Correlation between thermal conductivity and bond length alternation in carbon nanotubes: A combined reverse nonequilibrium molecular dynamics—Crystal orbital analysis

The thermal conductivity (λ) of carbon nanotubes (CNTs) with chirality indices (5,0), (10,0), (5,5), and (10,10) has been studied by reverse nonequilibrium molecular dynamics (RNEMD) simulations as a function of different bond length alternation patterns (Δr_i). The Δr_i dependence of the bond force constant (k_rx) in the molecular dynamics force field has been modeled with the help of an electronic band structure approach. These calculations show that the Δr_i dependence of k_rx in tubes with not too small a diameter can be mapped by a simple linear bond length–bond order correlation. A bond length alternation with an overall reduction in the length of the nanotube causes an enhancement of λ, whereas an alternation scheme leading to an elongation of the tube is coupled to a decrease of the thermal conductivity. This effect is more pronounced in carbon nanotubes with larger diameters. The formation of a polyene‐like structure in the direction of the longitudinal axis has a negligible influence on λ. A comparative analysis of the RNEMD and crystal orbital results indicates that Δr_i‐dependent modifications of λ and the electrical conductivity are uncorrelated. This behavior is in‐line with a heat transfer that is not carried by electrons. Modifications of λ as a function of the bond alternation in the (10,10) nanotube are explained with the help of power spectra, which provide access to the density of vibrational states. We have suggested longitudinal low‐energy modes in the spectra that might be responsible for the Δr_i dependence of λ. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Regiochemistry of S-alkyl-substituted alkynes in Pauson-Khand reactions. Is a correlation with X-ray data and charge distribution calculations of the Co(2)(CO)(6)-alkyne complexes possible?

[reaction: see text] Pauson-Khand reactions (PKR) of RSCtbd1;CR' (6-10) yielded in all cases as the main product the regioisomer with the alkyl-S group disposed alpha to the CO group (16a-22a). Correlation of these results with X-ray data and charge distribution calculations of the corresponding dicobalthexacarbonyl complexes proves that a recently postulated "trans effect" in these complexes is not suitable for predicting the regiochemical outcome of the PKR unambiguously.     

Schlüsselreaktionen einer synthese des sibirosamins

[2,3]-Sigmatropic rearrangement and vic. $\text{cis}$-oxyamination of 3-$\text{C}$-methyl-ald-m-enopyranosides are the key steps for the synthesis of a sibirosamine precursor.     

Buchbesprechungen

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Characterization and control of phase fluctuations in elongated Bose–Einstein condensates

Quasi-one-dimensional Bose–Einstein condensates (BECs) in elongated traps exhibit significant phase fluctuations even at very low temperatures. We present recent experimental results on the dynamic transformation of phase fluctuations into density modulations during time of flight and show the excellent quantitative agreement with the theoretical prediction. In addition we confirm that, under our experimental conditions, in the magnetic trap density modulations are strongly suppressed even when the phase fluctuates. We also discuss our theoretical results on control of the condensate phase by employing a time-dependent perturbation. Our results set important limitations on future applications of BECs in precision atom interferometry and atom optics, but at the same time suggest pathways to overcome these limitations. Received: 17 August 2002 / Published online: 15 January 2003 RID="*" ID="*"Corresponding author. Fax: +49-511/762-3023, E-mail: Helge.Kreutzmann@ITP.uni-hannover.de     

Syntheses and solid state structures of cyclic diynes with two chalcogen centres--a competition between weak interactions

In this paper we report the synthesis of cyclic diynes of the general formula mX2n. The letters m and n indicate the lengths of chains between two C triple bond C-X units where X indicates S, Se, or Te. The lengths of the bridges vary between m=4-8 and n=2-6. Structural investigations by means of X-ray diffraction reveal for most systems a chair-like conformation in the solid state. For 5S(2)2, 5S(2)3, 7S(2)5, 5Se(2)2 and 5Te(2)3 tubular structures were encountered. These structures can be traced back to weak XX or weak C-Hpi interactions.     

N-Aryl-N-Hydroxy Urethanes as Peroxidase Substrates

 N-Aryl-N-hydroxy urethanes (AHUs), which are promising N*OH mediators for oxidoreductase catalysis, are electrochemically active redox compounds with a redox potential of 0.35–0.40 V vs. SCE (0.59–0.64 V vs. NHE). Alkyl substituents in the carbamic acid residue have, as expected, only little influence on the redox potential. The highest potential was noticed for N-hydroxy-N-(4-cyanophenyl)-carbamic acid methyl ester. Recombinant Coprinus cinereus peroxidase (rCiP) catalyzes oxidation of the AHUs with apparent bimolecular constants k _ox of 2.5ċ10⁴–7.5ċ10⁴ M ⁻¹s⁻¹ at pH = 8.5 and 25°C. Structure-function connectivities of the substrates were analysed within the framework of the Marcus cross relationship and by using ab initio quantum chemical calculations. An excellent correlation of the redox potentials and the HOMO energies could be found. However, no correlation of log(k _ox) with redox potential and HOMO energy was indicated as predicted by theory. This was explained by specific docking of the substrates in the active center of rCiP.     

Untersuchung pharmazeutischer Pr?parate

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Zur Bestimmung des Schwefels im Eisen

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