Highly emissive,nine-coordinate enantiopure lanthanide complexes incorporating tetraazatriphenylenes as probes for DNA

The interaction of q = 0 delta- and lambda-Tb and Eu complexes with poly(dAdT), poly(dGdC) and calf-thymus DNA has been examined by absorption, emission and chiroptical spectroscopy and is sensitive to complex helicity, base-pair type and the nature of the lanthanide excited state.     

Korrelation der quantenchemischen und kinetischen Daten der Reaktion der aromatischen Diamine mit p-Tolylglycidyl?ther

Ohne Zusammenfassung     

Nonlinear perturbations and abstract evolution equations in general banach spaces

Summary Part I deals with the problem of determining sufficient conditions under which the sum of two m-accretive operators on a closed convex set Q₁ is m-accretive on Q₁. Part II is concerned with the initial value problem: u′+Au+g(u)=v, u(0)=u₀. Applications are given to the Boltzmann equation. Entrata in Redazione il 2 luglio 1975.     

Interactions in water-alcohol mixtures: Conductance of lithium picrate in solutions of water and isomeric pentanols at 25°C

Conductance measurements of lithium picrate in solutions of water in n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol and 3-methyl-1-butanol have been carried out at 25°C. Ionic association and conductance were found to change with water content and with the molecular structure of the alcohols (i.e. position of the OH group and degree of branching of the alkyl chain). These results indicate that both conductance and ion pair formation are not the consequence of the simple motion of ions in the electrical field as required by the continuum model. A more realistic approach, involving the internal structure of the solvent mixtures, has been considered.     

Substrate binding to vanadate-dependent bromoperoxidase from Ascophyllum nodosum: a vanadium K-edge XAS approach

The EXAFS region of vanadium K-edge XAS spectra of native vanadate-dependent bromoperoxidase (isoenzyme I) from Ascophyllum nodosum in the presence of the substrate bromide can be fitted to three shells (at 1.62, 1.73-1.78 and 1.99-2.07 A) in the first coordination sphere of vanadium plus two more distant shells at 4.1A, possibly corresponding to bromide, and 4.7 A due to light scatterers stemming from the protein pocket. Bromide does not directly bind to the vanadium centre. The XANES and the EXAFS features for the enzyme are essentially reproduced by model complexes of the general composition [VO(H(2)O)(n)(ONO)] (n= 1 or 2) where ONO is the dianion of a Schiff base from bromosalicylaldehydes (Brsal; with the Br substituent in the position 3, 4, 5 or 6) and amino acids. The 3-Brsal derivatives exhibit an outer sphere shell at 3.8 A, which is traced back to intermolecular contacts. The data obtained from EXAFS are compared to those obtained from single crystal X-ray diffraction of [VO(H(2)O)(2)(4-Brsal-gly)] and [VO(H(2)O)(2)(6-Brsal-gly)] (gly = glycinate). In the complex [VOBr(2)(ONO)']] ((ONO)' is the Schiff base from o-anisole and o-hydroxyaniline), the V-Br distance is 2.44 A.     

Synthesis of alpha-hydrazino ketones via regio- and stereoselective electrophilic amination of manganese enolates and enamines

A straightforward procedure for the regio- and stereoselective synthesis of alpha-hydrazino ketones is described. Manganese enolates and manganese enamines derived from ketones and from the corresponding N-sulfinylimines react with azodicarboxylate esters (DTBAD and DEAD) in a regioselective fashion to afford in good to excellent yields the kinetic alpha-hydrazino ketones as sole or highly prevalent products. When enantiopure N-sulfinyl manganese enamines were used the stereoselectivity of these reactions ranged from 40% to 68% ee.     

Synthesis and revision of the stereochemistry of a cyclopentenone natural product isolated from ascomycete strain A23-98

The 2-propenyl-4,5-dihydroxycyclopent-2-enones 4, 10 and 14 have been synthesised in optically active form. NMR data suggest the compounds 10 and 14 (but not 4) correspond to compounds isolated from ascomycete strain A23-98.     

MRI characterization of residual mediastinal masses in Hodgkin's disease: long-term follow-up

Our purpose was to evaluate the role of MRI in distinguishing fibrous from active residual masses in treated Hodgkin's disease. Forty patients with residual mediastinal mass larger than 1.5 cm underwent MRI 1, 3, 6, and 12 months after the end of cycles of prescribed chemotherapy or combined chemoradiotherapy. The MRI examinations were performed on a 0.5 and a 1.5 T systems, using T(1) before and after gadolinium injection and T(2)-weighted sequences. Each time the residual mass was evaluated in size and signal intensity on spin echo (SE) T(2)-weighted images and on SE T(1)-weighted images after contrast medium. Low signal intensity and low contrast enhancement were considered signs of inactive residues; homogeneous high signal intensity and high contrast enhancement were indicative of active residual disease; heterogeneous signal intensity and heterogeneous contrast enhancement were indicative of partial remission or necrotic/inflammatory phenomena. MR showed high diagnostic accuracy in the evaluation of Hodgkin's mediastinal residues after treatment, if performed at least 6 months after the end of therapy, reaching the highest sensitivity and specificity values at 12 month follow-up (considering the three parameters-T(2) signal intensity, contrast-enhancement, and size-all together). If we consider the single parameters individually, we can observe that size variation remains the more valuable parameter to predict or to exclude a relapse. MR diagnostic accuracy at the 6-month follow-up was lower due to the higher incidence of inhomogeneous pattern. The accuracy of MR performed at 1 and at 3 months after the end of therapy was not satisfying. This represents a clinical problem because the most important clinical decisions have to be taken just in this early post-treatment phase.     

Ternary complexes between cationic GdIII chelates and anionic metabolites in aqueous solution: an NMR relaxometric study

The (1)H and (17)O NMR relaxometric properties of two cationic complexes formed by Gd(III) with a macrocyclic heptadentate triamide ligand, L(1), and its Nmethylated analogue, L(2), have been investigated in aqueous media as a function of pH, temperature and magnetic field strength. The complexes possess two water molecules in their inner coordination sphere for which the rate of exchange has been found to be sensibly faster for the Nmethylated derivative and explained in terms of electronic effects (decrease of the charge density at the metal center) and perturbation of the network of hydrogen-bonded water molecules in the outer hydration sphere. The proton relaxivity shows a marked dependence from pH and decreases of about six units in the pH range 6.5 to 9.0. This has been accounted for by the displacement of the two water molecules by dissolved carbonate which acts as a chelating anion. The formation of ternary complexes with lactate, malonate, citrate, acetate, fluoride and hydrogenphosphate has been monitored by (1)H NMR relaxometric titrations at 20 MHz and pH 6.3 and the value of the affinity constant, K, and of the relaxivity of the adducts could be obtained. Lactate, malonate and citrate interact strongly with the complexes (log K > or =3.7) and coordinate in a bidendate mode by displacing both water molecules. Larger affinity constants have been measured for GdL(2). Acetate, fluoride and hydrogenphosphate form monoaqua ternary complexes which were investigated in detail with regard to their relaxometric properties. The NMR dispersion (NMRD) profiles indicate a large contribution to the relaxivity of the adducts from water molecules belonging to the second hydration shell of the complexes and hydrogen-bonded to the anion. A VT (17)O NMR study has shown a marked increase of the rate of water exchange upon binding which is explained by coordination of the anion in an equatorial site, thus leaving the water molecule in an apical position, more accessible for interactions with the solvent molecules of the second hydration shell which facilitate the exchange process.