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At least 595 records · Page 33

First Time-Resolved Leader Spectra Associated With a Downward Terrestrial Gamma-Ray Flash Detected at the Telescope Array Surface Detector

Optical emissions associated with Terrestrial Gamma ray Flashes (TGFs) have recently become important subjects in space-based and ground-based observations as they can help us understand how TGFs are produced during thunderstorms. In this paper, we present the first time-resolved leader spectra of the optical component associated with a downward TGF. The TGF was observed by the Telescope Array Surface Detector (TASD) simultaneously with other lightning detectors, including a Lightning Mapping Array (LMA), an INTerFerometer (INTF), a Fast Antenna (FA), and a spectroscopic system. The spectroscopic system recorded leader spectra at 29,900 frames per second (33.44 μs time resolution), covering a spectral range from 400 to 900 nm, with 2.1 nm per pixel. The recordings of the leader spectra began 11.7 ms before the -18 kA return stroke and at a height of 2.37 km above the ground. These spectra reveal that optical emissions of singly ionized nitrogen and oxygen occur between 167 μs before and 267 μs after the TGF detection, while optical emissions of neutrals (H I, 656 nm; N I, 744 nm, and O I, 777 nm) occur right at the moment of the detection. The time-dependent spectra reveal differences in the optical emissions of lightning leaders with and without downward TGFs.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Measuring characteristic differences between high- and low-performing discharges on the MegaJOuLe Neutron Imaging Radiography (MJOLNIR) DPF

A dense plasma focus (DPF) is a compact coaxial plasma gun, which completes its discharge as a Z-pinch, producing short (<100 ns) pulses of ions, x rays, and/or neutrons. Lawrence Livermore National Laboratory recently constructed and began operating a new device, the MJOLNIR (MegaJOuLe Neutron Imaging Radiography) DPF, which is designed for single-pulse flash neutron radiography. This device has achieved neutron yields of up to 4.1×10 11 neutrons/pulse at 3.3 MA peak current, and higher-current commissioning is under way. Like most DPFs, MJOLNIR exhibits variable yields in some configurations. Here, we present evidence of the role of parasitic current paths within the gun in stochastically influencing the yield. First through “conditioning shots,” where new hardware has been introduced, we show that increased run-down and run-in speeds correlate with higher yields. These observations are consistent with current being delivered to the electrodes but not to the main plasma sheath, degrading the implosion-driving force. Once nominal conditions are established, we correlate low-performing discharges with smaller current dip and associated voltage spike for a fixed machine configuration. A snow-plow model is able to recreate small-magnitude current dips through the introduction of a parasitic current path, and particle-in-cell simulations establish how parasitic current paths lower the ion beam energy available to produce neutrons. Finally, we observe an increased likelihood of shots with low yield and smaller current dip with increasing fill pressure.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Lockout/Tagout (LOTO) Simulator

The Lockout/Tagout (LOTO) Simulator is a portable training aid, or demonstration tool, designed to physically illustrate real-time critical-safety concepts of electrical lockout/tagout. The objective is to prevent misinterpretations of what is off and what is on during maintenance and repair of complex electrical systems. The simulator is designed in the form of a hinged box that opens up and stands on its own as an easel for demonstrations. On the outer face of the unit is a simulated circuit breaker box housing the switches. The breakers control the main power to the unit, a light bulb, and an electrical control cabinet. The light bulb is wired so that either of two breakers can provide power to it. When power is sent to the electrical control cabinet, a red indicator light illuminates. Inside the cabinet is the power supply from a personal computer. The power supply produces a 12-V dc output that is sent over to a small fan next to it, also from a computer, and an amber light on the front of the cabinet illuminates. A separate switch powers the fan on and off. The power supply is behind a plastic shield to protect against exposure to live conductors. Electrical banana jacks are mounted in the plastic shield to allow a voltmeter to be connected safely when opening the cabinet and taking a meter reading to verify de-energization as part of a simulation exercise. This LOTO simulator prototype is designed and fabricated as an all-in-one unit. All accessories can be stored inside the hinged case, and there is a handle on top for ease of transport. The circuit breaker labels attach with hook and loop fasteners so that they may be moved and changed to fit the training or demonstration scenario. The warning signs and labels on the electrical control box are magnetic, allowing for easy reconfiguration to emulate different equipment setups. A specially designed magnetic cover was made to disguise the indicator lights for demonstrations when these indicators are not used. The cover is disguised as an arc flash safety label that would typically be found on such a cabinet. One indicator light has a separate switch that can take it offline. This is to allow for demonstration to trainees on why it is important not to completely rely on indicator lights, but that they should always take a meter reading at the exposed conductors to absolutely verify de-energization before exposure. A clear plastic barrier and banana jacks inside the cabinet provide a safe way to plug in a voltmeter for demonstrations without exposure to the hazards of energized equipment. A small remote control unit is wired into the fan circuit. The remote allows the demonstrator to turn the fan on and off, provided that all of the breakers and switches leading to it are configured on as well. The remote feature was added in order to demonstrate the importance of starting the lockout/tagout task with energized equipment, then powering it down, isolating it, and locking it out to ensure that the correct breakers have been locked out.

Scheer, Jennifer↗

Proton-Coupled Electron Transfer in a Strongly Coupled Photosystem II-Inspired Chromophore–Imidazole–Phenol Complex: Stepwise Oxidation and Concerted Reduction

Proton-coupled electron-transfer (PCET) reactions were studied in acetonitrile for a Photosystem II (PSII) inspired [Ru(bpy) 2 (phen-imidazole-Ph(OH)( t Bu) 2 )] 2+ , in which Ru(III) generated by a flash-quench sequence oxidizes the appended phenol and the proton is transferred to the hydrogen bonded imidazole base. In contrast to related systems, the donor and acceptor are strongly coupled, as indicated by the shift in the Ru III/II couple upon phenol oxidation, and intramolecular oxidation of the phenol by Ru(III) is energetically favorable by both stepwise or concerted pathways. The phenol oxidation occurs via a stepwise ET-PT mechanism with k ET = 2.7 × 10 7 s ₋1 and a kinetic isotope effect (KIE) of 0.99 ± 0.03. The electron transfer reaction was characterized as adiabatic with λ DA = 1.16 eV and 280 < H DA < 540 cm ₋1 consistent with strong electronic coupling and slow solvent dynamics. Reduction of the phenoxyl radical by the quencher radical was examined as the analogue of the redox reaction between the PSII tyrosyl radical and the oxygen evolving complex (OEC). In our PSII-inspired complex, the recombination reaction activation energy is < 2 kcal mol ₋1 . In conclusion, the reaction is nonadiabatic (V PCET ~ 22 cm ₋1 (H) and 49 cm ₋1 (D)), concerted, and exhibits an unexpected inverse KIE of 0.55 that is attributed to greater overlap of the reactant vibronic ground state with the OD vibronic states of the proton acceptor due to the smaller quantum spacing of the deuterium vibrational levels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observation of asymmetric explosive density evolution in the deflagration-to-detonation transition for porous explosives

We report deflagration-to-detonation transition phenomena in cylindrical columns of porous explosives based on octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The HMX powder and LX-14 (95.5 wt. % HMX and 4.5 wt. % estane polyurethane) prills were observed with high-speed cameras and flash x rays under conditions that allow for precise scaling and registration of the recorded images. These experimental results test the conventional assumption of axisymmetric, effective one-dimensional burning. Polycarbonate confinement tubes allowed this direct imaging with steel spheres employed as radio-opaque fiducials. Spheres embedded in the explosive column revealed the displacement of the explosive prior to deflagration. X-ray and fast camera images show that a dense plug of compact explosive develops ahead of the deflagration front. The internal fiducials register both internal changes in the plug and changes in the position between successive x-ray images. Tantalum witness strips placed on the inner wall of the explosive channel revealed radial expansion of the tube bore at successive x-ray exposures, indicating the internal pressure of about 100 MPa just before detonation. Images indicate that the deflagration is not only asymmetric but also involves newly observed transient phenomena just before detonation. Furthermore, we typically see a brief but continuous increase in deflagration speed and the formation of a deflagration channel that bypasses the plug just prior to detonation. We hypothesize that these phenomena play an important role in the deflagration-to-detonation transition itself.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structures of the intermediates of Kok’s photosynthetic water oxidation clock

Inspired by the period-four oscillation in flash-induced oxygen evolution of photosystem II discovered by Joliot in 1969, Kok performed additional experiments and proposed a five-state kinetic model for photosynthetic oxygen evolution, known as Kok’s S-state clock or cycle. The model comprises four (meta)stable intermediates (S 0 , S 1 , S 2 and S 3 ) and one transient S 4 state, which precedes dioxygen formation occurring in a concerted reaction from two water-derived oxygens bound at an oxo-bridged tetra manganese calcium (Mn 4 CaO 5 ) cluster in the oxygen-evolving complex. This reaction is coupled to the two-step reduction and protonation of the mobile plastoquinone QB at the acceptor side of PSII. Here in this paper, using serial femtosecond X-ray crystallography and simultaneous X-ray emission spectroscopy with multi-flash visible laser excitation at room temperature, we visualize all (meta)stable states of Kok’s cycle as high-resolution structures (2.04–2.08 Å). In addition, we report structures of two transient states at 150 and 400 µs, revealing notable structural changes including the binding of one additional ‘water’, Ox, during the S 2 →S 3 state transition. Our results suggest that one water ligand to calcium (W3) is directly involved in substrate delivery. The binding of the additional oxygen Ox in the S 3 state between Ca and Mn1 supports O–O bond formation mechanisms involving O5 as one substrate, where Ox is either the other substrate oxygen or is perfectly positioned to refill the O5 position during O 2 release. Thus, our results exclude peroxo-bond formation in the S 3 state, and the nucleophilic attack of W3 onto W2 is unlikely.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Numerical investigation of laser-driven shock interaction with a deformable particle

A laser-driven shock propagating through an isolated particle embedded in a plastic (CH) target was studied using the radiation-hydrodynamic code FLASH. Preliminary simulations using IONMIX equations of state (EOS) showed significant differences in the shock Hugoniot of aluminum compared to experimental data in the low-pressure regime [O(10) GPa], resulting in higher streamwise compression and deformation of an aluminum particle. Hence, a simple modification to the ideal gas EOS was developed and employed to describe the target materials and examine the particle dynamics. The evolution of the pressure field demonstrated a complex wave interaction, resulting in a highly unsteady particle drag which featured two drag minima due to shock focusing at the rear end of the particle and rarefaction stretching due to laser shut-off. Although ~30% lateral expansion and ~25% streamwise compression were observed, the aluminum particle maintained considerable integrity without significant distortion. Additional simulations examined the particle response for a range of particle densities, sizes, and acoustic impedances. The data revealed that lighter particles such as aluminum gained significant momentum, reaching up to ~96% of the shocked CH's speed, compared to ~29% for the heavier tungsten particles. Despite the differences seen in the early stage of shock interaction, particles with varying acoustic impedances ultimately reached the same peak velocity. This identified particle-to-host density ratio is an important factor in determining the inviscid terminal velocity of the particle. In addition, the modified EOS model presented in this study could be used to approximate solid materials in hydrocodes that lack material strength models.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Fragmentation Dynamics of Fluorene Explored Using Ultrafast XUV-Vis Pump-Probe Spectroscopy

We report on the use of extreme ultraviolet (XUV, 30.3 nm) radiation from the Free-electron LASer in Hamburg (FLASH) and visible (Vis, 405 nm) photons from an optical laser to investigate the relaxation and fragmentation dynamics of fluorene ions. The ultrashort laser pulses allow to resolve the molecular processes occurring on the femtosecond timescales. Fluorene is a prototypical small polycyclic aromatic hydrocarbon (PAH). Through their infrared emission signature, PAHs have been shown to be ubiquitous in the universe, and they are assumed to play an important role in the chemistry of the interstellar medium. Our experiments track the ionization and dissociative ionization products of fluorene through time-of-flight mass spectrometry and velocity-map imaging. Multiple processes involved in the formation of each of the fragment ions are disentangled through analysis of the ion images. The relaxation lifetimes of the excited fluorene monocation and dication obtained through the fragment formation channels are reported to be in the range of a few tens of femtoseconds to a few picoseconds.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Kinetics and Products of Vinyl + 1,3-Butadiene, a Potential Route to Benzene

The reaction between vinyl radical, C 2 H3, and 1,3-butadiene, 1,3-C 4 H 6 , has long been recognized as a potential route to benzene, particularly in 1,3-butadiene flames, but the lack of reliable rate coefficients has hindered assessments of its true contribution. Here, by using laser flash photolysis and visible laser absorbance (λ = 423.2 nm), we measured the overall rate coefficient for C 2 H 3 + 1,3-C 4 H 6 , k 1 , at 297 K ≤ T ≤ 494 K and 4 ≤ P ≤ 100 Torr. k 1 was in the high-pressure limit in this range and could be fit by the simple Arrhenius expression k1 = (1.1 ± 0.2) × 10 –12 cm 3 molecule –1 s –1 exp(–9.9 ± 0.6 kJ mol –1 /RT). Using photoionization time-of-flight mass spectrometry, we also investigated the products formed. At T ≤ 494 K and P = 25 Torr, we found only C 6 H 9 adduct species, while at 494 K ≤ T ≤ 700 K and P = 4 Torr, we observed ≤~10% branching to cyclohexadiene in addition to C 6 H 9 . Quantum chemistry master-equation calculations using the modified strong collision model indicate that n-C 6 H 9 is the dominant product at low temperature, consistent with our experimental results, and predict the rate coefficient and branching ratios at higher T where chemically activated channels become important. Predictions of k 1 are in close agreement with our experimental results, allowing us to recommend the following modified Arrhenius expression in the high-pressure limit from 300 to 2000 K: k 1 = 6.5 × 10 –20 cm 3 molecule –1 s –1 T 2.40 exp(–1.76 kJ mol –1 /RT).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation

The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH 3 –$CH=CH$–CH 2 –CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature of the pyrolysis tube. The two separated functional groups (vinyl and nitrile) open up isomerization as an initial step in competition with unimolecular dissociation. Primary products were detected by keeping the 3-PN concentration low and limiting reaction times to the traversal time of the gas in the pyrolysis tube (~100 μs). The reaction is quenched and products are cooled by expansion into vacuum before interrogation over the 8–18 GHz region using chirped-pulse broadband methods. 118 nm VUV photoionization of the same reaction mixture provides a means of detecting all products with ionization potentials below 10.5 eV with minimal fragmentation. These results are combined with a detailed computational investigation of the C 5 H 7 N and related potential energy surfaces, leading to a consistent picture of the unimolecular decomposition of 3-PN. Loss of two H-atoms to form a 79 amu product is proven from its microwave transitions to contain trans-Z-2,4-pentadienenitrile, while no pyridine is observed. Methyl loss, HCN loss, and breaking the central C(2)–C(3) bond all occur following isomerization of the position of the double bond, thereby opening up low-energy pathways to these decomposition channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Muon tagging with flash ADC waveform baselines

Here, this manuscript describes an innovative method to tag muons using the baseline information of the Flash ADC (FADC) waveform of PMTs in the JSNS 2 (J-PARC Sterile Neutrino Search at J-PARC Spallation Neutron Source) experiment. The experiment is designed to search for evidence of sterile neutrinos, and a reliable method for muon tagging is an essential component for background rejection because the detector is located above ground, on the 3rd floor of the J-PARC Material and Life Science Experimental Facility (MLF). Cosmogenic muons that stop within the detector volume and produce a Michel electron are a particularly important background that must be rejected for our sterile neutrino search. Utilizing this innovative method, more than 99.8 % of Michel electrons can be rejected even without using information from the detector’s veto region PMTs. This technique can be employed by any experiments which uses a similar detector configuration.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Low–severity fire as a mechanism of organic matter protection in global peatlands: Thermal alteration slows decomposition

Worldwide, regularly-recurring wildfires shape many peatland ecosystems to the extent that fire-adapted species often dominate plant communities, suggesting that wildfire is an integral part of peatland ecology rather than an anomaly. The most destructive blazes are smoldering fires that are usually initiated in periods of drought and can combust entire peatland carbon stores. However, peatland wildfires more typically occur as low-severity surface-burns that arise in the dormant season when vegetation is desiccated, and soil moisture is high. In such low-severity fires, surface layers experience flash heating, but there is little loss of underlying peat to combustion. This study examines the potential importance of such processes in several peatlands that span a gradient from hemiboreal to tropical ecozones and experience a wide range of fire return intervals. We show that low-severity fires can increase the pool of stable soil carbon by thermally altering the chemistry of soil organic matter (SOM), thereby reducing rates of microbial respiration. Using XPS and FTIR, we demonstrate that low-severity fires significantly increase the degree of carbon-condensation and aromatization of SOM functional groups, particularly on the surface of peat aggregates. Laboratory incubations show lower CO 2 emissions from peat subjected to low-severity fire, and predict lower cumulative CO 2 emissions from burned peat after one to three years. Also, low-severity fires reduce the temperature sensitivity (Q 10 ) of peat, indicating that these fires can inhibit microbial access to SOM. The increased stability of thermally-altered SOM may allow a greater proportion of organic matter to survive vertical migration into saturated and anaerobic zones of peatlands where environmental conditions physiochemically protect carbon stores from decomposition for thousands of years. Furthermore, across latitudes, low-severity fire is an overlooked factor influencing carbon cycling in peatlands, which is relevant to global carbon budgets as climate-change alters fire regimes worldwide.

54 ENVIRONMENTAL SCIENCES↗

High-Field High-Repetition-Rate Sources for the Coherent THz Control of Matter

Ultrashort flashes of THz light with low photon energies of a few meV, but strong electric or magnetic field transients have recently been employed to prepare various fascinating nonequilibrium states in matter. Here we present a new class of sources based on superradiant enhancement of radiation from relativistic electron bunches in a compact electron accelerator that we believe will revolutionize experiments in this field. Our prototype source generates high-field THz pulses at unprecedented quasi-continuous-wave repetition rates up to the MHz regime. We demonstrate parameters that exceed state-of-the-art laser-based sources by more than 2 orders of magnitude. The peak fields and the repetition rates are highly scalable and once fully operational this type of sources will routinely provide 1 MV/cm electric fields and 0.3 T magnetic fields at repetition rates of few 100 kHz. In conclusion, we benchmark the unique properties by performing a resonant coherent THz control experiment with few 10 fs resolution.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The Coronae of Moderate-Mass Giants in the Hertzsprung Gap and the Clump

We have used the Roentgensatellit (ROSAT), the Extreme Ultraviolet Explorer (EUVE), and the Hubble Space Telescope (HST) to measure X-ray and ultraviolet emissions of moderate-mass (APPROX. 2-3 solar mass) giants in the Hertzsprung gap (spectral types early F to mid-G) and the post-helium flash "clump" (approx. G8-K0). Our motivation was to document the evolution of hot coronae (T greater than 10(exp 6)K) along the post-main-sequence trajectories traveled by such stars in order to gain insight concerning the "X-ray deficiency" of the F-GO giants and the strong braking of stellar rotation at the red edge of the Hertzsprung gap. With few exceptions, Hertzsprung gap and clump giants observed by ROSAT PSPC show hot (T approx. 10(exp 7)K) coronal energy distributions, regardless of any X-ray deficiency, EUVE spectra of gap star 31 Com (G0 111) indicate a broad coronal emission measure hump at approx. 10(exp 7.2)K, while the active clump giant beta Ceti (K0 III) displays a sharp peak at approx. 10(exp 6.8)K, as seen previously in the mixed clump/gap binary Capella (alpha Aur: G8 III + G0 III). The gap giants upsilon Peg (F8 III) and 24 UMa (G4 III) have EUV emissions of intermediate temperature (approx. 10(exp 7.0)K). The stars 31 Com, psi(sup 3) Psc (G0 III), and beta Cet exhibit redshifted transition zone (TZ: approx. 10(exp 5)K) lines in HST GHRS spectra, as reported earlier in Procyon (alpha CMi: F5 IV-V) and Capella G0. Such redshifts on the Sun are thought to signify flows in magnetic loops. beta Cas (F2 III)-a rare soft coronal source among the gap stars-displays blueshifts of C iv and 0 iv], although emissions at cooler and hotter temperatures are near the photospheric velocity. The remarkably broad line profiles of the fastest rotating gap giants suggest that the 10(exp 5) K "subcoronal " emission zones extend to h approx. R(sub *) above the photosphere, about 50 scale heights. In contrast to the TZ line redshifts, the upper chromospheric emissions (e.g., Mg II and Si III) of 31 Com and upsilon(sup 3) Psc have blueshifted cores. Blue-asymmetric peaks in the solar Mg a lines are thought to indicate dynamical heating in the chromosphere. Observations of the H(sub I) Ly(alpha) feature of 31 Com taken 9 months apart reveal striking profile changes, reminiscent of those noted previously in the Ly(alpha) blue peak of the Capella G0 star. We used the far-ultraviolet diagnostics, in combination with ROSAT X-ray photometry and EUVE high-excitation line strengths, to constrain physical models of the stellar outer atmospheres. Quasi-static magnetic loops can simulate the empirical coronal emission measures of the giant stars, but the inferred pressures for sensible loop lengths conflict with direct measurements of subcoronal densities. Furthermore, the high rate of emission at approx. 10(exp 5) K cannot be explained by thermal conduction down the legs of hot quasi-static loops. On the other hand, the possible existence of elongated (l - R(sub *) emission structures on the gap giants leads to a speculative scenario to explain the X-ray deficiency. It is based on the increased importance of the dynamical filling phase ("explosive evaporation") of the loop life cycle; conductive cooling, yielding TZ emissions at the footpoints, when the heating is interrupted; and the possibility for transitions between " hot " and " cool " energy balance solutions owing to dynamical suspension and centrifugal trapping of the cooling gas. The long loops might represent a vestigial global " magnetosphere " inherited from the main-sequence phase, which ultimately is disrupted near approx. G0 by the deepening convective envelope and growth of a more solar-like dynamo. Coronal emissions might be boosted temporarily as the X-ray deficiency is removed but soon would be quenched by wind braking previously inhibited by the magnetospheric "dead zone."

Ayres, Thomas R.↗

Opportunities and Challenges for Hydrotreating of Catalytic Fast Pyrolysis Oil to Fuels

Catalytic fast pyrolysis (CFP) provides a versatile platform for producing fuels to combat climate change and meet decarbonizing targets. In this contribution, we will discuss the hydroprocessing of CFP oils to a variety of fuels, including sustainable aviation fuel (SAF), diesel, and marine fuel. Both standalone and co-hydroprocessing with petroleum streams will be covered. Hydrotreating CFP oil at temperatures around 400 Degrees Celsius can produce a highly deoxygenated product with oxygen contents below the detection limit. However, the quality of fuel fractions produced has been a problem, manifesting as low octane numbers for the gasoline-range fraction and low cetane numbers for the diesel-range fraction. Incorporating an initial transition zone for hydrogenation during hydrotreating was shown to dramatically increase the diesel fraction cetane number from 24 to 45. A similar approach enabled the production of a cycloalkane-rich SAF fraction meeting key ASTM 4054 guidelines with respect to density, viscosity, heating value, volatility, freeze and flash point. Over 400 hours of hydrotreating for SAF was demonstrated with no signs of catalyst bed fouling, measured by pressure drop over the catalyst bed. Compared to other fuels, marine fuel is unique in that it does not require complete deoxygenation. We investigated the minimum hydrotreating requirements to produce fuel compatible with very low sulfur fuel oil, and the results suggested 30% reduction in hydrotreating costs for this approach. Co-hydroprocessing offers an opportunity to take advantage of refinery infrastructure and economies of scale although the operation is less flexible with respect to operating conditions. Co-hydroprocessing CFP oil with petroleum streams gave efficient deoxygenation at milder conditions (e.g. at temperatures of 320 Degrees Celsius) than required for standalone hydrotreating. Over 90% incorporation of biogenic carbon in the CFP oil was confirmed by carbon-14 analysis. Hydrotreating of CFP oil, whether by standalone or co-processing, can produce a variety of fuel cuts, whose quality can be tailored by changing process conditions. Challenges remain, including long-term catalyst performance and determining CFP oil quality requirements.

09 BIOMASS FUELS↗

Engineering endosomolytic nanocarriers of diverse morphologies using confined impingement jet mixing

The clinical translation of many biomolecular therapeutics has been hindered by undesirable pharmacokinetic (PK) properties, inadequate membrane permeability, poor endosomal escape and cytosolic delivery, and/or susceptibility to degradation. Overcoming these challenges merits the development of nanoscale drug carriers (nanocarriers) to improve the delivery of therapeutic cargo. Herein, we implement a flash nanoprecipitation (FNP) approach to produce nanocarriers of diverse vesicular morphologies by using various molecular weight PEG-bl-DEAEMA-co-BMA (PEG-DB) polymers. We demonstrated that FNP can produce uniform (PDI < 0.1) particles after 5 impingements, and that by varying the copolymer hydrophilic mass fraction, FNP enables access to a diverse variety of nanoarchitectures including micelles, unilamellar vesicles (polymersomes), and multi-compartment vesicles (MCVs). We synthesized a library of 2 kDa PEG block copolymers, with DEAEMA-co-BMA second block molecular weights of 3, 6, 12, 15, 20, and 30 kDa. All formulations were both pH responsive, endosomolytic, and capable of loading and cytosolically delivering small negatively charged molecules – albeit to different degrees. Using a B16.F10 melanoma model, we showcased the therapeutic potential of a lead FNP formulated PEG-DB nanocarrier, encapsulating the cyclic dinucleotide (CDN) cGAMP to activate the stimulator of interferon genes (STING) pathway in a therapeutically relevant context. Collectively, these data demonstrate that an FNP process can be used to formulate pH-responsive nanocarriers of diverse morphologies using a PEG-DB polymer system. As FNP is an industrially scalable process, these data address the critical translational challenge of producing PEG-DB nanoparticles at scale. Furthermore, the diverse morphologies produced may specialize in the delivery of distinct biomolecular cargos for other therapeutic applications, implicating the therapeutic potential of this platform in an array of disease applications.

36 MATERIALS SCIENCE↗

The effect of millisecond flash lamp annealing on electrical and structural properties of ZnO:Al/Si structures

The effect of millisecond flash lamp annealing (FLA) on aluminum doped ZnO (AZO) films and their interface with Si have been studied. The AZO films were deposited by magnetron sputtering on Si (100) substrates. The electrical and structural properties of the film and AZO/Si structures were characterized by current–voltage, capacitance–voltage, and deep level transient spectroscopy measurements, X-ray diffraction, and secondary ion mass spectrometry. The resistivity of the AZO film is reduced to a close to state-of-the-art value of 2 × 10{sup −4} Ω cm after FLA for 3 ms with an average energy density of 29 J/cm{sup 2}. In addition, most of the interfacial defects energy levels are simultaneously annealed out, except for one persisting shallow level, tentatively assigned to the vacancy-oxygen complex in Si, which was not affected by FLA. Subsequent to the FLA, the samples were treated in N{sub 2} or forming gas (FG) (N{sub 2}/H{sub 2}, 90/10%{sub mole}) ambient at 200–500 °C. The latter samples maintained the low resistivity achieved after the FLA, but not the former ones. The interfacial defect level persisting after the FLA is removed by the FG treatment, concurrently as another level emerges at ∼0.18 eV below the conduction band. The electrical data of the AZO films are discussed in term of point defects controlling the resistivity, and it is argued that the FLA promotes formation of electrically neutral clusters of Zink vacancies (V{sub Zn}'s) rather than passivating/compensating complexes between the Al donors and V{sub Zn}'s.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Pyrolysis of the Simplest Carbohydrate, Glycolaldehyde (CHO-CH 2 OH), and Glyoxal in a Heated Microreactor

Both glycolaldehyde and glyoxal were pyrolyzed in a set of flash-pyrolysis microreactors. The pyrolysis products resulting from CHO-CH 2 OH and HCO-CHO were detected and identified by vacuum ultraviolet (VUV) photoionization mass spectrometry. Complementary product identification was provided by argon matrix infrared absorption spectroscopy. Pyrolysis pressures in the microreactor were about 100 Torr, and contact times with the microreactors were roughly 100 μs. At 1200 K, the products of glycolaldehyde pyrolysis are H atoms, CO, CH 2 =O, CH 2 =C=O, and HCO-CHO. Thermal decomposition of HCO-CHO was studied with pulsed 118.2 nm photoionization mass spectrometry and matrix infrared absorption. Under these conditions, glyoxal undergoes pyrolysis to H atoms and CO. Tunable VUV photoionization mass spectrometry provides a lower bound for the ionization energy IE (CHO-CH 2 OH) ≥ 9.95 ± 0.05 eV. The gas-phase heat of formation of glycolaldehyde was established by a sequence of calorimetric experiments. The experimental result is Δ f H 298 (CHO-CH 2 OH) = -75.8 ± 1.3 kcal mol -1 . Fully ab initio , coupled cluster calculations predict Δ f H 0 (CHO-CH 2 OH) of -73.1 ± 0.5 kcal mol -1 and Δ f H 298 (CHO-CH 2 OH) of -76.1 ± 0.5 kcal mol -1 . The coupled-cluster singles doubles and noniterative triples correction calculations also lead to a revision of the geometry of CHO-CH 2 OH. We have found that the O-H bond length differs substantially from earlier experimental estimates, due to unusual zero-point contributions to the moments of inertia.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗