New Silver Nanosensor for Nickel Traces. Part II: Urinary Nickel Determination Associated to Smoking Addiction

A new fluorescence silver nanosensor assisted by surfactant has been recently synthesized and applied to ultra trace nickel determination. The methodology was validated by the standard addition method and satisfactorily applied to nickel determination in urine without previous treatment, coming from subjects with different smoking addiction levels and second hand smokers. Within-day precision was better than 0.011 CV. The reproducibility (between-days precision) was also evaluated over 3 days by performing six determinations each day with a CV of 0.025. The proposed methodology represents a promising approach in the area of biological monitoring due to its low operation cost, simplicity of instrumentation, high sampling speed and non-polluting solvents. Obtained results of urinary nickel concentration were successfully correlated with the tobacco addiction.Fil: Talio, María Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Luconi, M. O.. Universidad Nacional de San Luis; ArgentinaFil: Fernandez, Liliana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

New Silver Nanosensor for Nickel Traces: Synthesis, Characterization and Analytical Parameters

A new fluorescence silver nanosensor assisted by surfactant has been synthesized and applied to ultra trace nickel determination. Operational variables which influence nanomaterial synthesis have been studied and optimized. Synthesis was very fast and simple using non polluting solvents; silver chemical reduction was carried out at room temperature. Spectroscopic studies were carried out in order to assure the uniformed of nanomaterial obtained. Fluorescent signal of silver nanoparticles resulted enhanced in presence of Ni(II). At optimal experimental conditions, a detection limit of 0.036 pg·L-1 and quantification limit 0.12 pg·L-1 were obtained. The calibration sensitivity was 2 × 1014 L·pg-1·cm-1 for the new methodology, with a range of linearity of six orders of magnitude between 0.12 and 2.93 × 105 pg·L-1. The tolerance levels for potential interferent ions were studied with good results. The proposed methodology represents a promising approach for Ni(II) traces quantification due to its low operation cost, simplicity of instrumentation, high sampling speed and non-polluting solvents.Fil: Talio, María Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Luconi, Marta Olga. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; ArgentinaFil: Fernandez, Liliana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

Green Photoluminescent Methodology for Aluminium Traces Quantification in 24-Hour Urine of Subjects with Different Exposition to Tobacco Smoke

The aim of this work has been to evaluate the aluminium Al(III) traces contents in 24-hours urine samples from subjects with different tobacco smoke exposition using a new methodology using 1,4-dihydroxy-9,10-anthraquinone (Quinizarine, QZ) as a fluorosphore. Biological samples were tested using commercial reagent strips and clinical parameters. Al(III) was determined complexing with QZ followed by a solid phase extraction step using Nylon membranes as solid support. The analyte was subsequently quantified by solid surface fluorescence (SSF, λem= 573, λexc= 490) with a detection limit of 0.88 µg L-1 and quantification limit of 2.69 µg L-1. The calibration curve was linear from 2.69 to 499.13 µg L-1 Al(III) (R2 =0.9973). Urine samples were successfully analysed with an average recovery close to 100%. Solid phase extraction step showed efficacy to eliminate foreign ions and the highly fluorescent matrix own of urine. Results were validated by electrothermal atomic absorption spectrometry (ETAAS) with an adequate concordance. The new methodology has low operation cost with simple instrumentation and without organic solvent.Fil: Santarossa, Debora Gimena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Talio, María Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Fernandez, Liliana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentina. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; Argentin

Lead monitoring and control in tobacco products and E-cigarettes by molecular fluorescence

A new methodology for lead traces determination has been developed based on the quenching effect on fluorescent emission of the complex formed by the metal with 8‑hydroxyquinoline and o-phenanthroline at λ em = 365 nm (λ exc = 250 nm). Experimental variables that influence on fluorimetric sensitivity were optimized using uni-variation assays. The calibration graph using zero th order regression was linear from 1.21 μg L −1 to 518 μg L −1 , with correlation coefficient better than 0.999. Under the optimal conditions, the limits of detection and quantification were of 0.42 μg L −1 and 1.21 μg L −1 respectively. The proposed method showed good sensitivity, adequate selectivity with good tolerance to foreign ions, and was applied to the determination of trace amounts of lead in leachate of tobacco products and refill solutions for e-cigarettes with satisfactory results. The trueness of the recommended procedure was assessed trough parallel analysis of the samples by ICP-MS. The proposed method represents an innovative application of luminescence to metal analysis comparable in sensitivity and accuracy to atomic spectroscopies.Fil: Talio, María Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Pereyra, Fernando. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; ArgentinaFil: Acosta, Mariano. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; ArgentinaFil: Fernandez, Liliana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentina; Argentin

Determination of nickel in cigarettes smoke by molecular fluorescence

Smoking represents the main avoidable cause of disease and death in the world. Cigarette smoke contains over 4700 chemical compounds including 60 known carcinogens. The inhalation of tobacco smoke is one of the most significant sources of nickel exposure for occupationally unexposed population. The aim of this work was to evaluate nickel contents present in cigarette smoke by using an automatic sample preparation step and solid surface fluorescence. A total of 250 cigarettes (brands available in Argentine) were smoked in a smoking device applying vacuum and forcing the mainstream smoke to pass through a filter holder containing a Nylon membrane treated with eosin dye (eo). Nickel present in smoke cigarette was selectively retained by eo as an association compound. Chemically enriched nickel on nylon membranes was subsequent quantified by spectrofluorimetry (Λem=545nm, Λexc=515nm), reaching quantitative recovery with a detection limit of 1.56ngL-1 and quantification limit of 5.52ngL-1. The calibration sensitivity using zeroth order calibration was 1 1012ngL-1 (r2=0.9992) for the methodology with a linear range of 5.52 to 5.17 104ngL-1 Ni(II). Standard addition method was satisfactorily applied to nickel determination in mainstream smoke cigarettes of twenty brands. Results can be good correlated with urinary nickel contents coming from fifty subjects with different levels of addiction.Fil: Talio, María Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Luconi, Marta Olga. Universidad Nacional de San Luis; ArgentinaFil: Fernandez, Liliana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

Determination of lead traces in honey using a fluorimetric method

Heavy traces metals may be present in honey being their detection very important for the quality control and it also serves as an indicator of environmental pollution. A new methodology for lead traces determination has been developed based on the quenching effect of the metal on fluorescent emission of 8-hydroxyquinoline and o-phenanthroline at λem = 360 nm (λexc = 250 nm). Experimental variables that influence on fluorimetric sensitivity were optimized by uni-variation assays. The calibration graph using zeroth order regression was linear from 0.105 μg L-1 to 51.8 μg L-1, with correlation coefficient better than 0.998. Under the optimal conditions, the limits of detection and quantification were of 0.035 μg L−1 and 0.105μg L−1, respectively. The trueness of the methodology was assessed trough parallel samples analysis by ICP-MS. The proposed method showed good sensitivity, adequate selectivity with good tolerance to foreign ions, and was applied to the determination of lead trace amounts in honey from San Luis city (Argentina) with satisfactory results.Fil: Talio, María Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Muñoz, Vanesa Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Acosta, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Fernandez, Liliana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

Direct Cadmium Monitoring in Cigarette Filters Leachate by Molecular Fluorescence

This work proposes a new direct flourimetric methodology for cadmium traces quantification based on its association with azo-reagent SPADNS and rhodamine B dye. Experimental variables that influence on fluorimetric sensibility were optimized using uni-variation assays. The calibration graph using zeroth order calibration was linear from 0.192 to 1.26 104 ìg·L.1, with a correlation coefficient of 0.99. Under the optimal conditions, it was obtained a limit of detection of 0.057 ìg·L.1 and a limit of quantification of 0.192 ìg·L.1. The method showed good sensitivity, adequate selectivity with good tolerance to foreign ions, and was applied to the determination of trace amounts of cadmium in filters leachates coming from unsmoked, automatically smoked and smokers smoked cigarettes with satisfactory results. The proposed method represents an innovative application of luminescence to metal analysis comparable in sensitivity and accuracy to atomic spectroscopies.Fil: Talio, María Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Bonfiglioli, Adolfo. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; ArgentinaFil: Luconi, Marta Olga. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; ArgentinaFil: Fernández, Liliana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentina; Argentin

Metsulfuron-methyl determination in environmental samples by solid surface fluorescence

A new environmental friendly methodology for metsulfuron-methyl quantification based on the fluorescent signal enhancement of rhodamine B dye has been developed. A cationic surfactant (cetyltrimethylammonium bromide, CTAB) and an anionic one (sodium dodecylsulfate) were employed to preconcentrate the herbicide using a coacervation phenomenon, in sodium borate buffer medium (pH 9.2). The coacervate phase was collected on a nylon membrane (0.45 μm) and the solid surface fluorescence signal was determined (λexc = 515 nm, λem = 565 nm). Experimental variables that influence on preconcentration step and fluorimetric sensitivity have been studied and optimized using response surface methodology. Under optimal working conditions, a LOD of 0.17 μg L−1 and a LOQ 0.53 μg L−1 was obtained. The zeroth order regression calibration was linear from 0.53 to 5.00 μg L−1. The method showed adequate sensitivity and selectivity, and was applied to the determination of trace amounts of metsulfuron-methyl in environmental water samples. The proposed methodology implies an alternative to traditional techniques for metsulfuron-methyl monitoring using an accessible instrument in control laboratories, representing a contribution in the toxicological and environmental areas for the monitoring of MSM in environmental samples, in agreement with the Green Chemistry.Fil: Alesso, Magdalena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Almeida, César Américo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Talio, María Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Fernandez, Liliana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

New Analytical Methodology for Sb(III) Traces Quantification as Emergent Contaminant in Drinks Packaged PET Samples by Solid Surface Fluorescence

Emerging contaminants constitute a set of substances that are released into the environment for which regulations are currently not established for their environmental monitoring, being antimony one of them. A new methodology for Sb(III) traces monitoring by solid surface fluorescence is proposed. The metal was complexed with alizarine (Az) as fluorosphore reagent in alcaline medium in presence of the bile salt sodium cholate. To isolate the analyte of matrix constituents, a preconcentration/separation strategy on filter paper was introduced prior to determination step. The solid surface fluorescence was measured λem = 450 nm and λexc = 363 nm using a solid sampler holder. Under optimal conditions, the limits of detection and quantification of proposed methodology were 0.08 and 0.24 μg·L-1, respectively, showing a linear range from 0.24 to 304.4 μg·L-1 with good sensitivity and adequate selectivity. It was applied to the Sb(III) traces determination present in drinking water and beverages samples packaged in polyethylene terephthalate (PET) bottles widely consumed in Argentina. The combination of a preconcentration step on common filter paper and the inherent sensitivity of photoluminescent methods have permitted to achieve sensitivity similar to atomic spectroscopies using a lower price instrument typical in control laboratories. Precision and accuracy were tested with excellent agreement. Results were truenessed by ETAAS with satisfactory concordance.Fil: Talio, María Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Feresin, Valentina. Universidad Nacional de San Luis; ArgentinaFil: Muñoz, Vanesa Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Acosta, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Fernandez, Liliana Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

Development of a green and efficient methodology for the heterocyclic aromatic amine determination in biomass samples generated from cigarette combustion and tobacco

A green methodology was developed for the analysis of ten heterocyclic aromatic amines (HAAs) in biomass samples from cigarette combustion such as mainstream smoke, paper ashes, as well as tobacco and paper wraps. The cellulose filter used for sample collection was also evaluated. This strategy was based on ultrasound-assisted extraction (UAE) associated with a solid-phase extraction procedure employing multi-walled carbon nanotubes (MWCNTs-SPE) as a cleanup step followed by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Under optimal experimental conditions, the linearity of the method was in the range from 0.08 to 160 ng cig-1, with correlation coefficients (R2) higher than 0.991. The limits of detection resulted to be between 0.03 and 0.63 ng cig-1. Concentrations of the HAAs in the mainstream smoke were from 5.7 to 145.2 ng cig-1 and in paper ashes from 0.1 to 0.6 ng cig -1, while in tobacco were between 1.0 and 38.5 ng cig-1. Meanwhile, no HAA contribution was observed in the case of paper wraps and the filter used for sample collection. The knowledge of the presence and the concentration levels of the selected HAAs in each cigarette’s physical component after its combustion is essential to understand the formation processes and contribution during cigarette burning. Besides, this is the first report about the presence of some HAAs in the proposed samples. Finally, a comparative study was employed to classify the sustainability of several recent approaches for HAA extraction from cigarette combustion samples using Green Certificate as a metric tool.Laboratorio de Investigación y Desarrollo de Métodos Analíticos (LIDMA