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Biomedical subjects

W A Bonner

Publications and source records attributed to W A Bonner.

At least 19 recordsLinked to original sources

Supernovae, neutron stars and biomolecular chirality.

Recent theoretical and experimental investigations of the origin of biomolecular chirality are reviewed briefly. Biotic and abiotic theories are evaluated critically with the conclusion that asymmetric photochemical processes with circulary polarized light (CPL), particularly asymmetric photolyses, constitute the most viable mechanisms. Solar CPL sources appear too weak and random to be effective. We suggest an alternative CPL source, namely, the synchrotron radiation from the neutron star remnants of supernova explosions. This could asymmetrically process racemic compounds in the organic mantles of the dust grains in interstellar clouds, and the resulting chiral molecules could be transferred to Earth by cold accretion as the solar system periodically traverses these interstellar clouds.

Biological Evolution

Beta-decay, bremsstrahlen, and the origin of molecular chirality.

A brief review is presented of the Vester-Ulbricht beta-decay Bremsstrahlen hypothesis for the origin of optical activity, and of subsequent experiments designed to test it. Certain of our experiments along these lines, begun in 1974 and involving the irradiation of racemic and optically active amino acids in a 61.7 KCi 90Sr-90Y Bremsstrahlen source, have now been completed and are described. After 10.89 years of irradiation with a total Bremsstrahlen dose of 2.5 X 10(9) rads, crystalline DL-leucine, norleucine, and norvaline suffered 47.2, 33.6, and 27.4% radiolysis, respectively, but showed no evidence whatsoever of asymmetric degradation. D- and L-Leucine underwent about 48% radiolysis and showed 2.4-2.9% radioracemization. Other samples in solution were too severely degraded to analyze. Probable intrinsic reasons for the failure of the Vester-Ulbricht mechanism to afford asymmetric radiolysis in the present and related experiments involving beta-decay Bremsstrahlen are enumerated.

Amino Acids

The radiolysis and racemization of leucine on proton irradiation.

D- and L-Leucine have been subjected to 39-55 percent radiolysis using 0-11 MeV protons, both with the proton beam passing through the sample or being absorbed by it, and with quenching the sample immediately on completion of irradiation or after a 21-day interval. Racemization was small (1.1-1.7 percent) and comparable in all cases, suggesting that radioracemization and secondary degradative effects were not important factors in our recent unsuccessful attempts to induce optical activity in DL-leucine by partial radiolysis using 0-11 MeV longitudinally polarized protons.

Dose-Response Relationship, Radiation

The radiolysis and radioracemization of amino acids on silica surfaces.

L-Leucine, deposited on both 1-quartz powder and on a commercial amorphous silica preparation (Syloid 63), has been subjected to irradiation in a 60Co gamma-ray source, and the ensuing radiolysis and radioracemization have been determined gas chromatographically. The radiolysis and radioracemization observed for leucine on 1-quartz were rather similar to those noted for a crystalline L-leucine control. L-Leucine on Syloid 63, however, was vastly more susceptible to radiolysis as compared to the L-leucine control, and radioracemization was also markedly enhanced - each increasing with larger radiation dosage. L-Isovaline showed a similar, but diminished, enhancement of radiolysis sensitivity when adsorbed on the Syloid surface, but underwent no radioracemization whatsoever. The divergent results of the control and quartz-leucine irradiations versus the Syloid-leucine and Syloid-isovaline irradiations are interpreted qualitatively in terms of the surface area parameters of the two silica adsorbents and the amino acid adsorbates.

Amino Acids

Search for effect of longitudinally polarized protons on optically active amino acid.

As a test of the Vester-Ulbricht hypothesis that the specific optical activity of contemporary biology arose from a differential action of polarized nuclear particles, DL-leucine has been irradiated with protons of both positive and negative longitudinal polarization. Neither kind of protons caused by measurable decomposition difference in the two optical isomers of the amino acid.

Chromatography, Gas

The radioracemization of amino acids by ionizing radiation: geochemical and cosmochemical implications.

A number of optically active amino acids, both in the solid state and as sodium or hydrochloride salts in aqueous solution, have been exposed to ionizing radiation from a 3000 Ci60Co gamma-ray source to see if radioracemization might accompany their well-known radiolysis. gamma-Ray doses causing 55--68% radiolysis of solid amino acids typically engendered 2--5% racemization, while aqueous solutions of the sodium salts of amino acids which underwent 53--66% radiolysis showed 5--11% racemization. Amino acid hydrochloride salts in aqueous solution, on the other hand, showed little or no radioracemization accompanying their radiolysis. Both radiolysis and radioracemization were roughly proportional to gamma-ray dose in the range studied (1--36 x 10(6) rads). Mechanisms for the radioracemization of amino acids in the solid state and as aqueous sodium salts are discussed, and the absence of radioracemization for aqueous hydrochloride salts is rationalized. Isovaline, a non-protein amino acid which has been isolated from the Murchison meteorite, contains no alpha-hydrogen atom and is therefore incapable of racemization via the chemical mechanisms by which ordinary amino acids racemize. Nevertheless, isovaline suffers radioracemization in the solid state to an extent comparable to that shown by ordinary amino acids, as do its sodium and hydrochloride salts in the solid state. The sodium salt of isovaline in aqueous solution, however, fails to racemize during its radiolysis. Several implications of the newly described phenomenon of radiomization are pointed out for the fields of geochemistry and cosmochemistry.

Amino Acids

Radiolysis, racemization and the origin of molecular asymmetry in the biosphere.

An investigation has been undertaken to determine whether ionizing radiation might engender racemization of optically active amino acids, along with their usual radiolysis. As prototypes, crystalline D- and L-leucine, as well as aqueous solutions of their sodium salts were exposed to the radiation from a 3000 Ci 60Co gamma-ray source. Gamma-ray doses which caused about 68% radiolysis of solid leucine left a residue which was about 5% racemized, while racemization proved even greater at lower doses for the dissolved sodium salts. In aqueous solution both percent degradation and percent racemization of the sodium salts were proportional to gamma-ray dosage within the range employed (1--27 x 10(6) rads). Implications of these observations for the origin of molecular asymmetry by the beta-decay parity violation mechanism are discussed.

Gamma Rays

On the origin of biological chirality via natural beta-decay.

Experimental evidence that longitudinally polarized electrons having the handedness characteristic of terrestrial beta-decay electrons preferentially remove D-leucine from a racemic mixture, coupled with the probable presence of 14C in pre-biotic molecules, offers a plausible hypothesis for the origin of biomolecular handedness.

Carbon Radioisotopes

On the origin of molecular "handedness" in living systems.

Elementary particle effects (beta-decay) provide at best only a weakly handed radiation in the biologically effective energy ranges. Global magnetic effects coupled to sunlight are randomized by paleomagnetic reversals. Hence a persistent terrestrial handed bias at possible local biopoetic sites offers a more promising explanation for the origin of the "handedness" of the molecules found among living systems on earth. Magnetite in lava flows maintains a handed bias for surface catalysis through many magnetic reversals. Magnetite contaminated with sulfur has already been proposed by Granick as a biopoetic site because it provides a weak source of chemical energy derived by photochemical conversion. Indirect evidence for this hypothesis has been provided by the molecular structure of ferredoxin - a single strand of the 14 primordial amino acids wrapped around an FeS core. Lava flows have been suggested as biopoetic sites by Fox, since their temperature and chemical composition might allow for the rapid synthesis of prebiotic compounds at the surface of the primitive earth. The additional fact that magnetite in lave flows also provides a persistent handed site for surface catalysis offers a further argument for the experimental investigation of this specific biopoetic environment.

Biological Evolution

Asymmetric adsorption by quartz: a model for the prebiotic origin of optical activity.

One mechanism previously proposed for the abiotic accumulation of molecules of one chirality in nature is asymmetric adsorption on the chiral surfaces of optically active quartz crystals. Earlier literature in this field is reviewed, with the conclusion that previous investigations of this phenomenon, using optical rotation criteria, have afforded ambiguous results. We now have studied the adsorption of radioactive D- and L-alanine on powdered d- and l-quartz, using change in radioactivity level as a criterion for both gross and differential adsorption. d-Quartz preferentially adsorbed D-alanine from anhydrous dimethyl-formamide solution, and l-quartz L-alanine. The differential adsorption varied between 1.0 and 1.8%. The implications of these observations are discussed from the viewpoint of early chemical evolution and the origin of optically active organic compounds in nature.

Alanine