Dispersion Forces Research Articles

Ion‐Pairing Chromonic Liquid Crystals via Alternately Stacked Assembly of Amphiphilic Charged π‐Electronic Systems

In this study, a new assembly strategy for lyotropic chromonic liquid crystals (LCLCs) is proposed using iπ–iπ interactions, mainly comprising electrostatic and dispersion forces, between charged π‐electronic systems to form stacking structures supported by the hydration of triethylene glycol (TEG) units. Meso‐TEG‐aryl‐substituted porphyrin AuIII complex, an amphiphilic π‐electronic cation, showed diverse states and assembly modes in ion pairs depending on the coexisting counteranions. The PCCp– ion pair formed a hexagonal columnar (Colh) LC phase based on a charge‐by‐charge assembly, suggesting the formation of an ordered arrangement of charged p‐electronic systems through iπ–iπ interactions, with reduced interactions between the TEG chains. Furthermore, in the presence of water, LCLC behaviors in the Colh and nematic columnar phases according to the amount of water were observed for the PCCp– ion pair via iπ–iπ interactions. Magnetic‐field‐induced orientation of the charge‐by‐charge columnar structures upon dehydration was observed. Furthermore, single‐stranded charge‐by‐charge columnar structures, as components of the LCLCs, were observed using transmission electron microscopy (TEM).

Strength of London Dispersion Forces in Organic Structure Directing Agent-Zeolite Assemblies.

Herein, we study the London dispersion forces between organic structure directing agents (OSDAs)-here tetraalkyl-ammonium or -phosphonium molecules-and silica zeolite frameworks (FWs). We demonstrate that the interaction energy for these dispersion forces is correlated to the number of H atoms in OSDAs, irrespective of the structures of OSDAs or FWs, and of variations in charges and thermal motions. All calculations considered-DFT-D3 and BOMD undertaken by us, and molecular mechanics from an accessible database-led to the same trend. The mean energy of these dispersion forces is ca. -2 kcal.mol-1 per H for efficient H-O contacts.

Theoretical insights into the diverse stabilizing effects of fenchyl alcohol/thymol eutectic solvent on carotenoids

Carotenoids, a class of vital natural pigments, are known for their antioxidant properties and are integral to various industrial applications. However, their instability during processing and storage has limited their broader utilization. This study investigated the stabilizing effects of a fenchyl alcohol/thymol-based deep eutectic solvent (DES) on a spectrum of carotenoids, including lutein, zeaxanthin, astaxanthin, and β-carotene. Through a combination of ab initio molecular dynamics (AIMD) simulations and quantum chemical calculations, we elucidated the molecular interactions and stabilization mechanisms within the DES environment (methanol as the benchmark). Our findings reveal that the DES could exert varying degrees of influence on the stability of different types of carotenoids. The temperature-dependent behavior of carotenoids in the DES suggested a complex interplay between hydrogen bonding, dispersion forces, and the inherent structural properties of carotenoids. AIMD simulations provided a detailed picture of the structural organization and hydrogen bond network topology within the DES, highlighting the role of temperature on the stability and orientation of solvent molecules around carotenoids. Energy decomposition analysis (EDA), Hirshfeld surface analysis, and visual study of interactions further dissected the non-covalent interactions, emphasizing the significance of electrostatic and dispersion forces-driven non-covalent interactions (van der Waals dispersion interactions) in stabilizing carotenoids within the DES matrix. In comparison to methanol, the interactions between components of the eutectic system and the target molecules demonstrate enhanced dynamism, increased complementarity, and a greater variety of interaction patterns. This research presented a novel perspective on the use of DESs for the stabilization of carotenoids, offering potential solutions to enhance their industrial applicability and performance. The insights gained from this study are crucial for the development of sustainable and eco-friendly solvent systems, aligning with the growing demand for green chemistry in the pharmaceutical, cosmetic, and food industries.

Optical and Supramolecular Properties of Cyclometalated Palladium Nanostructures with Tumor Targeting Properties in Living Mice: A Quantum Mechanics Interpretation.

The recent discovery that metallophilic interactions between cyclometalated palladium supramolecular nanostructures - with efficient tumour accumulation rate in a skin melanoma model - maintain excellent photodynamic properties even in a hypoxic microenvironment has inspired the present study focused on the theoretical predictions of optical properties of the bis-cyclometalated palladium compound in different contexts. More specifically, structural and UV/Vis absorption properties of both monomeric and dimeric forms of this anticancer drug are well reproduced with a Time-Dependent Density Functional Theoretical (TD-DFT) approach based on Exchange-Correlation (XC) hybrid functionals in conjunction with conductor-like and polarization solvation effects. A further novelty is represented by a fine investigation of the supramolecular interactions between the different subunits of the drug via dispersion force correction and Quantum Theory of Atoms in Molecules (QTAIM). This contribution while supporting the photoexcitation properties derived in laboratory following the self-assembly of monomeric units when passing from dimethyl sulfoxide (DMSO) to a H2O/DMSO mixture at 298 K, shed some light on the nature of the chemical interactions modulating the formation of nano-size aggregates.

Quantitative Characterization of Fluorine-Centered Noncovalent Interactions in Crystalline Benzanilides.

Six isomeric molecules, featuring a minimum of three fluorine atoms on either the benzoyl or aniline side, have been synthesized, crystallized and characterized through single crystal X-ray diffraction (SCXRD). In addition, two other compounds, containing six fluorine atoms, three on each of the benzoyl and aniline side of the benzanilide scaffold have also been characterized through SCXRD. This current study aims to augment the capacity for hydrogen bond formation, specifically involving organic fluorine, by elevating the acidity of the involved hydrogens through the incorporation of highly electronegative fluorine atoms, in the presence of strong N-H⋅⋅⋅O=C H-bonds. Lattice energy calculations and assessment of intermolecular interaction energies elucidate the contributions of electrostatics and dispersion forces in crystal packing. The topological analysis of the electron density is characterized by the presence of bond critical points (BCPs) involving C-H⋅⋅⋅F and F⋅⋅⋅F contacts, thus establishing the bonding nature of these interactions which play a crucial role in the crystal packing in addition to the presence of traditional N-H⋅⋅⋅O=C H-bonds.

Optimization of damping function parameters for -D3 and -D4 dispersion models for Hartree-Fock based symmetry-adapted perturbation theory.

Symmetry-adapted perturbation theory (SAPT) directly computes intermolecular interaction energy in terms of electrostatics, exchange-repulsion, induction/polarization, and London dispersion components. In SAPT based on Hartree-Fock ("SAPT0") or based on density functional theory, the most time-consuming step is the computation of the dispersion terms. Previous work has explored the replacement of these expensive dispersion terms with simple damped asymptotic models. We recently examined [Schriber et al. J. Chem. Phys. 154, 234107 (2021)] the accuracy of SAPT0 when replacing its dispersion term with Grimme's popular -D3 correction, reducing the computational cost scaling from O(N5) to O(N3). That work optimized damping function parameters for SAPT0-D3/jun-cc-pVDZ using estimates of the coupled-cluster complete basis set limit [CCSD(T)/CBS] on a 8299 dimer dataset. Here, we explore the accuracy of SAPT0-D3 with additional basis sets, along with an analogous model using -D4. Damping parameters are rather insensitive to basis sets, and the resulting SAPT0-D models are more accurate on average for total interaction energies than SAPT0. Our results are surprising in several respects: (1) improvement of -D4 over -D3 is negligible for these systems, even charged systems where -D4 should, in principle, be more accurate; (2) addition of Axilrod-Teller-Muto terms for three-body dispersion does not improve error statistics for this test set; and (3) SAPT0-D is even more accurate on average for total interaction energies than the much more computationally costly density functional theory based SAPT [SAPT(DFT)] in an aug-cc-pVDZ basis. However, SAPT0 and SAPT0-D3/D4 interaction energies benefit from significant error cancellation between exchange and dispersion terms.

Driving Forces in the Formation of Paracetamol Cocrystals and Solvate with Naphthalene, Quinoline and Acridine.

Paracetamol is an important analgesic and antipyretic drug showing poor tabletability. Among the various approaches used to improve this property, understanding the forces that govern the crystal packing is revealed to be crucial. We prepared three stable compounds: (par)2∙(nap) (1), (par)∙(quin) (2), and (par)∙(acr) (3) (nap-naphthalene, quin-quinoline, acr-acridine) being cocrystals or solvate. The structural studies showed that all the reported compounds are composed of alternately arranged layers of paracetamol and coformer. Several supramolecular motifs in the paracetamol layer were identified: R44(22) in (1); R64(20) and R22(8) in (2); and R22(8), R42(12), and R44(26) rings in (3). The stability of the crystal network was studied by interactions analysis performed by Hirshfeld surface and fingerprint approaches and the energy between the closest units in the crystal network was calculated. It showed that the strongest interactions were found between blocks connected by N-H⋯O=C and O-H⋯O/N hydrogen bonds due to an important coulombic factor. The dispersive energy becomes important for tail-to-tail (and head-to-tail) arranged paracetamol units, and it prevails in the case of stacking interactions between coformer molecules. The importance of dispersive forces increases with the size of the aromatic system of the coformer. XAS studies confirmed the successful preparation of compounds and provided some details about electron structure.

Solvent Attenuation of London Dispersion in Polycyclic Aromatic Stacking.

Solvent competition for London dispersion attenuates its energetic significance in molecular recognition processes. By varying both the stacked contact area and the solvent, here we experimentally deconvolute solvent attenuation using molecular balances. Experimental stacking energies (phenyl to pyrene) correlated strongly with calculations only when dispersion was considered. Such calculations favoured stacking by up to -27 kJ mol-1 in the gas phase, but it was weakly disfavoured in our solution-phase experiments (+0.5 to +4.6 kJ mol-1). Nonetheless, the propensity for stacking increased with contact area and in solvents with lower bulk polarisabilities that compete less for dispersion. Experimental stacking energies per unit change in solvent accessible area ranged from -0.02 kJ mol-1 Å-2 in CS2, to -0.05 kJ mol-1 Å-2 in CD2Cl2, but were dwarfed by the calculated gas-phase energy of -0.6 kJ mol-1 Å-2. The results underscore the challenge facing the exploitation of dispersion in solution. Solvent competition strongly but imperfectly cancels dispersion at molecular recognition interfaces, making the energetic benefits difficult to realise.

Solvent Attenuation of London Dispersion in Polycyclic Aromatic Stacking

AbstractSolvent competition for London dispersion attenuates its energetic significance in molecular recognition processes. By varying both the stacked contact area and the solvent, here we experimentally deconvolute solvent attenuation using molecular balances. Experimental stacking energies (phenyl to pyrene) correlated strongly with calculations only when dispersion was considered. Such calculations favoured stacking by up to −27 kJ mol−1 in the gas phase, but it was weakly disfavoured in our solution‐phase experiments (+0.5 to +4.6 kJ mol−1). Nonetheless, the propensity for stacking increased with contact area and in solvents with lower bulk polarisabilities that compete less for dispersion. Experimental stacking energies per unit change in solvent accessible area ranged from −0.02 kJ mol−1 Å−2 in CS2, to −0.05 kJ mol−1 Å−2 in CD2Cl2, but were dwarfed by the calculated gas‐phase energy of −0.6 kJ mol−1 Å−2. The results underscore the challenge facing the exploitation of dispersion in solution. Solvent competition strongly but imperfectly cancels dispersion at molecular recognition interfaces, making the energetic benefits difficult to realise.

Resolving Coffee Waste and Water Pollution-A Study on KOH-Activated Coffee Grounds for Organophosphorus Xenobiotics Remediation.

This study investigates using KOH-activated coffee grounds (KACGs) as an effective adsorbent for removing organophosphorus xenobiotics malathion and chlorpyrifos from water. Malathion and chlorpyrifos, widely used as pesticides, pose significant health risks due to their neurotoxic effects and environmental persistence. Spent coffee grounds, abundant biowaste from coffee production, are chemically activated with KOH to enhance their adsorptive capacity without thermal treatment. This offers a sustainable solution for biowaste management and water remediation. Adsorption kinetics indicating rapid initial adsorption with high affinity were observed, particularly for chlorpyrifos. Isotherm studies confirmed favorable adsorption conditions, with higher maximum adsorption capacities for chlorpyrifos compared to malathion (15.0 ± 0.1 mg g-1 for malathion and 22.3 ± 0.1 mg g-1 for chlorpyrifos), highlighting its potential in mitigating water pollution. Thermodynamic analysis suggested the adsorption process was spontaneous but with the opposite behavior for the investigated pesticides. Malathion interacts with KACGs via dipole-dipole and dispersion forces, while chlorpyrifos through π-π stacking with aromatic groups. The reduction in neurotoxic risks associated with pesticide exposure is also shown, indicating that no more toxic products were formed during the remediation. This research contributes to sustainable development goals by repurposing biowaste and addressing water pollution challenges through innovative adsorbent materials.

Cuprophilic Interactions in Polymeric [Cu10O2(Mes)6]n.

The properties of cuprophilic compounds and the underlying fundamental principles responsible for the Cu(I)···Cu(I) interactions have been the subject of intense research as their diverse structural and physical attributes are being explored. In this light, we performed a new study of the compound [Cu10O2(Mes)6] reported by Haakansson et al. using state of the art experimental and theoretical analysis techniques. Doing this, we found the compound to be a polymer in the solid state, best written as [Cu10O2(Mes)6]n, with unsupported Cu(I)···Cu(I) contacts linking the monomers (2.776 Å). The monomeric unit also exhibits various cuprophilic contacts bridged by mesityl and/or oxo ligands. The compound was analyzed in its solid state, revealing luminescent properties resulting from two distinct fluorescent emissions, as well as in solution, in which its polymeric structure reversibly decomposes. A quantum theory of atoms in molecules (QTAIM) analysis based on density functional theory (DFT) calculations allows to characterize the various Cu(I)···Cu(I) contacts, in which only a few, and not necessarily the shortest, are associated with a bond critical point. Additionally, an energy decomposition analysis of the bonding between monomers indicates that it is dominated by dispersion forces in which the ligands play a dominant role, resulting in bonding energies significantly larger than found in previous DFT investigations based on less bulky models.

An Ultramicroporous Zinc‐Based Zeolitic Imidazolate Framework‐8 for the Adsorption of CO2, CH4, CO, N2 and H2: A Combined Experimental and Theoretical Study

AbstractAn alternative synthesis route to obtain ultramicroporous zeolitic imidazolate framework‐8 (ZIF‐8) is reported that is rapid and does not require organic solvent or heating. The polyethylene glycol‐templated ZIF‐8 nanoparticles (<50 nm size) exhibited a high BET (Brunauer, Emmett and Teller) surface area of 1853 m2/g, a total pore volume of 0.73 cm3/g, and 0.54 nm ultramicropores. A new approach is introduced here to better understand gas adsorption in porous metal organic frameworks (MOFs) that combines theoretical and experimental isotherm data obtained for five gases with statistical physics modelling. The multiscale analytical model reveals that the gas molecules, irrespective of their structure, adsorb in a mixed orientation at low temperature, and a parallel multi‐molecular orientation at higher temperature. The number of gas molecules adsorbed per site ranged from 0.83–2.2 while the number of adsorbent layers ranged between 1.4–5.6, depending on the gas and the temperature. The multilayer adsorption processes involved adsorption energies from 2.85 kJ/mol–9.77 kJ/mol for all gases, consistent with physisorption via van der Waals and London dispersion forces. The initial adsorption energies were higher and therefore stronger. A particularly high capacity for CO2 of 1088 mg(CO2)/g at 298 K was observed while H2 adsorption was only 9 mg(H2)/g. The other gases adsorbed at 145 mg/g–245 mg/g at 298 K. Thermodynamic functions that governed the adsorption process such as the internal energy, the enthalpy, and Gibbs free energy, are also reported, as well as the adsorption entropies, for the 5 gases.

Modeling Intermolecular Interactions with Exchange-Hole Dipole Moment Dispersion Corrections to Neural Network Potentials.

Neural network potentials (NNPs) are an innovative approach for calculating the potential energy and forces of a chemical system. In principle, these methods are capable of modeling large systems with an accuracy approaching that of a high-level ab initio calculation, but with a much smaller computational cost. Due to their training to density-functional theory (DFT) data and neglect of long-range interactions, some classes of NNPs require an additional term to include London dispersion physics. In this Perspective, we discuss the requirements for a dispersion model for use with an NNP, focusing on the MLXDM (Machine Learned eXchange-Hole Dipole Moment) model developed by our groups. This model is based on the DFT-based XDM dispersion correction, which calculates interatomic dispersion coefficients in terms of atomic moments and polarizabilities, both of which can be approximated effectively using neural networks.

Sorption interactions and behavior of bentonite-lignite based composite toward immobilization of dyes, pharmaceuticals and surfactants

The presence of dyes, pharmaceuticals, and surfactants in the environment results from extensive industrial and societal progress, prompting the need to explore efficient and safe techniques for their removal. Common concentrations in wastewater can range from micrograms to milligrams per liter, which is concerning due to their persistence and potential health impacts. The sustainable approach of using a nonconventional, eco-friendly mineral-organic composite might address this environmental issue. This study focuses on utilizing a composite of bentonite (BEN) and lignite (LIG) as a sorbent for dyes: Rhodamine b (RB), Remazol brilliant blue r (RBBR), pharmaceuticals: ibuprofen (IB), sulfamethoxazole (STX), and surfactant: sodium dodecylbenzenesulfonate (SDBS) from both synthetic solutions and real wastewater. BEN was chosen for its high cation exchange capacity, while LIG was selected for its ability to adsorb both anionic and cationic formsdiverse functional groups. The composite with BEN to LIG ratio of 20:80 (BL 20:80) demonstrated superior sorption capacity. The adsorption performance is quantified, showing removal efficiencies of up to 18.9 mg RBBR/g, 22.8 mg RB/g, 1.77 mg IB/g, 1.47 mg STX/g, and 4.7 mg SDBS/g. Sorption efficiency is influenced by factors such as the initial sorbate concentration, the pH of the solution, the form of sorbates, and the adsorbents textural, physicochemical (point of zero charge pHZPC), ion-exchange capacity, hydrophobicity/hydrophilicity) properties. Generally, STX and RB is favored by slightly acidic conditions (pH 4–7), while RBBR and IB are favored by alkaline conditions (pH > 7). The complex physical sorption mechanism includes hydrogen bonding, electrostatic and dispersion forces, as well as π-π interactions. Nuclear magnetic resonance spectroscopy (NMR) suggests that a significant portion of the hydrogen bonding interactions contributes to RB adsorption. The sorption results indicate that the specially-designed mineral composite can effectively remove various chemically distinct organic compounds from real wastewater. Subsequent investigations will focus on the granulated BL 20:80 composite and its applicability in dynamic column systems. This aligns with the ongoing development of purification technologies.

Computational fluid dynamics simulation of cryogenic vertical upflow boiling under Earth gravity

This study presents numerical simulations and their validation for flow boiling of liquid nitrogen (LN2) in a vertical upflow orientation, with a primary aim to understand the complex two-phase flow and heat transfer phenomena important to space applications. The computational fluid dynamics (CFD) model utilized the coupled level set volume of fluid (CLSVOF) method, incorporating additional source terms for bubble collision dispersion force and shear lift force in the momentum conservation equation to enhance simulation accuracy. The simulations were conducted for two mass velocities (G = 526 and 804 kg/m2s) and three different heat flux levels (approximately 10%, 30%, and 70% of critical heat flux (CHF) under Earth gravity. The model was validated against measured wall temperature data acquired from the authors’ previous experimental studies, demonstrating average deviations of less than 2.8 K across all operating conditions. The simulated two-phase flow contours illustrated various flow patterns, including bubbly, slug, churn, and annular. Both mass velocity and heat flux were observed to impact the onset of nucleate boiling (ONB), bubble nucleation, growth, and coalescence, and overall vapor structure. The simulations also offered insight into axial and radial void fraction and velocity profiles, revealing local flow acceleration trends synchronized with void fraction development. A comparison between predicted and measured bulk fluid temperature profiles showed excellent agreement, further validating the CFD model’s accuracy and practical usefulness for two-phase cryogenic flow boiling simulations in space applications.

Surface Thermodynamic Properties of Styrene–Divinylbenzene Copolymer Modified by Supramolecular Structure of Melamine Using Inverse Gas Chromatography

The surface thermodynamic properties of polymers and copolymers modified by supramolecular structures are used in several industrial processes, such as selective adsorption, paints, coatings, colloids, and adhesion applications. Background: Inverse gas chromatography at infinite dilution was proved to be the best technique to determine the surface properties of solid surfaces by studying the adsorption of some model polar and non-polar organic molecules adsorbed on solid surfaces at different temperatures. Methods: The retention volume of adsorbed solvents is a valuable parameter that was used to obtain the London dispersive and polar free energies and the London dispersive surface energy of styrene–divinylbenzene copolymer modified by supramolecular structure of melamine using both the Hamieh thermal model and our new methodology consisting of the separation of the two polar molecules and the dispersive free energy of their interaction. This led to the determination of the polar acid and base surface energy, and the Lewis acid–base constants of the various solid materials. Results: Following our new methodology, all surface energetic properties of styrene–divinylbenzene copolymer modified by melamine at different percentages were determined as a function of temperature. Conclusions: It was observed that the styrene–divinylbenzene copolymer exhibited the highest London dispersive surface energy, which decreased when the melamine percentage increased. All materials presented higher Lewis basicity and this Lewis basicity increased with the percentage of melamine.

ANN based optimization of nano-beam oscillations with intermolecular forces and geometric nonlinearity

In this study, we investigate the effect of Van der Waals and Casimir forces on the mathematical model of nano-electromechanical systems (NEMS) such as nano-beam actuators that contain cantilever and double cantilever beams. The singular nonlinear boundary value problem governing the beam-type actuators, including geometric nonlinearity is solved by using an intelligent strength of feedforward artificial neural networks (ANNs) and hybridization of optimization algorithms such as arithmetic optimization algorithm (AOA) and active set algorithm (ASA). The proposed ANN-AOA-AS algorithm is employed to quantify the effect of changes in applied voltage, dispersion forces, geometric nonlinearity parameters, and initial axial strain on the deflection of the beam. Furthermore, to validate the results obtained by the proposed algorithm, statistical analyses are conducted to compare the approximate solutions with state-of-the-art methodologies available in the latest literature. In addition, performance indicators are defined such as mean square error (MSE), Nash–Sutcliffe efficiency (NSE), mean absolute deviations (MAD), root mean square error (RMSE), and Error in Nash–Sutcliffe efficiency (ENSE) to study the accuracy and efficiency of the solutions. The results show that these indicators’ mean percentage values lie around 10−4 to 10−6 which reflects the perfect modeling of the approximate solutions.

Lead Oxide Modified Graphite Electrodes for Electrochemical Degradation of Congo Red Dye in Aqueous Solution

Congo red (CR) dye in aqueous solution was decolorized by an electrolysis process using graphite (G) and lead dioxide modified graphite (G/PbO2) as anode materials in a two-electrode batch reactor. The electrodeposited lead dioxide film was characterized by scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) and atomic force microscopy (AFM). Comparative performance assessment of the anode materials under different process parameters reveals that the lead dioxide film improved the electrocatalytic effect of the modified electrode. The adjustment of the deposition bath pH from 1.5 to 3 resulted in the formation of uniform agglomeration and disappearance of particulates, while addition of sodium dodecyl sulphate (SDS) gave better adhesion of film to substrate. The degradation rate (DR) observed for the G/PbO2 (1.0 × 10−2 cm2) was higher than that of the unmodified electrode (0.87 × 10−2 cm2). Increase in applied voltage from 25 to 30 V at 23 mA/mm2 improved the degradation efficiency (DE) from 84.7% to 91.32% for graphite and from 96.09% to 99.98% for G/PbO2, with 0.5 M KCl. The prime degradation time of 45 min was recorded for graphite anode which reduced to 30 min for G/PbO2 anode. CR degraded to compounds with smaller molecular weight and better stability as observed from GC-MS analysis and computational total energy study, respectively. The modification of the graphite electrode surface by electrodepositing PbO2 film improved the DE and the prime reaction time. These findings present significant suggestions for the design of advanced electrodeposition and electrocatalytic systems for wastewater treatment applications.

Effects of Heterogeneous Mixing of Imidazolium-Based Ionic Liquids with Alcohols on Complex Formation of Ni(II) Ion.

Understanding the complex formation of metal ions in room-temperature ionic liquids (ILs) is essential for the application of ILs in solvent extraction. Nevertheless, the research on metal complex formation in ILs lags behind other applications. The complex formation equilibria may be influenced by specific interactions among the metal ion, ligand molecule, and IL cation and anion. In the present investigation, the complex formation of Ni2+ with ethanol (EtOH) and methanol (MeOH) molecules in ILs, 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([CNmim][TFSA], where N represents the alkyl chain lengths of 2 and 8) was discussed in terms of the microscopic interactions among alcohol molecules, [CNmim]+ and [TFSA]-, and the mesoscopic mixing states of alcohols in [CNmim][TFSA], with N = 2-12. The microscopic interaction of alcohol molecules with the imidazolium ring H atoms in the ILs was evaluated by using ATR-IR and 1H and 13C NMR spectroscopies. The self-hydrogen bonding of alcohol molecules was clarified from the O-H stretching vibration of alcohol molecules. MeOH molecules can be more strongly hydrogen-bonded with themselves than EtOH molecules due to the less steric hindrance and the weaker dispersion force of MeOH with the IL cation's alkyl chain. In fact, small-angle neutron scattering (SANS) experiments revealed the more heterogeneous mixing of MeOH with the ILs by the self-hydrogen bonding among MeOH molecules than EtOH. The longer the IL cation's alkyl chain, the more the MeOH clusters significantly form. In contrast, the formation of EtOH clusters becomes weaker with elongating the alkyl chain. Ultraviolet (UV)-visible spectroscopic measurements on Ni2+-[CNmim][TFSA]-alcohol solutions with N = 2 and 8 revealed that di-, tetra-, and hexa-alcohol-Ni2+ complexes are formed in both the ILs. With N = 2, the stabilities of Ni2+-EtOH and Ni2+-MeOH complexes are comparable in the IL. However, with N = 8, the complexes are more stable in the EtOH solutions than in the MeOH solutions. This is because the less heterogeneous mixing of EtOH molecules with the IL results in the larger enthalpic contribution in the complex formation, as shown by the thermodynamic parameters estimated by the van't Hoff plots on the stability constants at several temperatures.

Quantitative analysis of intermolecular forces in cellulose microfibrils and hemicellulose with AFM nano-colloidal probes

It is an interesting research topic to study the interfacial interactions between hemicellulose and cellulose, specifically how hemicellulose's structure affects its binding to cellulose nanofibers. Our research proposes that dispersion interaction play an important role in this interfacial interaction, more so than electrostatic forces when considering the adherence of cellulose to xylan. To quantify these interactions, the Atomic Force Microscope (AFM) colloidal probe technique is applied to measure the intermolecular forces between cellulose nanofibers, which are attached to the probe and xylan. These measured forces are then analyzed in relation to the length, diameter and functional groups of the nanocellulose, as well as the molecular weight and side chains of the xylan. Moreover, the predominance of dispersion forces by contrasting the adhesive forces before and after the grafting of a large nonpolar group onto xylan. This modification significantly reduces contact between the cellulose and xylan backbone, thereby markedly diminishing the dispersion interactions. Parallel to the AFM experiments, molecular dynamics (MD) simulations corroborate the experimental results and support our hypotheses. Collectively, these findings contribute to a deeper understanding of polysaccharide interactions within lignocellulose.