Pulsed EPR Dipolar Spectroscopy under the Breakdown of the High-Field Approximation: The High-Spin Iron(III) Case

Pulsed EPR dipolar spectroscopy (PDS) offers several methods for measuring dipolar coupling and thus the distance between electron-spin centers. To date, PDS measurements to metal centers were limited to ions that adhere to the high-field approximation. Here, the PDS methodology is extended to cases where the high-field approximation breaks down on the example of the high-spin Fe³⁺/nitroxide spin-pair. First, the theory developed by Maryasov et al. (Appl. Magn. Reson. 2006 , 30, 683–702) was adapted to derive equations for the dipolar coupling constant, which revealed that the dipolar spectrum does not only depend on the length and orientation of the interspin distance vector with respect to the applied magnetic field but also on its orientation to the effective g-tensor of the Fe³⁺ ion. Then, it is shown on a model system and a heme protein that a PDS method called relaxation-induced dipolar modulation enhancement (RIDME) is well-suited to measuring such spectra and that the experimentally obtained dipolar spectra are in full agreement with the derived equations. Finally, a RIDME data analysis procedure was developed, which facilitates the determination of distance and angular distributions from the RIDME data. Thus, this study enables the application of PDS to for example, the highly relevant class of high-spin Fe³⁺ heme proteins.     

Particle image velocimetry investigation of a finite amplitude pressure wave

Particle image velocimetry is used to study the motion of gas within a duct subject to the passage of a finite amplitude pressure wave. The wave is representative of the pressure waves found in the exhaust systems of internal combustion engines. Gas particles are accelerated from stationary to 150 m/s and then back to stationary in 8 ms. It is demonstrated that gas particles at the head of the wave travel at the same velocity across the duct cross section at a given point in time. Towards the tail of the wave viscous effects are plainly evident causing the flow profile to tend towards parabolic. However, the instantaneous mean particle velocity across the section is shown to match well with the velocity calculated from a corresponding measured pressure history using 1D gas dynamic theory. The measured pressure history at a point in the duct was acquired using a high speed pressure transducer of the type typically used for engine research in intake and exhaust systems. It is demonstrated that these are unable to follow the rapid changes in pressure accurately and that they are prone to resonate under certain circumstances.     

Characterizing the influence of reinforcing resin on the structure and the mechanical response of filled isoprene rubber

In the present study, a specific type of reinforcing resin behavior is investigated using various mechanical approaches as well as microscopic techniques such as transmission electron microscopy and atomic force microscopy. Based on these observations, it could be concluded that the reinforcing resin introduces a synergistic effect with carbon black in order to strengthen the system. This is implied since the percolation threshold is significantly reduced and the morphology of the filler aggregates changes toward higher compactness, i.e., an increase of volume-to-size ratio with the addition of resin.     

Synthesis of μ2-Oxo-Bridged Iron(III) Tetraphenylporphyrin–Spacer–Nitroxide Dimers and their Structural and Dynamics Characterization by using EPR and MD Simulations

Iron(III) porphyrins have the propensity to form μ₂-oxo-dimers, the structures of which resemble two wheels on an axle. Whereas their crystal structure is known, their solution structure and internal dynamics is not. In the present work, the structure and dynamics of such dimers were studied by means of electron paramagnetic resonance (EPR) spectroscopy and quantum chemistry based molecular dynamics (MD) simulations by using the semiempirical tight-binding method (GFN-xTB). To enable EPR investigation of the dimers, a nitroxide was attached to each of the tetraphenylporphyrin cores through a linear and a bent linker. The inter-nitroxide distance distributions within the dimers were determined by continuous-wave (cw)-EPR and pulsed electron–electron double resonance (PELDOR or DEER) experiments and, with the help of MD, interpreted in terms of the rotation of the porphyrin planes with respect to each other around the Fe–O–Fe axis. It was found that such rotation is restricted to the four registers defined by the phenyl substituents. Within the registers, the rotation angle swings between 30° and 60° in the proximal and between 125° and 145° in the distal register. With EPR, all four angles were found to be equally populated, whereas the 30° and 145° angles are strongly favored to the expense of the 60° and 125° angles in the MD simulation. In either case, the internal dynamics of these dimers thus resemble the motion of a step motor.     

SLIM: A Short‐Linked,Highly Redox‐Stable Trityl Label for High‐Sensitivity In‐Cell EPR Distance Measurements

The understanding of biomolecular function is coupled to knowledge about the structure and dynamics of these biomolecules, preferably acquired under native conditions. In this regard, pulsed dipolar EPR spectroscopy (PDS) in conjunction with site‐directed spin labeling (SDSL) is an important method in the toolbox of biophysical chemistry. However, the currently available spin labels have diverse deficiencies for in‐cell applications, for example, low radical stability or long bioconjugation linkers. In this work, a synthesis strategy is introduced for the derivatization of trityl radicals with a maleimide‐functionalized methylene group. The resulting trityl spin label, called SLIM, yields narrow distance distributions, enables highly sensitive distance measurements down to concentrations of 90 nm , and shows high stability against reduction. Using this label, the guanine‐nucleotide dissociation inhibitor (GDI) domain of Yersinia outer protein O (YopO) is shown to change its conformation within eukaryotic cells.     

Determination of the Absolute Configuration of Perylene Quinone‐Derived Mycotoxins by Measurement and Calculation of Electronic Circular Dichroism Spectra and Specific Rotations

Altertoxins I–III, alterlosins I and II, alteichin (alterperylenol), stemphyltoxins I–IV, stemphyperylenol, stemphytriol, 7‐epi‐8‐hydroxyaltertoxin I, and 6‐epi‐stemphytriol are mycotoxins derived from perylene quinone, for which the absolute configuration was not known. Electronic circular dichroism (ECD) spectra were calculated for these compounds and compared with measured spectra of altertoxins I–III, alteichin, and stemphyltoxin III and with reported Cotton effects. Specific rotations were calculated and compared with reported specific rotations. The absolute configuration of all the toxins, except for stemphyltoxin IV, could thus be determined. The validity of the assignment was high whenever reported ECD data were available for comparison, and the validity was lower when the assignment was based only on the comparison of calculated and reported specific rotations. ECD spectra are intrinsically different for toxins with a biphenyl substructure and for toxins derived from dihydroanthracene.     

Difficulties in the growth and characterization of non-linear optical materials: A case study of salts of amino acids

In the crystallographic literature, there is an ever-increasing number of publications on crystals that are referred to as ‘new non-linear optical materials’, many of them reporting salts of amino acids. However, the term NLO material is used improperly in most cases. In fact, the establishment of any crystal species as such a material requires several experimental and computational procedures, which are seldom satisfied when characterizing a supposedly new species. Here, some frequent hazards and problems are addressed and observations of papers reporting amino acid compounds as supposedly new NLO materials are made.     

Poly (methyl methacrylate) grafted wheat straw for economical and eco-friendly treatment of oily wastewater

Cellulose - The sustainable development of oil–gas and petrochemical industries necessitates the development of cost-effective and eco-friendly technologies to treat mass-produced oily...