One-pot synthesis of aziridines from vinyl selenones and variously functionalized primary amines

Variously substituted aziridines were conveniently prepared by an aza-Michael Initiated Ring Closure (aza-MIRC) reaction starting from vinyl selenones and primary amines, aminoalcohols or diamines. The reactions proceed in very high yields at room temperature in toluene or water. A significant rate acceleration was observed under aqueous conditions.     

One-pot amide synthesis from allyl or benzyl halides and amines by Pd-catalysed carbonylation

Amides can be prepared from allyl or benzyl halides and primary or secondary amines, using Pd(0) catalyst under CO pressure, in a one-pot synthesis. The reaction proceeds through the acyl palladium halide formation which undergoes an acylic nucleophilic substitution from the amine.     

The Role of Ion Pairs in the Second‐Order NLO Response of 4‐X‐1‐Methylpiridinium Salts

A series of 4‐X‐1‐methylpyridinium cationic nonlinear optical (NLO) chromophores (X=(E)‐CH?CHC₆H₅; (E)‐CH?CHC₆H₄‐4′‐C(CH₃)₃; (E)‐CH?CHC₆H₄‐4′‐N(CH₃)₂; (E)‐CH?CHC₆H₄‐4′‐N(C₄H₉)₂; (E,E)‐(CH?CH)₂C₆H₄‐4′‐N(CH₃)₂) with various organic (CF₃SO₃^?, p‐CH₃C₆H₄SO₃^?), inorganic (I^?, ClO₄^?, SCN^?, [Hg₂I₆]^2?) and organometallic (cis‐[Ir(CO)₂I₂]^?) counter anions are studied with the aim of investigating the role of ion pairing and of ionic dissociation or aggregation of ion pairs in controlling their second‐order NLO response in anhydrous chloroform solution. The combined use of electronic absorption spectra, conductimetric measurements and pulsed field gradient spin echo (PGSE) NMR experiments show that the second‐order NLO response, investigated by the electric‐field‐induced second harmonic generation (EFISH) technique, of the salts of the cationic NLO chromophores strongly depends upon the nature of the counter anion and concentration. The ion pairs are the major species at concentration around 10^?3 M , and their dipole moments were determined. Generally, below 5×10^?4 M , ion pairs start to dissociate into ions with parallel increase of the second‐order NLO response, due to the increased concentration of purely cationic NLO chromophores with improved NLO response. At concentration higher than 10^?3 M , some multipolar aggregates, probably of H type, are formed, with parallel slight decrease of the second‐order NLO response. Ion pairing is dependent upon the nature of the counter anion and on the electronic structure of the cationic NLO chromophore. It is very strong for the thiocyanate anion in particular and, albeit to a lesser extent, for the sulfonated anions. The latter show increased tendency to self‐aggregate.     

Magnetic particles functionalized with PAMAM-dendrimers and antibodies: a new system for an ELISA method able to detect Ara h3/4 peanut allergen in foods

An innovative enzyme-linked immunosorbent assay (ELISA) format based on antibody-coated magnetic micro-particles (MPs) for the sensitive detection of Ara h3/4 allergen in food is described. The immunosupport is suspended in the incubation solutions and the MPs with the captured allergen can be easily harvested on a magnet, separated from the solutions, and washed using an easy-to-use, fast and selective approach that allows its detection and quantification. Two differently coated MPs, ProteinA-Pn-b and MP-NH₂-PAMAM G 1.5 -Pn-b immunosupports, were tested. The functionalization of the MPs with PAMAM-sodium carboxylate dendrimers elicits a major stability on the immunoglobulin activity resulting in a threefold enhancement of the analytical sensitivity for the assay with respect to a ProteinA immobilization. Validation was carried out on two different matrices: corn flakes and biscuits. In the case of MP-NH₂-PAMAM G 1.5 -Pn-b immunosupport, limit of detection was found to be 0.2 mg peanuts/kg matrix in both matrices; the linear response range was demonstrated from 2.5 to 15 mg peanuts/kg matrix by performing statistical tests (homoscedasticity and Mandel fitting tests). Good accuracy and recovery (>80 ± 2%) were obtained. Different food samples were tested and the results were compared with those obtained with a commercially available ELISA kit. The results obtained in this work demonstrated the applicability of the immunomagnetic ELISA methods on real samples and the possibility to perform the assay with significantly reduced reagent and sample consumption.     

Application of the new electroanalytical technique AGNES for the determination of free Zn concentration in river water

Absence of gradients and Nernstian equilibrium stripping (AGNES) is a recently developed electroanalytical technique specifically designed for the direct determination of free concentrations of metal ions. AGNES is applied here to the determination of free Zn concentration in a river water sample. The method has been validated with synthetic solutions of low ionic strengths containing Zn and 2,6-pyridinedicarboxylic acid and then applied to synthetic river waters and to a natural sample collected from Besòs River in Montcada i Reixac (Catalonia, North-Eastern Spain). In the river sample, an average free Zn concentration of 12.8(4) nM was obtained, while the total dissolved Zn concentration was 0.51(8)?μM. To control and maintain pH and pCO₂ constant during AGNES measurements, a novel device for N₂/CO₂ mixed purging has been developed.     

Lignin Chemistry: Biosynthetic Study and Structural Characterisation of Coniferyl Alcohol Oligomers Formed In Vitro in a Micellar Environment

Model coniferyl alcohol lignin (the so‐called dehydrogenative polymerisate, DHP) was produced in water under homogeneous conditions guaranteed by the presence of a micellised cationic surfactant. A complete study of the activity of the enzymatic system peroxidase/H₂O₂ under our reaction conditions was reported and all the reaction products up to the pentamer were characterised by ¹H NMR spectroscopy and ESI mass spectrometry. Our system, and the molecules that have been generated in it, represent a closer mimicry of the natural microenvironment since an enzyme, under micellar conditions, reproduces the cell system better than in buffer alone. On the basis of the oligomers structures a new biosynthetic perspective was proposed that focused attention on a coniferyl alcohol dimeric quinone methide as the key intermediate of the reaction. A formal, strictly alternate sequence of a radical and an ionic step underlines the reaction, thus generating ordered oligolignols structures. Alternatively to other model lignins, our olignols present a lower degree of radical coupling between oligomeric units. This offers a closer biosynthetic situation to the observation of a low rate of radical generation in the cell wall.     

Creation and evolution of net proton hyperpolarization arising from para-hydrogenation

When a hydrogenation reaction is carried out with gaseous hydrogen enriched in its para- isomer in the earth magnetic field (prior to adiabatic insertion of the sample in the NMR magnet), enhanced proton longitudinal order (represented by 2I(z)(A)I(z)(B)) is created but also difference of enhanced polarizations (I(z)(A)-I(z)(B)). In a first part, it is shown theoretically and experimentally that the longitudinal relaxation time of this polarization difference is roughly twice the ones of individual polarizations. The second part is devoted to a pulse sequence designed for transforming this difference into net hyperpolarization. The evolution of this global hyperpolarization is studied experimentally in a third part and it is observed that a fraction of hyperpolarization possesses an effective longitudinal relaxation time similar to the one of the initial polarization difference. Those experimental results are interpreted by numerical calculations based on Solomon-type equations including the longitudinal order and possibly dipolar-csa cross correlation rates.     

ToF-SIMS and XPS study of ancient papers

The surface composition of 18th century papers was investigated by means of ToF-SIMS and XPS. The aim of the present study was to explore the possibility of using these surface sensitive methods to obtain information which can help to determine the manufacturing process, provenance and state of conservation of ancient papers. The ToF-SIMS results indicate that the analyzed papers were sized by gelatin and that alum was added as hardening agent. The paper sheets produced in near geographical areas but in different paper mills exhibit a similar surface composition and morphology of the fibers as shown by the ToF-SIMS measurements. The ToF-SIMS and the XPS results indicate that a significant fraction of the cellulose fibers is not covered by the gelatin layer. This was observed for the ancient papers and for a modern handmade paper manufactured according to the old recipes.     

Assessment of clinical data of nonlinear stochastic deconvolution versus block-circulant singular value decomposition for quantitative dynamic susceptibility contrast magnetic resonance imaging

Dynamic susceptibility contrast magnetic resonance imaging (DSC-MRI) allows the noninvasive assessment of brain hemodynamics alterations by quantifying, via deconvolution, the cerebral blood flow (CBF) and mean transit time (MTT). Singular value decomposition (SVD) and block-circulant SVD (cSVD) are the most widely adopted deconvolution method, although they bear some limitations, including unphysiological oscillations in the residue function and bias in the presence of delay and dispersion between the tissue and the arterial input function. A nonlinear stochastic regularization (NSR) has been proposed, which performs better than SVD and cSVD on simulated data both in the presence and absence of dispersion. Moreover, NSR allows to quantify the dispersion level. Here, cSVD and NSR are compared for the first time on a group of nine patients with severe atherosclerotic unilateral stenosis of internal carotid artery before and after carotid stenting to investigate the effect of arterial dispersion. According to region of interest-based analysis, NSR characterizes the pathologic tissue more accurately than cSVD, thus improving the quality of the information provided to physicians for diagnosis. In fact, in 7 (78%) of the 9 subjects, CBF and MTT maps provided by NSR allow to correctly identify the pathologic hemisphere to the physician. Moreover, by emphasizing the difference between pathologic and healthy tissues, NSR may be successfully used to monitor the subject's recovery after the treatment and/or surgery. NSR also generates dispersion level and non-dispersed CBF and MTT maps. The dispersion level provides information on CBF and MTT estimates reliability and may also be used as a clinical indicator of pathological tissue state complementary to CBF and MTT, thus increasing the clinical information provided by DSC-MRI analysis.