Conformations of cycloundecane

Cycloundecane (1) was shown to exist at -183.1 degrees C as a mixture of the [12323] (approximately 59%) and [335] (approximately 41%) conformations. Populations were determined from the (13)C NMR spectrum, and assignments were based on the (13)C spectra, calculated free energies and chemical shifts, and information from the literature, including X-ray studies of solid derivatives and calculated barriers.     

Inverted sapphyrin: a new family of doubly N-confused expanded porphyrins

The synthesis of an inverted, methoxylated sapphyrin derivative is described. This system, wherein inversion of pyrrolic nitrogen atoms is configurationally enforced via the use of a 3,3'-bipyrrolic precursor, displays what is best described as "weak aromaticity" as judged from its spectroscopic features and supporting theoretical calculations.     

7-Chloro-4-methyl-6-nitro-2H-chromen-2-one: a novel type of reagent for fluorescence analysis

Starting from 7-chloro-4-methyl-2H-chromen-2-one 1 we have obtained a new reagent for fluorescence analysis. The synthesised key compound 7-chloro-4-methyl-6-nitro-2H-chromen-2-one 2 forms highly fluorescent derivatives with different amines, which can be introduced by nucleophilic substitution of the chloro atom. Two examples are given which describe the preparation of these derivatives. Additionally, we demonstrate that an increase of fluorescence can be achieved, if a reduction step is performed after the substitution.     

Darstellung von 2′,3′-Dideoxy-2′-hydroxymethyl-nucleosiden

Zusammenfassung Die Synthese von geschützten 2,3-Dideoxy-2-hydroxymethyl-nucleosiden wird beschrieben. Die durch ein Mehrstufenverfahren aus Isopropylidenglycerol erhaltenen Nucleoside können als Bausteine zur Darstellung von Oligonucleotiden verwendet werden, deren 2- und 5-Positionen über eine Etherbrücke verbunden sind.

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Synthesis of 2,3-dideoxy-2-hydroxymethyl nucleosides

Summary The synthesis of protected 2,3-dideoxy-2-hydroxymethyl nucleosides is presented. The nucleosides, obtained in a multi-step procedure starting from isopropylideneglycerol, may be used as building blocks for the synthesis of 2,5-ether linked oligonucleotides.

     

Determination of manganese in some pyrolusite ores of Myanmar by neutron activation analysis

Manganese in pyrolusite ores from various regions of Myanmar was determined by thermal neutron activation analysis using an Am(Be) neutron source. The induced activities of⁵⁶Mn were monitored by a -counting technique.     

Conformational study of cis-1,4-di-tert-butylcyclohexane by dynamic NMR spectroscopy and computational methods. Observation of chair and twist-boat conformations

[reaction: see text] Low-temperature 13C NMR spectra of cis-1,4-di-tert-butylcyclohexane (1) showed signals for the twist-boat (1a) and chair (1b) conformations. 13C NMR signals were assigned to specific carbons based on the different populations, different symmetries (time-averaged C(2v) for 1a and time-averaged C(s) for 1b), and calculated chemical shifts (GIAO, HF/6-311+G*). In addition to slow ring inversion and interconversion of the chair and twist-boat conformations, slow rotation of the tert-butyl groups was found. Most of the expected 13C peaks were observed. Free-energy barriers of 6.83 and 6.35 kcal/mol were found for interconversion of 1a (major) and 1b (minor) at -148.1 degrees C. Conformational space was searched with Allinger's MM3 and MM4 programs, and free energies were obtained for several low-energy conformations 1a-c. Calculations were repeated with ab initio methods up to the HF/6-311+G* level. Molecular symmetries, relative free energies, relative enthalpies and entropies, frequencies, and NMR chemical shifts were obtained. A boat conformation (1d; C(2v) symmetry) was generated and optimized as a transition state by ab initio, MM3, and MM4 calculations.     

Glass transition temperature of polymer nanocomposites: Prediction from the continuous‐multilayer model

The continuous‐multilayer model introduced in our previous study for the T_g behavior of thin films is adapted to nanocomposite systems. T_g enhancement in both thin films and nanocomposites with attractive interfacial interactions can be explained by the same model. Various shapes of nanoparticles are proposed to rationalize the adaptation of the one‐dimensional model for the T_g behavior of thin film to three‐dimensional system such as nanocomposite. The tendency of predicted T_g enhancements in poly(methyl methacrylate) and P2VP nanocomposites with silica particles are qualitatively fit to experimental data in literatures. For the further quantitative fitting, the model is partially modified with the consideration for other factors affecting T_g deviation in nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2281–2287, 2009     

Analysis of dynamic mixed mode stress fields in bimaterials by the method of caustics

The equations of caustics for dynamically extending curvilinear interface cracks are derived where optical isotropy and anisotropy of the material have been considered, respectively. The equations have been obtained by applying the method of generalized complex potentials. Moreover, an algorithm for the determination of stress intensity factors from experimentally obtained caustics is presented for the case of dynamic crack extension.