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C-Nitroso compounds (RNO, R = alkyl and aryl) are byproducts of drug metabolism and bind to heme proteins, and their heme-RNO adducts are isoelectronic to ferrous nitroxyl (NO−/HNO) complexes. Importantly, heme-HNO compounds are key intermediates in the reduction of NO to N2O and nitrite to ammonium in the nitrogen cycle. Ferrous heme-RNO complexes act as stable analogs of these species, potentially allowing for the investigation of the vibrational and electronic properties of unstable heme-HNO intermediates. In this paper, a series of six-coordinate ferrous heme-RNO complexes (where R = iPr and Ph) were prepared using the TPP2− and 3,5-Me-BAFP2− co-ligands, and tetrahydrofuran, pyridine, and 1-methylimidazole as the axial ligands (bound trans to RNO). These complexes were characterized using different spectroscopic methods and X-ray crystallography. The complex [Fe(TPP)(THF)(iPrNO)] was further utilized for nuclear resonance vibrational spectroscopy (NRVS), allowing for the detailed assignment of the Fe–N(R)O vibrations of a heme-RNO complex for the first time. The vibrational properties of these species were then correlated with those of their HNO analogs, using DFT calculations. Our studies support previous findings that RNO ligands in ferrous heme complexes do not elicit a significant trans effect. In addition, the complexes are air-stable, and do not show any reactivity of their RNO ligands towards NO. So although ferrous heme-RNO complexes are suitable structural and electronic models for their HNO analogs, they are unsuitable to model the reactivity of heme-HNO complexes. We further investigated the reaction of our heme-RNO complexes with different Lewis acids. Here, [Fe(TPP)(THF)(iPrNO)] was found to be unreactive towards Lewis acids. In contrast, [Fe(3,5-Me-BAFP)(iPrNO)2] is reactive towards all of the Lewis acids investigated here, but in most cases the iron center is simply oxidized, resulting in the loss of the iPrNO ligand. In the case of the Lewis acid B2(pin)2, the reduced product [Fe(3,5-Me-BAFP)(iPrNH2)(iPrNO)] was identified by X-ray crystallography. [ABSTRACT FROM AUTHOR]

The Hayabusa2 mission sampled Ryugu, an asteroid that did not suffer extensive thermal metamorphism, and returned rocks to the Earth with no significant air exposure. It therefore offers a unique opportunity to study the redox state of carbonaceous Cb‐type asteroids and evaluate the overall redox state of the most primitive rocks of the solar system. An analytical framework was developed to investigate the iron mineralogy and valence state in extraterrestrial material at the micron scale by combining x‐ray diffraction, conventional Mössbauer (MS), and nuclear forward scattering (NFS) spectroscopies. An array of standard minerals was analyzed and cross‐calibrated between MS and NFS. Then, MS and NFS spectra on three Ryugu grains were collected at the bulk and the micron scales. In Ryugu samples, iron is essentially accommodated in magnetite, clay minerals (serpentine–smectite), and sulfides. Only a single set of Mössbauer parameters was necessary to account for the entire variability observed in MS and NFS spectra, at all spatial scales investigated. These parameters therefore make up a fully consistent iron mineralogical model for the Ryugu samples. As far as MS and NFS spectroscopies are concerned, Ryugu grains are overall similar to each other and share most of their mineralogical features with CI‐type chondrites. In detail however, no ferrihydrite is found in Ryugu particles even at the very sensitive scale of Mössbauer spectroscopy. The typical Fe3+/Fetot of clay minerals is much lower than typical redox ratios measured in CI chondrites (Fe3+/Fetot = 85%–90%). Furthermore, magnetite from Ryugu is stoichiometric with no significant maghemite component, whereas up to 12% of maghemite was previously identified in the Orgueil's so‐called magnetite. These differences suggest that most CI meteorites suffered terrestrial alteration and that the preterrestrial composition of these carbon‐rich samples was less oxidized than previously measured. However, it is not clear yet whether or not the parent bodies of CI chondrites were as reduced as Ryugu. Finally, the high spatial resolution of NFS allows to disentangle the redox state and the crystal chemistry of iron accommodated in serpentine and smectite. The most likely polytype of serpentine is lizardite, containing <35% of Fe3+, a fraction of which being tetrahedrally coordinated. Smectite is more oxidized (Fe3+/Fetot > 65%) and mainly contains octahedral ferric iron. This finding implies that these clays formed from highly alkaline fluids and the spatial variability highlighted here may suggest a temporal evolution or a spatial variability of the nature of this fluid. [ABSTRACT FROM AUTHOR]

Ultraviolet (UV) networks are widely applied in complex electromagnetic environments. Designing an efficient multi-node medium access control (MAC) protocol for these networks is important. In this study, we proposed an enhanced clustering time division multiple access (TDMA) MAC protocol based on clustering and learning automata (LA). Subsequently, the effects of the network topology, class of service, and number of cluster nodes on the network performance under the proposed protocol were analyzed. Then, the protocol was compared with the TDMA protocol and clustering system. Results revealed that it obtained a better network performance, proving its suitability for multi-node UV networking. [ABSTRACT FROM AUTHOR]

The 57Fe isomer shift (IS) of pure iron has been measured up to 100 GPa using synchrotron Mössbauer spectroscopy in the time domain. Apart from the expected discontinuity due to the α → ε structural and spin transitions, the IS decreases monotonically with increasing pressure. The absolute shifts were reproduced without semi-empirical calibrations by periodic density functional calculations employing extensive localized basis sets with several common density functionals. However, the best numerical agreement is obtained with the B1WC hybrid functional. Extension of the calculations to 350 GPa, a pressure corresponding to the Earth's inner core, predicted the IS range of 0.00 to −0.85 mm/s, covering the span from Fe(0) to Fe(VI) compounds measured at ambient pressure. The calculations also reproduced the pressure trend from polymorphs of prototypical iron oxide minerals, FeO and Fe2O3. Analysis of the electronic structure shows a strong donation of electrons from oxygen to iron at high pressure. The assignment of formal oxidation to the Fe atom becomes ambiguous under this condition. [ABSTRACT FROM AUTHOR]

The transport of hydrogen into Earth's deep interior may have an impact on lower mantle dynamics as well as on the seismic signature of subducted material. Due to the stability of the hydrous phases δ‐AlOOH (delta phase), MgSiO2(OH)2 (phase H), and ε‐FeOOH at high temperatures and pressures, their solid solutions may transport significant amounts of hydrogen as deep as the core‐mantle boundary. We have constrained the equation of state, including the effects of a spin crossover in the Fe3+ atoms, of (Al, Fe)‐phase H: Al0.84Fe3+0.07Mg0.02Si0.06OOH, using powder X‐ray diffraction measurements to 125 GPa, supported by synchrotron Mössbauer spectroscopy measurements on (Al, Fe)‐phase H and δ‐(Al, Fe)OOH. The changes in spin state of Fe3+ in (Al, Fe)‐phase H results in a significant decrease in bulk sound velocity and occurs over a different pressure range (48–62 GPa) compared with δ‐(Al, Fe)OOH (32–40 GPa). Changes in axial compressibilities indicate a decrease in the compressibility of hydrogen bonds in (Al, Fe)‐phase H near 30 GPa, which may be associated with hydrogen bond symmetrization. The formation of (Al, Fe)‐phase H in subducted oceanic crust may contribute to scattering of seismic waves in the mid‐lower mantle (∼1,100–1,550 km). Accumulation of 1–4 wt.% (Al, Fe)‐phase H could reproduce some of the seismic signatures of large, low seismic‐velocity provinces. Our results suggest that changes in the electronic structure of phases in the (δ‐AlOOH)‐(MgSiO2(OH)2)‐(ε‐FeOOH) solid solution are sensitive to composition and that the presence of these phases in subducted oceanic crust could be seismically detectable throughout the lower mantle. Plain Language Summary: Hydrogen can be transported into the interior of the Earth by phases which contain hydrogen in their crystal structure. Interpretation of measured seismic velocities relies on understanding the elastic properties of minerals, including their equation of state. In this study, we use X‐ray diffraction and Mössbauer spectroscopy to constrain the equation of state for a particular hydrous phase known as (Al, Fe)‐phase H and understand pressure‐induced related effects due to changes in the electronic structure of Fe atoms. Our results imply that only a small amount of this phase needs to be transported to the deep mantle to reproduce observed seismic velocities at the edges of large structures known as low seismic‐velocity provinces. The presence of (Al, Fe)‐phase H in subducted oceanic crust may also contribute to the scattering of seismic waves in shallower regions of Earth's interior. Key Points: The equation of state of (Al, Fe)‐phase H (Al0.84Fe3+0.07Mg0.02Si0.06OOH) is constrained by powder X‐ray diffraction to 125 GPaThe equation of state and synchrotron Mössbauer spectroscopy measurements reveal a spin crossover of Fe3+ in (Al, Fe)‐phase H (48–63 GPa)Accumulation of 1–4 wt. % (Al, Fe)‐phase H may explain seismic velocities at edges of large, low seismic velocity provinces [ABSTRACT FROM AUTHOR]

Average Bit Error Rate (BER), outage probability and average channel capacity expressions of a Modulating Retro-Reflector (MRR) optical communication system based on an Airy beam under weak turbulence are derived. The effects of propagation distance, width parameter and exponential truncation factor of the Airy beam itself on the communication performance of the system are discussed. Meanwhile, the performance of the system based on the Gaussian beam is compared with the same turbulence condition and propagation distance. The simulation results show that under the same conditions, the system based on the Airy beam shows a lower outage probability, average BER and larger average channel capacity compared to the system based on the Gaussian beam. Moreover, the advantages of the Airy beam are more significant as the average signal-to-noise ratio (SNR) increases. [ABSTRACT FROM AUTHOR]

Poly(arylene ether)s with different molecular weights were synthesized via a two‐step nucleophilic substitution polymerization by adjusting reaction parameters based on phenolphthalein (PHT) and decafluorobiphenyl (DFBP). The chemical structures and properties were identified by Fourier transform infrared, NMR, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, dynamic thermomechanical analysis (DMA), and so forth. The number‐average molecular weight (Mn) of the resulting polymers was in the range of 23.0–49.3KDa. FPAEs (polyarylether including perfluorobiphenyl structure) were demonstrated to have outstanding thermo‐resistance with 5% weight loss temperature of about 482–520°C (N2) and high‐glass transition temperature (about 240–250°C). FPAEs can be dissolved in conventional organic solvents, possessing excellent film‐forming properties. The good mechanical properties of FPAEs were confirmed by the DMA data, with Young's modulus greater than 1.0 Gpa and modulus retention rate at 230°C >67%. FPAEs also showed good hydrophobicity and low‐water absorption, in particular, FPAE‐1 (FPAE‐1‐5 were the polycondensation products of PHT and DFBP, just the polymerization conditions were slightly modified) exhibited favorable dielectric properties: at 1 MHz, the dielectric constant and dielectric loss was 2.58 and 0.0053, respectively. Thus, FPAE‐1 has broad prospective applications in microelectronic devices and communication technology. [ABSTRACT FROM AUTHOR]

We have performed and analyzed the first combined 151Eu and 57Fe nuclear resonant vibrational spectroscopy (NRVS) for naturally abundant KEu(III)[Fe(II)(CN)6] and Eu(III)[Fe(III)(CN)6] complexes. Comparison of the observed 151Eu vs.57Fe NRVS spectroscopic features confirms that Eu(III) in both KEu(III)[Fe(II)(CN)6] and Eu(III)[Fe(III)(CN)6] occupies a position outside the [Fe(CN)6] core and coordinates to the N atoms of the CN− ions, whereas Fe(III) or Fe(II) occupies the site inside the [Fe(CN)6]4− core and coordinates to the C atoms of the CN− ions. In addition to the spectroscopic interest, the results from this study provide invaluable insights for the design and evaluation of the nanoparticles of such complexes as potential cellular contrast agents for their use in magnetic resonance imaging. The combined 151Eu and 57Fe NRVS measurements are also among the first few explorations of bi-isotopic NRVS experiments. [ABSTRACT FROM AUTHOR]