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Carbon nanoallotropes are important nanomaterials with unusual properties and promising applications. High pressure synthesis has the potential to open new avenues for controlling and designing their physical and chemical characteristics for a broad range of uses but it remains little understood due to persistent conceptual and experimental challenges, in addition to fundamental physics and chemistry questions that are still unresolved after many decades. Here we demonstrate sub-nanosecond nanocarbon synthesis through the application of laser-induced shock-waves to a prototypical organic carbon-rich liquid precursor—liquid carbon monoxide. Overlapping large-scale molecular dynamics simulations capture the atomistic details of the nanoparticles’ formation and evolution in a reactive environment and identify classical evaporation-condensation as the mechanism governing their growth on these time scales., Carbon nanomaterials have widespread application but fundamental aspects of their formation are still unclear. Here the authors explore the shock-induced synthesis of carbon nanoallotropes from liquid CO by time-resolved reflectivity and computations identifying the growth mechanism at the sub-nanosecond timescale

The response of rapidly compressed highly oriented pyrolytic graphite (HOPG) normal to its basal plane was investigated at a pressure of ∼80 GPa. Ultrafast x-ray diffraction using ∼100 fs pulses at the Materials Under Extreme Conditions sector of the Linac Coherent Light Source was used to probe the changes in crystal structure resulting from picosecond timescale compression at laser drive energies ranging from 2.5 to 250 mJ. A phase transformation from HOPG to a highly textured hexagonal diamond structure is observed at the highest energy, followed by relaxation to a still highly oriented, but distorted graphite structure following release. We observe the formation of a highly oriented lonsdaleite within 20 ps, subsequent to compression. This suggests that a diffusionless martensitic mechanism may play a fundamental role in phase transition, as speculated in an early work on this system, and more recent static studies of diamonds formed in impact events.

As theoretically hypothesized for several decades in group IV transition metals, we have discovered a dynamically stabilized body-centered cubic (bcc) intermediate state in Zr under uniaxial loading at sub-nanosecond timescales. Under ultrafast shock wave compression, rather than the transformation from alpha-Zr to the more disordered hex-3 equilibrium omega-Zr phase, in its place we find the formation of a previously unobserved nonequilibrium bcc metastable intermediate. We probe the compression-induced phase transition pathway in zirconium using time-resolved sub-picosecond x-ray diffraction analysis at the Linac Coherent Light Source. We also present molecular dynamics simulations using a potential derived from first-principles methods which independently predict this intermediate phase under ultrafast shock conditions. In contrast with experiments on longer timescale (> 10 ns) where the phase diagram alone is an adequate predictor of the crystalline structure of a material, our recent study highlights the importance of metastability and time dependence in the kinetics of phase transformations.

The predictive models that describe the fate and transport of radioactive materials in the atmosphere following a nuclear incident (explosion or reactor accident) assume that uranium-bearing particulates would attain chemical equilibrium during vapor condensation. In this study, we show that kinetically driven processes in a system of rapidly decreasing temperature can result in substantial deviations from chemical equilibrium. This can cause uranium to condense out in oxidation states (e.g., UO3 vs UO2) that have different vapor pressures, significantly affecting uranium transport. To demonstrate this, we synthesized uranium oxide nanoparticles using a flow reactor under controlled conditions of temperature, pressure, and oxygen concentration. The atomized chemical reactants passing through an inductively coupled plasma cool from ∼5000 to 1000 K within milliseconds and form nanoparticles inside a flow reactor. The ex situ analysis of particulates by transmission electron microscopy revealed 2-10 nm crystallites of fcc-UO2 or α-UO3 depending on the amount of oxygen in the system. α-UO3 is the least thermodynamically preferred polymorph of UO3. The absence of stable uranium oxides with intermediate stoichiometries (e.g., U3O8) and sensitivity of the uranium oxidation states to local redox conditions highlight the importance of in situ measurements at high temperatures. Therefore, we developed a laser-based diagnostic to detect uranium oxide particles as they are formed inside the flow reactor. Our in situ measurements allowed us to quantify the changes in the number densities of the uranium oxide nanoparticles (e.g., UO3) as a function of oxygen gas concentration. Our results indicate that uranium can prefer to be in metastable crystal forms (i.e., α-UO3) that have higher vapor pressures than the refractory form (i.e., UO2) depending on the oxygen abundance in the surrounding environment. This demonstrates that the equilibrium processes may not dominate during rapid condensation processes, and thus kinetic models are required to fully describe uranium transport subsequent to nuclear incidents.

Ultrafast (130-fs) x-ray diffraction at the Linac Coherent Light Source has been applied to observe shockmelting, which is driven by a rapid (120-ps) laser pulse impinging on a thin (few micrometers) bilayer ofaluminum/zirconium. At a pressure of 100 GPa in the aluminum (130 GPa in the zirconium), there is rapidmelting of both metals and the recrystallization of zirconium into the bcc β phase. We observe the solidificationof the melt starting a few hundred picoseconds following the shock melting, out to 50 ns when the zirconiumis fully crystallized into the bcc β phase at a residual temperature of approximately 2000 K. The pressure isobtained directly from the early time x-ray data, whereas the additional information from the x-ray line widthand intensity at longer times inform a model of crystal nucleation and growth.

This paper applies a small-scale research model to elicit the ordinary theology of a group of practising Christians within a local congregation on the issue of assisted dying (AD). Valid and informative data is produced which questions whether formal church opposition to AD is as clear, and as widely held among practicing Christians, as currently assumed.

We use a recently developed plasma-flow reactor to experimentally investigate the formation of oxide nanoparticles from gas phase metal atoms during oxidation, homogeneous nucleation, condensation, and agglomeration processes. Gas phase uranium, aluminum, and iron atoms were cooled from 5000 K to 1000 K over short-time scales (∆t In-situ emission spectroscopy is used to measure the variation in monoxide/atomic emission intensity ratios as a function of temperature and oxygen fugacity. Condensed oxide nanoparticles are collected inside the reactor for ex-situ analyses using scanning and transmission electron microscopy (SEM, TEM) to determine their structural compositions and sizes. A chemical kinetics model is also developed to describe the gas phase reactions of iron and aluminum metals. The resulting sizes and forms of the crystalline nanoparticles (FeO-wustite, eta-Al2O3, UO2, and alpha-UO3) depend on the thermodynamic properties, kinetically-limited gas phase chemical reactions, and local redox conditions. This work shows the nucleation and growth of metal oxide particles in rapidly-cooling gas is closely coupled to the kinetically-controlled chemical pathways for vapor-phase oxide formation.

The shock response of polymers is important for a number of commercial and defense-related applications, but it is difficult to obtain empirical shock response data over the wide range of preparations and aging conditions typically found in such applications. Ultrafast compression is useful to characterize polymer shock response over a wide range of polymer initial conditions due to the high throughput of this method. To establish greater confidence in ultrafast compression experiments and to characterize the detailed shock response of several variations in a single base polymer, the results of sub-nanosecond shock compression experiments in ∼5 μm thick layers of the polydimethylsiloxane (PDMS)-based elastomeric rubbers Sylgard-184, SE1700, and an unfilled, end-linked model PDMS network are presented. The results of conventional ultrafast shock etalon measurements to time-of-flight measurements for similar thickness layers of irradiated and unirradiated SE1700 are compared. Good agreement between the shock response measured by these two ultrafast shock methods, as well as consistency between ultrafast data and long time scale gas gun data is found. From measurements across a variety of PDMS formulations, a statistically significant variation in the shock response with the quasistatic elastic modulus is presented. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018.

We have performed a detailed x-ray diffraction structural study of Zr under pressure and unambiguously identify the existence of a first-order isostructural bcc-to-bcc phase transition near 58 GPa. First-principles quantum molecular dynamics calculations support the existence of this phase transition, in excellent agreement with experimental results, triggered by anharmonic effects. Our results highlight the potential ubiquity of anharmonically driven isostructural transitions within the periodic table under pressure and call for follow-up experimental and theoretical studies.

The availability of pulsed x rays on short timescales has opened up new avenues of research in the physics and chemistry of shocked materials. The continued installation of shock platforms such as gas guns and high power lasers placed at beamline x-ray facilities has advanced our knowledge of materials shocked to extreme conditions of pressure and temperature. In addition, theoretical advancements have made direct correspondence with high-pressure x-ray experiments more viable, increasing the predictive capability of these models. In this paper, we discuss both recent experimental results and the theory and modeling that has been developed to treat these complex situations. Finally, we discuss the impact that new platforms and increased beam time may have on the future direction of this field.

The chemical and physical processes involved in the shock-to-detonation transition of energetic solids are not fully understood due to difficulties in probing the fast dynamics involved in initiation. Here, we employ shock interferometry experiments with sub-20-ps time resolution to study highly textured (110) pentaerythritol tetranitrate (PETN) thin films during the early stages of shock compression using ultrafast laser-driven shock wave methods. We observe evidence of rapid exothermic chemical reactions in the PETN thin films for interface particle velocities above ∼1.05 km/s as indicated by shock velocities and pressures well above the unreacted Hugoniot. The time scale of our experiment suggests that exothermic reactions begin less than 50 ps behind the shock front for these high-density PETN thin films. Thermochemical calculations for partially reacted Hugoniots also support this interpretation. The experimentally observed time scale of reactivity could be used to narrow possible initiation mechanisms.

High-temperature chemistry in laser ablation plumes leads to vapor-phase speciation, which can induce chemical fractionation during condensation. Using emission spectroscopy acquired after ablation of a SrZrO3 target, we have experimentally observed the formation of multiple molecular species (ZrO and SrO) as a function of time as the laser ablation plume evolves. Although the stable oxides SrO and ZrO2 are both refractory, we observed emission from the ZrO intermediate at earlier times than SrO. We deduced the time-scale of oxygen entrainment into the laser ablation plume using an 18O2 environment by observing the in-growth of Zr18O in the emission spectra relative to Zr16O, which was formed by reaction of Zr with 16O from the target itself. Using temporally resolved plume-imaging, we determined that ZrO formed more readily at early times, volumetrically in the plume, while SrO formed later in time, around the periphery. Using a simple temperature-dependent reaction model, we have illustrated that the fo...

The emerging material, topological insulator, has provided new opportunities for spintronic applications, owing to its strong spin-orbit character. Topological insulator based heterostructures that display spin-charge coupling driven by topology at surfaces have great potential for the realization of novel spintronic devices. Here, we report the observation of anomalous photogalvanic effect in (${\mathrm{Bi}}_{0.5}{\mathrm{Sb}}_{0.5}$)${}_{2}{\mathrm{Te}}_{3}$ thin films grown on GaAs substrate. We demonstrate that the magnitude, direction, and temperature dependence of the helicity-dependent photocurrent (HDPC) can be modulated by the gate voltage. From spatially resolved photocurrent measurements, we show that the line profile of HDPC in (${\mathrm{Bi}}_{0.5}{\mathrm{Sb}}_{0.5}$)${}_{2}{\mathrm{Te}}_{3}$/GaAs is unaffected by the variation of beam size, in contrast to the photocurrent response measured in a (${\mathrm{Bi}}_{0.5}{\mathrm{Sb}}_{0.5}$)${}_{2}{\mathrm{Te}}_{3}$/mica structure.

This paper argues that there are good reasons why church and academy need better to hear and take account of the ordinary theology (hereafter O.Th) of practising Christians. It is an important form of practical theology which not only can inform current theological debates and even challenge existing theological norms, but also provide deep learning experiences both for ordinary theologians and those ministering to them. To facilitate the articulation of O.Th, trained theological reflectors are needed who can listen to ordinary Christian people with a ‘theological ear’ and become ‘people’s theologians’. Also needed is a workable model for small-scale research into O.Th. Empirical research into O.Th has hitherto been undertaken by the application of significant resource, either by an individual researcher (often the doctoral thesis) or a team. Such resource-intensive endeavour has provided important data on various aspects of O.Th, and has put O.Th firmly on the research map. However, there is a clear need for O.Th research to become something which can be more easily undertaken by ministers and others in roles of pastoral responsibility and theological education. A research model based on an expanded pastoral cycle makes this possible.

We report results from ultrafast compression experiments conducted on β-HMX single crystals. Results consist of nominally 12 picosecond time-resolved wave profile data, (ultrafast time domain interferometry –TDI measurements), that were analyzed to determine high-velocity wave speeds as a function of piston velocity. TDI results are used to validate calculations of anisotropic stress-strain behavior of shocked loaded energetic materials. Our previous results derived using a 350 ps duration compression drive revealed anisotropic elastic wave response in single crystal β-HMX from (110) and (010) impact planes. Here we present results using a 1.05 ns duration compression drive with a 950 ps interferometry window to extend knowledge of the anisotropic dynamic response of β-HMX within eight microns of the initial impact plane. We observe two distinct wave profiles from (010) and three wave profiles from (010) impact planes. The (110) impact plane wave speeds typically exceed (010) impact plane wave speeds at t...

Here we review the scaling of pulse energy with duration for sub-ns laser-driven dynamic compression experiments, which suggests that extreme pressures (multiple Mbar) might be achieved in rapidly equilibrating materials with substantially lower energy than used in traditional experiments. For instance, conventional scaling of pressure with laser intensity indicates that pressures well into the multiple Mbar range should be accessible by compressing with a hundreds of picosecond duration drive pulse with some tens of mJ of energy – orders of magnitude less than required for conventional experiments. Via a related scaling argument, we also show that the throughput of time-resolved pulsed x-ray dynamic compression experiments (such as those performed at x-ray free electron lasers) varies as the inverse square of the time scale of the experiment. The strong variation of throughput with the scale of the experiment should be a significant consideration in the design of such experiments – to obtain high through...

Measuring the volume of a material compressed quasi-statically to a high-pressure typically involves the determination of a primitive crystal cell volume using x-ray diffraction (XRD) techniques. The accumulation of pressure dependent volumes leads to an understanding of the material’s equation of state, (EOS); however, in the case of low-symmetry (e.g. triclinic) materials with twining features, and large primitive cells, conventional XRD approaches can be technically problematic and lead to ambiguous or mathematically under-determined lattice constants. To resolve this long-standing issue, we examined the utility of a “direct” approach toward determining a material’s volume by measuring surface area and sample height using optical microscopy and interferometry respectively. To test the validity of our proposed approach, we first compared our results from pressurized Triamino-Trinitrobenzene (TATB, SG P-1) with a published EOS determined by synchrotron XRD measurements of Stevens et al.. A near-perfect m...

We report the adiabatic sound speeds for super- critical fluid carbon monoxide along two isotherms, from 0.17 to 2.13 GPa at 297 K and from 0.31 to 3.2 GPa at 600 K. The carbon monoxide was confined in a resistively heated diamond-anvil cell, and the sound speed measurements were conducted in situ using a recently reported variant of the photoacoustic light scattering effect. The measured sound speeds were then used to parametrize a single site dipolar exponential-6 intermolecular potential for carbon monoxide. PρT thermodynamic states, sound speeds, and shock Hugoniots were calculated using the newly parametrized intermolecular potential and compared to previously reported experimental results. Additionally, we generated an analytical equation of state for carbon monoxide by fitting to a grid of calculated PρT states over a range of 0.1−10 GPa and 150−2000 K. A 2% mean variation was found between computed high- pressure solid-phase densities and measured dataa surprising result for a spherical interaction potential. We further computed a rotationally dependent fluid to β-solid phase boundary; results signal the relative magnitude of short-range rotational disorder under conditions that span existing phase boundary measurements.

Allergic asthma is a heterogeneous inflammatory disorder of the airways characterized by chronic airway inflammation and airway hyperresponsiveness. Numbers of CD8 + IL-13 + T cells are increased in asthmatics and during the development of experimental asthma in mice. In an atopic environment rich in IL-4, these CD8 + T cells mediate asthmatic responses, but the mechanisms regulating the conversion of CD8 + effector T cells from IFN-γ– to pathogenic IL-13–producing effector cells that contribute to an asthma phenotype have not been defined. Here, we show that cholesterol side-chain cleavage P450 enzyme, Cyp11a1, is a key regulator of CD8 + T-cell conversion. Expression of the gene, protein, and enzymatic activity of Cyp11a1 were markedly increased in CD8 + T cells differentiated in the presence of IL-2 plus IL-4 compared with cells differentiated in IL-2 alone. Inhibition of Cyp11a1 enzymatic activity with aminoglutethimide or reduction in the expression of Cyp11a1 using short hairpin RNA prevented the IL-4–induced conversion of IFN-γ– to IL-13–producing cells without affecting expression of the lineage-specific transcription factors T-box expressed in T cells (T-bet) or GATA binding protein 3 (GATA3). Adoptive transfer of aminoglutethimide-treated CD8 + T cells into sensitized and challenged CD8-deficient recipients failed to restore airway hyperresponsiveness and inflammation. We demonstrate that Cyp11a1 controls the phenotypic conversion of CD8 + T cells from IFN-γ to IL-13 production, linking steroidogenesis in CD8 + T cells, a nonclassical steroidogenic tissue, to a proallergic differentiation pathway.

We will present results from a steady-state inductively coupled plasma-based flow reactor designed to investigate chemical kinetics for combustion, fusion energy, and nuclear forensics applications with high signal to noise. Article not available.

Shock compression studies of pressed and confined ultrafine 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) powder were conducted using ultrashort ~300 ps, ~50 GPa shock waves. The recovered decomposition products were characterized using X-ray photoelectron spectroscopy, infrared spectroscopy, and Raman spectroscopy. A substantial amount of shock-related chemistry was observed. Approximately 75% of the nitrogen atoms were liberated as gas-phase species, along with ~33% of the oxygen atoms, as a result of the applied shock. Furthermore, we observe C 1s binding energies suggesting the formation of sp(3) hybridized amorphous carbon. For comparison, a carbon nitride material was also prepared and characterized by thermally pyrolizing TATB. The shock-compressed TATB and the thermally pyrolized TATB are qualitatively different, suggesting that, carbon nitrides, a possible indicator of nitrogen-rich heterocycles precursors, are not a major product class for strongly overdriven shock conditions. These experimental conditions were, however, not detonation conditions, and the possible formation of nitrogen-rich heterocycles in actual detonations still exists.

Elucidation of geodynamic, geochemical, and shock-induced processes is often limited by challenges to determine accurately molecular fluid equations of state (EOS). High-pressure liquid-state react...

The time scale and/or products of photoinduced decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) were investigated at ambient pressure and compared with products formed at 8 GPa. Ultrafast time-resolved infrared and steady-state Fourier transform IR (FTIR) spectroscopies were used to probe TATB and its products after photoexcitation with a 5 ns pulse of 532 nm light. At ambient pressure, transient spectra of TATB indicate that the molecule has significantly decomposed within 60 ns; transient spectra also indicate that formation of CO(2), an observed decomposition product, is complete within 30-40 mus. Proof of principle time-resolved experiments at elevated pressures were performed and are discussed briefly. Comparison of steady-state FTIR spectra obtained at ambient and elevated pressure (ca. 8 GPa) indicate that the decomposition products vary with pressure. We find evidence for water as a decomposition product only at elevated pressure.

High-speed spectroscopy confirms predictions of the emission of terahertz radiation when a laser-induced acoustic wave passes across the interface between two piezoelectric materials.

The microstructure and properties of a material depend on dynamic processes such as defect motion, nucleation and growth, and phase transitions. Transmission electron microscopy (TEM) can spatially resolve these nanoscale phenomena but lacks the time resolution for direct observation. We used a photoemitted electron pulse to probe dynamic events with “snapshot” diffraction and imaging at 15-nanosecond resolution inside of a dynamic TEM. With the use of this capability, the moving reaction front of reactive nanolaminates is observed in situ. Time-resolved images and diffraction show a transient cellular morphology in a dynamically mixing, self-propagating reaction front, revealing brief phase separation during cooling, and thus provide insights into the mechanisms driving the self-propagating high-temperature synthesis.

Distinct physical mechanisms for the generation of temporally coherent, narrow bandwidth optical radiation are few and rare in nature. Such sources, including lasers, have widespread applications ranging from spectroscopy to interferometry. We review the recent theoretical prediction of a new type of temporally coherent optical radiation source in the 1–100 THz frequency range that can be realized when crystalline polarizable materials like NaCl are subject to a compressive shock wave.

Although recent years have seen significant advances in the spatial resolution possible in the transmission electron microscope (TEM), the temporal resolution of most microscopes is limited to video rate at best. This lack of temporal resolution means that our understanding of dynamic processes in materials is extremely limited. High temporal resolution in the TEM can be achieved, however, by replacing the normal thermionic or field emission source with a photoemission source. In this case the temporal resolution is limited only by the ability to create a short pulse of photoexcited electrons in the source, and this can be as short as a few femtoseconds. The operation of the photo-emission source and the control of the subsequent pulse of electrons (containing as many as 5 x 10(7) electrons) create significant challenges for a standard microscope column that is designed to operate with a single electron in the column at any one time. In this paper, the generation and control of electron pulses in the TEM to obtain a temporal resolution10(-6)s will be described and the effect of the pulse duration and current density on the spatial resolution of the instrument will be examined. The potential of these levels of temporal and spatial resolution for the study of dynamic materials processes will also be discussed.

Model studies of the ligand photodissociation process of carboxymyoglobin have been conducted by using amplified few-cycle laser pulses short enough in duration (

High-quality, few-cycle pulses over the complete tuning range of a noncollinear parametric amplifier system and a variety of sample conditions have been readily generated using a compressor based on deformable mirror adaptive optics. These broadband pulses are compressed to 7 fs pulse duration in a compact, glassless combination of static negatively chirped mirrors and a zero-dispersion stretcher with a deformable mirror for the manipulation of the spectral phase. These ultra-short pulses are then used to investigate with very high resolution the early-time dynamics of deoxy- and carboxymyoglobin after the photoinitiated dissociation of the carbon monoxide ligand.

We present the development of a steady state plasma flow reactor to investigate gas phase physical and chemical processes that occur at high temperature (1000 < T < 5000 K) and atmospheric pressure. The reactor consists of a glass tube that is attached to an inductively coupled argon plasma generator via an adaptor (ring flow injector). We have modeled the system using computational fluid dynamics simulations that are bounded by measured temperatures. In situ line-of-sight optical emission and absorption spectroscopy have been used to determine the structures and concentrations of molecules formed during rapid cooling of reactants after they pass through the plasma. Emission spectroscopy also enables us to determine the temperatures at which these dynamic processes occur. A sample collection probe inserted from the open end of the reactor is used to collect condensed materials and analyze them ex situ using electron microscopy. The preliminary results of two separate investigations involving the condensation of metal oxides and chemical kinetics of high-temperature gas reactions are discussed.

We have measured vibronic emission spectra of an oxide of uranium formed after laser ablation of the metal in gaseous oxygen. Specifically, we have measured the time-dependent relative intensity of a band located at approximately 593.6 nm in 16O2. This band grew in intensity relative to neighboring atomic features as a function time in an oxygen environment but was relatively invariant with time in argon. In addition, we have measured the spectral shift of this band in an 18O2 atmosphere. Based on this shift, and by comparison with earlier results obtained from free-jet expansion and laser excitation, we can confirm that the oxide in question is UO, consistent with recent reports based on laser ablation in 16O2 only.

We apply ultrafast optical interferometry to measure the Hugoniot of an oxygen-balanced mixture of nitromethane and hydrogen peroxide (NM/HP) and compare with Hugoniot data for pure nitromethane (NM) and a 90% hydrogen peroxide/water mixture (HP), as well as theoretical predictions. We observe a 2.1% percent mean pairwise difference between the measured shockwave speed (at the measured piston speed) in unreacted NM/HP and the corresponding "universal" liquid Hugoniot, which is larger than the average standard deviation of our data, 1.4%. Unlike the Hugoniots of both HP and NM, in which measured shock speeds deviate to values greater than the unreacted Hugoniot for piston speeds larger than the respective reaction thresholds, in the NM/HP mixture we observe shock speed deviations to values lower than the unreacted Hugoniot well below the von Neumann pressure (≈28 GPa). Although the trend should reverse for high enough piston speeds, the initial behavior is unexpected. Possible explanations range from mixing effects to a complex index of refraction in the reacted solution. If this is indeed a signature of chemical initiation, it would suggest that the process may not be kinetically limited (on a ~100 ps time scale) between the initiation threshold and the von Neumann pressure.

Metabolomics is an emerging field which enables profiling of samples from living organisms in order to obtain insight into biological processes. A vital aspect of metabolomics is sample preparation whereby inconsistent techniques generate unreliable results. This technique encompasses protein precipitation, liquid-liquid extraction, and solid-phase extraction as a means of fractionating metabolites into four distinct classes. Improved enrichment of low abundance molecules with a resulting increase in sensitivity is obtained, and ultimately results in more confident identification of molecules. This technique has been applied to plasma, bronchoalveolar lavage fluid, and cerebrospinal fluid samples with volumes as low as 50 µl. Samples can be used for multiple downstream applications; for example, the pellet resulting from protein precipitation can be stored for later analysis. The supernatant from that step undergoes liquid-liquid extraction using water and strong organic solvent to separate the hydrophilic and hydrophobic compounds. Once fractionated, the hydrophilic layer can be processed for later analysis or discarded if not needed. The hydrophobic fraction is further treated with a series of solvents during three solid-phase extraction steps to separate it into fatty acids, neutral lipids, and phospholipids. This allows the technician the flexibility to choose which class of compounds is preferred for analysis. It also aids in more reliable metabolite identification since some knowledge of chemical class exists.

The dynamics of carboxy-myoglobin (MbCO) in water are studied from photodissociation of the ligand to bimolecular recombination over 12 decades in time to fully characterize the protein functions. Heterodyne-detected transient grating spectroscopy is used to resolve the dynamics of the protein from 10 ns to a few ms and provides a direct observation of the ligand escape. The process is well described by a bi-exponential function with decay rates of 50 and 725 ns at 20°C, suggesting that ligand escape occurs via a well defined pathway. Transient absorption in the Q-band (550–630 nm) also reveals the sensitivity of the electronic transition to the ligand motions. The dynamic range is extended by 10 6 through femtosecond coherence spectroscopy with 7 fs pulses to enable the observation of vibrational modes of energies >1500 cm −1 . The power spectrum is calculated by singular value decomposition and vibrational modes involved in the photodissociation are directly observed. The picture that is emerging is that proteins couple solid-like domains to fluid regions to facilitate functions and transport of ligands in and out of the protein to the active site.

Sample preparation remains a challenge in untargeted metabolomics studies and no method currently results in complete extraction of all metabolite classes in human plasma. Because a large variety of molecules, with vast differences in dynamic range, could be involved in human disease, there is an urgent need to develop analytical techniques that result in comprehensive coverage of metabolites. Furthermore, analysis of more focused molecular classes could be necessary to more fully interrogate markers of human disease. However, such techniques, which generally involve multiple steps, often result in high variability. We have optimized a combined liquid-liquid and solid phase extraction method for plasma and have compared that to traditional methanol precipitation using spiked internal standards as controls. This method, based largely on previously published methods, results in 5 separate fractions enriched for aqueous species, phospholipids, fatty acids, neutral lipids, and hydrophobic lipids. Using liquid chromatography mass spectrometry as the analytical method, we detect over 3,806 metabolites using the new method versus 1,851 metabolites using methanol alone. Qualitative analysis and quantitative analysis of both internal standards (ISTDs) and endogenous metabolites demonstrate excellent reproducibility with CV’s below 15% for the combined method compared to 30% using the methanol method. While both methods have applications for clinical metabolomics, fractionation resulted in greater overall coverage and can be used for initial classification of molecular species.

We have used a 45 μJ laser pulse to accelerate the free surface of fine-grained tantalum films up to peak velocities of ∼1.2 km s−1. The films had thicknesses of ∼1–2 μm and in-plane grain widths of ∼75–150 nm. Using ultrafast interferometry, we have measured the time history of the velocity of the surface at different spatial positions across the accelerated region. The initial part of the histories (assumed to correspond to the “elastic precursor” observed previously) exhibited measured strain rates of ∼0.6 to ∼3.2 × 109 s−1 and stresses of ∼4 to ∼22 GPa. Importantly, we find that elastic amplitudes exhibit little variation with strain rate for a constant peak surface velocity, even though, via covariation of the strain rate with peak surface velocity, they vary with strain rate. Furthermore, by comparison with data obtained at lower strain rates, we find that amplitudes are much better predicted by peak velocities rather than by either strain rate or sample thickness.

Here we report quasi-isentropic dynamic compression and thermodynamic characterization of solid, precompressed deuterium over an ultra fast time scale (< 100 ps) and a microscopic length scale (< 1 im). We further report a fast transition in dynamically compressed solid deuterium that is consistent with the ramp to shock transition, with a time scale of less than 10 ps. These results suggest that high density dynamic compression of hydrogen may be possible on microscopic length scales.

We have directly resolved shock structures in pure aluminum in the first few hundred picoseconds subsequent to a dynamic load at peak stresses up to 43 GPa and strain rates in excess of ${10}^{10}\text{ }\text{ }{\mathrm{s}}^{\ensuremath{-}1}$. For strong shocks we obtain peak stresses, strain rates, and rise times. From these data, we directly validate the invariance of the dissipative action in the strong shock regime, and by comparing with data obtained at much lower strain rates show that this invariance is observed over at least 5 orders of magnitude in the strain rate. Over the same range, we similarly validate the fourth-power scaling of the strain rate with the peak stress (the Swegle-Grady relation).

Extrapolating from a brief survey of the literature, we outline a vision for the future development of time-resolved electron probe instruments that could offer levels of performance and flexibility that push the limits of physical possibility. This includes a discussion of the electron beam parameters (brightness and emittance) that limit performance, the identification of a dimensionless invariant figure of merit for pulsed electron guns (the number of electrons per lateral coherence area, per pulse), and calculations of how this figure of merit determines the trade-off of spatial against temporal resolution for different imaging modes. Modern photonics' ability to control its fundamental particles at the quantum level, while enjoying extreme flexibility and a very large variety of operating modes, is held up as an example and a goal. We argue that this goal may be approached by combining ideas already in the literature, suggesting the need for large-scale collaborative development of next-generation time-resolved instruments.

Our simulations and experiments demonstrate a new physical mechanism for detecting acoustic waves of THz frequencies. We find that strain waves of THz frequencies can coherently generate radiation when they propagate past an interface between materials with different piezoelectric coefficients. By considering AlN/GaN heterostructures, we show that the radiation is of detectable amplitude and contains sufficient information to determine the time-dependence of the strain wave with potentially sub-picosecond, nearly atomic time and space resolution. This mechanism is distinct from optical approaches to strain wave measurement. We demonstrate this phenomenon within the context of high amplitude THz frequency strain waves that spontaneously form at the front of shock waves in GaN crystals. We also show how the mechanism can be utilized to determine the layer thicknesses in thin film GaN/AlN heterostructures.

The dynamic transmission electron microscope (DTEM) is introduced as a novel tool for in situ processing of materials. Examples of various types of dynamic studies outline the advantages and differences of laser-based heating in the DTEM in comparison to conventional (resistive) heating in situ TEM methods. We demonstrate various unique capabilities of the drive laser, namely, in situ processing of nanoscale materials, rapid and high temperature phase transformations, and controlled thermal activation of materials. These experiments would otherwise be impossible without the use of the DTEM drive laser. Thus, the potential of the DTEM as a new technique to process and characterize the growth of a myriad of micro and nanostructures is demonstrated.

We present the first experimental observations of terahertz frequency radiation emitted when a terahertz frequency acoustic wave propagates past an interface between materials of differing piezoelectric coefficients. We show that this fundamentally new phenomenon can be used to probe structural properties of thin films. Then, we present molecular dynamics simulations showing that detectable THz frequency radiation can be emitted when a wurtzite structure crystal transforms to a rocksalt structure under shock compression on picosecond timescales. We show that information about the kinetics of the transformation is contained in the time‐dependence of the THz field.

Our simulations and experiments demonstrate a new physical mechanism for detecting acoustic waves of THz frequencies. Detectable THz-frequency radiation is generated when the acoustic wave passes a piezoelectric interface.

Publisher Summary This chapter describes the various time-resolving electron optical techniques that are developed for a fast study of transient effects in freestanding films and on surfaces of bulk materials down to the nanosecond time scale. Hydrodynamic instabilities in confined laser pulse-produced melts and their solidification and evaporation are discussed in the chapter, as they are of major concern to micromachining with laser pulses. The mechanisms uncovered by high-speed electron microscopy are described. There are three different time-resolving techniques distinguished by the number of spatial coordinates in the image: (1) short-time-exposure imaging, (2) streak imaging, and (3) image intensity tracking. There are several types of electron microscopes that probe different zones of the specimen. Transmission microscopes uncover the volume processes of free-standing films that often mimic bulk material. Properties of the top layers of a surface are successfully studied by the photoelectron microscope. Reflection electron microscopy gives access to the space above the surface of the specimen. These three types of electron microscopes are adapted to investigations of fast processes in their specific domain.

Using molecular dynamics simulations and analytics, we find that strain waves of terahertz frequencies can coherently generate radiation when they propagate past an interface between materials with different piezoelectric coefficients. By considering AlN/GaN heterostructures, we show that the radiation is of detectable amplitude and contains sufficient information to determine the time dependence of the strain wave with potentially subpicosecond, nearly atomic time and space resolution. We demonstrate this phenomenon within the context of high amplitude terahertz frequency strain waves that spontaneously form at the front of shock waves in GaN crystals.