A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO}^(8-10)

Given the importance of Fe–NO complexes in both human biology and the global nitrogen cycle, there has been interest in understanding their diverse electronic structures. Herein a redox series of isolable iron nitrosyl complexes stabilized by a tris(phosphine)borane (TPB) ligand is described. These structurally characterized iron nitrosyl complexes reside in the following highly reduced Enemark–Feltham numbers: {FeNO}^8, {FeNO}^9, and {FeNO}^(10). These {FeNO}^(8–10) compounds are each low-spin, and feature linear yet strongly activated nitric oxide ligands. Use of Mössbauer, EPR, NMR, UV/Vis, and IR spectroscopy, in conjunction with DFT calculations, provides insight into the electronic structures of this uncommon redox series of iron nitrosyl complexes. In particular, the data collectively suggest that {TPBFeNO}^(8–10) are all remarkably covalent. This covalency is likely responsible for the stability of this system across three highly reduced redox states that correlate with unusually high Enemark–Feltham numbers

CYP99A3: functional identification of a diterpene oxidase from the momilactone biosynthetic gene cluster in rice

Rice (Oryza sativa) produces momilactone diterpenoids as both phytoalexins and allelochemicals. Strikingly, the rice genome contains a biosynthetic gene cluster for momilactone production, located on rice chromosome 4, which contains two cytochromes P450 mono-oxygenases, CYP99A2 and CYP99A3, with undefined roles; although it has been previously shown that RNAi double knock-down of this pair of closely related CYP reduced momilactone accumulation. Here we attempted biochemical characterization of CYP99A2 and CYP99A3, which ultimately was achieved by complete gene recoding, enabling functional recombinant expression in bacteria. With these synthetic gene constructs it was possible to demonstrate that, while CYP99A2 does not exhibit significant activity with diterpene substrates, CYP99A3 catalyzes consecutive oxidations of the C19 methyl group of the momilactone precursor syn-pimara-7,15-diene to form, sequentially, syn-pimaradien-19-ol, syn-pimaradien-19-al and syn-pimaradien-19-oic acid. These are presumably intermediates in momilactone biosynthesis, as a C19 carboxylic acid moiety is required for formation of the core 19,6-γ-lactone ring structure. We further were able to detect syn-pimaradien-19-oic acid in rice plants, which indicates physiological relevance for the observed activity of CYP99A3. In addition, we found that CYP99A3 also oxidized synstemod- 13(17)-ene at C19 to produce, sequentially, syn-stemoden-19-ol, syn-stemoden-19-al and syn-stemoden-19-oic acid, albeit with lower catalytic efficiency than with syn-pimaradiene. Although the CYP99A3 syn-stemodene derived products were not detected in planta, these results nevertheless provide a hint at the currently unknown metabolic fate of this diterpene in rice. Regardless of any wider role, our results strongly indicate that CYP99A3 acts as a multifunctional diterpene oxidase in momilactone biosynthesis

Cp* Noninnocence Leads to a Remarkably Weak C–H Bond via Metallocene Protonation

Metallocenes, including their permethylated variants, are extremely important in organometallic chemistry. In particular, many are synthetically useful either as oxidants (e.g., Cp_2Fe^+) or as reductants (e.g., Cp_2Co, Cp*_2Co, and Cp*_2Cr). The latter have proven to be useful reagents in the reductive protonation of small-molecule substrates, including N_2. As such, understanding the behavior of these metallocenes in the presence of acids is paramount. In the present study, we undertake the rigorous characterization of the protonation products of Cp*_2Co using pulse electron paramagnetic resonance (EPR) techniques at low temperature. We provide unequivocal evidence for the formation of the ring-protonated isomers Cp*(exo/endo-η^4-C_5Me_5H)Co^+. Variable temperature Q-band (34 GHz) pulse EPR spectroscopy, in conjunction with density functional theory (DFT) predictions, are key to reliably assigning the Cp*(exo/endo-η^4-C_5Me_5H)Co^+ species. We also demonstrate that exo-protonation selectivity can be favored by using a bulkier acid and suggest this species is thus likely a relevant intermediate during catalytic nitrogen fixation given the bulky anilinium acids employed. Of further interest, we provide physical data to experimentally assess the C–H bond dissociation free energy (BDFE_(C–H)) for Cp*(exo-η^4-C_5Me_5H)Co^+. These experimental data support our prior DFT predictions of an exceptionally weak C–H bond (<29 kcal mol^(–1)), making this system among the most reactive (with respect to C–H bond strength) to be thoroughly characterized. These data also point to the propensity of Cp*(exo-η^4-C_5Me_5H)Co to mediate hydride (H–) transfer. Our findings are not limited to the present protonated metallocene system. Accordingly, we outline an approach to rationalizing the reactivity of arene-protonated metal species, using decamethylnickelocene as an additional example

Global Navigation Satellite Systems disciplined oscillator synchronisation of multistatic radar

A fundamental challenge in the practical implementation of multistatic radar systems (MSRS) is the requirement for precise time and frequency synchronisation between the spatially separated radar nodes. The authors evaluate the performance of different classes of commercially available Global Navigation Satellite Systems (GNSS) timing receivers, Local Oscillators (LO) and GNSS Disciplined Oscillators (GNSSDOs) to determine the limitations of using one‐way GNSS Time and Frequency Transfer (TFT) in this application. From evaluating the performance of three pairs of GNSSDOs, it is concluded that one‐way GNSS TFT will likely be suitable only for the synchronisation of fully spatially coherent MSRS with carrier frequencies up to 100 MHz and waveform bandwidths up to 20 MHz. Whereas, in the case of short‐term spatially coherent MSRS, synchronisation of systems with carrier frequencies up to a few GHz and waveform bandwidths of over 100 MHz will likely be possible. The performance of the different classes of GNSSDOs during GNSS denial (holdover) are evaluated, where it is concluded that frequency offsets between LOs at the point of GNSS denial will often significantly contribute, or even dominate, the holdover performance. Analysis of two practical multistatic radar measurements verifies the function of using the GNSSDOs for wireless synchronisation of the ARESTOR MSRS

Fe-Mediated Nitrogen Fixation with a Metallocene Mediator: Exploring pK_a Effects and Demonstrating Electrocatalysis

Substrate selectivity in reductive multi-electron/proton catalysis with small molecules such as N_2, CO_2, and O_2 is a major challenge for catalyst design, especially where the competing hydrogen evolution reaction (HER) is thermodynamically and kinetically competent. In this study, we investigate how the selectivity of a tris(phosphine)borane iron(I) catalyst, P_3^BFe^+, for catalyzing the nitrogen reduction reaction (N_2RR, N_2-to-NH_3 conversion) versus HER changes as a function of acid pK_a. We find that there is a strong correlation between pKa and N_2RR efficiency. Stoichiometric studies indicate that the anilinium triflate acids employed are only compatible with the formation of early stage intermediates of N_2 reduction (e.g., Fe(NNH) or Fe(NNH_2)) in the presence of the metallocene reductant Cp*_2Co. This suggests that the interaction of acid and reductant is playing a critical role in N–H bond forming reactions. DFT studies identify a protonated metallocene species as a strong PCET donor and suggest that it should be capable of forming the early stage N–H bonds critical for N_2RR. Furthermore, DFT studies also suggest that the observed pK_a effect on N_2RR efficiency is attributable to the rate and thermodynamics, of Cp*_2Co protonation by the different anilinium acids. Inclusion of Cp*_2Co^+ as a co-catalyst in controlled potential electrolysis experiments leads to improved yields of NH_3. The data presented provide what is to our knowledge the first unambiguous demonstration of electrocatalytic nitrogen fixation by a molecular catalyst (up to 6.7 equiv NH_3 per Fe at −2.1 V vs Fc^(+/0))

Population characteristics of Shovelnose Sturgeon during low- and high-water conditions in the lower Platte River, Nebraska

Cycles of low- and high-water periods (i.e., years) in river systems are natural occurrences, but understanding how cyclical climatological patterns affect fishes, especially long-lived species, is unclear. We assessed Shovelnose Sturgeon population dynamics between a period of low- (2001-2004) and high- (2009-2012) water years in the lower Platte River, Nebraska. Low-flow periods in the lower Platte River can cause disconnection(s) between upstream and downstream reaches resulting in isolated pools and elevated water temperatures leading to stressful situations for aquatic life and possible mortality. Our data show no measurable differences between key population indices between flow condition periods which is consistent with current paradigms for long-lived fish species. Shovelnose Sturgeon relative weights were generally \u3e 80 during both low- and high-water periods and the size structure did not differ between the two periods. Shovelnose Sturgeon abundances, however, were greater during high-water conditions compared to low-water conditions (Kruskal-Wallis: χ2 = 6.15, d.f. = 1, P = 0.01). Shovelnose Sturgeon may have migrated to more suitable habitats during low-water periods to seek refuge allowing these individuals to return during more suitable conditions. Shovelnose Sturgeon and other riverine fish have evolved in a variable environment and have been able to endure relatively minor anthropogenic changes within the lower Platte River. Rivers like the lower Platte River that have retained much of their original physical features and flow regimes are likely key components for the resistance and resilience of riverine species. However, as alterations to landscapes continue and uncertainty exists surrounding future climate predictions, it is unknown how these riverine species will be able to adapt to future changes. The reduction in anthropogenic changes that disrupt flow regimes and increasing connectivity among river systems could provide more fish refuge during stressful conditions helping to protect these riverine species

An Experimental Study of Radar-Centric Transmission for Integrated Sensing and Communications

This study proposes a dual-function radar and communication (DFRC) system that utilizes radar transmission parameters as modulation indexes to transmit data to the users while performing radar sensing as its primary function. The proposed technique exploits index modulation (IM) using the center frequency of radar chirps, their bandwidths, and polarization states as indexes to modulate the communication data within each radar chirp. By utilizing the combination of these indexes, the proposed DFRC system can reach up to 17 Mb/s throughput, while observing a robust radar performance. Through our experimental study, we also reveal the trade-off between the radar sensing performance and communication data rate, depending on the radar waveform parameters selected in the DFRC system. This study also demonstrates the implementation of the proposed DFRC system and presents its real-time over-the-air experimental measurements. Consequently, the simulation results are verified by real-time over-the-air experiments, where ARESTOR, a high-speed signal processing and experimental radar platform, has been employed