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M P Jacobsen

Publications and source records attributed to M P Jacobsen.

9 recordsLinked to original sources

Calcium-dependent structural changes in scallop heavy meromyosin.

The mechanism of calcium regulation of scallop myosin is not understood, although it is known that both myosin heads are required. We have explored possible interactions between the heads of heavy meromyosin (HMM) in the presence and absence of calcium and nucleotides by sedimentation and electron microscope studies. The ATPase activity of the HMM preparation was activated over tenfold by calcium, indicating that the preparation contained mostly regulated molecules. In the presence of ADP or ATP analogs, calcium increased the asymmetry of the HMM molecule as judged by its slower sedimentation velocity compared with that in EGTA. In the absence of nucleotide the asymmetry was high even in EGTA. The shift in sedimentation occurred with a sharp midpoint at a calcium level of about 0.5 microM. Sedimentation of subfragment 1 was not dependent on calcium or on nucleotides. Modeling accounted for the observed sedimentation behavior by assuming that both HMM heads bent toward the tail in the absence of calcium, while in its presence the heads had random positions. The sedimentation pattern showed a single peak at all calcium concentrations, indicating equilibration between the two forms with a t(1/2) less than 70 seconds. Electron micrographs of crosslinked, rotary shadowed specimens indicated that 81 % of HMM molecules in the presence of nucleotide had both heads pointing back towards the tail in the absence of calcium, as compared with 41 % in its presence. This is consistent with the sedimentation data. We conclude that in the "off" state, scallop myosin heads interact with each other, forming a rigid structure with low ATPase activity. When molecules are switched "on" by binding of calcium, communication between the heads is lost, allowing them to flex randomly about the junction with the tail; this could facilitate their interaction with actin in contracting muscle.

Animals↗

Analysis of sedimentation equilibrium distributions reflecting nonideal macromolecular associations.

A rigorous statistical-mechanical approach is adopted to derive general quantitative expressions that allow for the effects of thermodynamic nonideality in equilibrium measurements reflecting interaction between dissimilar macromolecular reactants. An analytical procedure based on these expressions is then formulated for obtaining global estimates of equilibrium constants and the corresponding reference thermodynamic activities of the free reactants in each of several sedimentation equilibrium experiments. The method is demonstrated by application to results from an ultracentrifugal study of an electrostatic interaction between ovalbumin and cytochrome c (Winzor, D. J., M. P. Jacobsen, and P. R. Wills. 1998. Biochemistry. 37:2226-2233). It is demonstrated that reliable estimates of relevant thermodynamic parameters are extracted from the data through statistical analysis by means of a simple nonlinear fitting procedure.

Biophysical Phenomena↗

Direct analysis of sedimentation equilibrium distributions reflecting complex formation between dissimilar reactants.

Procedures are developed for the characterization of thermodynamically ideal complex formation between dissimilar macromolecular reactants by direct analysis of sedimentation equilibrium distributions. Studies of an electrostatic interaction between ovalbumin and cytochrome c are used to illustrate the application of analyses pertaining to (i) the situation in which separate sedimentation equilibrium distributions for the two macromolecular constituents are available, (ii) that in which the experimental record reflects the distribution of only one constituent, and (iii) the situation in which a composite distribution for both constituents is the sole experimental record. An association constant of 63 000 (+/- 2000) M-1 is obtained for the 1:1 interaction between ovalbumin and cytochrome c under the conditions examined (pH 6.3, I 0.03). Because of their inherent simplicity, these direct analytical procedures offer potential for accommodating the effects of thermodynamic nonideality in dissimilar reactant systems.

Animals↗

An ultracentrifugal approach to quantitative characterization of the molecular assembly of a physiological electron-transfer complex: the interaction of electron-transferring flavoprotein with trimethylamine dehydrogenase.

The interaction between two physiological redox partners, trimethylamine dehydrogenase and electron-transferring flavoprotein, has been characterized quantitatively by analytical ultracentrifugation at 4 degrees C. Analysis of sedimentation-equilibrium distributions obtained at 15 000 rpm for mixtures in 10 mM potassium phosphate, pH 7.5, by means of the psi function [Wills, P. R., Jacobsen, M. P. & Winzor, D. J. (1996) Biopolymers 38, 119-130] has yielded an intrinsic dissociation constant of 3-7 microM for the interaction of electron-transferring flavoprotein with two equivalent and independent sites on the homodimeric enzyme. This investigation indicates the potential of sedimentation equilibrium for the quantitative characterization of interactions between dissimilar macromolecules.

Bacteria↗

Thermodynamic analysis of the effects of small inert cosolutes in the ultracentrifugation of noninteracting proteins.

Considerations of the effect of a small cosolute on the sedimentation equilibrium distribution for a noninteracting protein have led to the development of a simple procedure for evaluating both the molecular weight of the protein and the second virial coefficient describing the excluded volume interaction between protein and cosolute. Its application is illustrated by analysis of sedimentation equilibrium distributions for bovine thyroglobulin and horse liver alcohol dehydrogenase in the presence of a range of sucrose concentrations, and also of those for aldolase in the presence of urea to obtain the subunit molecular weight of this tetrameric enzyme. The effects of sucrose concentration on the sedimentation coefficients of thyroglobulin, catalase, and horse liver alcohol dehydrogenase are also examined to demonstrate that the second virial coefficients for protein-cosolute excluded volume interaction may be determined, albeit with less precision, from the cosolute concentration required to render the sedimentation coefficient zero by virtue of its effect on the buoyancy term. These findings serve to reinforce the fact that the effects of small cosolutes usually ascribed to changes in "protein solvation" are envisaged more realistically in terms of excluded volume.

Alcohol Dehydrogenase↗

Characterization of the interactions of NADH with the dimeric and tetrameric states of methaemoglobin.

The binding of NADH to the dimeric (alpha beta) and tetrameric (alpha 2 beta 2) states of human aquomethaemoglobin has been characterized by sedimentation equilibrium studies of the effect of the concentration of free ligand on the macromolecular state of the haemoprotein. Both macromolecular states of aquomethaemoglobin exhibit a single binding site for NADH, which interacts approximately tenfold more strongly (6000 cf. 700 M-1) with the tetramer under the conditions studied (pH 6.0, I 0.10). Because the structure of aquomethaemoglobin resembles that of the deoxy state of haemoglobin, there is a high probability that organic phosphates also bind to dimeric deoxyhaemoglobin, a phenomenon which is not considered in thermodynamic treatments of the interplay between oxygen binding and its allosteric inhibition by 2,3-bisphosphoglycerate. Fortunately, the equilibrium constant for deoxyhaemoglobin self-association is so large that neglect of the interaction between allosteric inhibitor and dimeric haemoglobin is an oversight that should have no deleterious implications in the resultant thermodynamic analysis of the interplay between the preferential interactions of oxygen and organic phosphate with the various macromolecular states of deoxyhaemoglobin.

Binding Sites↗

Stabilizing effect of sucrose against irreversible denaturation of rabbit muscle lactate dehydrogenase.

Measurements of the kinetics of activity loss by rabbit muscle lactate dehydrogenase in acetate-chloride buffer, pH 5.0, I 0.20, have shown that the enzyme exhibits greater stability against irreversible inactivation when the buffer is supplemented with sucrose (0.1 M-0.5 M). On the basis of sedimentation equilibrium distributions obtained for enzyme in the absence and presence of sucrose (0.5 M), the lactate dehydrogenase is essentially dimeric in both environments. The observed stabilization of enzyme activity has therefore been considered in terms of the space-filling effects of sucrose on an isomerization equilibrium between native and unfolded forms of dimeric lactate dehydrogenase, which precedes irreversible inactivation of the unfolded isomer. Interpretation of the kinetic results on that basis has led to the conclusion that the initial stage of enzyme unfolding entails a minor change in volume and/or asymmetry of the lactate dehydrogenase that gives rise to a 4% increase in the second virial coefficient describing excluded volume interactions between dimeric enzyme and sucrose.

Animals↗

Effects of molecular crowding on protein self-association: a potential source of error in sedimentation coefficients obtained by zonal ultracentrifugation in a sucrose gradient.

Theoretical and experimental studies have illustrated a potential source of error in sedimentation coefficients obtained by sucrose density gradient centrifugation of proteins undergoing reversible self-association. The error stems from the excluded volume (molecular crowding) effect of the sucrose on the activity coefficients of monomeric and polymeric states. The consequent displacement of the equilibrium position in favor of polymeric state(s) is a function of sucrose concentration, and can therefore result in failure to detect the equilibrium coexistence of monomer if 5% sucrose suffices to displace the equilibrium completely toward dimer. In less extreme situations, it may result in the evaluation of an average sedimentation coefficient whose magnitude is a function of sucrose concentration and hence of the distance migrated into the sucrose gradient. These features are illustrated by the results of computer-simulated sedimentation of reversibly dimerizing systems in a sucrose gradient, and by conventional sedimentation velocity experiments on yeast enolase.

Centrifugation, Zonal↗