Organogel Phase Research Articles

Silk Fibroin-Based Shape-Memory Organohydrogels with Semicrystalline Microinclusions.

Inspired by nature, we designed organohydrogels (OHGs) consisting of a silk fibroin (SF) hydrogel as the continuous phase and the hydrophobic microinclusions based on semicrystalline poly(n-octadecyl acrylate) (PC18A) as the dispersed phase. SF acts as a self-emulsifier to obtain oil-in-water emulsions, and hence, it is a versatile and green alternative to chemical emulsifiers. We first prepared a stable oil-in-water emulsion without an external emulsifier by dispersing the n-octadecyl acrylate (C18A) monomer in an aqueous SF solution. To stabilize the emulsions for longer times, gelation in the continuous SF phase was induced by the addition of ethanol, which is known to trigger the conformational transition in SF from random coil to β-sheet structures. In the second step, in situ polymerization of C18A droplets in the emulsion system was conducted under UV light in the presence of a photoinitiator to obtain high-strength OHGs with shape-memory function, and good cytocompatibility. The incorporation of hydrophilic N,N-dimethylacrylamide and noncrystallizable hydrophobic lauryl methacrylate units in the hydrogel and organogel phases of OHGs, respectively, further improved their mechanical and shape-memory properties. The shape-memory OHGs presented here exhibit switchable viscoelasticity and mechanics, a high Young's modulus (up to 4.3 ± 0.1 MPa), compressive strength (up to 2.5 ± 0.1 MPa), and toughness (up to 0.68 MPa).

Studies on Span based Soy-bigels with HPMC

Organogels owing to their lipophilic nature and better stability over other gel preparations may have a wide range of application but leaching of oily phase restricts their application. Use of hydrogel is limited by its stability problems and syneresis at atmospheric condition. Attempts to overcome such drawbacks can be overcome by combining both lipophilic organogel and hydrophilic hdydrogel phases in a single formulation, bigel. The present study deals with the development and evaluation of soy-bigel by mixing organogel of soybean oil (prepared with Span 40 or Span 60) and hydrogel of HPMCK4M or HPMCK15M in a definite ratio. Four batches of soy-bigels were prepared by mixing organogel with 18%w/v Span and 3% HPMC hydrogel. Formulations were examined for compatibility by FTIR spectroscopy, characterized for physical appearance, pH, rheological behavior, in vitro drug release pattern and thermal stability study. FTIR study confirmed compatibility between paracetamol and components of bigel. Soy-bigels were found to possess satisfactory organoleptic properties and applicability parameters and demonstrated pseudoplastic flow behavior. Better drug release was observed in soy-bigel prepared with Span 40 and HPMCK4M (OHP2) which followed Kormeyer-Peppas model with non-Fickian diffusion. Diffusion-controlled drug release gradually decreased in gels of matrix type developed with Span 60 and either grade of HPMC (OHS1 and OHS2). Soy-bigels prepared from Span 40 and either grades of HPMC demonstrated thermal stability on exposure to 5 freeze-thaw cycles. Thus, soy-bigels prepared from Span 40 and HPMCK4M exhibited satisfactory rheological property and improved drug release and can ideally be selected as a topical base for drug delivery.

Discotic mesogens based on triphenylene-fused benzimidazole or perimidine: facile synthesis, mesomorphism, optical properties and self-assembly

ABSTRACT Four new mesomorphic triphenylene-fused nitrogen-containing heterocyclic systems, including three benzimidazole and one perimidine derivatives with extended triphenylene core of different sizes are synthesised from the condensation reaction between aromatic diamines and our developed triphenylene dicarboxylic anhydrides. These discotic mesogens self-assemble into supramolecular columnar hexagonal mesophases with high clearing transition temperatures, demonstrating a strong tendency for π-stacking aggregation in the LC state owing to their good planar molecular structures. Four triphenylene-fused mesogens exhibit strong absorption bands in the range of 262 nm to 450 nm and corresponding emission bands between 468 nm and 615 nm, respectively. Both the experimental results and computational calculations show that the mesomorphic and electronic properties of four mesogens are strongly affected by the expansion of triphenylene core and the electronic nature of the nitrogenated benzimidazole or perimidine ring. Besides, these mesogens also possess higher HOMO energies and narrower HOMO-LUMO gaps than parent anhydride. Furthermore, the solution of TDPI or TDP in THF at a concentration as low as 0.45 wt % exhibited organogel phases due to strong intermolecular π-π interactions between the large aromatic cores. All these properties qualify this new type of discotic liquid crystals as potential applications as organic semiconductor materials and sensors.

A novel hydrogelator based on dimeric-dehydrocholic acid derivative

A dimeric-dehydrocholic acid derivative (DDAD) was synthesized and studied for its gelation ability in the potassium hydroxide solution. The DDAD-based gels were further investigated for their thermal stabilities and morphological structures by using the vial inversion method, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Interestingly, the TEM and AFM images of the DDAD-based gels indicated that the supramolecular structures were composed of longer fibers. Importantly, Fourier transformation infrared spectra further revealed that the main driving forces in gel formation involve multiple hydrogen bonding, electrostatic, and dipole–dipole interactions among the gelator molecules. The X-ray diffraction analysis showed that the molecular packings in both the DDAD powders and the organogel phase were highly disordered. Based on these results, a mechanism for the formation of hydrogels is proposed. These findings present a novel hydrogelator and an insight into developing new types of gels as potential soft materials.

Exploring the Molecular-Level Architecture of the Active Compounds in Liquisolid Drug Delivery Systems Based on Mesoporous Silica Particles: Old Tricks for New Challenges.

A general, easy-to-implement strategy for mapping the structure of organic phases integrated in mesoporous silica drug delivery devices is presented. The approach based on a few straightforward solid-state NMR techniques has no limitations regarding concentrations of the active compounds and enables straightforward discrimination of various organic phases. This way, among a range of typical arrangements of the active compounds and solvent molecules, a unique, previously unknown organogel phase of the self-assembled tapentadol in glucofurol as a solvent was unveiled and clearly identified. Subsequently, with an aid of 2D 1H-1H MAS NMR and high-level quantum-chemical calculations this uncommon low-molecular-weight organogel phase, existing exclusively in the porous system of the silica carrier, was described in detail. The optimized model revealed the tendency of tapentadol molecules to form hydrophobic arrangements through -OH···π interactions combined with π-π stacking occurring in the core of API aggregates, thus precluding the formation of hydrogen bonds with the solvent. Overall, the proposed experimental approach allows for clear discrimination of a variety of local structures of active compounds loaded in mesoporous silica drug delivery devices in reasonably short time being applicable for advancement of novel drug delivery systems in pharmaceutical industry.

Super organogelator based on tetrathiafulvalene with four amide derivatives and its F4TCNQ charge-transfer complex

A new series of tetrathiafulvalene-based organogelators endowed with four hydrophobic chains incorporating amide groups was synthesised and characterised. The resulting transparent organogels were obtained with organic solvents such as cyclohexane, carbon tetrachloride and chlorobenzene. Additionally, the length of the alkyl chain influenced the gelation ability of organogels. Considering the results, we concluded that compounds were ‘super gelators’. Interestingly, the gelators reacted with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane to form charge-transfer (CT) complexes and binary organogels. 1HNMR and FT-IR revealed that cooperation of hydrogen bonding, π–π and CT interactions was the main driving force for formation of the native and CT gels. The scanning electron microscopy images of native xerogels revealed characteristic gelation morphologies of three-dimensional cross-linking networks, whereas the morphologies of CT complex xerogels showed amorphous rod-like aggregates. X-ray powder diffraction studies suggested that both gelator and CT complex maintained lamellar molecular packing mode in organogel phase.

Impact of a Surfactant on the Electroactivity of Proteins at an Aqueous–Organogel Microinterface Array

The impact of surfactant addition to the organic phase on the electroactivity of proteins at the aqueous-organogel interface was examined by voltammetry. The presence of bis(2-ethylhexyl)sulfosuccinate (AOT) in the organogel phase, as the sodium salt, caused marked changes in the peak currents for myoglobin detection. The protein desorption voltammetric peak exhibited a 6-fold increase in the current compared to the corresponding experiment without surfactant. Interfacial coverage showed a 17-fold increase in the adsorbed protein at the interface, from 50 pmol cm(-2), in the absence of surfactant, to 850 pmol cm(-2), in the presence of 10 mM surfactant. Additionally, the presence of the surfactant resulted in a second pair of adsorption/desorption peaks at lower potentials and in a change in the capacitance of the system. The formation of surfactant-protein and surfactant-protein-organic anion deposits is proposed on the basis of these features, leading to increased voltammetric signals for myoglobin, hemoglobin, and cytochrome c. The mechanism of protein-surfactant interaction was probed by using the surfactant as the anion in the organic phase electrolyte salt. Repetitive cyclic voltammetry of cytochrome c showed that in the presence of surfactant there was an enhancement of the signal, caused by a buildup of the protein-surfactant-electrolyte anion assembly at the interface. These findings provide the basis for surfactant-modified interfaces to enhance the electroanalytical performance for protein detection.

Supramolecular gels based on monopyrrolotetrathiafulvalene and its TCNQ charge-transfer complex

A novel series of monopyrrolotetrathiafulvalene (monopyrrolo-TTF)-based low molecular-mass organic gelators (LMOGs) were synthesized and characterized. Electrochemical investigations exhibited two reversible one-electron redox couples. The gelators could gelate some saturated hydrocarbons and alcohols. The FE-SEM images of xerogels revealed the characteristic gelation morphologies of microporous structures. The gelators reacted with tetracyano-p-quinodimethane (TCNQ) to form the charge-transfer (CT) complexes and the binary organogels, and the morphologies of binary gels changed to regular network and fiber in cyclohexane and n-hexane, respectively. XRD studies suggest that both the gelator and the CT complex maintain the lamellar molecular-packing mode in the organogel phase. The gel–sol transition of the organogel and the CT complex gel could be stimulated by fluorine and chlorine ions.

“Relaxometry” experiments and analysis of dispersion curves: An illustrative example of toluene in liquid and in organogel phases

AbstractAt very low or low frequency, the so‐called dispersion curves (longitudinal relaxation rate as a function of the measurement frequency) are obtained with a “relaxometer,” which is generally run according to the “field‐cycling” technique. Because of the very poor field homogeneity, relaxation times of a single (broad) signal are measured. When going to higher fields, with standard nuclear magnetic resonance spectrometers (possibly with variable field capacities), different lines are resolved. We show how the relaxation rates pertaining to these lines can be connected to the results obtained via the relaxometer. Among other things, we demonstrate why the magnitude mode (generally used for processing the relaxometer data) must be used with caution when several lines are resolved. Actually, we could obtain accurate 1H dispersion curves in a very broad frequency range (5 kHz–400 MHz), and we show that a decomposition into several Lorentzian curves proves to be adequate, as far as paramagnetic relaxation due to dissolved oxygen is concerned. The method will be applied i) to nondegassed liquid toluene, ii) to the same solvent involved in the formation of an organogel. In that latter case, a low frequency contribution to the dispersion curve (possibly non‐Lorentzian) reveals the part of the solvent within the organogel structure. The algorithm used for analyzing these dispersion curves is described. © 2012 Wiley Periodicals, Inc. Concepts Magn Reson Part A 40A: 80–89, 2012.

Solvent Dynamical Behavior in an Organogel Phase As Studied by NMR Relaxation and Diffusion Experiments

An organogelation process depends on the gelator-solvent pair. This study deals with the solvent dynamics once the gelation process is completed. The first approach used is relaxometry, i.e., the measurement of toluene proton longitudinal relaxation time T(1) as a function of the proton NMR resonance frequency (here in the 5 kHz to 400 MHz range). Pure toluene exhibits an unexpected T(1) variation, which has been identified as paramagnetic relaxation resulting from an interaction of toluene with dissolved oxygen. In the gel phase, this contribution is retrieved with, in addition, a strong decay at low frequencies assigned to toluene molecules within the gel fibers. Comparison of dispersion curves of pure toluene and toluene in the gel phase leads to an estimate of the proportion of toluene embedded within the organogel (found around 40%). The second approach is based on carbon-13 T(1) and nuclear Overhauser effect measurements, the combination of these two parameters providing direct information about the reorientation of C-H bonds. It appears clearly that reorientation of toluene is the same in pure liquid and in the gel phase. The only noticeable changes in carbon-13 longitudinal relaxation times are due to the so-called chemical shift anisotropy (csa) mechanism and reflect slight modifications of the toluene electronic distribution in the gel phase. NMR diffusion measurements by the pulse gradient spin-echo (PGSE) method allow us to determine the diffusion coefficient of toluene inside the organogel. It is roughly two-thirds of the one in pure toluene, thus indicating that self-diffusion is the only dynamical parameter to be slightly affected when the solvent is inside the gel structure. The whole set of experimental observations leads to the conclusion that, once the gel is formed, the solvent becomes essentially passive, although an important fraction is located within the gel structure.

Synthesis and Gelation Behavior of 4′-Propyl-1,1′-bi(cyclohexyl)-4-one 4-Alkoxybenzoylhydrazone

Abstract A series of new alkoxybenzoylhydrazones of 4′-propyl-1,1′-bi(cyclohexyl)-4-one were prepared as novel low molecular weight organogelators (LMOGs). Their gelation behaviors in 10 solvents were tested. Some of the compounds could form stable gels in bulk organic solvents and self-assemble into fibrous microstructures in organogel phase. FTIR and 1H NMR spectroscopy studies revealed that hydrogen bonding between the gelator molecules was one of the main driving forces for the formation of the gels.

Rapid access to C 3- and C s-symmetric AAT organogelators via ring opening of a common benzotrifuranone precursor

Presented is a rapid and general approach to functionalised 1-aza-adamantanetrione (AAT) donor-σ-acceptor molecules from a phloroglucinol-derived trilactone, benzotrifuranone (BTF). Ten C 3-symmetric AATs bearing diverse aryl amide substituents are accessed in two synthetic steps: (1) the exhaustive ring opening of BTF with aromatic amine nucleophiles (performed in up to 91% yield) and (2) cyclisation with hexamethylenetetramine (performed in up to 75% yield). Additionally, stepwise ring opening of BTF allows synthesis of phloroglucinol intermediates with two unique aryl amide substituents and ultimately C s-symmetric AATs. Of the novel AATs prepared, three (including the C s-symmetric hybrid) are effective gelators of chlorinated solvents (critical gelation concentration (CGC) = 0.2–0.4 wt%) and one, with naphthyl substituents, forms translucent gels from aromatic solvents (CGC∼0.3 wt%). The combination of AATs with moderately electron-poor and electron-rich aromatic substituents results in functional complementarity and gelation at concentrations below what is required for the individual components. Electron microscopy of the gel morphologies shows high aspect ratio fibres underlying the gel network superstructures in most cases. Polarised optical microscopy has allowed imaging of representative native organogel phases, and reveals striking morphology differences between gels that also share different optical and/or thermal stability properties.

Quasi Temperature Independent Electron Mobility in Hexagonal Columnar Mesophases of an H-Bonded Benzotristhiophene Derivative

Reported here are the unique properties of N,N′,N′′-(3,4,5-tridodecyloxyphenyl)benzo[b,b′,b′′]tristhiophene-2,2′,2′′-tricarboxamide 3 as a new H-bonded discotic liquid crystal. Polarized optical microscopy and thermal analysis as well as variable temperature IR spectroscopy and X-ray diffraction confirm the presence of two thermotropic H-bonded hexagonal columnar mesophases that cover a temperature range from <−50 to 280 °C. Intermediate lyotropic mesophases of the highly viscous material aid the alignment of the hexagonal columnar mesophases, which is essential for a detailed structural characterization and applications. Solutions of 3 in heptane at concentrations as low as 1 wt % display isotropic organo-gel phases that consist of H-bonded networks of 3 but do not contain columnar stacks. 2D-X-ray diffraction studies on aligned samples of the thermotropic hexagonal columnar mesophases and DFT calculations on a tetramer of 3 reveal a helical columnar stacking of the individual benzotristhiophene units. C...

Strategy to Control the Chromism and Fluorescence Emission of a Perylene Dye in Composite Organogel Phases

Composite organogels based on 1,3,5-tris(4-dodecyloxybenzoylamino)phenylbenzene (DBAPB), a known gelator, and N,N'-di(octadecyl)-perylene-3,4,9,10-tetracarboxylic diimide (C18PTCDI), a nongelator dye, have been achieved, leading to controllable color and emitting color changes. SEM images and XRD patterns revealed that the packing of the DBAPB-based gelator could almost be maintained in the composite gels. The temperature-dependent UV-vis absorption and temperature-dependent fluorescence emission spectra illustrated that the color and emitting color of the composite gels could be controlled by the content of C18PTCDI as well as the temperature in the gel phases. When the content of C18PTCDI was 1 mol %, C18PTCDI could be isolated as unimolecules in the composite gel, which was yellow and gave bright greenish-yellow emission under 365 nm light. For the mixed systems containing 2-10 mol % C18PTCDI, the fresh gels, which were obtained after cooling the hot solutions for a short time, were yellow and produced greenish-yellow emission under 365 nm illumination. However, the corresponding stable composite gels, which were obtained via prolonging the cooling time, were red and emitted weak red emission excited by UV light as a result of the formation of C18PTCDI aggregates. The reversible color and emitting color changes could be realized in the gel phases over a narrow temperature range. Moreover, the excitation energy of DBAPB could be transferred to C18PTCDI in the composite gels, leading to obvious emission quenching of the former.

Rheological Characterization of a New Type of Colloidal Dispersion Based on Nanoparticles of Gelled Oil

The rheological properties of a new type of colloidal dispersion based on nanoparticles of gelled oil have been characterized. The nanoparticles (mean diameter approximately 250 nm) were viscoelastic droplets of dicaprylyl ether gelled by 12-hydroxystearic acid (HSA) and were stabilized in aqueous solutions by cetyltrimethylammonium bromide. The effects of the volume fraction of the dispersed organogel phase and of the organogelator concentration upon viscoelasticity of the dispersion were investigated and compared to the corresponding emulsion (without HSA). The shear viscosity of the dispersions of organogel droplets and the elastic and viscous moduli (G' and G'') were found to increase when the proportion of organogelator was increased. More surprisingly, the shear-thinning behavior was also more pronounced. The rheological behavior of the dispersions could be explained by strong interactions between some gelled particles. This hypothesis was supported by electron microscopy observations showing some particles bridged together by ribbons of HSA fibers.

Self-Assembled Nanostructures of a Cholesterol-Saccharide Conjugate which Acts as an Amphiphilic Gelator of Organic Solvents

New cholesterol-saccharide conjugate gelator N-cholesteryl succinyl glucosamine (1) was synthesized and its gelation ability was evaluated in organic solvents in this study. It could gelate 1-butanol, iso-butanol, 4-heptanol, cyclohexanol and 1-octanol under the concentration of 5.0 mg/mL. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), circular dichroism (CD) and small-angle X-ray diffraction (SAXRD) were used to analyze the aggregation mode of 1 in the organogel phase. 1 exhibited a fibrous structure composed of thin micellar fibrils with ca.9∼10 nm diameters and these fibrils were packed into a disordered hexagonal mesophase structure with an interlayer distance of 8.01 nm. CD spectra showed that 1 adopted the helical arrangement in the aggregation. A hierarchical self-assembly model was proposed to explain the transition from molecular to primary and secondary structure. Moreover, sol-gel polymerization of tetraethoxysilane (TEOS) was carried out using 1 in the gel phase. The silica obtained from the 1 + 1-butanol gel showed the tubular structure with ca. 100 nm outer diameter.

Ion-Transfer Voltammetric Determination of the β-Blocker Propranolol in a Physiological Matrix at Silicon Membrane-Based Liquid|Liquid Microinterface Arrays

In this work, the ion-transfer voltammetric detection of the protonated beta-blocker propranolol in artificial saliva is presented. Cyclic voltammetry, differential pulse voltammetry, and differential pulse stripping voltammetry (DPSV) were employed in the detection of the cationic drug based on ion-transfer voltammetry across arrays of microinterfaces between artificial saliva and an organogel phase. It was found that the artificial saliva matrix decreased the available potential window for ion-transfer voltammetry at this liquid|liquid interface but transfer of protonated propranolol was still achieved. The DPSV method employed a preconditioning step as well as a preconcentration step followed by analytical signal generation based on the back-transfer of the drug across the array of microinterfaces. The DPSV peak current response was linear with drug concentration in the artificial saliva matrix over the concentration range of 0.05-1 microM (i(p) = -8.13 (nA microM(-1))(concentration) + 0.07 (nA), R = 0.9929, n = 7), and the calculated detection limit (3s(b)) was 0.02 microM. These results demonstrate that DPSV at arrays of liquid|liquid microinterfaces is a viable analytical approach for pharmaceutical determinations in biomimetic matrixes.

Electrochemically Modulated Liquid−Liquid Extraction of Ionized Drugs under Physiological Conditions

Electrochemically modulated liquid-liquid extraction (EMLLE) enables the selective extraction and separation of ions from mixtures by choice of an applied interfacial potential difference. The extraction of ionized drugs from artificial urine is reported in this paper. The artificial urine matrix was characterized by cyclic voltammetry at the interface between two immiscible electrolyte solutions (ITIES), showing that components of that aqueous phase truncate the available potential window at the ITIES. The transfer of three cationic drugs from aqueous artificial urine to the 1,2-dichloroethane organic electrolyte phase was examined. Both propranolol and timolol were found to transfer across the artificial urine-organic interface. However, sotalol transfer was not possible within the available potential window. Extraction of propranolol and timolol from artificial urine into an organogel phase, by electrochemically modulated liquid-liquid extraction, was examined. The application of potentials positive of the drugs' formal transfer potentials enabled the selective extraction of both propranolol and timolol, with a higher potential being required for timolol. This work demonstrates the practical utility of EMLLE for the selective extraction of target compounds from a complex sample matrix.

Distinct Kinetic Pathways Generate Organogel Networks with Contrasting Fractality and Thixotropic Properties

The kinetics of the isothermal transformation of sols, comprised of a low molecular-mass organogelator (LMOG) and an organic liquid, to their organogel phases have been followed by circular dichroism (CD), fluorescence, small angle neutron scattering (SANS), and rheological methods. The thixotropic properties (in the sense that severe shearing followed by rest lead to reestablishment of viscoelasticity) of the gels have been examined as well by rheological measurements. The compositions of the samples were either 5alpha-cholestan-3beta-yl N-(2-naphthyl) carbamate (CNC) in an n-alkane (n-octane or n-dodecane) or 3beta-cholesteryl N-(2-naphthyl) carbamate (CeNC) in ethyl acetate. Values of Df, the mass fractal dimension of the microcrystalline self-assembled fibrillar networks (SAFINs) in the gels, have been extracted from the kinetic data using a model developed by Dickinson (J. Chem. Soc., Faraday Trans. 1997, 93, 111). The Df values, 1.1-1.3 for the CeNC gels and 1.3-1.4 or 1.6-1.8 (depending on the temperature of incubation of the sol phase) for CNC gels, are consistent with the gel network structures observed by optical microscopy. In addition, comparison of the temperature dependence of both n (the Avrami component) and K (the Avrami "rate constant") for CeNC/ethyl acetate gelation with those reported previously for gelation of CNC/n-alkane sols demonstrate that the very small change of a single bond in CNC to a double bond in CeNC causes significant differences in their gelation abilities and gel properties. The rheological measurements on CNC/n-alkane gels with spherulitic SAFIN units, formed by incubation of their sols at < or =28 degrees C, indicate that they are thixotropic. Gels with the same chemical composition but formed by incubation of their sols at > or =30 degrees C, leading to fiberlike SAFIN units, remain liquidlike after shearing regardless of the periods they are at rest. The time-dependent viscoelastic properties of the gel networks are treated according to a stretched exponential model. The observations from these studies provide detailed insights into the mechanisms of formation of molecular organogel phases and demonstrate the extreme sensitivity of the SAFINs and viscoelastic properties of such organogels to slight modifications in LMOG structure or sample history.

Electrochemically Modulated Liquid−Liquid Extraction of Ions

The development of ion extraction methods under electrochemical control via electrochemistry at the interface between two immiscible electrolyte solutions is discussed. A hydrodynamic flow injection system was used for the potentiostatic extraction of non-redox-active species from a flowing aqueous phase into a stationary organogel phase. The ions tetraethylammonium, 4-octylbenzenesulfonate (4-OBSA-), and p-toluenesulfonate (p-TSA-) were studied as model analytes. The extraction study comprised examination of the influence of extraction potentials, aqueous-phase flow rate, and target species concentration. The extraction process can be monitored in situ by means of the ion-transfer current, which has opposing signs for anions and cations. Hydrodynamic voltammograms were obtained from these experiments. The selective extraction of 4-OBSA-, from its mixture with p-TSA-, as well as coextraction of both anions is shown. The results demonstrate the utility of electrochemical modulation for the controlled extraction of ions from an aqueous phase into an organogel electrolyte phase. This offers potential benefits for various analytical processes including sample preparation and cleanup.