Triplet Photochemistry of Suprofen in Aqueous Environment and in the β-Cyclodextrin Inclusion Complex

The photodecarboxylation of suprofen in the carboxylate form was studied in aqueous medium as a function of the temperature, the concentration and the presence of oxygen by steady-state and time-resolved photochemical techniques. The process is characterized by an activation energy of 9–10 kcal/mol, the precursor state being the lowest triplet which is of π,π* nature. The reactivity of the drug was also studied in the β-cyclodextrin inclusion complex and an additional photoreaction involving the macrocycle as reactive species was observed. Representative NMR and circular dichroism measurements were performed. Singlet molecular oxygen formation was also investigated.     

Effects of processing on five selected metals in the durum wheat food chain

The concentration levels of five metals, namely Cd, Cr, Fe, Ni and Pb, were investigated along the durum wheat processing chain, from grain to the final product. Cadmium and Pb are well-known toxic elements and their levels in wheat grain are regulated by the European legislation. Chromium, Fe and Ni were included in the study as markers of metal release from equipment during processing. Durum wheat grain, semolina and pasta were sampled at an industrial plant for milling and pasta making. Samples were taken at different stages along processing in order to elucidate the influence of each stage on the element content. Samples of the water used for grain tempering and dough preparation were also collected. The whole analytical procedure, from sampling to final analytical determinations, was carried out according to a pre-established quality assurance protocol. Analyses were performed by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES).Milling was the key process influencing the concentrations of the studied elements and reduced the metal levels according to a definite element-specific pattern. Purity of the water used as ingredient, element deposition from plant air and metal release from equipment were identified as critical issues in contamination control during processing. In the conditions of this study, it was found that a simple relationship can be established between the original concentrations in durum wheat grain and those in pasta for Cd and Fe, while for Pb, Cr and Ni, a greater uncertainty in the estimation of the levels in the final product is expected.     

On vibronic coupling in nonradiative transitions of polyatomic molecules

The vibronic coupling between quasidegenerate adiabatic Born—Oppenheimer states has been calculated by going beyond the Condon approximation. A simplified model in which accepting modes are distorted (non-totally symmetric) and of the same frequency, has been considered. The decay rate obtained with this approach is one order of magnitude larger than in the Condon scheme and seems to be practically independent of the symmetry of the accepting modes.     

Best approximation by polynomial operators in banach spaces

The problem of approximation in the space of bounded linear operators ? (E;G) between normed spaces E and G by compact operators has been extensively studied in the last few years.

Recently Deutsch, Mach and Saatkamp ([2]) have considered the problem of approximating elements of ?(E;G) by the subset K _N(E;G) of operators whose range is at most N dimensional. We consider in this paper the problem of approximating operators (not necessarily linear) beteen normed spaces E and G by continuous homogeneous polynomials, and in particular by such polynomials which have finite-dimensional range.     

Relevance of Sb(III), Sb(V), and Sb-containing nano-particles in urban atmospheric particulate matter

A quick and reliable analytical method for the separation and quantification of extractable Sb(III) and Sb(V) in atmospheric particulate matter (PM) by ion chromatography(IC)-inductively coupled plasma-mass spectrometry (ICP-MS) has been optimized, validated on pairs of real, equivalent PM₁₀ samples and applied to a field monitoring campaign in a urban site. Both Sb(III) and Sb(V) forms were detected in real samples with Sb(III)/Sb(V) ratios up to 1.5. These two Sb species accounts only for a portion, of variable magnitude, of the total extractable Sb (10–70%); anyway, no other soluble Sb species were detected in the samples. The analysis of size-segregated samples collected by a 13-stage impactor showed that the recovery of [Sb(III) + Sb(V)] versus total extractable Sb is almost quantitative in the coarse fraction while it is below than 10% in the fine fraction. In the extracted solution from particles below 1 μm we could highlight the presence of Sb-containing suspended solid nano-particles, which probably constitute the missing fraction. The contribution of nano-particles can be estimated as the difference between ICP-MS and IC-ICP-MS data, as small size solid bodies are able to pass through the nebulizer and reach the plasma torch, while they are retained by the chromatographic column. The aggregation state of these nano-particles seems to be easily altered when they are suspended in a water solution; a similar behavior could be hypothesized when in contact with biological fluids. It has been confirmed that brake pad abrasion is the prevalent source of Sb(III) in PM and that Sb(V) may be formed by oxidation during the braking processes. Differing from other environmental matrices, there is no evidence of any spontaneous oxidative conversion within the two species.     

Identification of plant sterols in hexaploid and tetraploid wheats using gas chromatography with mass spectrometry

Free sterols from hexaploid and tetraploid free-threshing wheats (Triticum aestivum L. and T. durum Desf.) and from their respective hulled wheats (T. spelta L. and T. dicoccon Schrank) were analysed by gas chromatography with mass spectrometry. The qualitative analysis of sterols showed a similar pattern either between hexaploid (T. aestivum, T. spelta) and tetraploid (T. durum, T. dicoccon) wheats or between free-threshing (T. aestivum, T. durum) and hulled (T. spelta, T. dicoccon) wheats. However, quantitative differences were found between tetraploid and hexaploid wheats, in that free sterol amounts in tetraploid wheats were 40% higher than in hexaploid ones. The mass spectra of the sterols were classified into four groups, taking into account the structural features of rings A and B. Typical mass spectral fragmentations of the four classes, and additional evidence related to the side chain of each molecule, were investigated together with their chromatographic behaviour, allowing identification of all the detected sterols.     

Photophysical Properties of Rufloxacin in Neutral Aqueous Solution

The photophysical properties of rufloxacin, 9-fluoro-2_r3-dihydro-10-(4-methyl-l-pyrazinyl)-7-oxo-7-H-pyri-do[l,2,3-de]-l,4-benzothiazin-6-carboxylic acid, a fluoroquinolone antibacterial drug exhibiting photosensitizing action toward biological substrates, were studied in aqueous solutions at neutral pH. The lowest excited electronic states of the zwitterion were characterized by both experimental techniques and theoretical methods. Steady-state and time-resolved emission, triplet-state absorption and singlet oxygen production were investigated. The results indicate that the lowest excited singlet is a fluorescent, relatively long-lived state (φ_r= 0.075, T_r? 4.5 ns) with an efficient intersystem crossing to the triplet manifold (φ_isc? 0-⁷)- The lowest triplet is a long-lived state (T_T? 10 μs at 295 K in 0.01 M phosphate buffer), with properties that make it a good candidate for being the precursor of the photodecarboxylation of the drug. It is quenched by oxygen at a rate of 1.7 times 10⁹M^-1 s-¹ and singlet oxygen is formed with a quantum yield of 0.32 in air-saturated solutions.     

Nanopatterning in a compact setup using table top extreme ultraviolet lasers

The recent development of table top extreme ultraviolet (EUV) lasers have enabled new applications that so far were restricted to the use of large facilities. These compact sources bring now to the laboratory environment the capabilities that will allow a broader application of techniques related to nanotechnology and nanofabrication. In this paper we review the advances in the utilization of EUV lasers in nanopatterning. In particular we show results of the nanopatterning using a table-top capillary discharge laser producing 0.12-mJ laser pulses with 1.2-ns time duration at a wavelength λ = 46.9 nm. The nanopatterning was realized by interferometric lithography using a Lloyd’s mirror interferometer. Two standard photoresists were used in this work, polymethyl methacrylate (PMMA) and hydrogen silsesquioxane (HSQ). Pillars with a full width half maximum (FWHM) diameter of 60 nm and holes with FWHM diameter of 130 nm were obtained over areas in excess of 500×500 μm².     

Ordering phenomena in cooling granular mixtures

We report two phenomena, induced by dynamical correlations, that occur during the free cooling of a two-dimensional mixture of inelastic hard disks. First, we show that, due to the onset of velocity correlations, the ratio of the kinetic energies associated with the two species changes from the value corresponding to the homogeneous cooling state to a value approximately given by the mass ratio m(1)/m(2) of the two species. Second, we report a novel segregation effect that occurs in the late stage of cooling, where interconnected domains appear. Spectral analysis of the composition field reveals the emergence of a growing characteristic length.     

Analytische Aspekte der Oxydation organischer Stickstoffverbindungen mit Chromsäure. IV

Zusammenfassung Die schon früher vorgeschlagene Halbmikromethode zur Bestimmung der N-N-Gruppierung wurde an einer Reihe aromatischer Azoverbindungen erprobt. Sie beruht auf der Oxydation der Substanz mit einem Chromsäure-Schwefelsäure-Gemisch in einer geschlossenen Apparatur. Die Azogruppen werden als elementarer Stickstoff abgespalten, der im Azotometer gesammelt und gemessen wird. Durch die Rücktitration der unverbrauchten Chromsäure kann außerdem die Oxydationszahl der untersuchten Substanz bestimmt werden.

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Summary The semimicro method previously suggested for the determination of the N-N-grouping was tested on a number of aromatic azo compounds. It is based on oxidation of the sample with a chromic-sulfuric acid mixture in a closed apparatus. The azo groups are split off as elementary nitrogen which is collected in an azotometer and measured. In addition the oxidation number of the material being studied can be found by backtitration of the unconsumed chromic acid.

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Résumé On a mis à l'épreuve la semimicrométhode déjà préconisée auparavant, pour le dosage du groupe N-N, sur une série de composés azo-aromatiques. Elle repose sur l'oxydation de la substance par un mélange d'acide chromique et d'acide sulfurique, en système clos. Les groupes azoïques se trouvent dissociés à l'état d'azote élémentaire que l'on récupère et que l'on dose dans l'azotomètre. On peut déterminer, de plus, l'indice d'oxydation de la substance étudiée par titrage en retour de l'acide chromique non consommé.

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III. Mitteilung siehe 1.