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81.
Ultrafast transient absorption spectroscopy was used to study the conformational relaxation dynamics of 1,3,5-cis-hexatriene (Z-HT) produced in the photochemical ring-opening reaction of 1,3-cyclohexadiene (CHD) in methanol and n-propanol solvents. The results are compared with earlier investigations performed using cyclohexane and hexadecane solvents [Anderson, N. A.; Pullen, S. H.; Walker II, L. A.; Shiang, J. J.; Sension, R. J.; J. Phys. Chem. A 1998, 102, 10588-10598.]. The conformational relaxation between hot cZc-HT, cZt-HT, and tZt-HT, where the labels c and t designate cis and trans configurations about the single bonds, is much faster in alcohol solvents than in alkane solvents. The hot Z-HT produced in the photochemical ring-opening reaction evolves from the conformationally strained cZc-HT form to the more stable cZt-HT form on a time scale of 2 ps in alcohols compared with 6 ps in alkanes. The overall decay of the internal vibrational temperature of the hot Z-HT is faster in alcohols (5-6 ps) than alkanes (12-20 ps) and is weakly dependent on the specific alcohol or alkane solvent. A small population of cZt-HT (5-10%) is trapped as the solute equilibrates with the surrounding solvent following UV excitation of CHD or direct UV excitation of Z-HT. The influence of solvent on conformational relaxation of Z-HT was investigated further by probing the temperature dependence of the decay of this thermally equilibrated cZt-HT population. The apparent barrier for the cZt --> tZt conformational isomerization is lower in alcohols (17.4 kJ/mol) than in alkanes (23.5 kJ/mol). However the equilibrium Arrhenius prefactor (A(h)) is an order of magnitude smaller for alcohols (ca. 4 x 10(12)) than alkanes (ca. 6 x 10(13)) resulting in an absolute rate of decay that is faster in the alkane than in the alcohol solvents. These results are discussed in the context of transition state theory and Kramers' theory for condensed phase reaction dynamics. 相似文献
82.
83.
Muñoz J Barril X Hernández B Orozco M Luque FJ 《Journal of computational chemistry》2002,23(5):554-563
A similarity index based on the hydrophilic/hydrophobic properties of molecules is presented. Such an index is defined based on the fractional partition of the free energy of solvation developed within the framework of the self-consistent reaction field MST model, which divides the free energy of solvation or the free energy of transfer into contributions assigned to the surface elements defining the solute/solvent interface. These surface contributions can be integrated to derive atomic or group contributions. The suitability of the index to compute the molecular similarity based on hydrophobic/hydrophilic properties is examined by considering their application in a variety of test systems, including structure-activity relationships, absorption properties, and molecular recognition. The similarity index is expected to be a very powerful tool in molecular similarity studies for compounds of chemical, biochemical, and pharmaceutical interest. 相似文献
84.
A systematic study of the suitability of PM3-derived molecular electrostatic potentials (MEPs) is presented. Forty-six MEP minima, 81 electrostatic charges, and 17 electrostatic dipoles were determined at the PM3 level and compared with those obtained from the ab initio 6-31G* wave function, as well as from the semiempirical MNDO and AM1 wave functions. The statistical results of the comparison analysis between semiempirical and ab initio 6-31G* MEPs show that PM3 is in general reliable for the study of the MEP minima but a mediocre method as a source of electrostatic charges. © 1993 John Wiley & Sons, Inc. 相似文献
85.
A new strategy to evaluate accurate electrostatic charges from semiempirical wave functions is reported. The rigorous quantum mechanical molecular electrostatic potentials computed from both MNDO and AM1 wave functions are fitted to the point-charge molecular electrostatic potential to obtain the electrostatic charges. The reliability of this strategy is tested by comparing the semiempirical electrostatic charges for 21 molecules with the semiempirical Mulliken charges and with the ab initio STO-3G and 6-31G* electrostatic charges. The ability of the dipoles derived from the semiempirical electrostatic and Mulliken charges as well as from the SCF charge distributions to reproduce the ab initio 6-31G* electrostatic dipoles and the gas phase experimental values is determined. The statistical analysis clearly point out the goodness of the semiempirical electrostatic charges, specially when the MNDO method is used. The excellent relationships found between the MNDO and 6-31G* electrostatic charges permit to define a scaling factor which allows to accurately reproduce the 6-31G* electrostatic charge distribution as well as the experimental dipoles from the semiempirical electrostatic charges. 相似文献
86.
Bustos E Manríquez J Orozco G Godínez LA 《Langmuir : the ACS journal of surfaces and colloids》2005,21(7):3013-3021
Gold bead electrodes were modified with submonolayers of 3-mercaptopropionic acid or 2-aminoethanethiol and further reacted with poly(amidoamine) (PAMAM) dendrimers (generation 4.0 and 3.5, respectively) to obtain films on which Prussian Blue (PB) was later absorbed to afford mixed and stable electrocatalytic layers. Experiments carried out with these novel materials not only showed an improved surface coverage of PB on the dendrimer modified electrodes as compared to PB modified gold electrodes prepared under acidic conditions, but also showed an increased stability at neutral pH values for one of the dendrimer containing substrates where the PB film on a bare gold electrode is simply not formed. The dendrimer modified electrodes were also tested as electrocatalytic substrates for the electroxidation of L(+)-ascorbic acid (AA), and it was found that their sensitivity as well as the corresponding detection limits were improved as compared to the voltammetric response of a Au-PB modified electrode. On the basis of UV-visible (UV-vis) spectroscopy and electrochemical experiments, it is suggested that the PB molecules are located within the dendritic structure of the surface attached PAMAM dendrimers. 相似文献
87.
Cabrera Pérez Laura C. Padilla-Martínez Itzia I. Cruz Alejandro Correa Basurto José Miliar García Ángel Hernández Zavala Argelia A. Gómez López Modesto Rosales Hernández Martha C. 《Molecular diversity》2020,24(4):1-14
Molecular Diversity - 11-Beta hydroxysteroid dehydrogenase type 1 (11β-HSD1) regulates cortisol levels mainly in adipose, hepatic and brain tissues. There is a relationship between the high... 相似文献
88.
D.Y. Medina S. Orozco I. Hernandez R.T. Hernandez C. Falcony 《Journal of Non》2011,357(22-23):3740-3743
In this work the characterization of europium doped lanthanum oxide films prepared by ultrasonic spray pyrolysis is reported. The films were prepared from lanthanum and europium nitrates over a corning glass substrate. The films structure was analyzed by X-ray diffraction, Microscopy Electronic and energy dispersive spectroscopy analysis. Photoluminescence and Raman scattering were performed. The excitation spectrum consists of the charge transfer peak at 280 nm and several lines in the 350–450 nm range corresponding to f–f transitions. The emission spectrum, excited at 280 nm, shows five peaks at 580, 595, 615, 652 and 698 nm, corresponding to the transitions of trivalent europium ion. The optical properties of films were compared with the one obtained from powders prepared by precipitation and heating of the precursor material. 相似文献
89.
90.
Voytas P. A. Behr J. A. Ghosh A. Gwinner G. Orozco L. A. Simsarian J. E. Sprouse G. D. Xu F. 《Hyperfine Interactions》1996,97(1):527-534
The techniques of laser cooling and trapping now make it possible to observe large samples of stable atoms in a small volume at low temperature. This capability was recently extended to radioactive isotopes. This opens up new opportunities for the investigation of fundamental symmetries through measurements using radioactive atoms. In this paper we will discuss several fundamental measurements in atomic systems and how the ability to trap radioactive atoms will play an important role in improving the precision of such measurements. Measurements of the effects of the weak interaction are of particular note since they are becoming quite precise. In particular, we will describe in detail the system developed at Stony Brook to trap radioactive alkali atoms and measure weak interaction effects in francium isotopes. 相似文献