Black hole particle emission in higher-dimensional spacetimes

In models with extra dimensions, a black hole evaporates both in the bulk and on the visible brane, where standard model fields live. The exact emissivities of each particle species are needed to determine how the black hole decay proceeds. We compute and discuss the absorption cross sections, the relative emissivities, and the total power output of all known fields in the evaporation phase. Graviton emissivity is highly enhanced as the spacetime dimensionality increases. Therefore, a black hole loses a significant fraction of its mass in the bulk. This result has important consequences for the phenomenology of black holes in models with extra dimensions and black hole detection in particle colliders.     

Self-organized-criticality model consistent with statistical properties of edge turbulence in a fusion plasma

The statistical properties of the intermittent signal generated by a recent model for self-organized criticality are examined. A successful comparison is made with previously published results of the equivalent quantities measured in the electrostatic turbulence at the edge of a fusion plasma. This result reestablishes self-organized criticality as a potential paradigm for transport in magnetic fusion devices, overriding shortcomings pointed out in earlier works [E. Spada, Phys. Rev. Lett. 86, 3032 (2001)10.1103/PhysRevLett.86.3032; V. Antoni, Phys. Rev. Lett. 87, 045001 (2001)10.1103/PhysRevLett.87.045001].     

A combined Raman, DFT and MD study of the solvation dynamics and the adsorption process of pyridine in silver hydrosols

The adsorption of pyridine onto silver colloids has been investigated by Raman spectroscopy experiments and by ab initio DFT and MP2 calculations. The solvation dynamics of the pyridine in water has been studied by a molecular dynamics simulation. The results are compared with the latest available experimental and theoretical data. It is found that the pyridine is essentially hydrogen bonded to one solvent molecule. Calculations based on pyridine-water and pyridine-Ag(+) complexes allow the reproduction of the experimentally observed Raman features and explain the adsorption process of the ligand in silver hydrosols.     

Organocatalytic regioselective Michael additions of cyclic enones via asymmetric phase transfer catalysis

Cyclohexanone and cycloheptanone can be enantioselectively functionalized in the 3-position with up to 92% ee and 87% ee, respectively, by the base-promoted dimerization of the corresponding enones using 3,4,5-tribenzyloxybenzyl cinchoninium bromide, as a new effective catalyst.     

Dealing with a local heating effect when measuring catalytic solids in a reactor with Raman spectroscopy

In continuation of our previous work on the applicability of the G(R(infinity)) correction factor for the quantification of Raman spectra of coke during propane dehydrogenation experiments (Phys. Chem. Chem. Phys., 2005, 7, 211), research has been carried out on the potential of this correction factor for the quantification of supported metal oxides during reduction experiments. For this purpose, supported chromium oxide catalysts have been studied by combined in situ Raman and UV-Vis spectroscopy during temperature programmed reduction experiments with hydrogen as reducing agent. The goal was to quantify on-line the amount of Cr(6+) in a reactor based on the measured in situ Raman spectra. During these experiments, a significant temperature effect was observed, which has been investigated in more detail with a thermal imaging technique. The results revealed a temperature 'on the spot' that can exceed 100 degrees C. It implies that Raman spectroscopy can have a considerable effect on the local reaction conditions and explains observed inconsistencies between the in situ UV-Vis and Raman data. In order to minimize this heating effect, reduction of the laser power, mathematical matching of the spectroscopic data, a different cell design and a change in reaction conditions has been evaluated. It is demonstrated that increasing the reactor temperature is the most feasible method to solve the heating problem. Next, it allows the application of in situ Raman spectroscopy in a reliable quantitative way without the need of an internal standard.     

Protein-cofactor interactions in bacterial reaction centers from Rhodobacter sphaeroides R-26: effect of hydrogen bonding on the electronic and geometric structure of the primary quinone. A density functional theory study

The effect of hydrogen bonding to the primary quinone (Q(A) and Q(*)(-)(A)) in bacterial reaction centers was studied using density functional theory (DFT) calculations. The charge neutral state Q(A) was investigated by optimizing the hydrogen atom positions of model systems extracted from 15 different X-ray structures. From this analysis, mean values of the H-bond lengths and directions were derived. It was found that the N(delta)-H of His M219 forms a shorter H-bond to Q(A) than the N-H of Ala M260. The H-bond of His M219 is linear and more twisted out of the quinone plane. The radical anion Q(*)(-)(A) in the protein environment was investigated by using a mixed quantum mechanics/molecular mechanics (QM/MM) approach. Two geometry optimizations with a different number of flexible atoms were performed. H-bond lengths were obtained and spectroscopic parameters calculated, i.e. the hyperfine and nuclear quadrupole couplings of magnetic nuclei coupled to the radical. Good agreement was found with the results provided by EPR/ENDOR spectroscopy. This implies that the calculated lengths and directions of the H-bonds to Q(*)(-)(A) are reliable values. From a comparison of the neutral and reduced state of Q(A) it was concluded that the H-bond distances are shortened by approximately 0.17 Angstroms (His M219) and approximately 0.13 Angstroms (Ala M260) upon single reduction of the quinone. It is shown that the point-dipole approximation can not be used for an estimation of H-bond lengths from measured hyperfine couplings in a system with out-of-plane H-bonding. In contrast, the evaluation of the nuclear quadrupole couplings of (2)H nuclei substituted in the hydrogen bonds yields H-bond lengths close to the values that were deduced from DFT geometry optimizations. The significance of hydrogen bonding to the quinone cofactors in biological systems is discussed.     

Optical properties of single semiconductor nanocrystals

We present an overview of the current progress in the understanding of the (steady state) optical properties of individual II-VI semiconductor nanocrystals. We begin with a presentation of the conceptual development of the theory required to model the electronic structure of these systems. This is followed by an overview of the current experimental results obtained from the spectroscopy of individual semiconductor nanocrystals, and in particular, we focus on the study of photoluminescence intermittency (blinking) and spectral diffusion. Where possible, we link the experimental observations to the predictions of current theories. We conclude that the surface of small semiconductor crystals plays an important role in determining their optical properties.     

Comparison of hydrogen bonding in 1-octanol and 2-octanol as probed by spectroscopic techniques

Liquid 1-octanol and 2-octanol have been investigated by infrared (IR), Raman, and Brillouin experiments in the 10-90 degrees C temperature range. Self-association properties of the neat liquids are described in terms of a three-state model in which OH oscillators differently implicated in the formation of H-bonds are considered. The results are in quantitative agreement with recent computational studies for 1-octanol. The H-bond probability is obtained by Raman data, and a stochastic model of H-bonded chains gives a consistent picture of the self-association characteristics. Average values of hydrogen bond enthalpy and entropy are evaluated. The H-bond formation enthalpy is ca. -22 kJ/mol and is slightly dependent on the structural isomerism. The different degree of self-association for the two octanols is attributed to entropic factors. The more shielded 2-isomer forms larger fractions of smaller, less cooperative, and more ordered clusters, likely corresponding to cyclic structures. Signatures of a different cluster organization are also evidenced by comparing the H-bond energy dispersion (HBED) of OH stretching IR bands. A limiting cooperative H-bond enthalpy value of 27 kJ/mol is found. It is also proposed that the different H-bonding capabilities may modulate the extent of interaggregate hydrocarbon interactions, which is important in explaining the differences in molar volume, compressibility, and vaporization enthalpy for the two isomers.     

Stereoselective synthesis of the cytotoxic macrolide FD-891

[reaction: see text] A total synthesis of the naturally occurring, cytotoxic macrolide FD-891 is described. Three fragments were first stereoselectively constructed using mainly asymmetric aldol and allylation reactions. The complete framework was then assembled using two Julia-Kocienski olefinations to connect the three fragments and a Yamaguchi reaction to close the macrolactone ring.     

Do hydroxyl radical-water clusters, OH(H2O)n, n = 1-5, exist in the atmosphere?

It has been speculated that the presence of OH(H2O)n clusters in the troposphere could have significant effects on the solar absorption balance and the reactivity of the hydroxyl radical. We have used the G3 and G3B3 model chemistries to model the structures and predict the frequencies of hydroxyl radical/water clusters containing one to five water molecules. The reaction between hydroxyl radical clusters and methane was examined as a function of water cluster size to gain an understanding of how cluster size affects the hydroxyl radical reactivity.