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Supercapacitors have a wide range of applications in high-technology fields. The desolvation of organic electrolyte cations affects the capacity size and conductivity of supercapacitors. However, few relevant studies have been published in this field. In this experiment, the adsorption behavior of porous carbon was simulated with first-principles calculations using a graphene bilayer with a layer spacing of 4–10 Å as a hydroxyl-flat pore model. The reaction energies of quaternary ammonium cations, acetonitrile, and quaternary ammonium cationic complexes were calculated in a graphene bilayer with different interlayer spacings, and the desolvation behavior of TEA+ and SBP+ ions was described. The critical size for the complete desolvation of [TEA(AN)]+ was 4.7 Å, and the partial desolvation size ranged from 4.7 to 4.8 Å. The critical size for the complete desolvation of [SBP(AN)]+ was 5.2 Å, and the partial desolvation size ranged from 5.2 to 5.5 Å. As the ionic radius of the quaternary ammonium cation decreased, the desolvation size showed a positive trend. A density of states (DOS) analysis of the desolvated quaternary ammonium cations embedded in the hydroxyl-flat pore structure showed that the conductivity of the hydroxyl-flat pore was enhanced after gaining electrons. The results of this paper provide some help in selecting organic electrolytes to improve the capacity and conductivity of supercapacitors.

Water-insoluble cationic poly(vinyl alcohol) (PVA) films were fabricated using a mixed aqueous solution of PVA and poly([2-(methacryloyloxy)ethyl]trimethylammonium chloride (METAC)-co-methacrylic acid (MAAc)-co-5-methacrylamido-1,2-benzoxaborole (MAAmBO)) copolymer (3D). The surface of the PVA film is typically negatively charged, and simple fabrication methods for water-insoluble PVA films with cationic surface charges are required to expand their application fields. METAC, which has a permanent positive charge owing to the presence of a quaternary ammonium cation, was selected as the cationic unit. The MAAc and MAAmBO units were used as two types of cross-linking structures for the thermal cross-linking of the hydroxy and carboxy groups of the MAAc unit (covalent bonding) as well as the diol and benzoxaborole groups of the MAAmBO unit (dynamic covalent bonding). The films were thermally cross-linked at 135 °C for 4 h without the addition of materials. After immersion in surplus water at 80 °C for 3 h, the cross-linked PVA/3D films retained almost 100% of their weights. The ζ-potential of the water-insoluble PVA/3D film was 9.4 ± 0.8 mV. The PVA/3D film was strongly dyed using anionic acid red 1 (AR1) because of its positively charged surface. Interestingly, it could also be slightly dyed using cationic methylene blue (MB) and became transparent (original state) after immersion in water for 2 days. These results suggested that positive and negative charges coexisted in the PVA/3D film, and the surface properties were positively inclined. Moreover, the degree of hemolysis of the PVA/3D films was similar to that of the negative control, which showed high blood compatibility. To our knowledge, this is the first report on the fabrication of water-insoluble cationic PVA films using two types of cross-linking structures containing carboxy and benzoxaborole groups. The cross-linked PVA films were analyzed using Fourier transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC), and contact angle (CA) and ζ-potential measurement, as well as by determining the mechanical properties, adsorption of charged molecules, and biocompatibility. These readily fabricated water-insoluble PVA films with positive charges can show potential applications in sensors, adsorption systems, and antimicrobial materials.

A Good's buffer ionic liquid (GB-IL) composed of quaternary ammonium cations and Good's buffer anions is first introduced into a microemulsion system as a self-buffering and biocompatible electrolyte. The effects of the constituting ions of a GB-IL and their concentrations on the phase behavior of the anionic surfactant SDBS stabilized n-octane–H2O microemulsion system were studied for the first time using the e–β fish-like phase diagram method. The result indicates that the phase behavior of the above microemulsion system is greatly affected by GB-IL cations with a longer alkyl chain on the cation being more favorable for phase inversion. Compared with NaCl, a GB-IL of the same concentration is more efficient for achieving phase inversion, due to the dual role of an electrolyte and a co-alcohol. In addition to the phase behavior, the stability of horseradish peroxidase (HRP) solubilized in an SDBS stabilized bicontinuous microemulsion is also affected by a GB-IL. It is found that the variation of the cationic alkyl chain has a negligible effect on the microemulsion microstructure, but has a significant influence on the stability of the solubilized HRP. At a fixed concentration of the GB-IL, the quaternary ammonium cation with a longer alkyl chain is better for the stabilization of the HRP activity. For a given GB-IL, a higher level of the GB-IL results in a better HRP stability. More importantly, the GB-IL-buffered microemulsion, at the same level of the buffering salt, is more advantageous than the phosphate-buffered one for the stabilization of the HRP activity. This advantage is more pronounced for higher concentrations of the GB-IL. This difference in the HRP stability, caused by the buffering salts, should be ascribed to the microemulsion microstructure effect as well as the Hofmeister effect. The present study provides a guideline for the construction of a bicontinuous microemulsion with a simplified composition and stabilizing effect on the solubilized enzyme.

Numerous biologically active acids can be transformed into an ionic form in a facile way and combined with appropriate quaternary ammonium cation to improve their application properties or biological activity. This study describes the synthesis of new quaternary ammonium salts with anions of gibberellic acid, a common plant growth regulator from the gibberellin group, or l-tryptophan, an important precursor of auxin biosynthesis. The surface-active tetrapentylammonium ion and natural substances such as acetylcholine, choline, and quinine were the sources of cations. Novel salts of gibberellic acid and l-tryptophan were obtained with high yields exceeding 97% as a result of the metathesis reaction or the neutralization of quaternary ammonium hydroxides. Phase transition temperatures, thermal and chemical stability, and solubility in solvents with different polarities were determined for all obtained salts. On the basis of studies regarding the influence of synthesized salts on the post-harvest longevity and quality of leaves of Convallaria majalis, it was established that the biological activity of the natural plant regulators in most cases was maintained. Therefore, it can be concluded that the conversion of the active substance into the form of a quaternary ammonium salt results in obtaining novel forms of plant growth regulators with favourable physicochemical properties while maintaining the efficacy of the biological active ingredients. Graphic abstract

In this work, an artificial electrode/electrolyte (E/E) interface, made by coating the electrode surface with a quaternary ammonium cation (R4 N+ ) surfactant, was successfully developed, leading to a change in the CO2 reduction reaction (CO2 RR) pathway. This artificial E/E interface, with high CO2 permeability, promotes CO2 transportation and hydrogenation, as well as suppresses the hydrogen evolution reaction (HER). Linear and branched surfactants facilitated formic acid and CO production, respectively. Molecular dynamics simulations show that the artificial interface provided a facile CO2 diffusion pathway. Moreover, density-functional theory (DFT) calculations revealed the stabilization of the key intermediate, OCHO*, through interactions with R4 N+ . This strategy might also be applicable to other electrocatalytic reactions where gas consumption is involved.

Highly stable symmetric and asymmetric squaraine fluorophores have been synthesized featuring an internal salt bridge between a quaternary ammonium cation and the central oxycyclobutenolate ring of the chromophore. Some of our newly synthesized symmetric and asymmetric compounds display increased molar absorptivity, quantum yield in serum, and thermal/photochemical stability over previously reported squaraine-based dyes. Consequently, both classes show great promise in resurfacing the normal environment-labile squaraine dyes as novel imaging agents and scaffolds for fluorescence sensing. Furthermore, incorporating a covalent attachment point away from the conjugated system allows for biological tagging applications without disturbing the optimum optical characteristics of the newly designed fluorophore.

An extraction method employing dispersive liquid–liquid microextraction (DLLME) and ICP-OES has been developed for rapid separation, pre-concentration and determination of ultra-trace amount of Au(III). The extraction of the analyte was performed in the presence of a quaternary ammonium cation, N-Methyl-N, N, N-trioctylammonium chloride, (Aliquat 336) as an extractant based on ion-association extraction system. 1-octanol and acetonitrile were used as extraction and disperser solvents, respectively. The variables affecting the extraction conditions were optimized. Calibration curve in the range of 0.3–100 ng mL−1, the detection limit of 0.09 ng mL−1, enrichment factor of 150 and extraction recovery of 74% were obtained. The precision (R.S.D. %) of the method was 6% for 5 replicates and recoveries of 10 ng mL−1 Au(III). The combined DLLME method with ICP-OES can readily determine Au(III) at trace (μg L−1) level using only 10 mL of sample solution (tap, lake, and mining water) and ore sample without interference by the matrices. This methodology is simple, fast, and low cost which can be used in routine analytical laboratories.

Bifunctional Al-III porphyrins with quaternary ammonium halides, 2-Cl and 2-Br, worked as excellent catalysts for the copolymerization of cyclohexene oxide (CHO) and CO2 at 120 degrees C. Turnover frequency (TOF) and turnover number (TON) reached 10 000 h(-1) and 55 000, respectively, and poly(cyclohexene carbonate) (PCHC) with molecular weight of up to 281 000 was obtained with a catalyst loading of 0.001 mol%. In contrast, bifunctional Mg-II and Zn-II counterparts, 3-Cl and 4-Cl, as well as a binary catalyst system, 1-Cl with bis(triphenylphosphine)iminium chloride (PPNCl), showed poor catalytic performances. Kinetic studies revealed that the reaction rate was first-order in [CHO] and [2-Br] and zero-order in [CO2], and the activation parameters were determined: Delta H double dagger = 12.4 kcal mol(-1), Delta S double dagger = -26.1 cal mol(-1) K-1, and Delta G double dagger = 21.6 kcal mol(-1) at 80 degrees C. Comparative DFT calculations on two model catalysts, Al-III complex 2' and Mg-II complex 3', allowed us to extract key factors in the catalytic behavior of the bifunctional Al-III catalyst. The high polymerization activity and carbonate-linkage selectivity originate from the cooperative actions of the metal center and the quaternary ammonium cation, both of which facilitate the epoxide-ring opening by the carbonate anion to form the carbonate linkage in the key transition state such as TS3b (Delta H double dagger = 13.3 kcal mol(-1), Delta S double dagger = -3.1 cal mol(-1) K-1, and Delta G double dagger = 14.4 kcal mol(-1) at 80 degrees C).

In this study, a method of removing an anionic surfactant sodium dodecyl sulfate (SDS) from an aqueous solution by cellulose modified with quaternary ammonium cation was discussed. Cellulose, as the adsorbent, was obtained from medical cotton balls, and the quaternary ammonium cation (synthesized from dodecyl dimethyl tertiary amine and epichlorohydrin) was grafted onto the sixth hydroxyl group of D-glucose in the cellulose by the Williamson reaction under alkaline conditions. The modified cellulose was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS); and the zeta potential of the material was also measured after confirmation of the synthesis of quaternary ammonium salts by nuclear magnetic resonance (NMR). From these analyses, a peak of the quaternary ammonium group was observed at 1637 cm−1; and it was found that the surface of the material exhibited a positive charge in pH 2–7. The optimal conditions for SDS adsorption by modified cellulose were pH of 7, contact time of 3 h, and temperature of 60 °C in this study. Typical adsorption isotherms (Langmuir and Freundlich) were determined for the adsorption process, and the maximal adsorption capacity was estimated as 32.5 mg g−1. The results of adsorption kinetics were more consistent with the pseudo-second-order equation, indicating that the adsorption process was mainly controlled by chemical adsorption. Furthermore, thermodynamic analysis indicated that the adsorption process of SDS on the modified cellulose was endothermic and spontaneous and that an increasing temperature was conducive to adsorption.

Specific and nonspecific non-covalent molecular association of biomolecules is characteristic for electrospray-ionization mass spectrometry analysis of biomolecules. Understanding the interaction between two associated molecules is of significance not only from the biological point of view but also gas phase analysis by mass spectrometry. Here we reported a formation of non-covalent dimer of quaternary ammonium denatonium cation with +1 charge detected in the positive ion mode electrospray ionization mass spectrometry analysis of denatonium benzoate. Hydrogen deuterium exchange of amide and carbon-bonded hydrogens revealed that charge neutralization of one denatonium cation is the consequence of amide hydrogen dissociation. DFT (Density Functional Theory) calculations proved high thermodynamic stable of formed dimer stabilized by the short and strong N..H-N hydrogen bond. The signal intensity of the peak characterizing non-covalent dimer is low intensity and does not depend on the sample concentration. Additionally, dimer observation was found to be instrument-dependent. The current investigation is the first experimental and theoretical study on the quaternary ammonium ions dimer. Thus the present study has great significance for understanding the structures of the biomolecules as well as materials.

Bacterial colonization and biofilm formation on indwelling medical devices potentially cause serious and life-threatening infections. Technologies to prevent bacterial colonization and biofilm formation on biomedical devices are in great demand. Here, we report the preparation of coating monomers by conjugating rosin acid-derived maleopimaric acid quaternary ammonium cation (MPA-N+) with different chain of lengths allyloxy polyethylene glycol (APEG; either MW 1200 or 2400). The monomers of the cation plus its linker conjugates (APEG1200/2400-MPA-N+) were further grafted onto the surface of silicone rubber slides (PDMS) via plasma/UV-induced surface polymerization to form antimicrobial and antifouling coatings. The dual-functional coatings exhibited excellent antimicrobial activities against gram-negative and positive bacteria, and they effectively prevented biofilm formation. The coatings also greatly reduced protein adsorption and platelet adhesion, indicating their excellent antifouling capability. In addition, the APEG1200/2400-MPA-N+ cation coatings were biocompatible towards mammalian cells, as shown by in vitro cytotoxicity assays using rabbit erythrocytes and attached human aorta smooth muscle cells. In addition, the APEG2400-MPA-N+ coating exhibited significant anti-infective activity in a rodent subcutaneous infection model. We show that the APEG2400-MPA-N+ coating is an effective strategy for the prevention of infections associated with indwelling biomedical devices.

The ion-specific hydration states of zwitterionic poly(3-( N-2-methacryloyloxyethyl- N, N-dimethyl)ammonatopropanesulfonate) (PMAPS) brushes in various aqueous solutions were investigated by neutron reflectivity (NR) and atomic force microscopy (AFM). The asymmetric hydration state of the PMAPS brushes was verified from the NR scattering-length density profiles, while the variation in their swollen thickness was complementary as determined from AFM topographic images. PMAPS brushes got thicker in any salt solutions, while the extent of swelling and the dimensions of swollen chain structure were dependent on the ion species and salt concentration in the solutions. Anion specificity was clearly observed, whereas cations exhibited weaker modulation in ion-specific hydration states. The anion specificity could be ascribed to ion-specific interactions between the quaternary ammonium cation in sulfobetaine and the anions. The weak cation specificity was attributed to the intrinsically weak cohesive interactions between the weakly hydrated sulfonate anion in sulfobetaine and the strongly hydrated cations. The ion-specific hydration of PMAPS brushes was largely consistent with the ion-specific aggregation state of the PMAPS chains in aqueous solutions.

Molecularly imprinted polymers have emerged as cost-effective and rugged artificial selective sorbents for combination with different sensors. In this study, quaternary ammonium cations, as functional monomers, were systematically evaluated to design imprinted polymers for glyphosate as an important model compound for electrically charged and highly water-soluble chemical compounds. To this aim, a small pool of monomers were used including (3-acrylamidopropyl)trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium chloride, and diallyldimethylammonium chloride. The simultaneous interactions between three positively charged monomers and glyphosate were preliminary evaluated using statistical design of the experiment method. Afterwards, different polymers were synthesized at the gold surface of the quartz crystal microbalance sensor using optimized and not optimized glyphosate-monomers ratios. All synthesized polymers were characterized using atomic force microscopy, contact angle, Fourier-transform infrared, and X-ray photoelectron spectroscopy. Evaluated functional monomers showed promise as highly efficient functional monomers, when they are used together and at the optimized ratio, as predicted by the statistical method. Obtained results from the modified sensors were used to develop a simple model describing the binding characteristics at the surface of the different synthesized polymers. This model helps to develop new synthesis strategies for rational design of the highly selective imprinted polymers and to use as a sensing platform for water soluble and polar targets. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

Angle‐resolved X‐ray photoelectron spectroscopy and contact‐angle measurements guided by a signal attenuation model are utilized to extract molar composition and anion enrichment in the vacuum interface of a binary ionic liquid mixture, having a common quaternary ammonium cation and two different anions. By using the intensity ratio of the F1s peaks belonging to the two different anions recorded at the full electron take‐off angle range, from 0° to 80°, we have determined that only a fractionally covered and anion enriched surface layer can predict the AR‐XPS data, which is also consistent with surface tension measurements. Moreover, the more bulky and non‐spherical anion enrichment is evident even at the conventional and the so assumed bulk sensitive take‐off angle of 0°. This methodology provides a surface enrichment factor of the molecular ions and clearly serves as an experimental evidence for recently debated surface layering and/or island structure in ionic liquid systems.

A co-crystal of rosiglitazone (Rsg) with berberine (Bbr), Rsg-Bbr, was prepared by the solvent evaporation method and characterized. The results showed that the electrostatic attraction existed between the nitrogen anion of rosiglitazone and the quaternary ammonium cation of berberine, and C-H&middot, &middot, O hydrogen bonds were formed between Rsg and Bbr. In the crystal structure, rosiglitazone molecules stack into a supramolecular layer through &pi, &pi, interactions while &pi, interactions between berberine cations also result in a similar layer. The co-crystal presented a low moisture adsorption curve in the range of 0&minus, 95% relative humidity values at 25 &deg, C. The improved dissolution rate of rosiglitazone in pH = 6.8 buffer solution could be achieved after forming co-crystal.

Montmorillonite clays could be promising sorbents to mitigate toxic compound exposures. Bisphenols A (BPA) and S (BPS) as well as phthalates, dibutyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP), are ubiquitous environmental contaminants linked to adverse health effects. Here, we combined computational and experimental methods to investigate the ability of montmorillonite clays to sorb these compounds. Molecular dynamics simulations predicted that parent, unamended, clay has higher binding propensity for BPA and BPS than for DBP and DEHP; carnitine-amended clay improved BPA and BPS binding, through carnitine simultaneously anchoring to the clay through its quaternary ammonium cation and forming hydrogen bonds with BPA and BPS. Experimental isothermal analysis confirmed that carnitine-amended clay has enhanced BPA binding capacity, affinity and enthalpy. Our studies demonstrate how computational and experimental methods, combined, can characterize clay binding and sorption of toxic compounds, paving the way for future investigation of clays to reduce BPA and BPS exposure.

The preference of open chain of growing macromolecule vs. possible cyclic form was examined for the bifunctional cobalt(III)-salen catalyst for the copolymerization of CO2 with epoxides. A variety of possible isomers was considered (resulting from trans/cis-β salen arrangement, different mutual orientation of quaternary ammonium-chains, and possible binding modes). To explore the conformational space, a combined approach was applied, utilizing semiempirical (PM7) MD and the DFT calculations. The preference of the open and cyclic macromolecules attached to the metal center was compared with the corresponding results for isolated model macromolecules, and the systems built of the macromolecule interacting with the tetra-butyl ammonium cation. Result shows that the cyclic structures are strongly preferred for isolated ions, with relatively low cyclization barriers. In the field of positive point charge, the open structures are strongly preferred. For the ions interacting with tetrabutyl ammonium cation, the cyclic structures are preferred, due to delocalization of the positive charge in the cation. For the complexes involving model and “real” Co(III)-salen catalysts, the open structures are strongly preferred. The possible cyclization by dissociation of alkoxide and its transfer to the neighborhood of quaternary ammonium cation is characterized by high activation barriers. Further, the transfer of alkoxide from the metal center to the cation is less likely than the transfer of carbonate, since the metal-alkoxide bond-energy energy is much stronger than energy of metal-carbonate bonding, as shown by ETS-NOCV results. The conclusions are in qualitative agreement with experimental data showing high selectivity towards copolymer formation in the copolymerization processes catalyzed by bifunctional Co(III) salen-complexes.

Despite advanced sterilized and aseptic techniques, biomaterial-associated infections are still posing a great threat to human life. Therefore, constructing antimicrobial coating that exerts potent antimicrobial activity combined with low cytotoxicity is of great significance. Herein, an antimicrobial coating on the surface of silicone elastomer (PDMS) has been successful constructed, which based on maleopimaric acid quaternary ammonium cation (MPA-N+). The surface morphology and chemical composition of modified PDMS (PDMS-g-MPA-N+) were confirmed by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), and X-ray photoelectron spectroscopy (XPS). The PDMS-g-MPA-N+ possess excellent antimicrobial activity against both Gram-positive bacterial (Staphylococcus aureus) and Gram-negative bacterial (Escherichia coli, Pseudomonas aeruginosa) strains. In addition, confocal laser scanning microscopy imaging demonstrated that it also can effectively inhibit bacterial biofilm formation over 5 days. Most importantly, PDMS-g-MPA-N+ exhibited excellent biocompatibility, which induced no significant hemolysis and cytotoxicity toward mammalian cells. The study demonstrated that the silicone elastomer surface grafted with MPA-N+ enabled the incorporation of a renewable biomass to effectively combat bacteria and biofilm formation for biomedical applications. Keywords: Quaternary ammonium salt, Rosin acid, Antimicrobial coating, Healthcare, Biocompatibility

Attempt has been made to explain why different aliphatic quaternary ammonium tribromides (QATBs) show different levels of efficiency in bromination reactions. For this study, tetrabutyl ammonium tribromide (TBATB, [N(C4H9)4]Br3), and cetyl trimethyl ammonium tribromide (CTMATB, [N(CH3)3C16H33]Br3) were used as representative examples. UV–Vis Spectroscopic method was employed to measure the thermodynamic parameters of the reactions. Influence of quaternary ammonium cation on tribromide (Br3−) performance was assessed with the aid of Density Functional Theory (B3LYP/6-311++G(d,p)) by determining the dissociation energy of the QATBs, energies of pairs of their frontier orbitals, which are HOMO and LUMO and calculation of dipole moments.

In this work, methacrylate-type ionic liquid (IL) monomers containing a quaternary ammonium cation and two different counter-anions were synthesized and used as co-monomers to obtain functional poly(alkyl methacrylates) (PAMAs). They were then evaluated as friction and wear reducing additives for lubricants. The effect of molecular weight, polymer topology (random or diblock), and IL counter anion on friction and wear behavior of polymer PAO (poly-alpha olefin) solutions have been investigated. The results were compared to those of PAO solutions additized with a small molecule, non-polymeric ionic liquid, or non-ionic copolymers containing 2-(dimethylamino)ethyl methacrylate (DMAEMA) as the polar comonomer. No clear correlation between polymer molecular weight and friction or wear behavior was observed. Random ionic liquid copolymers led to lower wear volumes than their block counterparts. Polymers containing dicyanamide (DCA) counter anion showed lower wear volume compared to those containing bis((trifluoromethyl)sulfonyl)imide (TFSI) anion. Surprisingly, none of the IL copolymers studied outperformed the DMAEMA containing block copolymer in terms of wear volume reduction, suggesting the IL moiety had no beneficial effect on wear.

Adsorption processes of 4GL on two different bentonite-based sorbents were compared: i) Sodium-bentonite in the presence of a cationic surfactant CTAMB; ii) organobentonite alone. This latter was prepared by exchanging the inorganic cation of bentonite with a quaternary ammonium cation at 100% of the clay's CEC. Batch adsorption studies were conducted to evaluate the effect of various parameters such as the quaternary ammonium cation (CTAMB) loading, contact time and initial 4GL concentration. From the kinetic study, it is interesting to note that Organobentonite exhibits faster kinetics compared to Na-bentonite/CTAMB system. The comparison between isotherm plots makes clear that the presence of CTAMB in solution changes the 4GL isotherm. Compared to organobentonite, the adsorption capacity is higher when CTAMB was present in solution. In this case, the results of 4GL adsorption by bentonite obey to Langmuir model. While for organobentonite, all models seem to be applicable. The difference between the two methods is confirmed by XRD analysis. The performance shown by Organobentonite and Na-bentonite/CTAMB system was suitable compared to other adsorbents, reflecting a promising future utilization in wastewater treatment.