Minglei Tian

Application of ionic liquid for extraction and separation of bioactive compounds from plants

In recent years, ionic liquids (ILs), as green and designer solvents, have accelerated research in analytical chemistry. This review highlights some of the unique properties of ILs and provides an overview of the preparation and application of IL or IL-based materials to extract bioactive compounds in plants. IL or IL-based materials in conjunction with liquid-liquid extraction (LLE), ultrasonic-assisted extraction (UAE), microwave-assisted extraction (MAE), high performance liquid chromatography (HPLC) and solid-phase extraction (SPE) analytical technologies etc., have been applied successfully to the extraction or separation of bioactive compounds from plants. This paper reviews the available data and references to examine the advantages of IL and IL-based materials in these applications. In addition, the main target compounds reviewed in this paper are bioactive compounds with multiple therapeutic effects and pharmacological activities. Based on the importance of the targets, this paper reviews the applications of ILs, IL-based materials or co-working with analytical technologies. The exploitation of new applications of ILs on the extraction of bioactive compounds from plant samples is expected to increase.

Solid-phase extraction of tanshinones from Salvia Miltiorrhiza Bunge using ionic liquid-modified silica sorbents.

New ionic liquid-modified silica sorbents were developed by the surface chemical modification of the commercial silica using synthesized ionic liquids. The obtained ionic liquid-modified particles were successfully used as a special sorbent in solid-phase extraction process to isolation of cryptotanshinone, tanshinone I and tanshinone IIA from Salvia Miltiorrhiza Bunge. Different washing and elution solvents such as water, methanol and methanol-acetic acid (90/10, v/v) were evaluated. A comparison of ionic liquid-modified silica cartridges and traditional silica cartridge show that higher recovery was observed using ionic liquid-modified silica sorbents. A quantitative analysis was conducted by high-performance liquid chromatography using a C(18) column (5 microm, 150 mm x 4.6 mm) with methanol-water (78:22, v/v, and containing 0.5% acetic acid) as a mobile phase. Good linearity was obtained from 0.5 x 10(-4) to 0.5mg/mL (r(2)>0.999) with the relative standard deviations less than 4.8%.

Application of ionic liquids in high performance reversed-phase chromatography.

Ionic liquids, considered “green” chemicals, are widely used in many areas of analytical chemistry due to their unique properties. Recently, ionic liquids have been used as a kind of novel additive in separation and combined with silica to synthesize new stationary phase as separation media. This review will focus on the properties and mechanisms of ionic liquids and their potential applications as mobile phase modifier and surface-bonded stationary phase in reversed-phase high performance liquid chromatography (RP-HPLC). Ionic liquids demonstrate advantages and potential in chromatographic field.

Separation of phenolic acids from natural plant extracts using molecularly imprinted anion-exchange polymer confined ionic liquids.

Polymer-confined ionic liquids were used for the separation of phenolic acids from natural plant extract by utilizing an anion-exchange mechanism. They were synthesized using molecular imprinting technique to reduce non-directional ion-ion interactions during anion-exchange and other interactions with interference substances that could decrease selectivity. A suitable sorbent for phenolic acid separation could be identified based on the adsorption behaviors of phenolic acids on different polymer-confined ionic liquids. Thus, the developed ionic liquid-based molecularly imprinted anion-exchange polymer (IMAP) achieved high recovery rates by solid-phase extraction of phenolic acids from Salicornia herbacea L. extract: 90.1% for protocatechuic acid, 95.5% for ferulic acid and 96.6% for caffeic acid. Moreover, the phenolic acids were separable from each other by repeated solid phase extraction cycles. The proposed method could be used to separate other phenolic acids or organic acids from complex samples.

Solid‐phase extraction of liquiritin and glycyrrhizic acid from licorice using ionic liquid‐based silica sorbent

A new ionic liquid-based silica sorbent was developed by a process involving surface chemical modification of commercial silica using a synthesized ionic liquid. The obtained particles were successfully used as a special sorbent in a solid-phase extraction process to isolate liquiritin and glycyrrhizic acid from licorice. Different washing and elution solvents, such as water, methanol/water (v/v), and pure methanol were evaluated. Ionic liquid-based silica sorbent was compared with traditional C(18) sorbent and it exhibited higher selectivity. Quantitative analysis was carried out by using a C(18) column. Good linearities of two compounds were obtained from 5x10(-4) to 0.2 mg/mL (r(2)>0.99) with the relative standard deviations <1.0%. The target compounds in commercial herbal medicines containing licorice were determined, and the bound rates between the target compounds and protein were obtained by this sorbent.

Task-specific ionic liquid-assisted extraction and separation of astaxanthin from shrimp waste

Astaxanthin, as an outstanding antioxidant reagent, was successfully extracted from shrimp waste by the ionic liquids based ultrasonic-assisted extraction. Seven kinds of imidazolium ionic liquids with different cations and anions were investigated in this work and one task-specific ionic liquid in ethanol with 0.50molL(-1) was selected as the solvent. At the optimized ultrasonic extraction conditions, the extraction amount of astaxanthin increased 98% (92.7microg g(-1)) compared to the conventional method (46.7microg g(-1)). Furthermore, the extracted solution was isolated through the solid-phase extraction with a molecularly imprinted polymer sorbent. After loading the samples on molecularly imprinted polymer cartridge, the different washing and elution solvents, such as water, methanol, n-hexane, acetone and dichloromethane, were evaluated, and finally, astaxanthin was separated from the shrimp waste extract.

Determination of enrofloxacin and ciprofloxacin in milk using molecularly imprinted solid-phase extraction

A molecularly imprinted solid-phase extraction procedure was developed for the simultaneous identification of enrofloxacin and its active metabolite, ciprofloxacin, in milk samples. Water-compatible molecularly imprinted polymers synthesized in a water-methanol system show a high degree of cross-reactivity for enrofloxacin and ciprofloxacin in aqueous environments. The imprinted particles were applied as selective sorbents in a solid-phase extraction process focusing upon complex milk matrices, which allowed the matrix compounds present in milk samples to be removed effectively. The extracts were sufficiently clean for further chromatographic analysis, and no interference originating from the biological matrix was observed. The mean recoveries of enrofloxacin and ciprofloxacin from milk sample were 82.6-93.5% and 81.2-94.8%, respectively, with the RSD less than 7.5%. This method is simple and sensitive, and is therefore an alternative tool to the existing HPLC methods for analyzing residual enrofloxacin and ciprofloxacin in biological samples.

Ultrasonication-assisted extraction and preconcentration of medicinal products from herb by ionic liquids.

Ionic liquid-based extraction of medicinal or useful compounds from plants was investigated as an alternative to supercritical fluid, cloud point and conventional organic solvent extractions. The method integrated extraction and preconcentration. Medicinal products were first extracted by an ionic liquid solution, part of which was then converted to a hydrophobic form by anion metathesis for preconcentration. The remaining soluble ionic liquid acted as a dispersive agent to enhance the efficiency of preconcentration. Protein in the extract was precipitated spontaneously without addition of further solvents. Ultrasonication assisted this method for extraction and preconcentration of cryptotanshinone, tanshinone I and tanshinone II A from Salvia Miltiorrhiza Bunge. 0.233 mg g(-1), 0.695 mg g(-1) and 0.682 mg g(-1) of each, respectively, were extracted using [OMIM][Cl], and preconcentrated in a [OMIM][PF(6)] phase at respective concentrations of 148.1, 507.1 and 486.1 μg mL(-1). The method exhibited potential applicability with other medicinal products.

Solid-phase extraction of matrine and oxymatrine from Sophora Flavescens Ait using amino-imidazolium polymer

A new, polymer-confined, ionic liquid sorbent was developed by a process involving polymerization and modification. The obtained particles were successfully used as a special sorbent in SPE process to isolate matrine and oxymatrine from Sophora Flavescens Ait. Different washing and elution solvents, such as ethanol, methanol, acetonitrile and methanol/triethylamine (90:10, v/v), were evaluated. Compared with the C(18) and NH(2) sorbents, the amino-imidazolium polymer sorbent exhibited higher selectivity. Quantitative analysis was carried out by using a C(18) column. The two compounds exhibited good linearity from 5x10(-3) to 0.50 mg/mL (r(2)>0.99). The bound amounts between target compounds and proteins were obtained by this sorbent. After three recycles of amino-imidazolium polymer, the extract amounts of the target compounds were not significantly decreased.

Selective extraction and separation of oxymatrine from Sophora flavescens Ait. extract by silica-confined ionic liquid.

This study highlighted the application of a two-stepped extraction method for extraction and separation of oxymatrine from Sophora flavescens Ait. extract by utilizing silica-confined ionic liquids as sorbent. The optimized silica-confined ionic liquid was firstly mixed with plant extract to adsorb oxymatrine. Simultaneously, some interference, such as matrine, was removed. The obtained suspension was then added to a cartridge for solid phase extraction. Through these two steps, target compound was adequately separated from interferences with 93.4% recovery. In comparison with traditional solid phase extraction, this method accelerates loading and reduces the use of organic solvents during washing. Moreover, the optimization of loading volume was simplified as optimization of solid/liquid ratio.