Decay of neutron-rich Ga isotopes near N = 50 at PARRNe

The PARRNe facility has been used to produce neutron-rich isotopes ^83,84Gaby the ISOL method. Their decay has been studied, and β-γ coincidence and γ-γ coincidence data were collected as a function of time. The first two excited levels in ⁸³Ge and the first excited level in ⁸⁴Ge have been measured for the first time.     

Liquid-liquid phase equilibria of aqueous two-phase systems containing salts and polyethylene glycol

Liquid-liquid phase equilibria of the ternary systems: (a) polyethylene glycol - ammonium sulfate- water and (b) polyethylene glycol - sodium carbonate -water have been determined experimentally at 15°, 25°, 35° and 45°C and for two different molecular weights of the polymer (Avg. M.W. 1000 and 2000). Details of the glass cell and of the equilibration and analytical procedures used are described. Equilibrium data along with phase diagrams are presented. Finally the effect of temperature and of the molecular weight of the polymer are also discussed.     

Interactions between hen egg-white lysozyme, PEG2,000, and PLA50 at the air-water interface

In this paper, we compared the efficiency of polymer films, made of a poly(ethylene glycol) (PEG2,000)/poly(d,l-lactide) (PLA50) mixture, or a PEG2,000-PLA50 copolymer, to prevent adsorption of a model protein, the hen egg-white lysozyme (HEWL), at the air-water interface. This was achieved by analyzing the surface pressure/surface area curves, and the X-ray reflectivity data of the polymer films spread on a Langmuir trough, obtained in absence or in presence of the protein. For both the mixture and the copolymer, the amount of protein adsorbed at the air-water interface decreases when the density of the polymer surface coverage increases. It was shown that even in a condensed state, the polymer film made by the mixture can not totally prevent HEWL molecules to adsorb and penetrate the polymer mixed film, but however, protein molecules would not be directly exposed to the more hydrophobic phase, i.e. the air phase. It was also shown that the configuration adopted by the copolymer at the interface in its condensed state would prevent adsorption of HEWL molecules for several hours; this would be due in particular to the presence of PEG segments in the interfacial film.     

Merging organometallic chemistry with polyoxometalate chemistry

A series of polyoxomolybdate-incorporated organometallic complexes has been obtained by reaction of [MBr(CO)5] or solvated M(CO)3+ ions (M = Mn or Br) with (nBu4N)2[Mo2O7] in methanol, sometimes in the presence of triols of the type RC(CH2OH)3 (R = Me or CH2OH). Their molecular structures are related to those of previously described polyoxoalkoxomolybdates through the formal replacement of fac-MoO2(OR)+ units by topologically equivalent fac-M(CO)3+ units. Representative pairs of structurally related clusters include [Mo2O6(OMe)4-Re(CO)32]2- and [Mo4O10(OMe)6]2-, [Mo2O4MeC(CH2O)32Mn(CO)3]- and [Mo3O6(OMe)MeC(CH2O)32]-, [Mo2O4HOCH2C(CH2O)32Mn(CO)32] and [Mo4O8(OEt)2MeC(CH2O)32], [Mo6O16(OMe)2MeC(CH2O)32-Mn(CO)32]2- and [Mo8O20(OMe)4-MeC(CH2O)32]2-. Although the frameworks of the majority of derivatives are based on tetranuclear units which display the common rhomb-like structure, the alternative cubane-type arrangement is observed in [Mo2O5(OMe)5M(CO)32]-.     

Investigation of the reactivity of arylamines, organo-hydrazines and tolylisocyanate towards [PW12-xMxO40]n- Keggin anions

Reaction of K7[A,alpha-PW9Mo2O39] with Na2MoO4.2H2O in a mixture of water/dioxane/hydrochloric acid and further precipitation with (Bu4N)Br provided (Bu4N)3[A,alpha-PW9Mo3O40](3). Analogous reaction with K7-xNax[alpha-PW11O39] is an alternative to the synthesis of (Bu4N)3[alpha-PW11O39{MoVIO}]2. Multinuclear NMR and ESI mass spectrometry have been used to interpret the reaction of (Bu4N)x[alpha-PW11O39{ReO}](x=3 1; x=4 1I), (Bu4N)x[alpha-PW11O39{MoO}](x=3 2; x=4 2I) and (Bu4N)3[A,alpha-PW9Mo3O40]3 by organohydrazines, arylamines, tolylisocyanate and tetraphenylphosphine imide.     

Exploring the self-assembly of dumbbell-shaped polyoxometalate hybrids,from molecular building units to nanostructured soft materials

The formation of hierarchical nanostructures using preformed dumbbell-like species made of covalent organic–inorganic polyoxometalate (POM)-based hybrids is herein described. In this system, the presence of charged subunits (POM, metal linkers, and counter ions) in the complex molecular architecture can drive their aggregation, which results from a competition between the solvation energy of the discrete species and intermolecular electrostatic interactions. We show that the nature of the POM and the charge of the metal linker are key parameters for the hierarchical nanoorganization. The experimental findings were corroborated with a computational investigation combining DFT and molecular dynamics simulation methods, which outlines the importance of solvation of the counter ion and POM/counter ion association in the aggregation process. The dumbbell-like species can also form gels, in the presence of a poorer solvent, displaying similar nanoorganization of the aggregates. We show that starting from the designed molecular building units whose internal charges can be controlled by redox trigger we can achieve their implementation into soft nanostructured materials through the control of their supramolecular organization.

The formation of hierarchical nanostructures using supramolecular dumbbell-like species made of organic–inorganic polyoxometalate-based hybrids is investigated by combination of SAXS and computational methods.     

Coordination chemistry of the soluble metal oxide analogue [Mo5O13(OCH3)4(NO)]3- with manganese carbonyl species

The reactions of neutral or cationic manganese carbonyl species towards the oxo-nitrosyl complex [Na(MeOH)[Mo(5)O(13)(OCH(3))(4)(NO)]](2-) have been investigated in various conditions. This system provides an unique opportunity for probing the basic reactions involved in the preparation of solid oxide-supported heterogeneous catalysts, that is, mobility of transition-metal species at the surface and dissolution-precipitation of the support. Under nitrogen and in the dark, the reaction of in situ generated fac-[Mn(CO)(3)](+) species with (nBu(4)N)(2)[Na(MeOH)-[Mo(5)O(13)(OMe)(4)(NO)]] in MeOH yields (nBu(4)N)(2)[Mn(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]] at room temperature, while (nBu(4)N)(3)[Na[Mo(5)O(13)(OMe)(4)(NO)](2)[Mn(CO)(3)](2)] is obtained under reflux. The former transforms into the latter under reflux in methanol in the presence of sodium bromide; this involves the migration of the fac-[Mn(CO)(3)](+) moiety from a basal kappa(2)O coordination site to a lateral kappa(3)O site. Oxidation and decarbonylation of manganese carbonyl species as well as degradation of the oxonitrosyl starting material and reaggregation of oxo(methoxo)molybdenum fragments occur in non-deareated MeOH, and both (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(16)(OMe)(2)](2)[Mn(CO)(3)](2)] and (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(13)(OMe)(4)(NO)](2)] as well as (nBu(4)N)(2)[MnBr[Mo(5)O(13)(OMe)(4)(NO)]] have been obtained in this way. The rhenium analogue (nBu(4)N)(2)[Re(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]] has also been synthesized. The crystal structures of (nBu(4)N)(2)[Re(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]], (nBu(4)N)(3)[Na[Mo(5)O(13)(OMe)(4)(NO)](2)[Mn(CO)(3)](2)], (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(16)(OMe)(2)](2)[Mn(CO)(3)](2)], (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(13)(OMe)(4)(NO)](2)] and (nBu(4)N)(2)[MnBr[Mo(5)O(13)(OMe)(4)(NO)]] have been determined.     

New Perspectives in Polyoxometalate Chemistry by isolation of compounds containing very large moieties as transferable building blocks: (NMe4)5[As2Mo8V4AsO40] · 3H2O, (NH4)21[H3Mo57V6(NO)6O183(H2O)18] · 65 H2O, (NH2Me2)18(NH4)6[Mo57V6(NO)6O183(H2O)18] · 14 H2O,and (NH4)12[Mo36(NO)4O108(H2O)16] · 33 H2O

The compounds (NMe₄)₅[As₂Mo₈V₄AsO₄₀] · 3 H₂O 2a , (NH₄)₂₁[H₃Mo₅₇V₆(NO)₆O₁₈₃(H₂O)₁₈] · 65 H₂O 3a , (NH₂Me₂)₁₈(NH₄)₆[Mo₅₇V₆(NO)₆O₁₈₃(H₂O)₁₈] · 14 H₂O 3b and (NH₄)₁₂[Mo₃₆(NO)₄O₁₀₈(H₂O)₁₆] · 33 H₂O 4a ( 3a and 4a were not correctly reported in the literature regarding to their composition, structures and the oxidation states of the metal centres) which contain large isolated anionic species, have been prepared (among them 3a, 3b , and 4a in rather high yield) and characterized by complete crystal structure analysis as well as IR/Raman, UV/VIS/NIR, ESR spectroscopy and magnetic susceptibility measurements, redox titrations, bond valence sum calculations, elemental analyses and thermogravimetric studies. Perspectives for polyoxometalate chemistry referring to the synthesis of “extremely” large nanoscaled species are discussed, together with the occurrence of a large transferable {Mo₁₇} building block in the compounds 3a, 3b and 4a which also exists in the corresponding iron compound Na₃(NH₄)₁₂[H₁₅Mo₅₇Fe₆(NO)₆O₁₈₃(H₂O)₁₈] · 76 H₂O 7a .