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1.
Indermeet Kohli Taylor L. Braunberger Amanda F. Nahhas Fatima N. Mirza Mohsen Mokhtari Alexis B. Lyons Nikiforos Kollias Eduardo Ruvolo Henry W. Lim Iltefat H. Hamzavi 《Photochemistry and photobiology》2020,96(1):208-214
Human skin is exposed to visible light (VL; 400–700 nm) and long-wavelength ultraviolet A1 (UVA1) radiation (370–400 nm) after the application of organic broad-spectrum sunscreens. The biologic effects of these wavelengths have been demonstrated; however, a dose–response has not been investigated. Ten subjects with Fitzpatrick skin phototype IV-VI were enrolled. Subjects were irradiated with 2 light sources (80–480 J cm−2): one comprising VL with less than 0.5% UVA1 (VL+UVA1) and the other pure VL. Skin responses were evaluated for 2 weeks using clinical and spectroscopic assessments. 4-mm punch biopsies were obtained from nonirradiated skin and sites irradiated with 480 J cm−2 of VL+UVA1 and pure VL 24 h after irradiation. Clinical and spectroscopic assessments demonstrated a robust response at VL+UVA1 sites compared with pure VL. Histology findings demonstrated a statistically significant increase in the marker of inflammation (P < 0.05) and proliferation (P < 0.05) at the irradiated sites compared with nonirradiated control. Threshold doses of VL+UVA1 resulting in biologic responses were calculated. Results indicate that approximately 2 h of sun exposure, which equates to VL+UVA1 dose (~400 J cm−2), is capable of inducing inflammation, immediate erythema and delayed tanning. These findings reinforce the need of photoprotection beyond the UV range. 相似文献
2.
Polysubstituted indoles can be prepared directly from functionalized nitroalkanes under very mildly acidic conditions in a simple, one-pot, two-stage procedure. 相似文献
3.
We introduce and study Hopf monads on autonomous categories (i.e., monoidal categories with duals). Hopf monads generalize Hopf algebras to a non-braided (and non-linear) setting. In particular, any monoidal adjunction between autonomous categories gives rise to a Hopf monad. We extend many fundamental results of the theory of Hopf algebras (such as the decomposition of Hopf modules, the existence of integrals, Maschke's criterium of semisimplicity, etc.) to Hopf monads. We also introduce and study quasitriangular and ribbon Hopf monads (again defined in a non-braided setting). 相似文献
4.
Alexis C. Kaporis Lefteris M. Kirousis Yannis C. Stamatiou Malvina Vamvakari Michele Zito 《Discrete Applied Mathematics》2007,155(12):1525-1538
The problem of determining the unsatisfiability threshold for random 3-SAT formulas consists in determining the clause to variable ratio that marks the experimentally observed abrupt change from almost surely satisfiable formulas to almost surely unsatisfiable. Up to now, there have been rigorously established increasingly better lower and upper bounds to the actual threshold value. In this paper, we consider the problem of bounding the threshold value from above using methods that, we believe, are of interest on their own right. More specifically, we show how the method of local maximum satisfying truth assignments can be combined with results for the occupancy problem in schemes of random allocation of balls into bins in order to achieve an upper bound for the unsatisfiability threshold less than 4.571. In order to obtain this value, we establish a bound on the q-binomial coefficients (a generalization of the binomial coefficients). No such bound was previously known, despite the extensive literature on q-binomial coefficients. Finally, to prove our result we had to establish certain relations among the conditional probabilities of an event in various probabilistic models for random formulas. It turned out that these relations were considerably harder to prove than the corresponding ones for unconditional probabilities, which were previously known. 相似文献
5.
6.
As ab initio electronic structure calculations become more accurate, inherent sources of error in classical transition state theory such as barrier recrossing and tunneling may become major sources of error in calculating rate constants. This paper introduces a general method for diabatically constructing the transverse eigensystem of a reaction path Hamiltonian in systems with many degenerate transverse frequencies. The diabatically constructed reaction path Hamiltonian yields smoothly varying coupling constants that, in turn, facilitate reactive flux calculations. As an example we compute the dynamically corrected rate constant for the chair to boat interconversion of cyclohexane, a system with 48 degrees of freedom and a number of degenerate frequencies. The transmission coefficients obtained from the reactive flux simulations agree with previous results that have been calculated using an empirical potential. Furthermore, the calculated rate constants agree with experimental values. Comparison to variational transition state theory shows that, despite finding the true bottleneck along the reaction pathway, variational transition state theory only accounts for half of the rate constant reduction due to recrossing trajectories. 相似文献
7.
Ataloglou T Bourikas K Vakros J Kordulis C Lycourghiotis A 《The journal of physical chemistry. B》2005,109(10):4599-4607
In the present work we studied, for the first time, the kinetics of adsorption of the Co(H(2)O)(6)(2+) species on the "electrolytic solution/gamma-Al(2)O(3)" interface at pH = 7 and 25 degrees C for a very broad range of Co(II) surface concentrations ranged from 0.03 to 6 theoretical Co(H(2)O)(6)(2+) surface layers. Moreover, we studied the surface dissolution of gamma-alumina in the presence of the Co(H(2)O)(6)(2+) ions in the impregnating solution, the contribution of the Co(II) desorption on the whole deposition process and the deposition isotherm. It was found that under the conditions where the deposition has taken place, the dissolution of the gamma-alumina surface is negligible even in the presence of the Co(H(2)O)(6)(2+) species in the impregnating solution. It was, moreover, inferred that the Co(II) desorption does not participate significantly to the whole deposition process. It was found that the deposition kinetics may be described by the following kinetic expression r(Co,bulk) = k'C(Co,bulk)(2), which relates the rate of disappearance of the Co(H(2)O)(6)(2+) ions from the impregnating solution, r(Co,bulk,) with their concentration C(Co,bulk). This kinetic expression may be derived assuming the following deposition scheme: nS + 2[Co(H(2)O)(6)(2+)] --> S(n) - [Co(H(2)O)(x,x)(<)(6)(2+)](2), where S represents the surface reception sites. The above expressions indicated that two Co(H(2)O)(6)(2+) ions are involved, from the side of the interface, in the reaction with the reception sites. It seems probable that the deposition step involves the simultaneous adsorption and dimerization of the two interfacial Co(H(2)O)(6)(2+) ions through (hydr)oxobridges. On the other hand, the sigmoidal form of the deposition isotherm and the dependence of the apparent rate constant, k', on the interfacial Co(II) concentration suggested that the already deposited Co(II) species may be involved in the reception sites, S, promoting the adsorption and resulting to the formation of multinuclear complexes and Co(II) surface precipitates. Finally, reasonable interface potential values for oxides were determined for the first time using kinetic results. 相似文献
8.
[reaction: see text]. Rate constants for hydrogen abstraction from phenols by a prefluorescent-TEMPO probe are reported. The nitroxide is employed as a potential model of peroxyl radicals. The probe works by nitroxide suppression of the fluorescence of the chromophore. The fluorescence is restored when the nitroxide abstracts a hydrogen atom to produce the diamagnetic hydroxylamine. The phenols studied in this project exhibited rate constants between 0.003 and 0.2 M(-1) s(-1). A deuterium isotope effect of 10 for TROLOX confirms that the mechanism is dominated by hydrogen transfer. 相似文献
9.
In situ diffuse reflectance UV-visible spectroscopy was used to measure the dynamics of catalyst reduction and oxidation during propane oxidative dehydrogenation (ODH) on VOx/gamma-Al2O3. Transients in UV-visible intensity in the near-edge region were analyzed using a mechanistic model of ODH reactions. Rate constants per site for the kinetically relevant reduction step (C-H bond activation) measured using this analysis are slightly larger than those obtained from steady-state ODH rates normalized by surface V. The ratio of these values provides a measure of the fraction of the V surface sites that are active for ODH (0.6-0.7, for V surface densities of 2.3-34 V nm(-2)). This suggests that some of the V atoms are either inaccessible or inactive. Reoxidation rate constants, which cannot be obtained from steady-state analysis, are 10(3)-10(5) times larger than those for the C-H bond activation reduction step. 相似文献
10.
Christophe Hoarau Alexis Du Fou de Kerdaniel Pierre Grandclaudon Francis Marsais 《Tetrahedron letters》2005,46(49):8573-8577
The efficient and regioselective palladium-catalyzed C-2 arylation of ethyl 4-oxazolecarboxylate 1 with phenyliodide is described. The different parameters (solvent, base, ligand and catalyst) for the optimal conditions of this arylation process have been screened. 相似文献