User-friendly platform for analysis of high mass intact proteins and glycopeptides by laser desorption/ionization-mass spectrometry based on copper oxide particles.

Matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) based on micro/nanostructured materials with different natures has received increasing attention for the analysis of a wide variety of analytes. However, up to now, only a few studies have shown the application of simple platforms in MALDI-MS for the identification of intact proteins. The present work reports on the application of copper oxide particles (Cu2O PS), obtained by a greener route, in combination with low amounts of 2,5-dihydroxybenzoic acid (DHB) as a novel hybrid platform. The combined Cu2O PS@DHB matrix, containing only 2.5 mg mL-1 of particles and 10 mg mL-1 of DHB, was easily applicable in MALDI-MS without surface modification of target plates. Under optimal conditions, the analysis of intact proteins up to 150,000 Da was possible, including immunoglobulin G, bovine serum albumin, and cytochrome C with adequate spot-to-spot signal reproducibility (RSD < 10%). In addition, the analysis of glycopeptides from IgG digests was carried out to prove the multipurpose application of the Cu2O PS@DHB platform in the low m/z range (2500-3000 Da). From the obtained results, it can be concluded that the optical and surface properties of as-synthesized Cu2O PS are likely to be responsible for the superior performance of Cu2O PS@DHB in comparison with conventional matrices. In this sense, the proposed user-friendly methodology opens up the prospect for possible implementation in bioanalysis and diagnostic research.

Microwave-assisted synthesis of copper oxide particles and its application for determination of imazapyr in environmental samples.

Imazapyr (IMA) is currently applied as pre- and post-emergence herbicide for control of weeds in crops. Because of its extensive use, IMA residues may reach water sources and soils. Consequently, its accurate measurement is demanded for timely actions with minimal involved steps and analysis time. Herein, copper oxide particles (Cu2O PS) were proposed as chemical sensor for determination of IMA residues. Cu2O PS were prepared by a facile microwave-assisted method using glucose as reducing agent and polyvinylpyrrolidone as stabilizer. The effect of main experimental parameters on the conversion rate of the Cu2O PS were analyzed by the response surface methodology. Obtained particles were thoroughly characterized in order to determine the particle size distribution, morphology, surface charge, optical and surface properties for further application. Determination of IMA was only based on the localized surface plasmon resonance band of Cu2O PS at 473 nm. Under optimal conditions, the method was evaluated in the concentration range between 80.0 and 1,000 µg L-1 showing a limit of detection about 101 µg L-1 (R2 >0.98). The applicability of the proposed methodology to determine IMA in soil and water samples was assessed with satisfactory recoveries (104-121.8%) displaying a good implementation prospect in environmental complex matrices.

Capillary electrophoresis coupled to chemometrics for analysis of carbon dots in nanoparticles mixtures.

Since their discovery in 2004, carbon dots (CDs) have attracted attention due to their intrinsic physicochemical properties and the easy synthesis from simple precursors. However, quantification of CDs in mixtures of nanoparticles with similar sizes and surface functionality is still a challenging issue for research applications or regulatory purposes. In this work, CDs and silver nanoparticles were first synthesized under alkaline conditions by using glucose as precursor and capping agent, respectively. Mixtures of these nanoparticles were made at micromolar range, without purification, and then analyzed by CE-DAD, using an electrolyte solution composed of 20 mM sodium borate and 20 mM SDS at pH 8.5, in a total time of <15 min. The three-way electrophoretic data were then decomposed by advanced chemometric models, parallel factor analysis and multivariate curve resolution-alternating least-squares. The explained variances for both models were 95.8% (parallel factor analysis) and 85.3% (multivariate curve resolution-alternating least-squares). In both cases, the quality of the results was verified by the root mean square standard deviation coefficient variation, which resulted lower than 5%, and no significant bias was observed at 95% of statistical confidence. Satisfactory prediction for CDs concentration was obtained with recovery values between 80.0% and 115%.

Green-tea-synthesized silver nanoparticles as a sensing platform for determination of tetracycline in honey samples.

BACKGROUND: Silver nanoparticles (AgNPs) can be easily obtained in aqueous solution by chemical reduction using appropriate reducing agents and stabilizers. The development of environmentally friendly methods using non-toxic solvents and reagents has become an alternative for the synthesis of these particles and their future application as sensor probes for agricultural products. In this work, a straightforward method based on green tea extracts as reducing and capping agent is proposed for the synthesis of AgNPs, followed by their evaluation as a sensing platform for determination of tetracycline in honey samples. RESULTS: Highly stable nanoparticles were easily obtained by combining green tea aqueous extracts and ultrasound irradiation for 2 min. The as-synthesized AgNPs, spherical in shape and with average size of 8.5 nm, were evaluated for determination of tetracycline by following the changes on the localized surface plasmon resonance band at 450 nm induced by the presence of this antibiotic at pH 5.8. The method was successfully applied in the concentration range between 200 and 800 µg L-1 with R2 > 0.996 and limit of detection of 52.7 µg L-1 . Multiple honey samples were analyzed, and the recovery values obtained ranged between 82.8% and 116%, with relative standard deviation values lower than 6.69%. CONCLUSION: The results obtained demonstrate that the AgNPs synthesized using just green tea extracts represent a promising and sustainable alternative tool for the cost-effective determination of tetracycline antibiotics in honey. © 2021 Society of Chemical Industry.

In-line coupled single drop liquid-liquid-liquid microextraction with capillary electrophoresis for determining fluoroquinolones in water samples.

A simple in-line single drop liquid-liquid-liquid microextraction (SD-LLLME) coupled with CE for the determination of two fluoroquinolones was developed. The method is capable to quantify trace amount of analytes in water samples and to improve the sensitivity of CE detection. For the SD-LLLME, a thin layer of organic phase was used to separate a drop of 0.1 M NaOH hanging at the inlet of the capillary from the aqueous donor phase. By this way, the analytes were extracted to the acceptor phase through the organic layer based on their acidic/basic dissociation equilibrium. The drop was immersed into the organic phase during 10 min for extraction and then it is directly injected into the capillary for the analysis. Parameters such as type and volume of organic solvent phase, aqueous donor, and acceptor phases and extraction time and temperature were optimized. The enrichment factor was calculated, resulting 40-fold for enrofloxacin (ENR) and sixfold for ciprofloxacin (CIP). The linear range were 20-400 µg/L for ENR and 60-400 µg/L for CIP. The detection limits were 10.1 µg/L and 55.3 µg/L for ENR and CIP, respectively, and a good reproducibility was obtained (4.4% for ENR and 5.6% for CIP). Two real water samples were analysed applying the new method and the obtained results presented satisfactory recovery percentages (90-100.3%).

Determination of sulfonylureas in cereal samples with electrophoretic method using ionic liquid with dispersed carbon nanotubes as electrophoretic buffer.

A capillary electrophoresis method to determine four sulfonylureas in grain samples was developed using 10mM of 1-butyl-3-methyl imidazolium tetrafluoroborate (bminBF4) as electrophoretic buffer solution. 2mgL(-1) of Surfactant Coated-Single Wall-Carbon Nanotubes (SC-SWCNTs) was added to the buffer solution to improve the resolution. In this way, the separation of nicosulfuron, ethoxysulfuron, sulfometuron methyl and chlorsulfuron was carried out in 16min without using organic solvents. A clean up-preconcentration procedure was done prior to inject the sample into the CE instrument, in order to achieve the established maximum residue limits (MRLs). So, the detection limits (LODs) for each analytes were between 16.8 and 26.6µgkg(-1). The relative standard deviations (RSDs) were in the range 1.9-6.7%. A recovery study using the so-called matrix matched calibration demonstrates that no matrix interferences were found throughout the determination. The recovery percentages were ranged between 80% and 113%.

Determination of fluoroquinolones in bovine milk samples using a pipette-tip SPE step based on multiwalled carbon nanotubes prior to CE separation.

A simple CE-UV method was developed for the simultaneous determination of ciprofloxacin, norfloxacin, and ofloxacin in milk samples. The optimum separation was obtained using a 20 mM ammonium dihydrogenphosphate solution with 2 mM cetyltrimethylammonium bromide at pH 3.0 as the BGE. Satisfactory resolution for structurally very similar analytes, like norfloxacin and ciprofloxacin, was achieved without including any organic solvent. Milk samples were prepared using a simple/extraction procedure based on acidic protein precipitation followed by an SPE step using only 5 mg of multiwalled carbon nanotubes as the sorbent material. The LODs for the three compounds were between 7.5 and 11.6 µg/L and the RSDs for the peak areas were between 2.6 and 4.9%. The complete method was applied to spiked real milk samples with satisfactory recoveries for all analytes (84-106%).

Micellar nanotubes dispersed electrokinetic chromatography for the simultaneous determination of antibiotics in bovine milk.

A method to determine four antibiotics for veterinary use (ciprofloxacin, enrofloxacin, florfenicol, and chloramphenicol) of different families (fluoroquinolones and amphenicols) in bovine milk was developed. The determination of the analytes was carried out using micellar electrokinetic capillary chromatography (MEKC) with a common sodium borate-SDS buffer solution containing single-walled carbon nanotubes (SWCNTs). In this way, a great improvement in the electrophoretic resolution and the separation efficiency was achieved compared to MEKC. An online reverse electrode polarity-stacking mode (REPSM) was carried out to enhance sensitivity. This step was performed in only 2 min and it allowed a stacked percentage of 103. That means that all the amount of injected analytes is effectively stacked. When this stacking procedure was combined with an off-line preconcentration step, based on SPE, analytes could be detected in lower concentration than the established maximum residue limits (MRLs). The LODs for the four compounds were between 6.8 and 13.8 µg L(-1) and the RSD values were between 1.1% and 6.6%. The whole method was applied to spiked real samples with acceptable precision and satisfactory recoveries.

A simple and fast method for chlorsulfuron and metsulfuron methyl determination in water samples using multiwalled carbon nanotubes (MWCNTs) and capillary electrophoresis.

A new method to determine metsulfuron methyl (MSM) and chlorsulfuron (CS) in different water samples was developed. It consists in a solid phase extraction (SPE) procedure using multiwalled carbon nanotubes (MWCNTs) as sorbent material in combination with capillary zone electrophoretic determination. To carry out the pre-concentration step, a simple flow injection system was developed and optimized. Thus, 250 µL of aqueous solution containing methanol 50% (v/v) and acetonitrile 2% (v/v) as eluent, 10 mL of sample and a flow rate of 1.15 mL min(-1) were selected. The CE variables also were optimized. A rapid determination and good resolution of two herbicides were obtained within 9 min using a simple electrophoretic buffer (50 mmol L(-1) sodium tetraborate with 3% of methanol, pH=9.0). Under the optimum conditions, the calibration curves were linear between 0.5 and 6 µg L(-1) for MSM and CS with R(2)=0.995 and 0.997, respectively. The repeatability of the proposed method, expressed as relative standard deviation (RSD), varied between 4.1% and 5.4% (n=10) and the detection limits for MSM and CS were 0.40 and 0.36 µg L(-1), respectively. Good results were achieved when the proposed method was applied to spiked real water samples. The recoveries percentages of the two analytes were over the range 86-108%.