Vibration-rotation interaction in HCNO caused by accidental resonances and enhanced by the quasilinearity of the molecule

The recent assignment of the vibrational spectrum of the quasilinear molecule HCNO revealed several near coincidences between vibrational energy levels involving the two bending modes, ν₄ (skeletal bending mode) and ν₅ (HCN-bending mode), and the lowest-lying stretching mode, ν₃ (NO stretching mode). By considering the correlation between the energy levels of a linear and a bent molecular model of HCNO, it is seen that resonance interactions which would be of third or higher order in a linear molecule Hamiltonian would be of first or second order in the Hamiltonian of a bent molecule, and thus might be significant in the quasilinear molecule HCNO. In this way we were able to identify the type of observed interaction occurring between three pairs of nearly coincident levels, (00010, 00002), (00020, 00012), and (00100, 00004). Anomalous centrifugal distortion effects had been observed and reported earlier for the pure rotational transitions arising from molecules in the 00010, 00020, and 00002 levels. Rotational transitions arising from molecules in the 00004 and 00100 vibrational states of HCNO and the 00100 state of DCNO are reported here for the first time. For two pairs of levels, (00010, 00002) and (00100, 00004), we could determine the magnitude of the coefficients of the interaction matrix elements from an analysis of the centrifugal distortion effects.     

Book Review

Abstract

A Guide to Organophosphorus Chemistry, by Louis D. Quin, an internationally recognized authority, published by John Wiley and Sons (http://www.wiley.com/chemistry) ISBN 0-471-31824-8, $94.95, 394pp.

Aminophosphonic and Aminophosphinic Acids: Chemistry and Biological Activity. Editors: Valery P. Kukhar (Ukrainian Academy of Sciences) and Harry R Hudson (University of North London). Published by John Wiley and Sons Ltd., Chichester, UK, on 31 March, 2000. ISBN 0 471-89149-5, 175.00 Pounds sterling, 634 pages.

Phosphorus Ylides. Chemistry and Application in Organic Synthesis, by Oleg I. Kolodiazhnyi. Published by Wiley-VCH, 1999, ISBN 3-527-29531-3, 220SF, 555 pages.     

Synthesis of (E)-Nitro Olefins by Copper Mediated Addition-Elimination Reaction of Organometallics to 2-Nitro-1-phenylthiopropene

The reaction of various organometallics with 2-nitro-1-phenylsulfonylpropene 2a and 2-nitro-1-phenylthiopropene 2b was investigated. While in the case of lithium and magnesium organyls the addition products 4 were formed, transmetallation with CuCN led exclusively to (E)-nitro olefins 3.     

Combined QCM-D/GE as a tool to characterize stimuli-responsive swelling of and protein adsorption on polymer brushes grafted onto 3D-nanostructures

A combined setup of quartz crystal microbalance and generalized ellipsometry can be used to comprehensively investigate complex functional coatings comprising stimuli-responsive polymer brushes and 3D nanostructures in a dynamic, noninvasive in situ measurement. While the quartz crystal microbalance detects the overall change in areal mass, for instance, during a swelling or adsorption process, the generalized ellipsometry data can be evaluated in terms of a layered model to distinguish between processes occurring within the intercolumnar space or on top of the anisotropic nanocolumns. Silicon films with anisotropic nanocolumnar morphology were prepared by the glancing angle deposition technique and further functionalized by grafting of poly-(acrylic acid) or poly-(N- isopropylacrylamide) chains. Investigations of the thermoresponsive swelling of the poly-(N-isopropylacrylamide) brush on the Si nanocolumns proved the successful preparation of a stimuli-responsive coating. Furthermore, the potential of these novel coatings in the field of biotechnology was explored by investigation of the adsorption of the model protein bovine serum albumin. Adsorption, retention, and desorption triggered by a change in the pH value is observed using poly-(acrylic acid) functionalized nanostructures, although generalized ellipsometry data revealed that this process occurs only on top of the nanostructures. Poly-(N-isopropylacrylamide) is found to render the nanostructures non-fouling properties.     

(Diazoalkyl)Phosphoranes from [4 + 1]-cycloadditions of tetrahalo-orthobenzoquinones to (diazoalkyl)phosphanes [1]

The (diazoalkyl)phosphanes 4a–e undergo [4 + 1]-cycloaddition reactions with the tetrahalo-orthobenzoquinones 5a,b to furnish the previously unknown (diazoalkyl)phosphoranes 6a–h . The structure of product 6h has been investigated by X-ray crystallography.     

2,4-Dimethoxycarbonyl-1,1,3,3-tetrakis(dimethylamino)-1λ5,3λ5-diphosphete

1,1,3,3 - Tetrakis(dimethylamino) - 1λ⁵,3λ⁵ - diphosphete, 1 , reacts with cyanoformic acid methyl ester to form two isomers of the title compound 2 . Properties, NMR, mass, and IR spectra of 2 , as well as the molecular and crystal structure of the E isomer of 2 , are described and discussed.