Distance-dependent fluorescence quenching ofN-acetyl-l-tryptophanamide by acrylamide

We examined the time-dependent intensity decays ofN-acetyl-l-tryptophanamide (NATA) when collisionally quenched by acrylamide in propylene glycol over a range of temperatures. The intensity decays of NATA became increasingly heterogeneous in the presence of acrylamide. The NATA intensity decays were not consistent with the Collins-Kimball radiation boundary condition (RBC) model for quenching. The steady-state Stern-Volmer plots show significant upward curvature, and quenching of NATA by acrylamide was observed even in vitrified propylene glycol, where translational diffusion cannot occur during the lifetime of the excited state. These frequencydomain and steady-state data indicate a through-space quenching interaction between NATA and acrylamide, and the results are consistent with a rate constant for quenching that depends exponentially on the fluorophore-quencher separation distance. The exponential distance-dependent rate of quenching also explains the upward curvature of the Stern-Volmer plot, and the steady-state data aid in determining the interaction distance between NATA and acrylamide. These results suggest that the distance-dependent quenching rates need to be considered in the interpretation of acrylamide quenching of proteins.     

Distance distributions and dynamics of a zinc finger peptide from fluorescence resonance energy transfer measurements

Time-resolved fluorescence resonance energy transfer (FRET) measurements were used to measure distance distributions and intramolecular dynamics (site-to-site diffusion) of a 28-residue single-domain zinc finger peptide in the absence and presence of zinc ion. Energy transfer was measured between TRP₁₄ and a N-terminal DNS group. As expected, the TRP-to-DNS distance distribution for zinc-bound peptide is shorter and narrower (R _av=11.2 Å,hw=2.8 Å) than the metal-free peptide (R _av=20.1 Å,hw=14.5 Å). The degree of mutual donor-to-acceptor diffusion (D) was also determined for these distributions. For zinc-bound peptide there is no detectible diffusion (D0.2 Ų/ns), whereas for metal-free peptide a considerable amount of motion is occurring between the donor and the acceptor (D=12 Ų/ns). These results indicate that the zinc-bound peptide folds into a unique, well-defined conformation, whereas the metal-free conformation is flexible and rapidly changing. The absence of detectible mutual site-to-site diffusion between the donor and the acceptor in the metal-bound zinc finger peptide indicates that intramolecular motion is essentially frozen out, on the FRET time scale, as a consequence of zinc coordination.Dedicated to the memory of Barbara D. Wells.     

Review of fluorescence anisotropy decay analysis by frequency-domain fluorescence spectroscopy

This didactic paper summarizes the mathematical expressions needed for analysis of fluorescence anisotropy decays from polarized frequency-domain fluorescence data. The observed values are the phase angle difference between the polarized components of the emission and the modulated anisotropy, which is the ratio of the polarized and amplitude-modulated components of the emission. This procedure requires a separate measurement of the intensity decay of the total emission. The expressions are suitable for any number of exponential components in both the intensity decay and the anisotropy decay. The formalism is generalized for global analysis of anisotropy decays measured at different excitation wavelengths and for different intensity decay times as the result of quenching. Additionally, we describe the expressions required for associated anisotropy decays, that is, anisotropy decays where each correlation time is associated with a decay time present in the anisotropy decay. And finally, we present expressions appropriate for distributions of correlation times. This article should serve as a reference for researchers using frequency-domain fluorometry.     

Tunable THz metamaterials based on an array of paraelectric SrTiO<Subscript>3</Subscript> rods

This work presents theoretical and experimental investigations of a tunable metamaterial which exhibits negative permeability in the THz frequency range. The tunability is obtained by temperature changes, and the sample consists of an array of high-permittivity SrTiO₃ (STO) rods micromachined by a femtosecond laser. Structures exhibiting a negative permeability on multiple frequency bands are also investigated and a proper choice of the dimensions of the pattern allows us to achieve a substantial broadening of the frequency band with negative μ.     

d-d excitations in manganites probed by resonant inelastic x-ray scattering

We report a study of electronic excitations in manganites exhibiting a range of ground states, using resonant inelastic x-ray scattering (RIXS) at the Mn K edge. Excitations with temperature dependent changes correlated with the magnetism were observed as high as 10 eV. By calculating Wannier functions, and finite-q response functions, we associate this dependence with intersite d-d excitations. The calculated dynamical structure factor is found to be similar to the RIXS spectra.     

Delayed resonator with acceleration feedback – Complete stability analysis by spectral methods and vibration absorber design

This paper deals with the problem of active vibration suppression using the concept of delayed resonator (DR) absorber with acceleration feedback. A complete dynamic analysis of DR and its coupling with a single degree of freedom mechanical system are performed. Due to the presence of a delay in the acceleration feedback, the dynamics of the resonator itself, as well as the dynamics of combined system are of ‘neutral’ character. On this system, spectral methods are applied to perform a complete stability analysis. Particularly, the method of cluster treatment of characteristic roots is used to determine stability boundaries in the space of the resonator parameters. Based on this analysis, a methodology to select the resonator parameters is proposed in order to guarantee desirable suppression characteristics and to provide safe stability margins. An example case study is included to demonstrate these analytical results.     

Surface energy and solute strain energy effects in surface segregation

Previous models of surface segregation have generally been based on the assumption that a decrease in surface free energy constitutes the predominant driving force for the phenomenon. In contrast, grain boundary segregation models have been founded on the postulate that the major driving force for that phenomenon is the reduction in lattice strain energy which accompanies the transfer of misfitting solute atoms from the lattice to the boundary. These two concepts have been combined here into a single unified formalism of surface segregation. In addition, the temperature dependence of surface composition of both nickel-rich and gold-rich nickelgold alloys has been measured by Auger electron spectroscopy. Comparisons of the predictions of the combined formalism with the experimental results show excellent agreement between measured and calculated heats of adsorption (segregation). Furthermore, the present formalism provides estimates of the entropies of adsorption which can be used to explain apparent incompatibilities between the behavior of gold-rich and nickel-rich alloys.     

Interdiffusion in the Co-Ni system-I concentration penetration curves and interdiffusion coefficients

The interdiffusion in the Co-Ni system has been investigated in the temperature range of 950 to 1150 °C, by means of diffusion specimens of pure Co and Ni. The concentration curvesN(x, t) obtained with the aid of an JXA-3 A JEOL electron microprobe were evaluated using the smoothing cubic spline method by means of the Boltzmann-Matano equation. The obtained interdififusion coefficient values ¯D increase with the increasing Ni concentration and satisfy the Arrhenius equation at temperaturesH 990 °C. At lower temperatures the influence of high diffusivity paths may be effective, resulting in higher ¯D values. No expressive influence of atomic (Ni₃Co) or magnetic order on the interdiffusion has been detected. The activation enthalpyH values were found almost concentration independent. A Kirkendall effect study has been carried out with positive results which are presented in Part II of this paper. A new method for the determination of diffusants concentration in the Kirkendall plane was proposed. With the use of this method and of Darken equations the intrinsic diffusion coefficients were calculated. These results are given in Part III.     

Photoelectrocatalytic decomposition of gaseous isopropanol in a polymer electrolyte photoreactor

A photoelectrochemical reactor constructed as a proton exchange membrane fuel cell was utilized to electrochemically enhance the photocatalytic decomposition of gas-phase isopropanol. Nafion membrane was employed to serve as solid electrolyte to establish an electrochemical circuit for the gaseous photocatalytic reaction. The electrical current density of photoanode was found to correspond to the variation of the applied bias and relative humidity of the inlet gas. Photocatalytic decomposition rate was remarkably increased by 20 % by applying a bias potential of 5 V. The effect of relative humidity exhibited multiple effects for membrane conductivity of Nafion and efficiency of photocatalytic decomposition reaction.