Conformational implications of some nucleotide sequences

The conformational properties of some nucleotide sequences result in their ability to bind specifically some ligands or tobe recognized by specific proteins. In order to investigate the dependence of conformational behavior of the DNA duplex on nucleotide sequence, we analyzed the interaction energy of nucleic acid bases as a function of conformational parameters and base sequence. Extended regions of minimum energy values were found for different sequences. Although these regions (valleys) largely overlap, each one shows specificity for a particular sequence. This suggests that a specific pathway of changes in conformational parameters exists for each sequence. the changes may be accompanied by considerable shifts (2–3 Å) of the atom positions and an only slight variation (1–2 kcal/mol) of energy. Even small shifts in other directions can cause a drastic energy increase. For some nucleotide sequences, the energetically preferable conformations are the B-like ones (e.g., ApA, TpA), whereas for others the A-like ones are preferable (e.g., GpG, ApT). IN general, Pyr-Pur sequences have a tendency to a larger τ and smaller H and D than Pur-Pyr sequences. A large body of experimental data on nucleic acid structure in fibers and in solutions can be explained by results obtained.     

Self-inhibition or the lack of it in the pyrolyses of neopentane and n-hexane

Published data show that in its early stages (up to 3% decomposition), the pyrolysis of n-hexane in the ranges 723–823 K and 10–100 Torr is not inhibited by the olefin products, in contrast with neopentane pyrolysis which is very strongly inhibited in similar conditions. Detailed consideration of the chain mechanisms for the two pyrolyses shows that the reactivity of the chain terminating radical towards hydrogen abstraction from an allylic C? H bond in product olefin is the factor which determines whether or not observable self-inhibition occurs. Thus, n-hexane pyrolysis, whose chain decomposition is terminated by recombination and disproportionation of ethyl, is not significantly self-inhibited, whereas that of neopentane which is terminated by recombination of methyl is very strongly inhibited because methyl is 14× more reactive than ethyl. The implications for other alkanes are briefly discussed.     

HPLC studies of isomeric chromium-N-benzoylphenylhydroxylaminates

Summary N-Benzoylphenylhydroxylarnine complexes of some metals have been investigated by HPLC. The green chromium complex formed by this reagent shows conclusive evidence of the presence of geometrical isomers. It is photosensitive and changes to a brown modification when irradiated with ultra violet or visible light. Elution behaviour of the complexes has been studied with different solvent mixtures. Attempts have been made to characterize the complexes from different measurements.

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Untersuchung von isomeren Chrom-N-benzoylphenylhydroxylaminaten durch HPLC

     

High reliability atomic absorption spectrometry of major and minor elements in biological materials

Summary Reliable analytical information is of fundamental importance for decisions of far-reaching impact in many regulatory, medical and scientific areas and disciplines. It is however at times elusive. Although the technique of atomic absorption spectrometry (AAS) as become widely established in analytical laboratories throughout the world for the determination of inorganic elements, only few AAS-based methods have reached official status and even fewer have attained reference method status. Research is underway to delineate impacts of a number of parameters on method performance to lead to protocols for standard and reference flame AAS (FAAS) methods for the reliable measurement of major and minor levels of elements of nutritional and toxicological pertinence in clinical and biological materials. Factors investigated include preparation of standards, calibration techniques, sampling and sample decomposition, solution preparation, instrumental parameters, and measurement protocols. Examples of some pronounced effects of sample decomposition and calibration techniques are presented as well as indications of the excellent performance of well-applied AAS procedures determined by use of standard reference materials and comparison with other techniques of analysis. Reference will be made to the determination of the major and minor nutrient elements Na, K, Mg, Ca, Mn, Fe, Cu and Zn in plant biological reference materials.Formerly at Plant Research Centre, Agriculture Canada, Ottawa, Ontario K1A OC6, CanadaContribution No. 1030 from Plant Research Centre     

When maths really is rocket science

Two problems in projectiles are discussed which generate interestingloci.     

Influence of the energy and velocity spread in the electron beam on the starting conditions and efficiency of a gyrotron

We study theoretically the influence of the spread of initial energies and velocities in the electron beam on the starting conditions and efficiency of a gyrotron. We compare various analytical and numerical models and the results of experimental studies of gyrotrons in which the interaction takes place at the first and second harmonics of the cyclotron frequency. The aftercavity interaction of the electron beam with the high-frequency field in the output waveguide transition is taken into account. The influence of the energy spread on the recuperation efficiency is estimated. Permissible spreads of the initial energies and electron velocities are determined. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 49, No. 2, pp. 121–133, February 2006.     

Synthesis and conformational study of 1,2,3,4,5,6,7,8-octahydro-1,6-naphthiridines

A new class of endocyclic enamines, 1,6-disubstituted 1,2,3,4,5,6,7,8-octahydro-1,6-naphthiridines, was synthesized from 4-piperidone imines by successive subjecting the latter to lithiation with lithium diethylamide, to alkylation with 1-bromo-3-chloropropane, and to intramolecular cyclization. All stages were carried out as a unique process without isolation of the intermediate compounds. A thorough optimization of the process conditions, workup, and product storage was carried out. The conformational study of 1,6-disubstituted 1,2,3,4,5,6,7,8-octahydro-1,6-naphthiridines was performed.