The Radical Anions of Some Substituted [2.2]Paracyclophanes

The radical anions of the following substituted [2.2]paracyclophanes have been characterized by ESR. and ENDOR. spectroscopy: 4, 16-dicyano- ( o - 2 ), 4, 12-dicyano- ( p - 2 ), 4,5,12,13-tetracyano- ( 3 ) and 4,5,12,13-tetrakis (alkoxycarbonyl)- [2.2]paracyclophanes ( 4-R , where R = Me, Et, iPr or tBu is the ester alkyl group); 4,5-bis(methoxycarbonyl)[2.2]paracyclophane-12, 13-dicarboxylic anhydride ( 5 ); [2.2]paracyclophane-4,5:12, 13-tetracarboxylic bisanhydride ( 6 ) and bisimides ( 7-R , where R = H, D, Me or Ph is the substituent at the imide N-atom). Comparison of the hyperfine data for these radical anions with those for analogously substituted derivatives of benzene indicates that the most prominent coupling constants are approximately halved on passing from the latter to the former. Lowering of the symmetry, as a consequence of ion pairing, has been observed for the radical anions 4- i Pr \documentclass{article}\pagestyle{empty}\begin{document}$^{\ominus \atop \dot{}}$\end{document} and 4- t Bu \documentclass{article}\pagestyle{empty}\begin{document}$^{\ominus \atop \dot{}}$\end{document} associated with the counterion K ⊕ in 1,2-dimethoxyethane at 183 K, but not for 4-Me \documentclass{article}\pagestyle{empty}\begin{document}$^{\ominus \atop \dot{}}$\end{document} and 4-Et \documentclass{article}\pagestyle{empty}\begin{document}$^{\ominus \atop \dot{}}$\end{document} under the same conditions. This result suggests that the migration of K ⊕ between the preferred sited in two equivalent ion pairs is slowed down by the steric hindrance arising from the bulky iPr and tBu ester groups.     

In vivo observation of oxygen-supersaturated water in the human mouth and stomach

In recent years, a rising number of different table waters supersaturated with oxygen have hit the market with claims of both positive health effects and an increase in athletic performance. A scientific validation of these claims needs additional knowledge on the fate of the oxygen supersaturation in the human digestive tract. Taking advantage of the fact that molecular oxygen is paramagnetic, MRI can be applied to observe the behavior of oxygen-supersaturated water after oral uptake. In this contribution we report results obtained on several healthy volunteers. On the basis of these results we can conclude that oral uptake of oxygen-supersaturated drinking water with a low content in CO(2) leads to a considerable increase in the oxygenation in the lumen of the oral cavity and of the stomach. Comparing the observed contrast changes with those brought about by conventional contrast agents, even the highly oxygen-supersaturated waters still perform rather poorly.     

On a conjecture of Murty and Simon on diameter 2-critical graphs

A graph G is diameter 2-critical if its diameter is two, and the deletion of any edge increases the diameter. Murty and Simon conjectured that the number of edges in a diameter 2-critical graph of order n is at most n²/4 and that the extremal graphs are complete bipartite graphs with equal size partite sets. We use an association with total domination to prove the conjecture for the graphs whose complements have diameter three.     

Small subgraphs in random graphs and the power of multiple choices

The standard paradigm for online power of two choices problems in random graphs is the Achlioptas process. Here we consider the following natural generalization: Starting with G₀ as the empty graph on n vertices, in every step a set of r edges is drawn uniformly at random from all edges that have not been drawn in previous steps. From these, one edge has to be selected, and the remaining r−1 edges are discarded. Thus after N steps, we have seen rN edges, and selected exactly N out of these to create a graph GN.In a recent paper by Krivelevich, Loh, and Sudakov (2009) [11], the problem of avoiding a copy of some fixed graph F in GN for as long as possible is considered, and a threshold result is derived for some special cases. Moreover, the authors conjecture a general threshold formula for arbitrary graphs F. In this work we disprove this conjecture and give the complete solution of the problem by deriving explicit threshold functions N₀(F,r,n) for arbitrary graphs F and any fixed integer r. That is, we propose an edge selection strategy that a.a.s. (asymptotically almost surely, i.e. with probability 1−o(1) as n→∞) avoids creating a copy of F for as long as N=o(N₀), and prove that any online strategy will a.a.s. create such a copy once N=ω(N₀).     

1,N6‐Etheno‐2′‐deoxytubercidin hemihydrate

The title compound [systematic name: 7‐(2‐deoxy‐β‐d ‐erythro‐pentofuranosyl)‐7H‐imidazo[1,2‐c]pyrrolo[2,3‐d]pyrimidine hemihydrate], 2C₁₃H₁₄N₄O₃·H₂O or (I)·0.5H₂O, shows two similar conformations in the asymmetric unit. These two conformers are connected through one water molecule by hydrogen bonds. The N‐glycosylic bonds of both conformers show an almost identical anti conformation with χ = −107.7 (2)° for conformer (I‐1) and −107.0 (2)° for conformer (I‐2). The sugar moiety adopts an unusual N‐type (C3′‐endo) sugar pucker for 2′‐deoxyribonucleosides, with P = 36.8 (2)° and τ_m = 40.6 (1)° for conformer (I‐1), and P = 34.5 (2)° and τ_m = 41.4 (1)° for conformer (I‐2). Both conformers and the solvent molecule participate in the formation of a three‐dimensional pattern with a `chain'‐like arrangement of the conformers. The structure is stabilized by intermolecular O—H...O and O—H...N hydrogen bonds, together with weak C—H...O contacts.     

A note on total reinforcement in graphs

In this note we prove a conjecture and improve some results presented in a recent paper of Sridharan et al. [N. Sridharan, M.D. Elias, V.S.A. Subramanian, Total reinforcement number of a graph, AKCE Int. J. Graphs Comb. 4 (2) (2007) 197-202].     

Time-resolved Laue diffraction of excited species at atomic resolution: 100 ps single-pulse diffraction of the excited state of the organometallic complex Rh2(μ-PNP)2(PNP)2·BPh4

The polychromatic Laue technique has been applied in 100 ps delay synchrotron pump-probe experiments of the triplet excited state of a Rh(I) dinuclear complex. The observed contraction of the Rh-Rh distance of 0.154 (13) ? is less than predicted by a series of theoretical calculations, a difference attributed to the constraining effect of the crystal lattice.     

Fast, ligand- and solvent-free synthesis of 1,4-substituted buta-1,3-diynes by Cu-catalyzed homocoupling of terminal alkynes in a ball mill

A method for the Glaser coupling reaction of alkynes by using a vibration ball mill has been developed. The procedure avoids the use of ligands and solvents during the reaction. Aryl- and alkyl-substituted terminal alkynes undergo homocoupling if coground with KF-Al(2)O(3) and CuI as a milling auxiliary and catalyst. Furthermore, an alternative protocol has been developed incorporating 1,4-diazabicyclo[2.2.2]octane (DABCO) as an additional base allowing the use of KF-Al(2)O(3) with a lower KF loading. Besides Cu salts, the homocoupling of phenylacetylene is also catalyzed by Ni or Co salts, as well as by PdCl(2). TMS-protected phenylacetylene could be directly converted into the homocoupling product after in situ deprotection of the alkyne by fluoride-initiated removal of the trimethylsilyl group.     

Heuristic chemistry--addition reactions

Organic chemistry is often considered a difficult subject requiring great effort to achieve expert status. Only once this level has been reached, judging, deciding, and recalling chemical information will be fast and guided by heuristic strategies. These principles, used intuitively, improve the efficiency and speed of problem-solving and decision-making procedures. Establishing these strategies in teaching and learning chemistry should significantly help students acquire well-structured procedural knowledge early in their education. In an attempt to improve conceptual thinking in teaching organic chemistry, in this contribution we develop a heuristic view of addition reactions and propose a new way of perceiving this class of organic reactions.