Application of Molecularly Imprinted Polymers (MIP) and Magnetic Molecularly Imprinted Polymers (mag-MIP) to Selective Analysis of Quercetin in Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (FAPA-MS) and in Electrospray Ionization Mass Spectrometry (ESI-MS).

Molecularly imprinted polymer (MIP) and magnetic molecularly imprinted polymer (mag-MIP) for solid extraction and pre-concentration of quercetin have been successfully prepared by thermal polymerization method using quercetin (Q) as a template, acrylamide (AA) as a functional monomer, and ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent. The MIP and mag-MIP were successfully applied in analysis of quercetin by mass spectrometry (MS) methods. To perform ambient plasma ionization experiments, a setup consisting of the heated crucible, a flowing atmospheric-pressure afterglow (FAPA) plasma ion source, and amaZon SL ion trap (Bruker, Bremen, Germany) was used. The heated crucible with programmable temperature allowed desorption of the analytes from MIPs structure which resulted in their direct introduction into the ion stream. The results of Q-MIP/Q-mag-MIP and FAPA-MS measurements were compared with those of the analysis of quercetin by the ESI-MS method without extractions and pre-concentration of analytes on polymers. Limits of detection (LOD) for quercetin solutions in both positive and negative ESI-MS were established at 10-8 M and 10-7 M, respectively. The linearity (R2 = 0.9999) of the proposed analytical procedure for quercetin determination in positive ions was provided in the range between 10-4 M and 10-7 M. Moreover, the same parameters were established for FAPA-MS in positive ions, reaching LOD at 0.005 mg/gMIP and the linearity of the method in the range of 0.015-0.075 mg/gMIP with the correlation coefficient value R2 = 0.9850.

Adsorption and selectivity studies of direct and magnetite-cored molecularly imprinted polymers (MIPs and magMIPs) towards chosen chalcones investigated with various analytical methods.

The following article presents a method for obtaining molecularly imprinted polymers (MIPs) dedicated to trans-chalcone (TC) and 2',4'-dihydroxy-3-methoxychalcone (DHMC). The synthetic protocol optimized with a choice of the most suitable functional monomer led to the synthesis of MIPs and their non-imprinted equivalents (NIP) performed via direct polymerization or on the surface of magnetite nanoparticles. The characterized materials were investigated for adsorption isotherms of TC and DHMC, which led to satisfactory values of maximal adsorption capacity, reaching 131.58 and 474.71 mg g-1, respectively. Moreover, all the polymers were studied for the adsorption kinetics and the selectivity towards four structurally different chalcones, which proved the proper selectiveness towards the template molecules. Also, the kinetic profiles of chalcones' adsorption on the synthesized MIPs showed a quasi-plateau reached already after 2 hours, indicating high sorption effectiveness. The studies involved the use of various analytical techniques, which afforded a comprehensive and reliable description of the materials' adsorption efficacy. It was found that the materials successfully bind the MIP-complementary analytes and also structurally similar chalcones, with slightly lower intensity.

Environmental impact of molecularly imprinted polymers used as analyte sorbents in mass spectrometry.

The molecularly imprinted polymers (MIPs) with the following herbicides used as templates 2,4-dichlorophenoxyacetic acid (2,4-D) or 4-chloro-2-methylphenoxy- acetic acid (MCPA) were synthesized by precipitation polymerization technique using 4-vinylpyridine (4-VP) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, and 2,2'-azobisisobutyronitrile (AIBN) as an initiator in methanol solvent. For the flavonoid MIPs, rutin (Ru) and quercetin (Q) were used as templates and synthesized via a similar technique, utilizing acrylamide (AA) as a functional monomer. Analysis of binding in the molecularly imprinted and non-imprinted polymer (NIP) has proved that MIP shows a higher affinity towards the analytes, compared to NIP. MIP was used to determine analytes in water using the Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (FAPA-MS) technique. In this approach, the method limit of detection (MLOD) of 2,4-D, MCPA, Ru, and Q in MIP was 4, 3, 10, and 5 µg in 1 g MIP, respectively. The release kinetics of the analytes from MIP and their stability in water was studied. The cultures of Tetradesmus obliquus (Turpin) M.J. Wynne and Daphnia magna Straus were used for in vivo toxicity studies revealing that only Ru-MIP and Q-MIP had negative effect on the living organisms used in the bioassays.

Molecularly Imprinted Polymers and Magnetic Molecularly Imprinted Polymers for Selective Determination of Estrogens in Water by ESI-MS/FAPA-MS.

Qualitative and quantitative analysis of estrogens content in natural water is a difficult task. An important problem in the analysis of hormones in water is the quantitative determination of their individual species. Low detection limits and instability of estrogen derivatives are the main challenges. Magnetic molecularly imprinted polymers (mag-MIPs) in combination with Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (FAPA-MS) were successfully used for analysis of estrogen hormones in water samples. The aim of the study was to obtain mag-MIPs selective to estrone (E1) and ß-estradiol (E2) for solid phase extraction and pre-concentration of estrogens. Due to their superior analyte binding properties at low concentrations (0.03 g in 1 g of polymer structure) and possibility of magnetic separation, mag-MIPs were proven to be very convenient and efficient adsorbent materials. In addition, MS analyses were performed using two ionization sources: ESI- and FAPA-MS. For both estrogens, LOD was significantly lower for FAPA-MS analysis (0.135 µgL-1 for E1 and E2) than for ESI-MS analysis (27 µgL-1 for E1 and 13.6 µgL-1 for E2). The total estrogen concentration in the environmental water sample was determined as: cE1 = 0.271 µgL-1 and cE2 = 0.275 µgL-1.

Analysis of Amygdalin in Various Matrices Using Electrospray Ionization and Flowing Atmospheric-Pressure Afterglow Mass Spectrometry.

Amygdalin is a natural cyanogenic compound that plants produce in the fight against insects and herbivores. Excessive amounts of amygdalin by animals and humans can potentially lead to fatal intoxication. However, studies confirm that amygdalin has antitumor properties, including the ability to inhibit the proliferation of cancer cells and to induce their apoptosis. The analysis of amygdalin in various matrices is an important analytical problem today. The publication presents the methodology of direct determination of amygdalin in water, sewage, and biological materials using electrospray ionization mass spectrometry (ESI-MS) and a new analytical method using flowing atmospheric-pressure afterglow mass spectrometry (FAPA-MS). The methods of analyte pre-concentration using a magnetic, molecularly imprinted polymer (mag-MIP) and the influence of interferents on the recorded spectra were discussed. Analytical parameters in ESI-MS and FAPA-MS methods were established. The linearity range was 4.5 µg L-1-45 mg L-1 in positive mode ESI-MS and FAPA-MS. The limit of detection (LOD) for ESI-MS was 0.101 ± 0.003 µg L-1 and the limit of quantification (LOQ) was 0.303 ± 0.009 µg L-1. In FAPA-MS, the LOD was 0.050 ± 0.002 µg L-1 and the LOQ was 0.150 ± 0.006 µg L-1. The content of amygdalin in various matrices was determined.