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Enzymatic Nitrogen Insertion into Unactivated C–H Bonds
No full textSelective functionalization of aliphatic C–H bonds, ubiquitous in molecular structures, could allow ready access to diverse chemical products. While enzymatic oxygenation of C–H bonds is well established, the analogous enzymatic nitrogen functionalization is still unknown; nature is reliant on pre-oxidized compounds for nitrogen incorporation. Likewise, synthetic methods for selective nitrogen derivatization of unbiased C–H bonds remain elusive. In this work, new-to-nature heme-containing nitrene transferases were used as starting points for the directed evolution of enzymes to selectively aminate and amidate unactivated C(sp3)–H sites. The desymmetrization of methyl- and ethylcyclohexane with divergent site selectivity is offered as demonstration. The evolved enzymes in these lineages are highly promiscuous and show activity towards a wide array of substrates, providing a foundation for further evolution of nitrene transferase function. Computational studies and kinetic isotope effects (KIEs) are consistent with a stepwise radical pathway involving an irreversible, enantiodetermining hydrogen atom transfer (HAT), followed by a lower-barrier diastereoselectivity determining radical rebound step. In-enzyme molecular dynamics (MD) simulations reveal a predominantly hydrophobic pocket with favorable dispersion interactions with the substrate. By offering a direct path from saturated precursors, these enzymes present a new biochemical logic for accessing nitrogen-containing compounds
Magnetar Bursts Due to Alfvén Wave Nonlinear Breakout
No full textThe most common form of magnetar activity is short X-ray bursts, with durations from milliseconds to seconds, and luminosities ranging from 10³⁴–10⁴³ erg s⁻¹. Recently, an X-ray burst from the galactic magnetar SGR 1935+2154 was detected to be coincident with two fast radio burst (FRB) like events from the same source, providing evidence that FRBs may be linked to magnetar bursts. Using fully 3D force-free electrodynamics simulations, we show that such magnetar bursts may be produced by Alfvén waves launched from localized magnetar quakes: a wave packet propagates to the outer magnetosphere, becomes nonlinear, and escapes the magnetosphere, forming an ultra-relativistic ejecta. The ejecta pushes open the magnetospheric field lines, creating current sheets behind it. Magnetic reconnection can happen at these current sheets, leading to plasma energization and X-ray emission. The angular size of the ejecta can be compact, ≲1 sr if the quake launching region is small, ≲0.01 sr at the stellar surface. We discuss implications for the FRBs and the coincident X-ray burst from SGR 1935+2154
Experimental and Theoretical Comparison of Potential-dependent Methylation on Chemically Exfoliated WS₂ and MoS₂
No full textReductant-activated functionalization is shown to enhance the methylation of chemically exfoliated MoS₂ (ceMoS₂) and ceWS₂ by introducing excess negative charge to facilitate a nucleophilic attack reaction. Relative to methylation in the absence of a reductant, the reaction produces a twofold increase in coverage of ceWS₂, from 25 to 52% coverage per WS₂. However, at every potential, the methyl coverage on ceWS₂ was ∼20% lower than that on ceMoS₂. We applied grand canonical density functional theory to show that at constant potential, more negative charge is present on 1T′-MoS₂ than on 1T′-WS₂, making methylation both thermodynamically and kinetically more favorable for 1T′-MoS₂ than 1T′-WS₂. This effect was moderated when the reactions were compared at constant charge, emphasizing the importance of comparing the reactivity of materials at nominally identical electrode potentials
The VLA/ALMA Nascent Disk And Multiplicity (VANDAM) Survey of Orion Protostars. V. A Characterization of Protostellar Multiplicity
No full textWe characterize protostellar multiplicity in the Orion molecular clouds using Atacama Large Millimeter/submillimeter Array 0.87 mm and Very Large Array 9 mm continuum surveys toward 328 protostars. These observations are sensitive to projected spatial separations as small as ∼20 au, and we consider source separations up to 10⁴ au as potential companions. The overall multiplicity fraction (MF) and companion fraction (CF) for the Orion protostars are 0.30 ± 0.03 and 0.44 ± 0.03, respectively, considering separations from 20 to 10⁴ au. The MFs and CFs are corrected for potential contamination by unassociated young stars using a probabilistic scheme based on the surface density of young stars around each protostar. The companion separation distribution as a whole is double peaked and inconsistent with the separation distribution of solar-type field stars, while the separation distribution of Flat Spectrum protostars is consistent solar-type field stars. The multiplicity statistics and companion separation distributions of the Perseus star-forming region are consistent with those of Orion. Based on the observed peaks in the Class 0 separations at ∼100 au and ∼10³ au, we argue that multiples with separations 10³ au to <10³ au, and that some companions between 10³ and 10⁴ au must be (or become) unbound
Matrix Product States with Large Sites
No full textWe explore various ways to group orbitals into clusters in a matrix product state (MPS). We explain how a generic cluster MPS can often lead to an increase in computational cost and instead propose a special cluster structure, involving only the first and last orbitals/sites, with a wider scope for computational advantage. This structure is a natural formalism to describe correlated multireference (MR) theories. We demonstrate the flexibility and usefulness of this approach by implementing various uncontracted MR configuration interaction, perturbation, and linearized coupled cluster theories using an MPS with large cluster sites. Applications to the nitrogen dimer, the chromium dimer, and benzene, including up to triple excitations in the external space, demonstrate the utility of an MPS with up to two large sites. We use our results to analyze the quality of different multireference approximations
Frustration Dynamics and Electron-Transfer Reorganization Energies in Wild-Type and Mutant Azurins
No full textLong-range electron tunneling through metalloproteins is facilitated by evolutionary tuning of donor–acceptor electronic couplings, formal electrochemical potentials, and active-site reorganization energies. Although the minimal frustration of the folding landscape enables this tuning, residual frustration in the vicinity of the metallocofactor can allow conformational fluctuations required for protein function. We show here that the constrained copper site in wild-type azurin is governed by an intricate pattern of minimally frustrated local and distant interactions that together enable rapid electron flow to and from the protein. In contrast, sluggish electron transfer reactions (unfavorable reorganization energies) of active-site azurin variants are attributable to increased frustration near to as well as distant from the copper site, along with an exaggerated oxidation-state dependence of both minimally and highly frustrated interaction patterns
A Transiting, Temperate Mini-Neptune Orbiting the M Dwarf TOI-1759 Unveiled by TESS
No full textWe report the discovery and characterization of TOI-1759 b, a temperate (400 K) sub-Neptune-sized exoplanet orbiting the M dwarf TOI-1759 (TIC 408636441). TOI-1759 b was observed by TESS to transit in Sectors 16, 17, and 24, with only one transit observed per sector, creating an ambiguity regarding the orbital period of the planet candidate. Ground-based photometric observations, combined with radial-velocity measurements obtained with the CARMENES spectrograph, confirm an actual period of 18.85019 ± 0.00014 days. A joint analysis of all available photometry and radial velocities reveals a radius of 3.17 ± 0.10 R_⊕ and a mass of 10.8 ± 1.5 M_⊕. Combining this with the stellar properties derived for TOI-1759 (R_⋆ = 0.597 ± 0.015 R_⊙; M_⋆ = 0.606 ± 0.020 M_⊙; T_(eff) = 4065 ± 51 K), we compute a transmission spectroscopic metric (TSM) value of over 80 for the planet, making it a good target for transmission spectroscopy studies. TOI-1759 b is among the top five temperate, small exoplanets (T_(eq) 200 days seem to be present in our radial velocities. While our data suggest both could arise from stellar activity, the later signal’s source and periodicity are hard to pinpoint given the ∼200 days baseline of our radial-velocity campaign with CARMENES. Longer baseline radial-velocity campaigns should be performed in order to unveil the true nature of this long-period signal
Seismic Mapping of Subglacial Hydrology Reveals Previously Undetected Pressurization Event
No full textUnderstanding the dynamic response of glaciers to climate change is vital for assessing water resources and hazards, and subglacial hydrology is a key player in glacier systems. Traditional observations of subglacial hydrology are spatially and temporally limited, but recent seismic deployments on and around glaciers show the potential for comprehensive observation of glacial hydrologic systems. We present results from a high-density seismic deployment spanning the surface of Lemon Creek Glacier, Alaska. Our study coincided with a marginal lake drainage event, which served as a natural experiment for seismic detection of changes in subglacial hydrology. We observed glaciohydraulic tremor across the surface of the glacier that was generated by the subglacial hydrologic system. During the lake drainage, the relative changes in seismic tremor power and water flux are consistent with pressurization of the subglacial system of only the upper part of the glacier. This event was not accompanied by a significant increase in glacier velocity; either some threshold necessary for rapid basal motion was not attained, or, plausibly, the geometry of Lemon Creek Glacier inhibited speedup. This pressurization event would have likely gone undetected without seismic observations, demonstrating the power of cryoseismology in testing assumptions about and mapping the spatial extent of subglacial pressurization
An integrative approach: using transcriptomic data and network analysis of transcriptional reprogramming in tomato response to PSTVd variants
No full textViroids are minimal pathogens of angiosperms, consisting of non-coding RNAs that cause severe diseases in agronomic crops. Symptoms associated with viroid infection are linked to developmental alterations due to genetic regulation. To understand the global molecular mechanisms of host response, we implemented an omics approach to identify master transcription regulators (MTRs) and their differentially expressed targets in tomato infected with mild and severe variants of PSTVd. Our approach integrates root and leaf transcriptomic data, gene regulatory network analysis, and identification of affected biological processes. Overall, our results reveal that specific bHLH, MYB, and ERF transcription factors regulate genes involved in molecular mechanisms underlying critical signaling pathways. Functional enrichment of regulons shows that bHLH-MTRs are linked to metabolism and plant defense, while MYB-MTRs are involved in signaling regulation and hormone-related processes. Strikingly, a member of the bHLH-TF family have a potential specific role as a microprotein involved in the post-translational regulation of hormone signaling events. For the severe variant, ERF-MTRs are characteristic, while ZNF-TF, tf3a-TF, BZIP-TFs, and NAC-TF act as unique MTRs. Altogether, our results lay a foundation for further research on the PSTVd and host genome interaction, providing evidence for identifying potential key genes that influence symptom development in tomato plants
In situ architecture of human kinetochore-microtubule interface visualized by cryo-electron tomography
No full textAbstractFaithful segregation of chromosomes during mitosis relies on a carefully coordinated and intricate interplay between the centromere, kinetochore, and spindle microtubules. Despite its importance, the architecture of this interface remains elusive. Here we used in situ cryo-electron tomography to visualize the native architecture of the kinetochore-microtubule interface in human U2OS cells at different stages of mitosis. We find that the centromere forms a pocket-like structure around kinetochore microtubules. Two morphologically distinct fibrillar densities form end-on and side-on connections to the plus-ends of microtubules within this centromeric pocket. Our data suggest a dynamic kinetochore-microtubule interface with multiple interactions between outer kinetochore components and spindle microtubules