Reactivity of nucleosides with a hydroxyl radical in non-aqueous medium

DNA damage: The reactivity of HO(.) with silylated 2'-deoxyribonucleosides was investigated in acetonitrile by means of a time-resolved technique. The obtained rate constants were in general slightly lower than those reported for the natural nucleosides in water. Analysis of the reaction mixture by UPLC-MS revealed that HO(.) attack occurred at the nucleobase (see scheme).     

Isolation and structure elucidation of ovatoxin-a, the major toxin produced by Ostreopsis ovata

Since 2005, the benthic dinoflagellate Ostreopsis cf. ovata has bloomed across the Mediterranean basin, provoking serious toxic outbreaks. LC/MS studies have identified a number of palytoxin-like compounds, termed ovatoxins, along with trace amounts of putative palytoxin as the causative agents of the O. cf. ovata -related human sufferings. So far, any risk assessment for ovatoxins as well as establishment of their allowance levels in seafood has been prevented by the lack of pure toxins. The present paper reports on the isolation, NMR-based structural determination, and preliminary mouse lethality evaluation of ovatoxin-a, the major toxic compound contained in O. cf. ovata extracts. Availability of pure ovatoxin-a will open the double prospect of fully evaluating its toxicity and preparing reference standards to be employed in LC/MS quantitative analyses. Elucidation of ovatoxin-a's complex structure will ultimately herald the understanding of the molecular bases of ovatoxins bioactivity.     

Recent advances in propylene polymerization with MgCl2 supported catalysts

The role of Lewis bases in MgCl₂ supported catalysts for olefin polymerization is a subject of continuous interest and discussion in order to obtain more and more active and stereospecific catalysts and to explain their stereoregulating mechanism. Through molecular calculation and conformational analysis it was possible to identify chelating diethers that have the correct oxygen-oxygen distance necessary to tightly coordinate with the Mg ions of the support, even in the presence of other strong Lewis acids, and unable to give secondary reactions with TiCl₄, AlR₃, Ti-C and Ti-H bonds. The use of these donors has allowed the synthesis of catalytic systems that are both highly active and stereospecific even in the absence of external donors. Kinetic data of propylene polymerization with these catalyst systems are reported. The importance of the distance between the donor atoms in bifunctional Lewis bases has been proved also in the case of new classes of internal donors. Molecular modelling studies have enabled us to formulate models of active sites, located on some corners of MgCl₂ crystallites, whose chirality is induced by the presence of a donor molecule in their environment. These models could explain, at least in part, the exceptional increase of isotactic polymer productivity observed for stereospecific catalyst systems, containing only the internal donor, with respect to catalysts lacking the Lewis base and could account for the influence of the donor on the molecular properties of the obtained polymers.     

GC-MS analysis of aroma of Medemia argun (mama-n-khanen or mama-n-xanin), an ancient Egyptian fruit palm

The fruits of the edible and medicinal Egyptian palm, Medemia argun, were collected from Aswan in Egypt and the essential oil (EO) from fruits and headspace (HS) of the seeds and fleshy mesocarps were analyzed by GC and GC-MS. Results obtained by GC-MS analysis indicated a high variability in the oil and in the headspace from seeds and mesocarps. Sesquiterpene derivatives were the main group of volatiles in the EO from fruits and in the HS from seeds (45.0 and 64.0%, respectively), while oxygenated hydrocarbon derivatives were the main constituents in the HS obtained from fleshy mesocarps (96.5%). The different chemical composition of the headspace obtained from the seeds and mesocarps of M. argun can be correlated with the different roles that the different constituents play in the prevention of dehydration of the fruits in the desert region from where the plant was collected.     

Organocatalytic enantioselective synthesis of 2,3-dihydropyridazines

We have developed an efficient procedure for the easy and straightforward preparation of functionalized dihydropyridazines as highly enantiopure materials by reaction of pyruvaldehyde 2-tosyl hydrazone with a variety of α,β-unsaturated aldehydes using a chiral secondary amine as catalyst. The overall process consists of a cascade reaction involving an initial aza-Michael reaction, in which the stereocentre is installed, followed by an intramolecular aldol reaction/dehydration step.     

Formation of Pegylated polyurethane and Lysine-coated polyurea nanoparticles obtained from O/W nano-emulsions

The present work describes the formation of Pegylated polyurethane and Lysine-coated polyurea nanoparticles obtained from O/W nano-emulsions via an interfacial polycondensation process in the aqueous solution/polysorbate 80/diisocyanate/medium chain triglyceride systems. The initial nano-emulsions were prepared using the phase inversion composition (PIC) method. Dynamic light scattering studies revealed the changes in the particle size occurring during the process of nanoparticle formation. Well-defined polymeric nanoparticles with a small particle diameter (below 80 nm) and low polydispersity index were obtained using a highly hydrophilic component (polyethylene glycol or lysine) and an aliphatic diisocyante monomer. FT-IR and AFM studies showed that the polymeric matrix of nanoparticles was built by copolymers derived from reaction between the diisocyanate and the hydroxyl groups of both nonionic surfactant and the highly hydrophilic component. Pegylated-polyurethane and lysine-coated polyurea nanoparticles designed in this study are promising tools for future applications in biomedical sciences.     

Molecularly imprinted SPE and MEKC with in-capillary sample preconcentration for the determination of digoxin in human urine

Molecularly imprinted solid-phase extraction (MISPE) combined with MEKC was used for clean-up, preconcentration and determination of digoxin in the presence of its aglycon digoxin (digoxigenin) in human urine samples. In addition, the use of an in-capillary sample concentration electrophoretic technique by sweeping was investigated to enhance the concentration sensitivity in MEKC. The highly selective, fast and effective sample pretreatment by MISPE along with the preconcentration by sweeping could overcome the low sensitivity of the highly efficient capillary electrophoresis separation with UV detection. The optimization of the variables affecting the separation as well as MISPE conditions procedure was carried out to select the best conditions of selectivity and sensitivity to determine digoxin at low concentration levels in urine. To demonstrate the suitability of the developed method several analytical characteristics (selectivity, linearity, accuracy, precision, and LOD) were evaluated. Satisfactory results were obtained in terms of linearity (r > 0.99), recovery (95.4-96.5% with RSD from 1.3% to 2.6%), precision (RSD from 0.3% to 1.7% for migration times and from 2.1% to 7.3% for corrected peak areas), and sensitivity (LODs of 6 μg/L with 5 mL of sample or 1.2 μg/L with 25 mL). The proposed MISPE-MEKC method was satisfactorily applied to the analysis of spiked human urine samples achieving a concentration factor up to 7500-fold.     

Thermal reactions of tributyltin hydride with alpha-azido esters: unexpected intervention of tin triazene adducts under both nonradical and radical conditions

Thermal reaction of various alpha-azido esters with Bu(3)SnH in refluxing benzene results in smooth production of 3-(tributylstannyl)-1-triazene adducts affording cyclized 1,2,3-triazol-4-ones in preference to reduced amines and thence provides a new useful method for the preparation of these triazole derivatives. In the presence of AIBN the occurrence of triazene products still remains important or even exclusive and, consequently, generation of the expected stannylaminyl radicals is seriously limited. With 2-azidomalonates and alpha-azido-beta-keto esters stannyltriazenes can similarly occur in the absence of the radical initiator, but in the latter cases the ensuing triazenes undergo preferential cyclization onto the ketone moiety to give reactive hydroxytriazolines. Contrary to alpha-azido esters, in the presence of AIBN alpha-azido-beta-keto esters as well as azidomalonates give rise only to the usual stannylaminyl radicals. A possible explanation for the different behavior of the mono- and dicarbonyl azides in the presence of AIBN is put forward.     

The correct assignment of stereochemistry in di‐μ‐dichlorido‐bis{bis[2‐(5‐benzylsulfonyl)‐3‐fluoro‐2‐(pyridin‐2‐yl)phenyl‐κ2N,C1]iridium(III)} toluene monosolvate

The title complex, [Ir₂(C₁₈H₁₃FNO₂S)₄Cl₂]·C₇H₈, was crystallized from dichloromethane solution under a toluene atmosphere. It is a dimeric complex in which each of the two Ir^III centres is octahedrally coordinated by two bridging chloride ligands and by two chelating cyclometalated 2‐(4‐benzylsulfonyl‐2‐fluorophenyl)pyridine ligands. The crystal structure analysis unequivocally establishes the trans disposition of the two cyclometalated ligands bound to each Ir^III centre, contrary to our previous hypothesis of a cis disposition. The latter was based on the ¹H NMR spectra of a series of dimeric benzylsulfonyl‐functionalized dichloride‐bridged iridium complexes, including the compound described in the present work [Ragni et al. (2009). Chem. Eur. J. 15 , 136–148]. The toluene solvent molecules, embedded in cavities in the crystal structure, are highly disordered and could not be modelled successfully; their contribution was removed from the refinement using the SQUEEZE routine in the program PLATON [Spek (2009). Acta Cryst. D 65 , 148–155].     

Gold internal standard correction for elemental imaging of soft tissue sections by LA-ICP-MS: element distribution in eye microstructures

Laser ablation coupled to inductively coupled plasma mass spectrometry has been developed for the elemental imaging of Mg, Fe and Cu distribution in histological tissue sections of fixed eyes, embedded in paraffin, from human donors (cadavers). This work presents the development of a novel internal standard correction methodology based on the deposition of a homogeneous thin gold film on the tissue surface and the use of the ¹⁹⁷Au⁺ signal as internal standard. Sample preparation (tissue section thickness) and laser conditions were carefully optimized, and internal normalisation using ¹⁹⁷Au⁺ was compared with ¹³C⁺ correction for imaging applications. ²⁴Mg⁺, ⁵⁶Fe⁺ and ⁶³Cu⁺ distributions were investigated in histological sections of the anterior segment of the eye (including the iris, ciliary body, cornea and trabecular meshwork) and were shown to be heterogeneously distributed along those tissue structures. Reproducibility was assessed by imaging different human eye sections from the same donor and from ten different eyes from adult normal donors, which showed that similar spatial maps were obtained and therefore demonstrate the analytical potential of using ¹⁹⁷Au⁺ as internal standard. The proposed analytical approach could offer a robust tool with great practical interest for clinical studies, e.g. to investigate trace element distribution of metals and their alterations in ocular diseases.