Abstract: Several years ago, Theorell and Czerlinski conducted experiments on the system of horse liver alcohol dehydrogenase, reduced nicotinamide adenine dinucleotide and imidazole, using the first version of the temperature jump apparatus with detection of changes in fluorescence. These early experiments were repeated with improved instrumentation and confirmed the early experiments in general terms. However, the improved detection system allowed to measure a slight concentration dependence of the relaxation time of around 3 ms. Furthermore, the chemical relaxation time was smaller than the one determined earlier (by factor 2). The data were evaluated much more rigorously than before, allowing an appropriate interpretation of the results. The observed relaxation time is largely due to rate constants in an interconversion of ternary complexes, which are faster than three (of the four) dissociation rate constants, determined previously by Theorell and McKinley-McKee.1,2 This fact contributed to earlier difficulties of finding any concentration dependence. However, the binding of imidazole to the binary enzyme-coenzyme complex can be made to couple kinetically into the interconversion rate of the two ternary complexes. The observed signal derives largely from the ternary complex(es). A substantial fluorescence signal change is associated with the observed relaxation process, suggesting a relocation of the imidazole in reference to the nicotinamide moiety of the bound coenzyme. Nine models are considered with two types of coupling of pre-equilibria (none-all). Quantitative evaluations favor the model with two ternary complexes connected by an interconversion outside the four-step (bimolecular) cycle. The ternary complex outside the cycle has much higher fluorescence yield than the one inside. The interconversion equilibrium is near unity for imidazole. If it would be shifted very much to the side of the “dead-end” complex (as in isobutyramide?!), stimulating action could not take place.

Abstract: Chemical relaxation studies on the system horse liver alcohol dehydrogenase, nicotinamide adenine dinucleotide, and ethanol were conducted observing fluorescence changes between 400 and 500 nm. Temperature-jump experiments were performed at pH 6.5, 7.0, 8.0, and 9.0; concentration-jump experiments at pH 9.0. The reciprocal of the slowest relaxation time was found to be linearly dependent upon the enzyme concentration for relatively low enzyme concentrations, as predicted earlier. Use of the wide pH-range necessitated expression of the four apparent dissociation constants of the catalytic reaction cycle in terms of pH-independent constants. The system was described in terms of only one (or two) catalysis-linked protons not associated with the electron transfer. Protonic steps in a buffered system are in rapid equilibrium, too fast to be measured with the equipment available. Assuming only two of the four bimolecular reaction steps in the four-step cycle are fast compared to the remaining two, six cases may be considered with six expressions for the reciprocal of the slowest relaxation time. Comparison with the experimental data revealed that the bimolecular reaction steps governing the slowest relaxation time change with pH. Above the effective time resolution of the temperature-lump instrument with fluorescence detection (0.1 msec) only one other relaxation time was detectable and only at pH 9. This relaxation time, found to be independent of the concentration of all reactants within experimental error (r = 10 +/- 5 msec), is most likely due to an interconversion among ternary complexes.

Abstract: The extent to which humans and nonhumans share numerical competency is a matter of debate. Some researchers argue that nonhumans, lacking human language, possess only a simple understanding of small quantities, generally less than four. Animals that have, however, received some training in human communication systems might demonstrate abilities intermediate between those of untrained nonhumans and humans. Here I review data for a Grey parrot (Psittacus erithacus) that has been shown to quantify sets of up to and including six items (including heterogeneous subsets) using vocal English labels, to comprehend these labels fully, and to have a zero-like concept. Recent research demonstrates that he can also sum small quantities. His success shows that he understands number symbols as abstract representations of real-world collections, and that his sense of number compares favorably to that of chimpanzees and young human children.

Abstract: Chimpanzees (Pan troglodytes) and rhesus macaques (Macaca mulatta) selected either Arabic numerals or colored squares on a computer monitor in a learned sequence. On shift trials, the locations of 2 stimuli were interchanged at some point. More errors were made when this interchange occurred for the next 2 stimuli to be selected than when the interchange was for stimuli later in the sequence. On mask trials, all remaining stimuli were occluded after the 1st selection. Performance exceeded chance levels for only 1 selection after these masks were applied. There was no difference in performance for either stimulus type (numerals or colors). The data indicated that the animals planned only the next selection during these computerized tasks as opposed to planning the entire response sequence.