Biomedical subjects
Publications and source records attributed to J D Roberts.
Natural-abundance (13)C nuclear magnetic resonance spectra are reported for some simple terpenes and carotenes. The techniques involved in the assignment of the resonances to specific carbons are outlined. The potential of this nondegradative procedure for structural analysis is demonstrated for the investigation of carbon atoms in chemical and biochemical systems.
A variable-temperature, proton noise-decoupled, (13)C nmr spectral study of the chair-chair interconversion in 1,1,3,3-tetramethylcyclohexane has demonstrated the utility of (13)C spectra for probing conformational equilibria. There is a much larger chemical-shift difference between the carbons of axial and equatorial methyl groups than between the protons of these methyl groups, 133 Hz compared to 7.5 Hz. Comparison of the activation parameters determined from the (13)C spectra of 1,1,3,3-tetramethylcyclohexane with those determined from a variable-temperature (19)F study on 2,2,6,6-tetramethyl-1,1-difluorocyclohexane shows that the introduction of a gem-difluoro group into the ring causes significant steric interactions. The (13)C chemical shifts for 1,1,3,3-tetramethylcyclohexane reflect the importance of the methyl-methyl 1,3-diaxial interactions.
The proton-decoupled (13)C nmr spectrum of 1,1-difluorocyclohexane has been examined at room temperature and at -90 degrees C. There are only minor changes in the one-bond and two-bond carbon-fluorine scalar coupling constants at the lower temperature; however, the triplet observed for C-3 ((3)J(CF) = 4.7 Hz) collapses to a doublet ((3)J(CF) = 9.5 Hz) at -90 degrees C. It is proposed that only the equatorial fluorine is coupled with the C-3 carbon as the result of operation of a back-lobe orbital interaction.
The chemical shifts of (13)C in natural abundance have been obtained from nuclear magnetic resonance spectra of scyllo-, myo-, chiro-, and epi-inositols at 15.1 MHz. A set of empirical substitutent parameters were derived and shown to be moderately successful in correlating the (13)C resonance-line positions for these substances. The substituent parameters conform generally to the idea that steric hindrance or porximity effects are of special importance in influencing chemical shifts of carbons in cyclohexane systems.
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The fidelity of DNA synthesis catalyzed by the 180-kDa catalytic subunit (p180) of DNA polymerase alpha from Saccharomyces cerevisiae has been determined. Despite the presence of a 3'----5' exonuclease activity (Brooke et al., 1991, J. Biol. Chem., 266, 3005-3015), its accuracy is similar to several exonuclease-deficient DNA polymerases and much lower than other DNA polymerases that have associated exonucleolytic proofreading activity. Average error rates are 1/9900 and 1/12,000, respectively, for single base-substitution and minus-one nucleotide frameshift errors; the polymerase generates deletions as well. Similar error rates are observed with reactions containing the 180-kDa subunit plus an 86-kDa subunit (p86), or with these two polypeptides plus two additional subunits (p58 and p49) comprising the DNA primase activity required for DNA replication. Finally, addition of yeast replication factor-A (RF-A), a protein preparation that stimulates DNA synthesis and has single-stranded DNA-binding activity, yields a polymerization reaction with 7 polypeptides required for replication, yet fidelity remains low relative to error rates for semiconservative replication. The data suggest that neither exonucleolytic proofreading activity, the beta subunit, the DNA primase subunits nor RF-A contributes substantially to base substitution or frameshift error discrimination by the DNA polymerase alpha catalytic subunit.
Six novel peptides belonging to the tachykinin and bombesin families were isolated and sequenced from extracts of the skin of the Australian myobatrachid frog Pseudophryne güntheri. One of these peptides (PG-L) was of the bombesin family and may be considered an N-elongation of the litorin/ranatensin molecule, with which it shares an identical spectrum of activity on isolated smooth muscle preparations. The other five peptides were of the tachykinin family with two of these peptides (PG-SPI and PG-SPII) related to substance P and three (PG-KI, PG-KII and PG-KIII) to kassinin. In contrast to the basic nature of substance P, the PG-SP peptides showed a clear acidic character and displayed a more potent and sustained action on isolated smooth muscle preparations and rat blood pressure than did substance P. Two of the three PG-K peptides were more potent than kassinin; PG-KIII was considerably less potent. PG-KI and PG-KII were also present in a deamidated, poorly active, form.
The effect of oxygen partial pressure (Po(2)) on development and hatching was investigated in aquatic embryos of the myobatrachid frog, Crinia georgiana, in the field and in the laboratory. Eggs from 29 field nests experienced widely variable Po(2) but similar temperatures. Mean Po(2) in different nests ranged between 2.9 and 19.3 kPa (grand mean 12.9 kPa), and mean temperature ranged between 11.9 degrees and 16.8 degrees C (grand mean 13.7 degrees C). There was no detectable effect of Po(2) or temperature on development rate or hatching time in the field, except in one nest at 2.9 kPa where the embryos died, presumably in association with hypoxia. Laboratory eggs were incubated at 15 degrees C at a range of Po(2) between 2 and 25 kPa. Between 5 and 25 kPa, there was almost no effect of Po(2) on development rate to stage 26, but the embryos hatched progressively earlier-at earlier stages and lower gut-free body mass-at lower Po(2). At 2 kPa, development was severely delayed, growth of the embryo slowed, and morphological anomalies appeared. A high tolerance to low Po(2) may be an adaptation to embryonic development in the potentially hypoxic, aquatic environment.
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