SPECTROSCOPY AND FLUORESCENCE QUENCHING OF TYROSINE IN LIMA BEAN TRYPSIN/CHYMOTRYPSIN INHIBITOR AND MODEL PEPTIDES

The effects of citrate ion concentration and pH on the optical spectra and fluorescence decay have been measured for several tyrosine model compounds and lima bean trypsin/chymotrypsin inhibitor, a protein containing one tyrosine at position 69 and seven disulfides but no tryptophan, in order to determine the location and environment of Tyr 69. Tyrosine in the protein is protected from citrate collisional quenching, as indicated by the dynamic quenching constant 9 to 15 times smaller than those for the model peptides. Static quenching remains, with a Stern-Volmer constant of about 1.0 M-1, somewhat smaller than those of L-tyrosine, tyrosine-glutamate, and leucine-tyrosine-leucine. The elevated pKa of Tyr 69, greater than or equal to 11.6, also indicates protein protection from solvent ions. Though Coulomb repulsion of the Glu 70/citrate pair may play a role in the shielding of Tyr 69 from citrate, our measurements indicate that steric effects of the protein structure are more important. Tyrosinate emission in the protein at neutral pH is minimal.     

The metallic state

Metals contain free electrons. Various theoretical and practical implications of this characteristic feature of the metallic state are discussed. Recent views which emphasize ease of ionization, unsaturated metallic bonds, and screening of electrical charges by free electrons, as the basis for distinguishing between metals, semi-conductors, and insulators, are described. The importance of the free electron bond for the crystal structures, cohesive properties, and alloy behaviour of metals is emphasized, and the principles underlying the engineering strength properties of matter and the design of creep-resistant alloys are briefly discussed in terms of free electrons and dislocations in solids.     

Probability-based protein identification by searching sequence databases using mass spectrometry data

Several algorithms have been described in the literature for protein identification by searching a sequence database using mass spectrometry data. In some approaches, the experimental data are peptide molecular weights from the digestion of a protein by an enzyme. Other approaches use tandem mass spectrometry (MS/MS) data from one or more peptides. Still others combine mass data with amino acid sequence data. We present results from a new computer program, Mascot, which integrates all three types of search. The scoring algorithm is probability based, which has a number of advantages: (i) A simple rule can be used to judge whether a result is significant or not. This is particularly useful in guarding against false positives. (ii) Scores can be compared with those from other types of search, such as sequence homology. (iii) Search parameters can be readily optimised by iteration. The strengths and limitations of probability-based scoring are discussed, particularly in the context of high throughput, fully automated protein identification.     

Inelastic electron scattering from hydrogen at 50° and 60°

Inelastic electron scattering cross sections have been measured for four-momentum transfers between 4.1 GeV² and 30.5 GeV². At the large scattering angles of this experiment, the dominant contribution to the cross section comes from the W₁ structure function. In the conventional scaling variables, x and x′, this structure function does not exhibit scaling behavior, and at fixed x or x′ it is found to decrease with increasing four-momentum transfer.     

Modelling hydrogen in silicate materials

The expectation that the hydroxyl analogue state of positive muons implanted in quartz should be stabilized by a suitable charge compensation centre is supported by preliminary data. The diamagnetic fraction correlates with aluminium content over the narrow range investigated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Transitions,with change in parity,produced in 107,109Ag by coulomb excitation

Some of the low-lying energy levels of ¹⁰⁷Ag and ¹⁰⁹Ag were excited by Coulomb excitation using α-particles from 4.8 to 7.2 MeV. Transitions to the isomeric state ($\text{7}\text{2}{}^{\mathrm{+}}$), involving a parity change, were observed both directly in the singles spectra and indirectly by the decay of the isomer. The isomer in both silver isotopes was populated by transitions from the $\text{5}\text{2}{}^{\mathrm{?}}$ level, which was strongly excited. The observed branching ratio in ¹⁰⁹Ag for the $\text{5}\text{2}{}^{\mathrm{?}}\text{→}\text{7}\text{2}{}^{\mathrm{+}}$ transition was (0.315 ± 0.09) % and for the $\text{5}\text{2}{}^{\mathrm{?}}\text{→}\text{9}\text{2}{}^{\mathrm{+}}$ transition was (0.055±0.03) %. The total rate of populating the $\text{7}\text{2}{}^{\mathrm{+}}$ level from the $\text{5}\text{2}{}^{\mathrm{?}}$ level was (0.215±0.04) % in ¹⁰⁷Ag. The level schemes have been discussed on the weak-coupling model, allowing admixtures of singleparticle wave functions to account for the weaker transitions.     

Radio-frequency μSR experiments at the ISIS pulsed muon facility

This paper explores the use of pulsed radio-frequency (RF) techniques to remove the frequency limitations imposed on conventional transverse muon spin rotation (μSR) experiments at a pulsed muon source by the finite muon pulse width. The implementation of the 90° pulse technique is demonstrated by observing the free precession signal of diamagnetic muons implanted in polythene, the change in signal amplitude as a function of RF pulse length is plotted and the precise condition for a 90° pulse determined. The technique is evaluated by comparing measurements made using conventional spin rotation experiments to those employing pulsed RF methods. The potential for applying standard NMR multiple-pulse methods to the μSR experiment is considered and the use of two-pulse RF sequences (90° _x ?τ?90° _x and 90° _x ?τ?180° _x ) to form a muon spin echo demonstrated.     

A-dependence of high-energy inelastic electron-nucleus scattering

Cross sections for inclusive inelastic electron scattering from H, D, Be, Al, Cu and Au have been measured at 6° for incident energies up to 19.5 GeV. Within the stated errors, the cross sections were found to be directly proportional to the sum of the constituent nucleon cross sections.     

Muon spin relaxation study of Zr(H2PO4)(PO4).2H2O

Muon spin relaxation has been used to study the muon dynamics in the layered zirconium phosphate Zr(H(2)PO(4))(PO(4)).2H(2)O as a function of temperature. Radiofrequency decoupling was used to establish the origin of the local dipolar field as coupling with (1)H spins. Muons were trapped at two sites, one identified as HMuO and the other consistent with PO-Mu on the basis of their zero-field second moments. Although a small decrease in the local nuclear dipolar field was seen with temperature, the muons remained essentially static over the temperature range 20-300 K.