ASU Scholarship Showcase

We present results from experiments at the Linac Coherent Light Source (LCLS) demonstrating that serial femtosecond crystallography (SFX) can be performed to high resolution (~2.5 Å) using protein microcrystals deposited on an ultra-thin silicon nitride membrane and embedded in a preservation medium at room temperature. Data can be acquired at a high acquisition rate using x-ray free electron laser sources to overcome radiation damage, while sample consumption is dramatically reduced compared to flowing jet methods. We achieved a peak data acquisition rate of 10 Hz with a hit rate of ~38%, indicating that a complete data set could be acquired in about one 12-hour LCLS shift using the setup described here, or in even less time using hardware optimized for fixed target SFX. This demonstration opens the door to ultra low sample consumption SFX using the technique of diffraction-before-destruction on proteins that exist in only small quantities and/or do not produce the copious quantities of microcrystals required for flowing jet methods.

Photosynthesis, a process catalysed by plants, algae and cyanobacteria converts sunlight to energy thus sustaining all higher life on Earth. Two large membrane protein complexes, photosystem I and II (PSI and PSII), act in series to catalyse the light-driven reactions in photosynthesis. PSII catalyses the light-driven water splitting process, which maintains the Earth’s oxygenic atmosphere. In this process, the oxygen-evolving complex (OEC) of PSII cycles through five states, S₀ to S₄, in which four electrons are sequentially extracted from the OEC in four light-driven charge-separation events. Here we describe time resolved experiments on PSII nano/microcrystals from Thermosynechococcus elongatus performed with the recently developed technique of serial femtosecond crystallography. Structures have been determined from PSII in the dark S₁ state and after double laser excitation (putative S₃ state) at 5 and 5.5 Å resolution, respectively. The results provide evidence that PSII undergoes significant conformational changes at the electron acceptor side and at the Mn₄CaO₅ core of the OEC. These include an elongation of the metal cluster, accompanied by changes in the protein environment, which could allow for binding of the second substrate water molecule between the more distant protruding Mn (referred to as the ‘dangler’ Mn) and the Mn₃CaO_x cubane in the S₂ to S₃ transition, as predicted by spectroscopic and computational studies. This work shows the great potential for time-resolved serial femtosecond crystallography for investigation of catalytic processes in biomolecules.

It has been suggested that the extended intensity profiles surrounding Bragg reflections that arise when a series of finite crystals of varying size and shape are illuminated by the intense, coherent illumination of an x-ray free-electron laser may enable the crystal’s unit-cell electron density to be obtained ab initio via well-established iterative phasing algorithms. Such a technique could have a significant impact on the field of biological structure determination since it avoids the need for a priori information from similar known structures, multiple measurements near resonant atomic absorption energies, isomorphic derivative crystals, or atomic-resolution data. Here, we demonstrate this phasing technique on diffraction patterns recorded from artificial two-dimensional microcrystals using the seeded soft x-ray free-electron laser FERMI. We show that the technique is effective when the illuminating wavefront has nonuniform phase and amplitude, and when the diffraction intensities cannot be measured uniformly throughout reciprocal space because of a limited signal-to-noise ratio.

We investigate near-field radiative heat transfer between Indium Tin Oxide (ITO) nanowire arrays which behave as type 1 and 2 hyperbolic metamaterials. Using spatial dispersion dependent effective medium theory to model the dielectric function of the nanowires, the impact of filling fraction on the heat transfer is analyzed. Depending on the filling fraction, it is possible to achieve both types of hyperbolic modes. At 150 nm vacuum gap, the heat transfer between the nanowires with 0.5 filling fraction can be 11 times higher than that between two bulk ITOs. For vacuum gaps less than 150 nm the heat transfer increases as the filling fraction decreases. Results obtained from this study will facilitate applications of ITO nanowires as hyperbolic metamaterials for energy systems.

A film-coupled metamaterial structure is numerically investigated for enhancing the light absorption in an ultrathin photovoltaic layer of crystalline gallium arsenide (GaAs). The top subwavelength concave grating and the bottom metallic film could not only effectively trap light with the help of wave interference and magnetic resonance effects excited above the bandgap, but also practically serve as electrical contacts for photon-generated charge collection. The energy absorbed by the active layer is greatly enhanced with the help of the film-coupled metamaterial structure, resulting in significant improvement on the short-circuit current density by three times over a free-standing GaAs layer at the same thickness. The performance of the proposed light trapping structure is demonstrated to be little affected by the grating ridge width considering the geometric tolerance during fabrication. The optical absorption at oblique incidences also shows direction-insensitive behavior, which is highly desired for efficiently converting off-normal sunlight to electricity. The results would facilitate the development of next-generation ultrathin solar cells with lower cost and higher efficiency.

In this work, we report the design of a wavelength-tunable infrared metamaterial by tailoring magnetic resonance condition with the phase transition of vanadium dioxide (VO₂). Numerical simulation based on the finite-difference time-domain method shows a broad absorption peak at the wavelength of 10.9 μm when VO₂ is a metal, but it shifts to 15.1 μm when VO₂ changes to dielectric phase below its phase transition temperature of 68 °C. The large tunability of 38.5% in the resonance wavelength stems from the different excitation conditions of magnetic resonance mediated by plasmon in metallic VO₂ but optical phonons in dielectric VO₂. The physical mechanism is elucidated with the aid of electromagnetic field distribution at the resonance wavelengths. A hybrid magnetic resonance mode due to the plasmon-phonon coupling is also discussed. The results here would be beneficial for active control of thermal radiation in novel electronic, optical, and thermal devices.

In this work, we numerically demonstrate an infrared (IR) frequency-tunable selective thermal emitter made of graphene-covered silicon carbide (SiC) gratings. Rigorous coupled-wave analysis shows temporally-coherent emission peaks associated with magnetic polariton (MP), whose resonance frequency can be dynamically tuned within the phonon absorption band of SiC by varying graphene chemical potential. An analytical inductor–capacitor circuit model is introduced to quantitatively predict the resonance frequency and further elucidate the mechanism for the tunable emission peak. The effects of grating geometric parameters, such as grating height, groove width and grating period, on the selective emission peak are explored. The direction-independent behavior of MP and associated coherent emission are also demonstrated. Moreover, by depositing four layers of graphene sheets onto the SiC gratings, a large tunability of 8.5% in peak frequency can be obtained to yield the coherent emission covering a broad frequency range from 820 to 890 cm^-1. The novel tunable metamaterial could pave the way to a new class of tunable thermal sources in the IR region.

This study explores the capabilities of the Coherent X-ray Imaging Instrument at the Linac Coherent Light Source to image small biological samples. The weak signal from small samples puts a significant demand on the experiment. Aerosolized Omono River virus particles of ∼40 nm in diameter were injected into the submicrometre X-ray focus at a reduced pressure. Diffraction patterns were recorded on two area detectors. The statistical nature of the measurements from many individual particles provided information about the intensity profile of the X-ray beam, phase variations in the wavefront and the size distribution of the injected particles. The results point to a wider than expected size distribution (from ∼35 to ∼300 nm in diameter). This is likely to be owing to nonvolatile contaminants from larger droplets during aerosolization and droplet evaporation. The results suggest that the concentration of nonvolatile contaminants and the ratio between the volumes of the initial droplet and the sample particles is critical in such studies. The maximum beam intensity in the focus was found to be 1.9 × 10¹² photons per µm² per pulse. The full-width of the focus at half-maximum was estimated to be 500 nm (assuming 20% beamline transmission), and this width is larger than expected. Under these conditions, the diffraction signal from a sample-sized particle remained above the average background to a resolution of 4.25 nm. The results suggest that reducing the size of the initial droplets during aerosolization is necessary to bring small particles into the scope of detailed structural studies with X-ray lasers.

We numerically demonstrate a switchable metamaterial absorber/emitter by thermally turning on or off the excitation of magnetic resonance upon the phase transition of vanadium dioxide (VO2). Perfect absorption peak exists around the wavelength of 5 lm when the excitation of magnetic resonance is supported with the insulating VO2 spacer layer. The wavelength-selective absorption is switched off when the magnetic resonance is disabled with metallic VO2 that shorts the top and bottom metallic structures. The resonance wavelength can be tuned with different geometry, and the switchable metamaterial exhibits diffuse behaviors at oblique angles. The results would facilitate the design of switchable metamaterials for active control in energy and sensing applications.

Recently, near-field thermal radiation has attracted much attention in several fields since it can exceed the Planck blackbody limit through the coupling of evanescent waves. In this work, near-field radiative heat transfer between two semi-infinite dual uniaxial electromagnetic metamaterials with two different material property sets is theoretically analyzed. The near-field radiative heat transfer is calculated using fluctuational electrodynamics incorporated with anisotropic wave optics. The underlying mechanisms, namely, magnetic hyperbolic mode, magnetic surface polariton, electrical hyperbolic mode, and electrical surface polariton, between two homogeneous dual uniaxial electromagnetic metamaterials are investigated by examining the transmission coefficient and the spectral heat flux. The effect of vacuum gap distance is also studied, which shows that the enhancement at smaller vacuum gap is mainly due to hyperbolic mode and surface plasmon polariton modes. In addition, the results show that the contribution of s-polarized waves is significant and should not be excluded due to the strong magnetic response regardless of vacuum gap distances. The fundamental understanding and insights obtained here will facilitate the finding and application of novel materials for near-field thermal radiation.