113Cd NMR and fluorescence studies of multiple binding mechanisms of Cd(II) by the Suwannee River fulvic acid

The binding of Cd (II) by the fulvic acid from a Suwannee River (FA) was investigated at various pH values and reactants ratios by 113Cd NMR and fluorescence spectroscopy. The NMR results provided evidences that the FA-Cd interactions occur through a variety of binding modes and mechanisms. Different kinds of organically bound Cd-species were detected in the 1.8-10.8 pH range depending on the FA/Cd ratios. Labile complexes (amenable to Cd-aminoacidic and Cd-hydroxy interactions or outer-sphere complexes) were observed at low pH and FA/Cd levels while stronger interactions (of carboxylate-type or inner-sphere complexation) took place as the pH and/or the FA concentration were increased. At pH ca. 6 insoluble FA-Cd adducts were primarily produced but, at relatively large FA concentration, only soluble complexes, stable in the whole pH 1.8-10.8 range, were formed. A complementary analysis, by fluorescence spectroscopy, provided clear evidences of FA-Cd association/aggregation phenomena. While no noticeable effects occurred with soluble samples, the formation of insoluble adducts led to significant enhancements of the emission fluorescence spectra. Although other explanations could not be excluded, this result was accounted for by modifications of the optical properties of the ligand itself due to sedimentation of the heavier components. Fluorescence enhancement was also observed on samples before the effective precipitation and interpreted as spectroscopic evidence of the onset of aggregation phenomena.     

Magnetic properties and spin order of Sr7Fe10O22

The magnetic properties of Sr₇Fe₁₀O₂₂ have been investigated by means of magnetic susceptibility and Mössbauer absorption measurements. This compound proved to be antiferromagnetic with a Néel temperature T_N = 425 K; the magnetic susceptibility is constant from the lowest measuring temperature (78 K) up to T_N.The Mössbauer measurements and the analogies with “brownmillerite” type compounds indicate that iron ions occupy one octahedral and two tetrahedral different sites. An antiferromagnetic spin configuration with moments lying in the ab plane appears to be consistent with the experimental results. A small spontaneous magnetic moment was observed at room temperature with features resembling those of strontium hexaferrite; a weak ferromagnetic behavior can not however be excluded taking into account the aforementioned susceptibility behaviour.     

Quantum chemical study of the geometries and stabilities of the two valence-tautomers of C2H2F+

Non-empirical SCF-MO molecular wavefunctions were computed for the two limiting structures of C₂H₂F⁺ with full geometry optimization using double-zeta quality atomic orbital basis sets. The bridged structure (fluorenium ion) was found to be an energy maximum (transition state) about 31 kcal/mole higher than the open structure (fluoro-vinyl cation). The latter, contrary to the unsubstituted vinyl cation, is slightly (4.5 °) bent away from fluorine at the electron deficient centre.     

Investigating the interactions of hyaluronan derivatives with biomolecules. The use of diffusional NMR techniques

[Chemical structure: see text] The interactions between a biomaterial and biomolecules present in body fluids often determine the fate of the biomaterial. This paper presents a study on hyaluronan (HA)-containing materials (in soluble or colloidal form) that focuses on their interactions with lipids and proteins and for the first time uses PFG NMR as an analytical technique for probing these events. The interactions of HA-based polymers with phospholipids (DPPC and DPPG liposomes) are shown to depend both on charge and hydrophobicity factors. Despite the difference in behavior between albumin (substantially non-adhesive) and fibrinogen (adhesive), the interactions of the polymers with proteins do not seem to be based on hydrophobic effects but on surface polar interactions.     

Influence of the substituent on selective photocatalytic oxidation of aromatic compounds in aqueous TiO2 suspensions

Experimental results are reported showing that the photocatalytic oxidation of aromatic compounds containing an electron-donor group (EDG) gives rise mainly to ortho- and para-monohydroxy derivatives while in the presence of an electron-withdrawing group (EWG) all the monohydroxy derivatives are obtained.     

High-Q factor single mode circular photonic crystal nano-resonator

In this work, the analysis, fabrication and optical characterization of a two-dimensional circular photonic crystal (2D-CPC) nano-resonator based on an air/GaAs/air slab waveguide are presented. Four InAs/InGaAs quantum dots (QDs) stacked layers emitting around 1300 nm at room temperature were embedded in a GaAs waveguide layer grown on an Al_0.7Ga_0.3As layer and GaAs substrate. The patterning of the structure and the membrane release were achieved by using electron beam lithography, ICP plasma etching and selective wet etching of the AlGaAs sacrificial layer. The micro-luminescence spectrum recorded from the fabricated nano-cavity shows a narrow optical transition at the resonance wavelength of about 1282 nm with a FWHM and Q-factor of 6.2 Å and more than 2000, respectively.     

Merging lithium carbenoid homologation and enzymatic reduction: A combinative approach to the HIV-protease inhibitor Nelfinavir

An effective stereocontrolled synthesis of the HIV protease inhibitor Nelfinavir is reported. Two transformations were identified crucial for achieving success: the formation of a densely functionalized α-chloroketone via the homologation of a Weinreb amide with chloromethyllithium (LiCH₂Cl), followed by its erythro selective reduction into the corresponding chiral chlorohydrin. A commercially available enzyme P2-C02 was particularly well suited for this purpose, affording the key alcohol (in an excellent 99% de), which was then smoothly converted into the active biologically active agent.     

Clifford Fields and the Relativistic Equation of the Nucleon

A relativistic equation for free fields whichtake their values in the Clifford algebra associatedwith the Minkowski metric is shown to be interpretableas the equation of the nucleon. The internal symmetry group SU(2) arises naturally from theassociative algebra structure of the representationspace. The latter structure can be used to constructcoupling terms consistent with the transformationproperties of the interacting fields; in particular, itallows the familiar couplings of the nucleon field withthe electromagnetic field and with the -mesonfield.     

Anionic N-Fries rearrangement of N-alkyl-2-iodo anilides induced by iodine-magnesium exchange: application for synthesis of strained 1,2,3-trisubstituted indoles

A superior, mild, high-yielding one-pot process for rapid access to oxo anilides has been developed that involves three cascade reactions: iodine-magnesium exchange, regiospecific ortho N-Fries rearrangement, and in situ trapping of the formed aniline anion. Coupled with McMurry cyclization, the two-step process allows ready synthesis of strained 1,2,3-trisubstituted indoles regioselectively.     

Fatty acid composition and volatile compounds of caviar from farmed white sturgeon (Acipenser transmontanus)

The present study was conducted to characterize caviar obtained from farmed white sturgeons (Acipenser transmontanus) subjected to different dietary treatments. Twenty caviar samples from fish fed two experimental diets containing different dietary lipid sources have been analysed for chemical composition, fatty acids and flavour volatile compounds. Fatty acid make up of caviar was only minimally influenced by dietary fatty acid composition. Irrespective of dietary treatments, palmitic acid (16:0) and oleic acid (OA, 18:1 n-9) were the most abundant fatty acid followed by docosahexaenoic acid (DHA, 22:6 n-3) and eicopentaenoic (EPA, 20:5 n-3). Thirty-three volatile compounds were isolated using simultaneous distillation-extraction (SDE) and identified by GC-MS. The largest group of volatiles were represented by aldehydes with 20 compounds, representing the 60% of the total volatiles. n-Alkanals, 2-alkenals and 2,4-alkadienals are largely the main responsible for a wide range of flavours in caviar from farmed white surgeon.