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Org Lett ; 21(24): 10102-10105, 2019 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-31804842


We report the synthesis of novel polycatenar dibenzopentacenequinones 1 and 2 that are designed to form columnar liquid crystalline phases. The mesomorphic properties of these compounds were investigated by polarized optical microscopy, differential scanning calorimetry, and powder X-ray diffraction. While compound 1 exhibits two distinct columnar mesophases between 148 and 177 °C, fluorinated 2 exhibits a columnar mesophase from 121 to 336 °C. This dramatic stabilization of the columnar mesophase of 2 can be attributed to improved π-stacking as a result of arene-perfluoroarene interactions.

J Phys Chem Lett ; 10(3): 685-692, 2019 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-30681851


Gold nanoclusters have been the focus of numerous computational studies, but an atomistic understanding of their structural and dynamical properties at finite temperature is far from satisfactory. To address this deficiency, we investigate gold nanoclusters via ab initio molecular dynamics, in a range of sizes where a core-shell morphology is observed. We analyze their structure and dynamics using state-of-the-art techniques, including unsupervised machine-learning nonlinear dimensionality reduction (sketch-map) for describing the similarities and differences among the range of sampled configurations. In the examined temperature range between 300 and 600 K, we find that whereas the gold nanoclusters exhibit continuous structural rearrangement, they are not amorphous. Instead, they clearly show persistent motifs: a cationic core of 1-5 atoms is loosely bound to a shell which typically displays a substructure resulting from the competition between locally spherical versus planar fragments. Besides illuminating the properties of core-shell gold nanoclusters, the present study proposes a set of useful tools for understanding their nature in operando.

J Am Chem Soc ; 136(51): 17757-61, 2014 Dec 24.
Artigo em Inglês | MEDLINE | ID: mdl-25453899


We establish helical gold nanorods as the first examples of chiral recognition nanostructures by examining the simple chiral molecule CClHDT adsorbed on the helical Au40 nanorod. We calculate the vibrational circular dichroism (VCD) spectra of the R and S enantiomers of CClHDT adsorbed on the R (or S) enantiomer of Au40 using relativistic density functional theory. The highest adsorption energy is found when the Cl atom of CClHDT binds to a low-coordinated Au atom at the edge of Au40. There are three adsorption modes (essentially identical in energy) corresponding to three orientations of the HDT moiety. We show that, for each adsorption mode, the VCD spectra are distinctly different for the Au40(R)-ClHDT(R) and Au40(R)-CClHDT(S) complexes, and we give a qualitative explanation for this based on the principle of chirality transfer. For comparison with the results for Au40, we calculate the VCD spectra of the R and S enantiomers of CClHDT adsorbed on the achiral Au20 tetrahedral cluster. Again, there are three adsorption modes (essentially identical in energy) corresponding to three orientations of the HDT moiety. However, we show that, for each adsorption mode, the VCD spectra are mirror symmetric but otherwise essentially identical for the Au20-CClHDT(R) and Au20-CClHDT(S) complexes. Thus, the inherent chirality of the helical Au40 nanorod is essential for its chiral recognition functionality.

J Phys Chem A ; 118(30): 5667-79, 2014 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-25007345


Aromatic organoarsenicals, such as p-arsanilic acid (pAsA), are still used today as feed additives in the poultry and swine industries in developing countries. Through the application of contaminated litter as a fertilizer, these compounds enter the environment and interact with reactive soil components such as iron and aluminum oxides. Little is known about these surface interactions at the molecular level. We report density functional theory (DFT) calculations on the energies, optimal geometries, and vibrational frequencies for hydrated pAsA/iron oxide complexes, as well as changes in Gibbs free energy, enthalpy, and entropy for various types of ligand exchange reactions leading to both inner- and outer-sphere complexes. Similar calculations using arsenate are also shown for comparison, along with activation barriers and transition state geometries between inner-sphere complexes. Minimum energy calculations show that the formation of inner- and outer-sphere pAsA/iron oxide complexes is thermodynamically favorable, with the monodentate mononuclear complexes being the most favorable. Interatomic As-Fe distances are calculated to be between 3.3 and 3.5 Å for inner-sphere complexes and between 5.2 and 5.6 Å for outer-sphere complexes. In addition, transition state calculations show that activation energies greater than 23 kJ/mol are required to form the bidentate binuclear pAsA/iron oxide complexes, and that formation of arsenate bidentate binuclear complexes is thermodynamically -rather than kinetically- driven. Desorption thermodynamics using phosphate ions show that reactions are most favorable using HPO4(2-) species. The significance of our results for the overall surface complexation mechanism of pAsA and arsenate is discussed.

Ácido Arsanílico/química , Compostos Férricos/química , Modelos Químicos , Água/química , Arseniatos/química , Simulação por Computador , Entropia , Concentração de Íons de Hidrogênio , Íons/química , Cinética , Fosfatos/química , Termodinâmica , Vibração
Environ Sci Pollut Res Int ; 21(13): 8052-8, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24659456


This study examines gaseous chlorinated species generated from the reaction of sulfur dioxide (SO2) with sodium chlorite powder (NaClO2(s)) to obtain insight into the propensity of this process to enhance NO and Hg° oxidation. A packed bed reactor containing NaClO2(s) was used and the reaction temperature was set to 130 °C. Initially, we determined that the presence of SO2 enhances the oxidation of NO and Hg° by reaction with NaClO2(s). We then introduced NO2 into the gas mixture as a radical scavenger and determined that the chlorinated species generated by the reaction of SO2 with NaClO2(s) are OClO, Cl, ClO, and Cl2. Based on these results, we suggest that such gaseous chlorinated ones are responsible for the enhancement of NO and Hg° oxidation.

Cloretos/química , Compostos Clorados/síntese química , Dióxido de Enxofre/química , Mercúrio/química , Óxido Nítrico/química , Oxirredução
J Phys Chem A ; 113(4): 644-52, 2009 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-19123912


An examination of strong hydrogen bonds found in (ROH)(n)...FHF(-) clusters (n = 1 and 2; R = H, CH(3), C(2)H(5)) is presented. Excellent agreement is observed between thermochemical values obtained from high-pressure mass spectrometric measurements and those predicted from MP2(full)/6-311++G(d,p)//B3LYP/6-311++G(d,p) calculations. Calculated structures are examined, and insight into the geometric nature of the bonding for these systems is obtained. In the case of water binding to FHF(-), it was found that the large entropic advantage of one particular structure, which was not the most enthalpically favored, was significant enough to make it the predominant species within the ion source. In the case of methanol solvation, no evidence of secondary interaction of the methyl group and any other moiety could be found. The structural details revealed from calculations of the ethanol-solvated clusters indicate that secondary interactions between the terminal methyl group and FHF(-) have an impact on the length of the FHF and OHF bonds.

Álcoois/química , Flúor/química , Hidrogênio/química , Pressão , Teoria Quântica , Água/química , Gases/química , Ligação de Hidrogênio , Espectrometria de Massas , Modelos Moleculares , Conformação Molecular , Solventes/química , Temperatura