Comparison between Total Determination and Extractable Heavy Metals from River Sediments using Conventional and Microwave Accelerated Leaching Tests

Abstract

In the present study the concentration of heavy metals (Cu, Cr, Ni, Pb and Zn) in sediments collected from different sampling stations of the Leça river (Portugal) was determined, using Flame Atomic Absorption Spectrometry. In order to estimate the potential mobility of metals in these samples, the results of the total digestion were compared with those obtained by single extractions using EDTA and acetic acid as extractant solutions; in all samples studied, Cu and Zn were found to be the most mobile elements; Ni and Pb showed a smaller mobility in presence of either acidic medium and complexing ligands; Cr was found the least mobilizable element, given that the low extractability obtained with the two extractants tested in this work. In the single extraction tests, microwave energy was also employed to replace the conventional treatment and only in the case of the EDTA the results obtained were similar to those of the conventional procedure (recoveries between 90.16 and 98.76%); the precision (RSD, n=3) of the proposed microwave procedure for EDTA extractions was comparable to those of the conventional method with values always lower than 8% for all metals.     

Development and validation of a HPLC–UV based method for the extraction and quantification of methotrexate in the skin

An innovative and sensitive HPLC–UV method for the extraction and quantification of methotrexate (MTX) in skin layers was developed and validated. Owing to the physico-chemical characteristics of the drug and the nature of the tissue, it was necessary to use folic acid (FA) as an internal standard for MTX quantification in the dermis. MTX (and FA) analysis was performed on a Phenomenex Jupiter C₁₈ column, using a 50 mm sodium acetate buffer (pH 3.6) and methanol mixture (87:13, v/v) as mobile phase, pumped at 1 ml/min. The absorbance was monitored at 290 nm. The method was selective, linear in the range 0.11–8.49 μg/ml for extraction solvent and 0.05–8.94 μg/ml for pH 7.4 phosphate-buffered saline, precise and accurate, with lower limits of quantitation of 0.11 μg/ml (extraction solvent) and 0.05 μg/ml (pH 7.4 phosphate-buffered saline). The method developed is suitable for the quantification of MTX in skin layers at the end of in vitro permeation experiments; the overall mass balance was 96.5 ± 1.4%, in line with the requirements of the Organisation for Economic Co-operation and Development guideline for the testing of the chemicals (Skin absorption: in vitro method).     

Cladonia verticillaris (lichen) can exhibit defense mechanisms against Rn-222 under controlled conditions

Journal of Radioanalytical and Nuclear Chemistry - This study aimed to evaluate the effects of the Rn-222 progeny on the lichen Cladonia verticillaris under controlled conditions. The results...     

Synthesis and preliminary in vivo evaluations of polyurethane microstructures for transdermal drug delivery

ABSTRACT: BACKGROUND: Polymers have been considered as important materials in fabrication of microstructures for various medical purposes including drug delivery. This study evaluates polyurethane as material for hollow microstructures preparation. RESULTS: Polyurethane microstructures were obtained by interfacial polyaddition combined with spontaneous emulsification and present slightly acid pH values. Scanning electron microscopy revealed the existence of irregular shapes and agglomerated microstructures. The material is heat resistant up to 280 [DEGREE SIGN]C. Good results were recorded on murine skin tests in case of polyurethane microstructures based on isophorone diisocyanate. Mesenchymal stem cells viability presents good results for the same sample after 48 hours based on the Alamar Blue test. CONCLUSIONS: The research revealed the reduced noxiousness of this type of microstructures and consequently the possibility of their use for therapeutic purposes.     

The Compound Poisson Limit Ruling Periodic Extreme Behaviour of Non-Uniformly Hyperbolic Dynamics

We prove that the distributional limit of the normalised number of returns to small neighbourhoods of periodic points of certain non-uniformly hyperbolic dynamical systems is compound Poisson. The returns to small balls around a fixed point in the phase space correspond to the occurrence of rare events, or exceedances of high thresholds, so that there is a connection between the laws of Return Times Statistics and Extreme Value Laws. The fact that the fixed point in the phase space is a repelling periodic point implies that there is a tendency for the exceedances to appear in clusters whose average sizes is given by the Extremal Index, which depends on the expansion of the system at the periodic point. We recall that for generic points, the exceedances, in the limit, are singular and occur at Poisson times. However, around periodic points, the picture is different: the respective point processes of exceedances converge to a compound Poisson process, so instead of single exceedances, we have entire clusters of exceedances occurring at Poisson times with a geometric distribution ruling its multiplicity. The systems to which our results apply include: general piecewise expanding maps of the interval (Rychlik maps), maps with indifferent fixed points (Manneville-Pomeau maps) and Benedicks-Carleson quadratic maps.     

Iridium(I) Hydroxides: Powerful Synthons for Bond Activation

A family of iridium(I) hydroxides of the form [Ir(cod)(NHC)(OH)] (cod=1,5‐cyclooctadiene, NHC=N‐heterocyclic carbene) is reported. Single‐crystal X‐ray analyses and computational methods were used to explore the structural characteristics and steric properties of these new complexes. The model complex [Ir(cod)(IiPr)(OH)] (IiPr=1,3‐(diisopropyl)imidazol‐2‐ylidene) undergoes reaction with a wide variety of substrates including boronic acids and silicon compounds. In addition, O? H, N? H and C? H bond activation was achieved with alcohols, carboxylic acids, amines and various sp‐, sp²‐ and sp³‐hybridised carbon centres, giving access to a wide range of new Ir^I complexes. These studies have allowed us to explore the exciting reactivity of this motif, revealing a versatile and useful synthon capable of activating important chemical bonds under mild (typically room temperature) conditions. No additives were required and, in the case of X? H bond activation, water was the only waste product, rendering this an atom efficient procedure for bond activation. This system has great potential for the construction of new catalytic cycles for organic synthesis and small‐molecule activation.