Synthesis of novel deoxynucleoside S-methylphosphonic acids using S-(diisopropylphosphonomethyl)isothiouronium tosylate, a new equivalent of mercaptomethylphosphonate

The synthesis of the novel nucleotide analogues 5'-deoxynucleoside-5'-S-methylphosphonates, starting from 5'-deoxy-5'-haloribonucleosides, 5'-O-tosylribonucleosides, and 2'-O-triflylnucleosides, is described. The phosphonothiolation of these compounds was achieved using S-(diisopropylphosphonomethyl)isothiouronium tosylate, a new, odourless, and efficient equivalent of mercaptomethylphosphonate. The thiolate anion of mercaptomethylphosphonate was generated in situ from the isothiouronium salt in both protic and aprotic solvents using two equivalents of sodium iso-propoxide. The prepared nucleoside 5'-S-methylphosphonates were deprotected, and the free phosphonic acids were transformed into diphosphoryl derivatives (the NTP analogues). Both mononucleotides and NTP analogues were studied as substrates/inhibitors of several enzymes that are involved in the nucleoside/nucleotide metabolism.     

Determination of pK(a) values of N-heterocyclic bases by fluorescence spectrophotometry

Fluorimetry is a relatively fast and accurate means of determining the dissociation constants of sparingly soluble heterocyclic bases. Complications can arise, however, from the dependence of fluorescence on excited-state as well as ground-state acid-base chemistry. Several approaches to circumventing or compensating for this difficulty are discussed. To demonstrate the utility of the methods, the pK(a), values of the conjugate acids of two bases are evaluated by the methods described.     

UV-induced Coulomb crystallization of dust grains in high-pressuregas

A scheme for forming a Coulomb lattice of positively charged dust grains in a high-pressure (P>torr) gas is discussed theoretically. The grains are charged positively by photoemission in the presence of a flux of ultraviolet (UV) photons with energy larger than the work function of the grains, but lower than the ionization potential of the background gas. Methods for levitating and containing the dust using photophoretic forces (both UV and non-UV), gas drag, and electrostatic forces are considered     

Proceedings of the conference on organic chemistry at clusters and surfaces

The Proceedings of the Conference on Organic Chemistry at Clusters and Surfaces will comprise Volume 3, Number 3 (September 1992); Volume 3, Number 4 (December 1992); and Volume 4, Number 1 (March 1993).     

Glow discharge lamps as electron sources for electron impact excitation

It has been found possible to utilize the plasma in the discharge lamp of a conventional ultraviolet photoelectron spectrometer as an electron source f     

On duration and smoothing rules in a demisyllable-based isolated-word recognition system

In a recently proposed approach to isolated-word recognition, word reference templates are constructed from a universal set of demisyllable units by concatenating the appropriate demisyllables for each vocabulary item. A dynamic time warping (DTW) algorithm is used to align test and reference patterns optimally. Nevertheless some sort of syllable duration preadjustment is necessary because of the large potential difference in duration between isolated and in-context syllables. We have found that a simple rule that reduces the length of rhyme (final) demisyllables in nonword-final stressed syllables to approximately half their isolated-syllable duration provides recognition accuracy as high as that attained through use of complex, highly context-sensitive rules. In addition to its practical application, this result can be regarded as a further demonstration of the power of DTW. We have also investigated the requirements for parameter smoothing at demisyllable boundaries. We find that an optimal window duration for smoothing is about 60-90 ms, but that failure to smooth reduces recognition accuracy only about 2% in an 1109 word test set; that linear and parabolic smoothing are equally effective; and that it does not appear that recognition accuracy can be improved by smoothing in certain phonetic contexts only. Taken together, these results can be viewed as confirming the suitability of the demisyllable as the basic unit in recognition systems.