PMR investigation of organic cations—I: Trithienyl methyl carbonium ions

PMR spectral parameters are reported for the isomeric trithienyl carbonium ions. The low field shifts, relative to the corresponding carbinols, are discussed in relation to the delocalization of the positive charge into the thiophene ring bonded in position 2 or 3. A linear correlation is found between chemical shifts and π-charge densities and the proportionality constant is higher than that previously found for benzene derivatives. Vicinal coupling constants in these systems are satisfactorily in agreement with the corresponding calculated π-bond order.     

Convenient synthetic approach to 2,4-disubstituted quinazolines

[reaction: see text] 2,4-Dialkyl or aryl quinazolines have been prepared in three steps starting from easily available anilides. A photochemically induced Fries rearrangement of the anilides gave several ortho-aminoacylbenzene derivatives that were acylated at the NH2. These acylamides underwent rapid cyclization to 2,4-disubstituted quinazolines (and benzoquinazolines) in the presence of ammonium formate under microwave activation. This procedure is compatible with different functional groups and allowed also the preparation of new quinazolines derived from naturally occurring amino acids.     

Sc(III)-catalyzed enantioselective addition of thiols to α,β-unsaturated ketones in neutral water

This report concerns Lewis acid catalyzed enantioselective sulfa-Michael addition in neutral water by using a very efficient Sc(OTf)(3)/bipyridine 1 catalytic system. It is noteworthy that the protocol presented employs water as a reaction medium and allows us to obtain very high stereoselectivity and satisfactory yields for β-keto sulphides deriving from aliphatic thiols. The recovery and reuse of both the aqueous medium and the catalytic system is also reported.     

Synthesis of functionalized quinolines and benzo[c][2,7]naphthyridines based on a photo-Fries rearrangement

An efficient one-pot method for the synthesis of functionalized quinolines and tetrahydronaphthyridines has been developed. The photo-Fries rearrangement of p-substituted anilides afforded differently substituted o-amino ketones that reacted in situ with acetylenic Michael acceptors such as dimethyl acetylenedicarboxylate (DMAD) to give 6,4-disubstituted quinoline 2,3-dicarboxylates. Starting from anilides derived from β-alanine, a naphthyridine nucleus can also be assembled.     

Reconciling phase diffusion and Hartree–Fock approximation in condensate systems

Despite the weakly interacting regime, the physics of Bose–Einstein condensates is widely affected by particle–particle interactions. They determine quantum phase diffusion, which is known to be the main cause of loss of coherence. Studying a simple model of two interacting Bose systems, we show how to predict the appearance of phase diffusion beyond the Bogoliubov approximation, providing a self-consistent treatment in the framework of a generalized Hartree–Fock–Bogoliubov perturbation theory.     

A Protocol for Accessing the β-Azidation of α,β-Unsaturated Carboxylic Acids

This contribution reports the preparation and use of a new immobilized catalyst, PS-DABCOF (9), which has been specifically designed to access for the first time the efficient β-azidation of α,β-unsaturated carboxylic acids.     

Large bending behavior of creased paperboard. I. Experimental investigations

The large bending behavior of a creased paperboard is studied in the range of rotation θ ? [0°, 180°] – new results, apparently not reported previously in literature – with the aim to point out some crucial aspect involved in an adaptive robotic manipulation of the industrial cartons.The loading tests show a great variability of the mechanical behavior, depending dramatically on the crease indentation depth (also for the specimens obtained from the same carton): (a) when the damage induced during the crease formation is relatively small, the bending response is unusually complex: the moment constitutive function, m_L(θ), presents (up to) two peaks followed by unstable branches; (b) for greater indentation, the m_L(θ) is monotone.In the unloading case the response m_U(θ) is always monotone and is practically independent of the formation conditions of the crease. These behaviors can be easily described analytically using (piecewise) third degree splines.In a companion paper, the erection of a typical carton corner with unstable constitutive behavior is fully analyzed to detect the possible criticalities.     

Results of the search for strange quark matter and Q-balls with the SLIM experiment

The SLIM experiment at the Chacaltaya high altitude laboratory was sensitive to nuclearites and Q-balls which could be present in the cosmic radiation as possible Dark Matter components. It was sensitive also to strangelets, i.e. small lumps of Strange Quark Matter predicted at such altitudes by various phenomenological models. The analysis of 427 m² of Nuclear Track Detectors exposed for 4.22 years showed no candidate event. New upper limits on the flux of downgoing nuclearites and Q-balls at the 90% C.L. were established. The null result also restricts models for strangelets propagation through the Earth atmosphere.     

Synthesis of thia-Michael-Type Adducts between Naphthoquinones and N-Acetyl-L-Cysteine and Their Biological Activity

A series of naphthoquinones, namely, 1,4-naphthoquinone, menadione, plumbagin, juglone, naphthazarin, and lawsone, were reacted with N-acetyl-L-cysteine, and except for lawsone, which did not react, the related adducts were obtained. After the tuning of the solvent and reaction conditions, the reaction products were isolated as almost pure from the complex reaction mixture via simple filtration and were fully characterized. Therefore, the aim of this work was to evaluate whether the antitumor activity of new compounds of 1,4-naphthoquinone derivatives leads to an increase in ROS in tumor cell lines of cervical carcinoma (HeLa), neuroblastoma (SH-SY5Y), and osteosarcoma (SaOS2, U2OS) and in normal dermal fibroblast (HDFa). The MTT assay was used to assay cell viability, the DCF-DA fluorescent probe to evaluate ROS induction, and cell-cycle analysis to measure the antiproliferative effect. Compounds 8, 9, and 12 showed a certain degree of cytotoxicity towards all the malignant cell lines tested, while compound 11 showed biological activity at higher IC₅₀ values. Compounds 8 and 11 induced increases in ROS generation after 1 h of exposure, while after 48 h of treatment, only 8 induced an increase in ROS formation in HeLa cells. Cell-cycle analysis showed that compound 8 caused an increase in the number of G0/G1-phase cells in the HeLa experiment, while for the U2OS and SH-SY5Y cell lines, it led to an accumulation of S-phase cells. Therefore, these novel 1,4-naphthoquinone derivatives may be useful as antitumoral agents in the treatment of different cancers.     

A cognitive analysis of dragging practises in Cabri environments

Dragging in Dynamical Geometry Software (DGS) is described by introducing a hierarchy of its functions. This is suitable for classifying different attitudes and aims of students who investigate a geometric problem, such as exploring, conjecturing, validating and justifying. Moreover the hierarchy has cognitive features and can be used to describe the twofold modulities namely ascending and descending in which students interact with external representations (e.g. Cabri drawings). Switching from one modality to the other through dragging often allows them to produce fruitful conjectures and to pass from the empirical to the theoretical side of the question. The genesis of such different functions in students does not happen automatically but is the consequence of specific didactical interventions of the teacher in the pupils' apprenticeship of Cabri practises. A worked-out example illustrates the theoretical concepts introduced in the paper.