Optimized extraction of bioactive compounds from Herba Artemisiae Scopariae with ionic liquids and deep eutectic solvents

Ionic liquids with length of alkyl chain and different anions, deep eutectic solvents with choline chloride and 7 different hydrogen bond donors were applied as extraction additives after optimizing the extraction conditions to increase the extraction amounts of rutin, quercetin, and scoparone from Herba Artemisiae Scopariae. The extraction conditions were optimized as follows: refluxing with methanol with a solid/liquid ratio of 1:120 under 60°C for 60 min after changing the different extraction conditions of: extraction methods (dipping, ultrasonic, reflux and soxlet), extraction solvents (methanol, water and ethanol), extraction temperature (30, 40, 50, 60, 70 and 80°C), extraction time (30, 60, 80, 100 and 120 min), extraction ratio of solid to liquid (1:5, 1:10, 1:20, 1:50, 1:100, 1:120 and 1:150). Under these optimal conditions, the best preformed extraction additive among the 7 kinds of ionic liquids and 7 kinds of deep eutectic solvents extraction additives were selected and optimized with its contraction of 0.5mg/mL. Using the most effective extraction additive, [BMIM][Br], 10275.92 µg/g rutin, 899.73 µg/g quercetin, and 554.32 µg/g scoparone were obtained. Overall, ionic liquids and deep eutectic solvents have potential applications as extraction additives for the extraction of bioactive compounds from nature plants.     

Hybrid molecularly imprinted polymers modified by deep eutectic solvents and ionic liquids with three templates for the rapid simultaneous purification of rutin,scoparone, and quercetin from Herba Artemisiae Scopariae

Different kinds of deep eutectic solvents based on choline chloride and ionic liquids based on 1‐methylimidazole were used to modify hybrid molecularly imprinted polymers with the monomer γ‐aminopropyltriethoxysilane‐methacrylic and three templates (rutin, scoparone, and quercetin). The materials were adopted as solid‐phase extraction packing agents, and were characterized by FTIR spectroscopy and field emission scanning electron microscopy. The hybrid molecularly imprinted polymers modified by deep eutectic solvents had high recoveries and a strong recognition of rutin, scoparone, and quercetin in Herba Artemisiae Scopariae than those modified by ionic liquids. In the procedure of solid‐phase extraction, deep eutectic solvents‐2‐hybrid molecularly imprinted polymers were obtained with the best recoveries with rutin (92.27%), scoparone (87.51%), and quercetin (80.02%), and the actual extraction yields of rutin (5.6 mg/g), scoparone (2.3 mg/g), and quercetin (3.4 mg/g). Overall, the proposed approach with the high affinity of hybrid molecularly imprinted polymers might offer a novel method for the purification of complex samples.     

Ternary choline chloride/caffeic acid/ethylene glycol deep eutectic solvent as both a monomer and template in a molecularly imprinted polymer

A molecularly imprinted polymer based on a ternary deep eutectic solvent comprised of choline chloride/caffeic acid/ethylene glycol was prepared. The caffeic acid in the ternary deep eutectic solvent was used as both a monomer and template. The molecularly imprinted polymer based on the ternary deep eutectic solvent was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, field‐emission scanning electron microscopy, Brunauer–Emmett–Teller surface area analysis, atomic force microscopy, and elemental analysis. A series of molecularly imprinted polymers based on choline chloride/caffeic acid/ethylene glycol with different molar ratios was prepared and applied to the molecular recognition of polyphenols. A comparison of the recognition ability of molecularly imprinted polymers to polyphenols revealed that the choline chloride/caffeic acid/ethylene glycol (1:0.4:1, molar ratio) molecularly imprinted polymer had the best molecular recognition effect with 132 μg/g of protocatechuic acid, 104 μg/g of catechins, 80 μg/g of epicatechin, and 123 μg/g of caffeic acid in 6 h, as well as good molecular recognition ability for polyphenols from a Radix Asteris sample. These results show that the ternary deep eutectic solvent based molecularly imprinted polymer is a potential medium that can be applied to drug purification, drug delivery, and drug analysis.     

Ternary deep eutectic solvent magnetic molecularly imprinted polymers for the dispersive magnetic solid‐phase microextraction of green tea

Ternary deep eutectic solvent magnetic molecularly imprinted polymers grafted on silica were developed for the selective recognition and separation of theophylline, theobromine, (+)‐catechin hydrate, and caffeic acid from green tea through dispersive magnetic solid‐phase microextraction. A new ternary deep eutectic solvent was adopted as a functional monomer. The materials obtained were characterized by FTIR spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, NMR spectroscopy, and powder X‐ray diffraction. The practical recovery of the theophylline, theobromine, (+)‐catechin hydrate, and caffeic acid isolated with ternary deep eutectic solvent magnetic molecularly imprinted polymers in green tea were 91.82, 92.13, 89.96, and 90.73%, respectively, and the actual amounts extracted were 5.82, 4.32, 18.36, and 3.69 mg/g, respectively. The new method involving the novel material coupled with dispersive magnetic solid‐phase microextraction showed outstanding recognition, selectivity and excellent magnetism, providing a new perspective for the separation of bioactive compounds.     

Magnetic molecularly imprinted polymers for recognition and enrichment of polysaccharides from seaweed

New magnetic molecularly imprinted polymers with two templates were fabricated for the recognition of polysaccharides (fucoidan and alginic acid) from seaweed by magnetic solid‐phase extraction, and the materials were modified by seven types of deep eutectic solvents. It was found that the deep eutectic solvents magnetic molecularly imprinted polymers showed stronger recognition and higher recoveries for fucoidan and alginic acid than magnetic molecularly imprinted polymers, and the deep eutectic solvents‐4‐magnetic molecularly imprinted polymers had the best effects. The practical recovery of the two polysaccharides (fucoidan and alginic acid) purified with deep eutectic solvents‐4‐magnetic molecular imprinted polymers in seaweed under the optimal conditions were 89.87, and 92.0%, respectively, and the actual amounts extracted were 20.6 and 18.7 μg/g, respectively. To sum up, the developed method proved to be a novel and promising method for the recognition of complex polysaccharide samples from seaweed.     

Deep eutectic solvents for the purification of chloromycetin and thiamphenicol from milk

Deep eutectic solvents were used in both dispersive liquid–liquid microextraction and solid‐phase extraction for the purification of chloromycetin and thiamphenicol from milk. In the dispersive liquid–liquid microextraction procedure, deep eutectic solvents mixed with chloroform at different ratios (0:1–5:1, v/v) were used as the extraction agent to optimize the procedure, and the ratio of 2:1 v/v was found to be the best extraction agent with 87.23 and 83.17% recoveries of chloromycetin and thiamphenicol, respectively. Furthermore, deep eutectic solvents were also used to modify molecular imprinted polymers in solid‐phase extraction procedure, and the polymers were used to purify chloromycetin and thiamphenicol from milk. Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy were used to characterize the polymers. The solid‐phase extraction recoveries with deep eutectic solvents with molecularly imprinted polymers (chloromycetin and thiamphenicol, two templates), molecularly imprinted polymers (without deep eutectic solvents), and nonimprinted polymers (without a template) for chloromycetin were 91.23, 82.64, and 57.3%, respectively, and recoveries for thiamphenicol were 87.02, 79.03, and 52.27%, respectively. The recoveries of chloromycetin and thiamphenicol from milk in the solid‐phase extraction procedure were higher than using deep eutectic solvents mixed with chloroform as the extraction agent in the dispersive liquid–liquid microextraction procedure.     

Magnetic molecularly imprinted polymers based on silica modified by deep eutectic solvents for the rapid simultaneous magnetic‐based solid‐phase extraction of Salvia miltiorrhiza bunge,Glycine max (Linn.) Merr and green tea

Novel magnetic molecularly imprinted polymers (MMIPs) with multiple‐template based on silica were modified by four types of deep eutectic solvents (DESs) for the rapid simultaneous magnetic solid‐phase extraction (MSPE) of tanshinone Ⅰ, tanshinone ⅡA, and cryptotanshinone from Salvia miltiorrhiza bunge; glycitein, genistein, and daidzein from Glycine max (Linn.) Merr; and epicatechin, epigallocatechin gallate, and epicatechin gallate from green tea, respectively. The synthesized materials were characterized by Fourier transform infrared spectroscopy and field emission scanning electron microscopy. Single factor experiments were to explore the relationship between the extraction efficiency and four factors (the sample solution pH, amount of DESs for modification, amount of adsorbent, and extraction time). It was showed that the DES4‐MMIPs have better extraction ability than the MMIPs without DESs and the other three DESs‐modified MMIPs. The best extraction recoveries with DES4‐MMIP were tanshinone Ⅰ (85.57%), tanshinone ⅡA (80.58%), cryptotanshinone (92.12%), glycitein (81.65%), genistein (87.72%), daidzein (92.24%), epicatechin (86.43%), epigallocatechin gallate (80.92%), and epicatechin gallate (93.64%), respectively. The novel multiple‐template MMIPs materials modified by DES for the rapid simultaneous MSPE of active compounds were proved to reduce the experimental steps than single‐template technique, and increase the extraction efficiency.     

Pipette‐tip solid‐phase extraction based on deep eutectic solvent modified graphene for the determination of sulfamerazine in river water

A green and novel deep eutectic solvent modified graphene was prepared and used as a neutral adsorbent for the rapid determination of sulfamerazine in a river water sample by pipette‐tip solid‐phase extraction. Compared with conventional graphene, deep eutectic solvent modified graphene can change the surface of graphene with wrinkled structure and higher selective extraction ability. The properties of deep eutectic solvent modified graphene and graphene were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Static adsorption showed deep eutectic solvent modified graphene had a higher adsorption ability (18.62 mg/g) than graphene. Under the optimum conditions, factors such as kinds of washing solvents and elution solvents and volume of elution solvent were evaluated. The limits of detection and quantification were 0.01 and 0.03 μg/mL, respectively. The method recoveries of sulfamerazine were in the range of 91.01–96.82% with associated intraday relative standard deviations ranging from 1.63 to 3.46% and interday relative standard deviations ranging from 0.68 to 3.84%. Deep eutectic solvent modified graphene showed satisfactory results (recovery was 95.38%) and potential for rapid purification of sulfamerazine in river water sample in combination with the pipette‐tip solid‐phase extraction method.     

印迹分子聚合物结合低共熔溶剂用于山楂中咖啡酸的固相萃取

在相同的实验条件下,分别合成了以咖啡酸为模板的印迹分子聚合物和无模板分子聚合物。使用场发射扫描电镜法和吸附实验表征这两种聚合物材料的孔状结构和选择性吸附性能。然后利用印迹分子聚合物、无模板分子聚合物、C₁₈萃取小柱这3种材料结合固相萃取法纯化山楂提取物中的咖啡酸,提取率分别为3.46、1.01、1.17 μg/g。为了优化固相萃取过程,实验研究了不同洗脱剂的影响。分别利用用氯化胆碱和甘油、氯化胆碱和尿素(摩尔比均为1:2)合成出两种低共熔溶剂。甲醇与这两种低共熔溶剂分别以不同的体积比混合作为洗脱剂,用于优化咖啡酸的固相萃取过程。实验结果表明,印迹分子聚合物是一种良好的固相萃取材料;当甲醇和甘油基低共熔溶剂在体积比为3:1混合时,表现出最好的洗脱能力,得到咖啡酸的回收率为82.32%。     

Magnetic deep eutectic solvents molecularly imprinted polymers for the selective recognition and separation of protein

A novel and facile magnetic deep eutectic solvents (DES) molecularly imprinted polymers (MIPs) for the selective recognition and separation of Bovine hemoglobin (BHb) was prepared. The new-type DES was adopted as the functional monomer which would bring molecular imprinted technology to a new direction. The amounts of DES were optimized. The obtained magnetic DES-MIPs were characterized with fourier transform infrared spectrometry (FT-IR), thermogravimetric analysis (TGA), field emission scanning electron microscope (FESEM), dynamic light scattering (DLS), elemental analysis and vibrating sample magnetometer (VSM). The results suggested that the imprinted polymers were successfully formed and possessed a charming magnetism. The maximum adsorption capability (Q_max) and dissociation constant (K_L) were analyzed by Langmuir isotherms (R² = 0.9983) and the value were estimated to be 175.44 mg/g and 0.035 mg/mL for the imprinted particles. And the imprinted particles showed a high imprinting factor of 4.77. In addition, the magnetic DES-MIPs presented outstanding recognition specificity and selectivity so that it can be utilized to separate template protein from the mixture of proteins and real samples. Last but not least, the combination of deep eutectic solvents and molecular imprinted technology in this paper provides a new perspective for the recognition and separation of proteins.     

Determination of Chlorogenic Acid and Rutinum in Herba Artemisiae Scopariae with Multitemplate Molecularly Imprinted Polymers for Solid-phase Extraction with High-performance Liquid Chromatography

Novel multitemplate molecularly imprinted polymers were prepared using mixtures of chlorogenic acid and rutinum as molecular templates, acrylamide as a functional monomer, divinylbenzene as the cross-linker, and 20:80 methanol:acetone as the porogen. The polymers were assessed for solid-phase extraction (SPE) for the purification of two compounds from Herba Artemisiae Scopariae. The synthesized molecularly imprinted polymers were identified by infrared spectroscopy and scanning electron microscopy. Systematic characterization of the functional monomer and porogens on the recognition properties of the molecularly imprinted polymers were carried out. Comparison with single-template molecularly imprinted polymers showed that the multitemplate molecular polymers exhibited higher selectivity and adsorption capacity for multiple analytes. The optimization of washing solvent as 1:9 acetone:water and the elution solvent as 9:1 acetonitrile:acetic acid provided a reliable analytical method with strong recognition toward multiple analytes in Herba Artemisiae Scopariae extracts with satisfactory recoveries of 89.6% for chlorogenic acid and 93.8% for rutinum. These results demonstrate that the multitemplate molecularly imprinted polymers coupled with SPE are effective for the selective purification of bioactive compounds in complex samples.     

Three‐phase hollow‐fiber liquid‐phase microextraction based on deep eutectic solvent as acceptor phase for extraction and preconcentration of main active compounds in a traditional Chinese medicinal formula

A three‐phase hollow‐fiber liquid‐phase microextraction based on deep eutectic solvent as acceptor phase was developed and coupled with high‐performance capillary electrophoresis for the simultaneous extraction, enrichment, and determination of main active compounds (hesperidin, honokiol, shikonin, magnolol, emodin, and β,β′‐dimethylacrylshikonin) in a traditional Chinese medicinal formula. In this procedure, two hollow fibers, impregnated with n‐heptanol/n‐nonanol (7:3, v/v) mixture in wall pores as the extraction phase and a combination (9:1, v/v) of methyltrioctylammonium chloride/glycerol (1:3, n/n) and methanol in lumen as the acceptor phase, were immersed in the aqueous sample phase. The target analytes in the sample solution were first extracted through the organic phase, and further back‐extracted to the acceptor phase during the stirring process. Important extraction parameters such as types and composition of extraction solvent and deep eutectic solvent, sample phase pH, stirring rate, and extraction time were investigated and optimized. Under the optimal conditions, detection limits were 0.3–0.8 ng/mL with enrichment factors of 6–114 for the analytes and linearities of 0.001–13 μg/mL (r² ≥ 0.9901). The developed method was successfully applied to the simultaneous extraction and concentration of the main active compounds in a formula of Zi‐Cao‐Cheng‐Qi decoction with the major advantages of convenience, effectiveness, and environmentally friendliness.     

Preparation and characterization of molecularly‐imprinted polymers for extraction of sanshool acid amide compounds followed by their separation from pepper oil resin derived from Chinese prickly ash (Zanthoxylum bungeanum)

Molecularly imprinted polymers were prepared using the molecular structure analogs of sanshool as template molecule, 2‐vinylpyridine and β‐cyclodextrin as double functional monomers, ethylene dimethacrylate as cross linker, and azobisisobutyronitrile as initiator. The structural characteristics of the polymers were determined by Fourier‐transform infrared spectroscopy and scanning electron microscopy. Dynamic adsorption and isothermal adsorption were also investigated. The molecularly imprinted polymers were used to prepare a molecularly imprinted solid‐phase extraction column in order to separate acid amide components from pepper oil resin derived from Chinese prickly ash (Zanthoxylum bungeanum). After eluting, the percentage of acid amide components was enhanced to 92.40 ± 1.41% compared with 23.34 ± 1.21% in the initial pepper oil resin, indicating good properties of purification of molecularly imprinted polymers and potential industrial application.     

Deep eutectic solvents skeleton typed molecularly imprinted chitosan microsphere coated magnetic graphene oxide for solid‐phase microextraction of chlorophenols from environmental water

Novel molecularly imprinted chitosan microspheres were prepared on the surface of magnetic graphene oxide, with deep eutectic solvents both as a functional monomer and template. The prepared molecularly imprinted chitosan microspheres‐magnetic graphene oxide was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, Brunauer‐Emmett‐Teller surface area, thermogravimetric analysis were subsequently combined with solid‐phase micro‐extraction for simultaneous separation and enrichment of the extraction of chlorophenols from environmental water. Factors affecting the extraction efficiency of chlorophenols were optimized using response surface methodology. The actual extraction capacities under the optimal conditions (liquid to solid ratio = 3, cycles of adsorption/desorption = 5, 40°C extraction temperature, and extraction time for 35 min) were 86.90 mg/g. Compared to the traditional materials, the molecularly imprinted chitosan microspheres‐magnetic graphene oxide produced higher selectivity and extraction capacity.     

Polydopamine‐coated magnetic molecularly imprinted polymer for the selective solid‐phase extraction of cinnamic acid,ferulic acid and caffeic acid from radix scrophulariae sample

We describe novel cinnamic acid polydopamine‐coated magnetic imprinted polymers for the simultaneous selective extraction of cinnamic acid, ferulic acid and caffeic acid from radix scrophulariae sample. The novel magnetic imprinted polymers were synthesized by surface imprinting polymerization using magnetic multi‐walled carbon nanotubes as the support material, cinnamic acid as the template and dopamine as the functional monomer. The magnetic imprinted polymers were characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy and vibrating sample magnetometry. The results revealed that the magnetic imprinted polymers had outstanding magnetic properties, high adsorption capacity, selectivity and fast kinetic binding toward cinnamic acid, ferulic acid and caffeic acid. Coupled with high‐performance liquid chromatography, the extraction conditions of the magnetic imprinted polymers as a magnetic solid‐phase extraction sorbent were investigated in detail. The proposed imprinted magnetic solid phase extraction procedure has been used for the purification and enrichment of cinnamic acid, ferulic acid and caffeic acid successfully from radix scrophulariae extraction sample with recoveries of 92.4–115.0% for cinnamic acid, 89.4–103.0% for ferulic acid and 86.6–96.0% for caffeic acid.     

Optimization of heteroatom doped graphene oxide by deep eutectic solvents and the application for pipette‐tip solid‐phase extraction of flavonoids

In order to improve the permeation and adsorption properties of graphene oxide, heteroatoms and deep eutectic solvent were introduced in this study. After being modified, the structural properties of graphene oxide were improved and the materials were applied to the determination of myricetin and rutin in tea sample by pipette‐tip solid‐phase extraction method. The materials were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X‐Ray diffractomer, energy dispersive spectroscopy, atomic force microscope, and specific surface area by Brunauer–Emmett–Teller N₂ adsorption desorption analysis. Meanwhile, they were tested by static and dynamic adsorption. The result showed that the materials after modifying had better adsorption amount for myricetin and rutin than graphene oxide. The calibration graphs of myricetin and rutin in MeOH were linear over 0.10–500.00 µg/mL, and the limits of detection and quantification were in the range of 0.00546–0.0182 µg/mL and 0.00741–0.0247 µg/mL, respectively. A reliable analytical method was developed for recognition targets in tea sample by DES modified nitrogen‐doped graphene oxide with satisfactory extraction recoveries (myricetin 99.77%, rutin 98.14%). It was potential for the rapid purification of myricetin and rutin in tea sample combined with the pipette‐tip solid‐phase extraction.     

Extraction and determination of bioactive flavonoids from Abelmoschus manihot (Linn.) Medicus flowers using deep eutectic solvents coupled with high‐performance liquid chromatography

A highly efficient and ecofriendly extraction method using deep eutectic solvents was developed to extract bioactive flavonoids from Abelmoschus manihot (Linn.) Medicus flowers. First, a series of deep eutectic solvents using choline chloride as hydrogen bond acceptor with different hydrogen bond donors was successfully synthesized. Then, the types of deep eutectic solvents and the extraction conditions for bioactive flavonoids (hyperoside, isoquercitrin, and myricetin) were optimized based on the flavonoids extraction efficiencies. The optimized deep eutectic solvent for hyperoside and isoquercitrin extraction was composed of choline chloride and acetic acid with a molar ratio of 1:2. The optimized deep eutectic solvent for myricetin extraction was composed of one mole of choline chloride and two moles of methacrylic acid. The optimal extraction conditions were set as: solid to solvent ratio, 35:1 (mg/mL); extraction time, 30 min; extraction temperature, 30°C. Qualitative and quantitative analysis were performed using ultra high performance liquid chromatography with tandem mass spectrometry and high‐performance liquid chromatography. And the extraction efficiencies of hyperoside, isoquercitrin, and myricetin under optimal extraction conditions were calculated as 11.57, 5.64, and 1.11 mg/g, much higher than those extracted by traditional extraction solvents. Therefore, the prepared deep eutectic solvents can be selected as alternative solvent to extract bioactive flavonoids.     

Alcohol‐based deep eutectic solvent as a carrier of SiO2@Fe3O4 for the development of magnetic dispersive micro‐solid‐phase extraction method: Application for the preconcentration and determination of morin in apple and grape juices,diluted and acidic extract of dried onion and green tea infusion samples

In this study, a hydrophilic deep eutectic solvent was synthesized as a carrier and disperser of magnetic nanoparticles based on ferrofluid and used to develop the dispersive micro‐solid‐phase extraction method. Ethylene glycol/tetramethylammonium chloride deep eutectic solvent and SiO₂@Fe₃O₄ were used to provide the highly stable ferrofluid with strong sorbing properties without any additional stabilizer, which was employed to extract and determine morin in apple and grape juices, diluted and acidic extract of dried onion, and green tea infusion samples. The dispersibility of SiO₂@Fe₃O₄ and prevention of its aggregation in the sample solution were improved using the deep eutectic solvent‐based ferrofluid. Also, it facilitated the fast injection of sorbent into the sample solution that led to an increase of the contact surface between the sorbent and analyte, and reduction of the extraction time and consumption of the sorbent. The important experimental parameters influencing the extraction efficiency of morin were examined. Under the optimal conditions, a linear calibration curve was obtained in the range of 3–500 µg/L with a determination coefficient of 0.9994. The limits of detection and quantification were of 0.91 and 2.98 µg/L, respectively. While an extraction recovery of 97.7% with relative standard deviation of 3.8% (interday) was obtained via three replicated measurements on a 30 µg/L of morin standard solution, the enrichment factor was 39.1. Finally, this method was successfully used to extract and preconcentrate morin in various samples, followed with their determination by high‐performance liquid chromatography with ultraviolet detection.     

Metal-organic framework functionalized with deep eutectic solvent for solid-phase extraction of Rhodamine 6G in water and cosmetic products

An NH₂-MIL-53(Al)-DES(ChCl-Urea) nanocomposite was synthesized for extraction and determination of Rhodamine (Rh) 6G from environmental and cosmetic samples. The deep eutectic solvent (DES) was prepared by mixing choline chloride and urea in a mole ratio of 1:2. NH₂-MIL-53(Al)-DES(ChCl-Urea) nanocomposite was synthesized using the impregnation method at a ratio of 60:40 (w/w). The optimum conditions were determined after NH₂-MIL-53(Al)-DES(ChCl-Urea) characterization was performed. The optimum conditions were determined as pH 8, adsorbent amount of 15 mg, total adsorption-desorption time of 6 min, and enrichment factor of 20. The recovery values of the solid-phase extraction method for water and cosmetic samples under optimum conditions were between 95% and 106%. NH₂-MIL-53(Al)-DES(ChCl-Urea) nanocomposite was an economically advantageous adsorbent because of its reusability of 15 times. All analyses were performed using the ultraviolet-visible spectrophotometer. The linear range, limit of detection, and limit of quantification of the method were 100–1000, 9.80, and 32.68 μg/L, respectively. The obtained results showed that the synthesized nanocomposite is a suitable adsorbent for the determination of Rh 6G in water and cosmetic samples. The real sample applications were verified with the high-performance liquid chromatography system.     

Development of a validated strategy for the determination of tryptamine in human cerebrospinal fluid in the presence of competitors using molecularly imprinted polymers

This study presents a validated strategy for the determination of tryptamine in the presence of its competitors, which involves the molecularly imprinted solid‐phase extraction combined with high‐performance liquid chromatography coupled with fluorimetric detection. Tryptamine‐imprinted microscale sorbent was produced from 4‐vinylbenzoic acid and ethylene glycol dimethacrylate in methanol by precipitation polymerization, and its imprinting factor was equal to 15.4 in static experiments or 18.6 in dynamic binding experiments. The method for tryptamine determination in the presence of serotonin and l ‐tryptophan was validated using a complex matrix of bovine serum albumin yielding the recoveries of tryptamine that ranged between 98.7 and 107.0%. Very low limits of detection and limits of quantification for tryptamine (19.9 and 60.3 nmol/L, respectively) allow the quantification of tryptamine in human cerebrospinal fluid in the presence of tryptophan and serotonin.