DFT study of the EPR spectral pattern of propagating methacrylic radicals

The EPR spectral pattern observed in the bulk polymerization of methacrylic monomers was theoretically investigated by DFT methodology. The conformational analysis of the propagating radical by the rotation around the C–C_β bond, was performed using the B3LYP/6-31G^* computational scheme. To obtain accurate values of the isotropic hyperfine coupling constants (hfccs) a higher level protocol, B3LYP/TZVP//B3LYP/6-31G^*, was applied. The experimental 13-line spectrum registered at the first stage of the polymerization was assumed to correspond to a free rotating radical in a fluid medium and it was simulated just considering the most stable conformation. The 9-line spectrum registered at high conversions was interpreted in terms of highly hindered rotational conformers frozen in the very viscous medium. This spectrum was well reproduced by a model which considers the sum of the individual spectra of the conformations spread around the most probable. Each of these contributing spectra was obtained on the basis of the computed hfccs for the considered conformations and weighted by his relative Boltzmann population according to the DFT analysis. Besides, the calculated hfccs showed an excellent agreement with those predicted by the Heller–McConnell relationship, which confirms the coherence of the DFT methodology for this kind of calculations.     

Metal-catalyzed oxidation and epoxidation of alpha-hydroxy vinyl and dienyl sulfoxides

Treatment of acyclic alpha-hydroxyalkyl alpha,beta-unsaturated sulfoxides with t-BuOOH/VO(acac)2 results in rapid oxidation to the unsaturated sulfones followed by an unusual regio- and stereoselective epoxidation at the unsaturated sulfones; this methodology has been applied to the preparation of carbohydrate-like fragments.     

Rheology of viscoelastic mixed surfactant solutions: effect of scission on nonlinear flow and rheochaos

The linear and nonlinear rheology of viscoelastic mixed anionic-zwitterionic surfactant solutions has been systematically investigated. In the linear viscoelastic regime, these systems display nearly Maxwellian behavior with a unique relaxation time, tau0, and a characteristic elastic plateau modulus, G0. Linear rheological data were used to calculate the repitation and breaking times of the micelles, tau(rep) and tau(b), respectively. Surprisingly, the elastic modulus G0 significantly increases with salt concentration c(s), whereas tau(b) decreases by 1 order of magnitude. The strong effect of c(s) on the material parameters and microstructure of rodlike micelles allowed for the systematic investigation of the effect of these parameters on nonlinear flow. For samples with relatively long tau(b), the quasi-static flow diagram (stress vs shear rate) shows a stress peak followed by a metastable branch (a region of decreasing shear stress), whereas for samples with relatively short tau(b), this phenomenon is not observed. Transient flow responses corroborate quasi-static flow findings and further reveal the significance of microscopic dynamic parameters on flow behavior. Shear stress time series were recorded at constant shear rates, and above a critical shear rate, gamma(c2), stress fluctuations are observed. The amplitude of these stress fluctuations, Delta sigma, was found to scale as Delta sigma approximately equal to G0(tau(b)| gamma - gamma(c2)|)beta with beta approximately 0.5. This scaling is observed for micellar systems with tau(b) ranging from 0.12 to 0.01 s and G0 ranging from 1 x 10(3) to 7 x 10(3) dyn/cm2.     

Experimental and theoretical study of lanthanide complexes based on linear and macrocyclic polyaminopolycarboxylic acids containing pyrazolylethyl arms

We report the synthesis of two novel Gd(III)-complexes derived from linear and macrocyclic polyaminopolycarboxylic acids 1 and 2, which contain a 3,5- dimethylpyrazolyl-ethyl arm, and a study of their relaxivity properties. The relationships between the experimental and theoretical results have provided interesting information about the kinetic and thermodynamic stability of these complexes.     

Properties of two polymerizable surfactants aqueous solutions: dodecylethylmethacrylatedimethylammonium bromide and hexadecylethylmethacrylatedimethylammonium bromide. I. Critical micelle concentration

The aggregation of two polymerisable surfactants dodecylethylmethacrylatedimethylammonium bromide (C₁₂PS) and hexadecylethylmethacrylatedimethylammonium bromide (C₁₆PS) was studied with a battery of methods. Both surfactants form premicelles at low concentration, and show a critical micelle concentration and a transition between spherical and rod-like micelles. The micelle ionization degree and the adsorption at the air/solution interface were also studied. Results are interpreted on the basis of the conformation of the polar head group.     

Alkoxy-substituted difluoroboron benzoylmethanes for photonics applications: a photophysical and spectroscopic study

Two series of novel boron difluoride adducts (BDFs), namely [BF(2)(OO(R(n)))] (type I) and [BF(2)(OO(2R(n)))] (type II) (R = C(6)H(4)OC(n)H(2n+1); n = 10-18), containing β-diketonate ligands bearing 4-alkoxyphenyl substituents in position 1 or in positions 1,3 of the β-diketonate core, respectively, have been prepared. All of them display a strong interaction between the ligand and the BF(2) group, as deduced from the IR spectroscopic data, and strong blue-violet emission (λ(em)(max) from 400 to 440 nm), with fluorescence quantum yields from 0.69 to 0.84 (type I) and 0.48 to 0.66 (type II) and fluorescence lifetimes of 1.7 and 2.2 ns in diluted dichloromethane solution, respectively. The photophysical properties of I and II series of dyes are independent of the solvent polarity and the chain length of the alkoxyphenyl substituent(s). Moreover, they exhibit high photostability even under intense laser light. Contradicting previous interpretations, our detailed photophysical and spectroscopic study rules out excimer formation even in highly concentrated solution or in the solid state, demonstrating the resistance of these dyes to self-aggregation. All those features pave the way to the application of such fluorophores in OLEDs, solid dye lasers, chemical sensors and two-photon biological labels, to name a few.     

Study of the adsorption capacity to Co2+, Ni2+ and Cu2+ ions of an active carbon/functionalized polyamine hybrid material

The retention of Co²⁺, Ni²⁺ and Cu²⁺ metal ions from aqueous solution, on a functionalized hybrid material obtained by the anchorage of N-(4-amino-1,6-dihydro-1-methyl-5-nitroso-6-oxopyrimidin-2-yl)-N′-[bis(2-aminoethyl)] ethylenediamine ligand on a low-functionalized activated carbon, at pH 4.5 has been studied. The adsorption isotherms fit the Langmuir equation and the calculated maximum adsorption capacities were compared to those obtained by using the un-functionalized activated carbon as well as to other analogous hybrid materials as adsorbent of the same metal ions. These studies were carried out by rationalizing the resulting adsorption data regarding the stability constant values of the complexes formed by the three metal ions with the free tri-amine function of the ligand. The results demonstrate that the adsorption capacities of the activated carbon–ligand hybrid material towards the three metal-ions studied correlated with the stabilities of the tri-amine-metal-ion bonds formed during the adsorption processes.     

Electron ionisation mass spectral studies of bridgehead‐fused Δ2‐norbornanethiazolines

The electron ionisation (EI) mass spectra of a series of bridgehead‐fused Δ²‐norbornanethiazolines, a new class of bridgehead‐norbornane derivatives, have been studied and their cleavage mechanisms rationalised on the basis of the substituent shifts as well as on the identification of relevant peaks through accurate mass measurements and collision‐induced dissociation tandem mass spectrometric experiments. The fragmentation patterns of isomeric pairs of 6,6‐ and 10,10‐dimethylnorbornanethiazolines are almost identical, probably due to an initial isomerisation of molecular ion previous to the fragmentation. In general, the dominant peaks in the spectra of all the studied compounds originate from initial α‐cleavages of C(5)–C(6) or C(1)–C(10) bonds, followed by concomitant homolytic cleavage of C(1)–C(9) and C(7)–C(10) bonds. The driving force for this fragmentation pathway, directed by the gem‐dimethyl group, is the formation of a highly stabilised thiazolilmethyl cation which constitutes the base peak in all the spectra and allows the identification of these interesting ligands. Copyright © 2009 John Wiley & Sons, Ltd.     

Physical Properties and Prebiotic Activities (Lactobacillus spp.) of Gelatine-Based Gels Formulated with Agave Fructans and Agave Syrups as Sucrose and Glucose Substitutes

This research developed model foods of gelatine-based gels, where carbohydrates from Agave tequilana Weber var. Azul (agave syrups or/and agave fructans) were incorporated into gel formulations as healthy sucrose and glucose substitutes. The sugars (sucrose and glucose) were substituted by agave carbohydrates (agave syrups and agave fructans), obtaining the subsequent gel formulations: 100% agave syrup (F2 gel), 100% agave fructan (F3 gel), and 50% agave syrup–50% agave fructan (F4 gel). The unsubstituted gel formulation was used as a control (F1 gel). The prebiotic activities, physical properties, thermal stability (HP-TLC), and texture of gelatine-based gels were evaluated. The gel formulations showed translucent appearances with approximately 36 g/100 g of water and water activities values between 0.823 and 0.929. The HP-TLC analysis validated that agave fructans did not hydrolyse during the thermal process of gels production. Gels produced with agave syrup and agave fructan (F2-F4 gels) provided higher hardness, gumminess, and springiness values (p < 0.05) than those produced with glucose and sucrose (F1 gel). Gelatine-based gel formulations displayed prebiotic activities correlated to the ability of Lactobacillus plantarum, Lactobacillus paracasei, and Lactobacillus rhamnosus to use agave carbohydrates as carbon sources. Based on the prebiotic effect and physical and textural properties, the F2 and F4 gel formulations displayed the best techno-functional properties to produce gel soft candies.