Determination of the distance between the two neutral flavin radicals in augmenter of liver regeneration by pulsed ELDOR

Pulsed electron-electron double resonance (ELDOR) has been used to obtain structural information from a FAD-dependent sulfhydryl oxidase, Augmenter of Liver Regeneration (ALR). ALR is a homodimer with each subunit containing a noncovalently bound FAD cofactor. Both FADs may be converted into the blue neutral radical form by aerobic treatment with DTT. From three-pulse and four-pulse ELDOR experiments, a distance of 26.1 +/- 0.8 A could be determined between the FAD cofactors in human ALR. Taking into account the electron spin density distribution in a neutral flavin radical obtained from density functional theory calculations, a distance of 26.9 A could be estimated for the separation of the spin centers in the X-ray structure of rat ALR. The good agreement confirms that rat ALR may be used as a model for mechanistic discussions of human ALR. The experiments also demonstrate that neutral flavin radicals have the appropriate properties to be used as intrinsic spin labels for distance determinations in proteins.     

Evaluating the conformational entropy of macromolecules using an energy decomposition approach

We have developed a novel method to compute the conformational entropy of any molecular system via conventional simulation techniques. This method only requires that the total energy of the system is available and that the Hamiltonian is separable, with individual energy terms for the various degrees of freedom. Consequently the method, which we call the energy decomposition (Edcp) approach, is general and applicable to any large polymer in implicit solvent. Edcp is applied to estimate the entropy differences due to the peptide and ester groups in polyalanine and polyalanil ester. Ensembles over a wide range of temperatures were generated by replica exchange molecular dynamics, and densities of states were estimated using the weighted histogram analysis method. The results are compared with those obtained via evaluating the P ln P integral or employing the quasiharmonic approximation, other approaches widely employed to evaluate the entropy of molecular systems. Unlike the former method, Edcp can accommodate the correlations present between separate degrees of freedom. In addition, the Edcp model assumes no specific form for the underlying fluctuations present in the system, in contrast to the quasiharmonic approximation. For the molecules studied, the quasiharmonic approximation is observed to produce a good estimate of the vibrational entropy, but not of the conformational entropy. In contrast, our energy decomposition approach generates reasonable estimates for both of these entropy terms. We suggest that this approach embodies a simple yet effective solution to the problem of evaluating the conformational entropy of large macromolecules in implicit solvent.     

Analysis of trace impurities in semiconductor gas via cavity-enhanced direct frequency comb spectroscopy

Cavity-enhanced direct frequency comb spectroscopy (CE-DFCS) has demonstrated powerful potential for trace-gas detection based on its unique combination of high bandwidth, rapid data acquisition, high sensitivity, and high resolution, which is unavailable with conventional systems. However, previous demonstrations have been limited to proof-of-principle experiments or studies of fundamental laboratory science. Here, we present the development of CE-DFCS towards an industrial application—measuring impurities in arsine, an important process gas used in III–V semiconductor compound manufacturing. A strongly absorbing background gas with an extremely complex, congested, and broadband spectrum renders trace detection exceptionally difficult, but the capabilities of CE-DFCS overcome this challenge and make it possible to identify and quantify multiple spectral lines associated with water impurities. Further, frequency combs allow easy access to new spectral regions via efficient nonlinear optical processes. Here, we demonstrate detection of multiple potential impurities across 1.75–1.95 μm (5710–5130 cm⁻¹), with a single-channel detection sensitivity (simultaneously over 2000 channels) of ∼4×10⁻⁸ cm⁻¹ Hz^−1/2 in nitrogen and, specifically, an absorption sensitivity of ∼4×10⁻⁷ cm⁻¹ Hz^−1/2 for trace water doped in arsine.     

Claustrophobia in MRI: the role of cognitions

Purpose

This study aimed to investigate the role of cognitive and behavioural factors in the experience of claustrophobia in the context of magnetic resonance imaging (MRI) scanners.

Materials and Methods

One hundred and thirty outpatients attending an MRI unit completed questionnaires before and after their scans. Specific measures of experience in the scanner included subjective anxiety, panic symptoms, strategies used to stay calm and negative cognitions (such as ‘I will suffocate’ and ‘I am going to faint in here’). Other general measures used included anxiety, depression, health anxiety and fears of restriction and suffocation.

Results

The amount of anxiety experienced during the scan was related to the perceived amount of time spent having physical symptoms of panic. Cognitions reported concerned the following: suffocation, harm caused by the machine and lack of perceived control. The number of strategies patients used to cope in the machine was also a related factor. Neither position in the scanner, nor head coil use nor previous experience of being in the scanner was related to levels of anxiety.

Conclusion

The cognitions identified here may be used to construct a measure to identify those unable to enter the scanner or those most likely to become claustrophobic whilst undergoing the procedure and to further inform future brief, effective interventions.     

Cavity-enhanced direct frequency comb spectroscopy

Cavity-enhanced direct frequency comb spectroscopy combines broad spectral bandwidth, high spectral resolution, precise frequency calibration, and ultrahigh detection sensitivity, all in one experimental platform based on an optical frequency comb interacting with a high-finesse optical cavity. Precise control of the optical frequency comb allows highly efficient, coherent coupling of individual comb components with corresponding resonant modes of the high-finesse cavity. The long cavity lifetime dramatically enhances the effective interaction between the light field and intracavity matter, increasing the sensitivity for measurement of optical losses by a factor that is on the order of the cavity finesse. The use of low-dispersion mirrors permits almost the entire spectral bandwidth of the frequency comb to be employed for detection, covering a range of ～?10% of the actual optical frequency. The light transmitted from the cavity is spectrally resolved to provide a multitude of detection channels with spectral resolutions ranging from several gigahertz to hundreds of kilohertz. In this review we will discuss the principle of cavity-enhanced direct frequency comb spectroscopy and the various implementations of such systems. In particular, we discuss several types of UV, optical, and IR frequency comb sources and optical cavity designs that can be used for specific spectroscopic applications. We present several cavity-comb coupling methods to take advantage of the broad spectral bandwidth and narrow spectral components of a frequency comb. Finally, we present a series of experimental measurements on trace gas detections, human breath analysis, and characterization of cold molecular beams. These results demonstrate clearly that the wide bandwidth and ultrasensitive nature of the femtosecond enhancement cavity enables powerful real-time detection and identification of many molecular species in a massively parallel fashion.     

Terahertz quantum well infrared detectors

We report on recent measurements on GaAs/AlGaAs THz quantum well infrared photodetectors (QWIPs), investigating linewidth broadening as function of doping level. Structures with 3% and 2% Al content in the barrier were grown using molecular beam epitaxy (MBE) and metal-organic chemical vapor deposition (MOCVD), respectively. Linewidth widening with increasing doping of the GaAs quantum well could be observed in the detection spectra. The observed shift of peak detection wavelength for different well dopings fits with values obtained from wavefunction calculations, taking into account many-particle effects, namely exchange and correlation energies and the effect of depolarization on the absorption. In addition, activation energies extracted from dark current measurements as function of device temperature are also in agreement with the calculations.     

Geometric simulation of perovskite frameworks with Jahn-Teller distortions: applications to the cubic manganites

A new approach is presented for modeling perovskite frameworks with disordered Jahn-Teller (JT) distortions and has been applied to study the elastic response of the LaMnO3 structure to defects in the JT ordering. Surprisingly, antiphase domain boundary defects in the pattern of ordered JT octahedra, along the [110] and [110] bonding directions, are found to produce 1D stripe patterns rotated 45 degrees along a* directions, similar to stripe structures observed in these systems. Geometric simulation is shown to be an efficient and powerful approach for finding relaxed atomic structures in the presence of disorder in networks of corner-shared JT-distorted octahedra such as the perovskites. Geometric modeling rapidly relaxes large supercells (thousands of octahedra) while preserving the local coordination chemistry, and shows great promise for studying these complex systems.     

On a class of solutions in plane finite elasticity

Zusammenfassung Es werden endliche elastische Deformationen bei ebenen Verzerrungszuständen betrachtet, in welchen die Spannungen nur vom Azimut abhängen. Der allgemeine Charakter der Deformationen wird für inkompressible isotrope Materialien diskutiert; insbesondere werden zwei partikuläre Lösungen aufgestellt, die für alle Formen der Verzerrungsenergie gültig sind. Die Lösungen der ersten Klasse sind die erwarteten homogenen Deformationen, während diejenigen der zweiten Klasse in rotatorischen, von einem einzigen Parameter abhängigen Verformungen bestehen. Es wird die Lösung von Randwertproblemen für die Spannungen bei keilförmigen Gebieten im einzelnen für ein Mooney-Material untersucht und dabei gezeigt, dass gewisse besondere Eigenschaften der infinitesimalen Theorie auch in der nichtlinearen auftreten.

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The results presented in this paper were obtained in the course of research sponsored by the National Science Foundation.     

Reactions of organothallium compounds with olefins

Arylthallium compounds react with olefins in the presence of Li₂PdCl₄, the overall reaction being the replacement of an olefinic hydrogen by the aryl group.