Magnetic microsphere confined ionic liquid was synthesized by covalently bonding N-methylimidazolium on magnetic microspheres. The functionalized magnetic microspheres were characterized by Fourier transform infrared (FT-IR) spectrometry, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The prepared material was used for the preconcentration of three chlorophenols (CPs) in water combined with high-performance liquid chromatography (HPLC). Several conditions that probably affected the extraction efficiency such as standing time, eluent and its volume, sample pH and volume, were optimized. Under the optimal conditions, good recoveries (70.3-88.8%) were achieved with satisfactory relative standard deviations (RSDs) of less than 6.0%. The limits of detection for the three CPs were 0.20-0.35 μg L(-1). The results indicated that the ionic liquid-functionalized magnetic microspheres show significant promise for the analysis of CPs in environmental samples.

In this paper, a solid-phase extraction (SPE) method based on mixed hemimicelles of cetyltrimethyl ammonium bromide (CTAB) on silica-coated magnetic nanoparticles (MNPs) is developed for extraction and preconcentration of compounds from the biological samples. We selected rhein and emodin which are the major active anthraquinones of rhubarb as model analytes. A high performance liquid chromatography-fluorescence detection (HPLC/FLD) method was developed for the determination of rhein and emodin in urine and serum samples. The main factors influencing the extraction efficiency including the amount of surfactant, the concentration of MNPs, the shaking time and the desorption ability of organic solvents were investigated and optimized. No interferences were caused by proteins or endogenous compounds in urine and serum samples. Good linearities (r(2)>0.9995) for all calibration curves were obtained, and the limits of detection (LODs) for rhein and emodin were 0.2 and 0.5 ng/mL in urine samples and 7 and 10 ng/mL in serum samples, respectively. Satisfactory recoveries (92.76-109.90% and 97.53-107.72% for rhein and emodin) in the biological matrices were achieved.

In this paper, ionic liquid (IL)-coated magnetic Fe3O4 nanoparticles (NPs) as an adsorbent of mixed hemimicelles solid-phase extraction (SPE) was investigated for the preconcentration of polycyclic aromatic hydrocarbons (PAHs) from environmental samples. Due to the high surface area and excellent adsorption capacity of the Fe3O4 NPs after modification with ILs, satisfactory extraction recoveries can be achieved with only 80 mg Fe3O4 NPs, 50 mg IL, 300 mL solution at pH = 10 and 10 min for equilibration. A comprehensive study of the adsorption conditions such as the amount of Fe3O4 NPs and ILs, the solution pH, ionic strength, standing time, breakthrough volume, and desorption solvents was presented. The extraction ability of different coating agents, such as 1-hexadecyl-3-methylimidazolium bromide (C(16)mimBr), 1-decyl-3-methylimidazolium bromide (C(10)mimBr) and cationic surfactant cetyltrimethylammonium bromide (CTAB) was also compared. Under the optimized conditions, the recoveries for the water samples analysis were between 76 and 105% with relative standard deviations (RSDs) ranging from 3.9 to 6.9%, and the recoveries for soil samples were between 73 and 104% with RSDs ranging from 1.0 to 6.3%. In this method, only a small amount of C(16)mimBr (50 mg) and Fe3O4 NPs (80 mg) was needed to obtain satisfactory recoveries.

Amino acid ionic liquids (AAILs) have received great attention due to their potentials in catalysis and separations. In this work, functional AAILs were used as solvent and selector in chiral liquid–liquid extraction for the first time. The AAILs have shown distinct enantioselectivity in amino acid extraction. Using these functional AAILs as acceptor phase and ethylacetate as donor phase, more L-enantiomer of amino acid was extracted into the ionic liquid phase than that of D-enantiomer. The influencing factors, including AAILs structure, copper ion concentration, organic phase and amino acid concentration, were investigated. We found that the enantioselective enrichment of racemic amino acids was achieved through a chiral ligand-exchange mechanism. The enantioselectivity of single-step extraction was up to enantiomeric excess value of 50.6%. Moreover, the functional AAILs were found to be efficient extraction solvents for amino acids. The logarithm of distribution coefficient for L-Phe was in the range of 3.4–3.6 in the ionic liquid–ethylacetate two-phase system. This liquid–liquid extraction approach may extend the application of ionic liquids in chiral separations.

Nowadays, chromatographic methods are widely applied in contemporary chemistry, e.g.HPLC, HPLC–MS, etc. However, organic solvents are required here, sometimes even in large quantities, including toxic acetonitrile, methanol, etc. Hence, chemical methods with less or no use of organic solvents, the so-called green chemistry methods are attracting great interest. In this paper, a green micellar liquid chromatography (MLC) method is proposed, and the use of a micellar mobile phase to give a more sensitive and rapid separation than in conventional high-performance liquid chromatography (HPLC). As an example, the method was successfully applied to the analysis of cryptotanshinone (CT) and tanshinone IIA (TS), which are usually used as the bioactive markers in biological samples or herbal medicinal preparations. No extraction step is required. A C18 column and a micellar mobile phase of 0.15 M sodium dodecyl sulfate (SDS) and 6.4% n-butanol were used. No interferences were caused by proteins or endogenous compounds in the urine, serum samples and herbal medicinal preparations. The limits of detection (LODs) for CT and TS were 12.5 and 15 ng mL−1 in micellar solutions, 18 and 25 ng mL−1 in urine samples and 20 and 30 ng mL−1 in serum samples, respectively. Compared with conventional reversed-phase chromatography where methanol–water (75 : 25, v/v) is used as the mobile phase, the proposed MLC method is more sensitive and time-saving.

Recently, amino acid ionic liquids (AAILs) have attracted much research interest. In this paper, we present the first application of AAILs in chiral separation based on the chiral ligand exchange principle. By using 1-alkyl-3-methylimidazolium L-proline (L-Pro) as a chiral ligand coordinated with copper(II), four pairs of underivatized amino acid enantiomers-dl-phenylalanine (dl-Phe), dl-histidine (dl-His), dl-tryptophane (dl-Trp), and dl-tyrosine (dl-Tyr)-were successfully separated in two major chiral separation techniques, HPLC and capillary electrophoresis (CE), with higher enantioselectivity than conventionally used amino acid ligands (resolution (R(s))=3.26-10.81 for HPLC; R(s)=1.34-4.27 for CE). Interestingly, increasing the alkyl chain length of the AAIL cation remarkably enhanced the enantioselectivity. It was inferred that the alkylmethylimidazolium cations and L-Pro form ion pairs on the surface of the stationary phase or on the inner surface of the capillary. The ternary copper complexes with L-Pro are consequently attached to the support surface, thus inducing an ion-exchange type of retention for the dl-enantiomers. Therefore, the AAIL cation plays an essential role in the separation. This work demonstrates that AAILs are good alternatives to conventional amino acid ligands for ligand-exchange-based chiral separation. It also reveals the tremendous application potential of this new type of task-specific ILs.

One of the biggest challenges in analyzing traditional Chinese medicines (TCMs) is the complexity of the sample matrices. Sample preparation plays an important role in meeting the challenge because it can isolate and enrich the target analytes.

Ionic liquid surfactants are a class of ionic liquids (ILs), which can form micelles in the aqueous solution. In this paper, we demonstrate a novel extracting system based on the use of IL surfactants in ultrasonic-assisted extraction followed by HPLC analysis. No organic solvents were used in the extraction, making this method environmentally friendly and more attractive than the conventional organic solvent-based extraction methods. As an example, this method was applied to determine tanshinones in Chinese herbal medicine Salvia miltiorrhiza bunge. The effect of the carbon chain length of the IL cation, as well as other influencing factors on ultrasonic-assisted extraction, was investigated in detail. Under the optimized conditions, satisfactory extraction efficiency was achieved with the recoveries ranging from 87.5 to 107.6%, and the RSDs were lower than 6%. This work shows a promising prospect of the IL surfactants in the extraction of active ingredients from herbs.

Aristolochic acid analogues, including aristolochic acids (AAs) and aristolactams (ALs), are known to be nephrotoxic, carcinogenic and mutagenic. In this paper, a high-performance liquid chromatography–diode array detection–fluorescence detection (HPLC–DAD–FLD) method was developed for the simultaneous determination of six AAs together with five ALs. Baseline separation was obtained on an ODS C18 analytical column with 0.2% HAc/methanol gradient elution. The hyphenation of DAD and FLD allows the method to directly meet the analysis requirements of most herbal plants with high sensitivity and selectivity. For trace analysis, aristolochic acids were reduced to their corresponding aritstolactams in acidic solution containing iron powder, and then high sensitive detection and quantification were carried out. The method was successfully validated in the matrices of various Aristolochiaceae plants and their preparations. Linearities of around 3–4 orders of magnitude were obtained with correlation coefficients exceeding 0.9970. The detection limits were decreased to 0.2ng/ml. Satisfactory intra-day and inter-day precisions were achieved with RSDs less than 5.74%, and the average recovery factors were in the range of 94.5–99.2%.

Amino acid ionic liquids (AAILs) containing imidazolium cations and amino acid (AA) anions, were synthesized and applied as task-specific ionic liquids. A sensitive and fast liquid chromatography–mass spectrometry (LC–MS) method was established for the quantitative analysis of 20 AAILs. Using ion pairing-reversed phase liquid chromatography technique, heptafluorobutyric acid was used as ion-pairing reagent to increase the retention of AAILs. Based on the zwitterionity of amino acid, this method was proposed to determine both the cation and the anion of AAILs simultaneously. The limit of detection of this method is down to 1–15 ng/mL and the analysis time is less than 15 min. According to the analytical data of seven selected AAILs, we found that the content of amino acid anion is always lower than that of butyl methyl imidazolium cation in AAILs. Moreover, the molar ratio of imidazolium cation to amino acid anion is dependent on the chemical property of the amino acid. These results supplied useful information on the interaction of imidazolium cation with acidic, basic, neutral and non-polar amino acids in AAILs.

N-(2-Phenyl-indolyl)-acetic acid (PIAA), a new fluorescent derivatizing reagent, was used for the determination of diethylene glycol (DEG) by high-performance liquid chromatography with fluorescence detection. DEG was derivatized to ester by using PIAA in the presence of 1-ethyl-3-(3-dimethylaminopropyl)carbodimide hydrochloride (as dehydrating agent) and 4-(dimethylamino)pyridine (as base catalyst) in acetonitrile at 60 degrees C for 75 min. The influence of solvent, temperature, catalyst base, concentration of labeling reagent, and couple reagent on the derivatization was investigated. The fluorescence detection was performed with excitation at 340 nm and emission at 377 nm. Baseline separation was obtained on an Ultimate XB-C18 analytical column with water/acetonitrile gradient elution, good linearity was obtained within 0.5-50 microg/mL with a correlation coefficient of 0.9997. The limit of detection was 0.01 microg/mL (signal-to-noise ratio = 3). The method has been successfully applied to determine DEG in toothpaste samples with satisfactory recoveries ranging from 89.0 to 94.9%. The proposed method was shown to be a promising technique for the determination of DEG with high sensitivity.

Ionic liquids are often contaminated by trace-colored impurities. In this paper, a solid-phase extraction (SPE) method for purification of undiluted imidazolium ionic liquids was described. A SPE apparatus with octadecylsilyl (ODS) solid phase was proposed to separate these impurities from ionic liquids via hydrophobic interaction. Solid-phase extraction with ODS can improve the spectroscopic quality obviously for the tested ionic liquids. Without introducing any solvent to ionic liquid, the purified ionic liquid can be used directly in spectroscopic measurements. It was found that short alkyl chain ionic liquids were purified more efficiently than the long alkyl chain ones. This method can be used to purify the hydrogen-bonding anion containing ionic liquids, which cannot be decolorized efficiently by conventional active charcoal method. In comparison with other existing purification methods, ODS is advantageous to solve the purification problem of ionic liquids.

Dehydroandrographolide, andrographolide and geniposide are the main active constituents of many herbal medicines, e.g., Fructus gardeniae, Common Andrographis Herb. They are used as the markers to control the quality of such herbal medicines and their herbal preparations. In this paper, a simple and sensitive high-performance liquid chromatographic (HPLC) method coupled with photodiode array detection (DAD) and electrospray mass spectrometry (ESI/MS) were developed to determine the three compounds simultaneously in extracts of medicinal herbs and herbal preparations produced by different companies. The extracts were separated on a C18 reversed phase HPLC column, with a gradient solvent system, the time for the separation of the three target analytes was 10min. The abundance ions were recorded using selected ion monitoring (SIM) mode with m/z 297.3, 297.3 and 411.1 for dehydroandrographolide, andrographolide and geniposide, respectively. The limit of detection for dehydroandrographolide, andrographolide and geniposide were 20, 30 and 150ngmL−1, respectively. The proposed method was successfully applied to the determination of the contents of the compounds in related to medicinal herbs and preparations.

By optimizing the extraction, separation and analytical conditions, a simple, reliable and effective high-performance liquid chromatography method coupled with photodiode array detector (HPLC–DAD) is presented for simultaneous determination of nine aristolochic acid (AA) analogues, i.e., AA I, AA II, AA C, AA D, 7-OH AA I, aristolic acid, AL II, AL III and AL IV, in twelve medicinal herbs and two preparations. The separation was completed on a C18 column with aqueous methanol containing 0.2% (V/V) acetic acid as mobile phase. Linearities of around two orders of magnitude were obtained with correlation coefficients exceeding 0.9950. Satisfactory intra-day and inter-day precisions were achieved with R.S.D.s less than 4.35%, and the average recovery factors obtained were in the range of 88.4–98.8%. The proposed method appears to be suitable for use as a tool for safety assurance and quality control for commercially available suspect samples containing aristolochic acid analogues.

Aristolochic acid derivatives (AAs) and aristolactam derivatives (ALs) have been characterized by electrospray ionization mass spectrometry, and their fragmentation pathways are proposed. ALs exhibit a single ionization product [M+H]+, whereas AAs show multiple ionization products. By optimizing the chromatographic separation and mass spectrometric parameters, the precursor ions of the derivatives with the best responses were found, and the sensitivities in the determination of the nine derivatives were improved. Based on the investigation of ionization behaviour, a HPLC-DAD/ESI-MS (high-performance liquid chromatography-photodiode array detection/electrospray ionization mass spectrometry) method has been developed for simultaneous analysis of nine derivatives, i.e., AA I, AA II, AA C, AA D, 7-OH AA I, aristolic acid I, AL AII, AL IIIa and AL IVa, in nine medicinal herbs and two preparations. The method appears to be suitable for safety assurance and quality control of commercially available samples with good selectivity and suitable sensitivity.

The major active biological constituents in Citrus herbs are flavonoids, especially hesperidin, naringin and alkaloids, mainly synephrine, with beneficial medical effects on human health. They are used as the markers to control the quality of Citrus herbs. In this paper, a new ion pairing chromatographic method was developed to exclude the most polar solute (synephrine) from the viod volume and to maintain selectivity between the two other solutes (hesperidin and naringin). Perfluorinated carboxylic acids, which are appropriate for MS detection due to their volatility, were used as ion-pairing agents. The problems of the synephrine separation, such as band tailing and low retention, were solved successfully by using perfluorinated carboxylic acids. The effect of heptafluorobutyric acid (HFBA) was the best in the three investigated perfluorinated carboxylic acids. For the flavanone glycosides, the influence of the perfluorinated acids on retention time was rather weak. The two different kinds of the analytes were separated satisfactorily in one run using an isocratic eluent and the total analysis time takes less than 10 min. The abundance of pseudomolecular ions was recorded using selected ion monitoring (SIM) mode of m/z 135.1, 273.1 and 303.1 for synephrine, naringin and hesperidin, respectively. The contents of hesperidin, naringin and synephrine in several Citrus herbs were simultaneously determined by the proposed method.

The cationic gemini surfactant ethylene bis(1‐dodecyldimethylammonium) dibromide was used as a dynamic coating to control EOF and prevent wall adsorption of basic proteins in CE for the first time. This gemini surfactant shows a more powerful capability in EOF reversal than traditional single‐chained surfactant. The gemini surfactant reverses the EOF at a concentration level even less than 0.01 mM, and the EOF magnitude is affected by surfactant concentration, pH, ionic strength, and ions added in buffer. Highly efficient and rapid protein separation ( N >300 000) was obtained with buffer containing 2 mM gemini surfactant under pH ranging from 3 to 6. The effects of surfactant and buffer concentration on protein separation were investigated in detail. Under the optimal conditions, good repeatability (RSD of migration time <0.6% for run‐to‐run and <2.5% for day‐to‐day assays) and recovery (>90%) of tested proteins were obtained. This new dynamic coating is also suitable for biosample analysis.

Without adding any volatile organic solvents, aqueous solutions of room temperature ionic liquids (RTILs) were used as ‘green’ mobile phases to determine octopamine, synephrine and tyramine by liquid chromatography. The problems of the adrenergic amines separation, such as band tailing, low retention and low resolution were solved successfully by using RTIL. The effect of 1-ethyl-3-methylimidazolium tertafluoroborate ([EMIM][BF4]) was the best in the six investigated RTILs. The concentration of [EMIM][BF4], mobile phase pH and column temperature, which influenced the chromatographic behaviors of the analytes, were investigated in detail. The change of retention factors caused by pH shift was obviously suppressed by [EMIM][BF4]. The sensitivity, accuracy and repeatability of this method were found to be satisfactory. The contents of adrenergic amines in several Citrus herbs and extracts, such as Fructus aurantii immaturus, were simultaneously determined by this ‘green’ chromatographic method.