Ricerc@Sapienza

An analysis of the complex proton transfer processes in certain protic ionic liquids, based on amino acid anions, has been carried out through ab initio molecular dynamics in the view of finding naturally conductive and pure mediums. The systems analyzed here might serve as chemical prototypes for pure and dry ionic liquids where mobile protons can act as fast charge carriers. We have exploited the natural tendency of these liquids to form a complex network of hydrogen bonds.

The gas-phase structure of protonated β-methylaminoalanine was investigated using infrared multiple photon dissociation spectroscopy in the C-H, N-H, O-H stretching region (2700-3800 cm-1) and the fingerprint region (1000-1900 cm-1). Calculations using density functional theory methods show that the lowest energy structures prefer protonation of the secondary amine. Formation of hydrogen bonds between the primary and secondary amine, and the secondary amine and carboxylic oxygen further stabilize the lowest energy structure.

We present a computational analysis of the complex proton-transfer processes in two protic ionic liquids based on phosphorylated amino acid anions. The structure and the short time dynamics have been analyzed via ab initio and semi-empirical molecular dynamics. Given the presence of mobile protons on the side chain, such ionic liquids may represent a viable prototype of highly conductive ionic mediums. The results of our simulations are not entirely satisfactory in this respect.

We present a study by energy-dispersive X-ray diffraction of liquid 2-(2-hydroxyethoxy)ethan-1-ammonium nitrate, NH3CH2CH2(OCH2CH2OH)+NO3- (22HHEAN). This ionic liquid is derived from the parent ethylammonium nitrate (EAN) with an ether link in the chain and a hydroxyl group in the terminal position. The absence of peaks at low-q values in the experimental diffraction curve indicates that the added polar groups and the high conformational isomerism of the cations alter strongly the nanosegregation of the parent EAN liquid.

We explore the structure of two ionic liquids based on the choline cation and the monoanion
of the maleic acid. We consider two isomers of the anion (H-maleate, the cis-isomer and H-fumarate,
the trans-isomer) having different physical chemical properties. H-maleate assumes a closed structure
and forms a strong intramolecular hydrogen bond whereas H-fumarate has an open structure.
X-ray diffraction, infrared and Raman spectroscopy and molecular dynamics have been used

A synergic approach combining molecular dynamics (MD) simulations and X-ray absorption spectroscopy (XAS) has been used to investigate diluted (0.1 M) aqueous solutions of two lanthanide ions (Ln3+), namely, La3+ and Dy3+, with triflate, nitrate, and bis(trifluoromethylsulfonyl)imide (Tf2N-) as counterions. The different complexing ability of the three anions has been highlighted by the analysis of the MD simulations: Tf2N- does not form inner-sphere complexes, while a small amount of triflate coordinates both the La3+ and Dy3+ cations in their first solvation shell.

A synergic approach combining molecular dynamics (MD) simulations and X-ray absorption spectroscopy has been used to investigate diluted solutions of zinc bis(trifluoromethanesulfonyl)imide (Zn(Tf2N)2) in Tf2N- based ionic liquids (ILs) having different organic cations, namely the 1-butyl-3-methylimidazolium ([C4(mim)]+), 1,8-bis(3-methylimidazolium-1-yl)octane ([C8(mim)2]2+), N,N,N-trimethyl-N-(2-hydroxyethyl)ammonium ([Choline]+) and butyltrimethylammonium ([BTMA]+) ions.

Anthracyclines self-assemble in water into dimers. In the presence of sufficiently high salt (NaCl) concentrations, solutions of the antibiotic doxorubicin, but not those of the closely related molecules daunomycin and epirubicin, turn into gels barely compatible with the presence of small oligomers. The use of spectroscopic, scattering, imaging and computational techniques, allowed light to be shed on the self-assembly process that triggered doxorubicin gelification.

The self-association equilibria of doxorubicin hydrochloride (DX), at high drug and NaCl concentrations, are studied by temperature scan fluorescence spectroscopy, with the support of molecular dynamics (MD) calculations. Even though all anthracyclines show dimerization equilibria, DX only can further associate into long polymeric chains according to DXmon ⇄ DXdim ⇄ DXpol. This is reflected not only in the mechanical properties of DXpol solutions (behaving as thixotropic gels) but also in their spectroscopic behaviour.

The structural and dynamic properties of the Ba2+ cation in water have been studied by combining quantum mechanical (QM) calculations, molecular dynamics (MD) simulations, and extended X-ray absorption fine structure (EXAFS) spectroscopy. An effective Ba2+-water interaction potential, to be used in the MD simulation of a Ba2+ aqueous solution, has been developed by means of QM methods, and the validity of the whole procedure has been assessed by comparing the theoretical structural results with the EXAFS experimental data.