Hierarchical porphyrin self-assembly in aqueous solution

In aqueous solution meso-tetrakis(4-phosphonatophenyl)porphyrin shows self-aggregation processes controlled by the "sergeant-soldier rule". After partial protonation of the external phosphonic groups, it is possible (i) to further protonate the inner nitrogen atoms of the molecules or (ii) to allow, over time, the system to aggregate. Therefore, the two procedure lead to a different system evolution, producing species with different chemico-physical properties.     

Sequence and phosphorylation level determination of two donkey β‐caseins by mass spectrometry

Two coeluting components, with experimentally measured M_r values of 25529 and 24606 Da, were identified by reversed‐phase high‐performance liquid chromatography (RP‐HPLC) and mass spectrometric analysis in the dephosphorylated casein fraction of a milk sample collected from an individual donkey belonging to the Ragusano breed of the east of Sicily. By coupling enzymatic digestions, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) and RP‐HPLC/nano‐electrospray ionization tandem mass spectrometry (nESI‐MS/MS) analysis, the two proteins were identified as donkey β‐CNs and their sequences characterized completely, using the two known β‐CNs from mare as references. The two donkey β‐CNs, showing a mass difference of 923 Da, differ by the presence of the domain E²⁷SITHINK³⁴ in the full‐length component (M_r 25529 Da). In comparison with the mare's β‐CNs used as reference, they present nine amino acid substitutions: L→S³⁷, R→H⁵², S→N⁸¹, P→V⁸⁴, L→V⁹¹, R→Q²⁰³, P→L/I²⁰⁶, L→F²¹⁰ and A→P²¹⁹. Together, these substitutions account for the increase of 18 Da in the M_r of the donkey β‐CNs with respect to the counterparts from the mare. The molecular mass determination by ESI‐MS for the phosphorylated proteins showed that the full‐length component was composed of highly multi‐phosphorylated isoforms with five to seven phosphate groups. By analogy with the homologous mare's β‐CNs, the full‐length (226 amino acids) β‐CN was termed variant A, whereas the shorter (218 amino acids) β‐CN was termed variant A^Δ5. Copyright © 2009 John Wiley & Sons, Ltd.     

Complementary multiplicative hyperrings

In this paper the complementary hyperstructure obtained from a multiplicative hyperring is considered. Furthermore a characterization for such hyperstructures obtained starting from a strongly distributive multiplicative hyperring is given.     

Stabilization of catalytic sol-gel entrapped perruthenate

A combination of more stable counter-cation (tetraphenylphosphonium in place of tetrapropylammonium), of local basic microenvironment, and of a non-solubilizing reaction medium (supercritical CO₂) improves the life-cycle and reusability of catalytic ORMOSILs doped with perruthenate in the oxidation of alcohols with O₂. A number of different bases were co-entrapped and their effect on catalysis assessed in the oxidative dehydrogenation of benzyl alcohol in dense phase carbon dioxide at 22 MPa and 75 °C. The optimized catalyst retains most of its activity after five consecutive runs when a normal ORMOSIL-entrapped TPAP has become inactive. Deactivation of TPAP could be ascribed by EPR analysis to the formation of catalytically inactive RuO₂.     

On form dictating function: shape and structural effects in silica‐based funtional materials

Along with basic physicochemical properties, the morphology of sol‐gel materials, both on the macro‐, meso‐, and nanoscale, controls function and utility. Referring to recent achievements, we focus on the relation between form and activity for functional silica‐based materials to elucidate a few general concepts of usefulness in guiding research in this burgeoning field. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 10: 000–000; 2010: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900023     

Cobalt complexes in aqueous solutions as dioxygen carriers

This article provides a short survey on the thermodynamic and kinetic behaviour of cobalt complexes, which are able to bind molecular oxygen in aqueous solutions. The focus is on cobalt complexes with simple polyamines and with polynucleating ligands that share the same basic structure, in terms of them being elements of a sequence with increasing complexity. Ditopic polyazapolyoxalkanes and dicompartimental ligands containing a phenolic moiety are also considered. The aim is to elucidate the relation between the structure of the ligands and the behaviour of their cobalt complexes as donors and acceptors of dioxygen.     

Sol-Gel Microspheres Doped with Glycerol: A Structural Insight in Light of Forthcoming Applications in the Polyurethane Foam Industry

Porous silica-based microspheres encapsulating aqueous glycerol can be potential curing agents for one-component foams (OCFs). Such agents have the advantage of an enhanced sustainability profile on top of being environmentally friendly materials. A synthetically convenient and scalable sol-gel process was used to make silica and organosilica microspheres doped with aqueous glycerol. These methyl-modified silica microspheres, named “GreenCaps”, exhibit remarkable physical and chemical stability. The microspheres were characterized by scanning electron microscopy, transmission electron microscopy at reduced pressure, and cryogenic nitrogen adsorption—desorption analysis. The structure of the materials was also analyzed at the molecular level by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. As expected, the degree of methylation affects the degree of encapsulation and pore structure. Microspheres similarly methylated, however, can differ considerably in surface area and pore size due to the templating effect of glycerol on the organosilica structure. The results of the structure analysis reveal that glycerol is efficiently encapsulated, acts as a template, barely leaches over time, but is released by depressurization. A proper application of these microspheres can later on enhance both the environmental and health profile, as well as the technical performance (curing speed, foam quality, and froth thixotropy) of spray polyurethane foams.     

Synthesis of multifunctionalized building blocks via vinylogous addition of Chan’s diene to carbonyl and carbonyl-related electrophiles, mediated by molecular iodine

The synthesis of multifunctionalized β-ketoesters has been achieved by using molecular iodine as a catalyst under very mild conditions. The vinylogous addition of Chan’s diene 1 to carbonyl and carbonyl-related compounds (aldehydes, ketones, imines and acetals) occurred with high efficiencies and with complete γ-selectivity, giving a useful method for the synthesis of interesting libraries of different δ-functionalized β-ketoesters.