DISTRIBUTIONS OF FREE RADICALS AMONG AMINO ACIDS FROM LYOPHILIZED ULTRAVIOLET-IRRADIATED PROTEINS

Abstract— The effects of u.v.-irradiation at 254 nm upon lyophilized ribonuclease, lysozyme, insulin, and chymotrypsinogen have been investigated by electron spin resonance (ESR). enzymatic assay, and labeling of free radical sites with tritiated hydrogen sulfide (HST). The ESR signal of the irradiated protein diminishes on exposure to HST, and tritium becomes covalently bound to carbon. The distribution of tritium among the amino acids of each protein. studied as an indicator of the carbon free radical distribution, differs markedly from those observed previously to result from exposure to gamma radiation, electrical discharge. or hydrogen atoms. However, the earlier observation that the tritium distribution is influenced by protein conformation holds true as well for u.v.-irradiation. Moreover, the distributions of tritium among the amino acids of u.v.-irradiated proteins indicate a broad scattering of free radicals. Tyrosine and phenylalanine, residues that absorb light energy in the region of the wavelength employed, are not particularly important as radical carriers. Thus, for ribonuclease, these residues incorporated 3.8 and 1.5 per cent of the total tritium, but they absorb 51 and 12 per cent of the light, respectively. These results, together with the observed low recoveries of methionine, an amino acid that does not absorb at 254 nm, add weight to the concept that a migration of energy ensues after the initial absorption of light energy and that photolytic damage may thus be due to destruction of amino acids other than those initially absorbing the u.v.-radiation.     

Application of the integrated ion-current technique to the study of rare-earth chelates

Several substituted acetylacetones have been prepared and reacted with holmium to give tris chelates of the form HoL₃. One of these chelates has been converted to a tetrakis chelate of the form NaHoL₄. The mass spectra of these compounds have been studied and the integrated ion currents at significant m/e values have been related to the amounts of metal chelates evaporated into the ion source of the mass spectrometer. The shape of the integrated ion-current curve is shown to give information about the nature of the evaporation process. When the β-diketone (L) is asymmetrical as in the case of 1,1,1-trifluoro-5,5-dimethylhexan-2,4-dione, the existence of geometrical isomers of the chelate, HoL₃, is reflected in the shape of the integrated ion-current curve, which shows fine structure. The results of mass spectrometric studies are compared with those of the sublimation and gas chromatographic behaviour of the metal chelates.     

Enthalpies of absorption and solubility of CO2 in aqueous solutions of methyldiethanolamine

A flow mixing unit using a SETARAM C-80 calorimeter, developed for measuring the enthalpy of solution of two fluids, has been used to measure enthalpies of absorption of carbon dioxide in a 30 wt.% aqueous solution of methyldiethanolamine (MDEA) at three temperatures 313.15, 353.15, 393.15 K and three pressures 2.0, 5.0, 10.0 MPa. We have established that the effect measured by calorimetry corresponds not only to the absorption of CO₂ in the aqueous solution but also to the vaporisation of water into the carbon dioxide depending on the temperature and the pressure of the experiment. The enthalpies measured by calorimetry were compared with those calculated from solubility measurements and a reasonable agreement within the accuracy of measurement and calculation was found.     

Facile synthesis of alpha-substituted acrylate esters

Treatment of 5-monosubstituted Meldrum's acids with dimethylmethyleneimmonium iodide (Eschenmoser's iodide salt) in methanol gives alpha-substituted acrylate methyl esters in good yields. Easy access to 5-monosubstituted Meldrum's acids allowed us to synthesize a wide variety of alpha-substituted acrylate methyl esters. The reaction conditions are mild and tolerate many functional groups commonly used in organic synthesis; thus, this new method has potential as an alternative to conventional preparative methods for alpha-substituted acrylate esters.     

A study of the stability of alkaline-earth metal complexes with fluoride and chloride ions at various temperatures by potentiometry with ion-selective electrodes

The complexes of the alkaline earth metals with fluoride and chloride were studied over the temperature range 15-85 degrees . The stability constants of the MX(+) complexes were determined by potentiometry with fluoride and chloride ion-selective electrodes and the appropriate thermodynamic functions (DeltaH(0)(298), DeltaS(0)(298) and DeltaG(0)(298)) were calculated.     

Interactions of Al(III) with a neurofilament heptapeptide fragment: AcLysSerProValValGluGly

The solution state of the neurotoxic Al(III) in biological systems is discussed briefly, and the importance of the Al(III)-peptide and Al(III)-protein interactions in the various neurodegeneration processes is emphasised and evaluated. The possible involvement of Al(III) in the formation of Alzheimer's disease marker senile plaques and neurofilament tangles is discussed in light of the solution speciation of the Al(III)-AcLysSerProValValGluGly system and the structural features of the complexes formed.     

Spectroscopy on two coupled superconducting flux qubits

We have performed spectroscopy measurements on two coupled flux qubits. The qubits are coupled inductively, which results in a sigma(z)(1)sigma(z)(2) interaction. By applying microwave radiation, we observe resonances due to transitions from the ground state to the first two excited states. From the position of these resonances as a function of the applied magnetic field, we observe the coupling of the qubits. The coupling strength agrees with calculations of the mutual inductance.     

A Type Calculus for Executable Modelling Languages

There is considerable current interest in the design and constructionof directly executable modelling languages for mathematicalprogramming. The present research extends contemporary modellinglanguages by specifying a type calculus for an extended dimensionalsystem that determines if the model is well formed in the sensethat the objective function and constraints consist of homogeneouscomponents. Each variable, coefficient, constant, function,constraint, input, and output of the model is assigned a typethat consists of its concepts, quantities, and units of measurementwith optional scale factors. In checking the composition offunctions and constraints, the system can do automatic unitconversions and apply user-supplied conversions. The systemallows a hierarchy of concepts that provides inheritance ofquantities and automatic concept conversion. In addition, eachset in a model is typed so the system can check the validityof operations on indices.