Self-aggregation Behavior Research Articles

Self-aggregation behavior of well-defined PEO-based amphiphilic tri-block copolymers and their application as metal detectors

PMMA-b-PEO-b-PMMA tri-block copolymers were synthesized by anionic polymerization technique usingtelechelic1,1-diphenylethylene-terminated poly (ethylene oxide)as macroinitiators and Sec-BuLi four tri-block copolymers of PMMA-b-PEO-b-PMMA with different number average molecular weight ( M ¯ n ) were synthesized, and the structure of the macroinitiators and polymers was confirmed by FTIR. and1H NMR spectroscopic methods. Through the solvent-induced association, the aqueous solutions of PMMA-b-PEO-b-PMMA were formed. After that, hydrodynamic diameter, DLS and TEM were used to study the morphology of the resulting aqueous solutions. The polymer’s self-assembled nanostructures of core-shell flower-like spherical micelles structures were observed. Also, the PMMA hydrophobic content of the tri-block increases steadily and the core size of the micelles decreases significantly, due to reverse micelle formation in which the core is hydrophobic PMMA blocks and the corona is PEO block. This micelle is an excellent detector for metal ions and acts as a reducing agent for them to convert into pure nontoxic nanoparticles.

Manufacturing bioprocess of novel cream formulations based on polysaccharides “ulvans” from green seaweed Ulva lactuca: Effect of extraction procedures and concentrations on the optical and rheological properties of ulvan creams

This paper investigates a new manufacturing bioprocess for making of creams based on the sulphated polysaccharide “Ulvan” extracted from the green seaweed Ulva lactuca using different extraction processes and added at varying concentration from 1 to 5% (w/w).Regardless of the extraction procedure and concentration, the bio-macromolecule ulvan can produce successful cream formulations with and suitable materials that exhibit excellent rheology and optical properties, due to its molecular flexibility and self-aggregation behavior. Depending on the extraction procedures, we declare that the creams prepared with low concentrations from 1 to 3 % (w/w) of enzymatic-chemical extract (EE) and acidic extract (CA1), can successfully enhance the lightness, stability, thixotropic and viscoelastic behaviors, which are usually correlated to the physical properties and cross-linking characteristics of ulvans. Additionally, these creams demonstrate high skin absorption at temperatures between 5 and 29 °C. Interestingly, high concentrations of these ulvan extracts at beyond 3% (w/w) in the creams lead to more outstanding storage stability, increased strength and firmness, and enhanced lightness and pseudoplastic behavior, along with excellent skin absorption. These results have important implications for the industrial sector in the production and optimization of ulvan-based creams, especially cream based on CA1 incorporated at 3 % (w/w), as an efficient green-sustainable strategy.

Self-Aggregation Control of Porphyrin for Enhanced Selective Covalent Organic Network Membranes.

Covalent organic networks (CONs) are considered ideal for precise molecular separation compared with traditional polymer membranes because their pores have a sharp molecular weight cut-off and a robust structure. However, challenges remain with regard to tuning pores as a prerequisite for facile membrane fabrication to a defect-free layer. Herein, a highly conjugated amino-porphyrin is used and exploited its tunable stacking behavior to fabricate porphyrin-based polyamide CONs with ordered structures through interfacial polymerization with acyl chlorides. Controlling the self-aggregation behavior of the porphyrin and the conformation of the acyl chlorides can create different covalent networks. Acid-triggered porphyrin protonation offsets stacking to reduce the pore in the network from mesopore to micropore, enabling selective molecule transport. Furthermore, different acyl chloride ligands are used to control the interlayer bonding in CONs. Accordingly, the tailored pore diameters (0.48-0.78nm) are confirmed by the molecule rejections with performance stability over 25 days of operation, as well as under various conditions. This study leverages porphyrin chemistry and interfacial polymerization to fabricate a defect-free CON layer with a significantly lower molecular weight cut-off (< 330Da) than previously reported porphyrin-based membranes (>800Da). This will pave the way for the development of ideal topological membranes.

Bioactive Microgels with Tunable Microenvironment as a 3D Platform to Guide the Complex Physiology of Hepatocellular Carcinoma Spheroids.

Miniaturized three-dimensional tissue models, such as spheroids, have become a highly useful and efficient platform to investigate tumor physiology and explore the effect of chemotherapeutic efficacy over traditional two-dimensional monolayer culture, since they can provide more in-depth analysis, especially in regards to intercellular interactions and diffusion. The development of most tumor spheroids relies on the high proliferative capacity and self-aggregation behavior of tumor cells. However, it often disregards the effect of microenvironmental factors mediated by extracellular matrix, which are indispensable components of tissue structure. In this study, hepatocellular carcinoma (HCC) cells are encapsulated in bioactive microgels consisting of gelatin and hyaluronic acid designed to emulate tumor microenvironment in order to induce hepatic tumor spheroid formation. Two different subtypes of HCC's, HepG2 and Hep3B cell lines, are explored. The physicomechanical and biochemical properties of the microgels, controlled by changing the crosslinking density and polymer composition, are clearly shown to have substantial influence over the formation and spheroid formation. Moreover, the spheroids made from different cells and microgel properties display highly variable chemoresistance effects, further highlighting the importance of microenvironmental factors guiding tumor spheroid physiology.

Non-Fused π-Extension of Endcaps of Small Molecular Acceptors Enabling High-Performance Organic Solar Cells.

The modular structure of small molecular acceptors (SMAs) allows for versatile modifications of the materials and boosts the photovoltaic efficiencies of organic solar cells (OSCs) in recent years. As a critical component, the endcaps of SMAs have been intensively investigated and modified to control the molecular aggregation and photo-electronic conversion. However, most of the studies focus on halogenation or π-fusion extension of the endcap moieties, but overlook the non-fused π-extension approach, which could be a promising strategy to balance the self-aggregation and compatibility behaviors. Herein, we reported two new acceptors namely BTP-Th and BTP-FTh based on non-fused π-extension of the endcap by chlorinated-thiophene, of which the latter molecule has better co-planarity and crystallinity because of the intramolecular noncovalent interactions. Paired with donor PBDB-T, the optimal device of BTP-FTh reveals a greater efficiency of 14.81 % that that of BTP-Th (13.91 %). Nevertheless, the BTP-Th based device realizes a lower energy loss, enabling BTP-Th as a good candidate to serve as guest acceptor. As a result, the ternary solar cells of PM6 : BTP-eC9 : BTP-Th output a champion efficiency up to 18.71 % with enhanced open-circuit voltage. This study highlights the significance of rational decoration of endcaps for the design of high-performance SMAs and photovoltaic cells.

Recent Advances in Smart Self-Assembled Bioinspired Hydrogels: A Bridging Weapon for Emerging Health Care Applications from Bench to Bedside.

Stimuli-responsive low molecular weight hydrogel interventions for Biomedical challenges are a rapidly evolving paradigm in the bottom-up approach recently. Peptide-based self-assembled nano biomaterials present safer alternatives to their non-degradable counterparts as demanded for today's most urged clinical needs.Although a plethora of work has already been accomplished, programming hydrogelators with appropriate functionalities requires a better understanding as the impact of the macromolecular structure of the peptides and subsequently, their self-assembled nanostructures remain unidentified. Henceforth this review focuses on two aspects: Firstly, the underlying guidelines for building biomimetic strategies to tailor scaffolds leading to hydrogelation along with the role of non-covalent interactions that are the key components of various self-assembly processes. In the second section, it is aimed to bring together the recent achievements with designer assembly concerning their self-aggregation behaviour and applications mainly in the biomedical arena like drug delivery carrier design, antimicrobial, anti-inflammatory as well as wound healing materials. Furthermore, it is anticipated that this article will provide a conceptual demonstration of the different approaches taken towards the construction of these task-specific designer hydrogels. Finally, a collective effort among the material scientists is required to pave the path for the entrance of these intelligent materials into medicine from bench to bedside.

Physicochemical properties and biological activities of new berberine-based salts with syringic acid as well as 3,5-dimethoxybenzoic acid as anions: Effect of temperature, concentration and anion

Two novel berberine-based salts (berberine syringate ([BBR][SA]) and berberine 3,5-dimethoxybenzote ([BBR][DA])) were prepared and characterized. Their thermal stability, solubility and octanol–water partition coefficient in aqueous solution and simulated physiological fluids (simulated gastric, simulated body, simulated intestinal fluids) were determined. Self-aggregation and association behaviors of two salts in aqueous solution have been investigated by conductimetric method at different temperatures and limiting molar conductivity, critical aggregation concentration, etc for [BBR][SA] and [BBR][DA] were calculated. The minimum inhibitory concentration (MIC) and minimal bactericidal concentration (MBC) values of two salts were assessed to evaluate their antibacterial effects on four strains (Staphylococcus aureus, Bacillus subtilis, Candida albicans, and Streptococcus mutans). The effect of two synthetic salts on the esterase-like activity of BSA and their cytotoxicity evaluation against B16-F10 cancer cell line were also carried out. The obtained results were evaluated with regard to the influence of such parameters as temperature, concentration and the nature of the anion.

Transport Mechanism of Paracetamol (Acetaminophen) in Polyurethane Nanocomposite Hydrogel Patches-Cloisite® 30B Influence on the Drug Release and Swelling Processes.

This article describes the swelling and release mechanisms of paracetamol in polyurethane nanocomposite hydrogels containing Cloisite® 30B (organically modified montmorillonite). The transport mechanism, swelling and release processes of the active substance in nanocomposite matrix were studied using gravimetric and UV-Vis spectroscopic methods. Swelling and release processes depend on the amount of clay nanoparticles in these systems and the degree of crosslinking of PU/PEG/Cloisite® 30B hydrogel nanocomposites. The presence of clay causes, on the one hand, a reduction in free volumes in the polymer matrices, making the swelling process less effective; on the other hand, the high swelling and self-aggregation behavior of Cloisite® 30B and the interactions of paracetamol both with it and with the matrix, cause a change in the transport mechanism from anomalous diffusion to Fickian-like diffusion. A more insightful interpretation of the swelling and release profiles of the active substance was proposed, taking into account the "double swelling" process, barrier effect, and aggregation of clay. It was also proven that in the case of modification of polymer matrices with nanoparticles, the appropriate selection of their concentration is crucial, due to the potential possibility of controlling the swelling and release processes in drug delivery patches.

Synergistic mechanism of dodecylamine/octanol mixtures enhancing lepidolite flotation from the self-aggregation behaviors at the air/liquid interface

Surface tension measurements and molecular dynamics (MD) simulations were used to explore the flotation foam properties and self-aggregation behaviors of dodecylamine (DDA)/octanol (OCT) mixtures formed with different mole ratios at the air/liquid interface. Based on the surface and thermodynamic parameters, the DDA/OCT mixtures exhibited greater interfacial activities and adsorption capacities than their individual components. The MD simulations showed that DDA and OCT were aggregated through hydrogen bonding, coulombic forces and hydrophobic association. OCT was inserted into the DDA adsorption layer, causing the alkyl chains of both DDA and OCT to extend from water to air at varying heights and angles. The addition of OCT improved the hydration of the amino groups and reduced the overall number of hydrogen bonds. The stability of the flotation foam decreased, and the high viscosity and difficult defoaming of the DDA flotation foam were significantly improved. When the DDA/OCT mole ratio was 2:1, the included angle formed between the alkyl chains and the interface was maximized, leading to enhanced compatibility among the alkyl chains, and the hydrogen bond energy was relatively large, which showed a strong synergistic effect. The MD simulation findings were consistent with the results obtained from the lepidolite flotation and surface tension experiments conducted in this study; our results could provide a theoretical foundation for the selection of superior mixed collectors and frothers.

Synergistic roles of oxidation and self-aggregation in efficient ultrafiltration membrane fouling alleviation using a flow-through Sb-SnO2 anode during wastewater reclamation

The application of ultrafiltration (UF) in wastewater reclamation alleviates the demand for limited water supplies. However, the membrane fouling caused by the effluent organic matter (EfOM) becomes a major obstacle for UF application. In this study, a pre-oxidation strategy for UF using a Sb-SnO2 (ATO) anode in flow-through mode was proposed with the hopes to improve the performance of UF during wastewater reclamation. The results indicated that this flow-through ATO (FA) anode significantly outperformed a boron-doped diamond (BDD) anode in terms of EfOM degradation and membrane fouling control. It is noteworthy that apart from oxidation, the self-aggregation behavior of foulants was also involved in the mechanisms of membrane fouling mitigation. On the one hand, FA pre-oxidation relieved the burden of membrane fouling by decomposing the macromolecular EfOM into small molecular organic matter, and even mineralizing it. The effective destruction of unsaturated EfOM by FA pre-oxidation made a remarkable contribution to fouling mitigation due to the strong correlation between the total fouling index and UV254. On the other hand, the surface morphology of membrane and interface properties of foulants revealed the self-aggregation behavior of foulants. FA pre-oxidation made the foulants aggregate spontaneously and reduced the potential of forming a dense cake layer on the membrane surface, which was conductive for water permeation. Overall, FA pre-oxidation proved to be a feasible and chemical-free option for UF pretreatment to simultaneously produce high-quality reused water and alleviate membrane fouling during wastewater reclamation.

Polyurethane and nano-TiO2 modifiers mitigate aging of asphalt binders by inhibiting aggregation of polar molecules: A molecular dynamics study

The aim of this study was to employ molecular dynamics to investigate how the addition of polyurethane and nano-TiO2 modifiers affects the strengthening mechanism and anti-aging properties of asphalt binders. In this study, asphalt molecular model, nano-TiO2 cluster model, PU molecular model, and PU/nano-TiO2/asphalt molecular model were constructed. The radius of gyration, free volume, diffusion coefficient, and indicators of structural alterations were used to analyze the impacts of PU and nano-TiO2 modifiers on the molecular structure of asphalt. The results indicate that the aging process of asphalt introduces oxygen-containing active functional groups. These groups increase the interaction forces among polar molecules, resulting in the aggregation of polar molecules and the disruption of the original colloidal structure. The spatial barrier effect of polyurethane chains hinders the self-aggregation behavior of asphaltene molecules. Asphaltenes are adsorbed onto the nano-TiO2 clusters, thereby impeding the formation of large-sized polar molecular aggregates. The primary role of polyurethane and nano-TiO2 is to mitigate the aging-induced aggregation of asphaltene polar molecules, preserving asphalt performance. However, it's important to note that asphalt will inevitably undergo aging over time.

Molecular simulation on compatibility and mechanisms of SBS and PTW polymer modifiers in asphalt binder.

Ultrathin overlays are preventive maintenance measures; the tensile and shear stresses generated inside a structural layer under vehicle load are greater than those of conventional thickness asphalt pavement. Therefore, asphalt binders must use high-viscosity and elasticity unique cementing materials to ensure stability. To investigate the modification mechanism of styrene-butadiene-styrene (SBS)/ethylene-butyl acrylate-glycidyl methacrylate copolymer (PTW) high-viscosity modified asphalt binder suitable for ultrathin overlays, the compatibility and molecular behavior of SBS/PTW high-viscosity modified asphalt binder were analyzed by the molecular dynamics (MD) method. These research results provide a reference for preparing ultrathin overlay high-performance composite modified asphalt binder. SBS molecular models, PTW molecular models, asphalt binder molecular models, SBS/asphalt binder blend systems, and SBS/PTW/asphalt binder blend systems were sequentially constructed using Materials Studio (MS) software. The compatibility of SBS, PTW, and SBS/PTW with asphalt binder and the diffusion coefficients of SBS, PTW, and SBS/PTW in the asphalt binder were investigated separately using the MD method. The mechanical properties and molecular behavior of SBS, PTW, and SBS/PTW blended with asphalt binder were studied. The research results indicate that the compatibility of PTW with asphalt binder is better than that of SBS with asphalt binder. PTW can effectively decrease the solubility parameter of asphalt binder and improve the compatibility between SBS and asphalt binder. PTW effectively improves the diffusion coefficient and interaction energy of SBS in asphalt binder by up to 29% and 83%. In addition, SBS/PTW had a significant positive effect on the mechanical properties of the asphalt binders, increasing the elastic modulus (E), bulk modulus (K), and shear modulus (G) of the asphalt binder by 4.6%, 9.5%, and 3.5%, respectively, compared to SBS. The results indicate that the SBS/PTW modified asphalt binder composite can significantly improve the high-temperature shear resistance of asphalt binder. Meanwhile, SBS and PTW improve the self-aggregation behavior between asphalt binder component molecules. The distance between the center of mass of asphalt binder and resin system molecules is increased. PTW enhances the extensibility of the branched chains of asphalt binder component molecules and improves the interaction between asphalt binder components and the chains. This further enhances the density and stability of the asphalt binder molecular structure system, improving the physical properties of the asphalt binder.

Encapsulation Alleviates the Auto-browning of Epigallocatechin-3-gallate in Aqueous Solutions through Regulating Molecular Self-Aggregation Behavior.

Catechins are widely recognized for superb antioxidant capability, but their application as food antioxidants is hindered by susceptibility to auto-browning under high-moisture conditions. Here, we proposed a strategy of ordered encapsulation with cyclodextrin-based metal-organic frameworks (CD-MOFs) to alleviate the auto-browning phenomenon of catechins while preserving their antioxidant capability and demonstrated the feasibility of this strategy via selecting epigallocatechin-3-gallate (EGCG) as a model. Even in aqueous solutions, EGCG@CD-MOFs still possessed delayed browning, in contrast with pristine EGCG, characterized by suppressed efficiencies on the generation of oxidative dimers (theasinensin A) and semiquinone radicals. Mechanism insights revealed that ordered encapsulation brought dual regulations on the self-aggregation behavior of EGCG: EGCG@CD-MOFs exhibited a gradual structural collapse from the framework toward irregular aggregates as O-K bonds broke progressively, which restricted molecular mobility of EGCG, and EGCG molecular conformations became constrained by the structure of EGCG@CD-MOFs as well as rich intermolecular forces, even after structural collapse.

Non-aromatic single amino acid, lysine: A simple fluorescence sensor for selective detection of Cu2+ and Co2+ with colorimetric distinction by the virtue of its self-aggregation behaviour

Non-aromatic amino acids are mostly considered as non-emissive due to their lack of conventional fluorophores. However, at high concentrations, they can undergo conformational rigidification via self-aggregation and emit in the visible range. Herein, we have exploited that very property of non-aromatic amino acids as a fluorescence sensor. To the best of our knowledge, this is the first report demonstrating a single unmodified non-aromatic amino acid, Lysine (Lys) as a selective and sensitive fluorescence sensor for the detection of Cu2+ and Co2+ along with colorimetric distinction. An as-prepared aqueous solution of Lys (6.8 mM) served as a fluorescence sensor for Cu2+ and Co2+ with a detection limit of 420 nM and 460 nM, respectively in water. The instantaneous appearance of blue and pink color upon adding Cu2+ and Co2+, respectively to the Lys solution makes the system useful for their real-time analysis. The sensing of Cu2+ and Co2+ are also demonstrated through the fabrication of paper strips. Moreover, the sensor could detect Cu2+ and Co2+ in real water samples (lake water and tap water). The exceptionally low cost (<1 U.S. cent/10 mg Lys), reversibility of the sensor, and its ease of use uniquely qualify Lys as a remarkably simple fluorescent sensor.

Effect of molecular environment on asphaltene aggregation: a molecular dynamics study

Asphaltene deposition poses a significant threat to the safe production of crude oil as it tends to occur in forming porous media, wellbores, pipelines, and refining equipment. It is also responsible for the high viscosity of crude oil, making it challenging to recover heavy crude oil. This study investigates the impact of aliphatic chain length on asphaltene aggregation and the molecular properties of organic solvents and dispersants interacting with asphaltenes. To achieve this, two model asphaltenes, M1 and C5Pe, were used in molecular dynamics simulations using radial distribution function, root means square displacement, diffusion coefficient, solubility parameter, cohesion energy density, and interaction energy as characterization parameters. The simulations revealed that the aggregation onset of C5Pe and M1 occurs at 2–5 Å at room temperature and pressure, and π–π stacking is the primary mode of aggregation, with the presence of heteroatomic groups providing additional forces for stable aggregation. Additionally, it was found that the π–π interactions weakened with the increase of the side chain length. The study also investigated the molecular behavior of asphaltenes in six organic solvents and found that M1 was more soluble in aromatic solvents than C5Pe, and undesirable solvents could induce asphaltene aggregation. Furthermore, the effect of five dispersants on asphaltene aggregation was explored, with PIBSI, BEHP, B-DBSA, CTAB, and benzoic acid showing decreasing dispersing ability in that order at lower concentrations. However, at higher concentrations, the effect of some dispersants diminishes and triggers self-aggregation behavior.

Self-aggregation, dilational surface rheology and foaming properties of 1-O-dodecyl diglyceryl ether compared to n-dodecyl-β-D-maltoside and pentaethyleneglycol monododecyl ether

Diglyceryl alkyl esters are good foaming agents but the ester linker can be sensitive to pH, chemicals and temperature unlike the ether function. In this work, the foaming properties of a diglyceryl ether, namely 1-O-dodecyl diglyceryl ether (C12Gly2), are compared to those of n-dodecyl-β-D-maltoside (C12Glc2) and pentaethyleneglycol monododecyl ether (C12E5). The self-aggregation behaviour of C12Gly2 and adsorption at the air–water interface has been first investigated. For the three surfactants, the dynamic response of the interface, measured in oscillatory bubble interfacial rheology experiments below CMC, is compared and put in relation with their foaming properties. In particular, the foamability by air sparging at a concentration of 10 times the CMC, the foam stability over 1 h and the foam density are quantified.It is shown that C12Gly2 forms liquid crystals at low concentration (∼10CMC). C12E5, with a lower elasticity high frequency limit ε0, forms unstable foam with quick drainage and breakdown, whereas higher ε0 surfactants C12Gly2 and C12Glc 2 form much more stable foams, resulting from hydrogen bonds between the polar heads of C12Glc 2 and C12Gly2. Differences in C12Gly2 and C12Glc2 foams lay in initial bubble size (smaller for the C12Glc 2). In C12Gly2 foam, the main destabilization phenomenon is coalescence over drainage, and the foam volume only decreases by 30% in 1 h.

Studies on synthesis, physicochemical properties, biological activities of two novel berberine-based salts with DL-mandelate and cinnamate anions

Berberine (BBR) is a natural quaternary isoquinoline alkaloid which is derived from the traditional Chinese medicine Coptis chinensis and exerts various pharmacological effects. However, low solubility in water has greatly limited its clinical application. This study prepared two novel berberine-based salts (berberine DL-mandelate ([BBR][MAN]) and berberine cinnamate ([BBR][CIN])) to improve the physicochemical properties and bioavailability of berberine. Many techniques, like 1H and 13C NMR, FTIR, ESI-MS, and thermogravimetric analyzes were utilized to characterize two salts. The solubility and octanol/water partition coefficient in water and simulated body fluids (simulated body, simulated intestinal and simulated gastric fluids) were determined. Self-aggregation behaviors of two salts in water have been investigated by conductometry at different temperatures. The obtained critical aggregation concentration (cac) was used for the calculation of various thermodynamic properties namely standard Gibbs energy change (ΔGm0), enthalpy change (ΔHm0), and entropy change (ΔSm0) in the aggregation progress. The volumetric properties including the infinite dilution apparent molar volumes (V2,φ0), infinite dilution apparent molar expansibility (Eφ0) and thermal expansion coefficient (β) for [BBR][MAN] were also determined to study its solvation behavior in aqueous solution. In addition, the antibacterial effect of two salts on three strains (Staphylococcus aureus, Bacillus subtilis and Candida albicans) was measured, and the minimum inhibitory concentration (MIC) and minimal bactericidal concentration (MBC) values were obtained. The results show that [BBR][MAN] has better antibacterial effect than [BBR][CIN]. The esterase-like activity assay demonstrated a decrease in enzyme activity of BSA in presence of two berberine-based salts. Cytotoxicity evaluation shows that two salts have potent in vitro anticancer activities against B16-F10 cancer cell lines.

Effect of Self-Aggregation Behavior of Geminized Cationic Amphiphilic Macromolecules on the Removal Mechanism of Asphaltenes

Effect of Self-Aggregation Behavior of Geminized Cationic Amphiphilic Macromolecules on the Removal Mechanism of Asphaltenes

A surfactant-based quasi-hydrophobic deep eutectic solvent for dispersive liquid-liquid microextraction of gliflozins from environmental water samples using UHPLC/fluorescence detection

Despite the anticipated exceptional properties of deep eutectic solvents (DES) in microextraction techniques, their self-aggregation behaviour has only been sporadically studied in the previous literature. In the presented study, a novel surfactant-based quasi-hydrophobic deep eutectic solvent (DES) is synthesized and utilized in dispersive liquid-liquid microextraction (DLLME) of three gliflozins in environmental water samples as a proof-of-concept examples. The synthesized DES is composed of benzalkonium chloride (BZKCl) as a hydrogen bond acceptor and octanol (Oct) as a hydrogen bond donor. A full optimization of the extraction conditions was carried out including molar ratio and composition of DES, volume of DES, volume of water samples, extraction time and type of diluting solvent. Moreover, the extraction mechanism was thoroughly investigated, and it was established that the extraction of the target analytes is attributed to the analytes' incorporation into the micelles’ cores that facilitates mass transfer from the aqueous layer into DES layer. Furthermore, micelles formed by surfactant-based DES will provide adequate dispersion of extractant phase within water samples, which consequently improves the extraction efficiency. Micelles formation was confirmed by transmission electron microscopy (TEM). Furthermore, 1H NMR spectra verifies that the synthesized DES keeps its integrity even after extraction, which excludes any decomposition of DES after DLLME procedure. The extraction recovery is in an excellent agreement with the hydrophobicity of the investigated drugs, being the highest for the most hydrophobic one. The extracted analytes were separated by UHPLC coupled with fluorescence detection. Under the optimized experimental conditions, the method exhibits excellent linearity and a high detection sensitivity with a limit of detection of 0.5, 2.0 and 0.1 ng mL−1 for EMP (empagliflozin), DAP (dapagliflozin) and CAN (canagliflozin), respectively. The greenness of the developed microextraction approach was assessed by different greenness metrics such as Complex GAPI and AGREE tools. The developed method shows excellent greenness of synthetic procedure for preparation of DES, the environmentally benign nature of DLLME procedure as well as the greenness of the developed UHPLC approach.

Multi-scale analysis on the aggregation mechanism of oxygen-rich coal-derived asphaltene molecules

Significant differences exist in the structural features between coal-derived asphaltene and petroleum asphaltene (e.g., the degree of alkylation, aromatic nuclei size, heteroatom content, as well as morphology characteristics). The self-aggregation behavior exhibited by coal tar asphaltene for coal tar processing should be investigated in accordance with the structural characteristics of coal tar asphaltene. In this study, the focus was placed on the effect exerted by oxygen structure format, location and content on the aggregation behavior of asphaltene. The electrostatic potential (ESP) maps, theoretical reactivity parameters, molecular orbitals, dimerization interaction energies, and weak interactions of coal tar asphaltene were determined based on quantum chemistry. The self-aggregation behavior exhibited by coal-derived asphaltene was explored through molecular dynamics simulations. As indicated by the results of this study, the π-π interactions among asphaltenes were enhanced by the heteroatoms embedded in polycyclic aromatic hydrocarbons (PAHs). In the identical oxygen content, the π-π stacking of asphaltenes with five-membered heterocyclic structures turned out to be more intense. The carboxyl and hydroxyl were more likely to form hydrogen bonds, such that the stability of asphaltene aggregates was increased. Furthermore, as indicated by the molecular dynamics simulation results, the oxygen-containing structures far from PAHs exhibited small steric resistance and a higher probability of the formation of hydrogen bonds.