Search

Density functional theory methods were employed to clarify the adsorption/desorption behaviors of the thione-containing mercaptopurine and thioguanine drugs on the gold surface using both small Au 6 and Au 8 clusters as model reactants. Structural features, thermodynamic parameters, bonding characteristics, and electronic properties of the resulting complexes were investigated using the Perdew-Burke-Ernzerhof (PBE) and LC-BLYP functionals along with correlation-consistent basis sets, namely cc-pVDZ-PP for gold and cc-pVTZ for non-metals. Computed results show that the drug molecules tend to anchor on the gold cluster at the S atom with binding energies around -34 to -40 kcal/mol (in vacuum) and - 28 to -32 kcal/mol (in aqueous solution). As compared to Au 8 , Au 6 undergoes a shorter recovery time and a larger change of energy gap that could be converted to an electrical signal for selective detection of the drugs. Furthermore, interactions between the drugs and gold clusters are reversible processes and a drug release mechanism was also proposed. Accordingly, the drugs are able to separate from the gold surface due to either a slight change of pH in tumor cells or the presence of cysteine residues in protein matrices., (© 2020 Wiley Periodicals, Inc.)

Density functional theory (DFT) calculations are employed to examine the adsorption behaviors of cysteine on the gold surface using Au 6 and Au 8 species as model reactants. Computed results show that cysteine molecules prefer to bind with gold clusters via the S-atom of the thiol group in vacuum and thiolate group in water. The gas-phase adsorption energies are around 20.2 kcal/mol for Au 6 and 24.4 kcal/mol for Au 8 . In water environment, such values are slightly reduced for Au 6 (19.6 kcal/mol), but increased a little more for Au 8 (25.6 kcal/mol). As a result, if a visible light with a frequency of ν ≈ 6 × 10 14  Hz (500 nm) is applied, the time for the recovery of Au 6 and Au 8 from the most stable complexes will be about 0.38 and 9.3 × 10 3  s, respectively, at 298 K in water. The Au 6 is in addition found to benefit from a larger change of energy gap that could be converted to an electrical signal for detection of cysteine.

The transition point from a two-dimensional (2D) to a three-dimensional (3D) structure in a series of small gold clusters remains a topic of continuing debate. In the present study, coupled-cluster CCSD(T) and DFT calculations are performed to re-examine the relative energies of several low-lying isomers of Au12, aiming to shed new light on this issue. At odds with many previous reports on the preference of a planar di-capped elongated-hexagon structure, the Au12 size is found to energetically prefer a globular cup-like form with C2v symmetry. While DFT results are not able to assign the most stable form of Au12 as the relative energies between the lowest-lying isomers are strongly functional-dependent, coupled-cluster theory calculations point out the preference of a 3D structure for having a D3h symmetry. Such a prediction is further supported by a comparison of the vibrational spectra computed using the revTPSS density functional with the available experimental infrared ones that were previously recorded from the far-IR multiple photon dissociation (FIR-MPD) experiment. [ABSTRACT FROM AUTHOR]

The Au17 gold cluster was experimentally produced in the gas phase and characterized by its vibrational spectrum recorded using far-IR multiple photon dissociation (FIR-MPD) of Au17Kr. DFT and coupled-cluster theory PNO-LCCSD(T)-F12 computations reveal that, at odds with most previous reports, Au17 prefers two star-like forms derived from a pentaprism added by two extra Au atoms on both top and bottom surfaces of the pentaprism, along with five other Au atoms each attached on a lateral face. A good agreement between calculated and FIR-MPD spectra indicates a predominant presence of these star-like isomers. Stabilization of a star form arises from strong orbital interactions of an Au12 core with a five-Au-atom string. [ABSTRACT FROM AUTHOR]