Imidazolium Ionic Liquids Research Articles

Developing nano-micro size chitosan beads using imidazolium-based ionic liquid: A perspective

The aggressive search for unique materials in recent years has put forward chitosan and modified-chitosan as materials with unique structural and morphological characteristics for various important applications. Just as imidazolium-based ionic liquids are the commonly applied ionic liquids (ILs) type for chitosan modifications for various applications, their further modifications into beads for enhancing their properties is now gaining most attention. However, most of the currently prepared imidazolium ILs modified-chitosan beads are not in nano size due to preparation difficulties. In response to this and referencing the research works in the literature, the possible breakthrough directions including synthesis routes, and physical and mechanical transformation processes are proposed. These procedures are expected to provide certain theoretical and empirical basis, as well as technical guide for developing nano-micro size chitosan beads using imidazolium based ILs.

Ruthenium Nanoparticles Stabilized with Methoxy-Functionalized Ionic Liquids: Synthesis and Structure-Performance Relations in Styrene Hydrogenation.

A series of ruthenium nanoparticles (RuNPs) were synthesized by the organometallic approach in different functionalized imidazolium ionic liquids (FILs). Transmission electron microscopy (TEM) showed well-dispersed and narrow-sized RuNPs ranging from 1.3 to 2.2 nm, depending on the IL functionalization. Thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) allowed the interaction between the RuNPs and the ILs to be studied. The RuNPs stabilized by methoxy-based FILs (MEM and MME) displayed a good balance between catalytic activity and stability when evaluated in the hydrogenation of styrene (S) under mild reaction conditions. Moreover, the catalysts showed total selectivity towards ethylbenzene (EB) under milder reaction conditions (5 bar, 30 °C) than reported in the literature for other RuNP catalysts.

Ultrafast removal of ReO4−/TcO4− by radiation-induced grafting of imidazole ionic liquid on alkylated nano-silica microspheres

In this study, two different alkylated nano-silicas were synthesized from in-situ growth and post-modification method respectively, and the 1-vinyl-3-ethylimidazolium bromide ([C2VIm]Br) was grafted onto them by radiation-induced grafting technique to fabricate nano-silica based adsorbents for ReO4−/TcO4− removal. The charged imidazolium moieties were controllably immobilized onto the nano-size substates by adjusting the radiation dose and monomer concentration, and the resulting adsorbents (S(P)–Si-MPTS-IL) were characterized by FTIR, SEM, EA and TGA. Subsequently, their adsorption properties for ReO4− were systematically studied in batch adsorption experiments. Combining the advantages of both nano-silica and ionic liquid, the prepared adsorbents exhibited ultrafast uptake (within 1min), high selectivity, and good cyclic stability (5 cycles, 95% retention) against ReO4−. Besides, they showed excellent radiation resistance and the adsorption properties were basically unchanged after 1200 kGy. Finally, FTIR and XPS analysis confirmed that the mechanism of adsorption process was ion exchange. This study laid a foundation for the synthesis and application of novel nano-silica adsorbent for ReO4−/TcO4−.

The Preparation of Novel Amino Acid Imidazole Ionic Liquids and Their Application as Stationary Phase for Capillary Gas Chromatographic Separations

AbstractIn this paper, two new amino acid imidazole ionic liquids IL‐3 and IL‐4 were synthesized for the first time, and their separation performance as the stationary phase for capillary gas chromatography (GC) was tested. The statically coated IL‐3 and IL‐4 capillary columns exhibited moderate to high polarity, and achieved the column efficiency of 2242 plates/m and 2487 plates/m respectively determined by n‐octanol at 120 °C. Importantly, the IL‐3 and IL‐4 columns exhibited excellent separation capability for analytes with varying polarity, including n‐alkanes, arenes, esters, alcohols, bromoalkanes, halogenobenzenes, and halogenated anilines. In addition, the IL‐3 and IL‐4 columns presented high selectivity and separation capability for positional, structural and cis‐/trans‐isomers. In particular, they showed high separation performance of the chloroaniline, bromaniline, iodoaniline and xylidine isomers as an important environmental pollutant. The IL‐3 and IL‐4 columns displayed advantageous resolving capability over the commercial HP‐35 column for aromatic amine isomers, and the separation performance of IL‐4 with long carbon chain was better than that of IL‐3. Moreover, it was applied to determine isomer impurities in real samples, and showing huge potential in GC applications. This work demonstrates the potential of the amino acid imidazole ionic liquids as a new type of stationary phase in GC separations.

Intramolecular synergistic catalysis of ternary active sites of imidazole Ionic-liquid polymers immobilized on nanosized CoFe2O4@polystyrene composites for CO2 cycloaddition

The cycloaddition reaction of CO2 with epoxides is challenging, thereby requiring the development of environmentally friendly catalysts. Herein, a strategy was developed to construct a multifunctional heterogeneous magnetic catalyst (MPNPs-[ImR2NH2][ZnBr3]) of aminoethyl imidazole metal halide ionic liquids coated on nano-sized CoFe2O4@polystyrene for CO2 cycloaddition. The created catalytic system displayed the intramolecular synergy of ternary active sites (Zn2+, Br−, and –NH2), as well as coupling of catalysis and magnetic separation. In the absence of co-catalyst and solvent, MPNPs-[ImR2NH2][ZnBr3] exhibited excellent catalytic performance for CO2 cycloaddition (99.92% yield and 100% selectivity) at 120 ℃ with 0.16 mol% catalyst dosage in 2.5 h. By appropriately increasing the reaction duration and catalyst dosage, 98.83% conversion and 99.26% selectivity were achieved even at mild conditions of 60 °C and 0.1 MPa. After 10 cycles of reuse, the recycled MPNPs-[ImR2NH2][ZnBr3] demonstrated the same high-efficiency activity as the fresh catalyst, as well as excellent stability and magnetic separation. Based on the density functional theory (DFT) calculations, the intramolecular synergy of ternary active sites and the catalytic mechanism of bimolecular activation based on the multifunctional structure were proposed. This excellent catalyst was attributed to the intramolecular synergy of ternary active sites, large loading of active centers, lower internal diffusion resistance, the inert protective effect of polystyrene layer and the easily magnetic separation of CoFe2O4, highlighting a new direction for green catalytic chemistry.

A Z-scheme Heterojunctional Photocatalyst Engineered with Spatially Separated Dual Redox Sites for Selective CO2 Reduction with Water: Insight by In situ µs-transient Absorption Spectra.

Solar-driven CO2 reduction by water with a Z-scheme heterojunction affords an avenue to access energy storage and to alleviate greenhouse gas (GHG) emissions, yet the separation of charge carriers and the integrative regulation of water oxidation and CO2 activation sites remain challenging. Here, a BiVO4 /g-C3 N4 (BVO/CN) Z-scheme heterojunction as such a prototype is constructed by spatially separated dual sites with CoOx clusters and imidazolium ionic liquids (IL) toward CO2 photoreduction. The optimized CoOx -BVO/CN-IL delivers an ≈80-fold CO production rate without H2 evolution compared with urea-C3 N4 counterpart, together with nearly stoichiometric O2 gas produced. Experimental results and DFT calculations unveil the cascade Z-scheme charge transfer and subsequently the prominent redox co-catalysis by CoOx and IL for holes-H2 O oxidation and electrons-CO2 reduction, respectively. Moreover, in situ µs-transient absorption spectra clearly show the function of each cocatalyst and quantitatively reveal that the resulting CoOx -BVO/CN-IL reaches up to the electron transfer efficiency of 36.4% for CO2 reduction, far beyond those for BVO/CN (4.0%) and urea-CN (0.8%), underlining an exceptional synergy of dual reaction sites engineering. This work provides deep insights and guidelines for the rational design of highly efficient Z-scheme heterojunctions with precise redox catalytic sites toward solar fuel production.

Vapor-liquid equilibrium for dimethyl ether and three imidazolium ionic liquids as working pairs in absorption-refrigeration cycle

To overcome the shortcomings of traditional working pairs of H2O/LiBr and NH3/H2O, the combination of dimethyl ether (DME) and ionic liquids (ILs) have been studied recently. The solubilities of DME in [HMIM][BF4], [HMIM][PF6] and [HMIM][Tf2N] were firstly measured and correlated using NRTL equation. The thermodynamic performance of absorption refrigeration system (ARS) using those working pairs are compared with R152a/[HMIM][Tf2N], R1234ze(E)/[HMIM][Tf2N] and other DME/IL pairs which include [BMIM][BF4], [BMIM][PF6] and [BMIM][Tf2N]. Under the studied condition Tg/Ta/Tc/Te = 325–370 K/300 K/300 K/278 K, the maximum COPs of DME/[HMIM][Tf2N], DME/[BMIM][PF6] and R152a/[HMIM][Tf2N] in ARS are 0.592, 0.531 and 0.648, respectively, while that of R1234ze(E)/[HMIM][Tf2N] is only 0.345. DME/[BMIM][PF6] performs best at Tg = 350 K, but at Tg = 340 K, DME/[HMIM][Tf2N] shows better performance. The difference of optimal Tg between them is about 10 K. It shows that ARS of using DME/[HMIM][Tf2N] can utilize lower-grade waste heat. Our studies prove that DME/ILs are good choices to balance the environmental protection property and energy efficiency improve.

Experimental and DFT Studies on Electrochemical Performances of Ester-Containing Vinylimidazolium Ionic Liquids: Effect of the Ester Substituent and Anion

Four imidazolium ionic liquids (ILs) with vinyl and ester groups were synthesized and characterized by 1H NMR, 13C NMR, and element analysis. The refractive index, electrical conductivity (EC), and electrochemical stability window (ESW) of the ILs were determined. The effect of the alkyl chain length of the ester group and anions on electrochemical properties was analyzed by density functional theory (DFT) calculations. At the same temperatures, the EC of the ILs decreased with the increase of the alkyl chain length. The ester group and vinyl group of cations showed a negative effect on the EC. The ESW increased with the increase of the alkyl chain length. The introduction of the ester group and vinyl group decreased the cathodic limiting potential of ester-based vinylimidazolium cations. DFT simulations showed that the structure of the IL was closely related to the EC and ESW. The average hydrogen bond length increased with the increase of the alkyl chain length of the ester group. The absolute interaction energy of ILs decreased with the increase of the alkyl chain length. Introduction of the vinyl group and ester group into the imidazolium cation resulted in a stronger cation–anion interaction, strengthening the ion mobility and charge transfer, resulting in a lower EC. The information is useful for the design and optimization of ILs as electrolytes for energy storage applications.

The C-3 Functionalization of 1H-Indazole through Suzuki–Miyaura Cross-Coupling Catalyzed by a Ferrocene-Based Divalent Palladium Complex Immobilized over Ionic Liquid, as Well as Theoretical Insights into the Reaction Mechanism

The C-3 functionalization of 1H-indazole could produce a lot of highly valuable pharmaceutical precursors, which could be used for the treatment of cancer and many other inflammatory diseases. This work was focused on the C-3 functionalization of 1H-indazole through Suzuki–Miyaura cross-coupling of 3-iodo-1H-indazole with organoboronic acids, catalyzed by various palladium catalysts immobilized over imidazolium ionic liquids, as well as catalyst recycling. A series of reaction parameters, including the substrate, catalyst, and ionic liquid, were fully investigated. It is significant to note that the yields of the present Suzuki–Miyaura cross-coupling were mainly determined by the catalyst and the solvent used, more than the chemical structure of the substrate. Furthermore, ferrocene-based divalent palladium complexes showed better catalytic outputs compared to simple palladium salts. Moreover, using two imidazolium ionic liquids, BMImX (BMIm+ = 1-n-butyl-3-methylimidazolium, X− = BF4−, PF6−) not only improved the yields of cross-coupled products, but also avoided the formation of Pd(0) black, as compared to the non-ionic liquid facilitated reactions, and simultaneously making catalyst recycling more effective. On average, BMImBF4 performed better than BMImPF6. Additionally, scientific calculations revealed that 1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (PdCl2(dppf)) showed a lower energy barrier in the formation of intermediates than [1,1′-bis(di-tert-butylphosphino)ferrocene]dichloropalladium(II) (PdCl2(dtbpf)), leading to higher catalytic outputs. This work may contribute to the development of 1H-indazole-derived new pharmaceuticals.

Carboxy-functionalized imidazolium ionic liquid immobilized on MCM-41 as recyclable catalysts for carbon dioxide conversion to cyclic carbonates

Integrating multifunctional active sites into an appropriate porous material is a promising strategy to achieve great catalytic performance for CO2 cycloaddition. Herein, carboxy-functionalized imidazolium ionic liquid were successfully anchored onto the MCM-41 mesoporous silicates. The resultant MCM-41-Imi/COOH integrates hydrogen bond donor, Lewis base and nucleophilic ionic sites, and possesses a high surface area and mesopore structure. As-prepared catalyst achieves a good catalytic activity for CO2 cycloaddition with propylene oxide under cocatalyst- and solvent-free conditions. Moreover, the catalyst MCM-41-Imi/COOH exhibits the good cycling stability and versatility to various epoxides. In particular, the catalyst shows a satisfactory catalytic activity for catalyzing dilute CO2 conversion to cyclic carbonate. Furthermore, a possible reaction mechanism for the cycloaddition of CO2 with propylene oxide over the catalyst MCM-41-Imi/COOH was proposed.

Tailoring Phosphonium Ionic Liquids for a Liquid-Liquid Phase Transition.

The existence of more than one liquid state in a single-component system remains the most intriguing physical phenomenon. Herein, we explore the effect of cation self-assembly on ion dynamics in the vicinity of liquid-liquid and liquid-glass transition of tetraalkyl phosphonium ([Pmmm,n]+, m = 4, 6; n = 2-14) ionic liquids. We found that nonpolar local domains formed by 14-carbon alkyl chains are crucial in obtaining two supercooled states of different dynamics within a single ionic liquid. Although the nano-ordering, confirmed by Raman spectroscopy, still occurs for shorter alkyl chains (m = 6, n < 14), it does not bring calorimetric evidence of LLT. Instead, it results in peculiar behavior of ion dynamics near the liquid-glass transition and 20-times smaller size of the dynamic heterogeneity compared to imidazolium ionic liquids. These results represent a crucial step toward understanding the nature of the LLT phenomenon and offer insight into the design of efficient electrolytes based on ionic liquids revealing self-assembly behavior.

Imidazolium-based ionanofluid electrolytes with viscosity decoupled ion transport properties for lithium-ion batteries

A series of LiTFSI salt-doped ionanofluid electrolytes based on imidazolium ionic liquid that includes ionic liquid functionalized SnO2 nanoparticles were prepared through a simple solution-chemistry method. The obtained ionanofluid electrolytes exhibit high thermal stability, fragility, and substantially lower crystallinity than the original ionic liquid electrolytes. The temperature-dependent ion conductivity study indicates that in contrast to ionic liquid-based electrolytes, ionanofluid electrolytes are apparent to have viscosity-decoupled ion transport properties. The Li/LiFePO4 cell assembled with 15 wt% LiTFSI salt-doped ionanofluid electrolyte, having the highest Li+ ion transport ability with moderate ion conductivity, demonstrates appreciable cycling performance with excellent rate capability. The cell delivers a room temperature discharge capacity of about ∼ 141.2 mAhg−1 (∼88% of theoretical capacity (CTheo) of LiFePO4) at C/5 rate and is able to retain more than 96 % of the same with nearly 99 % coulombic efficiency after 50 charge–discharge cycles. The potentio-electrochemical impedance study reveal that the ionanofluid electrolyte able to form a stable passivation layer within the cell. The study establishes the enormous potential of ionanofluid electrolytes for practical applications in next-generation lithium-ion batteries.

Research on CO2 capture by imidazolium and alkali metal salt hybrid ionic liquids

In this work, several alkali metal salts, shortened by MBF4 and CH3OOM(MAc, M = Li+, Na+, K+), were mixed with [Bmim][BF4] or [Bmim][Ac] separately to prepare kinds of hybrid absorbents (i.e., [Bmim][BF4]-LiBF4, [Bmim][BF4]-NaBF4 and [Bmim][BF4]-KBF4 with the same anion of [BF4]-, [Bmim][Ac]-LiAc, [Bmim][Ac]-NaAc and [Bmim][Ac]-KAc with the same anion of acetate) to absorb CO2. The results show that the hybrid absorbents based on [Bmim][BF4] has a relatively enhanced absorption effect on CO2, while the hybrid absorbent based on [Bmim][Ac] has an inhibitory effect. When a low concentration of MBF4 was applied, LiBF4-[Bmim][BF4] shows higher CO2 capacity than NaBF4-[Bmim][BF4] and KBF4-[Bmim][BF4] solutions. With the concentration of MBF4 increase, NaBF4-[Bmim][BF4] and KBF4-[Bmim][BF4] become more favorable for CO2 absorption, which also appeared in the MAc-[Bmim][Ac] systems. According to the MD simulation results, Na+ and K+ have stronger attraction forces with CO2, and Na+ is easier to make the [BF4]- anions to aggregate around it. According to the MD calculations, for the [Bmim][BF4]-MBF4 hydrid systems, Na+ has the weakest ability to aggregate and form M+ layer hindering the contact of CO2 and anion. Combining with its strongest ability to attract the [BF4]- anion, a largest space of [Bmim][BF4] to accomodate more CO2 molecules is created. In comparison, for the physical–chemical absorbent [Bmim][Ac], the strong M+ aggregation and [Ac]- attraction by M+ are the main reasons for the decreased CO2 capacity, due to the reduced number of [Ac]- responsible for the chemically binding with CO2 during absorption.

Simultaneous enhancement of critical heat flux and heat transfer coefficient via in-situ deposition of ionic liquids during pool boiling

Two-phase heat transfer processes such as boiling are required to address waste heat management challenges. Among the various regimes, the nucleate boiling regime, which relies on the ebullition cycle to dissipate large amounts of heat within narrow temperature budgets is desired in such applications. However, an insulating vapor blankets the heater at higher heat fluxes to interrupt this high heat transfer coefficient (HTC) regime. This limiting heat flux beyond which a thermal runaway occurs in boiling systems is known as the critical heat flux (CHF). Accordingly, easy-to-implement and reliable strategies for simultaneous enhancement in HTC and CHF are desired. Typical surface modification/coating strategies used in this regard are often expensive and suffer from the issues of delamination and fouling. Here we utilize aqueous solutions of imidazolium ionic liquids (ImILs) to propose a facile, scalable, and robust strategy to address these issues. We show that the in-situ deposition of short-chain ImILs such as [C2mim][Cl] enhances heater surface wettability to remarkably increase the CHF to ≈1600kW/m2, i.e., ≈1.6× increase compared to the baseline case of pure water. We explain the mechanism of this atypical CHF enhancement with molecular additives via thorough surface tension, foamability, surface, and wettability characterization experiments. We next vary the hydrophobic chain length of the ImILs to facilitate a simultaneous enhancement in CHF and HTC. We perform a quantitative comparison with the existing studies in the literature to demonstrate the potential of our approach. Ease of implementation along with the flexibility to favorably manipulate the heater surface and the boiling fluid properties simultaneously by tuning the structure of ImILs are promising for current and future thermal management challenges.

Exploring the influence of the type of anion in imidazolium ionic liquids on its thermal stability

Exploring the influence of the type of anion in imidazolium ionic liquids on its thermal stability

Quantitative Relation between Ionic Diffusivity and Ionic Association in Ionic Liquid–Water Mixtures

Molecular dynamic simulations of aqueous mixtures of imidazolium ionic liquids (ILs) were performed to elucidate the dependence of the ionic diffusivity on the microscopic structures changed by water. Two distinct regimes of the average ionic diffusivity (Dave) were identified with the increased water concentrations: the jam regime with slowly increased Dave and the exponential regime with rapidly increased Dave, which are found to be directly correlated to the ionic association. Further analysis leads to two general relationships independent of IL species between Dave and the degree of ionic association: (i) a consistent linear relationship between Dave and the inverse of ion-pair lifetimes (1/τIP) in the two regimes and (ii) an exponential relationship between normalized diffusivities (D̃ave) and short-ranged interactions between cations and anions (Ẽions), with different interdependent strengths in the two regimes. These findings revealed and quantified the direct correlation between dynamic properties and ionic association in IL-water mixtures.

New Mn(III)/Fe(III) complexes with thiohydantoin-supported imidazolium ionic liquids for breast cancer therapy

This study offers, for the first time, the design and synthesis of hybrids integrating imidazolium ionic liquids (IMILs) and thiohydantoins (THs) motifs and their Mn/Fe(III) complexes for cancer therapeutic applications. The molecular structures of thiohydantoin-supported imidazolium ionic liquids (THIMILs) (4a-c) and their complexes were proposed based on microanalytical and spectroscopic investigations. On the other hand, the UV–Vis spectroscopic and magnetic measurements, as well as comparisons with previously reported comparable complexes, led to the postulation of square pyramidal and octahedral geometries for Mn(III)THIMIL and Fe(III)THIMIL complexes, respectively. According to the MTT cytotoxicity assay results, the new hybrids inhibited MCF-7 cell proliferation more effectively than HepG2 and selectively as well. The anti-breast cancer performance varies depending on the hybrid structure, dose, and treatment duration. Among the compounds tested, Fe(III)THIMIL analog (6b) was the most active and selective anti-MCF-7 agent (IC50 1.98±0.56 μM, SI 34.92). It was found that 6b has the capacity to trigger G2/M cell cycle arrest and apoptosis in MCF-7 cells, presumably through a p50 route. Meanwhile, the molecular docking of 6b with Bcl-2 and p50 proteins showed great promise in the field of cancer treatment by modulating the levels of expression in these proteins.

N-heterocyclic carbene-mediated oxidation of copper(I) in an imidazolium ionic liquid

Abstract The aerobic oxidation of copper(I) to copper(II) was studied in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium acetate [BMIm][OAc]. Temperatures above 100 °C promote the deprotonation of the C2 atom of the imidazolium ring and the dissolution of CuCl. 1H and 13C NMR spectra indicate the formation of the N-heterocyclic carbene (NHC) complex [NHC] CuICl under inert conditions. Upon aerobic oxidation, air-stable blue-green crystals of [BMIm]2[CuII 2(OAc)4Cl2] precipitate in high yield and the NHC is recovered. X-ray diffraction on a single-crystal of the complex salt revealed a monoclinic structure with space group P21/n. The centrosymmetric dinuclear acetate complex [Cu2(OAc)4Cl2]2– has the paddle-wheel motif and is weakly paramagnetic.

Magnetically-separable quasi-homogeneous catalyst: Brush-type ionic liquid polymer coated magnetic polymer microspheres for tandem reactions to produce 4H-pyrans/biodiesel

Employing magnetic polystyrene microspheres as the core and brush-type alkaline imidazolium ionic liquid polymers as the covalent bonds, a robust magnetically-separable quasi-homogeneous magnetic brush-type ionic liquid polymers ([Im][OH]/MP-B) was synthesized. Due to the features of brush-type ionic liquid polymer (BILPs), [Im][OH]/MP-B demonstrated high catalytic activity. With a broad variety of substrates, [Im][OH]/MP-B was applied in Knoevenagel-Michael tandem reactions for the synthesis of 4 H-pyrans (achieving 99.99% conversion and 93.6% yield) and transesterification tandem reactions for sustainable biodiesel production (achieving 99.9% conversion and 95.2% yield). Furthermore, the catalytic performance of [Im][OH]/MP-B was superior to that of [Im][OH]/MP-CL and [Im][OH]/MP-L and comparable with that of homogeneous catalysts. The reasonable and feasible reaction mechanism of magnetic ionic liquid polymers catalyzing tandem reactions was explored in-depth based on the catalytic performance and kinetics, which clearly demonstrated the catalytic activity and stability of [Im][OH]/MP-B. Notably, [Im][OH]/MP-B was effortlessly recovered by magnetic separation and reutilized numerous times with no evident change in catalytic performance, composition, or microstructure, indicating promising possibilities for ecologically friendly procedures. This work provides a potential strategy for the synthesis of magnetic BILPs for tandem reactions, which could serve as a platform for ecologically friendly and sustainable chemistry.

Phyllantin Extraction Using Imidazolium Ionic Liquids with Chloride and Bromide Anion by Microwaved Assisted Extraction Method

Phyllanthin is known to have therapeutic properties such as immunomodulator, nephroprotective, and anticancer. Phyllanthin is a lignan compound that is commonly found in plants of the Phyllanthus genus, one of which is green meniran (Phyllanthus niruri). Solvent Ionic Liquid (IL) is one of the alternative solvents that are widely used for the extraction of compounds from a plant. The purpose of this study were to compare the extraction yield of philanthine compounds from meniran herbs using IL solvent by Microwave Assisted Extraction (MAE) with methanol by maceration method, and to determine the IL solvent that could produce the highest phyllanthin content. Optimization were carried out using the independent variables IL solvent concentration (0.25 M, 0.75 M, and 1.25 M) and sample-solvent mixture (1:10, 1:12, and 1:14). The variable modeling is designed using Response Surface Methodology that produced 9 runs of combination of solvent concentration and sample-solvent mixture ratio. The phyllanthin assay was using High Performance Liquid Chromatography (HPLC) with ethanol-water mixture (66:34) as mobile phase and wavelength at 229 nm for detection. The optimum extraction conditions showed the best results for imidazolium chloride IL at 1st run with a concentration of 0.75 M, the sample-solvent mixture of 1:14 and phyllanthin content of 0.1783 mg/g while imidazolium bromide IL at 7th run with a concentration of 0.75 M and the sample-solvent mixture of 1:12 and phyllanthin content of 0.23 mg/g. However, the methanol maceration method could only extract phyllanthin as much as 0.1319 mg/g. Based on these results, the use of IL-MAE was more effective than the methanol maceration method due to higher phyllantin extract.