Organic Counterions Research Articles

Investigation the binding and partition properties of azithromycin drug using drug-surfactant mixed micelles in the presence of trisodium citrate electrolyte

The significance of mixed micelle in pharmaceutical industries is improving the binding and solubility of poorly water-soluble drugs. This work highlighted the effect of organic counterion (NAC) for improving the micellization association of zwitterionic (CAPB) and cationic drug (DPC) by surface tension measurements. The Corrin–Harkins (CH) approach assessed the CAPB, DPC and CAPB-DPC counterion binding values for DPC in the aqueous and NAC media at 25 °C. The counterion binding B for CAPB-DPC from αDPC 1.0–0.0 was found 0.536, 0.3801, 0.368, 0.355, 0.310 and 0.272 in the presence of NAC which indicated that DPC improved the counterion binding in the mixed micellar system. The Gibb’s free energy of micellization (ΔGmic°) were increased and became more negative, suggesting that the CAPB–DPC interaction was controlled by electrostatic interaction. Furthermore, the application of mixed micelle was utilized to enhance the binding constant (LogKb) and partition coefficient (LogKx) of the poorly water-soluble drug (AZI) in aqueous and NAC media at 25 °C using a UV spectrophotometer. From UV spectra, The LogKb and LogKx of AZI were lower in single micellar systems and higher in mixed micellar systems of CAPB-DPC. The maximum LogKb values at αDPC 0.4 were found 3.091, 3.233, 3.417, and 3.368 and LogKx values were found 4.749, 4.919, 5.087 and 5.049 in the presence of 0.0, 0.5, 3.0 and 20 mmol L−1 of NAC. AZI molecules are found in the palisade layer of mixed micelle when the DPC mole fraction is less than αDPC 0.6, while more than αDPC 0.6 causes steric hindrance, increasing hydrophobicity in the system. Furthermore, surfactant-drug mixed micelles could serve as poorly drug-solubilizing agents, as well as a multidrug delivery system in pharmaceutical applications.

Guanidinium and spermidinium decavanadates: as small biomimetic models to understand non-covalent interactions between decavanadate and arginine and lysine side chains in proteins

During the last three decades, numerous investigations have been conducted on polyoxidovanadates to treat several illnesses and inhibit enzymes. Numerous decavanadate compounds have been proposed as potential therapies for Diabetes mellitus, Cancer, and Alzheimer’s disease. Only six relevant functional proteins interacting with decavanadate, V10, have been deposited in the PDB. These are acid phosphatase, tyrosine kinase, two ecto-nucleoside triphosphate diphosphohydrolases (NTPDases), the human transient receptor potential cation channel (TRPM4), and the human cell cycle protein CksHs1. The interaction sites in these proteins mainly consist of Arginine and Lysine, side chains binding to the decavanadate anion. To get further knowledge regarding non-covalent interactions of decavanadate in protein environments, guanidinium and spermidinium decavanadates were synthesized, crystallized, and subjected to analysis utilizing various techniques, including FTIR, Raman, 51V-NMR, TGA, and X-ray diffraction. The DFT calculations were employed to calculate the interaction energy between the decavanadate anion and the organic counterions. Furthermore, the Quantum Theory of Atoms in Molecules (QTAIM) and Non-covalent Interaction-Reduced Density Gradient (NCI-RDG) analyses were conducted to understand the non-covalent interactions present in these adducts. Decavanadate can engage in electrostatic forces, van der Waals, and hydrogen bond interactions with guanidinium and spermidinium, as shown by their respective interaction energies. Both compounds were highly stabilized by strong hydrogen bond interactions N−H···O and weak non-covalent interactions C−H···O. In addition, the interactions between guanidinium and spermidinium cations and decavanadate anion form several stable rings. This study provides new information on non-covalent intermolecular interactions between decavanadate and small biomimetic models of arginine and lysine lateral chains in protein environments.

Influence of critical micelle concentration of choline-based long chain fatty acid soaps on their antibacterial activity against Methicillin resistant Staphylococcus aureus

HypothesisAntimicrobial resistance (AMR) is a pressing global health concern. ESKAPEE pathogens, such as Methicillin-resistant Staphylococcus aureus (MRSA) are notable of concern in healthcare settings due to their resistance to critical antibiotics. To combat AMR, the development of alternatives such as bacterial membrane-active agents is crucial. Fatty acids (FAs) have emerged as a sustainable, antibiotic-free solution with inherent antibacterial activity. However, long chain saturated fatty acids (LCFAs) sodium soaps exhibit poorly antibacterial properties in comparison to short chain FAs, believed to be linked to limited solubility in aqueous media. ExperimentsWe employed choline as a chaotropic organic counter-ion to enhance the solubility of LCFAs and investigated their antibacterial effects against MRSA. The optimal medium conditions for micelle formation for LCFAs was first investigated. Then, we determined the critical micelle concentration (CMC), micellar morphology, and aggregation number through surface tension measurements and small angle neutron scattering experiments. Antimicrobial activity was assessed using minimum bactericidal concentration (MBC) assays and time-kill experiments. FindingsWe have identified conditions where LCFAs are effective against MRSA for the first time, providing valuable insights for developing new antibacterial agents to fight AMR. LCFAs need to be used above their Krafft temperatures and CMC to exhibit antibacterial efficacy.

Preparation of a class of cucurbit[6]uril-light rare-earth-based supramolecular assemblies and its efficient detection of chloramphenicol

By introducing 4,4′-naphthalenedisulfonic acid (4,4′-H2BPs) as a structure-induced agent, four novel cucurbit[6]uril-based supramolecular assemblies have been successfully prepared in the cucurbit[6]uril (Q[6]) system with light rare-earth elements (La3+, Ce3+, Pr3+, Nd3+) under hydrothermal conditions. Crystal structure analysis shows that the assemblies 1 (La3+), 2 (Ce3+), 3 (Pr3+) are isomorphism 3D frameworks, where Q[6] can directly coordinate with light rare-earth metal ions to form 1D −Ln(III)- Q[6]-Ln(III)- chains, while the 4 (Nd3+) presents 3D structures stacking by the unit of Q[6]@Nd3+@Q[6]@Nd3+@Q[6], respectively. In these structures, 4,4′-H2BPs ligands all can act as an organic counter anion and bridging via the outer-surface interaction of cucurbit[n]uril (OSIQ) in the system, which is the main driving force from low-dimensional to high-dimensional. Meanwhile, the fluorescence sensing performance of the two assemblies for antibiotics was investigated, and the results showed that assembly 1 could be used as a promising fluorescent sensor material to detect chloramphenicol (CAP).

Unusual bending patterns of spermidine3+ bound to DNA double helix

Natural polyamines play a fundamental role in the cell cycle. Despite being recognized as the most abundant organic counterions of DNA in the cell nucleus, their interactions with DNA have not been fully characterized. In a recent work [S. Perepelytsya, T. Vasiliu, A. Laaksonen, L. Engelbrecht, G. Brancato, and F. Mocci, J. Molec. Liq.389, 122828 (2023)], we have shown how the interactions between spermidine3+ and the DNA double helix induce significant conformational variations in the polyamine molecule. Specifically, we found that DNA induces conformations that are not observed in solution. Following that study, we present here a detailed investigation of the most compact conformation of the polyamine, analyzing its connection to the interaction with the DNA duplex. The analysis reveals that anomalous bent conformations of the spermidine3+ molecule result from the interaction of all three amino groups of the polyamine with the DNA phosphate groups on the minor groove side of the double helix. The changes in dihedral angles of the bent spermidine3+ molecule can be explained in terms of conformational transformations of six- and seven-membered rings, analogous to cyclohexane and cycloheptane. The analysis of the position of spermidine3+ molecule along the DNA surface reveals a sequence specificity of this binding mode with a marked preference for the narrow minor groove of A-tracts. The formation of the anomalous bent conformations of spermidine3+ in the complex with the DNA double helix is expected to be of paramount importance in understanding the mechanisms underlying DNA’s biological function.

Quantitative Scrolling into Microporous Nanotubes of the Hydrous Layered Silicate Ilerite

AbstractThe synthetic hydrous layered silicate ilerite was quantitatively converted into microporous nanoscrolls (NS). Delamination of ilerite that was ion‐exchanged for N‐Methyl‐D‐glucaminium (Meg+), through one‐dimensional (1D) dissolution initially yields lamellar liquid crystalline (nematic) suspensions. Subsequent protonation with acetic acid of tangling Si‐O− to silanol groups reduces the pH‐dependent charge of the basal surfaces. Complete NS formation is then triggered by diluting the nematic suspension below 0.05 wt%. As scrolling commonly has been attributed to hydrophobic interaction of organic counterions, Meg+ was replaced by lithium ions but this showed no detrimental effect on the scrolling efficiency. The resulting NS have a typical length of 2–4 μm that corresponds well with typical diameters of the parent nanosheets. Ar‐physisorption isotherms showed a bimodal micropore size with maxima around 0.8 and 1.9 nm. We attribute the first to the tubular hollow inner diameter of the NS and the latter to wedgelike interparticle porosity. The material showed a large specific surface area of 226 m2 g−1.

Aryl selenonium vs. aryl sulfonium counterions in polyoxometalate chemistry: the impact of Se+ cationic centers on the photocatalytic reduction of dichromate.

A selenonium organic counter ion has been used in polyoxometalate chemistry to develop a new aryl selenonium polyoxometalate (POM) hybrid, and its photocatalytic properties have been explored in comparison with an aryl sulfonium POM-hybrid counterpart for the first time. The chalcogenonium counterions, namely, methyldiphenylsulfonium trifluoromethane sulfonate (MDPST) and methyldiphenylselenonium trifluoromethane sulfonate (MDPSeT), and their octamolybdate ([Mo8O26]4-) hybrids, 1 and 2, with the general formula (C13H13X)4[Mo8O26] (where X = S for 1 and Se for 2) were synthesized and characterized. Hybrids 1 and 2 vary in their chalcogenonium cationic center (S+vs. Se+), which enabled a direct comparison of their photocatalytic properties as a function of the cationic center. The photocatalytic activities of hybrids 1 and 2 were tested using the reduction of dichromate (Cr2O72-) as a model reaction under UV irradiation. A 99% photocatalytic reduction of Cr2O72- with a rate constant of 0.0305 min-1 was achieved with hybrid 2, while only a 67% reduction with a rate constant of 0.0062 min-1 was observed with hybrid 1 in 180 minutes. The better catalytic performance of hybrid 2 may be correlated to the larger atomic radii of Se than S, which helps in better stabilizing the photogenerated electron-hole (e--h+) pair on the POM cluster by polarizing its lone pair more efficiently compared to S. The catalytic recyclability was tested for up to 4 cycles using hybrid 2, and up to 98% reduction was obtained even after the 4th cycle. Recyclability tests and control experiments also indicated the generation of some elemental Se through possible cleavage of some C-Se bonds of MDPSe under prolonged UV exposure during catalysis, and the Se thus generated was found to contribute to the catalytic reduction of dichromate. This study, therefore, opens new avenues for aryl selenonium moieties and their POM hybrids for potential catalytic applications.

Exploring a new creatininium crystalline salt with succinic acid organic counterion: Structural establishment, spectroscopic analysis and theoretical simulation

This study elucidates the structural, vibrational, and electronic properties of a novel proton-transfer system derived from creatinine and succinic acid named bis (creatininium) succinate (I). Fourier maps and geometric evaluations confirm protonation at the imine sites. Spectroscopic analyses, involving both IR and Raman techniques, were conducted, highlighting the vibrational characteristics of key functional groups. The theoretical predictions of structural parameters and vibrational frequencies align well with experimental findings. Frontier Molecular Orbital analysis emphasized the distinct localization of HOMO and LUMO, hinting at potential intramolecular charge transfers. Molecular Electrostatic Potential maps provided a visual testament to regions of electron density and scarcity, offering predictive insights into reactivity. Hirshfeld surface analysis and fingerprint plots further illuminated the intermolecular interactions within the crystal structure, underscoring the significance of hydrogen bonding in lattice cohesion. The results present a comprehensive understanding of the compound's behaviour, potentially impacting fields demanding molecular stability and specificity.

Effect of different counterions on the self-assembly structures and properties of imidazole based ionic liquids surfactant: A molecular dynamics study

Self-assembly of ionic liquids (ILs) in solution has attracted wide attention due to their potential applications in various fields. The nature of counterions, especially aromatic counterions, will significantly affect the aggregation and morphological properties of ILs surfactants. In this paper, molecular dynamics (MD) simulations are applied to study the influence of three organic and inorganic counterions (phenolate (PO−), benzoate (BZ−), and Cl−) on the micellar structure of imidazolium (C14mim+) based ILs surfactant in aqueous solutions. Three micelles all possess prolate shape. The PO−, BZ−, and Cl− ions hardly affect the orientation and length of hydrophobic chains in micellar interior. Hydration numbers and average radial density distributions analyses show that interactions between micelles and water molecules are different in studied micelles. Surrounding water molecules penetrate into the deepest region in [C14mim][Cl] micelle. However, adsorbed Cl− ions are mainly located on micellar surface, not penetrating into micellar interior. Due to the intrinsic hydrophobicity of organic ions, both PO− and BZ− ions enter into deeper positions in micelles. Unlike Cl− ions, there exist π-interactions between adsorbed PO− and BZ− ions themselves. One interesting finding is that adsorbed PO− and BZ− ions can make micelle radius (Rg) increase but make solvent accessible surface area (SASA) decrease. Conversely, adsorbed Cl− ions make both Rg and SASA increase. Three MD models for different C14mim+ based micelles are proposed.

Adsorption and aggregation behavior of Gemini surfactants with organic counterions

Adsorption and aggregation behavior of Gemini surfactants with organic counterions

Impact of organic counterions on adsorption and aggregation of single-chained cobalt-based metallosurfactant: a comparison with the inorganic chloride counterion

Impact of organic counterions on adsorption and aggregation of single-chained cobalt-based metallosurfactant: a comparison with the inorganic chloride counterion

Supramolecular self-assembly of robust, ultra-stable, and high-temperature-resistant viscoelastic worm-like micelles

HypothesisWorm-like micelles are susceptible to heating owing to the fast dynamic exchange of molecules between micelles. Inhibition of such exchange could afford robust worm-like micelles, which is expected to largely improve rheology properties at high temperatures. ExperimentsA cationic surfactant docosyl(trimethyl)azanium chloride (DCTAC) and a strongly hydrophobic organic counterion 3-hydroxy naphthalene-2-carboxylate (SHNC) were used for the worm-like micelles fabrication. The microstructure was characterized using cryogenic transmission electron microscopy and small-angle neutron scattering, and the interactions between DCTAC and SHNC were characterized using nuclear magnetic resonance spectroscopy. Rheometer was employed to measure the rheological properties of the solution. FindingsSHNC/DCTAC at the molar ration of 1:2 forms ultra-stable worm-like micelles, whose viscosity remain stable at temperature up to 130 °C. SHNC is found to strongly adsorbs on DCTAC micelle with the orientation on the surface of micelle, keeping the naphthalene backbone entire penetration into the palisade layer while both carboxylic and hydroxyl groups protrude out of the micelle. With temperature increasing, this adsorption further strengthens, resulting in the growth contour length and accompanying the enhancement of rheological properties. One SHNC molecule and two DCTAC molecules are speculated to form a stable complex via multiple interactions including hydrophobic, cationic-π, and π-π interactions, which decreases the dynamic exchange of them between micelles. These findings are helpful to understand surfactant aggregates stability and assist the development of novel stable supramolecular nanostructures. Additionally, the excellent thermal stability of this worm-like micellar fluid makes it a potential high-temperature resistant clean fracturing fluid for deep oil reservoirs.

The Organic Ammonium Counterion Effect on Slow Magnetic Relaxation of the [Er(hfac)4]− Complexes

The first mononuclear anionic erbium complex [Er(hfac)4]− (hfac = hexafluoroacetylacetone) with an organic ammonium cation [(CH3)4N+] as the counterion was synthesized and structurally and magnetically characterized. The coordination geometries around the Er ions are square antiprisms with pseudo-D4d symmetry. The complex shows distinct field-induced slow magnetization relaxation, which is described by a combination of Orbach (Ueff/kB~28.54(8) K.) and direct mechanisms. Quantum chemical calculations were performed to analyze the magnetic properties of the complex under consideration.

Excellent photo actuation in crystal-polymer composite by transfer of mechanical energy

Transfer of strong photomechanical effect from dynamic crystals to hybrid polymer composite is an evolving field of research and holds high potential for actuation and photo-switch development. An organic counter anion (dinitrobenzoate) stabilized nitropentaamminecobalt(III) complex (Co-dnb-1) showing fast photomechanical motions under UV light (365 nm) was synthesized. Detailed experimental and theoretical studies attribute the photomechanical motion to the formation of metastable nitrito-coordinated species (Co-dnb-2) after irradiation. The energy difference between nitro-nitrito complexes was estimated to be 3.54 eV which is close to irradiation energy (3.4 eV). However, in a slow process, by absorbing energy of ∼0.4 eV/cation through external perturbations such as temperature, Co-dnb-2 recovers to the initial configuration. Three different crystal-polymer composite films (PCF-1–3) were fabricated using photoactive crystals with polyvinylalcohol (PVA), polyvinyldifluride(PVDF) and agarose polymers, respectively by solution casting method. The composite films show quick and excellent photo-actuation though, the extent varies with the polymers used. The actuation of the composite films starts immediately (<2–3 s) and can be deflected up to 90° within a few seconds of the onset of UV light. PCF-3 shows reversible photo-actuation measured up to multiple cycles. Dynamical transfer of photomechanical energy from crystal to composite films leads to successful assembly of a prototype photo-switch. The presented work provides a new dimension towards the development of smart functional composite materials as photo-actuators.

Supramolecular Structure of Tris(1,10-phenanthroline)zinc(II)-Cation and N,N′,N″-tris(carboxymethyl)-1,3,5-benzenetricarboxamide-Anion: Synthesis, Crystal Structure, Vibrational Spectra, and Theoretical Investigations

The present work reports on the synthesis, structural, spectroscopic, and theoretical studies of a new solid state ionic compound mainly composed of tris(1,10-phenanthroline)zinc(II) cations and N,N′,N″-tris(carboxymethyl)-1,3,5-benzenetricarboxamide anions. Colorless and well-shaped crystals were obtained from an alkaline aqueous methanolic solution, and single-crystal X-ray diffraction revealed a distinct supramolecular network. Powder diffraction techniques and Rietveld analysis confirmed the phase purity of the crystalline probes. The compound crystallizes in the orthorhombic space group Pbca with a cell volume of 9517.0 Å3. The complex cations [Zn(phen)3]2+ are interconnected via π–π-interactions and form a cationic layer network with holes. The organic counterion, as a dianion, forms dimeric units through π–π-interactions and hydrogen bonds, which also form an anionic layer network with honeycomb-like holes through cooperative classical hydrogen bonds of the O∙∙∙H–O and O∙∙∙H–N type with attractive secondary electrostatic interactions. Using the holes, the resulting supramolecular framework can be described as an interpenetrated network of separate anionic and cationic layers linked by further weaker non-covalent interactions such as C–H∙∙∙π and lone-pair∙∙∙π interactions. DFT calculations confirmed the experimentally observed spectroscopic (IR and Raman) findings. For a deeper insight into the structural arrangement in the crystal, the different Hirshfeld surfaces of the cation and anion, the pairwise interaction energies as well as the energy framework were calculated, supporting the dominance of attractive and repulsive electrostatic forces between the ions.

Kinetics, mechanism, and tautomerism in ametryn acid hydrolysis: From molecular structure to environmental impacts

The excessive use of pesticides and the demand for environmentally friendly compounds have driven the focus to detailed studies of the environmental destination of these compounds. Degradation by hydrolysis of pesticides, when released into the soil, can result in the formation of metabolites with potentially adverse effects on the environment. Moving in this direction, we investigated the mechanism of acid hydrolysis of the herbicide ametryn (AMT) and predicted the toxicities of metabolites through experimental and theoretical approaches. The formation of ionized hydroxyatrazine (HA) occurs with the release of the SCH3- group and the addition of H3O+ to the triazine ring. The tautomerization reactions privileged the conversion of AMT into HA. Furthermore, the ionized HA is stabilized by an intramolecular reaction that provides the molecule in two tautomeric states. Experimentally, the hydrolysis of AMT was obtained under acidic conditions and at room temperature with HA as the main product. HA was isolated in a solid state through its crystallization as organic counterions. The mechanism of conversion of AMT to HA and the experimental investigation of the reaction kinetics allowed us to determine the dissociation of CH3SH as the rate-controlling step in the degradation process that culminates in a half-life between 7 and 24 months under typical acid soil conditions of the Brazilian Midwest – region with strong agricultural and livestock vocation. The keto and hydroxy metabolites showed substantial thermodynamic stability and a decrease in toxicity compared to AMT. We hope that this comprehensive study will support the understanding of the degradation of s-triazine-based pesticides.

Charge-Selective Aggregation Behavior of Thermoresponsive Polyelectrolytes Having Low Charge Density in Aqueous Solutions of Organic Counterions

The aggregation behavior of thermoresponsive polyelectrolytes with low charge density in aqueous solutions of organic counterions was investigated. We synthesized two thermoresponsive polyelectrolytes: anionic poly(N-isopropylacrylamide-co-(3-sulfopropyl)acrylamide potassium) (P-NIP-SPAK) and cationic poly(N-isopropylacrylamide-co-(3-acrylamidepropyl)trimethylammonium chloride) (P-NIP-AAPTAC). The polyelectrolytes remained soluble in their aqueous solutions even above the lower critical soluble temperature of P-NIP owing to the strong hydration property of the ionic groups. The aggregation occurred when organic counterions were added to the solution. In these solution systems, the concentration of counterions exceeds those of ionic groups introduced into the polyelectrolytes. The aggregation behavior is attributed to the salting-out effect of counterions accommodated near the polyelectrolyte surface by electrostatic interaction. This aggregation behavior was utilized for the charge-selective recognition of amino acids. P-NIP-SPAK aggregated only when basic amino acids were added under acidic conditions, whereas P-NIP-AAPTAC aggregated only when acidic amino acids were added under basic conditions. The results herein demonstrate that P-NIP-SPAK and P-NIP-AAPTAC have the potential to be used as charge-selective polymer sensors for amino acids without having to strictly control the experimental conditions.

Mixed Organic Counterion Strategy Modulates the Self-Assembly of Polyoxometalate Hybrids into Toroids and Affects Their Photochromic and Photocatalytic Properties.

A series of five mixed-counterion polyoxometalate (POM) hybrids 1-5 have been developed starting from the [SiW12O40]4- cluster and two different aryl sulfonium counterions (ASCIs), (4-hydroxyphenyl)dimethylsulfonium (HPDS) and (4-formylphenyl)dimethylsulfonium (FPDS), bearing different functional groups -OH and -CHO, respectively. The HPDS/FPDS counterion ratio in hybrids 1-5 varied as 4:0 (1), 3:1 (2), 2:2 (3), 1:3 (4), and 0:4 (5), and it resulted in a morphological transition of the self-assembly of these hybrids. Hybrid 1 exhibited spherical self-assembly, while hybrid 5 exhibited large toroidal self-assembly predominantly. The hybrids 2-4 gave a mixture of spherical, dimpled spherical, and toroidal self-assemblies in varying amounts, indicating a gradual transition of self-assembly from spherical to toroidal as the percentage of FPDS increases in the system. A plausible explanation for the differences in the self-assembly properties of these hybrids has been proposed based on the differences in the H-bonding interactions of the two counterions with the dispersion medium. The HPDS and FPDS counterions exhibited different HOMO-LUMO gaps, and their varying percentages in hybrids 1-5 led to differences in optical band gaps and photochromic activities. Hybrid 2 showed the lowest band gap value and the best photochromic activity (t1/2 = 0.72 min) in the series. The influence of the mixed-counterion strategy in catalysis has been demonstrated by evaluating the photocatalytic activity of these hybrids toward rhodamine B dye degradation. The hybrid 4, exhibiting stable toroidal self-assembly, showed the best catalytic activity in the series, probably due to a combination of reasons such as the enhanced surface area due to toroid formation and also the presence of H-bonding -OH functionality on the counterion. Therefore, the present study suggests a new method for altering the self-assembly and the materials and catalytic properties of POM hybrids through a mixed-counterion strategy.

Separation of unsaturated C18 fatty acids using perfluorinated-micellar electrokinetic chromatography: I.Optimization and separation process.

Ammonium perfluorooctanoate (APFOA) was used as a surfactant for the separation of free unsaturated C18 fatty acids by micellar electrokinetic chromatography. A simple background electrolyte of 50mM APFOA water/methanol (90:10, v/v) at pH=10 enabled the repeatable separation of oleic acid, elaidic acid, linoleic acid, and alpha-linolenic acid in less than 20min. Separation conditions were optimized regarding various parameters (organic solvent, counterion, APFOA concentration, and pH). Because the repulsive interactions between fluorocarbon chains and hydrogenated chains are known to lead to segregation and phase separation, the choice of perfluorinated micelles to separate such perhydrogenated long-chain acids could appear astonishing. Therefore, the critical micelle concentration, the charge density, and the mobility of the micelles have been determined, resulting in a first description of the separation process.

Probing Pharmaceutical Strategies to Promote the Skin Delivery of Asiatic Acid from Hydrogels: Enhancement Effects of Organic Amine Counterions, Chemical Enhancers, and Microneedle Pretreatment.

Asiatic acid (AA) is a pentacyclic triterpene isolated from Centella asiatica, holding great promise for treating a variety of skin disorders. However, the dermal application of AA is limited by its poor solubility and permeability. This study aimed to identify a hydrogel formulation for AA and improve its skin penetration by various penetration enhancement methods. Four kinds of hydrogel bases were selected to prepare the AA hydrogel, in which different organic amines and chemical enhancers were incorporated in combination with microneedle pretreatment. The results showed that AA had good release profiles in the presence of hyaluronic acid as the hydrogel base and organic amines as the counter-ions. Diethylamine and Span 80 could promote drug penetration into the skin, and pretreatment with microneedles could further increase the drug permeability. In conclusion, the optimized hyaluronic acid hydrogel has great potential for use in the topical delivery of AA, and its penetration via the skin can be further improved by different pharmaceutical approaches.