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Dynamic surface and subsurface morphology and chemistry of socketed nanoparticles is monitored in situ for an important emerging class of nanoparticles.
The first step of the photoactivation mechanism of the orange carotenoid protein is the photodissociation of the dark-stable dimer aggregate.
Volumetric Additive Manufacturing (VAM) represents a revolutionary advancement in the field of Additive Manufacturing, as it allows for the creation of objects in a single, cohesive process, rather than in a layer-by-layer approach. This innovative technique offers unparalleled design freedom and significantly reduces printing times. A current limitation of VAM is the availability of suitable resins with the required photoreactive chemistry and from sustainable sources. To support the application of this technology, we have developed a sustainable resin based on polyglycerol, a bioderived (e.g., vegetable origin), colourless, and easily functionisable oligomer produced from glycerol. To transform polyglycerol-6 into an acrylate photo-printable resin we adopted a simple, one-step, and scalable synthesis route. Polyglycerol-6-acrylate fulfils all the necessary criteria for volumetric printing (transparency, photo-reactivity, viscosity) and was successfully used to print a variety of models with intricate geometries and good resolution. The waste resin was found to be reusable with minimal performance issues, improving resin utilisation and minimising waste material. Furthermore, by incorporating dopants such as poly(glycerol) adipate acrylate (PGA-A) and 10,12-pentacosadyinoic acid (PCDA), we demonstrated the ability to print objects with a diverse range of functionalities, including temperature sensing probes and a polyester excipient, highlighting the potential applications of these new resins.
Chemical transformations on catalyst surfaces occur through series and parallel reaction pathways. These complex networks and their behavior can be most simply evaluated through a three-species surface reaction loop (A* to B* to C* to A*) that is internal to the overall chemical reaction. Application of an oscillating dynamic catalyst to this reactive loop has been shown to exhibit one of three types of behavior: (1) a positive net flux of molecules about the loop in the clockwise direction, (2) a negative net flux of molecules about the loop in the counterclockwise direction, or (3) negligible flux of molecules about the loop at the limit cycle of reaction. Three-species surface loops were simulated with microkinetic modeling to assess the reaction loop behavior resulting from a catalytic surface oscillating between two or more catalyst surface energy states. Selected input parameters for the simulations spanned an 11-dimensional parameter space using 127 688 different parameter combinations. Their converged limit cycle solutions were analyzed for their loop turnover frequencies, the majority of which were found to be approximately zero. Classification and regression machine learning models were trained to predict the sign and magnitude of the loop turnover frequency and successfully performed above accessible baselines. Notably, the classification models exhibited a baseline weighted F1 score of 0.49, whereas trained models achieved weighted F1 scores of 0.94 and 0.96 when trained on the parameters used to define the simulations and derived rate constants, respectively. The trained models successfully predicted catalytic loop behavior, and interpretation of these models revealed all input parameters to be important for the prediction and performance of each model.
Catalytic reaction networks of multiple elementary steps operating under dynamic conditions via a programmed input oscillation are difficult to interpret and optimize due to reaction system complexity. To understand these dynamic systems, individual elementary catalytic reactions oscillating between catalyst states were evaluated to identify their three fundamental characteristics that define their ability to promote reactions away from equilibrium. First, elementary catalytic reactions exhibit directionality to promote reactions forward or backward from equilibrium as determined by a ratchet directionality metric comprised of the input oscillation duty cycle and the reaction rate constants. Second, catalytic ratchets are defined by the catalyst state of strong or weak binding that permit reactants to proceed through the transition state. Third, elementary catalytic ratchets exhibit a cutoff frequency which defines the transition in applied frequency for which the catalytic ratchet functions to promote chemistry away from equilibrium. All three ratchet characteristics are calculated from chemical reaction parameters including rate constants derived from linear scaling parameters, reaction conditions, and catalyst state. The characteristics of the reaction network’s constituent elementary catalytic reactions provided an interpretation of complex reaction networks and a method of predicting the behavior of dynamic surface chemistry on oscillating catalysts.
The catalytic hydroboration of alkenes with pinacolborane (HBpin) represents a valuable yet challenging transformation in main-group catalysis, furnishing alkyl pinacol boronic esters of broad synthetic utility. In this article, we demonstrate that simple, commercially available aryl and alkyl boronic acids and their corresponding boroxines act as efficient pre-catalysts for the anti-Markovnikov hydroboration of terminal alkenes with HBpin under solvent-free conditions. In particular, 3,4,5-trifluorophenylboronic acid promotes hydroboration at low loadings, displays broad functional-group tolerance, and operates under operationally simple conditions. Detailed 11 B NMR spectroscopic studies reveal that boronic acids and boroxines are not the catalysts themselves, instead they react with HBpin to generate the transient species RBH 2 ·BH 2 R and B 2 H 6 , which serve as catalytically active intermediates. These species rapidly undergo alkene hydroboration followed by transborylation with HBpin to regenerate the catalytically competent hydridoboranes and release the alkyl pinacol boronic ester products. At elevated temperature and in the absence of alkene substrate, B 2 H 6 undergoes thermal fragmentation into the catalytically inactive borane clusters B 5 H 9 and B 10 H 14 . Limitations in the hydroboration of internal alkenes are traced to the formation of sterically congested trialkylboranes that do not undergo transborylation.
Epitaxially strained germanium-on-silicon (Ge-on-Si) heterostructures are central to next-generation photonic and electronic devices, yet their performance remains strongly constrained by defect-limited carrier lifetimes. In this work, we investigate the impact of defects on the carrier lifetime in relaxed Ge-on-Si and strained Ge-on-Si heterostructures. High-resolution X-ray diffraction quantifies the strain-state in Ge and reveals signatures of strain relaxation due to lattice mismatch. Cross-sectional and plan-view transmission electron microscopy analyses enable direct visualization of interfacial defects and quantification of threading dislocation densities (TDDs) within the Ge layer. However, the presence of a dense misfit dislocation network obscures the threading dislocation signatures, preventing reliable TDD determination by plan-view transmission electron microscopy in strained-Ge (..epsilon..-Ge). To assess the defect density in this case, etch-pit density measurements were performed, providing an alternative means of quantifying the TDDs in the ..epsilon..-Ge layer. Carrier lifetime measurements by microwave-reflection photoconductive decay reveal a clear relationship with TDDs ranging from 5 x 103 cm-2 to 2 x 1010 cm-2, confirming Shockley-Read-Hall recombination as the limiting mechanism at lower defect densities, with TDD-dominated recombination at higher defect densities. The Ge-on-Si relaxed heterostructure exhibited lifetimes much lower (~12 ns) than the lattice-matched Ge on gallium arsenide (GaAs) (~158 ns) heterostructure. Introducing controlled tensile strain reduces defect formation, suppresses strain-relaxation pathways, and leads to measurable improvements in minority carrier lifetime from 12 ns to 171 ns. These results establish a direct relation between defect suppression and carrier recombination dynamics in both relaxed Ge-on-Si grown directly on Si and strained Ge-on-Si heterostructures incorporating compound-semiconductor buffer layers, offering a materials-driven pathway for engineering Ge with improved carrier lifetime for photonic applications.
Family 1 Coenzyme A transferases (CtfAB) from the extremely thermophilic bacterium, Thermosipho melanesiensis, has been used for in vivo acetone production up to 70°C. This enzyme has tentatively been identified as the rate-limiting step, due to its relatively low-binding affinity for acetate. However, existing kinetic and mechanistic studies on this enzyme are insufficient to evaluate this hypothesis. Here, kinetic analysis of purified recombinant T. melanesiensis CtfAB showed that it has a ping-pong bi-bi mechanism typical of Coenzyme A (CoA) transferases with Km values for acetate and acetoacetyl-CoA of 85 mM and 135 μM, respectively. Product inhibition by acetyl-CoA was competitive with respect to acetoacetyl-CoA and non-competitive with respect to acetate. Crystal structures of wild-type and mutant T. melanesiensis CtfAB were solved in the presence of acetate and in the presence or absence of acetyl-CoA. These structures led to a proposed structural basis for the competitive and non-competitive inhibition of acetyl-CoA: acetate binds independently of acetyl-CoA in an apparent low-affinity binding pocket in CtfA that is directly adjacent to a catalytic glutamate in CtfB. Similar to other CoA transferases, acetyl-CoA is bound in an apparent high-affinity binding site in CtfB with most interactions occurring between the phospho-ADP of CoA and CtfB residues far from the acetate binding pocket. This structural-based mechanism also explains the organic acid promiscuity of CtfAB. High-affinity interactions are predominantly between the conserved phospho-ADP of CoA, and the variable organic acid binding site is a low-affinity binding site with few specific interactions.
Active galactic nuclei (AGN) are thought to be responsible for the suppression of star formation in massive ~10 10 M ⊙ galaxies. While this process is a key feature in numerical simulations of galaxy formation, it has not been unambiguously confirmed in observational studies yet. The characterization of the star formation rate (SFR) in AGN host galaxies is challenging as AGN light contaminates most SFR tracers. Furthermore, the various SFR tracers are sensitive to different timescales of star formation from approximately a few to 100 Myr. We aim to obtain and compare SFR estimates from different tracers for AGN host galaxies in the Close AGN Reference Survey (CARS) to provide new observational insights into the recent SFR history of those systems. We constructed integrated panchromatic spectral energy distributions to measure the far infrared (FIR) luminosity as a tracer for the recent (< 100 Myr) SFR. In addition we used the integral-field unit observation of the CARS targets to employ the Hα luminosity decontaminated by AGN excitation as a proxy for the current (< 5 Myr) SFR. We find that significant differences in specific SFR of the AGN host galaxies as compared with the larger galaxy population disappear once cold gas mass, in addition to stellar mass, is used to predict the SFR for a specific AGN host. Only a tentative trend with the inclination of the host galaxy remains, such that SFR appears slightly lower than expected when the galaxies of unobscured AGN appear more edge-on along our line-of-sight, particular for dust-insensitive FIR-based SFRs. We identify individual galaxies with a significant difference in their SFR which can be related to a recent enhancement or decline in their SFR history that might be related to various processes including interactions, gas consumption, outflows, and AGN feedback. AGN can be present in various stages of galaxy evolution which makes it difficult to relate the SFR solely to the impact of the AGN. Our study shows that stellar mass alone is an insufficient parameter to estimate the expected SFR of an AGN host galaxy compared to the underlying non-AGN galaxy population. We do not find any strong evidence for a global positive or negative AGN feedback in the CARS sample. However, there is tentative evidence that (1) the relative orientation of the AGN engine with respect to the host galaxies might alter the efficiency of AGN feedback and that (2) the recent SFH is an additional tool to identify rapid changes in galaxy growth driven by the AGN or other processes.
Unconstrained physics spaces between two or more nuclear data observables in a library occur when their values can be simultaneously adjusted without violating the uncertainties in either differential information or simulations of relevant integral experiments. Differential data are often too imprecise to fully bound all nuclear data observables of interest for application simulations. Integral data are simulated with combinations of nuclear data so that an error in one observable may be hidden by a counterbalancing error in another. In this manner compensating errors may lurk within nuclear data libraries and these errors have the potential to undermine the predictive power of neutron transport simulations, particularly in situations where there is no conclusive validation experiment that resembles the application of interest. The EUCLID project (Experiments Underpinned by Computational Learning for Improvements in Nuclear Data) developed a preliminary workflow to identify these unconstrained physics spaces by bringing together results from a large collection of integral experiments with their simulated counter-parts as well as differential information that have a one-to-one correspondence to nuclear data. This wealth of information is processed by machine learning tools for subsequent refinement by human experts. Here, we show how the EUCLID work-flow is executed by applying it first to 239 Pu and then to 9 Be nuclear data in ENDF/B-VIII.0.
Cherenkov detectors can offer a significant advantage in spatial imaging applications when excellent timing response, low noise and cross talk, large area coverage, and the ability to operate in magnetic fields are required. We show that an array of Cherenkov detectors with crude energy resolution coupled with monochromatic photons resulting from a low-energy nuclear reaction can be used to produce a sharp image of material while providing large and inexpensive detector coverage. The analysis of the detector response to relative transmission of photons with various energies allows for reconstruction of material's effective atomic number further aiding in high-Z material identification.
Here, the effect of a local external electric field on the barrier potential of a tunneling gap is studied utilizing an emerging technique, synchrotron x-ray scanning tunneling microscopy. Here, we demonstrate that the shape of the potential barrier in the tunneling gap can be altered by a localized external electric field, generated by voltages placed on the metallic outer shield of a nanofabricated coaxial metal-insulator-metal tip, resulting in a controlled linear modulation of the tunneling current. Experiments at hard and soft x-ray synchrotron beamlines reveal that both the chemical contrast and magnetic contrast signals measured by the tip can be drastically enhanced, resulting in improved local detection of chemistry and magnetization at the surface.
The walls of the hohlraum used in experiments at the national ignition facility are heated by laser beams with intensities ∼1015 W/cm2, a wavelength of ∼1/3 μm, and pulse lengths on the order of a ns, with collisional absorption believed to be the primary heating mechanism. X-rays generated by the hot ablated plasma at the gold walls are then used to implode a target in the hohlraum interior. In addition to the collisional absorption of laser energy at the walls, non-linear laser-plasma interactions (LPI), such as stimulated Raman scattering and two plasmon decay, are believed to generate a population of supra-thermal electrons which, if present in the hohlraum, can have a deleterious effect on target implosion. We describe results of hohlraum modeling using a hybrid particle-in-cell code. To enable this work, new particle-based algorithms for a multiple-ion magneto-hydrodynamic (MHD) treatment, and a particle-based ray-tracing model were developed. The use of such hybrid methods relaxes the requirement to resolve the laser wavelength, and allows for relatively large-scale hohlraum simulations with a reasonable number of cells. But the non-linear effects which are believed to be the cause of hot electron generation can only be captured by fully kinetic simulations with good resolution of the laser wavelength. For this reason, we employ a two-tiered approach to hohlraum modeling. Large-scale simulations of the collisional absorption process can be conducted using the fast quasi-neutral MHD algorithm with fluid particle species. From these simulations, we can observe the time evolution of the hohlraum walls and characterize the density and temperature profiles. From these results, we can transition to smaller-scale highly resolved simulations using traditional kinetic particle-in-cell methods, from which we can fully model all of the non-linear laser-plasma interactions, as well as assess the details of the electron distribution function. We find that vacuum hohlraums should be stable to both two plasmon decay and stimulated Raman scattering instabilities for intensities ≤1015 W/cm2. In gas-filled hohlraums, shocks may be induced in the blowoff gold plasma, which leads to more complex density and temperatures profiles. The resulting effect on LPI stability depends strongly on the details of the profile, and it is possible for the gas-filled hohlraum to become unstable to two plasmon decay at 1015 W/cm2 if the quarter-critical surface reaches temperatures exceeding 1 keV.
Here, 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 16 O 2 . 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 18 O 2 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 16 O 2 only.
Here, 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.
Herein, we present Genarris, a Python package that performs configuration space screening for molecular crystals of rigid molecules by random sampling with physical constraints. For fast energy evaluations, Genarris employs a Harris approximation, whereby the total density of a molecular crystal is constructed via superposition of single molecule densities. Dispersion-inclusive density functional theory is then used for the Harris density without performing a self-consistency cycle. Genarris uses machine learning for clustering, based on a relative coordinate descriptor developed specifically for molecular crystals, which is shown to be robust in identifying packing motif similarity. In addition to random structure generation, Genarris offers three workflows based on different sequences of successive clustering and selection steps: the "Rigorous" workflow is an exhaustive exploration of the potential energy landscape, the "Energy" workflow produces a set of low energy structures, and the "Diverse" workflow produces a maximally diverse set of structures. The latter is recommended for generating initial populations for genetic algorithms. Here, the implementation of Genarris is reported and its application is demonstrated for three test cases. Published by AIP Publishing.
Powerful nanosecond laser-plasma processes are explored to generate discharge currents of a few 100 kA in coil targets, yielding magnetostatic fields (B-fields) in excess of 0.5 kT. The quasi-static currents are provided from hot electron ejection from the laser-irradiated surface. According to the model used in our paper, which describes the evolution of the discharge current, the major control parameter is the laser irradiance Ilasλ2las. The space-time evolution of the B-fields is experimentally characterized by high-frequency bandwidth B-dot probes and proton-deflectometry measurements. The magnetic pulses, of ns-scale, are long enough to magnetize secondary targets through resistive diffusion. We applied it in experiments of laser-generated relativistic electron transport through solid dielectric targets, yielding an unprecedented 5-fold enhancement of the energy-density flux at 60 μm depth, compared to unmagnetized transport conditions. These studies pave the ground for magnetized high-energy density physics investigations, related to laser-generated secondary sources of radiation and/or high-energy particles and their transport, to high-gain fusion energy schemes, and to laboratory astrophysics.
Magnetism at buried interfaces plays a crucial role in many emerging phenomena, but detection of interfacial magnetism in close proximity to a surface with elemental and chemical sensitivity is a challenging task. Here, we use a low temperature synchrotron x-ray scanning tunneling microscopy to investigate x-ray magnetic circular dichroism and near edge x-ray absorption fine structure of La 0.67 Sr 0.33 MnO 3 -LaNiO 3 superlattices in the absence of a magnetic field. In stark contrast to the weak magnetic signal of Mn when the La 0.67 Sr 0.33 MnO 3 layers are located on top, a robust x-ray magnetic circular dichroism signal is detected when they are buried underneath the LaNiO 3 layers. The near edge x-ray absorption fine structure reveals the valence states of the manganese while the oxygen K- edge x-ray absorption spectra show an increase in hole formation indicating a cogent charge transfer at the LaNiO 3 /La 0.67 Sr 0.33 MnO 3 interface. This work demonstrates that scanning tunneling microscopy can be extended to the synchrotron X-ray study of buried interfaces by controlling the sample-tip (e.g., detector) separation in the nanometer regime. The close sample-tip proximity further provides a path toward probing of small lateral areas with zero-field measurements in multi-domain samples.