Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes

Borrowing hydrogen (or hydrogen autotransfer) reactions represent straightforward and sustainable C-N bond-forming processes. In general, precious metal-based catalysts are employed for this effective transformation. In recent years, the use of earth abundant and cheap non-noble metal catalysts for this process attracted considerable attention in the scientific community. Here we show that the selective N-alkylation of amines with alcohols can be catalysed by defined PNP manganese pincer complexes. A variety of substituted anilines are monoalkylated with different (hetero)aromatic and aliphatic alcohols even in the presence of other sensitive reducible functional groups. As a special highlight, we report the chemoselective monomethylation of primary amines using methanol under mild conditions

MYSTIC: Michigan Young STar Imager at CHARA

We present the design for MYSTIC, the Michigan Young STar Imager at CHARA. MYSTIC will be a K-band, cryogenic, 6-beam combiner for the Georgia State University CHARA telescope array. The design follows the image-plane combination scheme of the MIRC instrument where single-mode fibers bring starlight into a non-redundant fringe pattern to feed a spectrograph. Beams will be injected in polarization-maintaining fibers outside the cryogenic dewar and then be transported through a vacuum feedthrough into the ~220K cold volume where combination is achieved and the light is dispersed. We will use a C-RED One camera (First Light Imaging) based on the eAPD SAPHIRA detector to allow for near-photon-counting performance. We also intend to support a 4-telescope mode using a leftover integrated optics component designed for the VLTI-GRAVITY experiment, allowing better sensitivity for the faintest targets. Our primary science driver motivation is to image disks around young stars in order to better understand planet formation and how forming planets might influence disk structures.Comment: Presented at the 2018 SPIE Astronomical Telescopes + Instrumentation, Austin, Texas, US

First report of an Ediacarian basement in the Western Alps: the Serre Chevalier crystalline unit (Briançonnais domain, France)

We report new LA-ICP-MS U-Pb zircon ages of varied crystalline rocks occurring in the Serre Chevalier crystalline terrain, an allochtonous basement unit located at the top of the Briançonnais nappes stack ∼5 km west of Briançon city. Mapped as an undifferentiated metasedimentary basement on the geological map at 1/50,000 scale, this unit actually displays varied lithologies including alternating micaschist, paragneiss, quartzite, coarse-grained conglomerate and felsic (leptynite) to mafic (amphibolite) gneiss of magmatic origin. All rocks were metamorphosed in response to a dominant pre-Alpine event under amphibolite facies conditions. Partial recrystallization under low-grade amphibolite to greenschist facies conditions was associated with alpine events. Zircon ages were obtained on four types of rocks: (i) a micaceous quartzite from the core of the metasedimentary unit displays a dominant age population around 610 Ma, with a minimal age of 580 Ma, and subordinated age populations at c. 940 Ma, 1825 Ma and 2100-2560 Ma ; (ii) a granite boulder from a coarse-grained conglomerate yields a well-defined age of 582 ± 5 Ma and subordinated inherited ages between 1800 and 2200 Ma. Zircon rims of probable metamorphic origin provide a concordant age of 492 ± 4 Ma ; (iii) a gneissic band in the vicinity of the conglomerate is dated at 597 ± 4 Ma ; (iv) a coarse-grained garnet amphibolite yields an age of 517 ± 3 Ma interpreted as the emplacement age of the protolith, either as intrusive unit cutting accross the sedimentary succession or lava intercalated within the sediments. The mainly Ediacarian record in the metasediments (quartzite and granite boulder in conglomerate) lead us to conclude that this material resulted from the erosion of a nearby Ediacarian (Cadomian ?) basement. The age of 517 Ma obtained on the amphibolite provides a minimum age for the sedimentary succession which deposition is therefore bracketed between 582 Ma and 517 Ma. This interval is comparable to that of the metasedimentary units of the Brioverian group of the Armorican Massif. Based on their low Th/U ratio, the 492 Ma-old zircon rims in the granite boulder are attributed to an Upper Cambrian metamorphic event

Fibrosis of the left atria during progression of heart failure is associated with increased matrix metalloproteinases in the rat

AbstractObjectivesThe purpose of this study was to determine the pathogenic factors and molecular mechanisms involved in fibrosis of the atria.BackgroundFibrosis is an important component of the pathophysiology of atrial fibrillation, especially when the arrhythmia is associated with heart failure (HF) or atrial dilation.MethodsWe used a rat model of myocardial infarction (MI) complicated by various degrees of left ventricular dysfunction and atrial dilation to study fibrosis and matrix metalloproteinase (MMP) activity in the left atrial (LA) myocardium by means of histologic, Western blot, zymographic, and immunohistologic techniques.ResultsThree months after surgical ligature of the left coronary artery, 27 rats had a large MI, 12 were in mild HF, and 15 in severe HF. Both groups had LA enlargement at the echocardiography. Masson’s trichrome and picrosirius staining of tissue sections revealed marked fibrosis at the periphery of trabeculae and also surrounding myolytic myocytes, in both mild and severe HF. In mild HF, the activity and expression of the matrilysin MMP-7 were increased (122%), whereas in severe HF, both MMP-7 (211%) and the gelatinase MMP-2 (187%) were up-regulated. There were no changes in the expression or activity of MMP inhibitors, TIMP-1, -2, and -4. Immunostaining of cryosections showed that MMP-2 was present in the interstitial spaces, whereas MMP-7 accumulated in myolytic myocytes.ConclusionsHemodynamic overload of the atria is an important pathogenic factor of fibrosis; MMP-7 appears to be involved in the early stage of this tissue remodeling process

Collisional evolution of the trans-Neptunian region in an early dynamical instability scenario

Any early or late dynamical instability in the outer Solar system should have left their footprint on the trans-Neptunian object (TNO) populations. Here, we study the collisional and dynamical evolution of such populations numerically by an updated version of ALICANDEP, which suitably takes into account the onset of an early dynamical instability. Key parameters for collisional and dynamical evolution are chosen to match results with current observables. The new model (ALICANDEP-22) considers an original region located between 22 and 30 au, containing 20-30 Earth mass from which bodies are either dynamically ejected from the region or implanted into the current plutinos and hot classical trans-Neptunian belt. An in situ population of objects is also present since the beginning, corresponding to the current cold-classical population. Collisional and dynamical evolution is allowed starting from initial conditions accounting for streaming instability models and observational constraints. ALICANDEP-22 successfully reproduces observational constraints as well as the shape of the size-frequency distribution expected for the Trojan population. The model concludes that Arrokoth is likely a primordial body but cannot be conclusive on the origin of comet 67P/Churyumov-Gerasimenko. The current presence of bodies larger than Pluto in the outer TNO population - waiting to be discovered - is compatible with the initial distributions that allow the model to match current constraints

The Small Separation A-Star Companion Population: First Results with CHARA/MIRC-X

We present preliminary results from our long-baseline interferometry (LBI) survey to constrain the multiplicity properties of intermediate-mass A-type stars within 80pc. Previous multiplicity studies of nearby stars exhibit orbital separation distributions well-fitted with a log-normal with peaks > 15au, increasing with primary mass. The A-star multiplicity survey of De Rosa et al. (2014), sensitive beyond 30au but incomplete below 100 au, found a log-normal peak around 390au. Radial velocity surveys of slowly-rotating, chemically peculiar Am stars identified a significant number of very close companions with periods $\leq$ 5 days, ~ 0.1au, a result similar to surveys of O- and B-type primaries. With the improved performance of LBI techniques, we can probe these close separations for normal A-type stars where other surveys are incomplete. Our initial sample consists of 27 A-type primaries with estimated masses between 1.44-2.49M$_{\odot}$ and ages 10-790Myr, which we observed with the MIRC-X instrument at the CHARA Array. We use the open source software CANDID to detect five companions, three of which are new, and derive a companion frequency of 0.19$^{+0.11}_{-0.06}$ over mass ratios 0.25-1.0 and projected separations 0.288-5.481 au. We find a probability of 10$^{-6}$ that our results are consistent with extrapolations based on previous models of the A-star companion population, over mass ratios and separations sampled. Our results show the need to explore these very close separations to inform our understanding of stellar formation and evolution processes.Comment: 14 pages, 3 figures, Accepted to the Astrophysical Journal on Nov. 2, 202