Carboxymethylated maltodextrin as a chiral selector for the separation of some basic drug enantiomers using capillary electrophoresis.

In this work, carboxymethylated maltodextrin (Cm-MD) was successfully synthesized as an efficient anionic chiral selector and applied for the enantiomer separation of some basic drugs including tramadol, venlafaxine, verapamil, hydroxyzine, citalopram, fluoxetine, and amlodipine by capillary electrophoresis (CE). The synthesized chiral selector was characterized by the nuclear magnetic resonance and Fourier transform infrared spectrophotometry. Under the optimized Cm-MD modified CE conditions (background electrolyte: phosphate buffer (pH 5.0, 50 mM) containing 5% (w/v) Cm-MD; applied voltage: 20 kV; and capillary column temperature: 25 °C), successful enantiomer separation of all studied chiral drugs were observed. By comparison of Cm-MD and MD for enantiomer separation of the model drugs, it was revealed that Cm-MD exhibits a higher resolution in comparison to the MD modified CE. This enhanced resolution could be attributed to the electrostatic interactions between the cationic drugs and anionic Cm-MD and opposite direction mobility of the host-guest complex relative to the chiral analyte. The optimized Cm-MD modified CE method was successfully used for the assay of the enantiomers of citalopram and venlafaxine in commercial tablets. The proposed method showed the linear range of 5.0-150.0 mg/L and 10.0-150.0 mg/L for both enantiomers of citalopram and venlafaxine, respectively. The limits of quantification were 5.0 and 10.0 mg/L for the enantiomers of citalopram and venlafaxine, respectively. The limit of detection for all enantiomers was found to be < 3.0 mg/L. Intra- and inter-day RSDs (n = 4) were less than 9.7%. The relative errors were less than 9.4% for all enantiomers. The obtained results in this research show that Cm-MD as a new, efficient and inexpensive chiral selector can be used for enantiomer separation of basic drugs using the CE technique.

Green hydrophobic maltodextrin nanosponges for magnetic solid-phase extraction of hypothalamic peptides from plasma samples.

In this work, for the first time, magnetic-phthalated maltodextrin nanosponges (M-PAMDNSs) were synthetized and introduced as efficient and green sorbents. The integration of phthaloyl groups as hydrophobic moieties into networks of maltodextrin nanosponges provided good enrichment for hypothalamic-related peptides (HRPs). The synthesized materials were characterized by 1H nuclear magnetic resonance spectroscopy, water contact angle, attenuated total reflection-Fourier transform infrared spectroscopy, dynamic light scattering, zeta potential, pH point of zero charge, acid-base titration, field-emission scanning electron microscopy, Brunauer-Emmett-Teller, and vibrating sample magnetometer. Under the optimized conditions (sorbent amount: 5.0 mg, desorption solvent volume and type: 300 µL of methanol: H2O: trifluoroacetic acid, extraction time: 15 min, and desorption time: 10 min), the developed magnetic solid-phase extraction (MSPE) method in combination with HPLC-UV was used as a novel and sensitive analytical method for the determination of HRPs in plasma samples. The proposed MSPE-HPLC-UV method provided good linearity (1.5-500 ng mL-1 R2 ≥ 0.9988), low limits of detection (0.1-0.2 ng mL-1) and quantification (0.4-0.8 ng mL-1), desirable precision (RSD ≤ 8.8%, n ₌ 5), satisfactory enrichment factor (EFs ≥ 66.0), and well relative recoveries (92.8-108.8%). Overall, the established method effectively expanded the analytical potential of MSPE approach for the quantification of HRPs in biological samples.

Liquid-Phase Microextraction Approaches for Preconcentration and Analysis of Chiral Compounds: A Review on Current Advances.

Chirality is a critical issue in pharmaceutics, forensic chemistry, therapeutic drug monitoring, doping control, toxicology, or environmental investigations as enantiomers of a chiral compound can exhibit different activities, i.e., one enantiomer can have the desired effect while the other one can be inactive or even toxic. To monitor enantioselective metabolism or toxicokinetic/toxicodynamic mechanisms in extremely low content in biological or environmental matrices, sample preparation is vital. The present review describes current status of development of liquid-phase microextraction approaches such as hollow fiber liquid-phase microextraction (HF-LPME), electromembrane extraction (EME), dispersive liquid-liquid microextraction (DLLME), and supramolecular solvent-based microextraction (SSME), used for sample preparation of enantiomers/chiral compounds. The advantages and limitations of the above techniques are discussed. Attention is also focused on chiral separation approaches commonly applied to study the stereo-selective metabolism or toxicokinetic/toxicodynamic mechanisms of enantiomers in the biological and environmental samples.

Introduction of maltodextrin nanosponges as green extraction phases: Magnetic solid phase extraction of fluoroquinolones.

In the present work, for the first time, fully green maltodextrin nanosponges (MDNSs) as extraction phases for the preparation of magnetic sorbents were introduced. All of the raw materials and synthetic methodologies used to prepare MDNSs follow the principles of green chemistry. Fluoroquinolones (FQs) (ofloxacin, ciprofloxacin, enrofloxacin, and moxifloxacin) were used as model analytes to assess the extraction performance of MDNSs in magnetic solid-phase extraction (MSPE) procedure. Under the optimized conditions, the developed MSPE was coupled with HPLC-UV to sensitively quantify trace levels of four FQs in tap water, wastewater, and river water samples. The proposed MSPE-HPLC-UV method provided wide linearity in the range of 0.25-500.0 ng mL-1 with determination coefficients ≥0.9997. Low limits of detection (LODs ≤0.06 ng mL-1) and quantification (LOQs ≤0.20 ng mL-1) were achieved. Furthermore, the developed green extraction phases compared with all other maltodextrin-based extraction phases were promising.

Selective extraction and determination of Cr(VI) in food samples based on tandem electromembrane extraction followed by electrothermal atomic absorption spectrometry.

In this study, electromembrane extraction (EME) combined with micro-EME (µ-EME) was used for the selective extraction of Cr(VI) from food samples (milk powder, Ocimum basilicum, and fish samples). Electrothermal atomic absorption spectrometry was used for the quantification of Cr(VI). Under the optimized extraction conditions, the extraction recovery of Cr(VI) was 73.7%. This proposed method provided a linear range from 0.01 to 5.0 ng/mL and the limit of detection (LOD) and limit of quantification (LOQ) were 0.003 and 0.010 ng/mL. The %RSD (n = 5) was in the range of 11.2-11.8% at 0.05, 1.0 and 2.5 ng/mL of Cr(VI), and the enrichment factor was 584. The accuracy of the method was evaluated by analysis of SRM 2700 as a certified reference material (CRM) and result was in good agreement with the certified value.

Magnetic solid-phase extraction of high molecular weight peptides using stearic acid-functionalized magnetic hydroxyapatite nanocomposite: determination of some hypothalamic agents in biological samples.

Therapeutic peptides have an important effect on physiological function and human health, so it is momentous to quantify and detect low levels of these biomolecules in biological samples for treatment and diagnostic purposes. In the present study, an efficient magnetic solid-phase extraction (MSPE) method was developed based on stearic acid-functionalized magnetic hydroxyapatite nanocomposite (MHAP/SA) as a novel and cost-effective adsorbent for extraction of five hypothalamic-related peptides (goserelin, octreotide, triptorelin, somatostatin, and cetrorelix) from biological samples. To characterize the morphology and physicochemical properties of MHAP/SA, Fourier transform infrared spectroscopy (FT-IR), energy-dispersive X-ray spectroscopy (EDS), field emission scanning microscopy (FE-SEM), CHNS elemental analysis, Brunauer-Emmett-Teller (BET), and vibrating sample magnetometry (VSM) were applied. Under optimum conditions, the proposed method (MSPE-HPLC-UV) represented favorable linearity with R2 ≥ 0.9987, suitable intra- and inter-day precisions (RSD ≤ 6.9% and RSD ≤ 8.1%, respectively, n = 3), and limits of detection and quantification in the range of 0.75-1.12 ng mL-1 and 2.50-3.75 ng mL-1, respectively. Eventually, the proposed method was used for the extraction and quantification of target therapeutic peptides in plasma and urine samples, and satisfactory relative recoveries were achieved in the range of 90.6-110.3%.

Recent advances and applications of cyclodextrins in magnetic solid phase extraction.

Cyclodextrins (CDs) as a family of cyclic oligosaccharides are toroidal with a hydrophobic interior and a hydrophilic exterior. They are well-known for their ability to form host-guest inclusion complexes with different compounds. They are used as chiral stationary phases in high performance liquid chromatography (HPLC) and gas chromatography (GC) or as chiral reagents in the background electrolyte of capillary electrophoresis (CE). In recent years, they have been used for modification of sorbents or as sorbents in solid phase extraction (SPE) procedures. Magnetic solid-phase extraction (MSPE), as a new type of SPE procedure, has received considerable attention due to its rapid phase separation process as compared to traditional extraction mode. This review covers the synthesis of CD-based magnetic sorbents (such as immobilization of CDs onto the different supports, production of nanosponges, and making hybrid substances with nanomaterials) and the use of these compounds in MSPE of different analytes from biological, environmental, and food samples. Also, prospects of CD-based sorbents for sample pre-treatment are also proposed.