Heart-cutting two-dimensional (size exclusion × reversed phase) liquid chromatography–mass spectrometry analysis of flavonol glycosides from leaves of Maytenus ilicifolia

Two-dimensional liquid chromatography–electrospray ionization mass spectrometry was employed to analyze flavonol glycosides present in leaves of Maytenus ilicifolia, frequently used in traditional Brazilian medicine. Since they contain many flavonol glycosides, including isomers, one-dimensional liquid chromatography did not give complete separation and identification, yielding overlapping of compounds with different molecular weights. Thus, employing size exclusion chromatography in the first and reversed phase in the second dimension, a great number of flavonol glycosides could be identified and its relative abundances determined. The majority of glycosides contained kaempferol or quercetin as aglycones, and glycosides with previously unreported structures were also present and characterized.     

The development of a gas chromatographic–mass spectrometric analytical procedure for the determination of lipids,proteins and resins in the same paint micro-sample avoiding interferences from inorganic media

This paper presents a GC–MS analytical procedure for determining proteinaceous materials, glycerolipids, natural waxes and terpenoid resins in the same paint micro-sample. The procedure is also reliable when high amounts of interfering inorganic pigments, dryers and charges are present. The characterisation of proteinaceous binders in a paint sample can be subject to analytical interferences by inorganic materials. Such materials may form complexes with functional groups of proteins, thus preventing their efficient derivatisation, which is necessary prior to GC analysis. For this reason an analytical procedure has been developed based on two extractions and a clean-up step, in order to obtain two fractions: a lipid-resinous fraction and a proteinaceous fraction. The lipid-resinous fraction is subjected to salification/saponification assisted by microwaves, followed by acidification, extraction, derivatisation and GC–MS analysis. The proteinaceous fraction is analysed by GC–MS after hydrolysis and derivatisation of the freed amino acids. The desalting step is applied before the hydrolysis, and is based on the use of the monolithic sorbent tip technology with a C4 stationary phase. Reference paint replicas of egg, casein and animal glue were prepared with and without several metals containing pigments, and used to develop and validate the analytical procedure. The procedure proved to be efficient in desalting the proteinaceous materials both from cations and anions. Although non quantitative, it is reliable in the analysis of samples whose content of extractable proteins is <1 μg, thus showing it to be suitable for the characterisation of paint samples. An example of how the analytical procedure was used to characterise a sample from a 15th century panel painting is also discussed.     

Complexity of Gaussian-radial-basis networks approximating smooth functions

Complexity of Gaussian-radial-basis-function networks, with varying widths, is investigated. Upper bounds on rates of decrease of approximation errors with increasing number of hidden units are derived. Bounds are in terms of norms measuring smoothness (Bessel and Sobolev norms) multiplied by explicitly given functions a(r,d)$a(r,d)$ of the number of variables d$d$ and degree of smoothness r$r$. Estimates are proven using suitable integral representations in the form of networks with continua of hidden units computing scaled Gaussians and translated Bessel potentials. Consequences on tractability of approximation by Gaussian-radial-basis function networks are discussed.     

Combining standard addition method and second-order advantage for direct determination of salicylate in undiluted human plasma by spectrofluorimetry

Second-order advantage turns possible a determination in the presence of unknown interferences. This work presented an application of the second-order advantage provided by parallel factor analysis (PARAFAC). The aim was the direct determination of salicylic acid (SA), the main product of aspirin degradation, in undiluted human plasma by spectrofluorimetry. The strategy of this analysis combined the use of PARAFAC, for extraction of the pure analyte signal, with the standard addition method, for a determination in the presence of a strong matrix effect caused by the quenching effect of the proteins present in the plasma. For each sample, four standard additions were performed, in triplicates. A specific PARAFAC model was built for each triplicate of each sample, from three-way arrays formed by 436 emission wavelengths, 7 excitation wavelengths and 5 measurements (sample plus 4 additions). In all the cases, the models were built with three factors and explained more than 99.90% of the total variance. The obtained loadings were related to SA and two background interferences. The scores related to SA were used for a linear regression in the standard addition method. Good results were obtained for determinations in the SA concentration range from 3.0 to 24.0 μg ml⁻¹, providing errors of prediction between 0.7 and 6.3%.     

A novel method to prepare inorganic water-soluble nanocrystals

Calcium sulphate dihydrate nanocrystals of 25-100 nm width have been synthesized in 100% purity and yield by means of a method--the cryo-vacuum process--consisting of rapid freezing of quasi-saturated solutions and subsequent vacuum assisted sublimation of water. Transmission electron microscopy reveals both curled nano-lamellae and smaller, irregular particles; electron diffraction patterns demonstrated that the particles are crystalline. This is a very powerful method for the 'clean' synthesis of moderately and completely water-soluble inorganic materials.     

Cu(I) dinuclear complexes with tripodal ligands vs monodentate donors: triphenylphosphine, thiourea, and pyridine. A 1H NMR titration study

Complexes [PPh3Cu(Tr(Mes,Me))] (1), [PPh3Cu(Tr(Me,o-Py))] (2), and [PPh3Cu(Br(Mes)pz(o-Py))] (3) (Tr(Mes,Me) = hydrotris[1,4-dihydro-3-methyl-4-mesityl-5-thioxo-1,2,4-triazolyl]borate; Tr(Me,o-Py) = hydrotris[1,4-dihydro-4-methyl-3-(2-pyridyl)-5-thioxo-1,2,4-triazolyl]borate; Br(Mes)pz(o-Py) = hydro[bis(thioxotriazolyl)-3-(2-pyridyl)pyrazolyl]borate; PPh3 = triphenylphosphine) were synthesized by the reaction of dinuclear complexes [Cu(Tr(Mes,Me))]2, [Cu(Tr(Me,o-Py))]2, [Cu(Br(Mes)pz(o-Py))]2, and PPh3. 1-3 were characterized by 1H, 13C, and 31P NMR spectroscopy and ESI-mass spectrometry. Crystal structure analyses were performed for 1 and 2. Both complexes crystallize in the triclinic P space group with the metal in a slightly distorted tetrahedral geometry (S3P coordination) bound by a kappa3-S3 ligand and a PPh3 molecule. The solution molecular structures were investigated by means of variable-temperature (210-310 K, CDCl3, 1-2; 200-310 K, CD2Cl2, 3) and NOESY NMR spectroscopy. The solution structures of 1-2 are in accordance with the X-ray structures, and the complexes do not exhibit fluxional behavior. On the other hand, 3 is subject to an equilibrium between two species with a coalescing temperature of approximately 260 K. DFT geometry optimizations suggest that the major species of 3 consists of the Br(Mes)pz(o-Py) ligand bound to Cu(I) in the kappa3-S2H fashion with two C=S groups and a [Cu...H-B] interaction. A PPh3 completes the copper coordination (S2HP coordination). The complex [TuCu(Tr(Mes,Me))] (4) (Tu = thiourea) was crystallized using an excess of Tu with respect to [Cu(Tr(Me,2-Py))]2 (approximately a 6:1 ratio). The metal adopts a distorted tetrahedral geometry with an overall S3H coordination determined by the bound kappa3-S2H ligand (two C=S groups and a [B-H...Cu] interaction) and by a Tu. The reactivity of dinuclear complexes [Cu(Tr(Mes,Me))]2, [Cu(Tr(Me,o-Py))]2, and [Cu(Br(Mes)pz(o-Py))]2 with monodentate ligands was investigated by means of NMR titrations with PPh3, Tu. and pyridine (Py), and formation constants for the adducts [DCu(L)] (D = monodentate donor, L = tripodal ligand) were determined.     

Enhanced electro-catalytic degradation of chloroorganic compounds in the presence of ultrasound

The application of finely divided (black) Pd and Pd-Fe powder in the sono-electro-catalytic reduction of chlorophenoxy herbicides (2,4-D) and chlorophenols (2,4-DCP) in aqueous solutions allows for effective destruction of toxic chlorinated aromatic compounds. At 20 degrees C complete conversion of these compounds is observed within 10 min. On bimetallic Pd/Fe catalyst, intermediates due to the oxidation reaction are detected in addition to the products of dechlorination. The bimetallic catalyst appears to be energetically and economically superior to the Pd. In both cases, the reaction times were considerably shortened in comparison with traditional electro-catalytic processes.     

General models of Einstein gravity with a non-Newtonian weak-field limit

We investigate Einstein theories of gravity, coupled to a scalar field j{\varphi} and point-like matter, which are characterized by a scalar field-dependent matter coupling function e^H(j){e^{H(\varphi)}} . We show that under mild constraints on the form of the potential for the scalar field, there are a broad class of Einstein-like gravity models—characterized by the asymptotic behavior of H—which allow for a non-Newtonian weak-field limit with the gravitational potential behaving for large distances as ln r. The Newtonian term GM/r appears only as sub-leading. We point out that this behavior is also shared by gravity models described by f (R) Lagrangians. The relevance of our results for the building of infrared modified theories of gravity and for modified Newtonian dynamics is also discussed.     

Atmospheric aqueous-phase photoreactivity: correlation between the hydroxyl radical photoformation and pesticide degradation rate in atmospherically relevant waters

In the present study, we investigated the correlation between the hydroxyl radical formation rate (R_˙OH) and the degradation of a pesticide (mesotrione) in synthetic cloud water solutions and in two real atmospheric cloud waters collected at the top of puy de Dôme station (France). Using terephthalic acid as the hydroxyl radical chemical probe, we established the linear correlation between the photogenerated hydroxyl radical under polychromatic wavelengths and the pesticide degradation rate: (m s^?1) = (1.61 ± 0.15) × 10^?1(m s^?1). Moreover, the formation rate of hydroxyl radical in two natural cloud waters was estimated considering H₂O₂ and NO₃^? and the difference between the predicted values and those experimentally obtained could be attributed to the presence of other photochemical sources: iron‐complexes and total organic matter. The organic constituents could play a dual role of sources and scavengers of photoformed hydroxyl radicals in the aqueous phase.     

Chemical fingerprinting of Equisetum arvense L. using HPTLC densitometry and HPLC

Equisetum arvense L. is a herbaceous medicinal plant, commonly known as horsetail, whose extracts have been reported to possess diuretic and haemostatic properties. The aim of this study was to evaluate the use of fingerprint chromatographic methods on commercially available raw materials or preparations of E. arvense L. in order to ascertain their quality and identify possible adulterants using HPLC and HPTLC densitometry. Two chromatographic methods were used to determine the chemical fingerprints of E. arvense and other allied species. The first was based on HPTLC identification followed by densitometric measurement at 350?nm. The second was based on HPLC separation. The ease of sample preparation and the possibility of simultaneous analysis of several samples in a short time make HPTLC a method of choice for the comprehensive quality evaluation of herbal products.