Nanophase separation and effects on properties of Ge–As–Se chalcogenide glasses

Nanophase separation in the bulk Ge–As–Se chalcogenide glasses was observed by SEM and supported by XRD and IR measurements. Effects of nanophase separation on glass transition temperature (T_g), microhardness (H_v), optical band gap (E_opt) and thermal expansion coefficient (α) were investigated in terms of glass rigidity transitions. According to the correlations between the properties and average coordination number Z, it is established that nanophase separation becomes more intensive when Z is larger than 2.64.     

Electrochemistry of coordination compounds: Part XIV. Polarographic behaviour of d8 ruthenium nitrosyl complexes

The voltammetric behaviour of the new complex, [Ru(NO)(Ph₂PCH₂CH₂CH₂PPh₂)₂]⁺, has been studied in 1,2-dimethoxyethane and the results compared with those obtained in the analogous reduction of [Ru(NO)(Ph₂PCH₂PPh₂)₂]⁺. The reduction proceeds in two reversible, one-electron steps. Stepwise reduction of these cationic complexes leads to two reversible, one-electron steps. Stepwise reduction of these cationic complexes leads to anionic complexes with formal oxidation number (?II) through the intermediate state which, in the case of Ph₂PCH₂CH₂PPh₂ ligand, is unstable and decays via a disproportionation pathway. A reduction-oxidation mechanism accounting for the chemical and electrochemical results is proposed.     

Gold dithiocarbamate derivatives as potential antineoplastic agents: design, spectroscopic properties, and in vitro antitumor activity

At present, cisplatin (cis-diamminodichloroplatinum(II)) is one of the most largely employed anticancer drugs as it is effective in the treatment of 70-90% of testicular and, in combination with other drugs, of ovarian, small cell lung, bladder, brain, and breast tumors. Anyway, despite its high effectiveness, it exhibits some clinical problems related to its use in the curative therapy, such as a severe normal tissue toxicity (in particular, nephrotoxicity) and the frequent occurrence of initial and acquired resistance to the treatment. To obtain compounds with superior chemotherapeutic index in terms of increased bioavailability, higher cytotoxicity, and lower side effects than cisplatin, we report here on some gold(I) and gold(III) complexes with dithiocarbamate ligands (DMDT = N,N-dimethyldithiocarbamate; DMDTM = S-methyl-N,N-dimethyldithiocarbamate; ESDT = ethylsarcosinedithiocarbamate), which have been synthesized, purified, and characterized by means of elemental analyses, conductivity measurements, mono- and bidimensional NMR, FT-IR, and UV-vis spectroscopy, and thermal analyses. Moreover, the electrochemical properties of the designed compounds have been studied through cyclic voltammetry. All the synthesized gold complexes have been tested for their in vitro cytotoxic activity. Remarkably, most of them, in particular gold(III) derivatives of N,N-dimethyldithiocarbamate and ethylsarcosinedithiocarbamate, have been proved to be much more cytotoxic in vitro than cisplatin, with IC50 values about 1- to 4-fold lower than that of the reference drug, even toward human tumor cell lines intrinsically resistant to cisplatin itself. Moreover, they appeared to be much more cytotoxic also on the cisplatin-resistant cell lines, with activity levels comparable to those on the corresponding cisplatin-sensitive cell lines, ruling out the occurrence of cross-resistance phenomena and supporting the hypothesis of a different antitumor activity mechanism of action.     

Electrochemistry of coordination compounds: Part XIX. Electrochemical study of some cationic hydrido-complexes of iron(II)

The Electrochemical behaviour of a series of cationic hydrido-complexes of Fe(II) of general formula trans-[FeH(L)(DPE)₂] (BPh₄)(L=N₂, C₂H₅N, C₆H₅CN, CH₂CHCN, CH₃CN, P(OCH₃)₃, P(OC₂H₅)₃, CO; DPE=1,2- bis(diphenylphosphino)ethane) has been investigated in 1,2-dimethoxyethane at the platinum electrode. The reduction of these d⁶ complexes has been found to proceed by an ECE mechanism in which a one-electron transfer, generating a transient d⁷ species, is followed by the fast loss of one of the neutral ligands and a further one-electron reduction of the pentacoordinated intermediates to the final d⁸ anionic hydrides. The reduced species are stabilized considerably at low temperature. The ligands, L, are divided into two groups according to their bonding properties, with particular references to their ability to act as π- acceptors. Weak π-bonders (N₂, C₂H₅N, C₆H₅CN, CH₂CHCN, CH₃CN) are lost in the chemical step interposed between the two charge-transfer processes, whereas strong π-accepting ligands (CO and P(OR)₃) favour dissocia tion of one end of a diphosphine.     

H→γγ: a comment on the indeterminacy of non-gauge-invariant integrals

We reanalyze the recent computation of the amplitude of the Higgs boson decay into two photons presented by Gastmans et al. [1, 2]. The reasons for why this result cannot be the correct one have been discussed in some recent papers. We address here the general issue of the indeterminacy of integrals with four-dimensional gauge-breaking regulators and to which extent it might eventually be solved by imposing physical constraints. Imposing gauge invariance as the last step upon R_ξ-gauge calculations with four-dimensional gauge-breaking regulators, allows us to recover the well known H→γγ result. However we show that in the particular case of the unitary gauge, the indeterminacy cannot be tackled in the same way. The combination of the unitary gauge with a cutoff regularization scheme turns out to be non-predictive.     

Complexes of organolead and organotin ions with 1-(2-pyridylazo)-2-naphthol

The stability constants of the complexes of 1-(2-pyridylazo)-2-naphthol with several organotin and lead ions were determined spectrophotometrically in aqueous 20% (v/v) dioxane and were shown to have very high values. The extraction of the complex of (C₂H₅)₂Pb²⁺ from water into chloroform was studied, and the formation of an extractable (C₂H₅)₂Pb(PAN)(OH) complex is postulated.     

Abelian surfaces over totally real fields are potentially modular

Publications mathématiques de l'IHÉS - We show that abelian surfaces (and consequently curves of genus 2) over totally real fields are potentially modular. As a consequence,...     

Mn–ferrite nanoparticles via reverse microemulsions: synthesis and characterization

Mn–ferrite nanoparticles were synthesized by thermal treatment at 800 °C of manganese and iron oxo-hydroxides obtained via water-in-oil microemulsions consisting of n-hexanol as continuous phase, cetyl trimethyl ammonium bromide (CTAB) as the cationic surfactant and aqueous solutions of metal salts and precipitant agent (tetramethyl ammonium hydroxide) as reagents. Nanoparticles were synthesized using a multi-microemulsion approach. Two different co-precipitation routes are described depending on the Fe(II) or Fe(III) precursor salts. The influence of salt concentration and digestion process on the final products was examined. The nanoparticles were characterized by X-ray diffraction accompanied by Rietveld analysis, transmission electron microscopy, thermal analysis, infrared spectroscopy, and SQUID magnetometry. In all the synthesis reported in this study MnFe₂O₄ was observed only after thermal treatment at 800 °C of the as-prepared precursors. Almost spherical nanocrystalline MnFe₂O₄ ranging from 12 to 39 nm was obtained starting from chlorides or mixed chloride–sulfate salts as precursors. Low values of reduced remanent magnetization (M _r/M _s) and coercive field (H _c) induce to believe that a fraction of superparamagnetic particle is present at room temperature.