Metallofullerenes as potential candidates for the explanation of astrophysical phenomena.

Detection of complex organic species in space has been one of the biggest challenges of the astrophysical community since the beginning of space exploration, with C60-fullerene representing one of the largest molecules so far detected. The presence of small metal-containing organic molecules, like MgNC or CaCN, in space, promoted the idea that C60 may also interact with metals and form metallofullerenes based on the fact that in certain circumstellar and interstellar environments, the ingredients for the formation of metallofullerenes, i.e., metal and fullerenes, are abundant. In this perspective, we summarized the current effort to explore the presence of metallofullerenes in space, which started soon after the discovery of fullerenes about 40 years ago. Several implications of astrophysical phenomena were briefly discussed and shown to be addressable as the possible consequence of metallofullerenes' presence. We highlighted the spectral fingerprints that might be followed to achieve the future detection of cosmic metallofullerenes from a combined effort of laboratory and quantum chemical calculations. These results are expected to gain great importance with the James Webb Space Telescope (JWST), whose capability of unprecedented high sensitivity and high spectral resolution in the far- to mid-infrared range could aid the unequivocal detection of metallofullerenes in space.

Synergy Effects in Heavy Metal Ion Chelation with Aryl- and Aroyl-Substituted Thiourea Derivatives.

Detection and removal of metal ion contaminants have attracted great interest due to the health risks that they represent for humans and wildlife. Among the proposed compounds developed for these purposes, thiourea derivatives have been shown as quite efficient chelating agents of metal cations and have been proposed for heavy metal ion removal and for components of high-selectivity sensors. Understanding the nature of metal-ionophore activity for these compounds is thus of high relevance. We present a theoretical study on the interaction between substituted thioureas and metal cations, namely, Cd2+, Hg2+, and Pb2+. Two substituent groups have been chosen: 2-furoyl and m-trifluoromethylphenyl. Combining density functional theory simulations with wave function analysis techniques, we study the nature of the metal-thiourea interaction and characterize the bonding properties. Here, it is shown how the N,N'-disubstituted derivative has a strong affinity for Hg2+, through cation-hydrogen interactions, due to its greater oxidizing capacity.

Density functional theory simulation of the adsorption of sulphur multilayers on Au(100).

The adsorption of sulphur multilayers on Au(100) has been studied using density functional theory (DFT) within the generalized gradient approximation (GGA). The first sulphur layer was adsorbed on the four-fold sites of the unreconstructed Au(100) surface forming a lattice. The experimental parameters of the lattice were reproduced taking into account the surface expansion of the topmost Au(100) layer. This expansion should occur when gold islands are formed after the lifting of hex-reconstruction, which allows the lateral movement of the gold atoms. The second sulphur layer, on top of the lattice, consisted of eight S atoms (octomer phase) in a quasi-rectangular arrangement. The structural optimization of the octomer phase was achieved in a specific spatial orientation with respect to the lattice. The analysis of Bader atomic charges and the projected density of states (PDOS) demonstrated that charge transfer from the Au(100) surface to the sulphur layers, sulphur chemisorption and sulphur-sulphur inter-layer mixing of electronic states control the formation of sulphur multilayers.