Tailored Functionalization of Natural Phenols to Improve Biological Activity.

Phenols are widespread in nature, being the major components of several plants and essential oils. Natural phenols' anti-microbial, anti-bacterial, anti-oxidant, pharmacological and nutritional properties are, nowadays, well established. Hence, given their peculiar biological role, numerous studies are currently ongoing to overcome their limitations, as well as to enhance their activity.

Similar, Yet Different: Long-Range Metal-Metal Coupling and Electron-Transfer Processes in Metal-Free 5,10,15,20-Tetra(ruthenocenyl)porphyrin.

The electronic structure, redox properties, and long-range metal-metal coupling in metal-free 5,10,15,20-tetra(ruthenocenyl)porphyrin (HTRcP) were probed by spectroscopic (NMR, UV-vis, magnetic circular dichroism (MCD), and atmospheric pressure chemical ionization (APCI)), electrochemical (cyclic voltammetry, CV, and differential pulse voltammetry, DPV), spectroelectrochemical, and chemical oxidation methods, as well as theoretical (density functional theory, DFT, and time-dependent DFT, TDDFT) approaches. It was demonstrated that the spectroscopic properties of HTRcP are significantly different from those in HTFcP (metal-free 5,10,15,20-tetra(ferrocenyl)porphyrin). Ruthenocenyl fragments in HTRcP have higher oxidation potentials than the ferrocene groups in the HTFcP complex.

KuQuinones Equilibria Assessment for Biomedical Applications.

A small library of pentacyclic quinoid compounds, called KuQuinones (KuQs), has been prepared through a one-pot reaction. KuQuinones complex structure is made up by two naphthoquinone units connected by a five-membered ring. Due to KuQs structural features, keto-enol tautomerization in solution likely occurs, leading to the generation of four different species, i.

Deposition of tetraferrocenylporphyrins on ITO surfaces for photo-catalytic O2 activation.

Tetraferrocenylporphyrins (TFcPs) are a class of compounds where the porphyrin macrocycle is functionalized with a ferrocenyl group at each of the four meso positions. TFcPs exhibit interesting electrochemical properties, mostly due to electronic communication between the ferrocenyl substituents and the porphyrin core. This leads to their capability to release and accept multiple electrons at distinct potentials through reversible and well distinguished processes.

Electronic properties of mono-substituted tetraferrocenyl porphyrins in solution and on a gold surface: assessment of the influencing factors for photoelectrochemical applications.

Two unsymmetric meso-tetraferrocenyl-containing porphyrins of general formula Fc3 (FcCOR)Por (Fc=ferrocenyl, R=CH3 or (CH2)5 Br, Por=porphyrin) were prepared and characterized by a variety of spectroscopic methods, whereas their redox properties were investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) approaches. The mixed-valence [Fc3 (FcCOR)Por](n+) (n=1,3) were investigated using spectroelectrochemical as well as chemical oxidation methods and corroborated with density functional theory (DFT) calculations. Inter-valence charge-transfer (IVCT) transitions in [Fc3 (FcCOR)Por](+) were analyzed, and the resulting data matched closely previously reported complexes and were assigned as Robin-Day class II mixed-valence compounds.

A sustainable two-phase procedure for V-catalyzed toluene oxidative bromination with H2O2-KBr.

A sustainable V(V) and Mo(VI) catalysed two-phase procedure for bromination of toluene under quite mild conditions is proposed; H2O2 is the primary oxidant and KBr is the bromine source; metal precursors are commercially available salts. The reaction is efficient without any additional solvent. By using PhCH3 as a solvent/substrate good yields, together with interesting selectivity toward the formation of PhCH2Br, are obtained with both metal ions.

A ferrocene-porphyrin ligand for multi-transduction chemical sensor development.

5,10,15,20-Tetraferrocenyl porphyrin, H2TFcP, a simple example of a donor-acceptor system, was tested as ligand for the development of a novel multi-transduction chemical sensors aimed at the determination of transition metal ions. The fluorescence energy transfer between ferrocene donor and porphyrin acceptor sub-units was considered. The simultaneously measured optical and potentiometric responses of solvent polymeric membranes based on H2TFcP permitted the detection of lead ions in sample solutions, in the concentration range from 2.

A small organic compound enhances the religation reaction of human topoisomerase I and identifies crucial elements for the religation mechanism.

The different steps of the human Top1 (topoisomerase I) catalytic cycle have been analysed in the presence of a pentacyclic-diquinoid synthetic compound. The experiments indicate that it efficiently inhibits the cleavage step of the enzyme reaction, fitting well into the catalytic site. Surprisingly the compound, when incubated with the binary topoisomerase-DNA cleaved complex, helps the enzyme to remove itself from the cleaved DNA and close the DNA gap, increasing the religation rate.

Effect of dietary iodine on thyroid hormones and energy blood metabolites in lactating goats.

Aim of this work was to evaluate if long-term dietary supplementation of potassium iodide (KI) to dairy goats can influence metabolic and hormonal parameters. Thirty Sarda crossbred dairy goats were divided into three groups, which were orally administered 0 (control group; CON), 0.45 (low iodine group; LI) or 0.

Unexpected one-pot synthesis of highly conjugated pentacyclic diquinoid compounds.

A new class of pentacyclic diquinoid compounds has been synthesized with a facile one-pot reaction of two molecules of 2-hydroxynaphthoquinone and 1-bromoalkanes in the presence of ferrocene. These molecules were isolated as enol tautomers that exhibit intramolecular hydrogen bond and extended electronic conjugation as proved by the intense absorption spectrum with a broad band between 400 and 600 nm. The spectroscopic and electrochemical characterization of this new class of compounds has been performed.

Oxidized graphene in ionic liquids for assembling chemically modified electrodes: a structural and electrochemical characterization study.

Dispersions of graphene oxide (GO) nanoribbons in ionic liquids, ILs (either 1-butyl-3-methylimidazolium chloride (BMIM-Cl-) or 1-butylpyridinium chloride (-Bupy-Cl-)) have been used to assemble modified screen printed electrodes (SPEs). The graphene oxide/ionic liquid dispersions have been morphologically and structurally characterized by the use of several techniques: X-ray photoelectron spectroscopy (XPS), Fourier transform-infrared (FT-IR) spectroscopy, high-resolution-transmission electron microscopy (HR-TEM). The assembled modified SPEs have then been challenged with various compounds and compared to several electro-active targets.

Tetraferrocenylporphyrins as active components of self-assembled monolayers on gold surface.

Novel tetraferrocenylporphyrins-containing self-assembled monolayers were prepared employing two different approaches. Self-assembled monolayers were characterized using UV-Vis spectroscopy and cyclic voltammetry (CV) whereas their photoelectrochemical properties were investigated by photocurrent generation (PG) experiments.

Vanadium and molybdenum peroxides: synthesis and catalytic activity in oxidation reactions.

Catalysis by transition metal ions in oxidation reactions with hydrogen peroxide and alkyl hydroperoxides is a leading topic in the pursuit of more sustainable and selective processes, to obtain compounds with high added value. The most recent achievements concerning the synthesis and characterization, as well as the key aspects of reactivity, of V(V) and Mo(VI) peroxo complexes have been collected here.

Long-range electronic communication in free-base meso-poly(ferrocenyl)-containing porphyrins.

H(2)FcPh(3)P [FcPh(3)P = 5-ferrocenyl-10,15,20-triphenyl porphyrin(2-)], cis-H(2)Fc(2)Ph(2)P [cis-Fc(2)Ph(2)P = 5,10-bisferrocenyl-15,20-diphenyl porphyrin(2-)], trans-H(2)Fc(2)Ph(2)P [trans-Fc(2)Ph(2)P = 5,15-bisferrocenyl-10,20-diphenyl porphyrin(2-)], and H(2)Fc(3)PhP [Fc(3)PhP = 5,10,15-trisferrocenyl-20-phenyl porphyrin(2-)] along with H(2)TPP [TPP = 5,10,15,20-tetraphenylporphyrin] and H(2)TFcP [TFcP = 5,10,15,20-tetraferrocenyl porphyrin(2-)] were isolated from the direct cross-condensation reaction between pyrrole, benzaldehyde, and ferrocene carboxaldehyde or from the reaction between ferrocenyl-2,2'-dipyrromethane and benzaldehyde, suggesting a scrambling reaction mechanism for the last approach. All compounds were characterized by UV-vis, MCD, and NMR spectroscopy; APCI MS and MS/MS methods; as well as high-resolution ESI MS spectrometry. The conformational flexibility of ferrocene substituents in all compounds was confirmed using variable-temperature NMR and computational methods.

Electron-transfer processes in metal-free tetraferrocenylporphyrin. Understanding internal interactions to access mixed-valence States potentially useful for quantum cellular automata.

Redox properties of H(2)TFcP [TFcP(2-) = 5,10,15,20-tetraferrocenylporphyrin(2-)] were investigated using cyclic voltammetry, differential pulse voltammetry, and square-wave voltammetry methods in a large variety of solvents and electrolytes. When DMF, THF, and MeCN were used with TBAP as the supporting electrolyte, the first oxidation wave was assigned to a single four-electron oxidation process reflecting simultaneous oxidation of all iron(II) centers into iron(III) centers in H(2)TFcP. When an o-DCB (1,2-dichlorobenzene)/TBAP combination was used in electrochemical experiments, four ferrocene substituents underwent two very diffuse, "two-electron" stepwise oxidations.

Metal-free and transition-metal tetraferrocenylporphyrins part 1: synthesis, characterization, electronic structure, and conformational flexibility of neutral compounds.

H(2)TFcP [TFcP = 5,10,15,20-tetraferrocenyl porphyrin(2-)] was prepared by a direct tetramerization reaction between pyrrole and ferrocene carbaldehyde in the presence of a BF(3) catalyst, while the series of MTFcP (M = Zn, Ni, Co and Cu) were prepared by a metallation reaction between H(2)TFcP and respective metal acetates. All compounds were characterized by UV-vis and MCD spectroscopy, APCI MS and MS/MS methods, high-resolution ESI MS and XPS spectroscopy. Diamagnetic compounds were additionally characterized using (1)H and (13)C NMR methods, while the presence of low-spin iron(ii) centers in the neutral compounds was confirmed by Mössbauer spectroscopy and by analysis of the XPS Fe 2p peaks, revealing equivalent Fe sites.

The cyclooligomerization of arylethynes in ionic liquids catalysed by ruthenium porphyrins: a case of real catalyst recycling.

An efficient cyclooligomerization of arylethynes, catalysed by ruthenium(II) porphyrins in environmentally friendly ionic liquids, with an effective recycling of the catalyst and easy isolation of the products is described.

The first solvent-free cyclotrimerization reaction of arylethynes catalyzed by rhodium porphyrins.

Different rhodium(III) porphyrin chlorides have been used as catalysts for the cyclotrimerization of several arylethynes, giving in many cases high yields in substituted benzenes and selectivities based on the steric hindrance of the macrocycles and on the substitution of the substrates.

Cadmium chronic administration to lactating ewes: reproductive performance, cadmium tissue accumulation and placental transfer.

20 lactating ewes were allotted to two groups: 10 subjects received orally 100 mg/day of CdCl2 for 108 consecutive days, and the remaining 10 acted as control. Reproductive performance in ewes and cadmium tissue accumulation, both in ewes and their lambs, were investigated. The results showed that in ewes: 1) the regular cadmium intestinal intake negatively influences all reproductive parameters; 2) cadmium is particularly accumulated in kidney and liver, but also in mammary gland, although at a distinctly lower level; 3) chronic administration does not increase cadmium placental transfer in lactating pregnant subjects.

[Effect of recombinant bovine somatotropin on the secretion and composition of milk in Sardinian ewes].

To verify the effect on the milk yield, 5 Sardinian ewes at 45 days from lambing were given two subcutaneous administrations, in a sustained-release vehicle, of recombinant bST in the dose of 3 mg/Kg of live weight, at 28 day intervals. Other 5 ewes of the same age, weight, distance from lambing and milk yield, were kept untreated. The observations lasted 56 days.

[Hematologic parameters of the white donkeys of Asinara].

In 14 albino donkeys (6 males and 8 females) aged 1-12 years, about 25% of the whole population, 30 blood parameters were determined, with automatic equipment, monthly, for 4 months. No significant differences between sexes or compared with other donkey breeds were found, in spite of the particular characteristics of the population and of their environment.

A comparison of metoprolol OROS with antenolol in the treatment of effort angina pectoris: a randomized double-blind study.

The antianginal efficacy of metoprolol OROS has been investigated in comparison with that of atenolol in a multicenter double-blind cross-over trial carried out in patients with stable effort angina. OROS (ORally OSmotic) is a new semi-permeable delivery system with very slow osmotic release of the active drug, which is maintained at virtually constant plasma levels throughout the 24 hours. At the end of a 2-week run-in period, 53 patients with chronic coronary artery disease and documented ischemia during bicycleergometric exercise test were given, on double-blind condition, metoprolol OROS 21/285 and atenolol 100 mg in random order for 4 weeks each.

[Effect of the sudden removal of lambs on the blood levels of prolactin, triiodothyronine and thyroxine in ewes].

The effect of the sudden removal of lambs, average age 42 days (36 to 54), on the blood level of PRL, T3 and T4 was checked, using a radioimmunological method, in 18 Sardinian ewes that had lambed in November (10 treated and 8 control). The two groups of animals, reared indoors in different sheep-folds, were subjected to the same management and feeding. Compared to day before the removal of the lambs, the blood PRL showed a sharp decrease which lasted 24 hours.

[The horses of Giara: variation of the thyroid activity and certain blood parameters between winter and summer].

The changes of some parameters in the blood serum of six Giara horses (3 males and 3 females) were checked weekly, in relation to the environmental temperature throughout a one winter and summer. T3, total lipids, triglycerides, urea nitrogen, creatinine, total protein, albumin, beta and gamma globulin showed significant difference between winter and summer and, with the exception of triglycerides, urea nitrogen and total protein were correlated to the environmental temperature. T4, glucose, uric acid and alpha globulin showed no difference between the two seasons and no correlation with the temperature.