Determination of 2-ethylhexyl Nitrate in Diesel Oil Using a Single Excitation Emission Fluorescence Spectra (EEF) and Chemometrics Analysis

A highly sensitive spectrofluorimetric method has been developed for the determination of 2-ethylhexyl nitrate in diesel fuel. Usually, this compound is used as an additive in order to improve cetane number. The analytical method consists in building the chemometric model as a first step. Then, it is possible to quantify the analyte with only recording a single excitation-emission fluorescence spectrum (EEF), whose data are introduced in the chemometric model above mentioned. Another important characteristic of this method is that the fuel sample was used without any pre-treatment for EEF. This work provides an interest improvement to fluorescence techniques using the rapid and easily applicable EEF approach to analyze such complex matrices. Exploding EEF was the key to a successful determination, obtaining a detection limit of 0.00434% (v/v) and a limit of quantification of 0.01446% (v/v).Fil: Insausti, Matías. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur. Departamento de Química; ArgentinaFil: Fernández Band, Beatriz Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur. Departamento de Química; Argentin

Advances in sensing ammonia from agricultural sources

Reducing ammonia emissions is one of the most difficult challenges for environmental regulators around the world. About 90% of ammonia in the atmosphere comes from agricultural sources, so that improving farm practices in order to reduce these emissions is a priority. Airborne ammonia is the key precursor for particulate matter (PM2.5) that impairs human health, and ammonia can contribute to excess nitrogen that causes eutrophication in water and biodiversity loss in plant ecosystems. Reductions in excess nitrogen (N) from ammonia are needed so that farms use N resources more efficiently and avoid unnecessary costs. To support the adoption of ammonia emission mitigation practices, new sensor developments are required to identify sources, individual contributions, to evaluate the effectiveness of controls, to monitor progress towards emission-reduction targets, and to develop incentives for behavioural change. There is specifically a need for sensitive, selective, robust and user-friendly sensors to monitor ammonia from livestock production and fertiliser application. Most currently-available sensors need specialists to set up, calibrate and maintain them, which creates issues with staffing and costs when monitoring large areas or when there is a need for high frequency sampling. This paper reports advances in monitoring airborne ammonia in agricultural areas. Selecting the right method of monitoring for each agricultural activity will provide critical data to identify and implement appropriate ammonia controls. Recent developments in chemo-resistive materials allow electrochemical sensing at room temperature, and new spectroscopic methods are sensitive enough to determine low concentrations in the order of parts per billion. However, these new methods still compromise selectivity and sensitivity due to the presence of ambient dust and other interferences, and are not yet suitable to be applied in agricultural monitoring. This review considers how ammonia measurements are made and applied, including the need for sensors that are suitable for routine monitoring by non-specialists. The review evaluates how monitoring information can be used for policies and regulations to mitigate ammonia emissions. The increasing concerns about ammonia emissions and the particular needs from the agriculture sector are addressed, giving an overview of the state-of-the-art and an outlook on future developments

Pluviómetro de bajo costo para mejorar la resolución espacio-temporal del registro de lluvias en condiciones de campo

Se presenta el prototipo de un pluviómetro autónomo, de bajo costo, construido con materiales accesibles y basado en hardware y software libre. Su funcionamiento se basa en lecturas periódicas del nivel de agua colectada en un reservorio cilindrico, mediante un sensor de distancia. Comparamos la precisión de dos sensores de distinto principio de funcionamiento: láser (IR) y ultrasonido (US).Sociedad Argentina de Informática e Investigación Operativ

Screening analysis of biodiesel feedstock using UV-vis, NIR and synchronous fluorescence spectrometries and the successive projections algorithm

This paper investigates the use of UV-vis, near infrared (NIR) and synchronous fluorescence (SF) spectrometries coupled with multivariate classification methods to discriminate biodiesel samples with respect to the base oil employed in their production. More specifically, the present work extends previous studies by investigating the discrimination of corn-based biodiesel from two other biodiesel types (sunflower and soybean). Two classification methods are compared, namely full-spectrum SIMCA (soft independent modelling of class analogies) and SPA-LDA (linear discriminant analysis with variables selected by the successive projections algorithm). Regardless of the spectrometric technique employed, full-spectrum SIMCA did not provide an appropriate discrimination of the three biodiesel types. In contrast, all samples were correctly classified on the basis of a reduced number of wavelengths selected by SPA-LDA. It can be concluded that UV-vis, NIR and SF spectrometries can be successfully employed to discriminate corn-based biodiesel from the two other biodiesel types, but wavelength selection by SPA-LDA is key to the proper separation of the classes.Fil: 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: Gomes, Adriano A.. Universidade Federal da Paraíba; BrasilFil: Cruz, Fernanda V.. Universidade Federal da Paraíba; BrasilFil: Pistonesi, Marcelo Fabian. 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: Ugulino de Araújo, Mário C.. Universidade Federal Da Paraíba; BrasilFil: Galvão, Roberto K.H.. Universidade Federal da Paraíba; BrasilFil: Pereira, Claudete F.. Universidade Federal da Paraíba; BrasilFil: 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

Acid ceramidase improves mitochondrial function and oxidative stress in Niemann-Pick type C disease by repressing STARD1 expression and mitochondrial cholesterol accumulation.

Niemann-Pick type C (NPC) disease, a lysosomal storage disorder caused by defective NPC1/NPC2 function, results in the accumulation of cholesterol and glycosphingolipids in lysosomes of affected organs, such as liver and brain. Moreover, increase of mitochondrial cholesterol (mchol) content and impaired mitochondrial function and GSH depletion contribute to NPC disease. However, the underlying mechanism of mchol accumulation in NPC disease remains unknown. As STARD1 is crucial in intramitochondrial cholesterol trafficking and acid ceramidase (ACDase) has been shown to regulate STARD1, we explored the functional relationship between ACDase and STARD1 in NPC disease. Liver and brain of Npc1−/− mice presented a significant increase in mchol levels and STARD1 expression. U18666A, an amphiphilic sterol that inhibits lysosomal cholesterol efflux, increased mchol levels in hepatocytes from Stard1f/f mice but not Stard1ΔHep mice. We dissociate the induction of STARD1 expression from endoplasmic reticulum stress, and establish an inverse relationship between ACDase and STARD1 expression and LRH-1 levels. Hepatocytes from Npc1+/+ mice treated with U18666A exhibited increased mchol accumulation, STARD1 upregulation and decreased ACDase expression, effects that were reversed by cholesterol extraction with 2-hydroxypropyl-β-cyclodextrin. Moreover, transfection of fibroblasts from NPC patients with ACDase, decreased STARD1 expression and mchol accumulation, resulting in increased mitochondrial GSH levels, improved mitochondrial functional performance, decreased oxidative stress and protected NPC fibroblasts against oxidative stress-mediated cell death. Our results demonstrate a cholesterol-dependent inverse relationship between ACDase and STARD1 and provide a novel approach to target the accumulation of cholesterol in mitochondria in NPC disease

Single excitation-emission fluorescence spectrum (EEF) for determination of cetane improver in diesel fuel

A highly sensitive spectrofluorimetric method has been developed for the determination of 2-ethylhexyl nitrate in diesel fuel. Usually, this compound is used as an additive in order to improve cetane number. The analytical method consists in building the chemometric model as a first step. Then, it is possible to quantify the analyte with only recording a single excitation-emission fluorescence spectrum (EEF), whose data are introduced in the chemometric model above mentioned. Another important characteristic of this method is that the fuel sample was used without any pre-treatment for EEF. This work provides an interest improvement to fluorescence techniques using the rapid and easily applicable EEF approach to analyze such complex matrices. Exploding EEF was the key to a successful determination, obtaining a detection limit of 0.00434% (v/v) and a limit of quantification of 0.01446% (v/v).Fil: 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: 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

Fast Determination of 2-Ethylhexyl Nitrate Diesel/Biodiesel Blends by Distillation Curves and Chemometrics

A new method for the quantification of 2-EHN (2-ethylhexyl nitrate) was developed and validated. In order to speed up and simplify the chemical analysis of diesel samples throughout inspection procedures, we propose a single analytical method to determine 2-ethylhexyl nitrate by using the distillation curves routine assay used to evaluate the quality of diesel (ASTM D86). This test was allied with multivariate calibration based on PLS (partial least squares) regression. The results were comparable with reference methodology. Using distillation curves of commercial diesel samples results in a prediction of the cetane improver content with relative standard deviations lower than 12% for all fuel samples. Since this correlation was established using commercial samples, the new approach is immediately applicable in the petrochemical industry, which needs an adaptation to biodiesel/diesel blends.Fil: 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: 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

Octyl p-methoxycinnamate loaded microemulsion based on Ocimum basilicum essential oil. Characterization and analytical studies for potential cosmetic applications

A O/W microemulsion based on biocompatible materials was designed for a potential topical use as UVB filter, antiinflamatory and mosquito repellent. Octyl-p-methoxy cinnamate (OMC) is one of the most widely used sunscreen compounds. Nevertheless, their efficiency as UV filter is affected by irradiation because a photolysis process occurs. Ocimum basilicum essential oil is utilized in traditional medicine and as repellent of insects, among others. Hence, the proposed O/W microemulsion consisted of 6.0% of Ocimum basilicum essential oil (oil phase), 23% of a 2:1 mixture of decaethylene glycol mono-dodecyl ether (surfactant) and ethanol (co-surfactant), and 71% of water. OMC was successfully loaded in the O/W microemulsion (1.5%). The loaded system presented a particle size of (12.60 ± 0.10) nm and a polydispersity index of 0.389 ± 0.042. A spherical morphology and droplet sizes in nanometric range were corroborated by transmission electronic microscopy. The higher photostability of OMC in the O/W microemulsion with respect to the free-OMC was demonstrated by calculating the photolysis kinetic constants (0.00186 s−1 and 0.00457 s−1, respectively) which were obtained through a photolysis study assisted by multivariate curve resolution-alternating least squares algorithm. Moreover, the stability of the system over time and under different conditions was demonstrated. On the other hand, a chromatographic analysis of the essential oil corroborated the presence of estragole (93.2%) which presents a documented antiinflammatory activity, and seven compounds with a well reported mosquito repellent activity, such as linalool (2.81%), cineole (0.57%), among others. On this form, the proposed O/W microemulsion presents optimal chemical and physicochemical characteristics for a potential application in cosmetic product.Fil: Volpe, Verónica. 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: Silva Do Nascimento, Danielle. 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: 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; Argentin

Fluorescence enhancement novel green analytical method for paraquat herbicide quantification based on immobilization on clay

A new green method was developed for the quantification of paraquat (PQ) in water samples based on the fluorescence emission enhancement of the herbicide signal after adsorption on sodium montmorillonite clay (MMT). Radiant emission processes are favored by increasing the molecular rigidity of the PQ since it adopts a planar position between the nano-sheets of the MMT. The advantages of the use of this clay are nontoxic, low cost and found in abundance in natural reserves. The proposed method was successfully used in determining PQ in natural water samples with recoveries of 73% to 95%. The fluorescence emission showed a good linear relationship with PQ concentrations from 2.0 to 8.0 μmol L-1 with a detection limit of 0.37 μmol L-1. The method is simple, inexpensive and does not require the use of reagents or organic solvents; which makes it very promising to achieve the goals of green chemistry. The proposed methodology could be the beginning of the development of future green sensors.Fil: Dominguez, Marina Alejandra. 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: Ilari, Romina. 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: Zanini, Graciela Pilar. 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

On line kinetic analysis of permeation profiles for UV filter loaded microemulsions using an automatic system with spectroscopic detection and a chemometric approach

The analysis of the permeation kinetics of new UV filter formulations is of great importance since the kinetic parameters are related to the effectiveness of the product over time. The dynamics of this process can be evaluated by means of the calculation of the permeation kinetic constants, which can be obtained from the respective permeation profiles. This paper is aimed at improving the analytical performance of permeation assays using an on-line automatic system with spectrometric detection avoiding the chromatographic procedure and the usually manual sampling steps required using the traditional Franz diffusion cell. Then, the kinetics of permeation of octyl p-methoxycinnamate loaded in different microemulsions through a synthetic membrane (polyamide) was analysed at real time by UV-Vis and fluorescence spectroscopies. The spectral data were obtained at regular intervals of time (5 min) during 60 min, and the concentration of the permeated UV-filter was at each time calculated using univariate linear calibration. The interference caused by the presence of basil essential oil (oily phase) in some microemulsion samples was overcome using synchronous fluorescence spectroscopy (Δλ = 60 nm) and partial least squares. In all cases, the permeation profiles were obtained (first-order kinetics) and the respective permeation kinetic constants were calculated. The validation of the proposed method was assessed by gas chromatographic-mass spectroscopy and non-significant differences for the obtained permeation kinetic constants were found between methods (p = 0.05). Additionally, a commercial sample was analysed with the proposed methods and the results were validated by high performance liquid chromatography technique.Fil: Silva Do Nascimento, Danielle. 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: Volpe, Verónica. 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: 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; Argentin