Rapid determination of total metals: synergic effect of ultrasound energy and ionic liquids on the digestion of sediment samples

Purpose: The aim of this study was to develop a new and rapid sample digestion procedure for metal extraction using ultrasonic energy together with a combination of an ionic liquid and mineral acids as extractants. Methods: A fixed mass of sediment (about 0.50 g) was extracted with a combination of low volumes of NaHCO3, HCl, HNO3, HF and the ionic liquid Bmim[BF4]. Afterwards, the mixture was sonicated for 20 min. After neutralizing the hydrofluoric acid excess, the extracts were filtered and measured by ICP OES where Cd, Cr, Cu, Ni, Pb and Zn were determined. Results: The recoveries in certified reference materials ranged from 92 to 102% for LGC-6137, from 88 to 98% for IAEA SL-1 and from 81 to 98% for MURST-ISS-A1, with a good precision (relative standard deviation (RSD) < 10.0% for all the certified reference materials). The new digestion procedure was successfully applied to the determination of metals in estuarine sediment samples, with a satisfactory precision (RSD < 9.5%). The results showed no significant statistical differences compared to those obtained by the conventional digestion procedure (with an α-error of 0.05). Conclusion: This approach has led to satisfactory results in the determination of the total metal concentrations for most of the elements studied using shorter analysis times than the conventional procedure, and small volumes of hydrofluoric acid. The new pretreatment method made it possible to satisfactorily assess the total metal concentrations in estuarine sediments.Fil: Alvarez, Silvana María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Llamas, Natalia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Álvarez, Mónica Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Marcovecchio, Jorge Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto Argentino de Oceanografía. Universidad Nacional del Sur. Instituto Argentino de Oceanografía; Argentina. Universidad Tecnológica Nacional; Argentina. Academia Nacional de Ciencias Exactas, Físicas y Naturales; ArgentinaFil: Garrido, Mariano Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Domini, Claudia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Drug Survival of Interleukin (IL)‑17 and IL‑23 Inhibitors for the Treatment of Psoriasis: A Retrospective Multi‑country, Multicentric Cohort Study

Background: Drug survival, defined as the length of time from initiation to discontinuation of a given therapy, allows comparisons between drugs, helps to predict patient's likelihood of remaining on a specific treatment, and achieving the best decision for each patient in daily clinical practice. Objective: The aim of this study was to provide data on drug survival of secukinumab, ixekizumab, brodalumab, guselkumab, tildrakizumab, and risankizumab in a large international cohort, and to identify clinical predictors that might have an impact on the drug survival of these drugs. Methods: This was a retrospective, multicentric, multi-country study that provides data of adult patients with moderate to severe psoriasis who started treatment with an interleukin (IL)-17 or IL-23 inhibitor between 1 February 2015 and 31 October 2021. Data were collected from 19 distinct hospital and non-hospital-based dermatology centers from Canada, Czech Republic, Italy, Greece, Portugal, Spain, and Switzerland. Kaplan-Meier estimator and proportional hazard Cox regression models were used for drug survival analysis. Results: A total of 4866 treatment courses (4178 patients)-overall time of exposure of 9500 patient-years-were included in this study, with 3164 corresponding to an IL-17 inhibitor (secukinumab, ixekizumab, brodalumab) and 1702 corresponding to an IL-23 inhibitor (guselkumab, risankizumab, tildrakizumab). IL-23 inhibitors had the highest drug survival rates during the entire study period. After 24 months of treatment, the cumulative probabilities of drug survival were 0.92 (95% confidence interval [CI] 0.89-0.95) for risankizumab, 0.90 (95% CI 0.88-0.92) for guselkumab, 0.80 (95% CI 0.76-0.84) for brodalumab, 0.79 (95% CI 0.76-0.82) for ixekizumab, and 0.75 (95% CI 0.73-0.77) for secukinumab. At 36 months, only guselkumab [0.88 (95% CI 0.85-0.91)], ixekizumab [0.73 (95% CI 0.70-0.76)], and secukinumab [0.67 (95% CI 0.65-0.70)] had more than 40 patients at risk of drug discontinuation. Only two drugs had more than 40 patients at risk of drug discontinuation at 48 months, with ixekizumab demonstrating to have a higher cumulative probability of drug survival [0.71 (95% CI 0.68-0.75)] when compared with secukinumab [0.63 (95% CI 0.60-0.66)]. Secondary failure was the main cause for drug discontinuation. According to the final multivariable model, patients receiving risankizumab, guselkumab, and ixekizumab were significantly less likely to discontinue treatment than those receiving secukinumab. Previous exposure to biologic agents, absent family history of psoriasis, higher baseline body mass index (BMI), and higher baseline Psoriasis Area and Severity Index (PASI) were identified as predictors of drug discontinuation. Conclusion: The cumulative probability of drug survival of both IL-17 and IL-23 inhibitors was higher than 75% at 24 months, with risankizumab and guselkumab demonstrating to have overall cumulative probabilities ≥ 90%. Biological agent chosen, prior exposure to biologic agents, higher baseline BMI and PASI values, and absence of family history of psoriasis were identified as predictors for drug discontinuation. Risankizumab, guselkumab, and ixekizumab were less likely to be discontinued than secukinumab

Albiglutide and cardiovascular outcomes in patients with type 2 diabetes and cardiovascular disease (Harmony Outcomes): a double-blind, randomised placebo-controlled trial

Background: Glucagon-like peptide 1 receptor agonists differ in chemical structure, duration of action, and in their effects on clinical outcomes. The cardiovascular effects of once-weekly albiglutide in type 2 diabetes are unknown. We aimed to determine the safety and efficacy of albiglutide in preventing cardiovascular death, myocardial infarction, or stroke. Methods: We did a double-blind, randomised, placebo-controlled trial in 610 sites across 28 countries. We randomly assigned patients aged 40 years and older with type 2 diabetes and cardiovascular disease (at a 1:1 ratio) to groups that either received a subcutaneous injection of albiglutide (30–50 mg, based on glycaemic response and tolerability) or of a matched volume of placebo once a week, in addition to their standard care. Investigators used an interactive voice or web response system to obtain treatment assignment, and patients and all study investigators were masked to their treatment allocation. We hypothesised that albiglutide would be non-inferior to placebo for the primary outcome of the first occurrence of cardiovascular death, myocardial infarction, or stroke, which was assessed in the intention-to-treat population. If non-inferiority was confirmed by an upper limit of the 95% CI for a hazard ratio of less than 1·30, closed testing for superiority was prespecified. This study is registered with ClinicalTrials.gov, number NCT02465515. Findings: Patients were screened between July 1, 2015, and Nov 24, 2016. 10 793 patients were screened and 9463 participants were enrolled and randomly assigned to groups: 4731 patients were assigned to receive albiglutide and 4732 patients to receive placebo. On Nov 8, 2017, it was determined that 611 primary endpoints and a median follow-up of at least 1·5 years had accrued, and participants returned for a final visit and discontinuation from study treatment; the last patient visit was on March 12, 2018. These 9463 patients, the intention-to-treat population, were evaluated for a median duration of 1·6 years and were assessed for the primary outcome. The primary composite outcome occurred in 338 (7%) of 4731 patients at an incidence rate of 4·6 events per 100 person-years in the albiglutide group and in 428 (9%) of 4732 patients at an incidence rate of 5·9 events per 100 person-years in the placebo group (hazard ratio 0·78, 95% CI 0·68–0·90), which indicated that albiglutide was superior to placebo (p&lt;0·0001 for non-inferiority; p=0·0006 for superiority). The incidence of acute pancreatitis (ten patients in the albiglutide group and seven patients in the placebo group), pancreatic cancer (six patients in the albiglutide group and five patients in the placebo group), medullary thyroid carcinoma (zero patients in both groups), and other serious adverse events did not differ between the two groups. There were three (&lt;1%) deaths in the placebo group that were assessed by investigators, who were masked to study drug assignment, to be treatment-related and two (&lt;1%) deaths in the albiglutide group. Interpretation: In patients with type 2 diabetes and cardiovascular disease, albiglutide was superior to placebo with respect to major adverse cardiovascular events. Evidence-based glucagon-like peptide 1 receptor agonists should therefore be considered as part of a comprehensive strategy to reduce the risk of cardiovascular events in patients with type 2 diabetes. Funding: GlaxoSmithKline

Ten millennia of hepatitis B virus evolution

Hepatitis B virus (HBV) has been infecting humans for millennia and remains a global health problem, but its past diversity and dispersal routes are largely unknown. We generated HBV genomic data from 137 Eurasians and Native Americans dated between ~10,500 and ~400 years ago. We date the most recent common ancestor of all HBV lineages to between ~20,000 and 12,000 years ago, with the virus present in European and South American hunter-gatherers during the early Holocene. After the European Neolithic transition, Mesolithic HBV strains were replaced by a lineage likely disseminated by early farmers that prevailed throughout western Eurasia for ~4000 years, declining around the end of the 2nd millennium BCE. The only remnant of this prehistoric HBV diversity is the rare genotype G, which appears to have reemerged during the HIV pandemic

Propuesta metodológica para una experiencia de laboratorio en la determinación de un principio activo en formulaciones farmacéuticas por fluorescencia molecular

Los trabajos prácticos de laboratorio en la asignatura Análisis Instrumental de la carrera de Farmacia en la Universidad Nacional del Sur, generalmente son guías estructuradas por el docente ("recetas"). La utilización de esta modalidad de enseñanza no brinda resultados satisfactorios en cuanto a la adquisición de las competencias esperadas por parte del alumno. Por este motivo se decidió implementar un cambio de metodología con el fin de promover una mayor participación del alumno y favorecer el trabajo en equipo. Para ello se adaptó un trabajo práctico cambiando la tradicional muestra de agua tónica que contiene sulfato de quinina por medicamentos con ese principio activo. Se permitió que los alumnos, separados en comisiones, decidieran la manera de trabajar en el laboratorio basados en una investigación y discusion previas con sus compañeros y el docente. Luego de realizado el trabajo práctico se realizó un tratamiento estadístico a los datos obtenidos y la presentación del informe correspondiente. Posteriormente, se llevó a cabo la discusión de esos resultados con el resto de sus compañeros. Paralelamente, se fomentó en el alumno la conciencia del cuidado del ambiente a través de la disposición de residuos.Fil: Llamas, Natalia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Domini, Claudia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Garrido, Mariano Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Alvarez, Mónica B.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Flow-injection spectrophotometric method with on-line photodegradation for determination of ascorbic acid and total sugars in fruit juices

This article reports a flow-injection spectrophotometric determination (FIA) with a photodegradation step to determine ascorbic acid and total sugars. The flow-injection system includes a simple ultraviolet photoreactor for the on-line photodegradation. The method is based on the determination of ascorbic acid at 300. nm before the photodegradation step, followed by UV irradiation and measurement of total sugars at 268. nm. The proposed method was used to determine ascorbic acid and total sugars in commercial and natural fruit juice samples. The method was validated by using spiked samples with recoveries in the range 96.4-108.3% for ascorbic acid, and 91.0-113.2% for total sugars. © 2010 Elsevier Inc.Fil: Llamas, Natalia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Di Nezio, Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Fernández Band, Beatriz Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Oxidized carbon nanotubes as sorbent for miniaturized solid-phase extraction of progestins from environmental water samples prior to their determination by HPLC-UV

A solid-phase extraction method is presented for micro-extraction of three progestins (levonorgestrel, 19-norethisterone acetate andmedroxyprogesterone acetate) from water samples. A mini-column was packed with 60 mg of oxidized multiwalled carbon nanotubesand coupled to a flow injection assembly. The extraction parameters, such as washing solution, eluent type, eluent volume, flow rateand sample volume, were optimized. Separation and determination were performed by HPLC with UV detection. The method has agood linear range (0.90?9.0 μg L−1), acceptable limits of detection (0.05?0.14 μg L−1) and low RSDs (0.8?4.6%). Attractive features ofthe method include low consumption of organic solvents and preconcentration factors of up to 100. The method was applied to analyzestream, underground and effluent water samples, and recoveries between 74 and 121% were obtained.Fil: Aguinaga Martinez, Maite Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Llamas, Natalia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Avila Orozco, Francisco David. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Domini, Claudia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Acebal, Carolina Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Second order advantage in the determination of amaranth, sunset yellow FCF and tartrazine by UV-vis and multivariate curve resolution-alternating least squares

A direct spectrophotometric method for the determination of three artificial colors - amaranth, sunset yellow FCF and tartrazine - in beverages samples is proposed. The spectra were recorded between 359 and 600 nm. The spectra of the samples (just filtrated), pure dyes (concentrations ranged between 0.01 and 1.8 mg L-1 for amaranth, 0.08 and 4.4 mg L-1 for sunset yellow and 0.04 and 1.8 mg L-1 for tartrazine) and synthetic mixtures were disposed in a column-wise augmented data matrix. This kind of data structure, analyzed by multivariate curve resolution-alternating least squares (MCR-ALS) makes it possible to exploit the so called 'second order advantage'. MCR-ALS algorithm was applied to the experimental data under the non-negativity and equality constraints. As a result, the concentration of each dye in the samples and their corresponding pure spectra were obtained. The results were validated using internal reference materials and no significant differences were found (α = 5%) between the reference values and the ones obtained with the proposed method. The second order advantage made it possible to obtain unbiased results even in the presence of interferences.Fil: Llamas, Natalia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Garrido, Mariano Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Di Nezio, Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Fernández Band, Beatriz Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

Automated turbidimetric determination of cyclamate in low calorie soft drinks and sweeteners without pre-treatment

A flow injection turbidimetric method for determination of cyclamate in low calorie soft drinks and sweeteners without pre-treatment is proposed. It was based on the oxidation of the sulphamic group of cyclamate, to sulphate by addition of nitrite. Then, a precipitate of sulphate was obtained by reaction with barium chloride, in presence of poly(vinyl alcohol) (PVA) in perchloric acid solution, at 30°C. The analytical signal was measured at 420 nm. The method presented a linear range between 0.015 and 0.120% (w/v) and the calibration graph was S = (7.792 ± 0.179) X - (0.114 ± 0.012), R2 = 0.999. A reproducibility of 5.9% was obtained from nine calibration graphs that were carried out on different days and with different conditions (standard solution, reagents solution, etc.). The detection and quantification limits were 0.006 and 0.02% (w/v), respectively, the sample throughput 45 h-1 (by considering the wash cycle and the time consuming to eliminate the clean solution from the system). The obtained results were agreement with that obtained with the standard method.Fil: Llamas, Natalia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Di Nezio, Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Fernández Band, Beatriz Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

An integrated on-line method for the preconcentration and simultaneous determination of metsulfuron methyl and chlorsulfuron using oxidized carbon nanotubes and second order fluorescent data

Trace amounts of two sulfonylurea herbicides widely used for crops protection, metsulfuron methyl (MSM) and chlorsulfuron (CSF) were simultaneously determined taking into account the different kinetic photodegradation behavior of their photoproducts in alkaline medium. As the analytes are present at trace concentration levels, a preconcentration by sorption on a mini-column packed with oxidized multiwall carbon nanotubes (ox-MWCNTs) at pH 3.0 was performed. The retained analytes were removed from the ox-MWCNTs mini-column with a mixture of ACN contained 10% (v/v) of NaOH pH 12.5. A total enrichment factor of 26-fold for a 14.50 mL sample volume was obtained. The eluate was photodegraded by UV radiation during 126 s and the fluorescent spectra corresponding to the analytes photoproducts were registered overtime between 300 and 500 nm. The kinetic second order data were analyzed by unfolded-partial least squares-residual bilinearization (U-PLS/RBL) and multidimensional-partial least squares-residual bilinearization (N-PLS/RBL) algorithms. The relative error of prediction (REP %) for N-PLS/RBL was 7.73% for MSM and 6.37% for CSF. In the case of U-PLS/RBL, this statistical parameter was 7.75% for MSM and 7.23% for CSF, respectively. The limits of detection (LOD) were 0.19 μg L-1 for MSM and 1.14 μg L-1 for CSF using N-PLS/RBL and 0.21 μg L-1 for MSM and 1.03 μg L-1 for CSF when U-PLS/RBL was applied. The entire procedure was performed in an on-line integrated fully automated flow system coupled to a low mercury UV lamp (15 W, 254 nm) and a spectrofluorometer. In this manner, the preconcentration, photodegradation and detection steps were performed in a reproducible way. After optimization, the method was successfully applied to the analysis of real water samples obtained in the south part of Buenos Aires province and used for irrigation and consumption.Fil: Acebal, Carolina Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Grunhut, Marcos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Llamas, Natalia Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Insausti, Matías. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Zelená, Lucie. Charles University. Department of Analytical Chemistry, Faculty of Pharmacy; República ChecaFil: Sklenářová, Hana. Charles University. Department of Analytical Chemistry, Faculty of Pharmacy; República ChecaFil: Solich, Petr. Charles University. Department of Analytical Chemistry, Faculty of Pharmacy; República ChecaFil: Fernández Band, Beatriz Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin