Infrared Multiphoton Dissociation Enables Top-Down Characterization of Membrane Protein Complexes and G Protein-Coupled Receptors

Membrane proteins are challenging to analyze by native mass spectrometry (MS) as their hydrophobic nature typically requires stabilization in detergent micelles that are removed prior to analysis via collisional activation. There is however a practical limit to the amount of energy which can be applied, which often precludes subsequent characterization by top-down MS. To overcome this barrier, we have applied a modified Orbitrap Eclipse Tribrid mass spectrometer coupled to an infrared laser within a high-pressure linear ion trap. We show how tuning the intensity and time of incident photons enables liberation of membrane proteins from detergent micelles. Specifically, we relate the ease of micelle removal to the infrared absorption of detergents in both condensed and gas phases. Top-down MS via infrared multiphoton dissociation (IRMPD), results in good sequence coverage enabling unambiguous identification of membrane proteins and their complexes. By contrasting and comparing the fragmentation patterns of the ammonia channel with two class A GPCRs, we identify successive cleavage of adjacent amino acids within transmembrane domains. Using gas-phase molecular dynamics simulations, we show that areas prone to fragmentation maintain aspects of protein structure at increasing temperatures. Altogether, we propose a rationale to explain why and where in the protein fragment ions are generated

SN 2022crv: IIb, Or Not IIb: That is the Question

We present optical and near-infrared observations of SN~2022crv, a stripped envelope supernova in NGC~3054, discovered within 12 hrs of explosion by the Distance Less Than 40 Mpc Survey. We suggest SN~2022crv is a transitional object on the continuum between SNe Ib and SNe IIb. A high-velocity hydrogen feature ($\sim$$-$20,000 -- $-$16,000 $\rm km\,s^{-1}$) was conspicuous in SN~2022crv at early phases, and then quickly disappeared around maximum light. By comparing with hydrodynamic modeling, we find that a hydrogen envelope of $\sim 10^{-3}$ \msun{} can reproduce the behaviour of the hydrogen feature observed in SN~2022crv. The early light curve of SN~2022crv did not show envelope cooling emission, implying that SN~2022crv had a compact progenitor with extremely low amount of hydrogen. The analysis of the nebular spectra shows that SN~2022crv is consistent with the explosion of a He star with a final mass of $\sim$4.5 -- 5.6 \msun{} that has evolved from a $\sim$16 -- 22 \msun{} zero-age main sequence star in a binary system with about 1.0 -- 1.7 \msun{} of oxygen finally synthesized in the core. The high metallicity at the supernova site indicates that the progenitor experienced a strong stellar wind mass loss. In order to retain a small amount of residual hydrogen at such a high metallicity, the initial orbital separation of the binary system is likely larger than $\sim$1000~$\rm R_{\odot}$. The near-infrared spectra of SN~2022crv show a unique absorption feature on the blue side of He I line at $\sim$1.005~$\mu$m. This is the first time that such a feature has been observed in a Type Ib/IIb, and could be due to \ion{Sr}{2}. Further detailed modelling on SN~2022crv can shed light on the progenitor and the origin of the mysterious absorption feature in the near infrared.Comment: 33 pages, 23 figures, submitted to Ap

Strong Carbon Features and a Red Early Color in the Underluminous Type Ia SN 2022xkq

We present optical, infrared, ultraviolet, and radio observations of SN 2022xkq, an underluminous fast-declining type Ia supernova (SN Ia) in NGC 1784 ($\mathrm{D}\approx31$ Mpc), from $<1$ to 180 days after explosion. The high-cadence observations of SN 2022xkq, a photometrically transitional and spectroscopically 91bg-like SN Ia, cover the first days and weeks following explosion which are critical to distinguishing between explosion scenarios. The early light curve of SN 2022xkq has a red early color and exhibits a flux excess which is more prominent in redder bands; this is the first time such a feature has been seen in a transitional/91bg-like SN Ia. We also present 92 optical and 19 near-infrared (NIR) spectra, beginning 0.4 days after explosion in the optical and 2.6 days after explosion in the NIR. SN 2022xkq exhibits a long-lived C I 1.0693 $\mu$m feature which persists until 5 days post-maximum. We also detect C II $\lambda$6580 in the pre-maximum optical spectra. These lines are evidence for unburnt carbon that is difficult to reconcile with the double detonation of a sub-Chandrasekhar mass white dwarf. No existing explosion model can fully explain the photometric and spectroscopic dataset of SN 2022xkq, but the considerable breadth of the observations is ideal for furthering our understanding of the processes which produce faint SNe Ia.Comment: 38 pages, 16 figures, accepted for publication in ApJ, the figure 15 input models and synthetic spectra are now available at https://zenodo.org/record/837925

Using Multitrait-Multimethod (MTMM) Techniques to Examine the Convergent and Discriminant Validity of Social Disorder

Objectives: Disorder has been measured by various data sources; however, little attention has been given to comparing the construct validity of different measures obtained through various methods in capturing social disorder and related phenomena. Methods: The multitrait-multimethod approach was used to triangulate the consistency between social disorder, prostitution and drug activity across resident surveys, systematic social observations, and police calls for service data. Results: Prostitution and drug activity showed convergent validity, while there was little evidence that social disorder was consistently measured across the three methods. None of the three social problem measures showed high discriminant validity. Drug activity seems to have highest trait-specific discriminant validity across measures, and prostitution is the most identifiable measure across data sources. Social disorder was found to have low discriminant validity. However, the agreement between databases varies across the type of social problems. Conclusions: Social disorder appears to the most difficult concept to define and measure consistently. The lack of correspondence across data sources cautions against the use of a single source of information in studying disorder. Future studies should explore the factors that shape perceptions of disorder and how to best measure disorder to test the broken windows thesis and related concepts

SN 2022crv: IIb, Or Not IIb: That is the Question

International audienceWe present optical and near-infrared observations of SN~2022crv, a stripped envelope supernova in NGC~3054, discovered within 12 hrs of explosion by the Distance Less Than 40 Mpc Survey. We suggest SN~2022crv is a transitional object on the continuum between SNe Ib and SNe IIb. A high-velocity hydrogen feature ($\sim$$-$20,000 --$-$16,000 $\rm km\,s^{-1}$) was conspicuous in SN~2022crv at early phases, and then quickly disappeared around maximum light. By comparing with hydrodynamic modeling, we find that a hydrogen envelope of $\sim 10^{-3}$\msun can reproduce the behaviour of the hydrogen feature observed in SN~2022crv. The early light curve of SN~2022crv did not show envelope cooling emission, implying that SN~2022crv had a compact progenitor with extremely low amount of hydrogen. The analysis of the nebular spectra shows that SN~2022crv is consistent with the explosion of a He star with a final mass of $\sim$4.5 -- 5.6 \msun that has evolved from a $\sim$16 -- 22 \msun zero-age main sequence star in a binary system with about 1.0 -- 1.7 \msun of oxygen finally synthesized in the core. The high metallicity at the supernova site indicates that the progenitor experienced a strong stellar wind mass loss. In order to retain a small amount of residual hydrogen at such a high metallicity, the initial orbital separation of the binary system is likely larger than $\sim$1000~$\rm R_{\odot}$. The near-infrared spectra of SN~2022crv show a unique absorption feature on the blue side of He I line at $\sim$1.005~$\mu$m. This is the first time that such a feature has been observed in a Type Ib/IIb, and could be due to \ion{Sr}2. Further detailed modelling on SN~2022crv can shed light on the progenitor and the origin of the mysterious absorption feature in the near infrared