Modification of the catalytic properties of the Au4 nanocluster for the conversion of methane-to-methanol: synergistic effects of metallic adatoms and a defective graphene support.

Decorating graphene with nano-clusters offers potential for a wide range of industrial applications. For catalysis, embedding precisely controlled mono- and bimetallic nanoclusters into graphene can greatly increase their catalytic activities, especially for oxidation reactions. The catalytic performance of a gold nanocluster can be modified dramatically by changing its electronic properties. The results of this work demonstrate by means of DFT calculations that by strategic doping and promotion from the support material the catalytic activity improvement of a gold-based catalyst for the partial oxidation reaction of methane can be drastically enhanced. The transition metal-mediated catalysis is significantly affected by the two spin-state reactivities over them. The investigated catalytic processes consist of N2O decomposition and methane hydroxylation over three subnanoclusters (Au5, Au4Pd, and Au4Pt) deposited on a single vacancy graphene support. It was found that graphene acts not only as a support but also supports the catalysis through charge transfer between the subnanocluster and graphene. Graphene-supported Au4Pd exhibits enhanced catalytic activity for both steps of methane-to-methanol conversion, whereas the supported Au5 is good for N2O decomposition but ineffective for methane hydroxylation, mainly due to the involvement of a very stable intermediate (methyl-hydroxo-grafted nanocluster). The activation energies for N2O decomposition, C-H bond activation and methanol formation over the supported Au4Pd cluster are 13.8, 15.7, and 24.9 kcal mol(-1), respectively. Without the graphene support, the catalytic trend is reversed and Au4Pd becomes an inert cluster for these reactions.

Gas sensing properties of platinum derivatives of single-walled carbon nanotubes: A DFT analysis.

The limitations of intrinsic carbon nanotube (CNT) based devices to examine toxic gases motivate us to investigate novel sensors which can possibly overcome sensitivity problems. Pt-CNT assemblies (with Pt deposited externally as well as internally Pt-doped ones) interacting with NO(2) and NH(3) are studied and compared with unmodified CNTs. DFT calculations show that Pt can enhance adsorption and charge transfer processes to a very large degree. Incoming gas molecules cause changes in the electronic structure and charge distribution of the Pt-substituted CNTs that are both larger and more far-reaching than in their unmodified counterparts. Their relatively high stability is unaffected by the complexation with NO(2) and NH(3). CNTs with defective surface were also investigated. The sensing performance of Pt-doped CNT is found to be superior to defected CNTs.

Structure and electronic properties of "DNA-gold-nanotube" systems: a quantum chemical analysis.

The development of novel DNA sensors is a crucial issue in the diagnosis of pathogenic and genetic diseases. We have used density functional theory (DFT) to investigate the performance of hybrid DNA sensors consisting of a gold atom (Au) deposited on two types of single-walled carbon nanotubes: armchair SWCNT(8,0)/Au and zigzag SWCNT(5,5)/Au and compared these with bare Au. We also chose adenine:thymine (A:T) as a Watson-Crick base pair of the DNA double helix. In the recognition probe, SWCNT/Au/A, adenine is immobilized on the SWCNT/Au supporter via its active N7 anchor point. After thymine hybridization (SWCNT/Au/A:T), the overall modulations compared with the original systems. Due to the complimentary functions of gold, which acts as a powerful electron withdrawing and transmitting group and of the SWNCTs, which act as electron collecting centers, respectively, the hybrid systems, "SWNCTs/Au", were found to exhibit more stability and sensitivity than the Au center alone. The changes in the HOMO-LUMO band gaps and in the atomic partial charges upon binding of thymine were rather small, but the change of the overall dipole moment was considerably larger in SWCNT/Au/A than it was in Au/A alone. The overall results suggest that the "SWCNTs/gold" system is a potential candidate for a nanostructure-based DNA sensor.

Quantitative structure-activity relationships and comparative molecular field analysis of TIBO derivatised HIV-1 reverse transcriptase inhibitors.

Quantitative structure-activity relationships (QSAR) and Comparative Molecular Field Analysis (CoMFA) have been applied in order to explain the structural requirements of HIV-1 reverse transcriptase (HIV-1 RT) inhibitory activity of TIBO derivatives on the MT-4 cells. The best QSAR model is satisfactory in both statistical significance and predictive ability. The derived structural descriptors indicate the importance of electronic contributions toward the HIV-1 RT inhibition of this class of compounds. However, it could not reveal any hydrophobic influence because of high collinearity between C2 and log P variables. In order to cope with steric interaction in the correlation, 3D-QSAR was performed using CoMFA. The obtained CoMFA model shows high predictive ability, rcv2 = 0.771, and clearly demonstrates its potential in the steric feature of the molecules through contour maps, explaining a majority (81.8%) of the variance in the data. Consequently, these results can be useful in identifying the structural requirements of TIBO derivatives and helpful for better understanding the HIV-1 RT inhibition. Eventually, they provide a beneficial basis to design new and more potent inhibitors of HIV-1 RT.

Structure-activity correlation study of HIV-1 inhibitors: electronic and molecular parameters.

Quantitative structure-activity relationships (QSARs) for 40 HIV-1 inhibitors, 1-[(2-hydroxyethoxy)-methyl]-6-(phenylthio)thymine and its derivatives, were studied. Fully optimized geometries, based on the semiempirical AMl method, were used to calculate electronic and molecular properties of all compounds. In order to examine the relation between biological activities and structural properties, multiple linear regression models were employed. A suitable QSAR model was obtained, showing not only statistical significance, but also predictive ability. The significant molecular descriptors used were atomic charges of two substituted carbon atoms in the thymine ring, hydration energies and molar refractivities of the molecules. These descriptors allowed a physical explanation of electronic and molecular properties contributing to HIV-1 inhibitory potency.