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Imaging CF3I conical intersection and photodissociation dynamics with ultrafast electron diffraction
(2018)
Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF3I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations.
The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction
(2019)
The ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a textbook example of electrocyclic reactions in organic chemistry and a model for photobiological reactions in vitamin D synthesis. Although the relaxation from the photoexcited electronic state during the ring-opening has been investigated in numerous studies, the accompanying changes in atomic distance have not been resolved. Here we present a direct and unambiguous observation of the ring-opening reaction path on the femtosecond timescale and subangstrom length scale using megaelectronvolt ultrafast electron diffraction. We followed the carbon-carbon bond dissociation and the structural opening of the 1,3-cyclohexadiene ring by the direct measurement of time-dependent changes in the distribution of interatomic distances. We observed a substantial acceleration of the ring-opening motion after internal conversion to the ground state due to a steepening of the electronic potential gradient towards the product minima. The ring-opening motion transforms into rotation of the terminal ethylene groups in the photoproduct 1,3,5-hexatriene on the subpicosecond timescale.
Suppression of the near-infrared OH night-sky lines with fibre Bragg gratings - first results
(2012)
The background noise between 1 and 1.8 ?mu m in ground-based instruments is dominated by atmospheric emission from hydroxyl molecules. We have built and commissioned a new instrument, the Gemini Near-infrared OH Suppression Integral Field Unit (IFU) System (GNOSIS), which suppresses 103 OH doublets between 1.47 and 1.7?mu m by a factor of 1000 with a resolving power of 10?000. We present the first results from the commissioning of GNOSIS using the IRIS2 spectrograph at the Anglo-Australian Telescope. We present measurements of sensitivity, background and throughput. The combined throughput of the GNOSIS fore-optics, grating unit and relay optics is 36?per cent, but this could be improved to 46?per cent with a more optimal design. We measure strong suppression of the OH lines, confirming that OH suppression with fibre Bragg gratings will be a powerful technology for low-resolution spectroscopy. The integrated OH suppressed background between 1.5 and 1.7 mu m is reduced by a factor of 9 compared to a control spectrum using the same system without suppression. The potential of low-resolution OH-suppressed spectroscopy is illustrated with example observations of Seyfert galaxies and a low-mass star. The GNOSIS background is dominated by detector dark current below 1.67 mu m and by thermal emission above 1.67 mu m. After subtracting these, we detect an unidentified residual interline component of 860 +/- 210 photons s-1 m-2?arcsec-2?mu m-1, comparable to previous measurements. This component is equally bright in the suppressed and control spectra. We have investigated the possible source of the interline component, but were unable to discriminate between a possible instrumental artefact and intrinsic atmospheric emission. Resolving the source of this emission is crucial for the design of fully optimized OH suppression spectrographs. The next-generation OH suppression spectrograph will be focused on resolving the source of the interline component, taking advantage of better optimization for a fibre Bragg grating feed incorporating refinements of design based on our findings from GNOSIS. We quantify the necessary improvements for an optimal OH suppressing fibre spectrograph design.
We have investigated the structural dynamics in photoexcited 1,2-diiodotetrafluoroethane molecules (C2F4I2) in the gas phase experimentally using ultrafast electron diffraction and theoretically using FOMO-CASCI excited-state dynamics simulations. The molecules are excited by an ultraviolet femtosecond laser pulse to a state characterized by a transition from the iodine 5p perpendicular to orbital to a mixed 5p parallel to sigma hole and CF2 center dot antibonding orbital, which results in the cleavage of one of the carbon-iodine bonds. We have observed, with sub-Angstrom resolution, the motion of the nuclear wave packet of the dissociating iodine atom followed by coherent vibrations in the electronic ground state of the C2F4I radical. The radical reaches a stable classical (nonbridged) structure in less than 200 fs.
Multiple P-T-d-t paths reveal the evolution of the final Nuna assembly in northeast Australia
(2020)
The final assembly of the Mesoproterozoic supercontinent Nuna was marked by the collision of Laurentia and Australia at 1.60 Ga, which is recorded in the Georgetown Inlier of NE Australia. Here, we decipher the metamorphic evolution of this final Nuna collisional event using petrostructural analysis, major and trace element compositions of key minerals, thermodynamic modelling, and multi-method geochronology. The Georgetown Inlier is characterised by deformed and metamorphosed 1.70-1.62 Ga sedimentary and mafic rocks, which were intruded byc. 1.56 Ga old S-type granites. Garnet Lu-Hf and monazite U-Pb isotopic analyses distinguish two major metamorphic events (M1 atc. 1.60 Ga and M2 atc. 1.55 Ga), which allows at least two composite fabrics to be identified at the regional scale-c. 1.60 Ga S1 (consisting in fabrics S1a and S1b) andc. 1.55 Ga S2 (including fabrics S2a and S2b). Also, three tectono-metamorphic domains are distinguished: (a) the western domain, with S1 defined by low-P(LP) greenschist facies assemblages; (b) the central domain, where S1 fabric is preserved as medium-P(MP) amphibolite facies relicts, and locally as inclusion trails in garnet wrapped by the regionally dominant low-Pamphibolite facies S2 fabric; and (c) the eastern domain dominated by upper amphibolite to granulite facies S2 foliation. In the central domain, 1.60 GaMP-medium-T(MT) metamorphism (M1) developed within the staurolite-garnet stability field, with conditions ranging from 530-550 degrees C at 6-7 kbar (garnet cores) to 620-650 degrees C at 8-9 kbar (garnet rims), and it is associated with S1 fabric. The onset of 1.55 GaLP-high-T(HT) metamorphism (M2) is marked by replacement of staurolite by andalusite (M2a/D2a), which was subsequently pseudomorphed by sillimanite (M2b/D2b) where granite and migmatite are abundant.P-Tconditions ranged from 600 to 680 degrees C and 4-6 kbar for the M2b sillimanite stage. 1.60 Ga garnet relicts within the S2 foliation highlight the progressive obliteration of the S1 fabric by regional S2 in the central zone during peak M2 metamorphism. In the eastern migmatitic complex, partial melting of paragneiss and amphibolite occurred syn- to post-S2, at 730-770 degrees C and 6-8 kbar, and at 750-790 degrees C and 6 kbar, respectively. The pressure-temperature-deformation-time paths reconstructed for the Georgetown Inlier suggest ac. 1.60 Ga M1/D1 event recorded under greenschist facies conditions in the western domain and under medium-Pand medium-Tconditions in the central domain. This event was followed by the regional 1.56-1.54 Ga low-Pand high-Tphase (M2/D2), extensively recorded in the central and eastern domains. Decompression between these two metamorphic events is ascribed to an episode of exhumation. The two-stage evolution supports the previous hypothesis that the Georgetown Inlier preserves continental collisional and subsequent thermal perturbation associated with granite emplacement.
OBJECTIVE: Higher plasma vitamin C levels are associated with lower type 2 diabetes risk, but whether this association is causal is uncertain. To investigate this, we studied the association of genetically predicted plasma vitamin C with type 2 diabetes.
RESEARCH DESIGN AND METHODS: We conducted genome-wide association studies of plasma vitamin C among 52,018 individuals of European ancestry to discover novel genetic variants. We performed Mendelian randomization analyses to estimate the association of genetically predicted differences in plasma vitamin C with type 2 diabetes in up to 80,983 case participants and 842,909 noncase participants. We compared this estimate with the observational association between plasma vitamin C and incident type 2 diabetes, including 8,133 case participants and 11,073 noncase participants.
RESULTS: We identified 11 genomic regions associated with plasma vitamin C (P < 5 x 10(-8)), with the strongest signal at SLC23A1, and 10 novel genetic loci including SLC23A3, CHPT1, BCAS3, SNRPF, RER1, MAF, GSTA5, RGS14, AKT1, and FADS1. Plasma vitamin C was inversely associated with type 2 diabetes (hazard ratio per SD 0.88; 95% CI 0.82, 0.94), but there was no association between genetically predicted plasma vitamin C (excluding FADS1 variant due to its apparent pleiotropic effect) and type 2 diabetes (1.03; 95% CI 0.96, 1.10).
CONCLUSIONS: These findings indicate discordance between biochemically measured and genetically predicted plasma vitamin C levels in the association with type 2 diabetes among European populations. The null Mendelian randomization findings provide no strong evidence to suggest the use of vitamin C supplementation for type 2 diabetes prevention.
Tasking machine learning to predict segments of a time series requires estimating the parameters of a ML model with input/output pairs from the time series. We borrow two techniques used in statistical data assimilation in order to accomplish this task: time-delay embedding to prepare our input data and precision annealing as a training method. The precision annealing approach identifies the global minimum of the action (-log[P]). In this way, we are able to identify the number of training pairs required to produce good generalizations (predictions) for the time series. We proceed from a scalar time series s(tn);tn=t0+n Delta t and, using methods of nonlinear time series analysis, show how to produce a DE>1-dimensional time-delay embedding space in which the time series has no false neighbors as does the observed s(tn) time series. In that DE-dimensional space, we explore the use of feedforward multilayer perceptrons as network models operating on DE-dimensional input and producing DE-dimensional outputs.
Distinct cellular roles for PDCD10 define a gut-brain axis in cerebral cavernous malformation
(2019)
Cerebral cavernous malformation (CCM) is a genetic, cerebrovascular disease. Familial CCM is caused by genetic mutations in KRIT1, CCM2, or PDCD10. Disease onset is earlier and more severe in individuals with PDCD10 mutations. Recent studies have shown that lesions arise from excess mitogen-activated protein kinase kinase kinase 3 (MEKK3) signaling downstream of Toll-like receptor 4 (TLR4) stimulation by lipopolysaccharide derived from the gut microbiome. These findings suggest a gut-brain CCM disease axis but fail to define it or explain the poor prognosis of patients with PDCD10 mutations. Here, we demonstrate that the gut barrier is a primary determinant of CCM disease course, independent of microbiome configuration, that explains the increased severity of CCM disease associated with PDCD10 deficiency. Chemical disruption of the gut barrier with dextran sulfate sodium augments CCM formation in a mouse model, as does genetic loss of Pdcd10, but not Krit1, in gut epithelial cells. Loss of gut epithelial Pdcd10 results in disruption of the colonic mucosal barrier. Accordingly, loss of Mucin-2 or exposure to dietary emulsifiers that reduce the mucus barrier increases CCM burden analogous to loss of Pdcd10 in the gut epithelium. Last, we show that treatment with dexamethasone potently inhibits CCM formation in mice because of the combined effect of action at both brain endothelial cells and gut epithelial cells. These studies define a gut-brain disease axis in an experimental model of CCM in which a single gene is required for two critical components: gut epithelial function and brain endothelial signaling.
Permanent genetic resources added to molecular ecology resources database 1 April 2011-31 May 2011
(2011)
This article documents the addition of 92 microsatellite marker loci to the Molecular Ecology Resources Database. Loci were developed for the following species: Anopheles minimus, An. sinensis, An. dirus, Calephelis mutica, Lutjanus kasmira, Murella muralis and Orchestia montagui. These loci were cross-tested on the following species: Calephelis arizonensi, Calephelis borealis, Calephelis nemesis, Calephelis virginiensis and Lutjanus bengalensis.
The near-infrared is an important part of the spectrum in astronomy, especially in cosmology because the light from objects in the early universe is redshifted to these wavelengths. However, deep near-infrared observations are extremely difficult to make from ground-based telescopes due to the bright background from the atmosphere. Nearly all of this background comes from the bright and narrow emission lines of atmospheric hydroxyl (OH) molecules. The atmospheric background cannot be easily removed from data because the brightness fluctuates unpredictably on short timescales. The sensitivity of ground-based optical astronomy far exceeds that of near-infrared astronomy because of this long-standing problem. GNOSIS is a prototype astrophotonic instrument that utilizes "OH suppression fibers" consisting of fiber Bragg gratings and photonic lanterns to suppress the 103 brightest atmospheric emission doublets between 1.47 and 1.7 mu m. GNOSIS was commissioned at the 3.9 m Anglo-Australian Telescope with the IRIS2 spectrograph to demonstrate the potential of OH suppression fibers, but may be potentially used with any telescope and spectrograph combination. Unlike previous atmospheric suppression techniques GNOSIS suppresses the lines before dispersion and in a manner that depends purely on wavelength. We present the instrument design and report the results of laboratory and on-sky tests from commissioning. While these tests demonstrated high throughput (approximate to 60%) and excellent suppression of the skylines by the OH suppression fibers, surprisingly GNOSIS produced no significant reduction in the interline background and the sensitivity of GNOSIS+IRIS2 is about the same as IRIS2. It is unclear whether the lack of reduction in the interline background is due to physical sources or systematic errors as the observations are detector noise dominated. OH suppression fibers could potentially impact ground-based astronomy at the level of adaptive optics or greater. However, until a clear reduction in the interline background and the corresponding increasing in sensitivity is demonstrated optimized OH suppression fibers paired with a fiber-fed spectrograph will at least provide a real benefit at low resolving powers.