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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,081 records · Page 60
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Estimating the Ultraviolet Emission of M Dwarfs with Exoplanets from Ca ii and Hα

M dwarf stars are excellent candidates around which to search for exoplanets, including temperate, Earth-sized planets. To evaluate the photochemistry of the planetary atmosphere, it is essential to characterize the UV spectral energy distribution of the planet’s host star. This wavelength regime is important because molecules in the planetary atmosphere such as oxygen and ozone have highly wavelength-dependent absorption cross sections that peak in the UV (900–3200 Å). We seek to provide a broadly applicable method of estimating the UV emission of an M dwarf, without direct UV data, by identifying a relationship between noncontemporaneous optical and UV observations. Our work uses the largest sample of M dwarf star far- and near-UV observations yet assembled. We evaluate three commonly observed optical chromospheric activity indices—Hα equivalent widths and log{sub 10} L Hα /L bol , and the Mount Wilson Ca ii H&K S and R HK ' indices—using optical spectra from the HARPS, UVES, and HIRES archives and new HIRES spectra. Archival and new Hubble Space Telescope COS and STIS spectra are used to measure line fluxes for the brightest chromospheric and transition region emission lines between 1200 and 2800 Å. Our results show a correlation between UV emission-line luminosity normalized to the stellar bolometric luminosity and Ca ii R HK ' with standard deviations of 0.31–0.61 dex (factors of ~2–4) about the best-fit lines. We also find correlations between normalized UV line luminosity and Hα log 10 L Hα /L bol and the S index. These relationships allow one to estimate the average UV emission from M0 to M9 dwarfs when UV data are not available.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Center for Astrophysics Optical Infrared Science Archive. I. FAST Spectrograph

We announce the public release of 141,531 moderate-dispersion optical spectra of 72,247 objects acquired over the past 25 yr with the FAST Spectrograph on the Fred L. Whipple Observatory 1.5 m Tillinghast telescope. We describe the data acquisition and processing so that scientists can understand the spectra. We highlight some of the largest FAst Spectrograph for the Tillinghast Telescope (FAST) survey programs, and make recommendations for use. The spectra have been placed in a Virtual Observatory–accessible archive and ready for download.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

DRAGraces: A Pipeline for the GRACES High-resolution Spectrograph at Gemini

This paper describes the software Data Reduction and Analysis for GRACES (DRAGraces), which is a pipeline reducing spectra from Gemini Remote Access to the CFHT ESPaDOnS Spectrograph (GRACES) at the Gemini North Telescope. The code is written in the IDL language. It is designed to find all the GRACES frames in a given directory, automatically determine the list of bias, flat, arc, and science frames, and perform the whole reduction and extraction within a few minutes. We compare the output from DRAGraces with that of the Open source Pipeline for ESPaDOnS Reduction and Analysis (OPERA), a pipeline developed at the Canada–France–Hawaii Telescope (CFHT) that also can extract GRACES spectra. Both pipelines were developed completely independently, yet they give very similar extracted spectra. They both have their advantages and disadvantages. For instance, DRAGraces is more straightforward and easy to use and is less likely to be derailed by a parameter that needs to be tweaked, while OPERA offers a more careful extraction that can be significantly superior when the highest resolution is required and when the signal-to-noise ratio is low. One should compare both before deciding which one to use for their science. Yet, both pipelines deliver a fairly comparable resolution power (R ~ 52.8k and 36.6k for DRAGraces and R ~ 58k and 40k for OPERA in high- and low-resolution spectral modes, respectively), wavelength solution, and signal-to-noise ratio per resolution element.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

A Multiwavelength Look at the GJ 9827 System: No Evidence of Extended Atmospheres in GJ 9827b and d from HST and CARMENES Data

GJ 9827 is a bright star hosting a planetary system with three transiting planets. As a multiplanet system with planets that sprawl within the boundaries of the radius gap between terrestrial and gaseous planets, GJ 9827 is an optimal target to study the evolution of the atmospheres of close-in planets with a common evolutionary history and their dependence from stellar irradiation. Here we report on the Hubble Space Telescope (HST) and CARMENES transit observations of GJ 9827 planets b and d. We performed a stellar and ISM characterization from the ultraviolet HST spectra, obtaining fluxes for Lyα and Mg ii of F(Lyα) = (5.42{sub −0.75}{sup +0.96}) × 10{sup −13} erg cm{sup −2} s{sup −1} and F(Mgii) = (5.64 ± 0.24) × 10{sup −14} erg cm{sup −2} s{sup −1}. We also investigated a possible absorption signature in Lyα in the atmosphere of GJ 9827b during a transit event from HST spectra, as well as Hα and He i signature for the atmosphere of GJ 9827b and d from CARMENES spectra. We found no evidence of an extended atmosphere in either of the planets. This result is also supported by our analytical estimations of mass loss based on the measured radiation fields for all three planets of this system, which led to a mass-loss rate of 0.4, 0.3, and 0.1 planetary masses per Gyr for GJ 9827b, c, and d, respectively. These values indicate that the planets could have lost their volatiles quickly in their evolution and probably do not retain an atmosphere at the current stage.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

WIYN Open Cluster Study. LXXXV. Li in NGC 2243: Implications for Stellar and Galactic Evolution

High-dispersion spectra in the Li λ6708 region have been obtained and analyzed in the old, metal-deficient cluster NGC 2243. From Hydra spectra for 29 astrometric and radial velocity members, we derive rotational velocities, as well as [Fe/H], [Ca/H], [Si/H], and [Ni/H] based on 17, 1, 1, and 3 lines, respectively. Using ROBOSPECT, an automatic equivalent width measurement program, we derive [Fe/H] = −0.54 ± 0.11 (MAD), for an internal precision for the cluster [Fe/H] below 0.03 dex. Given the more restricted line set, comparable values for [Ca/H], [Si/H], and [Ni/H] are −0.48 ± 0.19, −0.44 ± 0.11, and −0.61 ± 0.06, respectively. With E(B − V) = 0.055, appropriate isochrones imply (m − M) = 13.2 ± 0.1 and an age of 3.6 ± 0.2 Gyr. Using available VLT spectra and published Li abundances, we construct an Li sample of over 100 stars extending from the tip of the giant branch to 0.5 mag below the Li dip. The Li dip is well populated and, when combined with results for NGC 6819 and Hyades/Praesepe, implies a mass/metallicity slope of 0.4 M {sub ⊙}/dex for the high-mass edge of the Li dip. The A(Li) distribution among giants reflects the degree of Li variation among the turnoff stars above the Li dip, itself a function of stellar mass and metallicity and strongly anticorrelated with a v {sub rot} distribution that dramatically narrows with age. Potential implications of these patterns for the interpretation of Li among dwarf and giant field populations, especially selection biases tied to age and metallicity, are discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Detecting Atmospheric Molecules of Nontransiting Temperate Terrestrial Exoplanets Using High-resolution Spectroscopy in the Mid-infrared Domain

Motivated by the development of high-dispersion spectrographs in the mid-infrared (MIR) range, we study their application to the atmospheric characterization of nearby nontransiting temperate terrestrial planets around M-type stars. We examine the detectability of CO{sub 2}, H{sub 2}O, N{sub 2}O, and O{sub 3 }features in high-resolution planetary thermal emission spectra at 12–18 μm assuming an Earth-like profile and a simplified thermal structure. The molecular line width of such planets can be comparable to or broader than the Doppler shift due to the planetary orbital motion. Given the likely difficulty in knowing the high-resolution MIR spectrum of the host star with sufficient accuracy, we propose observing the target system at two quadrature phases and extracting the differential spectra as the planetary signal. In this case, the signals can be substantially suppressed compared with the case where the host star spectrum is perfectly known, as some parts of the spectral features do not remain in the differential spectra. Despite this self-subtraction, the CO{sub 2} and H{sub 2}O features of nearby (≲5 pc) systems with mid-/late-M host stars would be feasible with a 6.5 m class cryogenic space telescope, and orbital inclination could also be constrained for some of them. For CO{sub 2} and N{sub 2}O in a 1 bar Earth-like atmosphere, this method would be sensitive when the mixing ratio is 1–10{sup 3} ppm. The detectability of molecules except O{sub 3} is not significantly improved when the spectral resolution is higher than R≳10,000, although the constraint on the orbital inclination is improved. This study provides some benchmark cases useful for assessing the value of MIR high-resolution spectroscopy in terms of characterization of potentially habitable planets.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

The Galactic Chemical Evolution of Chlorine

We measured {sup 35}Cl abundances in 52 M giants with metallicities in the range −0.5 < [Fe/H] < 0.12. Abundances and atmospheric parameters were derived using infrared spectra from CSHELL on the NASA Infrared Telescope Facility and from optical echelle spectra. We measured Cl abundances by fitting a H{sup 35}Cl molecular feature at 3.6985 μm with synthetic spectra. We also measured the abundances of O, Ca, Ti, and Fe using atomic absorption lines. We find that the [Cl/Fe] ratio for our stars agrees with chemical evolution models of Cl, and the [Cl/Ca] ratio is broadly consistent with the solar ratio over our metallicity range. Both indicate that Cl is primarily made in core-collapse supernovae with some contributions from Type Ia supernovae. We suggest that other potential nucleosynthesis processes, such as the ν-process, are not significant producers of Cl. Finally, we also find our Cl abundances are consistent with H ii and planetary nebular abundances at a given oxygen abundance, although there is scatter in the data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

An Optical Overview of Blazars with LAMOST. I. Hunting Changing-look Blazars and New Redshift Estimates

The extragalactic γ-rays sky observed by the Fermi Large Area Telescope (LAT) is dominated by blazars. In the fourth release of the Fermi LAT Point Source Catalog (4FGL) are sources showing a multifrequency behavior similar to that of blazars but lacking an optical spectroscopic confirmation of their nature, known as blazar candidates of uncertain type (BCUs). We aim at confirming the blazar nature of BCUs and test if new optical spectroscopic observations can reveal spectral features, allowing us to get a redshift estimate for known BL Lac objects. We also aim to search for and discover changing-look blazars (i.e., blazars that show a different classification at different epochs). We carry out an extensive search for optical spectra available in the Large Sky Area Multi-object Fibre Spectroscopic Telescope (LAMOST) Data Release 5 (DR5) archive. We select sources out of the 4FGL catalog, the list of targets from our follow-up spectroscopic campaign of unidentified or unassociated γ-ray sources, and the multifrequency catalog of blazars: the Roma-BZCAT. We select a total of 392 spectra. We also compare some of the LAMOST spectra with those available in the literature. We classify 20 BCUs confirming their blazar-like nature. Then we obtain 15 new redshift estimates for known blazars. We discover 26 transitional (i.e., changing-look) blazars that changed their classification. Finally, we are able to confirm the blazar-like nature of six BL Lac candidates. All remaining sources analyzed agree with previous classifications. BL Lac objects are certainly the most elusive type of blazars in the γ-ray extragalactic sky.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Connecting Galactic Outflows and Star Formation: Inferences from Hα Maps and Absorption-line Spectroscopy at 1 ≲ z ≲ 1.5

We investigate the connection between galactic outflows and star formation using two independent data sets covering a sample of 22 galaxies between 1 ≲ z ≲ 1.5. The Hubble Space Telescope WFC3/G141 grism provides low spectral resolution, high spatial resolution spectroscopy yielding Hα emission-line maps from which we measure the spatial extent and strength of star formation. In the rest-frame near-UV, Keck/DEIMOS observes Fe ii and Mg ii interstellar absorption lines, which provide constraints on the intensity and velocity of the outflows. We compare outflow properties from individual and composite spectra with the star formation rate (SFR) and SFR surface density (Σ{sub SFR}), as well as the stellar mass and specific SFR (sSFR). The Fe ii and Mg ii equivalent widths (EWs) increase with both SFR and Σ{sub SFR} at ≳3σ significance, while the composite spectra show larger Fe ii EWs and outflow velocities in galaxies with higher SFR, Σ{sub SFR}, and sSFR. Absorption-line profiles of the composite spectra further indicate that the differences between subsamples are driven by outflows rather than the interstellar medium. While these results are consistent with those of previous studies, the use of Hα images makes them the most direct test of the relationship between star formation and outflows at z > 1 to date. Future facilities such as the James Webb Space Telescope and the upcoming Extremely Large Telescopes will extend these direct, Hα-based studies to lower masses and SFRs, probing galactic feedback across orders of magnitude in galaxy properties and augmenting the correlations we find here.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

An Optical Overview of Blazars with LAMOST. II. Gamma-Ray Blazar Candidates and Updated Classifications

Blazars represent the dominant class of associated γ-ray sources detected by the Fermi Large Area Telescope (LAT). However, in the more recent release of the Fourth Fermi-LAT Point Source Catalog (4FGL), ∼25% of the sources associated with lower-energy counterparts show a multifrequency behavior similar to that of blazars, but lacks an optical spectroscopic confirmation of their nature and are therefore classified as Blazar Candidates of Uncertain Type (BCUs). A particularly challenging task in blazar studies is to classify these BCUs and, when possible to estimate their redshifts, in particular for BL Lac objects, characterized by almost featureless optical spectra with only weak emission lines. Continuing our study of blazars with Large Sky Area Multi-Object Fiber Spectroscopic Telescope (LAMOST) optical spectral data, we perform an extensive search for optical spectra available in the LAMOST Data Release 6 archive. Our aim is confirming the blazar nature of BCUs and to test if new data can allow us to get a redshift estimate for BL Lac objects that lack measurement, as well as to search for and discover changing-look blazars. We selected sources out of the 4FGL catalog, the list of targets from our follow-up spectroscopic campaign of unidentified and/or unassociated γ-ray sources, and the Roma-BZCAT multifrequency catalog of blazars, finding a total of 42 sources with available LAMOST DR6 spectra. We confirmed the blazar-like nature of four blazar candidates . For the remaining 37 sources we confirm their previous classification.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

On the Utility of Transmission Color Analysis i: Differentiating Super-Earths and Sub-Neptunes

The majority of exoplanets found to date have been discovered via the transit method, and transmission spectroscopy represents the primary method of studying these distant worlds. Currently, in-depth atmospheric characterization of transiting exoplanets entails the use of spectrographs on large telescopes, requiring significant observing time to study each planet. Previous studies have demonstrated trends for solar system worlds using color–color photometry of reflectance spectra, as well as trends within transmission spectra for hot Jupiters. Building on these concepts, we have investigated the use of transmission color photometric analysis for efficient, coarse categorization of exoplanets and for assessing the nature of these worlds, with a focus on resolving the bulk composition degeneracy to aid in discriminating super-Earths and sub-Neptunes. We present our methodology and first results, including spectrum models, model comparison frameworks, and wave band selection criteria. We present our results for different transmission “color” metrics, filter selection methods, and numbers of filters. Assuming noise-free spectra of isothermal atmospheres in chemical equilibrium, with our pipeline, we are able to constrain atmospheric mean molecular weight in order to distinguish between super-Earth and sub-Neptune atmospheres with >90% overall accuracy using specific low-resolution filter combinations, . We also found that increasing the number of filters does not substantially impact this performance. This method could allow for broad characterization of large numbers of planets much more efficiently than current methods permit, enabling population- and system-level studies. Additionally, data collected via this method could inform follow-up observing time by large telescopes for more detailed studies of worlds of interest.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

A Data-scientific Noise-removal Method for Efficient Submillimeter Spectroscopy With Single-dish Telescopes

For submillimeter spectroscopy with ground-based single-dish telescopes, removing the noise contribution from the Earth’s atmosphere and the instrument is essential. For this purpose, here we propose a new method based on a data-scientific approach. The key technique is statistical matrix decomposition that automatically separates the signals of astronomical emission lines from the drift noise components in the fast-sampled (1–10 Hz) time-series spectra obtained by a position-switching (PSW) observation. Because the proposed method does not apply subtraction between two sets of noisy data (i.e., on-source and off-source spectra), it improves the observation sensitivity by a factor of √2. It also reduces artificial signals such as baseline ripples on a spectrum, which may also help to improve the effective sensitivity. We demonstrate this improvement by using the spectroscopic data of emission lines toward a high-redshift galaxy observed with a 2 mm receiver on the 50 m Large Millimeter Telescope. Since the proposed method is carried out offline and no additional measurements are required, it offers an instant improvement on the spectra reduced so far with the conventional method. It also enables efficient deep spectroscopy driven by the future 50 m class large submillimeter single-dish telescopes, where fast PSW observations by mechanical antenna or mirror drive are difficult to achieve.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

The Circumstellar Gas of Phi Leonis in the UV

HST UV spectra were obtained to study whether the φ Leo system has one or more stellar companions, as shown for the A-star dwarf, HR10, stellar pulsation, or transiting exocomets. During five partial HST observation sets spread over 13 months, redshifted gas with radial velocities up to +245 km s{sup -1} was observed on one occasion, with lower velocity infalling material seen twice. Blueshifted gas features with velocities as high as -150 km s{sup -1} with up to three features in two spectra were also seen. Low-mass stellar companions to late A stars are coronal sources. Assuming an age of 450 Myr, G-K companions to φ Leo, and multiple M-star companions would have been detected in the ROSAT All-Sky Survey data, but are not seen. Further, the star shows only 1 major pulsation component, suggesting it is single, excluding an A- or early F-star companion. Low covering factor absorption features with |v| ≤ 200 km s{sup -1} have been reported in optical spectra with variation on timescales consistent with nonradial pulsation. However, the highest velocity infall feature has a broader, continuous absorption profile extending from the stellar velocity to +245 km s{sup -1}, with a covering factor of ~25% which is more consistent with a transit by a body on a star-grazing orbit.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

NGEE Arctic, Canopy Spectral Reflectance, Utqiagvik (Barrow), Alaska, 2014-2016

Measurements of full-spectrum (i.e. 350-2500 nm) canopy spectral reflectance of Arctic plant species within the BEO, Barrow, Alaska. Spectra were collected using Spectra Vista Corporation (SVC) HR-2014i and Spectral Evolution (SE) PSR+ instruments mounted on a tripod or monopod together with a Spectralon white plate to calibrate each measurement under variable illumination conditions. Data were collected in Utqiagvik (Barrow), Alaska during the 2014 to 2016 period. Data package includes processed spectra (*.csv) files and original instrument output and processing files (*.zip).The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a 10-year research effort (2012-2022) to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Time‐Dependent Density Functional Theory of Narrow Band Gap Semiconductors Using a Screened Range‐Separated Hybrid Functional

Abstract Predicting the band structure and optical absorption spectra of narrow band gap semiconductors is challenging for electronic structure methods. Here, it is shown shown that density functional theory can yield accurate band structures and time‐dependent density functional theory (TDDFT) can yield accurate optical absorption spectra for these systems. This is achieved by using a screened range‐separated hybrid (SRSH) functional with a single empirical parameter, fit to reproduce the experimental band gap. By comparing TDDFT results based on the SRSH approach with those obtained based on the Heyd–Scuseria–Ernzerhof functional it is shown that screened long‐range exact exchange improves the accuracy of the TDDFT spectra for these systems.

Wing, Dahvyd↗
DOE OSTI2026

Electron-Deficient Phenazines: Synthesis, Structures, Redox, and Optoelectronic Properties in the Gas Phase, in Solution, and in the Solid State

High-temperature gas-phase reactions of 1,4-C4F8I2 with phenazine (PHNZ) afforded new thermally- and air-stable derivatives with cyclo-C4F8 substituents, viz. 1,2-PHNZ(C4F8), 2,3-PHNZ(C4F8), 1,2:6,7-PHNZ(C4F8)2, 1,2:7,8-PHNZ(C4F8)2, and 1,2:8,9-PHNZ(C4F8)2. Reactions in the presence of Cu powder resulted in reductive-defluorination/aromatization of some of the cyclo-C4F8 substituents to produce 2,3-PHNZ(C4F4), 2,3-PHNZ(C4HF3), and 1,2:6,7-PHNZ(C4F8)(C4F4), which are formally tri- or tetrafluoro derivatives of benzo[a]phenazine. Single-crystal X-ray diffraction structures of these compounds demonstrate the planarity of 2,3-PHNZ(C4F4) and 2,3-PHNZ(C4HF3) and ordered p-stacking in 1,2-PHNZ(C4HF3), 1,2-PHNZ(C4F4), 1,2-PHNZ(C4F8), and 2,3-PHNZ(C4F8). Low-temperature gas-phase photoelectron spectra of the PHNZ(C4F8)1,2 compounds show that they are strong electron acceptors, with the three PHNZ(C4F8)2 isomers having electron affinities exceeding that of C60. Cyclic voltammetry in acetonitrile show that the five PHNZ(C4F8)1,2 compounds exhibit reversible one-electron reductions with large positive shifts in their reduction potentials relative to unsubstituted PHNZ. Spectroelectrochemical absorption and EPR spectra of PHNZ(C4F8)1,2- • anion radicals and extensive DFT calculations revealed the significant role that the different substitution patterns have on determining the optoelectronic properties of the PHNZ(C4F8)1,2 derivatives and PHNZ(C4F8)1,2- • anion radicals. Time-resolved microwave conductivity measurements and photoluminescence spectra of blends of the PHNZ(C4F8)1,2 derivatives with the donor poly(3-hexylthiophene) (P3HT) were recorded to assess the possible use of the new compounds in optoelectronic devices.

Balser, Sebastian↗
DOE OSTI2022

Raman signatures of detonation soot

Soot generated from the detonation of nine explosives was investigated with Raman microspectroscopy and high-resolution transmission electron microscopy (HRTEM). The first order bands, located at approximately 1,580 (G), 1,350 (D1), 1,620 cm –1 (D2), 1,500 (D3), and 1,200 (D4), are used to provide information on the carbon allotropes and defects. The intensity ratios and the full-width at half-maximum provide an indication of the disorder in the material. The Raman spectra of soot acquired from the detonation of nine explosives showed differences which can be used to identify the precursor explosive. Overall, most differences in the spectra were correlated with the presence of amorphous carbon in the soot. In additional to identification of distinct bands in the spectra via deconvolution, principal component analysis was also used to differentiate the different types of soot. HRTEM performed on soot samples with different explosive precursors identified several distinct allotropes of carbon such as nanodiamonds, carbon onions, graphite fibers, and amorphous carbon.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2022

High-yield recombinant bacterial expression of 13 C-, 15 N-labeled, serine-16 phosphorylated, murine amelogenin using a modified third generation genetic code expansion protocol

Amelogenin constitutes ~ 90% of the enamel matrix in the secretory stage of amelogenesis, a still poorly understood process that results in the formation of the hardest and most mineralized tissue in vertebrates – enamel. Most biophysical research with amelogenin uses recombinant protein expressed in Escherichia coli. In addition to providing copious amounts of protein, recombinant expression allows 13 C- and 15 N-labelling for detailed structural studies using NMR spectroscopy. However, native amelogenin is phosphorylated at one position, Ser-16 in murine amelogenin, and a lingering question overshadowing decades of enamel research with recombinant amelogenin is the effect of phosphorylation on its biophysical properties. Using a modified genetic code expansion protocol we have expressed and purified uniformly 13 C-, 15 N-labeled murine amelogenin (pS16M179) with ~95% of the protein being correctly phosphorylated. Homogeneous phosphorylation was achieved using commercially available, enriched, 13 C-, 15 N-labeled media and protein expression was induced with isopropyl β-D-1-thiogalactopyranoside at 310 K. Phosphoserine incorporation was verified from one-dimensional 31P NMR spectra, comparison of 1 H- 15 N HSQC spectra, Phos-tag SDS PAGE, and mass spectrometry. Phosphorus-31 NMR spectra for pS16M179 under conditions known to trigger amelogenin self-assembly into nanospheres confirm nanosphere models with buried N-termini. Lambda phosphatase treatment of these nanospheres results in the dephosphorylation of pS16M179, confirming that smaller oligomers and monomers with exposed N-termini are in equilibrium with nanospheres. Such 13 C-, 15 N-labeling of amelogenin with accurately encoded phosphoserine incorporation will accelerate biomineralization research to understand amelogenesis and stimulate the expanded use of genetic code expansion protocols to introduce phosphorylated amino acids into proteins.

31P-NMR↗