Micellar solutions of sulfobetaine surfactants in water-ethylene glycol mixtures: surface tension, fluorescence, spectroscopic, conductometric, and kinetic studies

Micellization in water-ethylene glycol (EG) N-dodecyl, N-tetradecyl, and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SB3-12, SB3-14, and SB3-16, respectively) micellar solutions, with the weight percent of EG changing within the range 0-40, was studied by means of surface tension measurements. Information about the influence of the added EG on the aggregation number of the sulfobetaine micelles and on the polarity of the interfacial region of micelles was obtained through fluorescence and spectroscopic measurements. Surface tension measurements also provide information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, the surface pressure at the cmc, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. The Gordon parameter of the water-EG mixtures was also estimated by means of surface tension measurements. The thermodynamic and structural changes originated by the presence of EG control the micellar kinetic effects observed in the reaction methyl 4-nitrobenzenesulfonate + Br(-) occurring in the water-EG sulfobetaine micellar solutions. Information about the distribution of bromide ions between the bulk and micellar pseudophases was obtained through conductivity measurements. The kinetic micellar effects were quantitatively explained by using the pseudophase kinetic model.     

About the calculation of exchange coupling constants in polynuclear transition metal complexes

The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data.     

On the 2 and the 3-connectedness of ample divisors on a surface

Let X be a nonsingular complex projective surface and let D be an ample divisor on X such that the associated invertible sheaf is spanned by its global sections. We prove that D is 2-connected apart from a few cases we explicitly describe. We also provide a corresponding result for the 3-connectedness when D²10 and for the 4-connectedness when D²17 and D is very ample.     

Sugli insiemi di permutazioni strettamente k-transitivi (k ≥ 3)

Summary Let G be a sharply 3-transitive permutation set on a finite set E of even cardinality and let 1 be in G. The following theorems are proved. G is one of the known examples if and only if there exists a non-identity normal subgroup N of G and an element of E such that NG G.G is a group if and only if G for every G and for every G and for every G .By using the classification of finite single groups a result concerning sharply k-transitive permutation sets k>3 is also proved.

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Dedicato a Guido Zappa in occasione del suo 70° compleanno

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Lavoro eseguito nell'ambito dei progetti finanziati dal Ministero della Pubblica Istruzione.     

Interactions of dendrimers with selected amino acids and proteins studied by continuous wave EPR and Fourier transform EPR

Interactions of polyamidoamine dendrimers, termed Gn, where n indicates the generation (=number of amidoamine layers), at different protonation levels with selected amino acids and proteins have been investigated by means of continuous wave electron paramagnetic resonance (cw-EPR) and pulsed-EPR (electron spin-echo = ESE) analyses. A low-generation dendrimer (G2) and a high-generation one (G6) were labeled with nitroxides for the EPR measurements. Gly, Glu, Arg, and Leu were selected as representative of neutral(zwitterionic)-polar, acidic, basic, and low-polar amino acids, respectively. The water-soluble proteins alpha-chymotrypsin and albumin were selected on the basis of a basic and an acidic isoelectric point, respectively. The cw-EPR spectra were analyzed by computing the line shapes to extract information about the dendrimer-biomolecule interactions. In general, dendrimers at a high protonation level interact stronger with amino acids than those at a low level of protonation. However, even for highly protonated dendrimers, a synergistic effect between hydrophilic and hydrophobic interactions promoted the formation of stable Gn-amino acid adducts, as demonstrated by the enhanced interactions with Leu. As expected from acid-base interactions, stable adducts were formed between Arg and highly protonated dendrimers and between Glu and low level protonated dendrimers. The relatively strong dendrimer interactions with the protein chymotrypsin and the poor interactions of dendrimers with albumin demonstrated that the protonated amino groups of the dendrimers are predominantly involved in the interactions with these proteins and indicated a significant role in the interactions with the dendrimers of the hydrophobic external residues of chymotrypsin. Computer-aided analysis of the ESE experiments was consistent with the cw-EPR results and supported the conclusion of a partial complexation of the nitroxides of the dendrimer with Leu and alpha-chymotrypsin.     

The crystal structure of tris(acetonitrile)nitrosylbis(triphenylphosphine)iridium(III) dihexafluorophosphate. An unusual iridium nitrosyl hexacoordinate complex

Summary The structure of [Ir(NCMe)₃(NO)(PPh₃)₂][PF₆]₂ has been ] determined by x-ray methods. Crystals are orthorhombic, space groupPca 2₁ , witha = 21.753(14),b = 11.678(10),c = 18.474(12) Å and Z = 4. The structure has been solved from diffractometer data and refined by full-matrix leastsquares to R = 0.076 for 2776 observed reflections. The cation is a hexacoordinate and not a pentacoordinate species as expected. The extra acetonitrile molecule,trans to the nitrosyl ligand, is much more weakly bound to the metal atom [Ir-N 2.360(26) against 1.965(20) and 1.912(14) Å for the other two acetonitriles]. The nitrosyl is bent [Ir-N-O 111(1)° Å] and acts as the formally one-electron donor NO^–.     

Models of pesticides inside cavities of molecular dimensions. A role of the guest inclusion in the dechlorination process

The reduction mechanism of the pesticide vinclozoline (3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione) was studied in nonaqueous solvents in the confined environment of a cyclodextrin (CD) cavity. The effect of the cavity dimensions on the mechanism of the redox process was evaluated using glucose as a reference and using three cyclodextrin molecules of different cavity sizes, namely, alphaCD, betaCD, and gammaCD. In the absence of CD the main reduction product of vinclozoline in the first reduction step is dichloroaniline. An addition of glucose leads to a quantitative change of mechanism with 10 products in total. Addition of CD, however, leads exclusively to dechlorination of the phenyl ring. The degree of dechlorination depends strongly on the choice of cyclodextrin molecule. The importance of the complex formation equilibria in the change of the mechanism is supported by a series of semiempirical AM1 quantum-mechanical calculations. Very good correlation (correlation coefficient 0.995) was obtained between the complex stabilization energy of the inclusion complex and the degree of pesticide dechlorination. Additionally, we were able to show that the complexes are stabilized by the formation of intermolecular hydrogen bonds between the host and guest species. CD molecules do not simply act as proton donors in a nonaqueous environment, but also protect parts of the molecule included within the cavity and steer the degradation process toward fewer products.     

Oriented immobilization of Desulfovibrio gigas hydrogenase onto carbon electrodes by covalent bonds for nonmediated oxidation of H2

The orientation of hydrogenase bound covalently to a pyrolytic graphite edge electrode modified with a 4-aminophenyl monolayer can be modulated via electrostatic interactions during the immobilization step. At low ionic strength and when the amino groups of the electrode surface are mostly protonated, the hydrogenase is immobilized with the negatively charged region that surrounds its 4Fe4S cluster nearer to the protein surface facing the electrode. This allows direct electron transfer between the immobilized hydrogenase and the electrode, which is observed by the strong catalytic currents measured in the presence of the H2 substrate. Therefore, a very stable enzymatic electrode is produced that catalyzes nonmediated H2 oxidation.     

Reaction of allylsilanes and allylstannanes with alkynes catalyzed by electrophilic late transition metal chlorides

The intramolecular reaction of allylsilanes and allylstannanes with alkynes proceeds catalytically in the presence of Pt(II), Pd(II), Ru(II), and Au(III) chlorides. Although more limited, AgOTf also catalyzes the cyclization. Usually, PtCl2 as the catalyst in methanol or acetone gives the best results. The reaction proceeds by exo attack of the allyl nucleophile on the alkyne to form five- or six-membered ring carbocycles. The reaction generally proceeds with anti stereoselectivity. However, a terminally substituted trimethylsilyl derivative reacts by a syn-type addition. The intermediate alkenylpalladium complex has been trapped with allyl chloride to form an allylated derivative with an additional carbon-carbon bond.     

Separation and detection of oxidation products of fluorodeoxyglucose and glucose by high-performance liquid chromatography-electrospray ionisation mass spectrometry

2-Deoxy-2-[18F]fluoro-D-glucose ([18F] FDG), the most popular positron emitting radiopharmaceutical, may oxidise by autoradiolysis in aqueous solution. The aim of this work was to use LC-MS for determination of the oxidation products of fluorodeoxyglucose and glucose (Glc) obtained by oxidation with Fenton's reagent. Asahipak NH2P-50 polyamide silica column and acetonitrile-0.025% aqueous ammonium formate (80:20 (v/v)) eluent were utilised with an Agilent 1100 HPLC-MS instrument. Ten major oxidation products of FDG and Glc were separated and identified by mass spectrometry: 2-fluorogluconic acid, 2-fluoroglucuronic acid, 2-oxoerythronic acid, arabinose, arabonic acid, araburonic acid, erythrose, erythrulose, gluconic acid, and glucuronic acid. The most intensive electrospray ionisation signals were found in the negative ion spectra and were due to HCOO- adducts, the other acids being in their lactone forms.