Circular dichroism (CD) spectroscopy is a well-established technique for studying the secondary structures, dynamics, folding pathways, and interactions of soluble proteins, and is complementary to ...the high resolution but generally static structures produced by X-ray crystallography, NMR spectroscopy, and cryo electron microscopy. CD spectroscopy has special relevance for the study of membrane proteins, which are difficult to crystallise and largely ignored in structural genomics projects. However, the requirement for membrane proteins to be embedded in amphipathic environments such as membranes, lipid vesicles, detergent micelles, bicelles, oriented bilayers, or nanodiscs, in order for them to be soluble or dispersed in solution whilst maintaining their structure and function, necessitates the use of different experimental and analytical approaches than those employed for soluble proteins. This review discusses specialised methods for collecting and analysing membrane protein CD data, highlighting where protocols for soluble and membrane proteins diverge.
There remains considerable debate over the active form of gold under operating conditions of a recently validated gold catalyst for acetylene hydrochlorination. We have performed an in situ x-ray ...absorption fine structure study of gold/carbon (Au/C) catalysts under acetylene hydrochlorination reaction conditions and show that highly active catalysts comprise single-site cationic Au entities whose activity correlates with the ratio of Au(I):Au(III) present. We demonstrate that these Au/C catalysts are supported analogs of single-site homogeneous Au catalysts and propose a mechanism, supported by computational modeling, based on a redox couple of Au(I)-Au(III) species.
This work investigated the effects of low-frequency ultrasound (US) induced conformational variation of duck liver globular proteins (DLGPs) on the binding behavior of n-alkenals based on ...multi-spectroscopic analysis combined with headspace solid phase microextraction technique. Results suggested that US-treatments, with the frequency of 40 kHz and the power density of 26.7 W/L, induced obvious tertiary and quaternary structure changes of DLGPs, as revealed by fluorescence and ultraviolet–visible absorption spectroscopy, whereas the secondary and primary structures of DLGPs remained almost unaffected, suggesting the presence of molten-globule (MG) intermediates due to US-treatment. Meanwhile, the particles size and absolute values of ζ-potential exhibited significant increases as the functions of ultrasonic durations. According to multivariate results, the conformational variations, involving natural, MG and post-MG states, could be differentiated successfully. The US-induced conformational changes of DGLPs allowed it easier to interact with volatile n-alkenals, attributed to the enhanced hydrophobic interaction and covalent binding. Correspondingly, the headspace fractions of n-alkenals were greatly reduced after ultrasound pretreatments, with different degrees ranging from 5.61 to 59.39%, depending on chemical structures and processing conditions. This work suggests the great potential of specific conformational variations of DLGPs induced by ultrasonic pretreatments to modulate flavor features of protein-based products.
•The kinetics of ultrasound (US)-induced conformational changes were characterized.•The induced flexible structures by US could be identified by multivariate methods.•US markedly enhanced the interaction process between alkenals and DLGPs.•Hydrophobic interaction and Michael addition potentially dominated in alkenals-DLGPs binding.•Alkenals-DLGPs interaction process can be confirmed by fluorescence quenching.
Limited by the relatively sluggish charge‐carrier separation in semiconductors, the photocatalytic performance is still far below what is expected. Herein, a model of ZnIn2S4 (ZIS) nanosheets with ...oxygen doping is put forward to obtain in‐depth understanding of the role that doping atoms play in photocatalysis. It shows enhanced photocatalytic activity compared with pristine ZIS. The electron dynamics analyzed by ultrafast transient absorption spectroscopy reveals that the average recovery lifetime of photoexcited electrons is increased by 1.53 times upon oxygen incorporation into the ZIS crystals, indicating enhanced separation of photoexcited carriers in oxygen‐doped ZIS nanosheets. As expected, the oxygen‐doped ZIS nanosheets show a remarkably improved photocatalytic activity with a hydrogen evolution rate of up to 2120 μmol h−1 g−1 under visible‐light irradiation, which is 4.5 times higher than that of the pristine ZIS nanosheets.
Doping control: A model of ultrathin ZnIn2S4 nanosheets with oxygen doping offers insights into the influence of oxygen doping on the separation of photogenerated electron–hole pairs and the photocatalytic activity of catalysts at the atomic level. Experimental and theoretical studies reveal that the oxygen‐doped ZnIn2S4 ultrathin nanosheets have enhanced photocatalytic activity.
Abstract
The selection of high-redshift galaxies often involves spectral energy distribution (SED) fitting to photometric data, an expectation for contamination levels, and measurement of sample ...completeness—all vetted through comparison to spectroscopic redshift measurements of a sub-sample. The first JWST data are now being taken over several extragalactic fields to different depths and across various areas, which will be ideal for the discovery and classification of galaxies out to distances previously uncharted. As spectroscopic redshift measurements for sources in this epoch will not be initially available to compare with the first photometric measurements of
z
> 8 galaxies, robust photometric redshifts are of the utmost importance. Galaxies at
z
> 8 are expected to have bluer rest-frame ultraviolet (UV) colors than typically used model SED templates, which could lead to catastrophic photometric redshift failures. We use a combination of BPASS and
Cloudy
models to create a supporting set of templates that match the predicted rest-UV colors of
z
> 8 simulated galaxies. We test these new templates by fitting simulated galaxies in a mock catalog, Yung et al., which mimic expected field depths and areas of the JWST Cosmic Evolution Early Release Science Survey (
m
5
σ
∼ 28.6 over ∼100 arcmin
2
). We use EAZY to highlight the improvements in redshift recovery with the inclusion of our new template set and suggest criteria for selecting galaxies at 8 <
z
< 10 with the JWST, providing an important test case for observers venturing into this new era of astronomy.
Electrochemical impedance spectroscopy (EIS) study was done in order to go deeper into the electrochemical processes of Li/S battery in a common CR2032 coin-type cell. In order to separate the ...contributions of each electrode (i. e. lithium negative electrode and sulfur composite positive electrode), impedance measurements on symmetrical cells consisting of two previously cycled electrodes was used. This methodology enables to propose an overall interpretation of the different electrochemical phenomena present during cycling. Low temperature tests were also applied, which brought fruitful information concerning the kinetics of the reactions and allowed to confirm the chemical-physical interpretations performed on the cell cycled at 25°C.
ABSTRACT We present a comprehensive study of spectroscopic radius measurements of twelve neutron stars obtained during thermonuclear bursts or in quiescence. We incorporate, for the first time, a ...large number of systematic uncertainties in the measurement of the apparent angular sizes, Eddington fluxes, and distances, in the composition of the interstellar medium, and in the flux calibration of X-ray detectors. We also take into account the results of recent theoretical calculations of rotational effects on neutron star radii, of atmospheric effects on surface spectra, and of relativistic corrections to the Eddington critical flux. We employ Bayesian statistical frameworks to obtain neutron star radii from the spectroscopic measurements as well as to infer the equation of state from the radius measurements. Combining these with the results of experiments in the vicinity of nuclear saturation density and the observations of neutron stars, we place strong and quantitative constraints on the properties of the equation of state between times the nuclear saturation density. We find that around the preferred equation of state predicts radii between 10.1 and 11.1 km. When interpreting the pressure constraints in the context of high density equations of state based on interacting nucleons, our results suggest a relatively weak contribution of the three-body interaction potential.
The Baryon Oscillation Spectroscopic Survey (BOSS) is designed to measure the scale of baryon acoustic oscillations (BAO) in the clustering of matter over a larger volume than the combined efforts of ...all previous spectroscopic surveys of large-scale structure. BOSS uses 1.5 million luminous galaxies as faint as i = 19.9 over 10,000 deg super(2) to measure BAO to redshifts z < 0.7. Observations of neutral hydrogen in the Ly alpha forest in more than 150,000 quasar spectra (g < 22) will constrain BAO over the redshift range 2.15 < z < 3.5. Early results from BOSS include the first detection of the large-scale three-dimensional clustering of the Ly alpha forest and a strong detection from the Data Release 9 data set of the BAO in the clustering of massive galaxies at an effective redshift z = 0.57.We project that BOSS will yieldmeasurements of the angular diameter distance d sub(A) to an accuracy of 1.0% at redshifts z = 0.3 and z = 0.57 and measurements of H(z) to 1.8% and 1.7% at the same redshifts. Forecasts for Ly alpha forest constraints predict a measurement of an overall dilation factor that scales the highly degenerate D sub(A)(z) and H super(-1)(z) parameters to an accuracy of 1.9% at z ~ 2.5 when the survey is complete. Here, we provide an overview of the selection of spectroscopic targets, planning of observations, and analysis of data and data quality of BOSS.
Context.
The chemical composition of the Sun is a fundamental yardstick in astronomy, relative to which essentially all cosmic objects are referenced. As such, having accurate knowledge of the solar ...elemental abundances is crucial for an extremely broad range of topics.
Aims.
We reassess the solar abundances of all 83 long-lived elements, using highly realistic solar modelling and state-of-the-art spectroscopic analysis techniques coupled with the best available atomic data and observations.
Methods.
The basis for our solar spectroscopic analysis is a three-dimensional (3D) radiative-hydrodynamical model of the solar surface convection and atmosphere, which reproduces the full arsenal of key observational diagnostics. New complete and comprehensive 3D spectral line formation calculations taking into account of departures from local thermodynamic equilibrium (non-LTE) are presented for Na, Mg, K, Ca, and Fe using comprehensive model atoms with reliable radiative and collisional data. Our newly derived abundances for C, N, and O are based on a 3D non-LTE analysis of permitted and forbidden atomic lines as well as 3D LTE calculations for a total of 879 molecular transitions of CH, C
2
, CO, NH, CN, and OH. Previous 3D-based calculations for another 50 elements are re-evaluated based on updated atomic data, a stringent selection of lines, improved consideration of blends, and new non-LTE calculations available in the literature. For elements where spectroscopic determinations of the quiet Sun are not possible, the recommended solar abundances are revisited based on complementary methods, including helioseismology (He), solar wind data from the Genesis sample return mission (noble gases), sunspot observations (four elements), and measurements of the most primitive meteorites (15 elements).
Results.
Our new improved analysis confirms the relatively low solar abundances of C, N, and O obtained in our previous 3D-based studies: log
ϵ
C
= 8.46 ± 0.04, log
ϵ
N
= 7.83 ± 0.07, and log
ϵ
O
= 8.69 ± 0.04. Excellent agreement between all available atomic and molecular indicators is achieved for C and O, but for N the atomic lines imply a lower abundance than for the molecular transitions for unknown reasons. The revised solar abundances for the other elements also typically agree well with our previously recommended values, with only Li, F, Ne, Mg, Cl, Kr, Rb, Rh, Ba, W, Ir, and Pb differing by more than 0.05 dex. The here-advocated present-day photospheric metal mass fraction is only slightly higher than our previous value, mainly due to the revised Ne abundance from Genesis solar wind measurements:
X
surface
= 0.7438 ± 0.0054,
Y
surface
= 0.2423 ± 0.0054,
Z
surface
= 0.0139 ± 0.0006, and
Z
surface
/
X
surface
= 0.0187 ± 0.0009. Overall, the solar abundances agree well with those of CI chondritic meteorites, but we identify a correlation with condensation temperature such that moderately volatile elements are enhanced by ≈0.04 dex in the CI chondrites and refractory elements possibly depleted by ≈0.02 dex, conflicting with conventional wisdom of the past half-century. Instead, the solar chemical composition more closely resembles that of the fine-grained matrix of CM chondrites with the expected exception of the highly volatile elements.
Conclusions.
Updated present-day solar photospheric and proto-solar abundances are presented for 83 elements, including for all long-lived isotopes. The so-called solar modelling problem – a persistent discrepancy between helioseismology and solar interior models constructed with a low solar metallicity similar to that advocated here – remains intact with our revised solar abundances, suggesting shortcomings with the computed opacities and/or treatment of mixing below the convection zone in existing standard solar models. The uncovered trend between the solar and CI chondritic abundances with condensation temperature is not yet understood but is likely imprinted by planet formation, especially since a similar trend of opposite sign is observed between the Sun and solar twins.
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