Publications

Abstract Aromaticity is of continuing interest to the organic chemical community. We recently presented a model for the aromaticity of carbocyclic and heterocyclic derivatives of indane and indene, i.e. species defined as benzenes fused to 5-membered rings. The current note extends this model to related derivatives of tetralin and naphthalene, benzenes fused to 6-membered rings. Explicit species discussed herein are: benzopyran, both alpha- and beta-tetralone, coumarin and quinoline.

Abstract One of the major mysteries regarding firefly bioluminescence is its pH-dependent multicolor variation. At basic pH, the emission is on the yellow-green region, whereas at acid pH, the light emission is observed on the red region of the visible spectrum. Theoretical calculations using density functional theory, molecular mechanics, and semiempirical methods were made to investigate the effect exerted by intermolecular forces on light emission, and their modulation by polarity, and the differences in the conformation of the active site at basic and acid pH. Red emission is achieved by the weakening of the interactions of the emitter with ionic and hydrophobic molecules, by the polarization of the benzothiazole microenvironment, by ionization of the enzyme-emitter complex and by changes of the hydrogen bond network. Arg220, Glu346, Ala350, Leu344 and adenosine-5'-monophosphate have blue-shifting effects, while His247, Phe249, Gly341, Thr253, and Ile288 exert a redshifting one. (C) 2011 Wiley Periodicals, Inc. J Comput Chem 32: 2654-2663, 2011

Abstract In this paper, the first, second and mean (N-O) bond dissociation enthalpies (BDEs) were derived from the standard (p degrees = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, Delta H-r degrees(m)(g), at T = 298.15 K, of 2,2'-dipyridil N-oxide and 2,2'-dipyridil N,N'-dioxide. These values were calculated from experimental thermodynamic parameters, namely from the standard (p degrees = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, Delta H-f degrees(m)(cr), at T = 298.15 K, obtained from the standard molar enthalpies of combustion, Delta H-c degrees(m), measured by static bomb combustion calorimetry, and from the standard molar enthalpies of sublimation, at T = 298.15 K, determined from Knudsen mass-loss effusion method.

Abstract A study on the molecular structure and energetics of 10,11-dihydro-5H-dibenzo[a,d]cycloheptene (dibenzosuberane) was performed combining experimental calorimetric techniques and high level computational calculations. In the experimental work, the solid phase standard (p degrees = 0.1 MPa) molar enthalpy of formation of 10,11-dihydro-5H-dibenzo[a,d]cycloheptene was derived from its standard massic energy of combustion, at T = 298.15 K, measured by static bomb combustion calorimetry, in oxygen. The respective standard molar enthalpy of sublimation, at T = 298.15 K, was measured by Calvet microcalorimetry enabling the calculation of the standard molar enthalpy of formation (161.4 +/- 3.7) kJ . mol(-1), in the gaseous phase, at T = 298.15 K. In addition, computational calculations were performed using the density functional theory with the B3LYP hybrid functional and extended basis sets in order to obtain the molecular structure of 10,11-dihydro-5H-dibenzo[a,d]cycloheptene and that of related molecules. Estimates of the standard molar enthalpy of formation, in the gaseous phase, at T = 298.15 K, for 10,11-dihydro-5H-dibenzo[a,d]cycloheptene were performed using three different methods: G3(MP2)//B3LYP, MC3BB, and MC3MPW and appropriate homodesmic reactions. Computational estimates are in very good agreement with the experimental value.

Abstract The present work reports an experimental and computational study of the energetics of 1,2-benzisothiazol-3(2H)-one and 1,4-benzothiazin-3(2H, 4H)-one. The standard (p degrees = 0.1 MPa) massic energy of combustion, at T = 298.15K, of each compound was measured by rotating bomb combustion calorimetry, in oxygen that allowed the calculation of the respective standard molar enthalpy of formation, in the condensed phase, at T = 298.15 K. The standard molar enthalpies of sublimation, at T = 298.15 K, were measured by high-temperature Calvet microcalorimetry. From the combination of data obtained by both techniques we have calculated the standard molar enthalpies of formation, in the gaseous phase, at T =298.15 K. In addition, computational calculations were carried using the density functional theory with the B3LYP functional and the 6-31G* basis set and some correlations between structure and energetics were obtained for the keto and enol forms of both compounds. Using the G3(MP2)//B3LYP composite method and various appropriate reactions, the standard molar enthalpies of formation of 1,2-benzisothiazol-3(2H)-one and 1,4-benzothiazin-3(2H, 4H)-one, at T = 298.15 K. were computationally derived and compared with the experimental data. The aromaticity of 1,2-benzisothiazol-3(2H)-one, 1,4-benzothiazin-3(2H, 4H)-one and that of some related species was evaluated by analysis of nucleus independent chemical shifts (NICS).

Abstract In this work, we have determined the experimental standard (p degrees = 0.1 MPa) molar enthalpies of formation, in the gas phase, of 2,6-dimethy1-4-pyrone -(261.5 +/- 2.6) kJ . mol(-1) and 2-ethy1-3-hydroxy-4-pyrone -(420.9 +/- 2.8) kJ . mol(-1). These values were obtained by combining the standard molar enthalpy of formation in the condensed phase, derived from combustion experiments in oxygen, at T = 298.15 K, in a static bomb calorimeter, with the standard molar enthalpy of sublimation, at T = 298.15 K, obtained by Calvet microcalorimetry. Additionally, high-level density functional theory calculations using the B3LYP hybrid exchange-correlation energy functional with extended basis sets have been performed for these two compounds. Good agreement was obtained between the experimental and computational results. Using the same methodology, we calculated the standard molar enthalpy of formation of gaseous 2-methyl-3-hydroxy-4-pyrone.

Abstract The standard (p(o) = 0.1 MPa) molar energy of combustion in oxygen, at T = 298.15 K, of 7-hydroxycoumarin was measured by static bomb calorimetry. The value of the standard molar enthalpy of sublimation was obtained by Calvet microcalorimetry and corrected to T = 298.15 K. Combining these results, the standard molar enthalpy of formation of the compound, in the gas phase, at T = 29815 K, has been calculated, -(337.5 +/- 2.3) kJ.mol(-1). The values for the temperature of fusion, T(fusion), and for the fusion enthalpy, at T = T(fusion), are also reported. Additionally, high-level density functional theory calculations using the B3LYP hybrid exchange-correlation energy functional with extended basis sets, the MC3BB and MC3MPW methods and more accurate correlated computational techniques of the MCCM suite have been performed for the compound. The agreement between experiment and theory gives confidence to estimate the enthalpy of formation of the remaining hydroxycoumarins substituted in the benzene ring.

Abstract In this paper we report the standard (p degrees = 0.1 MPa) molar enthalpy of formation of quinazoline-2,4(1H,3H)-dione, in the gaseous phase, at T = 298.15 K, which was derived from a combined experimental and computational thermochemical work. The static bomb combustion calorimetry technique was used to determine the standard massic energy of combustion and consequently the standard molar enthalpy of formation, in the crystalline phase, at T = 298.15 K, and the Calvet microcalorimetry technique was employed to determine the standard molar enthalpy of sublimation, at T = 298.15 K. The obtained standard molar enthalpy of formation, in the gaseous phase, at T = 298.15 K, was: Delta(f)H(m)degrees(g) = (271.1 +/- 3.3) kJ . mol(-1). In addition, quantum chemical calculations were performed using the G3(MP2)//B3LYP composite method to assess the relative energetic stabilities of quinazoline-2,4(1H,3H)-dione and its tautomers (4-hydroxyquinazolin-2(1H)-one, 2-hydroxyquinazolin-4(1H)-one, 2-hydroxyquinazolin-4(3H)-one, and quinazolin-2,4-diol). Estimates of the standard molar enthalpy of formation, in the gaseous phase, of the most stable tautomer, quinazoline-2,4(1H,3H)dione, at T = 298.15 K, were obtained from the G3(MP2)//B3LYP calculations using appropriate isodesmic reactions and were further compared with the obtained experimental value. The aromaticity of quinazoline-2,4(1H,3H)-dione has also been assessed through the evaluation and analysis of the Nucleus Independent Chemical Shifts (NICS) and their most significant components for the benzene and pyrimidine rings.

Abstract A novel multi layer film containing a cationic phosphonium-derivatized Ni(salen)-type complex and poly(sodium-4-styrenesulfonate (NaPSS) was assembled onto quartz, mica, and metal surfaces using the layer-by-layer (LbL) technique. Spectroscopic (UV-vis) and gravimetric (QCM) responses for the multilayer films show regular stepwise growth and the signature of strong electrostatic interactions between the component layers. The gravimetric responses indicate the presence of substantial additional (net neutral) material in the PSS layers, which X PS shows is not polyelectrolyte or salt, so charge compensation is intrinsic; we deduce the presence of space-filling solvent. Direct electrostatic interaction of the two-component layers is enhanced by a secondary noncovalent interaction between the delocalized pi-systems of the two components. Permeability of the film to the redox probe [Fe(CN)(6)](3-/4-) was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Qualitatively similar results were obtained in the absence and presence of a precursor PSS/PAH multilayer, but with a general shift in kinetic and diffusional processes to longer time scales (lower frequencies) in the presence of the precursor layer and with increasing numbers of PSS/[Ni(salen)] bilayers. Quantitatively, the EIS data were interpreted using a capillary membrane model (CMM) to yield values of coverage, apparent charge transfer resistance, double-layer capacitance, pore size, and diffusion coefficient. The coverage values were consistent with a model in which there are no preferential growth sites and the surface charge density is independent of the number of bilayers.