Fluorescence and Rotational Dynamics of Dityrosine

We have examined the lifetimes and rotational correlation times of dityrosine emission by time-correlated single-photon counting. We first noticed dityrosine fluorescence in samples of tyrosine and tyrosine dipeptides by its characteristic red-shifted emission at 400 to 430 nm. The longer rotational correlation time relative to tyrosine proved that this fluorescence emanated from a distinct species. Comparison with the fluorescence properties of synthesized dityrosine established the identity of the emitting species. Fluorescence intensity decays of dityrosine are generally characterized by two decay components, one with a lifetime in the range of 150 to 800 ps and another between 2.5 and 4.5 ns. We found no evidence for an excited-state reaction, since a rising phase (negative-amplitude component) was not observed. In the pH range from 4 to 10, two ground-state species exist in equilibrium with pK _a 7. Both species exhibit two fluorescence decays. The average fluorescence lifetime increases gradually with pH over the pH range from 4 to 10 and decreases at pH 2. Anisotropy decays were measured for dityrosine and the alanine–dityrosine–alanine and leucine–dityrosine–leucine dipeptides. The rotational correlation times of dityrosine and dityrosine dipeptides increase linearly with van der Waals volumes. The slope indicates a stronger solute–solvent interaction than predicted with stick boundary conditions. It is suggested that these interactions result from the presence of two zwitterionic pairs.     

An improved water-filled impedance tube

A water-filled impedance tube capable of improved measurement accuracy and precision is reported. The measurement instrument employs a variation of the standardized two-sensor transfer function technique. Performance improvements were achieved through minimization of elastic waveguide effects and through the use of sound-hard wall-mounted acoustic pressure sensors. Acoustic propagation inside the water-filled impedance tube was found to be well described by a plane wave model, which is a necessary condition for the technique. Measurements of the impedance of a pressure-release terminated transmission line, and the reflection coefficient from a water/air interface, were used to verify the system.     

Enhanced thermal conductance at a copper-liquid helium interface in the presence of acoustic streaming

In a conventional Kapitza resistance experiment involving heat transfer across a copper surface into liquid helium, an acoustic streaming velocity field (at 10 MHz) was directed transverse to the surface normal. Ultrasound had no observable effect on the heat transfer to the superfluid phase (He-II), but in the normal fluid phase (He-I) the thermal conductance increased linearly with acoustic velocity amplitude, reaching a value 2.5 times the zero sound conductance for a sound velocity amplitude of 0.8 cm s^?1.     

Loop Groups, Anyons and the Calogero–Sutherland Model

The positive energy representations of the loop group of U(1) are used to construct a boson-anyon correspondence. We compute all the correlation functions of our anyon fields and study an anyonic W-algebra of unbounded operators with a common dense domain. This algebra contains an operator with peculiar exchange relations with the anyon fields. This operator can be interpreted as a second quantized Calogero–Sutherland (CS) Hamiltonian and may be used to solve the CS model. In particular, we inductively construct all eigenfunctions of the CS model from anyon correlation functions, for all particle numbers and positive couplings. Received: 12 May 1998 / Accepted: 4 August 1998     

A thioester substrate binds to the enzyme Arthrobacter thioesterase in two ionization states: evidence from Raman difference spectroscopy

4‐Hydroxybenzoyl‐CoA (4‐HB‐CoA) thioesterase from Arthrobacter is the final enzyme catalyzing the hydrolysis of 4‐HB‐CoA to produce coenzyme A and 4‐hydroxybenzoic acid in the bacterial 4‐chlorobenzoate dehalogenation pathway. Using a mutation E73A that blocks catalysis, stable complexes of the enzyme and its substrate can be analyzed by Raman difference spectroscopy. Here we have used Raman difference spectroscopy, in the non‐resonance regime, to characterize 4‐HB‐CoA bound in the active site of the E73A thioesterase. In addition, we have characterized complexes of the wild‐type enzyme complexed with the unreactive substrate analog 4‐hydroxyphenacyl‐CoA (4‐HP‐CoA). Both sets of complexes show evidence for two forms of the ligand in the active site: one population has the 4‐hydroxy group protonated, 4‐OH; while the second has the group as the hydroxide, 4‐O⁻. For bound 4‐HP‐CoA, X‐ray data show that glutamate 78 is close to the 4‐OH in the complex and it is likely that this is the proton acceptor for the 4‐OH proton. Although the pK_a of the 4‐OH group on the free substrate in aqueous solution is 8.6, the relative populations of ionized and neutral 4‐HB‐CoA bound to E73A remain invariant between pH 7.3 and 9.8. The invariance with pH suggests that the 4‐OH and the ‐COO⁻ of E78 constitute a tightly coupled pair where their separate pK_a ‘s lose their individual qualities. Narrow band profiles are seen in the CO double bond and C‐S regions, suggesting that the hydrolyzable thioester group is rigidly bound in the active site in a syn gauche conformation. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface characterization of Pt electrodes using underpotential deposition of H and Cu: Part I. Pt(100)

This paper is the first in a series describing the in situ surface characterization of platinum electrodes using H and Cu deposited at underpotentials. The surface of a Pt(100) electrode pretreated by simple flame annealing and quenching in aqueous sulfuric acid is shown to contain a high concentration of defects such as vacancies and self-adsorbed Pt atoms. Adsorbed hydrogen is more strongly bound at these defects than on a uniform Pt(100) surface. Potential cycling in 1 M HCl produces a higher concentration of defects, while oxide formation and reduction in 0.5 M H₂SO₄ has the opposite effect. The nature of (100)-like sites at a polycrystalline platinum electrode is also discussed.