Intramolecular hemiacetals. The acid-base-catalyzed ring-chain interconversion of 2-substituted 2-hydroxy-4,4-dimethylmorpholinium cations in aqueous solution.

The ring-chain tautomerism in aqueous solution of some aryl-substituted morpholinium salts (bromides), has been studied and equilibrium constants are reported. In the crystals the substrates exist entirely in their cyclic forms as hemiacetals, but in aqueous solution NMR measurements reveal that an equilibrium is established between the cyclic (hemiacetal) and the noncyclic (ketone) form, the degree of ring-opening being more pronounced with electron-donating aryl substituents at the carbonyl carbon. The kinetics of the ring-chain interconversion in water has been investigated spectrophotometrically by a 'pH jump' stopped-flow technique. General base catalysis is observed with a Br?nsted beta value apparently independent of substituent and equal to 0.60. The Hammett rho values for various base catalysts are close to those for very similar intermolecular reactions involving hemiacetal breakdown, leading to the suggestion of a 'normal' class n mechanism for base catalysis. For acid catalysis, however, a quite different situation is encountered, since no general acid but only (weak) catalysis by the hydronium ion can be detected. We believe this deviation from 'normal' general acid catalysis is caused by an electrostatic interaction, and we suggest that it might result from a change in the usual class e mechanism for general acid catalysis by a situation in which rate-limiting concerted proton transfer is replaced by rate-limiting preprotonation. This is supported by the observed drastic change in Hammett rho value for catalysis by the hydronium ion, compared with the 'normal' case. An interesting case is encountered for the 4-aminophenyl-substituted substrate, in which the amino group becomes protonated in acid solution, thus representing a new substituent. Despite this complication, the various equilibrium and rate constants may also be evaluated experimentally for this substrate.     

Variational bounds on shear-driven turbulence and turbulent Boussinesq convection

Based on earlier studies by Hopf (1941), Doering and Constantin (1992, 1994, 1995) have recently formulated a new “background” technique for obtaining upper bounds on turbulent fluid flow quantities. This method produces upper bounds on the limit supremum of long time averages, making no statistical assumptions about the flow in contrast to the well-known Howard-Busse approach. The full optimisation problems posed by this method for the momentum transport in turbulent Couette flow and the heat transport (with zero background flow) in turbulent Boussinesq convection are solved here for the first time at asymptotically large Reynolds number and Rayleigh number within Busse's multiple boundary layer approximation to extract the best (lowest) possible upper bounds available. Intriguingly, the original bounds isolated by Busse (1969, 1970) within the confines of statistical stationarity are recovered exactly using this new formalism. The optimal background velocity profile for turbulent Couette flow is found to be shearless in the interior thus differing from Busse's “ ” mean shear result. In the convective case, an interesting degeneracy in the formulation of the background variational problem leads to an indeterminacy in the optimal background temperature profile. Only for one special choice is the isothermal core feature of Busse's mean profile recovered.     

The missing part of the greenhouse effect

Summary Global average temperatures from 1860 to 1989 were analysed with a simple fitting procedure. The temperature records can be fitted with a rising exponential up to 1946 and with the same exponential minus an increasing cooling action from 1946 to 1989. It is shown that the results are compatible with the hypothesis of an albedo increase caused by SO₂ emissions. This hypothesis gives satisfactory explanations of the temperature drop in the years 1940–1970, of the different warming of the northern and southern hemispheres and of the slower warming observed over North America. The results give an indication that the greenhouse warming in the next years could be faster than predicted until now. Due to the relevance of its scientific content, this paper has been given priority by the Journal Direction.     

Mössbauer studies of iron uptake,ferritin and hemoglobin synthesis and denaturation in erythroid cell cultures

Mössbauer studies in murine (MEL) and human K-562 erythroleukemia cell lines have been utilized to study the fate of iron during intracellular Hb synthesis and denaturation. The results showed that ferritin can serve as an intermediate iron pool for Hb synthesis and for storage of iron released during intracellular Hb denaturation.     

Conformal symmetry and the role of torsion in a Maxwell-Einstein system

We develope a formalism which allows to treat Weyl symmetry with torsion as the gauge theory of the conformal group. The results of the standard Einstein—Cartan theroy are generalized and applied to the Maxwell-Einstein case.To my wife     

μSR studies of heavy fermion systems

We have performed both zero field and high transverse field measurements at dilution refrigerator temperatures on a number of heavy electron systems, examining the superconducting and magnetic properties of these interesting materials. Among the materials studied to date are UBe₁₃, URu₂Si₂ and U₆Fe. The magnetic field penetration depth in the superconducting state of UBe₁₃ is greater than 10000 Å, as no increase in the transverse field relaxation rate is observed belowT _c . A sharp increase in the precession frequency is seen, starting atT _c . This frequency shift shows little temperature dependence at low temperature; we found no clear evidence for unconventional superconductivity in this material. Zero field measurements in URu₂Si₂ show the weak antiferromagnetic transition at 17.5 K. Finally, we we found no clear evidence for unconventional superconductivity in this material. Zero field measurements in URu₂Si₂ show the weak antiferromagnetic transition at 17.5 K. Finally, we have observed relaxation in high transverse field due to the formation of a flux lattice in U₆Fe, a material where the electron effective mass is rather lighter than in other heavy fermion systems. The relaxation exhibits a sharp onset atT _c=3.9 K, and is flat at low temperatures as expected for a conventional superconductor.     

On composition of some general fractional integral operators

In the present paper we derive three interesting expressions for the composition of two most general fractional integral oprators whose kernels involve the product of a general class of polynomials and a multivariableH-function. By suitably specializing the coefficients and the parameters in these functions we can get a large number of (new and known) interesting expressions for the composition of fractional integral operators involving classical orthogonal polynomials and simpler special functions (involving one or more variables) which occur rather frequently in problems of mathematical physics. We have mentioned here two special cases of the first composition formula. The first involves product of a general class of polynomials and the Fox’sH-functions and is of interest in itself. The findings of Buschman [1] and Erdélyi [4] follow as simple special cases of this composition formula. The second special case involves product of the Jacobi polynomials, the Hermite polynomials and the product of two multivariableH-functions. The present study unifies and extends a large number of results lying scattered in the lierature. Its findings are general and deep.     

Temperature dependence of the rate constants for reactions of the carbonate radical with organic and inorganic reductants

Rate constants have been measured by pulse radiolysis for the reactions of the carbonate radical, CO₃^·?, with a number of organic and inorganic reactants as a function of temperature, generally over the range 5 to 80°C. The reactants include the substitution-inert cyano complexes of Fe^II, Mo^IV, and W^IV, the simple inorganic anions SO₃^2?, ClO₂^?, NO₂^?, I^?, and SCN^?, several phenolates, ascorbate, tryptophan, cysteine, cystine, methionine, triethylamine, and allyl alcohol. The measured rate constants ranged from less than 10⁵ to 3 × 10⁹ M^?1 s^?1, the activation energies ranged from ?11.4 to 18.8 kJ mol^?1, and the pre-exponential factors ranged from log A = 6.4 to 10.7. The activation energies for the metal complexes and inorganic anions generally decrease with increasing driving force for the reaction, as expected for an outer sphere electron transfer. For highly exothermic reactions, however, the activation energy appears to increase, probably reflecting the temperature dependence of diffusion. For many of the organic reactants, the activation energies were low and independent of driving force, suggesting that the oxidation is via an inner sphere mechanism.