Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism

The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the energies of the mercury 6p1/2 and 6p3/2 orbitals, making them energetically accessible for chemical bonding. In the absence of spin–orbit coupling, the predicted reaction mechanism is qualitatively different. This is the first example of relativity being decisive for the nature of an observed enzymatic reaction mechanism.Of relative importance: The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical. This reaction mechanism is a consequence of relativistic effects, and constitutes the first example of relativity being decisive for the nature of an enzymatic reaction mechanism. SOC=spin–orbit coupling.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/137374/1/anie201606001-sup-0001-misc_information.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137374/2/anie201606001.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137374/3/anie201606001_am.pd

Electronically Excited States of Vitamin B12: Benchmark Calculations Including Time-Dependent Density Functional Theory and Correlated Ab Initio Methods

Time-dependent density functional theory (TD-DFT) and correlated ab initio methods have been applied to the electronically excited states of vitamin B12 (cyanocobalamin or CNCbl). Different experimental techniques have been used to probe the excited states of CNCbl, revealing many issues that remain poorly understood from an electronic structure point of view. Due to its efficient scaling with size, TD-DFT emerges as one of the most practical tools that can be used to predict the electronic properties of these fairly complex molecules. However, the description of excited states is strongly dependent on the type of functional used in the calculations. In the present contribution, the choice of a proper functional for vitamin B12 was evaluated in terms of its agreement with both experimental results and correlated ab initio calculations. Three different functionals, i.e. B3LYP, BP86, and LC-BLYP, were tested. In addition, the effect of relative contributions of DFT and HF to the exchange-correlation functional was investigated as a function of the range-separation parameter, {\mu}. The issues related to the underestimation of charge transfer (CT) excitation energies by TD-DFT was validated by Tozer's L diagnostic, which measures the spatial overlap between occupied and virtual orbitals involved in the particular excitation. The nature of low-lying excited states was also analyzed based on a comparison of TD-DFT and ab initio results. Based on an extensive comparision against experimental results and ab initio benchmark calculations, the BP86 functional was found to be the most appropriate in describing the electronic properties of CNCbl. Finally, an analysis of electronic transitions and a new re-assignment of some excitations are discussed.Comment: Accepted by the Journal of Chemistry

Microlensing optical depth and event rate in the OGLE-IV Galactic plane fields

Searches for gravitational microlensing events are traditionally concentrated on the central regions of the Galactic bulge but many microlensing events are expected to occur in the Galactic plane, far from the Galactic Center. Owing to the difficulty in conducting high-cadence observations of the Galactic plane over its vast area, which are necessary for the detection of microlensing events, their global properties were hitherto unknown. Here, we present results of the first comprehensive search for microlensing events in the Galactic plane. We searched an area of almost 3000 square degrees along the Galactic plane (|b|<7, 0<l<50, 190<l<360 deg) observed by the Optical Gravitational Lensing Experiment (OGLE) during 2013-2019 and detected 630 events. We demonstrate that the mean Einstein timescales of Galactic plane microlensing events are on average three times longer than those of Galactic bulge events, with little dependence on the Galactic longitude. We also measure the microlensing optical depth and event rate as a function of Galactic longitude and demonstrate that they exponentially decrease with the angular distance from the Galactic Center (with the characteristic angular scale length of 32 deg). The average optical depth decreases from $0.5\times 10^{-6}$ at l=10 deg to $1.5\times 10^{-8}$ in the Galactic anticenter. We also find that the optical depth in the longitude range 240<l<330 deg is asymmetric about the Galactic equator, which we interpret as a signature of the Galactic warp.Comment: ApJS, in pres

Microlensing optical depth and event rate in the OGLE-IV Galactic plane fields

Searches for gravitational microlensing events are traditionally concentrated on the central regions of the Galactic bulge but many microlensing events are expected to occur in the Galactic plane, far from the Galactic Center. Owing to the difficulty in conducting high-cadence observations of the Galactic plane over its vast area, which are necessary for the detection of microlensing events, their global properties were hitherto unknown. Here, we present results of the first comprehensive search for microlensing events in the Galactic plane. We searched an area of almost 3000 square degrees along the Galactic plane (|b| < 7°, 0° < l < 50°, 190° < l < 360°) observed by the Optical Gravitational Lensing Experiment (OGLE) during 2013–2019 and detected 630 events. We demonstrate that the mean Einstein timescales of Galactic plane microlensing events are on average three times longer than those of Galactic bulge events, with little dependence on the Galactic longitude. We also measure the microlensing optical depth and event rate as a function of Galactic longitude and demonstrate that they exponentially decrease with the angular distance from the Galactic Center (with the characteristic angular scale length of 32°). The average optical depth decreases from 0.5 × 10⁻⁶ at l = 10° to 1.5 × 10⁻⁸ in the Galactic anticenter. We also find that the optical depth in the longitude range 240° < l < 330° is asymmetric about the Galactic equator, which we interpret as a signature of the Galactic warp

The Araucaria Project: A study of the classical Cepheid in the eclipsing binary system OGLE LMC562.05.9009 in the Large Magellanic Cloud

We present a detailed study of the classical Cepheid in the double-lined, highly eccentric eclipsing binary system OGLE-LMC562.05.9009. The Cepheid is a fundamental mode pulsator with a period of 2.988 days. The orbital period of the system is 1550 days. Using spectroscopic data from three 4-8-m telescopes and photometry spanning 22 years, we were able to derive the dynamical masses and radii of both stars with exquisite accuracy. Both stars in the system are very similar in mass, radius and color, but the companion is a stable, non-pulsating star. The Cepheid is slightly more massive and bigger (M_1 = 3.70 +/- 0.03M_sun, R_1 = 28.6 +/- 0.2R_sun) than its companion (M_2 = 3.60 +/- 0.03M_sun, R_2 = 26.6 +/- 0.2R_sun). Within the observational uncertainties both stars have the same effective temperature of 6030 +/- 150K. Evolutionary tracks place both stars inside the classical Cepheid instability strip, but it is likely that future improved temperature estimates will move the stable giant companion just beyond the red edge of the instability strip. Within current observational and theoretical uncertainties, both stars fit on a 205 Myr isochrone arguing for their common age. From our model, we determine a value of the projection factor of p = 1.37 +/- 0.07 for the Cepheid in the OGLE-LMC562.05.9009 system. This is the second Cepheid for which we could measure its p-factor with high precision directly from the analysis of an eclipsing binary system, which represents an important contribution towards a better calibration of Baade-Wesselink methods of distance determination for Cepheids.Comment: Accepted to be published in Ap

Molecular characterization of the PhiKo endolysin from Thermus thermophilus HB27 bacteriophage phiKo and its cryptic lytic peptide RAP-29

IntroductionIn the era of increasing bacterial resistance to antibiotics, new bactericidal substances are sought, and lysins derived from extremophilic organisms have the undoubted advantage of being stable under harsh environmental conditions. The PhiKo endolysin is derived from the phiKo bacteriophage infecting Gram-negative extremophilic bacterium Thermus thermophilus HB27. This enzyme shows similarity to two previously investigated thermostable type-2 amidases, the Ts2631 and Ph2119 from Thermus scotoductus bacteriophages, that revealed high lytic activity not only against thermophiles but also against Gram-negative mesophilic bacteria. Therefore, antibacterial potential of the PhiKo endolysin was investigated in the study presented here.MethodsEnzyme activity was assessed using turbidity reduction assays (TRAs) and antibacterial tests. Differential scanning calorimetry was applied to evaluate protein stability. The Collection of Anti-Microbial Peptides (CAMP) and Antimicrobial Peptide Calculator and Predictor (APD3) were used to predict regions with antimicrobial potential in the PhiKo primary sequence. The minimum inhibitory concentration (MIC) of the RAP-29 synthetic peptide was determined against Gram-positive and Gram-negative selected strains, and mechanism of action was investigated with use of membrane potential sensitive fluorescent dye 3,3′-Dipropylthiacarbocyanine iodide (DiSC3(5)).Results and discussionThe PhiKo endolysin is highly thermostable with melting temperature of 91.70°C. However, despite its lytic effect against such extremophiles as: T. thermophilus, Thermus flavus, Thermus parvatiensis, Thermus scotoductus, and Deinococcus radiodurans, PhiKo showed moderate antibacterial activity against mesophiles. Consequently, its protein sequence was searched for regions with potential antibacterial activity. A highly positively charged region was identified and synthetized (PhiKo105-133). The novel RAP-29 peptide lysed mesophilic strains of staphylococci and Gram-negative bacteria, reducing the number of cells by 3.7–7.1 log units and reaching the minimum inhibitory concentration values in the range of 2–31 μM. This peptide is unstructured in an aqueous solution but forms an α-helix in the presence of detergents. Moreover, it binds lipoteichoic acid and lipopolysaccharide, and causes depolarization of bacterial membranes. The RAP-29 peptide is a promising candidate for combating bacterial pathogens. The existence of this cryptic peptide testifies to a much wider panel of antimicrobial peptides than thought previously