Multi-phase extraction of ephedrine from Pinellia ternata and herbal medicine using molecular imprinted polymer coated ionic liquid-based silica.

INTRODUCTION: Ephedrine is a typical compound found in lots of plant species that is used in several medicines for the treatment of asthma and bronchitis. However, excess amounts are harmful to humans, so it needs to be removed. OBJECTIVE: This study developed a multi-phase extraction (MPE) method with a molecular imprinted polymer (MIP) coated ionic liquid (IL)-based silica (SiO2 @IL@MIP) to simultaneously extract and separate ephedrine from Pinellia ternata, 10 medicines, and urine samples. METHODS: IL was immobilized on silica. Subsequently, the IL was combined with the functional monomer, followed by the addition of the crosslinker and template. The resulting sorbent was applied to the MPE, and the extraction, washing and elution solvents were evaluated. RESULTS: Fourier-transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) confirmed the synthesis of SiO2 @IL@MIP. A maximum adsorption amount of 5.76 mg/g was obtained at 30°C at a neutral pH. In MPE, 10.00 mL of methanol could extract all the ephedrine from Pinellia ternata. The interference was removed by washing with 4.00 mL of water, ethanol, and acetonitrile. Finally, 8.00 mL of methanol/acetic acid (99:1, v/v) was applied as the elution solvent. The following were extracted: 5.50 µg/g of ephedrine from Pinellia ternata, 0.00-46.50 µg/g from the 10 herbal medicines, and 68.70-102.80 µg/mL in the urine samples. CONCLUSION: The proposed method was applied successfully to the simultaneously extraction and separation of ephedrine from plants and medicines. These results are expected to provide important data for the development of new methods for the separation and purification of bioactive compounds.

Determination of Heavy Metal Ions and Organic Pollutants in Water Samples Using Ionic Liquids and Ionic Liquid-Modified Sorbents.

Water pollution, especially by inorganic and organic substances, is considered as a critical problem worldwide. Several governmental agencies are listing an increasing number of compounds as serious problems in water because of their toxicity, bioaccumulation, and persistence. In recent decades, there has been considerable research on developing analytical methods of heavy metal ions and organic pollutants from water. Ionic liquids, as the environment-friendly solvents, have been applied in the analytical process owing to their unique physicochemical properties. This review summarizes the applications of ionic liquids in the determination of heavy metal ions and organic pollutants in water samples. In addition, some sorbents that were modified physically or chemically by ionic liquids were applied in the adsorption of pollutants. According to the results in all references, the application of new designed ionic liquids and related sorbents is expected to increase in the future.

Isolation of aristolochic acid I from herbal plant using molecular imprinted polymer composited ionic liquid-based zeolitic imidazolate framework-67.

Aristolochic acid I is a toxic compound found in the genus of Aristolochia plants, which are commonly used as herbal cough treatment medicines. To remove the aristolochic acid I in extract efficiently and selectively, a molecularly imprinted polymer composed of ethylimidazole ionic liquid-based zeolitic imidazolate framework-67 was synthesized and used as the adsorbent. Under the conditions optimized by the software design expert, the sorbent showed highest adsorption amount of 34.25 mg/g in methanol/water (95:5, v/v) at 39°C for 138 min. The sorbent was then applied to solid phase extraction to isolate aristolochic acid I from the extract of the herbal plant Fibraurea Recisa Pierre. 0.043 mg/g of aristolochic acid I was obtained after the loading, washing, and elution processes. The limit of detection of 2.41 × 10-5  mg/mL and good recoveries provided evidence for the accuracy of this method.

Dual ionic liquid-immobilized silicas for multi-phase extraction of aristolochic acid from plants and herbal medicines.

A convenient, and efficient multi-phase extraction method was used to isolate aristolochic acid from real samples. To increase the efficiency, a new dual ionic liquid-immobilized silica was used as a sorbent and the effects of the adsorption conditions were investigated. IM-BIM@Sil in a methanol/water (60:40, v/v) solution at 60 °C extracted the highest amount of aristolochic acid (16.69 mg/g) compared to the other sorbents examined. The sorbent was then applied to the multi-phase extraction of aristolochic acid. After extraction eight times, 2.4-70.9 × 10-3 mg/g of aristolochic acid was isolated from nine real samples after several washing and elution steps. The recoveries of aristolochic acid ranged from 70.0% to 110.6% with relative standard deviations of 3.5%-9.1%, highlighting the accuracy of this method.

Isolation of Aflatoxin B1 from Moldy Foods by Solid-Phase Extraction Combined with Bifunctional Ionic Liquid-Based Silicas.

A solid-phase extraction method was developed by using new bifunctional ionic liquid-based silicas as sorbents to isolate aflatoxin B1 from moldy corn and peanut. Firstly, according to the adsorption efficiency, two sorbents imidazolium chloride-butylimidazolium chloride-based silica (Sil@BIm-Im) and imidazolium chloride-hexylimidazolium chloride-based silica (Sil@HIm-Im) were selected. The RSM was introduced to optimize adsorption conditions such as methanol/water ratio, time, and pH. Sil@HIm-Im, which had the highest adsorption efficiency, was used in SPE as a sorbent. After 2.0 mL of loading samples, washing solvents were optimized as 6.0 mL and 4.0 mL of water for corn and peanut, 2.0 mL of acetonitrile, and 3.0 mL of methanol. 3.0 mL of methanol/acetic acid (2.0% vol.) was investigated as an elution solvent. Finally, 0.009 µg/g and 0.023 µg/g of aflatoxin B1 were obtained in corn and peanut extract with recoveries of 80.0%-103.3% and RSDs of 2.37%-6.58%.

High Performance Composite Polymer Electrolytes Doped With Spherical-Like and Honeycomb Structural Li0.1Ca0.9TiO3 Particles.

The spherical-like and honeycomb structural Li0.1Ca0.9TiO3 particles are prepared by spray drying combined with following calcination confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy dispersive X-ray spectrometer (EDS). The poly (vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP))-based composite polymer electrolytes (CPEs) modified with the particles are fabricated by phase inversion and activation processes. The characterization results show that the as-prepared CPE membranes possess the smoothest surface and most abundant micropores with the lowest crystallinity with adding the particles into the polymer matrix, which results in high ionic conductivity (3.947 mS cm-1) and lithium ion transference number (0.4962) at ambient temperature. The interfacial resistance can be quickly stabilized at 508 Ω after 5 days storage and the electrochemical working window is up to 5.2 V. Moreover, the mechanical strength of the membranes gains significant improvement without lowering the ionic conductivity. Furthermore, the assembled coin cell can also deliver high discharge specific capacity and preserve steady cycle performance at different current densities. Those outstanding properties may be ascribed to the distinctive structure of the tailored spherical-like and honeycomb structural Li0.1Ca0.9TiO3 particles, which can guarantee the desirable CPEs as a new promising candidate for the polymer electrolyte.

Separation of glucose and bioethanol in biomass with current methods and sorbents.

Glucose is primarily derived from plant metabolism; it is the primary source of energy for cellular respiration in living organisms. Bioethanol, which is used as fuel, can be obtained from the fermentation of biomass. This article summarizes the current methods of separating glucose and bioethanol. Glucose is generally analyzed by liquid chromatography using a range of sorbents. In the fermentation broth of glucose, the primary produced compound, ethanol, is dissolved in water. Nevertheless, ethanol should be separated to obtain high purity. Distillation is a widely used method and ionic liquids are added to ethanol-water systems to increase separation efficiency. This review discusses the application of new materials (based on silica and membrane) in the separation of ethanol from ethanol-water systems.

Evaluation of alcohol-based deep eutectic solvent in extraction and determination of flavonoids with response surface methodology optimization.

Deep eutectic solvents (DESs) are emerging rapidly as a new type of green solvent instead of an ionic liquid (IL), and are typically formed by mixing choline chloride with hydrogen bond donors. Few studies have applied DESs to the extraction and determination of bioactive compounds. Therefore, in the present study, DESs were used to extract flavonoids (myricetin and amentoflavone), which are well known and widely used antioxidants, to extend their applications. A range of alcohol-based DESs with different alcohols to choline chloride (ChCl) mixing ratios were used for extraction using several extraction methods. Other factors, such as temperature, time, water addition and solid/liquid ratio, were examined systematically using a response surface methodology (RSM). A total of 0.031 and 0.518 mg g(-1) of myricetin and amentoflavone were extracted under the optimized conditions: 35 vol% of water in ChCl/1,4-butanediol (1/5) at 70.0 °C for 40.0 min and a solid/liquid ratio of 1/1 (g 10 mL(-1)). Good linearity was obtained from 0.1 × 10(-3) to 0.1 mg mL(-1) (r(2)>0.999). The excellent properties of DESs highlight their potential as promising green solvents for the extraction and determination of a range of bioactive compounds or drugs.

Determination of organic acids in Salicornia herbacea by solid-phase extraction combined with liquid chromatography.

A solid-phase extraction (SPE) method for the determination of procatechuic acid, ferulic acid and caffeic acid in Salicornia herbacea L. (Hamcho) has been developed. The optimal conditions were obtained by using a C18 SPE cartridge. By using ethanol and acetonitrile /water/ trifluoracetic acid as washing and eluting solvents, most interfering compounds originating from the hamcho matrix were eliminated. The extracts were sufficiently clean to be directly injected into the HPLC for further chromatographic analysis. Good linearity was obtained from 0.1 to 200 microg/mL (r > 0.999) for procatechuic acid, 0.2 to 400 microg/mL (r > 0.999) for caffeic acid and 0.3 to 600 microg/mL (r > 0.999) for ferulic acid, with the relative standard deviations being less than 3.6%. The mean recoveries of procatechuic acid, ferulic acid and caffeic acid from hamcho were more than 79.2% and the detection limit (S/N = 3:1) was 0.02 microg/mL for procatechuic acid, 0.01 microg/mL for caffeic acid and 0.04 microg/mL for ferulic acid. This method is a viable alternative to the existing HPLC methods for analyzing the content of procatechuic acid, ferulic acid and caffeic acid in hamcho.

Evaluation of molecularly imprinted anion-functionalized poly(ionic liquid)s by multi-phase dispersive extraction of flavonoids from plant.

Molecularly imprinted anion-functionalized poly(ionic liquid)s (MAPILs) were prepared by radical polymerization for the multi-phase dispersive extraction (MPDE) of flavonoids from plants. Poly(ionic liquid)s were functionalized with different anions via anion metathesis to enhance their separation efficiency, called anion-functionalized poly(ionic liquid)s (APILs). A molecularly imprinting technique was introduced to produce specific recognition sites by forming complexes between the template molecules and anion-functionalized ionic liquid monomers to reduce the interactions with the interference substances and increase the selectivity. Multi-phase dispersive extraction (MPDE) was applied for separation instead of the traditional solid phase extraction method. The target compounds were first extracted by three-phase (sample-solvent-sorbent) dispersive extraction and cleaned up after removing the sample matrix. This method significantly decrease in the interference and analysis cost. A suitable sorbent for MPDE could be identified based on the adsorption behaviors of flavonoids on different MAPILs. The mean recovery yields of quercitrin, myricetin, and amentoflavone from Chamaecyparis obtusa under the optimized conditions were 88.07, 93.59, and 95.13%. This is a promising method for the extraction, separation and determination of flavonoids or other polyphenolic compounds from natural and other sources.

Multi-phase extraction of glycoraphanin from broccoli using aminium ionic liquid-based silica.

INTRODUCTION: Glucosinolates, a class of phytochemicals found in broccoli, have attracted recent interest due to the potential health benefits associated with their dietary intake. Glucoraphanin, the most common glucosinolate in broccoli can be converted to a known cancer chemopreventive agent. Multi-phase extraction in solid-phase extraction cartridges was developed to simultaneously extract and separate this compound. OBJECTIVE: Multi-phase extraction with functionalised ionic liquid-based silica as a sorbent was used to simultaneously extract and separate glucoraphanin from broccoli. METHODOLOGY: The sorbent and broccoli sample were packed into a single cartridge, and a fixed volume of water was then used to extract and remove the target compound from the sample to the sorbent over 15 repetitions. The sorbent was then washed with n-hexane to remove any interference and the target compound was eluted with water-1% acetic acid (vol.). RESULTS: Under the optimised condition, 0.038 mg/g of glucoraphanin was obtained by multi-phase extraction with 0.2 g of sorbent. CONCLUSION: The adsorption isotherm allowed investigation of the interactions between the sorbent and target compound and provided evidence for the accuracy of this method. The low deviation error, small amount of solvents required, highly selective separation and stability of the method justify further research.

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.

Simultaneous extraction and separation of flavonols and flavones from Chamaecyparis obtusa by multi-phase extraction using an ionic liquid-modified microsphere polymer.

INTRODUCTION: Flavonols and flavones, especially quercitrin, myricetin and amentoflavone, are the main anti-bacterial and anti-cancer compounds in Chamaecyparis obtuse. Multi-phase extraction is a new method that can extract and separate target compounds simultaneously. OBJECTIVE: An amino ionic liquid immobilised microsphere polymer was used as a multi-phase extraction sorbent to extract and separate quercitrin, myricetin and amentoflavone from Chamaecyparis obtusa. METHODOLOGY: The sorbent and Chamaecyparis obtusa powder were packed into a single cartridge. Using a fixed volume of methanol with five repetitions, the target compounds were extracted from the powder to the sorbent. The sorbent was then washed with n-hexane to remove any interfering species and the target compounds were eluted sequentially using water, methanol and methanol containing 1% acetic acid (vol.). RESULTS: Under the optimised conditions, 0.45 mg/g of quercitrin, 0.18 mg/g of myricetin and 0.12 mg/g of amentoflavone from 2.0 g of powder were obtained by multi-phase extraction using 0.3 g of sorbent. CONCLUSION: The method described has a low deviation error, requires a small amount of solvent and is highly selective and reproducible.

Facile synthesis and application of poly(ionic liquid)-bonded silica hybrid materials.

Facile methods were developed to prepare hybrid poly(ionic liquid)-bonded silica for a wide range of applications, particularly in analytical chemistry. The hybrid material obtained was evaluated by comparing its adsorption capacity with other conventional separation materials. In addition, the hybrid material has the potential for industrial scale production.

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.

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.

Separation of monosaccharides by solid-phase extraction with ionic liquid-modified microporous polymers.

Ionic liquid-modified porous polymers with large surface area and large amount of functional groups were developed and used in SPE to separate four monosaccharides. Adsorption isotherm showed that the sorbent with amino ionic liquid groups had the highest interaction with the target compounds. The mobile phase of acetonitrile/water 85:15 and 73:30 v/v can successfully separate the monosaccharides. The sorbent produced reproducible results and performed stably, demonstrating its potential applicability in the separation of extract from natural plant.

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.

Molecular imprinting in ionic liquid-modified porous polymer for recognitive separation of three tanshinones from Salvia miltiorrhiza Bunge.

Five ionic liquid-modified porous polymers with different imidazolium-based functional groups were obtained. A molecular imprinting technique was introduced to form the ordered functional groups in the porous structure. The adsorption isotherm was applied to investigate the interactions between the polymers and target compounds: cryptotanshinone; tanshinone I; tanshinone IIA. Thorough comparison revealed that the polymer with a carboxyl group possessed the highest reorganization of the three compounds. After that, the obtained polymer was applied as the sorbent in the solid-phase extraction process to separate the target compounds from methanol extract. The loading volume of extract solution on the sorbent was determined by adsorption isotherm equation and practical test. Under optimized washing and elution conditions, 0.35 mg/g of cryptotanshinone, 0.33 mg/g of tanshinone I, and 0.27 mg/g of tanshinone IIA from plant were obtained by quantitative HPLC analysis. Moreover, six commercial functional drinks containing tanshinones were purified and analyzed.

Chiral separation and determination of ofloxacin enantiomers by ionic liquid-assisted ligand-exchange chromatography.

A simple and accurate method for the separation and determination of ofloxacin enantiomers was developed by ionic liquid-assisted ligand-exchange high performance liquid chromatography. Both achiral and chiral ionic liquids were tested for their efficiency of ofloxacin enantiomeric separation. The effects of ligands, concentration of metal ion, organic modifier, pH of the mobile phase, and temperature were also investigated and evaluated. Optimal conditions were obtained on a conventional C(18) column, where the mobile phase consisted of methanol/water (20 : 80, v/v) (containing 4.0 mmol L(-1) amino acid ionic liquid and 3.0 mmol L(-1) copper sulfate) at a flow rate of 0.5 mL min(-1). Under this condition, the ofloxacin enantiomers could be baseline separated within 14 minutes; the proposed method was used to analyze different commercial ofloxacin medicines.