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At least 1,495 records · Page 83
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Structural basis for C-degron selectivity across KLHDCX family E3 ubiquitin ligases

Abstract Specificity of the ubiquitin-proteasome system depends on E3 ligase-substrate interactions. Many such pairings depend on E3 ligases binding to peptide-like sequences - termed N- or C-degrons - at the termini of substrates. However, our knowledge of structural features distinguishing closely related C-degron substrate-E3 pairings is limited. Here, by systematically comparing ubiquitylation activities towards a suite of common model substrates, and defining interactions by biochemistry, crystallography, and cryo-EM, we reveal principles of C-degron recognition across the KLHDCX family of Cullin-RING ligases (CRLs). First, a motif common across these E3 ligases anchors a substrate’s C-terminus. However, distinct locations of this C-terminus anchor motif in different blades of the KLHDC2, KLHDC3, and KLHDC10 β-propellers establishes distinct relative positioning and molecular environments for substrate C-termini. Second, our structural data show KLHDC3 has a pre-formed pocket establishing preference for an Arg or Gln preceding a C-terminal Gly, whereas conformational malleability contributes to KLHDC10’s recognition of varying features adjacent to substrate C-termini. Finally, additional non-consensus interactions, mediated by C-degron binding grooves and/or by distal propeller surfaces and substrate globular domains, can substantially impact substrate binding and ubiquitylatability. Overall, the data reveal combinatorial mechanisms determining specificity and plasticity of substrate recognition by KLDCX-family C-degron E3 ligases.

Science & Technology - Other Topics↗
DOE OSTI2018

A DFT analysis of the ground and charge-transfer excited states of Sc 3 N@I h –C 80 fullerene coupled with metal-free and zinc-phthalocyanine

Endohedral metallofullerenes and phthalocyanine derivatives are recognized as excellent active materials in organic photovoltaics (OPVs). The tri-metallic nitride endohedral C 80 fullerenes have greater absorption coefficients in the visible region and electron-accepting abilities similar to C 60 , which can allow for higher efficiencies in OPV devices. Here, we have investigated the ground and charge transfer excited states of two co-facial donor–acceptor (D–A) molecular conjugates formed by the non-covalent coupling of trimetallic nitride endohedral fullerene (Sc 3 N@I h –C 80 ) with metal-free (H 2 Pc) and zinc-phthalocyanine (ZnPc) chromophores using DFT calculations. The charge transfer (CT) excitation energies are calculated using the perturbative delta-SCF method that enforces orthogonality between the ground and excited states. The binding energies calculated using the PBE and DFT-D3 methods indicate that the dispersion effects play an important role in the stabilization of these complexes. The ground state dipole moment of the Sc 3 N@C 80 –H 2 Pc dyad is much larger than that of Sc 3 N@C 80 –ZnPc, but this is reversed in the excited state where the dipole moment of Sc 3 N@C 80 –ZnPc increases significantly. The lowest few excitation energies in the gas phase for the two complexes are very close, in the range of 1.51–2.66 eV for Sc 3 N@C 80 –ZnPc and 1.51–2.71 eV for the Sc 3 N@C 80 –H 2 Pc complex. However, the lower ionization potential and lower exciton binding energy make the Sc 3 N@C 80 –ZnPc dyad a better candidate for OPVs as compared to the Sc 3 N@C 80 –H 2 Pc dyad.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Green synthesis of reduced Ti 3 C 2 T x MXene nanosheets with enhanced conductivity, oxidation stability, and SERS activity

Transition metal carbides (MXenes) are an emerging family of highly conductive two-dimensional materials with additional functional properties introduced by surface terminations. Further modification of the surface terminations makes MXenes even more appealing for practical applications. Herein, we report a facile and environmentally benign synthesis of reduced Ti 3 C 2 T x MXene (r-Ti 3 C 2 T x ) via a simple treatment with L-ascorbic acid at room temperature. r-Ti 3 C 2 T x shows a six-fold increase in electrical conductivity, from 471 ± 49 for regular Ti 3 C 2 T x to 2819 ± 306 S m -1 for the reduced version. Additionally, we show an enhanced oxidation stability of r-Ti 3 C 2 T x as compared to regular Ti 3 C 2 T x . An examination of the surface-enhanced Raman scattering (SERS) activity reveals that the SERS enhancement factor of r-Ti 3 C 2 T x is an order of magnitude higher than that of regular Ti 3 C 2 T x . The improved SERS activity of r-Ti 3 C 2 T x is attributed to the charge transfer interaction between the MXene surface and probe molecules, re-enforced by an increased electronic density of states (DOS) at the Fermi level of r-Ti 3 C 2 T x . The findings of this study suggest that reduced MXene could be a superior choice over regular MXene, especially for the applications that employ high electronic conductivity, such as electrode materials for batteries and supercapacitors, photodetectors, and SERS-based sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Binding of saturated and unsaturated C 6 -hydrocarbons to the electrophilic anion [B 12 Br 11 ] – : a systematic mechanistic study

The highly reactive gaseous ion [B 12 Br 11 ] – is a metal-free closed-shell anion which spontaneously forms covalent bonds with hydrocarbon molecules, including alkanes. Herein, we systematically investigate the reaction mechanism for binding of [B 12 Br 11 ] – to the five hexane isomers yielding [B 12 Br 11 (C 6 H 14 )] – , as well as to cyclohexane and several hexene isomers (yielding [B 12 Br 11 (C 6 H 12 )] – ) using collision-induced dissociation (CID), infrared photodissociation spectroscopy (IRPD) and computational methods. CID of the different [B 12 Br 11 (C 6 H 14 )] – ions results in distinct fragmentation patterns dependent on the structure of the hexane isomer. Further, the observed fragmentation reactions provide insights into the addition mechanism of [B 12 Br 11 ] – to hexane. Based on the observed CID patterns, we identified that either B–C bond formation through heterolytic C–C or C–H bond cleavages or B–H bond formation through heterolytic C–H cleavage occur dependent on the structure of the hexane isomer. Meanwhile, we observe identical CID spectra of adducts originating from isomers of C 6 H 12 . Spectroscopic investigations of adducts of 1-hexene and cyclohexane indicate the same product structure with an open C 6 chain. Computational investigations evidenced that low lying transition states are present, which enable a ring opening reaction of cyclohexane when binding to [B 12 Br 11 ] – .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Growth mechanism and composition of ultrasmooth a-C:H:Si films grown from energetic ions for superlubricity

Growth mechanism and ion energy dependence of composition of ultrasmooth a-C:H:Si films grown from ionization of tetramethylsilane (TMS) and toluene mixture at a fixed gas ratio have been investigated by varying the applied bias voltage. The dynamic scaling theory is employed to evaluate the roughness evolution of a-C:H:Si films, and to extract roughness and growth exponents of α ∼ 0.51 and β ∼ 0, respectively. The atomically smooth surface of a-C:H:Si films with Ra ∼ 0.1 nm is thermally activated by the energetic ion-impact induced subsurface “polishing” process for ion dominated deposition. The ion energy (bias voltage) plays a paramount role in determining the hydrogen incorporation, bonding structure and final stoichiometry of a-C:H:Si films. The hydrogen content in the films measured by ERDA gradually decreases from 36.7 to 17.3 at. % with increasing the bias voltage from 0.25 to 3.5 kV, while the carbon content in the films increases correspondingly from 52.5 to 70.1 at. %. The Si content is kept almost constant at ∼9–10 at. %. Depending on the ion-surface interactions, the bonding structure of a-C:H:Si films grown in different ion energy regions evolves from chain-developed polymer-like to cross-linked diamond-like to sp{sup 2}-bonded a–C as revealed by XPS, Raman, and FTIR analysis. Such a structural evolution is reflected in their measured nanomechanical properties such as hardness, modulus, and compressive stress. An enhanced viscoplastic behavior (i.e., viscoplastic exponent of ∼0.06) is observed for polymeric a-C:H:Si films. A hydrogen content threshold (H > 20 at. %) exists for the as-grown a-C:H:Si films to exhibit superlow friction in dry N{sub 2} atmosphere. An extremely low friction coefficient of ∼0.001 can be obtained for polymer-like a-C:H:Si film. These near-frictionless a-C:H:Si films are strongly promising for applications in industrial lubricating systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Preparation & characterization of SiO{sub 2} interface layer by dip coating technique on carbon fibre for C{sub f}/SiC composites

Carbon fibres (C{sub f}) are one of the most important reinforced materials for ceramic matrix composites such as C{sub f} - SiC composites and they are generally sought for high temperature applications in as space application, nuclear reactor and automobile industries. But the major problem arise when C{sub f} reinforced composites exposed to high temperature in an oxidizing environment, C{sub f} react with oxygen and burnt away. In present work, we have studied the effect of silica (SiO{sub 2}) coating as a protective coating on C{sub f} for the C{sub f} / SiC composites. The silica solution prepared by the sol-gel process and coating on C{sub f} is done by dip coating technique with varying the withdrawing speed i.e. 2, 5, 8 mm/s with fixed dipping cycle (3 Nos.). The uniform silica coating on the C{sub f} is shown by the Scanning Electron Microscope (SEM) analysis. The tensile test shows the increase in tensile strength with respect to increase in withdrawing speed. The isothermal oxidation analysis confirmed enhancement of oxidation resistance of silica coated C{sub f} as compared tothe uncoated C{sub f}.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High-pressure high-temperature synthesis and characterization of B 10 C

The boron-rich boron carbide materials have been traditionally synthesized by adding boron powder to B 4 C material and subjecting it to hot pressing sintering for materials composition containing 8.8–20 at. % carbon in boron (composition range of B 10.4 C to B 4 C). Our study explores a synthesis route for B 10 C starting from high-purity boron and carbon and direct conversion under high pressure and high temperature (HPHT) conditions of 2000 °C and 6–8 GPa. Synthesis was verified via x-ray diffraction analysis, showing the conversion of the high-purity boron and carbon powder mixture into a hexagonal B 10 C structure (R-3m space group) with lattice parameters of a = b = 5.6115 Å and c = 12.197 Å. The concentration of boron was measured through x-ray photoelectron spectroscopy, confirming the B 10 C ratio. The measured nanoindentation mean hardness of B 10 C was 40 GPa. Raman spectroscopy of the HPHT synthesized sample shows characteristic vibrational breathing modes of boron icosahedron and an additional intense band at a vibrational frequency of 380 cm –1 . This Raman band, which appears notably weaker in earlier studies and B 4 C samples, is assigned to the linear chain of B–B–B and attributed to the maximal incorporation of boron within the hexagonal structure.

36 MATERIALS SCIENCE↗
DOE OSTI2020

One-colour (~220 nm) resonance-enhanced (S 1 –S 0 ) multi-photon dissociation of acetylene: probe of the C 2 A 1 Π u – X 1 Σ + g band by frequency-modulation spectroscopy

In a recent paper, we demonstrated that one-colour (~220 nm), resonance-enhanced (S 1 –S 0 ), photodissociation of acetylene generates strong $C_2$ Swan band ($d^3Π_g–a^3Π_u$) and $C_2$ Deslandres-d'Azambuja band ($C^1Π_g–A^1Π_u$) fluorescence, and long-lived (>3 µs) fluorescence from an electronically-excited $C_2$H * species. It was not known whether the $C_2A^1Π_u$ and $X^1Σ^+_g$ states are also directly populated in this process. In this paper, multiple vibration-rotation transitions between the $C_2A$-state v = 2 and the X-state v = 0 level are examined by time-resolved frequency-modulation (FM) spectroscopy. The photolysis laser wavelength is tuned into resonance at the one-photon level with S 1 –S 0 transitions that populate individual rotational levels of the S 1 $_{trans}$-conformer $3^2,3^3,$ and $3^4$ vibrational states. By comparing the phase of the FM signals from the $C_2A–X$ transitions with that from the Rb D 1 -line absorption transition, we determine that, for all of the probed A–X transitions, the X-state level is more populated than the A-state level. We propose that the acetylene S 1 level is excited by the second photon to an acetylene dissociation precursor state, which undergoes sequential C-H bond-breaking to produce the $C_2X$ state. The dissociation precursor is assigned as the $1^1B_g(trans-bent)/1^1B_1(cis-bent)$ valence state, which correlates to a doubly-excited configuration, $(1π_u)^2(1π_g)^2$, at linear geometry. Based on the rotational distributions of the $C_2X$-state fragments, we believe that at least one of the transition states involved in the photolysis via S 1 $3^4$ has a larger CC-H bend-angle for the departing H-atom than that involved in the S 1 $3^2$ and $3^3$ photolysis.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2013

THE C-FLAME QUENCHING BY CONVECTIVE BOUNDARY MIXING IN SUPER-AGB STARS AND THE FORMATION OF HYBRID C/O/Ne WHITE DWARFS AND SN PROGENITORS

After off-center C ignition in the cores of super asymptotic giant branch (SAGB) stars, the C flame propagates all the way down to the center, trailing behind it the C-shell convective zone, and thus building a degenerate ONe core. This standard picture is obtained in stellar evolution simulations if the bottom C-shell convection boundary is assumed to be a discontinuity associated with a strict interpretation of the Schwarzschild condition for convective instability. However, this boundary is prone to additional mixing processes, such as thermohaline convection and convective boundary mixing. Using hydrodynamic simulations, we show that contrary to previous results, thermohaline mixing is too inefficient to interfere with the C-flame propagation. However, even a small amount of convective boundary mixing removes the physical conditions required for the C-flame propagation all the way to the center. This result holds even if we allow for some turbulent heat transport in the CBM region. As a result, SAGB stars build in their interiors hybrid C-O-Ne degenerate cores composed of a relatively large CO core (M{sub CO} Almost-Equal-To 0.2 M{sub Sun }) surrounded by a thick ONe zone ({Delta}M{sub ONe} {approx}> 0.85 M{sub Sun }) with another thin CO layer above. If exposed by mass loss, these cores will become hybrid C-O-Ne white dwarfs. Otherwise, the ignition of C-rich material in the central core, surrounded by the thick ONe zone, may trigger a thermonuclear supernova (SN) explosion. The quenching of the C-flame may have implications for the ignition mechanism of SN Ia in the double-degenerate merger scenario.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2013

EXTENSIVE [C I] MAPPING TOWARD THE ORION-A GIANT MOLECULAR CLOUD

We have carried out wide-field (0.17 deg{sup 2}) and high-angular resolution (21.''3 {approx} 0.04 pc) observations in the [C I] line toward the Orion-A giant molecular cloud with the Atacama Submillimeter Telescope Experiment 10 m telescope in the On-The-Fly mode. The overall features of the [C I] emission are similar to those of the {sup 12}CO (J = 1-0) emission by Shimajiri et al. in 2011; the total intensity ratio of the [C I] to CO emission ranges from 0.05 to 0.2. The optical depth of the [C I] emission is found to be 0.1-0.75, suggesting optically thin emission. The column density of the [C I] emission is estimated to be (1.0-19) Multiplication-Sign 10{sup 17} cm{sup -2}. These results are consistent with the results of the previous [C I] observations with a low-angular resolution of 2.'2. In the nearly edge-on photon-dominated regions (PDRs) and their candidates of the Orion Bar, DLSF, M 43 Shell, and Region D, the distributions of the [C I] emission coincide with those of the {sup 12}CO emission, inconsistent with the prediction by the plane-parallel PDR model. In addition, the [C I] distribution in the Orion A cloud is found to be more similar to those of the {sup 13}CO (J = 1-0), C{sup 18}O (J = 1-0), and H{sup 13}CO{sup +} (J = 1-0) lines than that of the {sup 12}CO (J = 1-0) line, suggesting that the [C I] emission is not limited to the cloud surface, but is tracing the dense, inner parts of the cloud.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Search for C II emission on cosmological scales at redshift Z ~ 2.6

We present a search for C II emission over cosmological scales at high redshifts. The C II line is a prime candidate to be a tracer of star formation over large-scale structure since it is one of the brightest emission lines from galaxies. Redshifted C II emission appears in the submillimeter regime, which means it could potentially be present in the higher frequency intensity data from the Planck satellite is used to measure the cosmic infrared background (CIB). We search for C II emission over redshifts z = 2–3.2 in the Planck 545 GHz intensity map by cross-correlating the three highest frequency Planck maps with spectroscopic quasars and CMASS galaxies from the Sloan Digital Sky Survey III, which we then use to jointly fit C II intensity, CIB parameters, and thermal Sunyaev–Zeldovich (SZ) emission. We report a measurement of an anomalous emission I ν = 6.6 +5.0 –4.8 × 10 4 Jy sr –1 at 95 percent confidence, which could be explained by C II emission, favouring collisional excitation models of C II emission that tend to be more optimistic than models based on C II luminosity scaling relations from local measurements; however, a comparison of Bayesian information criteria reveals that this model and the CIB & SZ model are equally plausible. Thus, more sensitive measurements will be needed to confirm the existence of a large-scale C II emission at high redshifts. Lastly, we forecast that intensity maps from Planck cross-correlated with quasars from the Dark Energy Spectroscopic Instrument would increase our sensitivity to C II emission by a factor of 5, while the proposed Primordial Inflation Explorer could increase the sensitivity further.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

WE-EF-207-02: The Rotate-Plus-Shift C-Arm Trajectory: Theory and First Clinical Results

Purpose: The proposed method enables the acquisition of a complete dataset for 3D reconstruction of C-Arm data using less than 180° rotation. Methods: Typically a C–arm cone–beam CT scan is performed using a circle–like trajectory around a region of interest. Therefore an angular range of at least 180° plus fan–angle must be covered to ensure a completely sampled data set. This fact defines some constraints on the geometry and technical specifications of a C–arm system, for example a larger C radius or a smaller C opening respectively. This is even more important for mobile C-arm devices which are typically used in surgical applications.To overcome these limitations we propose a new trajectory which requires only 180° minusfan–angle of rotation for a complete data set. The trajectory consists of three parts: A rotation of the C around a defined iso–center and two translational movements parallel to the detector plane at the begin and at the end of the rotation (rotate plus shift trajectory). This enables the acquisition of a completely sampled dataset using only 180° minus fan–angle of rotation. Results: For the evaluation of the method we show simulated and measured data. The results show, that the rotate plus shift scan yields equivalent image quality compared to the short scan which is assumed to be the gold standard for C-arm CT today. Compared to the pure rotational scan over only 165°, the rotate plus shift scan shows strong improvements in image quality. Conclusion: The proposed method makes 3D imaging using C–arms with less than 180° rotation range possible. This enables integrating full 3D functionality into a C- arm device without any loss of handling and usability for 2D imaging.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

A Quantum Mechanical MP2 Study of the Electronic Effect of Nonplanarity on the Carbon Pyramidalization of Fullerene C 60

Among C 60 ’s diverse functionalities, its potential application in CO 2 sequestration has gained increasing interest. However, the processes involved are sensitive to the molecule’s electronic structure, aspects of which remain debated and require greater precision. To address this, we performed structural optimization of fullerene C 60 using the QM MP2/6–31G* method. The nonplanarity of the optimized icosahedron is characterized by two types of dihedral angles: 138° and 143°. The 120 dihedrals of 138° occur between two hexagons intersecting at C–C bonds of 1.42 Å, while the 60 dihedrals of 143° are observed between hexagons and pentagons at C–C bonds of 1.47 Å. NBO analysis reveals less pyramidal sp 1.78 hybridization for carbons at the 1.42 Å bonds and more pyramidal sp 2.13 hybridization for the 1.47 Å bonds. Electrostatic potential charges range from -0.04 a.u. to 0.04 a.u. on the carbon atoms. Second-order perturbation analysis indicates that delocalization interactions in the C–C bonds of 1.42 Å (143.70 kcal/mol) and 1.47 Å (34.98 kcal/mol) are 22% and 38% higher, respectively, than those in benzene. MP2/Def2SVP calculations yield a correlation energy of 13.49 kcal/mol per electron for C 60 , slightly higher than the 11.68 kcal/mol for benzene. However, the results from HOMO-LUMO calculations should be interpreted with caution. This study may assist in the rational design of fullerene C 60 derivatives for CO 2 reduction systems.

36 MATERIALS SCIENCE↗
DOE OSTI2016

STELLAR ORIGINS OF EXTREMELY {sup 13}C- AND {sup 15}N-ENRICHED PRESOLAR SIC GRAINS: NOVAE OR SUPERNOVAE?

Extreme excesses of {sup 13}C ({sup 12}C/{sup 13}C < 10) and {sup 15}N ({sup 14}N/{sup 15}N < 20) in rare presolar SiC grains have been considered diagnostic of an origin in classical novae, though an origin in core collapse supernovae (CCSNe) has also been proposed. We report C, N, and Si isotope data for 14 submicron- to micron-sized {sup 13}C- and {sup 15}N-enriched presolar SiC grains ({sup 12}C/{sup 13}C < 16 and {sup 14}N/{sup 15}N < ∼100) from Murchison, and their correlated Mg–Al, S, and Ca–Ti isotope data when available. These grains are enriched in {sup 13}C and {sup 15}N, but with quite diverse Si isotopic signatures. Four grains with {sup 29,30}Si excesses similar to those of type C SiC grains likely came from CCSNe, which experienced explosive H burning occurred during explosions. The independent coexistence of proton- and neutron-capture isotopic signatures in these grains strongly supports heterogeneous H ingestion into the He shell in pre-supernovae. Two of the seven putative nova grains with {sup 30}Si excesses and {sup 29}Si depletions show lower-than-solar {sup 34}S/{sup 32}S ratios that cannot be explained by classical nova nucleosynthetic models. We discuss these signatures within the CCSN scenario. For the remaining five putative nova grains, both nova and supernova origins are viable because explosive H burning in the two stellar sites could result in quite similar proton-capture isotopic signatures. Three of the grains are sub-type AB grains that are also {sup 13}C enriched, but have a range of higher {sup 14}N/{sup 15}N. We found that {sup 15}N-enriched AB grains (∼50 < {sup 14}N/{sup 15}N < ∼100) have distinctive isotopic signatures compared to putative nova grains, such as higher {sup 14}N/{sup 15}N, lower {sup 26}Al/{sup 27}Al, and lack of {sup 30}Si excess, indicating weaker proton-capture nucleosynthetic environments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

C{sub 2}N{sub 2} Vertical Profile in Titan’s Stratosphere

In this paper, we present the first measurements of the vertical distribution of cyanogen (C{sub 2}N{sub 2}) in Titan’s lower atmosphere at different latitudes and seasons, using Cassini’s Composite Infrared Spectrometer far-infrared data. We also study the vertical distribution of three other minor species detected in our data: methylacetylene (C{sub 3}H{sub 4}), diacetylene (C{sub 4}H{sub 2}), and H{sub 2}O, in order to compare them to C{sub 2}N{sub 2}, but also to get an overview of their seasonal and meridional variations in Titan’s lower stratosphere from 85 km to 225 km. We measured an average volume mixing ratio of C{sub 2}N{sub 2} of 6.2±0.8×10{sup −11} at 125 km at the equator, but poles exhibit a strong enrichment in C{sub 2}N{sub 2} (up to a factor 100 compared to the equator), greater than what was measured for C{sub 3}H{sub 4} or C{sub 4}H{sub 2}. Measuring C{sub 2}N{sub 2} profiles provides constraints on the processes controlling its distribution, such as bombardment by Galactic Cosmic Rays which seem to have a smaller influence on C{sub 2}N{sub 2} than predicted by photochemical models.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

HERSCHEL EXTREME LENSING LINE OBSERVATIONS: [C ii] VARIATIONS IN GALAXIES AT REDSHIFTS z = 1–3

We observed the [C ii] line in 15 lensed galaxies at redshifts 1 < z < 3 using HIFI on the Herschel Space Observatory and detected 14/15 galaxies at 3 σ or better. High magnifications enable even modestly luminous galaxies to be detected in [C ii] with Herschel . The [C ii] luminosity in this sample ranges from 8 × 10{sup 7} L {sub ⊙} to 3.7 × 10{sup 9} L {sub ⊙} (after correcting for magnification), confirming that [C ii] is a strong tracer of the ISM at high redshifts. The ratio of the [C ii] line to the total far-infrared (FIR) luminosity serves as a measure of the ratio of gas to dust cooling and thus the efficiency of the grain photoelectric heating process. It varies between 3.3% and 0.09%. We compare the [C ii]/FIR ratio to that of galaxies at z = 0 and at high redshifts and find that they follow similar trends. The [C ii]/FIR ratio is lower for galaxies with higher dust temperatures. This is best explained if increased UV intensity leads to higher FIR luminosity and dust temperatures, but gas heating does not rise due to lower photoelectric heating efficiency. The [C ii]/FIR ratio shows weaker correlation with FIR luminosity. At low redshifts highly luminous galaxies tend to have warm dust, so the effects of dust temperature and luminosity are degenerate. Luminous galaxies at high redshifts show a range of dust temperatures, showing that [C ii]/FIR correlates most strongly with dust temperature. The [C ii] to mid-IR ratio for the HELLO sample is similar to the values seen for low-redshift galaxies, indicating that small grains and PAHs dominate the heating in the neutral ISM, although some of the high [CII]/FIR ratios may be due to turbulent heating.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

Large-scale Spectroscopic Mapping of the ρ Ophiuchi Molecular Cloud Complex. I. The C{sub 2}H-to-N{sub 2}H{sup +} Ratio as a Signpost of Cloud Characteristics

We present 2.5-square-degree C{sub 2}H N = 1–0 and N{sub 2}H{sup +} J = 1–0 maps of the ρ Ophiuchi molecular cloud complex. These are the first large-scale maps of the ρ Ophiuchi molecular cloud complex with these two tracers. The C{sub 2}H emission is spatially more extended than the N{sub 2}H{sup +} emission. One faint N{sub 2}H{sup +} clump, Oph-M, and one C{sub 2}H ring, Oph-RingSW, are identified for the first time. The observed C{sub 2}H-to-N{sub 2}H{sup +} abundance ratio ([C{sub 2}H]/[N{sub 2}H{sup +}]) varies between 5 and 110. We modeled the C{sub 2}H and N{sub 2}H{sup +} abundances with 1D chemical models, which show a clear decline of [C{sub 2}H]/[N{sub 2}H{sup +}] with chemical age. Such an evolutionary trend is little affected by temperatures when they are below 40 K. At high density ( n {sub H} > 10{sup 5} cm{sup −3}), however, the time it takes for the abundance ratio to drop at least one order of magnitude becomes less than the dynamical time (e.g., turbulence crossing time of ∼10{sup 5} yr). The observed [C{sub 2}H]/[N{sub 2}H{sup +}] difference between L1688 and L1689 can be explained by L1688 having chemically younger gas in relatively less dense regions. The observed [C{sub 2}H]/[N{sub 2}H{sup +}] values are the results of time evolution, accelerated at higher densities. For the relatively low density regions in L1688 where only C{sub 2}H emission was detected, the gas should be chemically younger.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

The Origins of [C ii] Emission in Local Star-forming Galaxies

The [C ii] 158 μ m fine-structure line is the brightest emission line observed in local star-forming galaxies. As a major coolant of the gas-phase interstellar medium, [C ii] balances the heating, including that due to far-ultraviolet photons, which heat the gas via the photoelectric effect. However, the origin of [C ii] emission remains unclear because C{sup +} can be found in multiple phases of the interstellar medium. Here we measure the fractions of [C ii] emission originating in the ionized and neutral gas phases of a sample of nearby galaxies. We use the [N ii] 205 μ m fine-structure line to trace the ionized medium, thereby eliminating the strong density dependence that exists in the ratio of [C ii]/[N ii] 122 μ m. Using the FIR [C ii] and [N ii] emission detected by the KINGFISH (Key Insights on Nearby Galaxies: a Far- Infrared Survey with Herschel ) and Beyond the Peak Herschel programs, we show that 60%–80% of [C ii] emission originates from neutral gas. We find that the fraction of [C ii] originating in the neutral medium has a weak dependence on dust temperature and the surface density of star formation, and has a stronger dependence on the gas-phase metallicity. In metal-rich environments, the relatively cooler ionized gas makes substantially larger contributions to total [C ii] emission than at low abundance, contrary to prior expectations. Approximate calibrations of this metallicity trend are provided.

79 ASTRONOMY AND ASTROPHYSICS↗