Actuaciones de comprobación e investigación inspectoras: la devolución del Impuesto sobre el Valor Añadido como consecuencia de la calificación inspectora de contratos y operaciones mercantiles para regularizar el Impuesto sobre Sociedades

La calificación tributaria de los hechos o negocios efectuada durante las actuaciones de comprobación e investigación inspectoras, con propuestas de regularización-liquidación en Acta de Inspección, por un concepto impositivo determinado (Impuesto sobre Sociedades) hace nacer el deber y la obligación de la Administración tributaria de incluir en Plan de Inspección y proponer la regularización de los mismos hechos calificados por cualquier otro concepto impositivo procedente (Impuesto sobre el Valor Añadido). Y ello, aunque suponga el nacimiento del derecho a la devolución de ingresos indebidos a favor del sujeto inspeccionado. El incumplimiento de este deber por parte de la Inspección origina incertidumbre e indefensión jurídica del sujeto inspeccionado, con posible exigencia de responsabilidad administrativa, por negarle o impedir el ejercicio de sus derechos y el cumplimiento de sus obligaciones. El alcance expansivo a cualquier tributo de la aplicación de la calificación tributaria a unos hechos y circunstancias comprobadas por la Inspección durante sus actuaciones, puede llegar a producir novaciones de obligaciones tributarias con efectos sobre los plazos de caducidad o prescripción. El Ordenamiento tributario dispone de normas que permitan revocar los actos administrativos tributarios que no se ajusten a ellas, así como el señalamiento minucioso de los procedimientos a seguir para que los efectos generales de la calificación tributaria beneficien al sujeto de las actuaciones de comprobación e investigación inspectoras

New applicactions of non-conventional analytical detectors based on ionization processes

La tendencia hacia la simplificación, automatización y miniaturización de los procesos de medida ha englobado también a la información que se genera en los laboratorios. En este sentido, es deseable el empleo de procesos de medida que ofrezcan información analítica simple, rápida, fiable y fácil de interpretar para agilizar la toma de decisiones. Teniendo en cuenta las consideraciones anteriores, con el desarrollo de la Tesis Doctoral se ha pretendido desarrollar metodologías analíticas que permitan la mejora de propiedades analíticas, tanto básicas (sensibilidad, selectividad) como complementarias (rapidez, bajo coste, robustez), siendo el objetivo final, mejorar las determinaciones analíticas en diversas áreas como cosmética y alimentación. Para llevar a cabo la investigación se ha hecho uso de detectores no convencionales (espectrómetros de movilidad iónica) y de respuesta cuasi-universal como el detector evaporativo de dispersión de luz y el detector de transferencia de carga-corona en combinación con el empleo de sorbentes alternativos a los tradicionales (nanotubos de carbono) y nuevos medios de extracción (líquidos iónicos)

Cyclic voltammetry : a tool to quantify 2,4,6-trichloroanisole in aqueous samples from cork planks boiling industrial process

Chloroanisoles, namely 2,4,6-trichloroanisole, are pointed out as the primary responsible of the development of musty off-flavours in bottled wine, due to their migration from cork stoppers, which results in huge economical losses for wine industry. A prevention step is the detection of these compounds in cork planks before stoppers are produced. Mass spectrometry gas chromatography is the reference method used although it is far beyond economical possibilities of the majority of cork stoppers producers. In this work, a portable cyclic voltammetry approach was used to detect 2,4,6-trichloroanisole extracted from natural cork planks to the aqueous phase during the cork boiling industrial treatment process. Analyses were carried out under ambient conditions, in less than 15 min with a low use of solvent and without any sample pre-treatment. The proposed technique had detection (0.31±0.01 ng/L) and quantification (0.95±0.05 ng/L) limits lower than the human threshold detection level. For blank solutions, without 2,4,6-trichloroanisole addition, a concentration in the order of the quantification limit was estimated (1.0±0.2 ng/L), which confirms the satisfactory performance of the proposed methodology. For aqueous samples from the industrial cork planks boiling procedure, intra-day repeatabilities were lower than 3%, respectively. Also, 2,4,6-trichloroanisole contents in the aqueous samples determined by this novel approach were in good agreement with those obtained by GC-MS (correlation coefficient equal to 0.98), confirming the satisfactory accuracy of the proposed methodology. So, since this novel approach is a fast, low-cost, portable and user-friendly method, it can be an alternative and helpful tool for in-situ industrial applications, allowing accurate detection of releasable 2,4,6-trichloroanisole in an earlier phase of cork stoppers production, which may allow implementing more effective cork treatments to reduce or avoid future 2,4,6-trichloroanisole contaminations of wine.This work was partially supported by project PEst-C/EQB/LA0020/2011, financed by FEDER through COMPETE - Programa Operacional Factores de Competitividade and by FCT - Fundacao para a Ciencia e a Tecnologia (Portugal)

Analyzing complex mixtures of drug-like molecules: ion mobility as an adjunct to existing liquid chromatography-(tandem) mass spectrometry methods

The use of traveling wave ion mobility mass spectrometry (TWIMS) is evaluated in conjunction with, and as a possible alternative to, conventional LC-MS(/MS) methods for the separation and characterization of drug-like compounds and metabolites. As a model system we use an in vitro incubation mixture of the chemotherapeutic agent melphalan, which results in more than ten closely related hydrolysis products and chain-like oligomers. Ion mobility as a filtering tool results in the separation of ions of interest from interfering ions, based on charge state and shape/size. Different classes of chemical compounds often display different mobilities even if they show the same LC behavior – thereby providing an orthogonal separation dimension. Small molecules with identical or similar m/z that only differ in shape/size (e.g. isomers and isobars, monomers/dimers) can also be distinguished using ion mobility. Similar to retention times and mass-to-charge ratios, drift times are analyte-dependent and can be used as an additional identifier. We find that the compound melphalan shows two different drift times due to the formation of gas-phase charge isomers (protomers). The occurrence of protomers has important implications for ion mobility characterization of such analytes, and also for the interpretation of their fragmentation behavior (CID) in the gas phase

Comparative Study of the Determination of Parabens in Shampoos by Liquid Chromatography with Amperometric and Coulometric Detection

The simultaneous determination of four para-hydroxybenzoic acid esters (parabens) in shampoos was studied by liquid chromatography (LC) with amperometric (LC-AD) and coulometric (LC-CD) detection. The parabens were separated on an ODS C18 reversed column by isocratic elution with a mobile phase based on methanol-0.1M acetic acid (60:40%, v/v) with 0.02M NaClO4 at a flow rate of 0.8 mL min-1. The limit of detection (S/N>3) for the analytes was in the 15 -25 pg (injected mass) range at an applied potential of 1.20 V vs. Ag/AgCl using the LC-AD and in the 2 -3 pg range at a potential of 0.790 V vs. Pd using the LC-CD. The peak ratio of the internal standard peak (IS: 4-hydroxybenzoic acid secbutyl ester) versus the analyte peak was found to be related to the amount injected from 0.1 ng to 100ng (r=0.996 -0.999) with the LC-AD and from 0.050 ng to 100 ng range (r=0.999 -1.000) with the LC-CD. The relative standard deviation (RSD, n=10) was comprised between 1.8 to 3.5% by LC-AD (5 ng injected) and between 2.0 to 2.4% by LC-CD (0.5 ng injected). The determination of four most used parabens in ten different shampoos was successfully realized. © 2010 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.SCOPUS: ar.jFLWINinfo:eu-repo/semantics/publishe