Anticancer, biophysical and computational investigations of half-sandwich ruthenium(II) thiosemicarbazone complexes: The effect of arene versus thiacrown face-cap

A series of half-sandwich ruthenium complexes, two containing an arene face-cap and the other a thiacrown ether face-cap were synthesized to investigate the necessity of the arene for anticancer activity in this class of compounds. The complexes are formulated as [(h6-p-cymene)Ru(dmabTSC)Cl]PF6, [(h6-benzene)Ru(dmabTSC)Cl]PF6 (arene complexes), and [([9]aneS3(dmabTSC)Cl]PF6 (dmabTSC = dimethylaminobenzaldehye thiosemicarbazone). It was observed that none of the complexes showed good anticancer activity in vitro against HCT-116 and Caco-2 (colon adenocarcinoma) cells. All three complexes can bind strongly to calf-thymus DNA with binding constants on the order of 105 M-1. In addition they all bind strongly to human serum albumin with binding constants between 105 and 106 M. There appears to be a single binding site on the protein for these complexes. A computational investigation of these complexes and their hydrolysis products was carried out by molecular docking with DNA and topoisomerase II. From this analysis it is noted that the type of face-capping ligand had different effects on the two macromolecules. It is therefore noted that the knowledge gained from this study will be useful in identifying the type of complexes in this class that show useful metallodrug potential

Quantitative analyses of enhanced thermoelectric properties of modulation-doped PEDOT:PSS/undoped Si (001) nanoscale heterostructures

Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) has high electrical conductivity (∼10³ S cm⁻¹) but it exhibits a low Seebeck coefficient (<15 μV K⁻¹), resulting in a low power factor. Mixing PEDOT:PSS with nanostructured semiconductors can enhance the Seebeck coefficient and achieve an improved thermoelectric power factor. However, underlying mechanisms for those composite thermoelectric systems are scarcely understood so far. In this study, quantitative analyses on the electrical conductivity and Seebeck coefficient for the heterostructures of nanometer-thick PEDOT:PSS on single-crystal Si (001) on sapphire (SOS) are reported. The heterostructures have larger Seebeck coefficients up to 7.3 fold and power factors up to 17.5 fold relative to PEDOT:PSS. The electrical conductivity increased with decreasing combined thicknesses of PEDOT:PSS and Si, and the Seebeck coefficient increased with decreasing PEDOT:PSS thickness, which can be attributed to modulation doping caused by diffusion of holes from PEDOT:PSS into undoped Si. This hypothesis is supported by simulation per band alignment. The valence band offset between Si and PEDOT:PSS dominantly controls the electrical conductivity and Seebeck coefficient of the heterostructures. This study not only suggests mechanistic insights to increase the power factors of PEDOT:PSS-based composites but also opens the door for new strategies to enhance the thermoelectric efficiencies of heterostructured nanocomposite materials