Determination of different recreational drugs in hair by HS-SPME and GC/MS

A simple procedure combining headspace solid-phase microextraction (HS-SPME) and gas chromatography–mass spectrometry (GC/MS) to detect and quantify amphetamines, ketamine, methadone, cocaine, cocaethylene and ∆⁹-tetrahydrocannabinol (THC) in hair is described. This procedure allows, in a single sample, even scant, analysis of drugs requiring different analytical conditions. A hair sample (10 mg) is washed and subjected to acidic hydrolysis. Then the HS-SPME is carried out (10 min at 90 °C) for amphetamines, ketamine, methadone, cocaine and cocaethylene. For derivatization of analytes, the fibre is introduced into the headspace of another closed vial containing acetic anhydride. After a chromatographic run, an alkaline hydrolysis for THC analysis is carried out in the same vial containing the hair sample previously used. For adsorption, the solid-phase microextraction needle is inserted into the headspace of the vial and the fibre is exposed for 30 min at 150 °C. For derivatization of analytes, the fibre is introduced into the headspace of another closed vial containing N-methyl-N-(trimethylsilyl)trifluoroacetamide. The GC/MS parameters were the same for both chromatographic runs. The linearity was proved to be between 0.01 and 10.00 ng/mg. The repeatability (intra- and interday precision) was below 10% as the coefficient of variation for all compounds. The accuracy, as the relative recovery, was 96.2–103.5% (spiked samples) and 88.6–101.7% (quality control sample). The limit of detection ranged from 0.01 to 0.12 ng/mg, and the limit of quantification ranged from 0.02 to 0.37 ng/mg. Application of the procedure to real hair samples is described. To the best of our knowledge, the proposed procedure combining HS-SPME and GC/MS is the first one be to successfully applied to the simultaneous determination of most of the common recreational drugs, including THC, in a single hair sample.     

Characterization of low temperature dielectric processes in Poly(dicyclohexyl-itaconate)

Thermally stimulated depolarization current experiments (TSDC) have been carried out on poly(dicyclohexyl itaconate) (PDCHI) in the glassy state. The polymer exhibits three relaxation zones in the interval of temperature studied: a δ-relaxation at ∼130 K, a complex γ-process, in the temperature interval of 140 K to 200 K, and the β-process in the range of 210-270 K. The loss factor of PDCHI in the glassy zone has been reproduced from the partial depolarization data by using the elementary relaxation times and activation energies. The results show the existence of at least two relaxation processes in γ- and β-zones. A tentative explanation of the molecular origin of the observed secondary relaxations has been done by means of molecular mechanics (MM). At this respect, we perform a comparison of the relaxational data of PDCHI and those corresponding to PCHMA. This comparison allows us to confirm the relevant role played by the cyclohexyl ring in the δ- and γ-relaxations.     

Synthesis of the O-linked hexasaccharide containing β-D-Galf-(1→2)-β-D-Galf in Trypanosoma cruzi mucins

The hexasaccharide β-D-Galp-(1→2)-[β-D-Galp-(1→3)]-β-D-Galp-(1→6)-[β-D-Galf(1→2)-β-D-Galf(1→4)]-D-GlcNAc (1) is the largest carbohydrate structure released as alditol by reductive β-elimination from mucins of some strains of T. cruzi. The terminal β-D-Galp units are sites of sialylation by trans-sialidase which transfers sialic acid from the host to the parasite. Hexasaccharide 1 was synthesized by a [3 + 3]-convergent strategy based on a nitrile assisted glycosylation, using the trichloroacetimidate method. The β-D-Galf-(1→2)-β-D-Galf-D-GlcNAc synthon was sequentially constructed from the reducing end to the non-reducing end employing benzyl α-D-galactofuranoside as starting material for the internal Galf unit. The choice of this novel precursor, obtained in one-reaction step from galactose, allowed the introduction of an orthogonal and participating levulinoyl group at O-2. Thus, the diastereoselective construction of the Galf-β(1→4)-GlcNAc linkage by the trichloroacetimidate method of glycosylation was achieved. The (1)H NMR spectrum of alditol 2 was identical to the product released by β-elimination from the parasite mucin.     

Rare earth elements,thorium and uranium in ores of the North-Latium (Italy)

In geochemistry, the distribution of the Rare Earth Elements (REEs) in earth crust and mantle allows to understand geochemical cycles and origin and age of igneous rocks. In this article REEs (Ce, Dy, Eu, La, Nd, Sm, Tb, and Yb), Th and U in ores of the North-Latium (Bracciano area, Ceriti Mt., Fate Mt., Sabatini Mt., Vulsini Mt., Acqua Rossa basin), have been investigated for evaluating the extraction feasibility for industrial applications. 107 samples were irradiated in the rotating rack of the TRIGA Mark II reactor of the R.C. Casaccia (ENEA) at neutron flux of 2.6 × 10¹² n × cm⁻² × s⁻¹ for 12 h together with primary and secondary standards. The gamma spectrometry measurements were performed after 8 h, 3 and 30 days of decay by means of HPGe detector (FWHM 1.75 keV at 1332.5 keV, peak/Compton ratio 55.1, relative efficiency of 22%) connected to a multi-channel analyzer. The total REE mean content is 105 μg g⁻¹, ranging widely between 2.23 and 410.5 μg g⁻¹ (average coefficient of variation 112%). A similar behavior is found for Th and U: their average levels are 13.5 and 6.0 μg g⁻¹, respectively. A quite good correlation between REEs and Th (and U) is found for Ceriti Mt. (r ² > 0.8) whereas for the other areas the correlation is <0.7. The results obtained evidence the low U content in the investigated locations.     

Source apportionment of groundwater pollutants in Apulian agricultural sites using multivariate statistical analyses: case study of Foggia province

Background

Ground waters are an important resource of water supply for human health and activities. Groundwater uses and applications are often related to its composition, which is increasingly influenced by human activities.In fact the water quality of groundwater is affected by many factors including precipitation, surface runoff, groundwater flow, and the characteristics of the catchment area. During the years 2004-2007 the Agricultural and Food Authority of Apulia Region has implemented the project “Expansion of regional agro-meteorological network” in order to assess, monitor and manage of regional groundwater quality. The total wells monitored during this activity amounted to 473, and the water samples analyzed were 1021. This resulted in a huge and complex data matrix comprised of a large number of physical-chemical parameters, which are often difficult to interpret and draw meaningful conclusions. The application of different multivariate statistical techniques such as Cluster Analysis (CA), Principal Component Analysis (PCA), Absolute Principal Component Scores (APCS) for interpretation of the complex databases offers a better understanding of water quality in the study region.

Results

Form results obtained by Principal Component and Cluster Analysis applied to data set of Foggia province it’s evident that some sampling sites investigated show dissimilarities, mostly due to the location of the site, the land use and management techniques and groundwater overuse. By APCS method it’s been possible to identify three pollutant sources: Agricultural pollution 1 due to fertilizer applications, Agricultural pollution 2 due to microelements for agriculture and groundwater overuse and a third source that can be identified as soil run off and rock tracer mining.

Conclusions

Multivariate statistical methods represent a valid tool to understand complex nature of groundwater quality issues, determine priorities in the use of ground waters as irrigation water and suggest interactions between land use and irrigation water quality.

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Self-assembling and phase coexistence of SW trimers as complex amphiphile analogues. I. Simulations

We analyse by discrete molecular dynamics the self-assembly of SW trimer particles that contain a different number of attractive and repulsive spheres. They also have different geometries: linear, obtuse, rectangular and equilateral. We identify that some of these molecules exhibit liquid–vapour equilibria while others do not. For all of them, we show the morphological phase diagram built up from the different supra-molecular structures formed by each type of trimer. We simulated 14 different systems with a total of 321 states. The main features of the supra-molecular structures depend only on the composition and geometry of the trimer: triple SW trimers do not form supra-structures, double SW trimers and single SW trimers form monolayers, bilayers and worm-like micelles. The liquid–vapour coexistence properties are also exhibited. These trimers can be used to model complex amphiphiles beyond the standard ones, such as the Gemini and the Bola surfactants as well as colloidal particles.