Structural Elucidation of an Atropisomeric Entcassiflavan-(4β→8)-Epicatechin Isolated from Dalbergia monetaria L.f. Based on NMR and ECD Calculations in Comparison to Experimental Data

A rare dihydoxyflavan-epicatechin proanthocyanidin, entcassiflavan-(4β→8)-epicatechin, was isolated from Dalbergia monetaria, a plant widely used by traditional people from the Amazon to treat urinary tract infections. The constitution and relative configuration of the compound were elucidated by HR-MS and detailed 1D- and 2D-NMR measurements. By comparing the experimental electronic circular dichroism (ECD) spectrum with the calculated ECD spectra of all 16 possible isomers, the absolute configuration, the interflavan linkage, and the atropisomers could be determined.     

Modified electrode with reduced graphene oxide/poly(3-hydroxyphenylacetic acid): a new platform for oligonucleotide hybridization

Journal of Solid State Electrochemistry - This paper reports a new platform for oligonucleotide hybridization, prepared by electropolymerization of 3-hydroxyphenylacetic acid onto gold electrode...     

Generic structure of externally driven tearing modes instabilities

A major limit to steady state and advanced high operation of tokamaks of reactor class is due to the onset of tearing modes that develop magnetic and may cause loss of energy confinement or a major disruption. Here the structure of a classical problem about the effects of external control helical fields is analysed and it is shown to offer a general paradigm of response of low order classical and neoclassical tearing modes to a wide class of external perturbations. New results of principle on the structural stability of the response model are obtained, leading to a clear interpretation of the role of “seed islands" in the onset of neo-classical tearing modes and the role of finite ion larmor radius corrections to Ohm's law. Received 12 November 2001 and Received in final form 4 January 2002     

Adhesion hysteresis in dynamic atomic force microscopy

The effects of adhesion hysteresis in the dynamic‐dissipation curves measured in amplitude‐modulation atomic force microscopy are discussed. Hysteresis in the interaction forces is shown to modify the dynamics of the cantilever leading to different power dissipation curves in the repulsive and attractive regimes. Experimental results together with numerical simulations show that power dissipation, as measured in force microscopy, is not always proportional to the energy dissipated in the tip–sample interaction process. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High resolution NMR spectroscopy of heteroaromatic cations. II—pyrylium,thiapyrylium and seleninium cations

The barriers to internal rotation about the C? N bond in several thiopiperidides have been determined by the NMR technique. It was found that the barrier height (ΔG^?) increases in the series cinnamoylthiopiperidide<thiobenzoylpiperidide<phenylthioacetylpiperidide. This trend was discussed in terms of the electronic structure, using HMO calculations. For m-and p-substituted cinnamoylthiopiperidides the barriers were shown to increase with the electron withdrawing character of the substituent in the aromatic ring.     

Studies of silicophosphate derivatives by 31P-->29Si CP MAS NMR

We show that it is possible to efficiently transfer magnetization from ³¹P to ²⁹Si, using variable amplitude CP MAS experiment. This experiment is demonstrated by using Si₅O(PO₄)₆, the synthesis protocol of which is described. From the obtained results, we show that the experiment allows the spectral edition of ²⁹Si spectra from ³¹P→²⁹Si CP, enabling the studies of derivatives involving Si–O–P linkages, such as phosphosilicate glasses, microporous silicoaluminophosphates (SAPO) and bioactive phosphosilicates.     

The loss of tightness of time distributions for homeomorphisms of the circle

For a minimal circle homeomorphism we study convergence in law of rescaled hitting time point process of an interval of length 0$">. Although the point process in the natural time scale never converges in law, we study all possible limits under a subsequence. The new feature is the fact that, for rotation numbers of unbounded type, there is a sequence going to zero exhibiting coexistence of two non-trivial asymptotic limit point processes depending on the choice of time scales used when rescaling the point process. The phenomenon of loss of tightness of the first hitting time distribution is an indication of this coexistence behaviour. Moreover, tightness occurs if and only if the rotation number is of bounded type. Therefore tightness of time distributions is an intrinsic property of badly approximable irrational rotation numbers.