Comparison of inductively coupled plasma mass spectrometry techniques in the determination of platinum in urine: quadrupole vs. sector field

In recent years the increasing use of platinum (Pt) both in medical and in industrial applications has caused its growing anthropogenic emission and spread in the environment. Pt is released into the atmosphere by exhaust catalytic converters, and Pt compounds are often used in antitumour therapies. As a consequence, significant amounts of Pt can be detected in hospital wastewaters. This can lead to an increase in the exposure levels to Pt, especially in urban areas. It is therefore necessary to determine Pt reference values in the general population, by using suitable procedures able to achieve adequate analytical performances. Several measurements of Pt in biological fluids have been reported, but the analytical methods used for the determination of Pt often lack information about the uncertainty of the results, especially for low concentrations of urinary Pt in non-occupationally exposed subjects. The present paper considers the measurement of urinary Pt levels in a general population group from central Italy, by both quadrupole (Q) and sector field (SF) inductively coupled plasma mass spectrometry (ICP-MS). The two procedures were validated and their expanded uncertainties were evaluated. The limits of detection (LODs), calculated taking into account dilution factors, were 0.18 and 0.05 ng L(-1) of Pt for the Q and SF procedures, respectively. The median value observed was 4.13 ng L(-1) of Pt in urine, while the relative combined uncertainty at 5 ng L(-1) was below 20% with both ICP-MS techniques. These data are in good agreement with those reported in the literature for similar studies.     

Efficient hydroxycarbonylation of aryl iodides using recoverable and reusable carbon aerogels doped with palladium nanoparticles as catalyst

Electron-rich and electron-poor aryl iodides are converted, in high to excellent yields, into the corresponding carboxylic acids through a hydroxycarboxylation reaction catalyzed by a recoverable and reusable phosphine free palladium-carbon aerogel catalyst using lithium formate and acetic anhydride as an internal condensed source of carbon monoxide. The catalyst system can be reused several times without any appreciable loss of activity.     

Tachyonization of the ΛCDM cosmological model

In this work a tachyonization of the ΛCDM model for a spatially flat Friedmann–Robertson–Walker space–time is proposed. A tachyon field and a cosmological constant are considered as the sources of the gravitational field. Starting from a stability analysis and from the exact solutions for a standard tachyon field driven by a given potential, the search for a large set of cosmological models which contain the ΛCDM model is investigated. By the use of internal transformations two new kinds of tachyon fields are derived from the standard tachyon field, namely, a complementary and a phantom tachyon fields. Numerical solutions for the three kinds of tachyon fields are determined and it is shown that the standard and complementary tachyon fields reproduces the ΛCDM model as a limiting case. The standard tachyon field can also describe a transition from an accelerated to a decelerated regime, behaving as an inflationary field at early times and as a matter field at late times. The complementary tachyon field always behaves as a matter field. The phantom tachyon field is characterized by a rapid expansion where its energy density increases with time.     

Supramolecular structures and columnar mesophase induction in nondiscoid pyrazoles by complexation to rhodium(I)

Several new cis-[RhCl(CO)2(Ln)] complexes have been prepared using different polycatenar pyrazole ligands (Ln) in order to obtain columnar liquid crystalline arrangements. The topology of the ligand plays an essential role, and a mesophase is induced at room temperature from a nonmesogenic pyrazole only when it is symmetrically substituted with six decyloxy chains. The single-crystal structure of a methoxy-substituted analogue, 3,5-bis(3,4,5-trimethoxyphenyl)pyrazole, is formed by globular tetrameric structures held together by H-bonding. However, parallel dimers are present in the corresponding cis-chlorodicarbonylrhodium(I) complex, a situation that explains the induction of a columnar mesophase in the decyloxy-substituted complex. The XRD pattern of the mesophase is consistent with a hexagonal symmetry in which the columns are formed by molecules assembled in an antiparallel mode. The crystal-to-mesophase transition was also detected by spectroscopic techniques as a shift in the IR carbonyl stretching bands and the appearance of a charge-transfer band in the absorption spectrum with thermochromic behavior.     

One-pot thiol–amine bioconjugation to maleimides: simultaneous stabilisation and dual functionalisation

Maleimide chemistry is widely used in the site-selective modification of proteins. However, hydrolysis of the resultant thiosuccinimides is required to provide robust stability to the bioconjugates. Herein, we present an alternative approach that affords simultaneous stabilisation and dual functionalisation in a one pot fashion. By consecutive conjugation of a thiol and an amine to dibromomaleimides, we show that aminothiomaleimides can be generated extremely efficiently. Furthermore, the amine serves to deactivate the electrophilicity of the maleimide, precluding further reactivity and hence generating stable conjugates. We have applied this conjugation strategy to peptides and proteins to generate stabilised trifunctional conjugates. We propose that this stabilisation-dual modification strategy could have widespread use in the generation of diverse conjugates.

An alternative approach to maleimide conjugate stabilisation is presented, by the consecutive addition of a thiol and an amine to dibromomaleimides. The amine serves to simultaneously deactivate the maleimide and enable dual functionalisation.     

Regulation of the receptor-mediated cyclic AMP response of kidney to parathyroid hormone in the vitamin D-deficient rat.

Rats fed a diet deficient in vitamin D were found to exhibit a refractory cyclic AMP response of kidney slices to parathyroid hormone and a marked decrease in membrane parathyroid hormone-dependent adenylate cyclase activity. Both the characteristic calcium deficiency (hypocalcemia) and secondary elevation of circulating parathyroid hormone appeared before the first noticeable decrease in hormone-dependent enzyme activity. After repletion of D-deficient rats with vitamin D2, we found that serum calcium and parathyroid hormone were both restored to normal levels before the depressed enzyme response to the hormone was reversed. Moreover, infusion of parthyroid hormone into vitamin D-replete rats led to a marked reduction in parathyroid hormone-dependent adenylate cyclase activity, which was partly restored to control level 3 hours after discontinuing the hormone infusion. Taken as a whole, this study suggests that the elevated endogenous parathyroid hormone in the vitamin D-deficient rat is involved in the "down-regulation" of renal cyclic AMP responsiveness to the hormone. However, these experiments do not rule out the possibility that calcium deficiency and/or vitamin D per se participate in the regulation of the renal cyclic AMP response to parathyroid hormone.     

Measurements of electrostatic potentials and electric fields in some industrial applications: Basic principles

Electrostatic potentials or electric fields are often measured in order to characterize materials or to make a diagnostic of an industrial installation. Electrostatic probes or field mills are widely used and sometimes considered equivalent. However, experimental configurations must be carefully analyzed to make a valid interpretation. Depending on the instrument, results and influence on the analyzed system are very different. An analysis of different situations shows the electrostatic conditions imposed by each instrument and the concept of unperturbed surface potential. This paper analyses from an electrostatic point of view some measurement cases representative of industrial situations or described in standards.     

Uncertainty of inductively coupled plasma mass spectrometry based measurements: an application to the analysis of urinary barium, cesium, antimony and tungsten

The wide use of barium (Ba), cesium (Cs), antimony (Sb) and tungsten (W) in many industrial and agricultural fields causes the increased release of these metals into the environment, laying the basis for health risk. To assess the exposure for the general population, the development of adequate and reliable analytical techniques becomes compulsory. This study refers to the quantification of urinary Ba, Cs, Sb and W levels by both quadrupole (Q) and sector field (SF) inductively coupled plasma mass spectrometry (ICP-MS). The two procedures were compared for their performances and their measurement uncertainties. The limits of detection were (Q and SF) 23.0 and 5.21 ng L(-1) for Ba; 21.1 and 7.52 ng L(-1) for Cs; 1.09 and 0.43 ng L(-1) for Sb; and 0.36 and 0.49 ng L(-1) for W. The trueness was better than 93.3% and the precision less than 12% for both techniques. Relative expanded uncertainties of the analytical procedures, at the median levels found in the general population, were below 5% for all the elements with both ICP-MS techniques. The uncertainties related to the calibration and repeatability were the parameters most influencing the final analytical performance. The urinary median values observed in healthy subjects from central Italy were 1146, 4301, 60.8 and 48.5 ng L(-1) for Ba, Cs, Sb and W, respectively.     

Solid state (13)C NMR and FT-IR spectroscopy of the cocoon silk of two common spiders

The structure of the silk from cocoons of two common spiders, Araneus diadematus (family Araneidae) and Achaearanea tepidariorum (family Theridiidae) was investigated by means of (13)C solid state NMR and FT-IR spectroscopies. The combined use of these two techniques allowed us to highlight differences in the two samples. The cocoon silk of Achaearanea tepidariorum is essentially constituted by helical and beta-sheet structures, whereas that of Araneus diadematus shows a more complex structure, containing also beta-strands and beta-turns. Moreover, the former silk is essentially crystalline while the latter contains more mobile domains. The structural differences of the two cocoon silks are ascribed to the different habitat of the two species.