Exploring the Effect Mechanism of Alkyl Chain Lengths on the Tribological Performance of Ionic Liquids
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ABSTRACT:
SUBMITTER: Huang G
PROVIDER: S-EPMC10809665 | biostudies-literature | 2024 Jan
REPOSITORIES: biostudies-literature
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Project description:The effects of alkyl chain length on the crystallization kinetics and ion mobility of tetraalkylphosphonium, [P666,n][TFSI], (n = 2, 6, 8, and 12) ionic liquids were studied by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS) over a wide temperature range. The liquid-glass transition temperature (Tg) and ion dynamics examined over a broad T range were almost insensitive to structural modifications of the phosphonium cation. In contrast, the crystallization kinetics were strongly affected by the length of the fourth alkyl chain. Furthermore, the thermal history of the sample (cold vs melt crystallization) significantly impacted the crystallization rate. It has been found that the nature of crystallization phenomena is the same across the homologous series, while the kinetic aspect differs. Finally, electric conductivity in supercooled liquid and crystalline solid phases was measured for all samples, revealing significant ionic conductivity, largely independent of the cation structure.
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Project description:Ionic liquids (ILs) have become nearly ubiquitous solvents and their interactions with biomolecules has been a focus of study. Here, we used the fluorescence emission of DAPI, a groove binding fluorophore, coupled with molecular dynamics (MD) simulations to report on interactions between imidazolium chloride ([Imn,1]+) ionic liquids and a synthetic DNA oligonucleotide composed entirely of T/A bases (7(TA)) to elucidate the effects ILs on a model DNA duplex. Spectral shifts on the order of 500-1000 cm-1, spectral broadening (~1000 cm-1), and excitation and emission intensity ratio changes combine to give evidence of an increased DAPI environment heterogeneity on added IL. Fluorescence lifetimes for DAPI/IL solutions yielded two time constants 0.15 ns (~80% to 60% contribution) and 2.36-2.71 ns for IL up to 250 mM. With DNA, three time constants were required that varied with added IL (0.33-0.15 ns (1-58% contribution), ~1.7-1.0 ns (~5% contribution), and 3.8-3.6 ns (94-39% contribution)). MD radial distribution functions revealed that π-π stacking interactions between the imidazolium ring were dominant at lower IL concentration and that electrostatic and hydrophobic interactions become more prominent as IL concentration increased. Alkyl chain alignment with DNA and IL-IL interactions also varied with IL. Collectively, our data showed that, at low IL concentration, IL was primarily bound to the DNA minor groove and with increased IL concentration the phosphate regions and major groove binding sites were also important contributors to the complete set of IL-DNA duplex interactions.
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Project description:In this paper we report the effects of five imidazolium cations with varying alkyl chain lengths to study the effects of cation size on capacitance versus voltage behavior. The cations include ethyl-, butyl-, hexyl-, octyl-, and decyl-3-methylimidazolium, all paired with a triflate anion. We analyze the capacitance with respect to the cation alkyl chain length qualitatively and quantitatively by analyzing changes in the capacitance-potential curvature shape and magnitude across several standard scanning protocols and electrochemical techniques. Further, three transport properties (viscosity, diffusion coefficient, and electrical conductivity) are experimentally determined and integrated into the outcomes. Ultimately, we find higher viscosities, lower diffusion coefficients, and lower electrical conductivities when the alkyl chain length is increased. Also, capacitance values increase with cation size, except 1-octyl-3-methylimidazolium, which does not follow an otherwise linear trend. This capacitive increase is most pronounced when sweeping the potential in the cathodic direction. These findings challenge the conventional hypothesis that increasing the length of the alkyl chain of imidazolium cations diminishes the capacitance and ionic liquid performance in charge storage.
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Project description:The light-modulated isomerization and aggregation behavior of ionic liquids (ILs) in aqueous solutions holds fundamental and technological significance. Although several azobenzene-based photoresponsive ILs have been synthesized, there is still a lack of understanding regarding the aggregation mechanism, regularity of the alkyl chain length, and the position of the azobenzene (cis- and trans-) in these photoresponsive ILs. To elucidate the structure-property relationship of photoresponsive ILs, four types of azobenzene groups photosensitive ILs ([AzoCnDMEA]Br, n = 2,4,6,10) in both trans- and cis- configurations were investigated by density functional theory (DFT) calculations. We investigated the geometric properties of cations, H-bonds interactions of ionic pairs, microstructures of clusters, and the interactions between ILs and water molecules. It was found that the molecular volume of cis- is smaller than that of trans- cation structures. Despite multiple H-bonds between the anions and the ammonium group of cations, longer alkyl chains weaken anion-cation interactions. The interaction energies of trans- n[AzoC2DMEA]Br (1 ≤ n ≤ 4) clusters are stronger than those of cis-. Moreover, the interaction energy between trans-structures of photoresponsive ILs and water molecules is smaller than that of cis- structures based on the DFT calculations. The interaction energies per water molecule in the ILs-water clusters tend to saturation as the number of water molecules increases. The electrostatic interaction plays a crucial role in the stabilization of ILs and water systems. The structure-property relationship of photoresponsive ILs including the regularity of the alkyl chain length and the azobenzene position as well as the microscopic interaction mechanism of ILs and ILs-water clusters had been studied from theoretical calculation perspective. This work can contribute to an in-depth understanding of the microcosmic interactions of azobenzene-based photoresponsive ILs and aid in designing them in a "task-specific" way.
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Project description:Due to their ultrathin 2D laminated structure as well as excellent mechanical and thermal stabilities, ultrafine graphene-based nanoparticles exhibit fascinating advantages as highly-efficient lubricant additives. However, it remains a daunting challenge to achieve good and durable dispersion of these graphene-based nanoparticles in lubricating oils. Herein, we report a facile and efficient integration strategy involving particle size miniaturization, surface grafting with octadecyl alcohol (OA), and partial chemical reduction to prepare a novel long-chain alkyl functionalized ultrafine reduced graphene oxide (RGO-g-OA) with highly-dispersive capacity and superior tribological performance. The chemical composition and structural characteristics, microstructural morphology, and particle size distribution of RGO-g-OA were systematically investigated. Combining significantly improved lipophilicity derived from the long-chain alkyl grafting and partial chemical reduction with the small-size effect gave rise to outstanding long-term dispersion stability (as long as one month) of RGO-g-OA in the finished oil. Moreover, the friction coefficient and wear volume of finished oil with merely 0.005 wt% RGO-g-OA greatly reduced to 0.065 and 10 316 μm3, decreased by 9.7% and 44%, respectively, compared to those of pristine finished oil, demonstrating remarkable friction reduction and anti-wear performances. Consequently, owing to the characteristics of facile fabrication, durable dispersion stability, and superior tribological performance at an extremely low content, this novel nanoadditive shows a promising application potential in the tribology field.
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Project description:This work investigated the effect of the alkyl chain length of soluble methylimidazolium bromide ionic liquids (ILs) on their inhibition performance. The IL with a shorter alkyl chain length showed superior inhibition performance by suppressing clay swelling, mitigating clay dispersion, at room temperature. Particularly, the IL with an alkyl chain length of two (EmBr) reduced the sodium bentonite (Na-BT) swelling degree to 89% and achieved a cutting recovery of 81.9% after being rolled at room temperature, performing the best among all ILs. To systematically analyze the inhibition mechanism of ILs, X-ray diffraction (XRD), ζ potential, and particle size distribution have been carried out. The results revealed that the methylimidazolium with shorter alkyl chain length had better ability to enter the interlayer void by ion exchange and decrease interlayer distance, suppress the electrical double layer of the Na-BT particles and decrease the ζ potential, and promote the aggregation of Na-BT in water. It is also observed that high hot rolling temperature reduced the shale inhibiting performance of all ILs, and ILs with longer alkyl chain length had better ability to prevent cutting disintegration at high temperature. It is attributed to the variation of the hydrophilic characteristic of Na-BT at high temperature where EmBr no longer adsorbed the most on the surface and entered the interlayer voids of Na-BT. This study can be used as a reference to systematically explore the effect of the structure of shale inhibitors on their inhibiting performance and develop effective shale inhibitors.
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Project description:Solvents that stabilize protein structures can improve and expand their biochemical applications, particularly with the growing interest in biocatalytic-based processes. Aiming to select novel solvents for protein stabilization, we explored the effect of alkylammonium nitrate protic ionic liquids (PILs)-water mixtures with increasing cation alkyl chain length on lysozyme conformational stability. Four PILs were studied, that is, ethylammonium nitrate (EAN), butylammonium nitrate (BAN), hexylammonium nitrate (HAN), and octylammonium nitrate (OAN). The surface tension, viscosity, and density of PIL-water mixtures at low to high concentrations were firstly determined, which showed that an increasing cation alkyl chain length caused a decrease in the surface tension and density as well as an increase in viscosity for all PIL solutions. Small-angle X-ray scattering (SAXS) was used to investigate the liquid nanostructure of the PIL solutions, as well as the overall size, conformational flexibility and changes to lysozyme structure. The concentrated PILs with longer alkyl chain lengths, i.e., over 10 mol% butyl-, 5 mol% hexyl- and 1 mol% octylammonium cations, possessed liquid nanostructures. This detrimentally interfered with solvent subtraction, and the more structured PIL solutions prevented quantitative SAXS analysis of lysozyme structure. The radius of gyration (Rg) of lysozyme in the less structured aqueous PIL solutions showed little change with up to 10 mol% of PIL. Kratky plots, SREFLEX models, and FTIR data showed that the protein conformation was maintained at a low PIL concentration of 1 mol% and lower when compared with the buffer solution. However, 50 mol% EAN and 5 mol% HAN significantly increased the Rg of lysozyme, indicating unfolding and aggregation of lysozyme. The hydrophobic interaction and liquid nanostructure resulting from the increased cation alkyl chain length in HAN likely becomes critical. The impact of HAN and OAN, particularly at high concentrations, on lysozyme structure was further revealed by FTIR. This work highlights the negative effect of a long alkyl chain length and high concentration of PILs on lysozyme structural stability.
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Project description:Self-assembled monolayers (SAMs) of organic molecules are frequently employed to improve the electrical performance of organic field-effect transistors (OFETs). However, the relationship between SAM properties and OFET performance has not been fully explored, leading to an incomplete understanding of the system. This study investigates the effect of the SAM alkyl chain length on the crystalline phase of pentacene films and OFET performance. Two types of SAMs-with alkyl chain lengths of 10 (decyltrichlorosilane, DTS) and 22 (docosyltrichlorosilane, DCTS)-were examined, and variations in the performance of pentacene-based OFETs with the nature of the SAM treatment were observed. Despite the similar surface morphologies of the pentacene films, field-effect mobility in the DCTS-treated OFET was twice that in the DTS-treated OFET. To find the reason underlying the dependence of the OFET's electrical performance on the SAM alkyl chain length, X-ray diffraction measurements were conducted, followed by a phase analysis of the pentacene films. Bulk and thin-film phases were observed to coexist in the pentacene film grown on DTS, indicating several structural defects in the film; this can help explain the dependence of the OFET electrical performance on the SAM alkyl chain length, mediated by the different crystalline phases of pentacene.
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Project description:An electrochemical sensor was fabricated utilizing ionic liquids possessing cations with long alkyl chains such as trimethyl octadecylammonium and behenyl trimethylammonium and ascorbate anion. The ionic liquids were drop-coated onto the electrode. Thin modifying layers were prepared. Cyclic voltammetric investigations revealed electrostatic interactions between the electrochemical probes and the modified surface, proving that a positive charge was established at the film surface. Hence, negatively charged species such as nitrite can be pre-concentrated on the surface of presented modified electrodes. The fabricated electrodes have been used as a voltammetric sensor for nitrite. Due to the electrostatic accumulation properties of long alkyl cation, the assay exhibits a remarkable improvement in the voltammetric response toward nitrite oxidation. The influence of pH on the electrode response was thoroughly investigated, and the mechanism of the electrode was established. The developed sensor showed a linear electrochemical response in the range 1.0-50 μM with a detection limit of 0.1 μM. The electrode revealed good storage stability, reproducibility, and anti-interference ability. The determination of nitrite performed in curing salts brought satisfactory results.
| S-EPMC7838138 | biostudies-literature
Project description:To explore green gold leaching reagents, a series of imidazolium cyanate ionic liquids (ILs), 1-ethyl-3-methyl-imidazolium cyanate ([C2MIM][OCN]), 1-propyl-3-methyl-imidazolium cyanate ([C3MIM][OCN]) and 1-butyl-3-methyl-imidazolcyanate ([C4MIM][OCN]) were synthesized and characterized by Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR) and thermogravimetric (TG) analysis. In this research, the imidazolium cyanates were utilized as a solute, which not only decreased the usage of ILs but also increased their gold dissolution capability. The gold dissolution performances of three imidazolium cyanates were characterized by dynamic leaching test and Scanning Electron Microscopy (SEM). The results show that the all three imidazolium cyanates had a gold dissolution ability, and the shorter the carbon chain on the imidazole ring in imidazolium cyanate, the faster the gold dissolution rate. The gold dissolution performance of [C2MIM][OCN] was the best, and the weight loss of gold leaf was 2.9 mg/cm2 at 40 °C after 120 h dissolution in [C2MIM][OCN] mixed with 10 wt. % water. Besides this, the gold dissolution rate increased with the increase in the concentration of imidazolium cyanates as well as the reaction temperature. The gold dissolution performances of imidazolium cyanates in different solvents including water, acetonitrile, dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) were also investigated, and the weaker the polarity of the solvent, the more conducive it was to the gold dissolution reaction. The mechanism of gold dissolution by imidazolium cyanates was investigated through NMR spectroscopy and Electrospray Ionization Mass Spectrometry (ESI-MS). It was inferred that during the process of gold dissolution, Au was oxidized to Au+ and the imidazolium cations were deprotonated to form N-heterocyclic carbenes, which coordinated with gold to form gold complexes and achieve gold dissolution.
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