Reversible Clustering of Gold Nanoparticles under Confinement

A limiting factor of solvent‐induced nanoparticle self‐assembly is the need for constant sample dilution in assembly/disassembly cycles. Changes in the nanoparticle concentration alter the kinetics of the subsequent assembly process, limiting optical signal recovery. Herein, we show that upon confining hydrophobic nanoparticles in permeable silica nanocapsules, the number of nanoparticles participating in cyclic aggregation remains constant despite bulk changes in solution, leading to highly reproducible plasmon band shifts at different solvent compositions.     

New aspects on the transuranics transfer in the Palomares marine environment

The environmental contamination of transuranics following the Palomares accident in 1966 (Southern Spain) has been continuous monitored on land and scientific programs are still running. The study of the land to sea transfer of the contamination started in 1986, focussed on the depositional history recorded in marine sediments. At the continental shelf, south of the mouth of the Almanzora river, enhanced levels of plutonium and americium were found which could be related to the accident. Additional analysis of marine sediments, collected far from the impact point, showed the presence of a hot particle. The study of the chronology of this sediment core and the isotopic ratios are given in this paper to assess the origin and pathway of the particle. The route of this particle was found to be the aerial transfer at the time of the accident.     

A C2 Fragment as Four‐Electron σ Donor

The formation and X‐ray structure analysis of the Pt^IV complex [(CH₂C{PPh₂C₆H₄}₂)PtI₂] is reported. The molecule possesses the orthometalated ligand (PPh₃)₂C→CH₂, which serves via its C₂ fragment as an unprecedented four‐electron σ donor.     

Modelling the soundscape quality of urban waterfronts by artificial neural networks

The renewal of the urban waterfronts has become a major focus of attention for politicians and decision makers in the city’s management programs. The recognition of the patterns that define the waterfronts’ identity is essential to select new strategies of intervention for the environmental recovery. In order to create adequate environments for everyday life within a sustainable development, new links between human senses, human perception and design need to be created. Within this wide approach, the landscape and the soundscape play a significant role and can become a key driving force in the implementation of the changes. New techniques have to be tested to identify the sonic and visual parameters capable to explain the specificity of a waterfront. With this purpose, an artificial neural network (ANN) was developed, and the relative importance of the input variables was evaluated. The collected database was also analysed by multiple linear regression (MLR) to compare the outcomes of both models. The urban waterfront of Naples (Italy) was chosen as case study. The results obtained show that the performance of the neural network is better than the one of the linear regression (rANN = 0.949, rMLR = 0.639). The interpretation of the relative importance method is also quite satisfactory in the ANN.     

New ruthenium(II) complexes with enantiomerically pure bis- and tris(pinene)-fused tridentate ligands. Synthesis, characterization and stereoisomeric analysis

A new set of Ru-Cl complexes containing either the pinene[5,6]bpea ligand (L1) or the C3 symmetric pinene[4,5]tpmOMe (L2) tridentate ligand in combination with the bidentate (B) 2,2'-bipyridine (bpy) or 1,2-diphenylphosphinoethane (dppe) with general formula [RuCl(L1 or L2)(B)](+) have been prepared and thoroughly characterized. In the solid state, X-ray diffraction analysis techniques have been used. In solution, cyclic voltammetry (CV) and 1D and 2D NMR spectroscopy have been employed. DFT calculations have been also performed on these complexes and their achiral analogues previously reported in our group, to interpret and complement experimental results. Whereas isomerically pure complexes ([Ru(II)Cl(L2)(bpy)](BF4), 5 and [Ru(II)Cl(L2)(dppe)](BF4), 6) are obtained when starting from the highly symmetric [Ru(III)Cl3(L2)], 2, isomeric mixtures of cis, fac-[Ru(II)Cl(L1)(bpy)](BF4) (3b/3b'), trans,fac- (3a) and up/down,mer- (3c, 3d) isomers are formed when bpy is added to the less symmetric [Ru(III)Cl3(L1)], 1, in contrast to the case of the bulky dppe ligand that, upon coordination to 1, leads to the trans,fac-[Ru(II)Cl(L1)(dppe)](BF4) (4a) complex as a sole isomer due to steric factors.     

Polymerized mixed aggregates containing gadolinium complex and CCK8 peptide

Two novel amphiphilic unimers containing an aliphatic hydrophobic chain (PDA) with two C≡C triple bonds and hydrophilic heads presenting the chelating agent DTPAGlu and the CCK8 bioactive peptide, respectively, have been prepared by solid phase synthesis. Aggregates obtained by mixing together PDA-DTPAGlu, or its Gd(III) complex, and PDA-L2-CCK8 in 70/30 molar ratio before and after a polymerization process carried out by UV irradiation have been structurally characterized by means of small angle neutron scattering. The relaxivity properties of aggregates containing Gadolinium complexes have also been investigated. Elongated mixed micelles have been observed, in which the relaxivity value r _1p for each Gadolinium complex, measured at 20 MHz and 298 K, is around 12 mM^–1 s^–1.