytochemicals are computationally analyzed as eco-friendly corrosion inhibitors for iron surface protection. • DFT, SCC-DFTB and MD simulations reveal the chemical reactivity and bonding of these inhibitors. • Chicoric and Caffeic acids demonstrate superior metal surface bonding with multiple active sites. • Covalent bond formation and parallel adsorption on Fe(1 1 0) are confirmed by SCC-DFTB and PDOS. Investigating environmentally benign corrosion inhibitors is crucial for addressing the widespread issue of material deterioration. This research conducts a detailed computational evaluation of four phytochemicals − Taraxasterol (TTL), Chicoric acid (CHA), Tetrahydroridentin B (THR), and Caffeic acid (CFA) − for their potential in acting as sustainable inhibitors against iron surface corrosion. Utilizing Density Functional Theory (DFT) with B3LYP functional, self-consistent-charge density-functional tight-binding (SCC-DFTB), and molecular dynamics (MD) simulations, this study thoroughly examines both the global and local chemical reactivities, as well as the bonding interactions of these compounds with the Fe(1 1 0) surface. The findings reveal that CHA and CFA demonstrate remarkable adsorption properties, as demonstrated by their electronic features and bonding characteristics. Notably, Fukui function analyses identify multiple active sites in CHA and CFA, enhancing electron transfer and coordination with the metal surface. SCC-DFTB simulations show the formation of covalent linkages between these phytochemicals and iron atoms, resulting in their parallel arrangement on the Fe(1 1 0) surface, a finding supported by MD simulations. This research underscores the potential of CHA and CFA as corrosion inhibitors and provides a nuanced understanding of their molecular interactions, paving the way for further exploration and application in eco-friendly corrosion prevention. [ABSTRACT FROM AUTHOR]

[Display omitted] • Achieved 27 % higher yield of flavonol glycoside than ethanol by ternary DES. • Reached 94.63 % recovery rate of flavonol glycoside, and the DES reuse at least five cycles. • Interactions between DES and solute are dominated by hydrogen bonding and Van der Waals forces. • Ternary DES interacts more effectively with target compound. A novel ternary deep eutectic solvent (DES) was designed for the green and efficient extraction of flavonol glycosides (FG) from Ginkgo leaves. The DES consisted of a molar ratio of choline chloride/acetic acid/1,2-propylene glycol of 1:2:3. The optimal extraction conditions were determined to a solid-liquid ratio of 42 mg/mL, an extraction time of 11.8 h, and an extraction temperature of 51℃. The extraction yield of FG was 7.8 mg/g, which demonstrated a notable enhancement in comparison to conventional extraction. Kinetics and morphology analysis revealed that the extraction process involved considerable dissolution and diffusion of the solute. Additionally, a molecular investigation using density functional theory (DFT) indicated that the interaction between the DES and FG was primarily governed by hydrogen bonding and van der Waals force. Notably, the ternary DES exhibited stronger interactions with FG, which were the key factors for better extraction efficiency. Furthermore, efficient recovery of FG from the DES solution was also achieved, with a recovery rate of 94.63%. Moreover, the recovered DES could be reused directly at least five cycles. [ABSTRACT FROM AUTHOR]

[Display omitted] • The mechanism of action of anionic complex surfactants on coal was investigated by AFM and DFT. • The interaction mechanism between the anionic complex surfactant and the coal surface is electrostatic attraction. • The effect of anionic complex surfactants on the wettability of coal surfaces was investigated. • Anionic complex surfactants exhibit better performance on coal surfaces than any single surfactant. The objective of this study was to elucidate the cooperative modification mechanism of anionic composite pharmaceuticals on coal substrates. Composite pharmaceuticals were synthesized using sodium hexametaphosphate (SHMP) and sodium polycarboxylate to reduce coal hygroscopicity. The mesoscopic alteration process between the coal surfaces and the compound pharmaceuticals was examined via atomic force microscopy (AFM). AFM showed that SHMP was multilayer-adsorbed on coal via electrostatic and hydrogen bonding, while sodium polycarboxylate was single layer-adsorbed at the SHMP layer via electrostatic interactions. Composite pharmaceutical adhesion to coal was lower than that for individual pharmaceuticals, indicating synergistic effects. The mechanism underpinning the microscopic synergistic effect of complex pharmaceuticals on the coal surface was further examined using density functional theory (DFT) at the molecular scale. DFT calculations showed that the adsorption energy of SHMP binding to a sodium polycarboxylate molecule was greater than that of SHMP binding to two identical pharmaceutical molecules. The SHMP portion generally interacted with the aromatic coal nucleus via its ring structure, exposing the sodium polycarboxylate carbon chain to maximize the adsorption energy. Combining DFT and AFM provided insight into the composite pharmaceutical function, and a theoretical framework for coal flotation separation was established. [ABSTRACT FROM AUTHOR]

[Display omitted] • The Al3+ ion acts as an electron relay station for the electrostatic interaction. • The adsorption of Cr 2 O 7 2- on sp2 carbon containing defects can be promoted by Al3+. • The Cr 2 O 7 2- can be reduced by the coordination of Al3+. • The Cr 2 O 7 2- is reduced by the electrons transferred from sp2 carbon via Al3+ bridge center. The analysis of the influence of coexisting ion impurities on the adsorption behavior of Cr6+ on activated carbon at microscopic interfaces should be highlighted. Based on the research background on the adsorption treatment for waste solutions of chromic anhydride, this study reveals that coexisting Al3+ affects the adsorption behavior of Cr6+ on sp2 carbon structure-containing defects, as evidenced by density functional theory calculations. After conducting electronic environment analyses based on isolated Al3+–Cr 2 O 7 2− coordination and its adsorption models, the Al3+ ion acts as an electron relay station that srapidly transfer the electrons of the 2p orbital of the ortho -carbon atoms to Cr 2 O 7 2− owing to the saturation of its own p orbital. These findings lead to two conclusions: (i) the facilitated reduction of Cr6+ and its positive charge neutralized by approximately 0.16 Coulomp, and (ii) the increased adsorption energy of Cr 2 O 7 2− by 3.0 % and 14.6 % on the unelectron-neutralized and electron-neutralized (0 0 2) plane of sp2 C-containing defects, respectively, owing to the presence of Al3+. This is attributed to the decreased in 0.089 Hartree Gap value resulting from the energy change of the molecular orbital after Al3+ stable coordination with Cr 2 O 7 2−. Therefore, the reduced energy barrier facilitates the electron transfer from the 2p orbital of the edge carbon atom to the O–Al–O bridge via the Al3+ bridge. [ABSTRACT FROM AUTHOR]

[Display omitted] • Three ionic liquids (ILs) with Tryptophan ([Trp]-), Tyrosine ([Tyr] -) and Histidine ([His] -) anions coupled with propane sultone tethered cation ([1MeimPS]+) were synthesized. • Histidine based-IL ([1MeimPS][His]) demonstrated the maximum CO 2 sorption of 0.6767 mol fraction at 1 MPa. • A direct relationship between CO 2 capacity and pressure increase was found. • DFT analysis was performed to determine the interaction energies and comprehend the interaction between ILs and CO 2. • The QTAIM, and IRI indicated that the CO 2 predominantly interacted with anions through hydrogen bonding and van der Waal forces. • The current study provides a thorough knowledge of the CO 2 sorption of synthesized ILs. Ionic liquids (ILs) are a promising generation of sustainable and efficient CO 2 sorbents because of their inherent advantages in providing a flexible alternative to standard amine solutions. In this context, ILs based on amino acids can be excellent candidates for enhanced CO 2 sorption. Herein, three ILs consisting of distinctively tailored imidazolium cation paired with amino acid anions have been synthesized and characterized by both experimental techniques and DFT studies. The potential and influence of propane-sultone modified imidazolium cation [1MeimPS]+ and amino-acid anions ([Trp]-, [Tyr]-, [His]-), on CO 2 capacity were investigated at 298.15 K and pressures up to 4 MPa were evaluated. Among them, [1MeimPS][His], exhibited the notable capability in terms of CO 2 sorption (0.6767 mol fraction) at 1 MPa pressure and 298.15 K with the lowest viscosity recorded. Moreover, a direct association between CO 2 capacity and pressure rise was observed. CO 2 recyclability measurements revealed an exceptional CO 2 solubility even after four cycles. The DFT investigation was carried out to compute the interaction energies and investigate the underlying interaction between ILs and CO 2 , which corresponded very well with the experimental findings. The exploration of various interaction descriptors offered a deeper understanding of the interactions between ILs and CO 2. Frontier Molecular Orbitals (FMO) parameters showed that the suggested ILs are robust, viable and chemically reactive. The atoms in molecules theory (QTAIM) and Interaction Region Indicator (IRI) analysis revealed that the CO 2 mainly interacted with anions through hydrogen bonding and van der Waal forces. The NBO data implied that stable charge transfers occurred from CO 2 towards ILs. This study suggests a practical method for boosting CO 2 solubility by changing the physicochemical properties of ILs and makes this research a significant contribution to the recent literature and provide insights for more effective carbon capture systems and industrial applications. [ABSTRACT FROM AUTHOR]

• The DFT calculations of a thiophene derivative were performed. • Theoretical UV studies employing the TD-DFT/M06-2X method were conducted. • Topological analyses (ELF, LOL, RDG, charge transfer) to gain further insights into molecular properties. • ADMET profile of the title molecule was studied using online tools. • Molecular docking against select brain cancer target proteins was performed. Heterocyclic molecules display a wide spectrum of properties that span both material and biological domains. Material properties stem from their interactions in the bulk, where a large number of molecules of the same type get together resulting in an enhancement of properties. However, biological properties emanate from the interaction of a single or a few molecules with a biologically functional macromolecule. Computational tools offer a particularly useful way of theoretically studying molecules to arrive at a conclusion regarding such properties, even though they may vary when experimentally evaluated. This study concerns itself with the theoretical investigation comprising density functional theory calculations, topological analyses and in-silico biological evaluation of a thiophene compound, i.e. the title compound. Density functional theory was used to compute properties of the title molecule and their variations in unsolvated and solvated phases using Gaussian 09. The molecule in solvent phases encompassing organic polar protic, organic polar aprotic and inorganic polar protic nature have been subjected to theoretical investigations. The suitability of the molecule for deployment as a modern optical material is examined with positive results. Topological characteristics of the molecule were evaluated using Multiwfn 3.8 to examine electron density distribution and the possible resulting covalent, non-covalent and weak interactions because of such distribution. The potency of the molecule towards brain cancer was evaluated by molecular docking with Auto Dock Tools against two brain cancer protein targets 6ETJ and 6YPE with a good docking score of −6.63 and −6.21 kcal mol−1 respectively and the resulting interactions visualized and its pharmacokinetic properties obtained using online tools. [ABSTRACT FROM AUTHOR]

[Display omitted] • Synthesized using Knoevenegel and Michael addition reactions. • Spectroscopic and chemical parameters are investigated. • In silico analysis were carried out for leukemia-related proteins. • The anticancer activity under the in-vitro analysis was tested. • Topological analysis like ELF, LOL and RDG were analyzed. Herein, click chemistry was chosen to synthesize 2AIPC using Knoevenegel and Michael addition reactions. In this synthesis, Lewis base was attracted by the generation of sp3 hybridized carbanion at active methylene group in the reactants for propagation reaction proceeding towards conducting the Michael addition product. The synthesized 2AIPC was characterized by NMR(13C and 1H), UV, FTR and FT-IR analytical tools; it was also evaluated utilizing density functional theory. According to DFT analyses, the comparative study of the functional groups of 2AIPC molecule was successfully described using Raman and FT-IR spectra with simulated spectra. NLO behaviour and charge exchange utilizing the hyperpolarizability and FMO band gap characteristics were also investigated. Through computational studies using MEP, FUKUI, RDG, and NBO, intermolecular interaction and the reactive area of the synthesized molecule were demonstrated. Moreover, the anticancer activity under the in-vitro analysis was tested, and the molecule showed 61.04 % GI against the K-562 leukemia cells at 10-5 M. Molecular docking also evaluated cytotoxicity by in silico study against leukemia-related proteins (60QN, 6OQC, 1EMR, and 606F). The docked complexes showed binding affinities of −7.82, −7.1, −6.9, and −6.71 kcal/mol. A nucleophile elimination process at 2AIPC's main amino group may also increase the molecule's potential to be a more effective lead medication. [ABSTRACT FROM AUTHOR]

• A biochar gel was designed by combining alginate with biochar. • DFT calculation predicted that alginate can improve the adsorption performance of biochar. • MD simulation predicts that biochar can improve the reusability of alginate gel. • Biochar/alginate composite gel was synthesized by compounding activated platanus acerifolia leaf charcoal with alginate, and the experimental results achieved the expectations of the simulation. In this paper, activated biochar and alginate are combined to form gel for the removal of Pb(II) in water. This composite not only improves the adsorption performance of biochar for Pb(II), avoiding the drawback of difficult recovery of biochar but also enhances the structural stability of alginate gel in the recycling process by utilizing biochar. The adsorption mechanism of Pb(II) on functional group-modified carbon and alginate structures, as well as the structural stability of the adsorbent, were observed using density functional theory (DFT) and molecular dynamics (MD) simulations. The results indicate that the adsorption of carboxyl groups to Pb(II) is stronger than that of hydroxyl groups, and the adsorption performance of alginate is stronger than that of carbon. Carbon improves the stability of the composite adsorbent. The biochar/alginate composite gel was synthesized by compounding activated platanus acerifolia leaf charcoal with alginate and was used in the experiment of removing Pb(II) from water. The experimental results achieved the expectations of the simulation. The adsorption isotherms and kinetic data were analyzed and fitted. The results indicate that the adsorption isotherms conform to the Langmuir model, and the adsorption kinetics follow pseudo-second-order adsorption. [ABSTRACT FROM AUTHOR]

[Display omitted] • The excited-state antioxidant capacity for studied molecules is almost higher than that of the ground state. • Antioxidant capacity varies with the solvent polarity in both ground and excited states. • The 6-HF in acetonitrile in the S 1 state shows the highest antioxidant capacity in all cases. • The studied molecules protect against UV radiation and exhibit weaker fluorescence, promising to be used as sunscreens. Antioxidants have caught a widespread attention because of their applications in various fields such as biomedicine, food additives, cosmetics, and so on, but nevertheless studies on the antioxidant capacity of molecules after photoexcitation are still scarce and rare. In this work, by the application of the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods, based on the solvent effect, the antioxidant capacity of 4′-Hydroxyflavone (4′-HF), 6-Hydroxyflavone (6-HF), and 7-Hydroxyflavone (7-HF) in the S 0 and S 1 states are compared. In view of the frontier molecular orbitals (FMOs), depending on the HOMO energy, not only is it analyzed that the electron-donating capacity varies with the solvent, but also that the antioxidant capacity of the mostly molecules in the S 1 state is better than those in the S 0 state, in particular, the 6-HF in ACN in the S 1 state shows a strong antioxidant capacity and is most susceptible to attack by electrophilic radicals, which is also in accordance with the conclusions drawn from the orbital weighted (OW) Fukui functions and OW double descriptors, and global indices including vertical ionization potentials (VIPs), softness (S),and so on. Moreover, absorption spectra indicate the potential of these molecules to resist UV radiation and diminished or even quenched fluorescence intensity is caused by intramolecular charge transfer as evidenced by hole-electron analysis. On the basis of the above photophysical properties, it is shown that these three molecules are expected to be one of the ingredients of sunscreens. In a nutshell, this work not only proposed the influence of solvent effect on antioxidant capacity, but also found the advantage of antioxidant capacity in the S 1 state, which provides a strong support for exploring stronger antioxidant capacity. [ABSTRACT FROM AUTHOR]

[Display omitted] • Prepared stable 1:1 inclusion complexes of hydrophobic anticancer drug MNC with β-cyclodextrin. • Comprehensive characterization confirmed successful complexation via co-precipitation method. • Complexation significantly enhanced poor aqueous solubility of MNC. • Molecular modeling provided insights into host–guest interactions stabilizing the complex. • MNC: β-CD complex exhibited superior anticancer activity over free MNC and standard drug. 3-Nitro-2 H -chromene derivatives exhibit promising anticancer activities, but their clinical translation is hindered by poor aqueous solubility. Herein, we report a cyclodextrin complexation strategy to improve the solubility and therapeutic efficacy of 8-methoxy-2-(4-methoxy phenyl)-3-nitro-2 H -chromene (MNC), a potent anticancer agent. Solid inclusion complexes of MNC: β -cyclodextrin (β -CD) were synthesized by co-precipitation and kneading methods, and comprehensively characterized using UV–vis, Fluorescence, Fourier Transform Infrared (FT-IR), Differential scanning calorimetry (DSC), X-ray diffraction (XRD), Scanning electron microscope (SEM), 1H NMR, and mass spectrometric techniques. A 1:1 host–guest stoichiometry was verified by phase solubility and UV–Vis spectroscopic studies. β -CD complexation remarkably enhanced the aqueous solubility of hydrophobic MNC. Cytotoxicity evaluation against different human cancer cell lines such as breast cancer (MCF-7, MDA-MB-231), lung cancer (A549), and liver cancer (HepG2) demonstrated superior anticancer activity of the co-precipitated MNC: β -CD complex compared to free MNC and the chemotherapeutic 5-fluorouracil. Although the host–guest interaction energy obtained from molecular docking was modest (−5.1 kcal/mol), it facilitated effective MNC encapsulation and delivery by β -CD. Density functional theory (DFT) calculations provided further insights into the inclusion phenomenon. This cyclodextrin complexation approach paves the way for developing an effective MNC formulation with improved bioavailability and anticancer therapeutic efficacy. [ABSTRACT FROM AUTHOR]

[Display omitted] • The structure and interactions of [Cho][AA] ILs with different anionic alkyl chain length were investigated theoretically. • The robust hydrogen bonds dominate the interactions between [Cho]+ and [AA]−. • The anions aggregation becomes more pronounced with the elongation of anionic alkyl chain. • The hydrogen bond lifetimes roughly display an increasing trend with the elongation of anionic alkyl chain. The influences of the alkyl chain length of amino acid anions on the structure and interactions of choline-based amino acid ([Cho][AA]) ionic liquids were investigated based on density functional theory (DFT) and molecular dynamics (MD) simulations. The most stable configuration of the individual [Cho][AA] ion pair was determined, revealing negligible variations in the binding energy between choline cation ([Cho]+) and different amino acid anions ([AA]−). To further characterize the intermolecular interactions between charged entities, the atoms in molecules theory (AIM) and independent gradient model based on Hirshfeld partition (IGMH) were employed, which highlight the presence of robust hydrogen bonds between [Cho]+ and [AA] −, underscoring their significance in shaping the structure of [Cho][AA] ion pairs. The MD studies exhibited the aggregation of anions in [Cho][AA] ILs, which was attributed to side chain interactions of anions. This aggregation effect becomes more pronounced with the elongation of anionic alkyl chain. Simultaneously, radial distribution functions (RDF) analysis revealed a higher probability of hydrogen bonds occurring between [Cho]+ and [AA]− as the alkyl chain in [AA]− lengthened. Additionally, the hydrogen bond lifetimes roughly display an increasing trend as the alkyl chain of the [AA]− increases, which may be due to the reduced diffusion coefficients of ions. Hopefully, our results would contribute fundamental knowledge regarding the impact of alkyl chain length of anions on the structure and interactions in the choline-based amino acid ionic liquids. [ABSTRACT FROM AUTHOR]

[Display omitted] • Four imidazolium ([1MeimPS]+) based protic ionic liquids (PILs) are developed with potential amine-based structural functionalities. • All the reported PILs have shown excellent antioxidant potential depicting antiaging properties. • Glutamine based-IL ([1MeimPS][Gln]) showed selectively promising antioxidant activity. • Least IC 50 values are observed for Glutamine based-PIL ([1MeimPS][Gln]) indicating maximum antioxidant activity. • Maximum IC 50 values are observed for Proline based-PIL ([1MeimPS][Pro]) indicating least antioxidant activity. • Increased primary amine moieties enhanced the antioxidant activity by providing more radical scavenging sites. Sulfonyl hydroxide functionalized imidazolium based protic ionic liquids (PILs) have been evaluated as a new form of antioxidants. The antioxidant activity was performed using free radical quenching using UV–visible spectroscopy and cyclic voltammetry. The studies confirmed that the investigated ILs with variable anions exhibited substantial radical scavenging activity. In UV–Visible study, Glutamine based-IL ([1MeimPS][Gln]) showed least IC 50 value of 95 µM indicating maximum radical quenching activity as an oxidant, while proline based-IL ([1MeimPS]Pro]) exhibited highest IC 50 value of 675 µM, demonstrating least anti-oxidant activity. Moreover, cyclic voltammetry results complemented well the UV–visible findings with least IC 50 value of 90 µM for [1MeimPS][Gln], showing maximum antioxidant activity, and highest IC 50 value of 593 µM for [1MeimPS]Pro], exhibiting the least antioxidant activity. The presence of two primary amines moieties in glutaminate anion may be responsible for enhanced antioxidant activity by providing more active sites for radical quenching. Contrarily, lack of primary amine functionality in prolinate anion may contribute to reduced antioxidant activity of respective IL. The Density Functional Theory (DFT) calculations predicted that the trend of radical scavenging potential was comparable with the experimentally obtained IC 50 values. Molecular Electrostatic Potential (MESP) Maps illustrated that [1MeimPS][Pro] has the maximum red zones indicating a poor potential against electron scavenging capacity among all the studied ILs, while blue region in [1MeimPS][Gln], corresponding to low electron density, suggested strong attraction for the incoming electrons. Also, the high electronic distribution of HOMO orbital, appreciable stability, and significant chemical potential to attack on radical species provided by [1MeimPS][Gln] with the maximum radical scavenging potential. Furthermore, the associated LUMO energy for [1MeimPS][Pro] (−1.297 eV) is quite higher than that of [1MeimPS][Gln] (−1.422 eV) which reduced the ability of [1MeimPS][Pro] to attack free radicals of 2,2-diphenyl-1-picrylhydrazyl (DPPH) and thus have higher associated IC 50 values. This is also supported by the results of chemical hardness (η) and chemical potential (μ) descriptors values indicating [1MeimPS][Pro] is least stable and reactive than [1MeimPS][Gln]. These findings further explain the least IC 50 values observed experimentally and consequent enhanced antioxidant potential of [1MeimPS][Gln]. [ABSTRACT FROM AUTHOR]

• Hydrophobic deep eutectic solvents was synthesised for phenol extraction from aqueous media. • Effect of process parameters on extraction of phenol from aqueous phase was studied under different experimental parameters. • Thermodynamic study confirmed that phenol extraction using DESs is spontaneous in nature. • DFT calculation confirmed that synthesised DESs can effectively extract phenol from aqueous phase. Phenol is carcinogenic and toxic to human beings and therefore it is necessary to remove this toxic pollutant from water. Hydrophobic deep eutectic solvents (DESs) were prepared using trioctylamine (TOA) as hydrogen bond acceptor (HBA) and 2-hydroxybenzoic acid and 4-dodecylbenzenesulfonic acid as hydrogen bond donors (HBDs) for extraction of phenol from aqueous media. Fourier transformer infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA) were performed for functional group and thermal stability determination, respectively. Phenol extraction efficiency of DESs was studied under different experimental parameters, such as initial pH of phenol solution (2–10), contact time (1–15 min), mixing ratio of volume of DESs to aqueous media (V DES :V aq.) (1:10–1:50 mL), initial concentration of phenol (1000–5000 ppm) and temperature (25 °C–55 °C). More than 97 % extraction efficiency of DES for phenol was achieved using contact time of 5 min, initial phenol concentration of 2500 ppm, V DES :V aq in a ratio of 1:10 mL, and temperature of 25 °C. The values of ΔG° calculated for phenol extraction at various temperatures have negative values, confirming that the phenol movement from water phase to DESs phase is spontaneous in nature. Density functional theory (DFT) simulations were conducted to study the interaction of DESs with water and phenol. In addition, DFT was used to determine the interaction energy of DESs with water and phenol. The considerably higher interaction energies (−20.4 and 18.2 kcal/mol) obtained with both DESs for phenol over water emphasize the selective separation efficiency of DESs for phenol. The experimental results confirmed that these synthesised DESs can effectively extract phenol from the aqueous phase to the organic phase. [ABSTRACT FROM AUTHOR]

*The full list of abbreviations can be found in the Supplementary Materials. [Display omitted] • Deep Eutectic Solvents are formulated using non-conventional precursor materials, specifically salicylic acid and triethylenetetramine. • In-depth analysis of physicochemical properties and thermal stability positions these DESs as versatile candidates for industrial use, particularly as catalytic curing agents for epoxy resins. • Salicylic acid-based deep eutectic solvents possess superior properties compared to choline chloride-based deep eutectic solvents. • Successful initiation of crosslinking reactions for epoxy resin using the formulated deep eutectic solvents has been achieved. Curing agents for epoxy resins play a significant role in initiating crosslinking reactions resulting in the hardened and durable material with enhanced properties as per end-user applications. The industrial world still lacks efficient, environmentally friendly, and cheap curing agents for epoxy resins. Here, we report the development of deep eutectic solvents (DESs) based on N, N'-Bis(2-aminoethyl)ethane-1,2-diamine (commonly known as triethylenetetramine, TETA) as hydrogen bond donor (HBD), and salicylic acid (SA) and choline chloride (CC) as hydrogen bond acceptor (HBA). The formulated DESs are suggested to be relatively safe, affordable, and eco-friendly and the active groups in the DESs are capable of initiating crosslinking reactions. The physical stability of the formulated deep eutectic solvents was examined by polarizing optical microscopic (POM) analysis, which confirmed the absence of any crystals or residues. The purity was ensured by 13C nmr spectroscopy. Additionally, supportive evidence for the hydrogen bond formation between the constituents was gained from the outcomes of FTIR, 1H nmr, and mass spectrometry. Deep depression in melting points was confirmed from DSC studies, and TGA suggested better thermal stability for DESs than its constituents. Density functional theory (DFT) at B3LYP6-31G* of Gaussian computational framework was applied to energetically optimize the isolated structure and determine the bond lengths in angstroms. The structural characteristics and nonbonding interactions of DESs were investigated by the same. In addition, the density and rheological characteristics were assessed for the ideal utilization of the formulated DESs as epoxy resin curing agents. The detailed comparative studies demonstrated the advantages of deep eutectic solvents over conventional curing agents. The efficacy of the formulations as a curing agent was primarily confirmed from FTIR analysis and the curing behavior was investigated by DSC studies. [ABSTRACT FROM AUTHOR]

• Thermal decomposition characteristics of [Pmim]NO 3 and [Amim]NO 3 were explored. • The thermal pyrolysis mechanism of [Pmim]NO 3 and [Amim]NO 3 were evaluated. • Effect of alkyl side chain structure on thermal hazard of imidazole ILs was studied. Imidazole ionic liquid, as a green solvent, is one of the most widely used ionic liquids. Understanding its thermal safety characteristics and mechanism is the essential basis for its safe application. In this paper, the thermal hazard characteristics of two ionic liquids with typical structural characteristics are systematically studied, which were 1-allyl-3-methylimidazole nitrate and 1-propyl-3-methylimidazole nitrate ionic liquids. The thermal decomposition peculiarities of two ionic liquids were systematically analyzed by thermogravimetric analyzer, differential scanning calorimetry and accelerating rate calorimeter techniques, and the risk of thermal runaway is also evaluated. In addition, the pyrolysis products and microscopic pyrolysis mechanism of ionic liquids were studied via thermogravimetry-Fourier transform infrared spectroscopy, thermogravimetric mass spectrometry and density functional theory calculation, and the essential mechanism of thermal hazard were determined. The influence of substituent structure on the thermal hazard characteristics of imidazole nitrate ionic liquid was preliminarily analyzed from macroscopic experiment and microscopic mechanism two aspects. This study provides a theoretical basis for the safe application, design and development of imidazole nitrate ionic liquids. [ABSTRACT FROM AUTHOR]

[Display omitted] • Molar diamagnetic susceptibility values for some amino acids are reported for the first time. • The results obtained are evaluated in terms of electronic structure principles. • Molar diamagnetic susceptibility can be used in the introducing new chemical hardness, polarizability and entropy scales. One of the main aims of the theoretical chemists is to introduce new and useful approaches for the estimation of chemical reactivity descriptors of Conceptual Density Functional Theory (CDFT) like absolute hardness, polarizability and magnetizability. In addition to providing results close to experimental results, the methods developed for this purpose must also be easily applicable to many molecular systems and easy to learn. "Property Prediction from Structural Differences" method proposed by one of the authors of this article is based on the idea that various properties of molecules can be easily calculated by taking the sum of the functional group contributions in the structure of the molecule. The most important thing in the applying of the method is the reliable determination of functional group contributions. In the present paper, using "Property Prediction from Structural Differences" method, we predicted the molar diamagnetic susceptibilities of amino acids with reasonably good accuracy. The computed values are in good agreement with experimental data and the results of previously introduced theoretical models. The reason why amino acids were especially preferred in the study is the lack of the molar diamagnetic susceptibility data of some amino acids in the literature. Additionally, to test whether a molar diamagnetic susceptibility based scale can be proposed for the calculation of any CDFT based reactivity descriptor, DFT computations were also performed for amino acid molecules. The relationships between parameters were evaluated in terms of the electronic structure rules like Maximum Hardness, Minimum Polarizability, Minimum Magnetizability and Minimum Electrophilicity Principles. [ABSTRACT FROM AUTHOR]

• DFT and MD calculations were applied to study the CaO digestion process. • CaO digestion can be controlled by regulating H 2 O diffusivity with surfactants. • Long-chain surfactants chemisorbed on CaO facilitated the formation of pores. • Surfactants can modulate pore distribution by controlling crystal growth of Ca(OH) 2. Surfactants are widely used for structure modulation of calcium-based materials. However, the modification mechanisms underlying the CaO digestion improved by surfactants for Ca(OH) 2 production remain unclear. This study employed experiment methods, Density Functional Theory (DFT), and Molecular Dynamics methods (MD) to reveal the mechanism of surfactant modulation at a molecular level. The adsorption energy of Primary Alcohol Ethoxylate (AEO), Sodium Dodecyl Sulfate (SDS), H 2 O, and Dodecyl Trimethyl Ammonium Bromide (DTAB) on CaO(0 0 1) surface were −52.62, −51.98, –23.79, and 3.96 kcal/mol, respectively. The strong chemisorption of AEO and SDS on the surface of CaO improved its structure stability. AEO and SDS weakened the diffusion of H 2 O to CaO surface, thus causing the reaction between CaO and H 2 O to be suppressed. After being modulated by SDS and AEO, better crystallinity of Ca(OH) 2 and finer crystalline grains were observed with the formation of developed pore structure. AEO has a longer molecular chain, giving better modification performance. On the contrary, DTAB accelerated the diffusion of H 2 O to CaO surface, leading to more energy released and causing the fast growth of Ca(OH) 2 crystals, as evidenced by the much larger particle size compared to that of AEO and SDS. This process led to the creation of a larger pore structure. Desulfurization was used as a performance indicator to evaluate the surfactants modulation efficacy. The sulfur capacity of Ca(OH) 2 regulated by 1 % AEO was 100.05 mg/g, being the highest among the used surfactants. For comparison, the sulfur capacity without additives was 49.64 mg/g. This study shows that nonionic surfactants are an ideal choice for regulating the structure of Ca(OH) 2 , as they can effectively inhibit crystal growth. [ABSTRACT FROM AUTHOR]

• Selective depression of quartz flotation by 20 mg/L of TETA at pH 10 was reduced from 92.2 % to 22.5 % in carbonate ionic liquid. • ICP and zeta potentials revealed that selectively adsorbed TETA altered the setting on the quartz surface to the preferential adsorption of NaOL on the smithsonite surface. • XPS and QCM-D support that TETA effectively forms new complexes with Zn 5 (OH) 6 (CO 3) 2 (s) and chemisorbs at the quartz interface. • TETA's N hybridizes to generate covalent bonds with Zn on the Zn-quartz surface and ionic bonds with Zn on the smithsonite. In order to induce alterations in the mineral surface's hydrophobicity and subsequently separate smithsonite from quartz, the current study introduces an innovative amine depressant termed triethylenetetramine (TETA). Micro-flotation experiments clearly demonstrated that adding a relatively modest dosage (20 mg/L) of TETA at pH 10 reduced the recovery of quartz from 92.2 % to 22.5 % without reducing the recovery of smithsonite. ICP-OES and zeta potentials revealed that TETA selectively adsorbed on the quartz surface effectively reduced Zn2+ dissolution and altered the setting of the quartz surface to preferentially adsorb NaOL on the smithsonite surface. X-ray photoelectron spectroscopy (XPS) and Quartz crystal microbalance with dissipation (QCM-D) analyses support that TETA is more susceptible to Zn atoms in Zn 5 (OH) 6 (CO 3) 2(s) through a bonding process and preferentially chemisorbs on the quartz surface to the exclusion of Zn-CO 3 on the smithsonite surface. Density functional theory (DFT) calculations revealed that electron acceptance by Zn and electron loss by N resulted in hybridization reactions between Zn 2 s, 3d, 4p and N 2p orbitals to form stable Zn-N covalent bonds. Chemical bonds characterized by ionic bonding were formed between TETA and Zn atoms on the cleavage plane of smithsonite, which led to the susceptibility of TETA adsorption on the surface of smithsonite to be broken. [ABSTRACT FROM AUTHOR]

• Conceptual density functional theory correctly assesses hydrogen bond acidity/basicity. • Solubility can be described in terms of electrophilicity, nucleophilicity and molecular softness. • HBA can be associated with regional electrophilicity, HBB with regional nucleophilicity, and polarizability with global softness. We present a simple semi-empirical model for solubility in organic solvents, based on the conceptual density functional theory (CDFT) and inspired on the well-known empirical linear solvation energy relationships (LSER) proposed by Kamlet and Taft, where a multiparametric correlation between solubility and empirical descriptors including the hydrogen bond acidity (HBA) and basicity (HBB) plus an additional term describing the dipole polarizability of the solvents was presented. Herein, we set up an analogue model that describes HBA, HBB and dipole polarizability with electronic descriptors derived from the conceptual density functional theory. The main relevant results are as follows: (i) as expected, HBA and HBB properties are not absolute but regional properties, thereby suggesting that any solvent can display both properties with different weights (bifunctional solvents); (ii) while HBA can nicely be represented by a regional electrophilicity index, the HBB property can be accounted for by a regional nucleophilicity. The dipole polarizability is consistently represented by the global softness of the solvent molecule; (iii) the regionalization of these properties is achieved by defining electrophilic and nucleophilic basins within a given solvent molecule by using the electrophilic and nucleophilic Fukui Functions integrated within these basins. The resulting model is validated against the experimental solubility of vanillin and hesperidin in different organic solvents. Further perspectives of the present study should be of special interest in theoretical studies concerning ionic liquids and deep eutectic solvents. [ABSTRACT FROM AUTHOR]