358 research outputs found

    Ultrafast excited state dynamics of silver ion-mediated cytosine–cytosine base pairs in metallo-DNA

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    The following article appeared in The Journal of Chemical Physics 153.10 (2020): 105104 and may be found at ttps://doi.org/10.1063/5.0020463To better understand the nexus between structure and photophysics in metallo-DNA assemblies, the parallel-stranded duplex formed by the all-cytosine oligonucleotide, dC20, and silver nitrate was studied by circular dichroism (CD), femtosecond transient absorption spectroscopy, and time-dependent-density functional theory calculations. Silver(I) ions mediate Cytosine–Cytosine (CC) base pairs by coordinating to the N3 atoms of two cytosines. Although these silver(I) mediated CC base pairs resemble the proton-mediated CC base pairs found in i-motif DNA at first glance, a comparison of experimental and calculated CD spectra reveals that silver ion-mediated i-motif structures do not form. Instead, the parallel-stranded duplex formed between dC20 and silver ions is proposed to contain consecutive silver-mediated base pairs with high propeller twist-like ones seen in a recent crystal structure of an emissive, DNA-templated silver cluster. Femtosecond transient absorption measurements with broadband probing from the near UV to the near IR reveal an unusually long-lived (>10 ns) excited state in the dC20 silver ion complex that is not seen in dC20 in single-stranded or i-motif forms. This state is also absent in a concentrated solution of cytosine–silver ion complexes that are thought to assemble into planar ribbons or sheets that lack stacked silver(I) mediated CC base pairs. The large propeller twist angle present in metal-mediated base pairs may promote the formation of long-lived charged separated or triplet states in this metallo-DNAThe work at The Ohio State University was supported by a grant from the U.S. National Science Foundation (Grant No. CHE1800471). L.M.-F. thanks the MINECO project (No. CTQ2016- 76061-P) for financial support and the Centro de Computación Científica, CCC-UAM, for generous allocation of computational time. The authors declare no competing financial interes

    Building solids inside nano-space: from confined amorphous through confined solvate to confined ‘metastable’ polymorph

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    The nanocrystallisation of complex molecules inside mesoporous hosts and control over the resulting structure is a significant challenge. To date the largest organic molecule crystallised inside the nano-pores is a known pharmaceutical intermediate – ROY (259.3 g mol1). In this work we demonstrate smart manipulation of the phase of a larger confined pharmaceutical – indomethacin (IMC, 357.8 g mol1), a substance with known conformational flexibility and complex polymorphic behaviour. We show the detailed structural analysis and the control of solid state transformations of encapsulated molecules inside the pores of mesoscopic cellular foam (MCF, pore size ca. 29 nm) and controlled pore glass (CPG, pore size ca. 55 nm). Starting from confined amorphous IMC we drive crystallisation into a confined methanol solvate, which upon vacuum drying leads to the stabilised rare form V of IMC inside the MCF host. In contrast to the pure form, encapsulated form V does not transform into a more stable polymorph upon heating. The size of the constraining pores and the drug concentration within the pores determine whether the amorphous state of the drug is stabilised or it recrystallises into confined nanocrystals. The work presents, in a critical manner, an application of complementary techniques (DSC, PXRD, solid-state NMR, N2 adsorption) to confirm unambiguously the phase transitions under confinement and offers a comprehensive strategy towards the formation and control of nano-crystalline encapsulated organic solids

    First direct detection of an exoplanet by optical interferometry; Astrometry and K-band spectroscopy of HR8799 e

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    To date, infrared interferometry at best achieved contrast ratios of a few times 10410^{-4} on bright targets. GRAVITY, with its dual-field mode, is now capable of high contrast observations, enabling the direct observation of exoplanets. We demonstrate the technique on HR8799, a young planetary system composed of four known giant exoplanets. We used the GRAVITY fringe tracker to lock the fringes on the central star, and integrated off-axis on the HR8799e planet situated at 390 mas from the star. Data reduction included post-processing to remove the flux leaking from the central star and to extract the coherent flux of the planet. The inferred K band spectrum of the planet has a spectral resolution of 500. We also derive the astrometric position of the planet relative to the star with a precision on the order of 100μ\,\muas. The GRAVITY astrometric measurement disfavors perfectly coplanar stable orbital solutions. A small adjustment of a few degrees to the orbital inclination of HR 8799 e can resolve the tension, implying that the orbits are close to, but not strictly coplanar. The spectrum, with a signal-to-noise ratio of 5\approx 5 per spectral channel, is compatible with a late-type L brown dwarf. Using Exo-REM synthetic spectra, we derive a temperature of 1150±501150\pm50\,K and a surface gravity of 104.3±0.310^{4.3\pm0.3}\,cm/s2^{2}. This corresponds to a radius of 1.170.11+0.13RJup1.17^{+0.13}_{-0.11}\,R_{\rm Jup} and a mass of 104+7MJup10^{+7}_{-4}\,M_{\rm Jup}, which is an independent confirmation of mass estimates from evolutionary models. Our results demonstrate the power of interferometry for the direct detection and spectroscopic study of exoplanets at close angular separations from their stars.Comment: published in A&

    A survey of exoplanet phase curves with Ariel

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    The ESA-Ariel mission will include a tier dedicated to exoplanet phase curves corresponding to ∼ 10 % of the science time. We present here the current observing strategy for studying exoplanet phase curves with Ariel. We define science questions, requirements and a list of potential targets. We also estimate the precision of phase curve reconstruction and atmospheric retrieval using simulated phase curves. Based on this work, we found that full-orbit phase variations for 35-40 exoplanets could be observed during the 3.5-yr mission. This statistical sample would provide key constraints on atmospheric dynamics, composition, thermal structure and clouds of warm exoplanets, complementary to the scientific yield from spectroscopic transits/eclipses measurements

    Peering into the Young Planetary System AB Pic. Atmosphere, Orbit, Obliquity & Second Planetary Candidate

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    We aim to revisit the system AB Pic which has a known companion at the exoplanet/ brown-dwarf boundary. We based this study on a rich set of observations to investigate the companion's orbit and atmosphere. We composed a spectrum of AB Pic b merging archival VLT/SINFONI K-band data, with published spectra at J and H-band (SINFONI) and Lp-band (Magellan-AO), and photometric measurements (HST and Spitzer). We modeled the spectrum with ForMoSA, based on two atmospheric models: ExoREM and BT-SETTL13. We determined the orbital properties of b fitting the astrometric measurements from NaCo (2003 and 2004) and SPHERE (2015). The orbital solutions favor a semi-major axis of \sim190au viewed edge-on. With Exo-REM, we derive a Teff_{eff} of 1700±\pm50K and surface gravity of 4.5±\pm0.3dex, consistent with previous works, and we report for the first time a C/O ratio of 0.58±\pm0.08 (\simsolar). The posteriors are sensitive to the wavelength interval and the family of models used. Given the 2.1hr rotation period and our vsin(i) of \sim73km/s, we estimate for the first time the true obliquity to be \sim45 or \sim135deg, indicating a significant misalignment between the planet's spin and orbit orientations. Finally, the existence of a proper motion anomaly between the Hipparcos and Gaia eDR3 compared to our SPHERE detection limits and adapted radial velocity limits indicate the existence of a \sim6MJup_{Jup} inner planet orbiting from 2 to 10au (40-200mas). The possible existence of an inner companion, together with the likely miss-alignment of the spin axis orientation, strongly favor a formation path by gravitational instability or core accretion within a disk closer inside followed by dynamical interactions. Confirmation and characterization of planet c and access to a broader wavelength coverage for planet b will be essential to probe the uncertainties associated with the parameters.Comment: 17 pages, 13 Figures, 6 Tables. Accepted for publication in A&A (31 of October

    ARES. III. Unveiling the Two Faces of KELT-7 b with HST WFC3*

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    We present the analysis of the hot-Jupiter KELT-7 b using transmission and emission spectroscopy from the Hubble Space Telescope, both taken with the Wide Field Camera 3. Our study uncovers a rich transmission spectrum that is consistent with a cloud-free atmosphere and suggests the presence of H_{2}O and H^{−}. In contrast, the extracted emission spectrum does not contain strong absorption features and, although it is not consistent with a simple blackbody, it can be explained by a varying temperature–pressure profile, collision induced absorption, and H^{-}. KELT-7 b had also been studied with other space-based instruments and we explore the effects of introducing these additional data sets. Further observations with Hubble, or the next generation of space-based telescopes, are needed to allow for the optical opacity source in transmission to be confirmed and for molecular features to be disentangled in emission
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