Multi-class, multi-residue determination of 132 veterinary drugs in milk by magnetic solid-phase extraction based on magnetic hypercrosslinked polystyrene prior to their determination by high-performance liquid chromatography-tandem mass spectrometry.

A quantitative multi-class multi-residue analytical method was developed for the determination of veterinary drugs in milk by high-performance liquid chromatography - tandem mass spectrometry (HPLC-MS/MS). A total of 132 veterinary drugs investigated belonged to almost 15 classes including sulfonamides, ß-lactams, tetracyclines, quinolones, macrolides, nitrofurans, nitroimidazoles, phenicols, lincosamides, pleuromutilins, macrocyclic lactones, quinoxaline antibiotics, benzimidazoles, anthelmintics, coccidiostats and some others. A magnetic solid-phase extraction procedure was developed using magnetic hypercrosslinked polystyrene (HCP/Fe3O4) for the sample preparation prior to HPLC-MS/MS without deproteinization step. The results indicated recoveries of 85-107% for 14 sulfonamides, 85-120% for 13 ß-lactams, 89-115% for 4 tetracyclines, 82-119% for 14 quinolones, 82-115% for 8 macrolides, 97-109% for 4 nitrofurans, 84-115% for 10 nitroimidazoles, 89-114% for 3 phenicols, 86-111% for 3 lincosamides, 97-102% for 2 pleuromutilins, 72-88% for 4 macrocyclic lactones, 87-104% for 4 quinoxaline antibiotics, 76-119% for 21 benzimidazoles, 79-115% for 12 anthelmintics, 81-118% for 12 coccidiostats and 75-119 % for 5 unclassified drugs, with relative standard deviations (RSDs) of less than 20%, and the LOQs ranged from 0.05 to 1 µg kg-1. This methodology was then applied to field-collected real milk samples and trace levels of some veterinary drugs were detected.

Effect of amines on formation of gold/polyurethane foam nanocomposites and its sensing opportunities.

Effect of amines on formation of gold nanoparticles (AuNPs)/polymer nanocomposites has been observed and studied. Nanocomposites based on polyurethane foam and AuNPs were synthesized by interaction between the polymer modified with sodium borohydride and aqueous solution of tetrachloroauric acid. It has been shown that some amines cause a remarkable decrease of the surface plasmon resonance band of AuNPs in the nanocomposite material. Both aliphatic and aromatic amines as well as amines containing several amino groups were studied. A possible mechanism of the effect is discussed. It is probably based on stabilization of AuNPs with an amine that entails a decrease in the degree of their adsorption on PUF and appearance of the stabilized AuNPs in solution. The decrease of the nanocomposite surface plasmon resonance band is proportional to the concentration of amine in the solution. Based on this effect, a method for the determination of cetylamine, ß-naphthylamine and neomycin in water and medical formulations using a monitor calibrator as a portable household tool is proposed. Under the selected conditions, the detection limits for amines were in the range of 0.7-1.5 µM, the determination ranges were approximately an order of magnitude. The observed color change of the nanocomposite samples also provides a good basis for semiquantitative determinations.

Potentialities of differently-stabilized silver nanoparticles for spectrophotometric determination of peroxides.

One of the possible ways for using silver nanoparticles (AgNPs) in spectrophotometry is their application for the determination of oxidizing agents, based on oxidative destruction of these nanoobjects. This process depends on the structure of AgNPs surface layer, which is essentially affected by the chosen stabilizer. To assess influence of the nanoparticle stabilizer and the nature of the analyte, possibilities of AgNPs covered with stabilizers of three types (citrate, polyvinylpyrrolidone, and polyhexamethylene guanidinium) for the spectrophotometric determination of hydrogen peroxide and differently substituted organic peroxides were studied. The approach is based on AgNPs oxidation leading to discoloration of the solution monitored spectrophotometrically. Different selectivity of the oxidation depending on the stabilizer was shown. Effects of various factors (time of interaction, pH, concentration of AgNPs) on the oxidation and analytical performance of the procedure were investigated. The method allows for the determination of hydrogen peroxide, peracetic acid, m-chloroperbenzoic acid, and t-butylhydroperoxide in the range of 0.3-1.5, 0.1-0.8, 1.0-7.5, and 1-7 µg mL-1 and with the limits of detection of 0.1, 0.04, 0.3, and 0.3 µg mL-1, respectively. The analysis can be performed using either spectrophotometry or naked-eye detection.

Determination of pyrophosphate and sulfate using polyhexamethylene guanidine hydrochloride-stabilized silver nanoparticles.

Positively charged polyhexamethylene guanidine hydrochloride-stabilized silver nanoparticles (PHMG-AgNPs) were prepared and applied as a colorimetric probe for single-step determination of pyrophosphate and sulfate. The approach is based on the nanoparticles aggregation leading to change in their absorption spectra and color of the solution. Due to both electrostatic and steric stabilization these nanoparticles show decreased sensitivity relatively to many common anions, which allows for simple and rapid direct single-step determination of pyrophosphate and sulfate. Effects of different factors (time of interaction, pH, concentrations of anions and the nanoparticles) on aggregation of PHMG-AgNPs and analytical performance of the procedure were investigated. The method allows for the determination of pyrophosphate and sulfate in the range of 0.16-2µgmL-1 and 20-80µgmL-1 with RSD of 2-5%, respectively. The analysis can be performed using either spectrophotometry or naked-eye detection. Practical application of the method was shown by the example of pyrophosphate determination in baking powder sample.

Formation of core-shell Au@Ag nanorods induced by catecholamines: A comparative study and an analytical application.

Gold nanorods (AuNRs) stabilized by cetyltrimethylammonium bromide (CTAB) were synthesized and an interaction of catecholamines (CAs) with silver ions in the presence of the obtained AuNRs was studied. The reaction results into formation of core-shell Au@Ag nanorods (Au@AgNRs) and leads to a hypsochromic shift of the long-wave surface plasmon resonance (SPR) band in the absorption spectrum of AuNRs. The influence of a CA structure, excess of CTAB, interaction time, pH, concentration of AuNRs, silver ions and CAs on this interaction was studied. Based on correlation of the NRs spectral characteristics with the concentration of CAs, a method for spectrophotometric determination of dobutamine, epinephrine, norepinephrine and dopamine with detection limits 27, 18, 16 and 13 µg L(-1), respectively, has been developed. The method can be applied to the analysis of medicines.

Formation of plasmonic silver nanoparticles by flavonoid reduction: A comparative study and application for determination of these substances.

Formation of plasmonic silver nanoparticles by flavonoid reduction was studied. Effects of the nature and the concentration of a flavonoid and a stabilizer, composition of the solution and the interaction time were revealed. It was found that quercetin, dihydroquercetin, rutin and morin produced an intense surface plasmon resonance band of silver nanoparticles at 415 nm which was linearly related to the concentration of a flavonoid, while chrysin, naringenin and naringin did not produce any remarkable changes. It was used for the spectrophotometric determination of the former four flavonoids with the detection limits of 0.03; 0.06; 0.09 and 0.1 µg mL(-1), respectively. The developed method was applied for the determination of flavonoids in biologically active food additives.

Use of polyurethane foam and 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline for determination of nitrite by diffuse reflectance spectroscopy and colorimetry.

Polyurethane foam (PUF) has been suggested as a solid polymeric reagent for determination of nitrite. The determination is based on the diazotization of end toluidine groups of PUF with nitrite in acidic medium followed by coupling of polymeric diazonium cation with 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline. The intensely colored polymeric azodye formed in this reaction can be used as a convenient analytic form for the determination of nitrite by diffuse reflectance spectroscopy (c (min) = 0.7 ng mL(-1)). The possibility of using a desktop scanner, digital camera, and computer data processing for the numerical evaluation of the color intensity of the polymeric azodye has been investigated. A scanner and digital camera can be used for determination of nitrite with the same sensitivity and reproducibility as with diffuse reflectance spectroscopy. The approach developed was applied for determination of nitrite in river water and human exhaled breath condensate.

Polyurethane foams as solid chromogenic reagents for diffuse reflectance spectroscopy.

The chemical reactions of the functional groups in polyurethane foams (PUF) have been studied by use of diffuse reflectance spectroscopy and infrared spectroscopy. It was found that the functional groups are highly reactive towards diazotization by sodium nitrite, azo coupling with 4-nitrophenyldiazonium tetrafluoroborate, oxidation by active chlorine, and condensation with formaldehyde, resulting in the formation of intensely colored products. Heterogeneous chemical reactions of PUF with these compounds in aqueous solution proceed rapidly at room temperature and at low solute concentrations. PUF do not undergo degradation as a result of chemical interactions. The linear response of the Kubelka-Munk function to analyte concentration makes it possible to recommend PUF as solid chromogenic reagents for the determination of nitrite, nitrate, and 1- and 2-naphthols.

An empirical relationship between distribution coefficients of phenols by polyurethane foams and their octanol-water distribution constants and pK(a) values.

Sorption of phenol, 3-cresol, 2-, 3-, 4-nitrophenols, 2,4-, 2,6-dinitrophenol, 2,4,6-trinitrophenol, and 1-naphthol by polyether- and polyester-type polyurethane foams (PUF) was investigated. The effects of sorption time, pH, phenol concentration and the structure of tested phenols and PUF were studied. The mechanism of sorption of tested compounds on foams is discussed. It is shown that the hydrophobicity (logP, octanol-water distribution constant) and pK(a) values of the compounds play an important role in the sorption process. A regression equation connecting distribution coefficient of phenols by PUF with their hydrophobicity parameter and pK(a) values were derived. Good correlation between logD and values logP and pK(a) was observed.