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At least 235 records · Page 13

Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis

Ozonolysis of isoprene, one of the most abundant volatile organic compounds in the atmosphere, proceeds through methyl vinyl ketone oxide (MVK-oxide), methacrolein oxide, and formaldehyde oxide (CH 2 OO) Criegee intermediates. Our work her3e focuses on MVK-oxide, a four-carbon unsaturated carbonyl oxide intermediate, using vacuum ultraviolet photoionization at 118 nm and UV-visible induced depletion of the m/z = 86 mass channel to characterize its first π * ← π electronic transition. The electronic spectrum is broad and unstructured with its peak at 388 nm (3.2 eV). The MVK-oxide spectrum is shifted to a significantly longer wavelength than CH 2 OO and alkyl-substituted Criegee intermediates studied previously due to extended conjugation across the vinyl and carbonyl oxide groups. Electronic excitation results in rapid dissociation at λ ≤ 430 nm to methyl vinyl ketone and O 1 D products, the latter detected by 2 + 1 resonance enhanced multiphoton ionization using velocity map imaging. Complementary electronic structure calculations (CASPT2(12,10)/AVDZ) predict two π * ← π transitions with significant oscillator strength for each of the four conformers of MVK-oxide with vertical excitation energies (and corresponding wavelengths) in the 3.1-3.6 eV (350-400 nm) and 4.5-5.5 eV (220-280 nm) regions. The computed electronic absorption profile of MVK-oxide, based on a Wigner distribution of ground state configurations and summed over the four conformers, is anticipated to peak at 397 nm. UV-visible spectroscopy on the first π * ← π transition is shown by a combination of experiment and theory to provide a sensitive method for detection of the MVK-oxide Criegee intermediate that will enable further studies of its photochemistry and unimolecular and bimolecular reaction dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bragg fibres with an intermediate layer

This paper examines the effect of an intermediate layer between the core and periodic cladding of a Bragg fibre on its optical properties. It is shown that any TE{sub 0{kappa}} mode of a standard Bragg fibre can be transformed into the fundamental mode of a Bragg fibre with an intermediate layer by adjusting the thickness of the first cladding layer. Varying the thickness of the intermediate layer, one can tune the mode composition of the transmitted light in a periodic manner. The periodic variation of the optical loss with the thickness of the intermediate layer is due to resonances and antiresonances in this layer. The resonances correspond to two-mode light propagation through the fibre, whereas the antiresonances, to single-mode light propagation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Imaging active site chemistry and protonation states: NMR crystallography of the tryptophan synthase α-aminoacrylate intermediate

NMR-assisted crystallography-the integrated application of solid-state NMR, X-ray crystallography, and first-principles computational chemistry-holds significant promise for mechanistic enzymology: by providing atomic-resolution characterization of stable intermediates in enzyme active sites, including hydrogen atom locations and tautomeric equilibria, NMR crystallography offers insight into both structure and chemical dynamics. Here, this integrated approach is used to characterize the tryptophan synthase α-aminoacrylate intermediate, a defining species for pyridoxal-5'-phosphate-dependent enzymes that catalyze β-elimination and replacement reactions. For this intermediate, NMR-assisted crystallography is able to identify the protonation states of the ionizable sites on the cofactor, substrate, and catalytic side chains as well as the location and orientation of crystallographic waters within the active site. Most notable is the water molecule immediately adjacent to the substrate β-carbon, which serves as a hydrogen bond donor to the ε-amino group of the acid-base catalytic residue βLys87. From this analysis, a detailed three-dimensional picture of structure and reactivity emerges, highlighting the fate of the L-serine hydroxyl leaving group and the reaction pathway back to the preceding transition state. Reaction of the α-aminoacrylate intermediate with benzimidazole, an isostere of the natural substrate indole, shows benzimidazole bound in the active site and poised for, but unable to initiate, the subsequent bond formation step. When modeled into the benzimidazole position, indole is positioned with C3 in contact with the α-aminoacrylate C $\bar{β}$ and aligned for nucleophilic attack. Here, the chemically detailed, three-dimensional structure from NMR-assisted crystallography is key to understanding why benzimidazole does not react, while indole does.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct observation of intermediates in the SufS cysteine desulfurase reaction reveals functional roles of conserved active-site residues

Iron-sulfur (Fe-S) clusters are necessary for the proper functioning of numerous metalloproteins. Fe-S cluster (Isc) and sulfur utilization factor (Suf) pathways are the key biosynthetic routes responsible for generating these Fe-S cluster prosthetic groups in Escherichia coli. Although Isc dominates under normal conditions, Suf takes over during periods of iron depletion and oxidative stress. Sulfur acquisition via these systems relies on the ability to remove sulfur from free cysteine using a cysteine desulfurase mechanism. In the Suf pathway, the dimeric SufS protein uses the cofactor pyridoxal 5'-phosphate (PLP) to abstract sulfur from free cysteine, resulting in the production of alanine and persulfide. Despite much progress, the stepwise mechanism by which this PLP-dependent enzyme operates remains unclear. Here, using rapid-mixing kinetics in conjunction with X-ray crystallography, we analyzed the pre-steady-state kinetics of this process while assigning early intermediates of the mechanism. We employed H123A and C364A SufS variants to trap Cys-aldimine and Cys-ketimine intermediates of the cysteine desulfurase reaction, enabling direct observations of these intermediates and associated conformational changes of the SufS active site. Of note, we propose that Cys-364 is essential for positioning the Cys-aldimine for Cα deprotonation, His-123 acts to protonate the Ala-enamine intermediate, and Arg-56 facilitates catalysis by hydrogen bonding with the sulfhydryl of Cys-aldimine. Our results, along with previous SufS structural findings, suggest a detailed model of the SufS-catalyzed reaction from Cys binding to C–S bond cleavage and indicate that Arg-56, His-123, and Cys-364 are critical SufS residues in this C–S bond cleavage pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intermediate state trapping of a voltage sensor

Voltage sensor domains (VSDs) regulate ion channels and enzymes by undergoing conformational changes depending on membrane electrical signals. The molecular mechanisms underlying the VSD transitions are not fully understood. Here, we show that some mutations of I241 in the S1 segment of the Shaker Kv channel positively shift the voltage dependence of the VSD movement and alter the functional coupling between VSD and pore domains. Among the I241 mutants, I241W immobilized the VSD movement during activation and deactivation, approximately halfway between the resting and active states, and drastically shifted the voltage activation of the ionic conductance. This phenotype, which is consistent with a stabilization of an intermediate VSD conformation by the I241W mutation, was diminished by the charge-conserving R2K mutation but not by the charge-neutralizing R2Q mutation. Interestingly, most of these effects were reproduced by the F244W mutation located one helical turn above I241. Electrophysiology recordings using nonnatural indole derivatives ruled out the involvement of cation-Π interactions for the effects of the Trp inserted at positions I241 and F244 on the channel’s conductance, but showed that the indole nitrogen was important for the I241W phenotype. Insight into the molecular mechanisms responsible for the stabilization of the intermediate state were investigated by creating in silico the mutations I241W, I241W/R2K, and F244W in intermediate conformations obtained from a computational VSD transition pathway determined using the string method. The experimental results and computational analysis suggest that the phenotype of I241W may originate in the formation of a hydrogen bond between the indole nitrogen atom and the backbone carbonyl of R2. This work provides new information on intermediate states in voltage-gated ion channels with an approach that produces minimum chemical perturbation.

59 BASIC BIOLOGICAL SCIENCES↗

Photometric investigation of the totally eclipsing contact binary V12 in the intermediate-age open cluster NGC 7789

NGC 7789 is an intermediate-age open cluster with an age similar to the mean age of contact binary stars. V12 is a bright W UMa-type binary star with an orbital period of 0.3917 days. The first complete light curves of V12 in the V, R, and I bands are presented and analyzed with the Wilson–Devinney (W-D) method. The results show that V12 is an intermediate-contact binary (f=43.0(±2.2)%) with a mass ratio of 3.848, and it is a W-type contact binary where the less massive component is slightly hotter than the more massive one. The asymmetry of the light curves is explained by the presence of a dark spot on the more massive component. The derived orbital inclination (i=83{sub .}{sup ∘}6) indicates that it is a totally eclipsing binary, which suggests that the determined parameters are reliable. The orbital period may show a long-term increase at a rate of P-dot =+2.48(±0.17)×10{sup −6} days yr{sup −1} that reveals a rapid mass transfer from the less massive component to the more massive one. However, more observations are needed to confirm this conclusion. The presence of an intermediate-contact binary in an intermediate-age open cluster may suggest that some contact binaries have a very short pre-contact timescale. The presence of a third body and/or stellar collision may help to shorten the pre-contact evolution.

79 ASTRONOMY AND ASTROPHYSICS↗

THE INTERMEDIATE-MASS BLACK HOLE CANDIDATE IN THE CENTER OF NGC 404: NEW EVIDENCE FROM RADIO CONTINUUM OBSERVATIONS

We present the results of deep, high-resolution, 5 GHz Expanded Very Large Array (EVLA) observations of the nearby, dwarf lenticular galaxy and intermediate-mass black hole candidate (M{sub BH} {approx} 4.5 Multiplication-Sign 10{sup 5} M{sub Sun }), NGC 404. For the first time, radio emission at frequencies above 1.4 GHz has been detected in this galaxy. We found a modestly resolved source in the NGC 404 nucleus with a total radio luminosity of 7.6 {+-} 0.7 Multiplication-Sign 10{sup 17} W Hz{sup -1} at 5 GHz and a spectral index from 5 to 7.45 GHz of {alpha} = -0.88 {+-} 0.30. NGC 404 is only the third central intermediate-mass black hole candidate detected in the radio regime with subarcsecond resolution. The position of the radio source is consistent with the optical center of the galaxy and the location of a known, hard X-ray point source (L{sub X} {approx} 1.2 Multiplication-Sign 10{sup 37} erg s{sup -1}). The faint radio and X-ray emission could conceivably be produced by an X-ray binary, star formation, a supernova remnant, or a low-luminosity active galactic nucleus powered by an intermediate-mass black hole. In light of our new EVLA observations, we find that the most likely scenario is an accreting intermediate-mass black hole, with other explanations being either incompatible with the observed X-ray and/or radio luminosities or statistically unlikely.

79 ASTRONOMY AND ASTROPHYSICS↗

IPHAS J062746.41+014811.3: A DEEPLY ECLIPSING INTERMEDIATE POLAR

We present time-resolved photometry of a cataclysmic variable discovered in the Isaac Newton Telescope Photometric H{alpha} Survey of the northern galactic plane, IPHAS J062746.41+014811.3, and classify the system as the fourth deeply eclipsing intermediate polar known with an orbital period of P {sub orb} = 8.16 hr and a spin period of P {sub spin} = 2210 s. The system shows mild variations of its brightness that appear to be accompanied by a change in the amplitude of the spin modulation at optical wavelengths and a change in the morphology of the eclipse profile. The inferred magnetic moment of the white dwarf is {mu}{sub wd} {approx} (6-7) Multiplication-Sign 10{sup 33} G cm{sup 3}, and in this case IPHAS J062746.41+014811.3 will evolve either into a short-period EX Hya-like intermediate polar with a large P {sub spin}/P{sub orb} ratio or, perhaps more likely, into a synchronized polar. Swift observations show that the system is an ultraviolet and X-ray source, with a hard X-ray spectrum that is consistent with those seen in other intermediate polars. The ultraviolet light curve shows orbital modulation and an eclipse, while the low signal-to-noise ratio X-ray light curve does not show a significant modulation on the spin period. The measured X-ray flux is about an order of magnitude lower than would be expected from scaling by the optical fluxes of well-known X-ray-selected intermediate polars.

79 ASTRONOMY AND ASTROPHYSICS↗

THE MAGELLANIC INTER-CLOUD PROJECT (MAGIC). I. EVIDENCE FOR INTERMEDIATE-AGE STELLAR POPULATIONS IN BETWEEN THE MAGELLANIC CLOUDS

The origin of the gas in between the Magellanic Clouds (MCs)-known as the ''Magellanic Bridge'' (MB)-is puzzling. Numerical simulations suggest that the MB formed from tidally stripped gas and stars in a recent interaction between the MCs. However, the apparent lack of stripped intermediate- or old-age stars associated with the MB is at odds with this picture. In this paper, we present the first results from the MAGellanic Inter-Cloud program (MAGIC) aimed at probing the stellar populations in the inter-Cloud region. We present observations of the stellar populations in two large fields located in between the Large and Small Magellanic Clouds (LMC/SMC), secured using the WFI camera on the 2.2 m telescope in La Silla. Using a synthetic color-magnitude diagram technique, we present the first quantitative evidence for the presence of intermediate-age and old stars in the inter-Cloud region. The intermediate-age stars-which make up {approx}28% of all stars in the region-are not present in fields at a similar distance from the SMC in a direction pointing away from the LMC. This provides potential evidence that these intermediate-age stars could have been tidally stripped from the SMC. However, spectroscopic studies will be needed to confirm or rule out the tidal origin for the inter-Cloud gas and stars.

79 ASTRONOMY AND ASTROPHYSICS↗

Intermediate inflation from a non-canonical scalar field

We study the intermediate inflation in a non-canonical scalar field framework with a power-like Lagrangian. We show that in contrast with the standard canonical intermediate inflation, our non-canonical model is compatible with the observational results of Planck 2015. Also, we estimate the equilateral non-Gaussianity parameter which is in well agreement with the prediction of Planck 2015. Then, we obtain an approximation for the energy scale at the initial time of inflation and show that it can be of order of the Planck energy scale, i.e. M{sub P} ∼ 10{sup 18}GeV. We will see that after a short period of time, inflation enters in the slow-roll regime that its energy scale is of order M{sub P}/100 ∼ 10{sup 16}GeV and the horizon exit takes place in this energy scale. We also examine an idea in our non-canonical model to overcome the central drawback of intermediate inflation which is the fact that inflation never ends. We solve this problem without disturbing significantly the nature of the intermediate inflation until the time of horizon exit.

79 ASTRONOMY AND ASTROPHYSICS↗

Carrier Lifetimes in a I I I - V - N Intermediate-Band Semiconductor

Here we use transient absorption spectroscopy to measure carrier lifetimes in the multiband semiconductor GaP y As 1-x-y N x . These measurements probe the electron populations in the conduction band, intermediate band, and valence band as a function of time after an excitation pulse. Following photoexcitation of GaP 0.32 As 0.67 N 0.01 , we find that the electron population in the conduction band decays exponentially with a time constant τ CB =23 ps. The electron population in the intermediate band exhibits bimolecular recombination with recombination constant r = 2×10 -8 cm 3 /s. In our experiment, an optical pump pulse excites electrons from the valence band to the intermediate and conduction bands, and the change in interband absorption due to absorption saturation and induced absorption is probed with a delayed white-light pulse. We model the optical properties of our samples using the band anticrossing model to extract carrier densities as a function of time. Finally, these results not only identify the short minority-carrier lifetime as a key factor affecting the performance of GaP y As 1-x-y N x -based intermediate-band solar cells but also provide guidance on ways to address this issue.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Triangular lattice Hubbard model physics at intermediate temperatures

Moiré systems offer an exciting playground to study the many-body effects of strongly correlated electrons in regimes that are not easily accessible in conventional material settings. Motivated by a recent experiment on WSe 2 /WS 2 moiré bilayers [Y. Tang et al., Nature (London) 579, 353 (2020)], which realized a triangular superlattice with a small hopping (of approximately 10 Kelvin), with tunable density of holes, we explore the Hubbard model on the triangular lattice for intermediate temperatures t ≲ T < U. Employing finite-temperature Lanczos calculations and closely following the fitting protocols used in the experiment, we recover the observed trends in the reported Curie-Weiss temperature Θ with filling, using the reported interaction strength U/t=20. Here, we focus on the large increase of |Θ| on decreasing the density below half filling and the sign change of Θ at higher fillings, which signals the onset of ferromagnetism. The increase in |Θ| is also seen in the t–J model (the low-energy limit of the Hubbard model) in the intermediate temperature range, which we clarify is opposite to the trend in its high temperature limit. Differences between the low, intermediate, and high temperature regimes are discussed. Our numerical calculations also capture the crossover between short-range antiferromagnetic to ferromagnetic order in the intermediate temperature regime, a result broadly consistent with the experimental findings. We find that this behavior is a finite-temperature remnant of the underlying zero-temperature phase transition, which we explore with ground-state density matrix renormalization group calculations. We provide evidence of ferromagnetism characterized by weak (but robust) correlations that explain the small Θ seen in the experiment.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Numerical Study of Quantum Hall Bilayers at Total Filling ν T = 1 : A New Phase at Intermediate Layer Distances

We view the phase diagram of quantum Hall bilayer systems with total filing ν T = 1/2 + 1/2 of the lowest Landau level as a function of layer distances d . Based on numerical exact diagonalization calculations, we obtain three distinct phases, including an exciton superfluid phase with spontaneous interlayer coherence at small d , a composite Fermi liquid at large d , and an intermediate phase for 1.1 < d/l B < 1.8 (l B is the magnetic length). The transition from the exciton superfluid to the intermediate phase is identified by (i) a dramatic change in the Berry curvature of the ground state under twisted boundary conditions on the two layers and (ii) an energy level crossing of the first excited state. The transition from the intermediate phase to the composite Fermi liquid is identified by the vanishing of the exciton superfluid stiffness. Moreover, from our finite-size study, the energy cost of transferring one electron between the layers shows an even-odd effect and possibly extrapolates to a finite value in the thermodynamic limit, indicating the enhanced intralayer correlation. Our identification of an intermediate phase and its distinctive features shed new light on the theoretical understanding of the quantum Hall bilayer system at total filling ν T = 1 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Intermediate Yb valence in the Zintl phases Yb 14 MSb 11 (M=Zn,Mn,Mg): XANES, magnetism, and heat capacity

Yb 14 Mn Sb 11 is a magnetic Zintl compound as well as being one of the best high temperature p -type thermoelectric materials. According to the Zintl formalism, which defines intermetallic phases where cations and anions are valence satisfied, this structure type is nominally made up of 14 Yb 2 + , 1 MnSb 4 9 - , 1 Sb 3 7 - , and 4 Sb 3 - atoms. When Mn is replaced by Mg or Zn, the Zintl defined motifs become 13 Yb 2 + , 1 Yb 3 + , 1 (Mg, Zn) Sb 4 10 - , 1 Sb 3 7 - , and 4 Sb 3 - . The predicted existence of Yb 3 + based on simple electron counting rules of the Zintl formalism calls the Yb valence of these compounds into question. X-ray absorption near-edge structure, magnetic susceptibility, and specific heat measurements on single crystals of the three analogs show signatures of intermediate valence Yb behavior and in particular, reveal the heavy fermion nature of Yb 14 MgSb 11 . In these isostructural compounds, Yb can exhibit a variety of electronic configurations from intermediate ( M = Zn ), mostly 2+ ( M = Mn ), to 3+ ( M = Mg ). In all cases, there is a small amount of intermediate valency at the lowest temperatures. The amount of intermediate valency is constant for M = Mn , Mg and temperature dependent for M = Zn . The evolution of the Yb valence correlated to the transport properties of these phases is highlighted. The presence of Yb in this structure type allows for fine tuning of the carrier concentration and thereby the possibility of optimized thermoelectric properties along with unique magnetic phenomena.

36 MATERIALS SCIENCE↗

Thermal and photoinduced chemistry of the aromatic Criegee intermediate, benzaldehyde oxide: Implications for indoor air quality

Essential oils contain a complex mixture of volatile organic compounds, ranging from terpenes to aromatics. When released into the indoor air environment or into the atmosphere, they may undergo oxidation to generate complex reactive intermediates that affect indoor air quality. Cinnamaldehyde is one such aromatic molecule that is abundant in essential oils. When released into the indoor air environment, it may undergo oxidation to form a carbonyl oxide (Criegee intermediate) with an aromatic substituent: benzaldehyde oxide. In this manuscript, we present a high-level quantum chemical study that shows that, unlike smaller atmospherically relevant Criegee intermediates, benzaldehyde oxide is expected to undergo solar photolysis on timescales that are competitive with its ground state unimolecular and bimolecular chemistry. We show that aromatic substitution leads to a drastic bathochromic shift in the spectroscopically relevant excited states, revealing that photolysis in the indoor or outdoor environment should not be neglected when modeling the climate and air quality implications of Criegee intermediates with extended conjugation. Here, we predict a range of products that may be important for forming lower volatility compounds via tropospherically relevant photochemistry. To motivate future experimental validation of our results, we propose a viable synthetic procedure of the relevant precursor for generating and stabilizing benzaldehyde oxide.

atmospheric photochemistry↗

SU-E-T-334: Track Structure Simulations of Charged Particles at Low and Intermediate Energies: Cross Sections Needs for Light and Heavy Ions

Purpose/Methods: Monte Carlo (MC) track structure simulations follow the primary as well as all produced secondary particles in an event-by-event manner, from starting or ejection energy down to total stopping. They provide useful information on physics and chemistry of the biological response to radiation. They depend on reliable interaction cross sections and transport models of the considered radiation quality with biologically relevant materials. Most transport models focus on sufficiently fast and bare (i.e., fully ionized) ions and cross sections calculated within the (relativistic) first Born or Bethe approximations. These theories consider the projectile as a point particle and rely on proton cross sections and simple charge-scaling methods; they neglect the atomic nature of the ion and break down at low and intermediate ion energies. Heavier ions are used in particle therapy and slow to intermediate and low energies in the biologically interesting Bragg peak. Lighter and slower fragment ions, including alpha particles, protons, and neutrons are also produced in nuclear and break up reactions of charged particles. Secondary neutrons also produce recoil protons and ions, mainly in the intermediate energy range. Results/Conclusion: This work reviews existing models for track structure simulations and cross section calculations for light and heavy ions focusing on the low and intermediate energy range. It also presents new and updated aspects on cross section calculations and simulation techniques for ions and discusses the need for new models, calculations, and experimental data.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Phenomenology of Intermediate Molecular Dynamics at Metal-Oxide Interfaces

Reaction intermediates buried within a solid-liquid interface are difficult targets for physiochemical measurements. They are inherently molecular and locally dynamic, while their surroundings are extended by a periodic lattice on one side and the solvent dielectric on the other. Challenges compound on a metal-oxide surface of varied sites and especially so at its aqueous interface of many prominent reactions. Recently, phenomenological theory coupled with optical spectroscopy has become a more prominent tool for isolating the intermediates and their molecular dynamics. The following article reviews three examples of the SrTiO3-aqueous interface subject to the oxygen evolution from water: reaction-dependent component analyses of time-resolved intermediates, a Fano resonance of a mode at the metal-oxide–water interface, and reaction isotherms of metastable intermediates. The phenomenology uses parameters to encase what is unknown at a microscopic level to then circumscribe the clear and macroscopically tuned trends seen in the spectroscopic data.

Chemistry↗

AmeriFlux FLUXNET-1F US-Wi1 Intermediate hardwood (IHW)

This is the AmeriFlux Management Project (AMP) created FLUXNET-1F version of the carbon flux data for the site US-Wi1 Intermediate hardwood (IHW). This is the FLUXNET version of the carbon flux data for the site US-Wi1 Intermediate hardwood (IHW) produced by applying the standard ONEFlux (1F) software. Site Description - The Wisconsin Intermediate Hardwoods site is located in the Washburn Ranger District of the Chequamegon National Forest. A member of the northern coniferous-deciduous biome, surveys from the mid-19th century indicate the region consisted of a mixed stand of red, white, and jack pines. After extensive timber harvesting, wildfires, and farming activity, the region turned into a fragmented mosaic of stands of various ages and composition. The intermediate hardwoods site is one of ten sites that collectively represent the successional stages of development in the predominant stand types of a physically homogeneous landscape. In 2001, northern hardwood stands of all ages occupied 45% of the region.

Chen, Jiquan↗