The role of processing on phenolic bioaccessibility and antioxidant capacity of apple derivatives.

Fruit derivatives are commonly obtained by applying processing operations deemed responsible for the loss of phenol compounds, but very little information is available on the fate of phenols upon digestion of these products. The present study evaluated the effect of thermal and mechanical treatments, commonly applied to turn apple pulp into puree and homogenate, on phenolic bioaccessibility and antioxidant activity. Despite a 20 % decrease in polyphenols due to processing, their bioaccessibility was higher in apple derivatives (>20 %) compared to pulp (∼2 %).

Unrevealing the potentialities in food formulations of a low-branched dextran from Leuconostoc mesenteroides.

The search for novel exopolysaccharides (EPS) with targeted functionalities is currently a topic of great interest. This study aimed to investigate the chemical characteristics and technological properties of a novel EPS (named EPS_O) from Leuconostoc mesenteroides. EPS_O was a high-molecular-weight dextran (>6.

An exopolysaccharide from Leuconostoc mesenteroides showing interesting bioactivities versus foodborne microbial targets.

An exopolysaccharide (EPS_B3) produced by a Leuconostoc mesenteroides strain isolated from a semi-hard Italian cheese was chemically and biologically characterized. HPLC-SEC, NMR, FT-IR and monosaccharide composition experiments were performed. Antimicrobial, antibiofilm, bifidogenic, antioxidant, and DNA-protective activity of EPS_B3 were also studied.

Imprinting Pentaphyrin on Conductive Electropolymerized Dipyrromethane Films: A New Strategy towards the Synthesis of Photokilling Materials.

We report herein the synthesis and photoinduced bactericidal activity of two new polymeric materials, obtained by imprinting the photosensitizer 20-(4-carboxyphenyl)-2,13-dimethyl-3,12-diethyl-[22]pentaphyrin (PCox, 1) into suitable electropolymerized dipyrromethane films. 5-Phenyl-dipyrromethane (5-ph-DP) and 5-(4-pyridyl)dipyrromethane (5-py-DP) have been selected as the monomers for the synthesis of the materials in order to assess the correlation between the substituent in C5 and the capability in Pcox uptake. Both films have been tested in their photokilling ability toward Staphylococcus aureus by using a multi-LED blue lamp at a fluence rate of 40 W/m .

CNN pincer ruthenium complexes for efficient transfer hydrogenation of biomass-derived carbonyl compounds.

The ligand HCNNOMe (6-(4-methoxyphenyl)-2-aminomethylpyridine) is easily prepared from the commercially available 6-(4-methoxyphenyl)pyridine-2-carbaldehyde by the reaction of hydroxylamine and hydrogenation (H2, 1 atm) with Pd/C. The pincer complexes cis-[RuCl(CNNOMe)(PPh3)2] (1) and [RuCl(CNNOMe)(PP)] (PP = dppb, 2; and dppf, 3) are synthesized from [RuCl2(PPh3)3], HCNNOMe and PP (for 2 and 3) in 2-propanol with NEt3 at reflux and are isolated in 85-93% yield. Carbonylation of 1 (CO, 1 atm) gives [RuCl(CNNOMe)(CO)(PPh3)] (4) (79% yield) which cleanly reacts with Na[BArf4] and PCy3, affording the cationic trans-[Ru(CNNOMe)(CO)(PCy3)(PPh3)][BArf4] (5) (92% yield).

Preparation of monocarbonyl ruthenium complexes bearing bidentate nitrogen and phosphine ligands and their catalytic activity in carbonyl compound reduction.

Monocarbonyl complexes [RuCl(CO)(PR)(NN)] (R = Cy, NN = en 1, ampy 2; R = iPr; NN = en 3) have been prepared in a one pot reaction from [RuCl(CO)(dmf)(PPh)], PR and the NN ligand in CHCl. Treatment of [Ru(OAc)(CO)(PPh)] with NN ligands in methanol gives the cationic derivatives [Ru(OAc)(CO)(PPh)(NN)]OAc (NN = en 4, ampy 5) in which one acetate acts as a bidentate ligand, whereas the other is not coordinated. Diphosphine complexes [RuCl(CO)(PP)(PPh)] (PP = dppb 6, dppf 7, (R)-BINAP 8, (R,S)-Josiphos 9 and (R,R)-Skewphos 10) have been obtained starting from [RuCl(CO)(dmf)(PPh)] and the PP ligand in CHCl or toluene at reflux.

"Clicking" Porphyrins to Magnetic Nanoparticles for Photodynamic Therapy.

A method for the preparation of superparamagnetic iron oxide nanoparticle-porphyrin (SPION-TPP) conjugates through click chemistry, which can be used as novel theranostic nanoagents for photodynamic therapy is developed. The synthesis, characterisation, and evaluation of the photocytotoxicity profiles of the nanoconjugates prepared is reported. Upon light irradiation, SPION-TPP nanoconstructs promote a photodynamic effect in vitro in murine amelanotic melanoma B78-H1 cells, with IC values in the region of 800 nM, similarly to unbound TPP, whereas they remain non-cytotoxic in the dark.

Salt-assisted thermal desorption of mercury from contaminated dredging sludge.

In this study, we tested a new procedure for the decontamination of mercury-polluted dredging sludge (Marano-Grado Lagoon, northeastern Italy) based on cationic exchange associated with thermal desorption at a low temperature. Four mercury-polluted sludge slurries were treated using thermal desorption at 393 K for 2h. Three different salts, NaCl (sodium chloride), (CH(3))(4)NCl (tetramethylammonium chloride) and (C(4)H(9))(4)NCl (tetrabutylammonium chloride) were used as exchangers.

Metallation of pentaphyrin with Lu(III) dramatically increases reactive-oxygen species production and cell phototoxicity.

Photodynamic therapy (PDT) is an emerging cancer treatment modality based on the excitation of a nontoxic photosensitizer with harmless visible light to produce reactive-oxygen species (ROS) that induce apoptosis and/or necrosis in cancer cells. As the efficacy of this therapy strongly depends of the nature of the photosensitizer, there is a great interest to develop new photoactive molecules. Here we report for the first time the synthesis, characterization and bioactivity of metal complexes between the non-aromatic expanded porphyrin, namely 20-[[4'-(Trimethylsilyl)ethoxycarbonyl]phenyl-2,13-dimethyl-3,12-diethyl-[24] iso-pentaphyrin (PCRed) and Zn(II) [Zn(II)-PCRed] or Lu(III) [Lu(III)-PCRed].

Bench-scale tests on ultrasound-assisted acid washing and thermal desorption of mercury from dredging sludge and other solid matrices.

A series of ultrasonic assisted acid washing and thermal desorption tests were performed on sludge and other solid matrices with the aim to assay these removal technologies and to determine if the application of low frequency ultrasound was effective to enhance mercury removal. Unpolluted dredging sludge, 820 K calcinated dredging sludge, silica and alumina were characterized, polluted with a known concentration of mercury and treated both by acid washing and thermal desorption with and without low frequency ultrasound application. The acid washing was carried out by a 4% HNO(3) acid solution and the thermal desorption was performed in a 370-620K range.

SOLVERSTAT: a new utility for multipurpose analysis. An application to the investigation of dioxygenated Co(II) complex formation in dimethylsulfoxide solution.

A new utility for multipurpose analysis, SOLVERSTAT, taking advantage of the versatility of spreadsheets is here described. By means of this tool advanced statistical tests have introduced in Microsoft Excel Solver thus allowing regression diagnostic and discrimination between different models. The utility is here applied to the determination, by UV-Vis spectroscopy, of the stability constant for the uptake of molecular dioxygen by the 1:2 complex of Co(II) with N,N'-dimethylethylenediamine (dmen) in the aprotic solvent dimethylsulfoxide (dmso) at 298 K and in a medium adjusted to 0.

Long-range-distance NMR effects in a protein labeled with a lanthanide-DOTA chelate.

A two-thiol reactive lanthanide-DOTA (1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid) chelate, CLaNP-3 (CLaNP=caged lanthanide NMR probe), was synthesized for the rigid attachment to cysteine groups on a protein surface, and used to obtain long-range-distance information from the {15N,1H} HSQC spectra of the protein-lanthanide complex. The DOTA ring exhibits several isomers that are in exchange; however, single resonances were observed for most amide groups in the protein, allowing determination of a single, apparent magnetic-susceptibility tensor. Pseudocontact shifts caused by Yb-containing CLaNP-3 were observed for atoms at 15-35 A from the metal.

Synthesis and biological evaluation of new pentaphyrin macrocycles for photodynamic therapy.

This paper describes the synthesis and in-depth characterization of two new porphyrogenic macrocycles 1 and 2, and provides an evaluation of these molecules as photosensitizer agents. By tuning the reaction conditions and starting from readily available 1,9-diformyl-5-phenyldipyrromethane (4) and tripyrrane dicarboxylic acid (3), both the nonaromatic isopentaphyrin 1, composed of a 24 pi-electron macrocycle, and the aromatic pentaphyrin 2, composed of a 22 pi-electron macrocycle, were obtained in good yield and purity. Confocal laser microscopy and cytofluorimetry studies showed that the newly synthesized pentaphyrins penetrate the cell membranes and localize mainly in the cytoplasm.

Cobalt(II) dioxygen carriers based on simple diamino ligands: kinetic and ab initio studies.

The kinetics of the oxygenation reaction of CoL2(2+) complexes (L=ethylenediamine (en), N,N'-dimethylethylenediamnine (dmen)) have been investigated in dimethyl sulfoxide (dmso) at 298 K and in a medium adjusted to 0.1 mol dm(-3) with Et4NClO4 by means of a UV-vis spectrophotometric technique. The reaction mechanisms are consistent with the fast formation of superoxo 1:1 initial CoL2-O2 species (L=en, dmen), whereas the dimeric mu-peroxo (CoL2)2O2 adduct is formed only when L=en, in the rate determining step.