Millisecond Time Scale Research Articles

Tuning Electrocatalytic Oxygen Reduction Reaction with Dynamic Control of Electrochemical Interfaces.

Herein, we report the tuning of the activity and selectivity of the oxygen reduction reaction (ORR) through the dynamic regulation of the electrochemical interfaces to surpass the performance of conventional electrocatalysis. This is achieved by applying an oscillating potential between the ORR operating potential and anion adsorbing potential on a gold electrode. Oscillating potential enhances the selectivity for H2O2 by up to 1.35 times compared to the static potential, as confirmed by rotating ring-disk electrode and fluorescence assay measurements. We showed that the enhanced selectivity depends on dynamic adsorption and desorption of anions, and the enhancement occurs in the millisecond time scale or shorter. The transient selectivity to H2O2 can reach ∼97% within the first 5 ms after potential switching. Our results suggest that the dynamic interface can create a transient but unique microenvironment for new reactivity that cannot be reproduced under static conditions, which offers a new dimension in controlling electrocatalysis.

Reversible Photoinduced Ligand Substitution in a Luminescent Chromium(0) Complex.

Light-triggered dissociation of ligands forms the basis for many compounds of interest for photoactivated chemotherapy (PACT), in which medicinally active substances are released or "uncaged" from metal complexes upon illumination. Photoinduced ligand dissociation is usually irreversible, and many recent studies performed in the context of PACT focused on ruthenium(II) polypyridines and related heavy metal complexes. Herein, we report a first-row transition metal complex, in which photoinduced dissociation and spontaneous recoordination of a ligand unit occurs. Two scorpionate-type tridentate chelates provide an overall six-coordinate arylisocyanide environment for chromium(0). Photoexcitation causes decoordination of one of these six ligating units and coordination of a solvent molecule, at least in tetrahydrofuran and 1,4-dioxane solvents, but far less in toluene, and below detection limit in cyclohexane. Transient UV-vis absorption spectroscopy and quantum chemical simulations point to photoinduced ligand dissociation directly from an excited metal-to-ligand charge-transfer state. Owing to the tridentate chelate design and the substitution lability of the first-row transition metal, recoordination of the photodissociated arylisocyanide ligand unit can occur spontaneously on a millisecond time scale. This work provides insight into possible self-healing mechanisms counteracting unwanted photodegradation processes and seems furthermore relevant in the contexts of photoswitching and (photo)chemical information storage.

Sampling a Rare Protein Transition Using Quantum Annealing.

Simulating spontaneous structural rearrangements in macromolecules with classical molecular dynamics is an outstanding challenge. Conventional supercomputers can access time intervals of up to tens of μs, while many key events occur on exponentially longer time scales. Path sampling techniques have the advantage of focusing the computational power on barrier-crossing trajectories, but generating uncorrelated transition paths that explore diverse conformational regions remains a problem. We employ a hybrid path-sampling paradigm that addresses this issue by generating trial transition paths using a quantum annealing (QA) machine. We first employ a classical computer to perform an uncharted exploration of the conformational space. The data set generated in this exploration is then postprocessed using a path integral-based method to yield a coarse-grained network representation of the reactive kinetics. By resorting to a quantum annealer, quantum superposition can be exploited to encode all of the transition pathways in the initial quantum state, thus potentially solving the path exploration problem. Furthermore, each QA cycle yields a completely uncorrelated trial trajectory. We previously validated this scheme on a prototypically simple transition, which could be extensively characterized on a desktop computer. Here, we scale up in complexity and perform an all-atom simulation of a protein conformational transition that occurs on the millisecond time scale, obtaining results that match those of the Anton special-purpose supercomputer. Despite limitations due to the available quantum annealers, our study highlights how realistic biomolecular simulations provide potentially impactful new ground for applying, testing, and advancing quantum technologies.

Experimental method to determine the mode-I in-situ bond strength-toughness development during automated placement of uncured thermoset carbon/epoxy tows

In-situ bond strength toughness (IBST), commonly referred to as tow tackiness, is a first order property affecting the adherence quality and defect formation (e.g., wrinkles, folds) during automated tow placement (ATP) processing of uncured thermoset polymer matrix composite (PMC) tows. Tow-tow IBST develops over characteristic millisecond timescales (tc≤50ms) due to the rapid tow placement velocity of ∼1 m/s. In this paper, an experimental method is presented to determine millisecond timescale tow-tow mode-I IBST in terms of fracture mechanics-based traction-separation relationship. The test specimen consists of two tows bonded to rigid platens with a pre-crack between them to induce crack initiation. Experiments are performed using IM7-G/8552 carbon/epoxy prepregs for both long and short timescales at a constant debonding rate of 5 mm/s, contact pressure of 0.23 MPa, and bonding temperature of 40 °C. In addition, high-speed two-dimensional digital image correlation (2D-DIC) is used to image and measure the tow-tow interfacial deformation during debonding. The peak traction and apparent energy release rate are found to significantly decrease (about 60 %) at the short millisecond timescale contact hold times compared to longer (i.e., second) timescale.

Printable Block Molecular Assemblies with Controlled Exciton Dynamics.

Creating hierarchical molecular block heterostructures, with the control over size, shape, optical, and electronic properties of each nanostructured building block can help develop functional applications, such as information storage, nanowire spectrometry, and photonic computing. However, achieving precise control over the position of molecular assemblies, and the dynamics of excitons in each block, remains a challenge. In the present work, we demonstrate the first fabrication of molecular heterostructures with the control of exciton dynamics in each block. Additionally, these heterostructures are printable and can be precisely positioned using Direct Ink Writing-based (DIW) 3D printing technique, resulting in programmable patterns. Singlet excitons with emission lifetimes on nanosecond or microsecond timescales and triplet excitons with emission lifetimes on millisecond timescales appear simultaneously in different building blocks, with an efficient energy transfer process in the heterojunction. These organic materials also exhibit stimuli-responsive emission by changing the power or wavelength of the excitation laser. We foresee potential applications of these organic heterostructures in integrated photonics, where the versatility of fluorescence, phosphorescence, efficient energy transfer, printability, and stimulus sensitivity co-exist in a single nanowire. This article is protected by copyright. All rights reserved.

Limits on Optical Counterparts to the Repeating Fast Radio Burst 20180916B from High-speed Imaging with Gemini-North/‘Alopeke

We report on contemporaneous optical observations at ≈10 ms timescales from the fast radio burst (FRB) 20180916B of two repeat bursts (FRB 20201023 and FRB 20220908) taken with the ‘Alopeke camera on the Gemini-North telescope. These repeats have radio fluences of 2.8 and 3.5 Jy ms, respectively, approximately in the lower 50th percentile for fluence from this repeating burst. The ‘Alopeke data reveal no significant optical detections at the FRB position and we place 3σ upper limits to the optical fluences of <8.3 × 10−3 and <7.7 × 10−3 Jy ms after correcting for line-of-sight extinction. Together, these yield the most sensitive limits to the optical-to-radio fluence ratio of an FRB on these timescales with η ν < 3 × 10−3 by roughly an order of magnitude. These measurements rule out progenitor models where FRB 20180916B has a similar fluence ratio to optical pulsars, such as the Crab pulsar, or where optical emission is produced as inverse-Compton radiation in a pulsar magnetosphere or young supernova remnant. Our ongoing program with ‘Alopeke on Gemini-North will continue to monitor repeating FRBs, including FRB 20180916B, to search for optical counterparts on millisecond timescales.

Synaptotagmin 7 docks synaptic vesicles to support facilitation and Doc2α-triggered asynchronous release.

Despite decades of intense study, the molecular basis of asynchronous neurotransmitter release remains enigmatic. Synaptotagmin (syt) 7 and Doc2 have both been proposed as Ca2+ sensors that trigger this mode of exocytosis, but conflicting findings have led to controversy. Here, we demonstrate that at excitatory mouse hippocampal synapses, Doc2α is the major Ca2+ sensor for asynchronous release, while syt7 supports this process through activity-dependent docking of synaptic vesicles. In synapses lacking Doc2α, asynchronous release after single action potentials is strongly reduced, while deleting syt7 has no effect. However, in the absence of syt7, docked vesicles cannot be replenished on millisecond timescales. Consequently, both synchronous and asynchronous release depress from the second pulse onward during repetitive activity. By contrast, synapses lacking Doc2α have normal activity-dependent docking, but continue to exhibit decreased asynchronous release after multiple stimuli. Moreover, disruption of both Ca2+ sensors is non-additive. These findings result in a new model whereby syt7 drives activity-dependent docking, thus providing synaptic vesicles for synchronous (syt1) and asynchronous (Doc2 and other unidentified sensors) release during ongoing transmission.

Synaptotagmin 7 docks synaptic vesicles to support facilitation and Doc2α-triggered asynchronous release

Despite decades of intense study, the molecular basis of asynchronous neurotransmitter release remains enigmatic. Synaptotagmin (syt) 7 and Doc2 have both been proposed as Ca2+ sensors that trigger this mode of exocytosis, but conflicting findings have led to controversy. Here, we demonstrate that at excitatory mouse hippocampal synapses, Doc2α is the major Ca2+ sensor for asynchronous release, while syt7 supports this process through activity-dependent docking of synaptic vesicles. In synapses lacking Doc2α, asynchronous release after single action potentials is strongly reduced, while deleting syt7 has no effect. However, in the absence of syt7, docked vesicles cannot be replenished on millisecond timescales. Consequently, both synchronous and asynchronous release depress from the second pulse onward during repetitive activity. By contrast, synapses lacking Doc2α have normal activity-dependent docking, but continue to exhibit decreased asynchronous release after multiple stimuli. Moreover, disruption of both Ca2+ sensors is non-additive. These findings result in a new model whereby syt7 drives activity-dependent docking, thus providing synaptic vesicles for synchronous (syt1) and asynchronous (Doc2 and other unidentified sensors) release during ongoing transmission.

How nuclear receptors transition between active and inactive forms: An energetic perspective.

Nuclear receptors regulate transcriptional programs in response to the binding of natural and synthetic ligands. These ligands modulate the receptor by inducing dynamic changes in the ligand binding domain that shift the C-terminal helix (H12) between active and inactive conformations. Despite decades of study, many questions persist regarding the nature of the inactive state and how ligands shift receptors between different states. Here, we use molecular dynamics (MD) simulations to investigate the timescale and energetic landscape of the conformational transition between inactive and active forms of progesterone receptor (PR) bound to a partial agonist. We observe that the microsecond timescale is insufficient to observe any transitions; only at millisecond timescales achieved via accelerated MD simulations do we find the inactive PR switches to the active state. Energetic analysis reveals that both active and inactive PR states represent energy minima separated by a barrier that can be traversed. In contrast, little or no transition is observed between active and inactive states when an agonist or antagonist is bound, confirming that ligand identity plays a key role in defining the energy landscape of nuclear receptor conformations.

Resistive cooling of ions' center-of-mass energy in a Penning trap on millisecond time scales

Resistive cooling of ions' center-of-mass energy in a Penning trap on millisecond time scales

Interpreting pore-scale fluctuations: Predicting transport coefficients in multiphase flow through porous media using the Green–Kubo formulation—An experimental investigation

Flow fluctuations that are commonly associated with multiphase flow in porous media are studied using concepts from non-equilibrium thermodynamic and statistical mechanics. We investigate how the Green–Kubo formulation of the fluctuation dissipation theorem can be used to predict the transport coefficient from the two-phase extension of Darcy's law. Flow rate-time series data are recorded at the millisecond timescale using a novel experimental setup that allows for the determination of flow fluctuation statistics. By using Green–Kubo relations, a transport coefficient is predicted based on the integrated autocorrelation function. Notably, this coefficient aligned closely with the total effective phase mobility computed using Darcy's equation for multiphase flow, particularly in scenarios where a linear relationship between flow rate and pressure gradient was observed. Our results open a new field of coefficient explorations where microscale fluctuations during multiphase flow are directly linked to macroscale parameters.

Study of synchronous RF pulsing in dual frequency capacitively coupled plasma

Low-pressure multi-frequency capacitively coupled plasmas (CCPs) are used for numerous etch and deposition applications in the semiconductor industry. Pulsing of the radio-frequency (RF) sources enables control of neutral and charged species in the plasma on a millisecond timescale. The synchronous (i.e. simultaneous, in-phase) pulsing of both power sources in a dual frequency CCP is examined in this article. Due to the low gas pressure, modeling has been done using the electrostatic particle-in-cell/Monte Carlo collision method. The objective of this work is to investigate the sensitivity of the plasma properties to small changes in timing during synchronous pulsing of the two RF sources. It is demonstrated that small deviations in the on and off times of the two RF sources can lead to major changes in the plasma characteristics. This high sensitivity is of concern for process repeatability but can be utilized to enable better control of the dynamics of plasma-surface interaction. In the simulations, the pulsing parameters (on and off times and ramp rates) are varied and the temporal evolution of plasma characteristics such as electron density (ne ), species current at the electrode, and electron temperature are examined. It is demonstrated that if the low-frequency (LF) source is turned off a few μs before (or after) the high-frequency source, ne during the off-state is significantly higher (or lower) due to the frequency coupling effect. Similarly, turning on the LF source with a small delay results in a sharp increase in the plasma density when the RF sources are turned on.

Dynamic out-of-plane compression of paperboard — Influence of impact velocity on the surface

Processes that convert paperboard into finished products include, for example, printing, where the paperboard is subjected to rapid Z-directional (ZD) compression in the print nip. However, measuring and evaluating the relevant properties in the thickness direction of paperboard are not necessarily straightforward or easy. Measuring at relevant, millisecond deformation rates further complicates the problem. The aim of the present work is to elucidate some of the influences on the compressive stiffness. Both the initial material response and the overall compressibility of the paperboard is studied. In this project, the effect on the material response from the surface structure and the millisecond timescale recovery is explored.The method utilized is a machine called the Rapid ZD-tester. The device drops a probe in freefall on the substrate and records the probe position, thus acquiring the deformation of the substrate. The probe is also allowed to bounce several times on the surface for consecutive impacts before being lifted for the next drop. To investigate the time dependent stiffness behavior, the probe is dropped several times at the same XY position on the paperboard from different heights, thus achieving different impact velocities. The material response from drops and bounces combined allows study of the short-term recovery of the material. The material in the study is commercial paperboard. The paperboard samples are compared to material where the surface has been smoothed by grinding it. Our study shows that there is a non-permanent reduction in thickness and a stiffening per bounce of the probe, indicating a compaction that has not recovered in the millisecond timescale. Additionally, a higher impact velocity has an initial stiffening effect on the paperboard, and this is reduced by smoothing the surface.

Buckling mediated by mobile localized elastic excitations.

Experiments reveal that structural transitions in thin sheets are mediated by the passage of transient and stable mobile localized elastic excitations. These "crumples" or "d-cones" nucleate, propagate, interact, annihilate, and escape. Much of the dynamics occurs on millisecond time scales. Nucleation sites correspond to regions where generators of the ideal unstretched surface converge. Additional stable intermediate states illustrate two forms of quasistatic inter-crumple interaction through ridges or valleys. These interactions create pairs from which extended patterns may be constructed in larger specimens. The onset of localized transient deformation with increasing sheet size is correlated with a characteristic stable crumple size, whose measured scaling with thickness is consistent with prior theory and experiment for localized elastic features in thin sheets. We offer a new theoretical justification of this scaling.

From Milliseconds to Minutes: Melittin Self-Assembly from Concerted Non-Equilibrium Pressure-Jump and Equilibrium Relaxation Nuclear Magnetic Resonance.

Non-equilibrium kinetics techniques like pressure-jump nuclear magnetic resonance (NMR) are powerful in tracking changes in oligomeric populations and are not limited by relaxation rates for the time scales of exchange that can be probed. However, these techniques are less sensitive to minor, transient populations than are Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion experiments. We integrated non-equilibrium pressure-jump and equilibrium CPMG relaxation dispersion data to fully map the kinetic landscape of melittin tetramerization. While monomeric peptides weakly form dimers (Kd,D/M ≈ 26 mM) whose population never exceeds 1.6% at 288 K, dimers associate tightly to form stable tetrameric species (Kd,T/D ≈ 740 nM). Exchange between the monomer and dimer, along with exchange between the dimer and tetramer, occurs on the millisecond time scale. The NMR approach developed herein can be readily applied to studying the folding and misfolding of a wide range of oligomeric assemblies.

Quantifying a light-induced energetic change in bacteriorhodopsin by force spectroscopy

Ligand-induced conformational changes are critical to the function of many membrane proteins and arise from numerous intramolecular interactions. In the photocycle of the model membrane protein bacteriorhodopsin (bR), absorption of a photon by retinal triggers a conformational cascade that results in pumping a proton across the cell membrane. While decades of spectroscopy and structural studies have probed this photocycle in intricate detail, changes in intramolecular energetics that underlie protein motions have remained elusive to experimental quantification. Here, we measured these energetics on the millisecond time scale using atomic-force-microscopy-based single-molecule force spectroscopy. Precisely, timed light pulses triggered the bR photocycle while we measured the equilibrium unfolding and refolding of the terminal 8-amino-acid region of bR's G-helix. These dynamics changed when the EF-helix pair moved ~9 Å away from this end of the G helix during the "open" portion of bR's photocycle. In ~60% of the data, we observed abrupt light-induced destabilization of 3.4 ± 0.3 kcal/mol, lasting 38 ± 3 ms. The kinetics and pH-dependence of this destabilization were consistent with prior measurements of bR's open phase. The frequency of light-induced destabilization increased with the duration of illumination and was dramatically reduced in the triple mutant (D96G/F171C/F219L) thought to trap bR in its open phase. In the other ~40% of the data, photoexcitation unexpectedly stabilized a longer-lived putative misfolded state. Through this work, we establish a general single-molecule force spectroscopy approach for measuring ligand-induced energetics and lifetimes in membrane proteins.

On the Two Approaches to Incorporate Wave‐Particle Resonant Effects Into Global Test Particle Simulations

AbstractEnergetic electron dynamics in the Earth's radiation belts and near‐Earth plasma sheet are controlled by multiple processes operating on very different time scales: from storm‐time magnetic field reconfiguration on a timescale of hours to individual resonant wave‐particle interactions on a timescale of milliseconds. The most advanced models for such dynamics either include test particle simulations in electromagnetic fields from global magnetospheric models, or those that solve the Fokker‐Plank equation for long‐term effects of wave‐particle resonant interactions. The most prospective method, however, would be to combine these two classes of models, to allow the inclusion of resonant electron scattering into simulations of electron motion in global magnetospheric fields. However, there are still significant outstanding challenges that remain regarding how to incorporate the long term effects of wave‐particle interactions in test‐particle simulations. In this paper, we describe in details two approaches that incorporate electron scattering in test particle simulations: stochastic differential equation (SDE) approach and the mapping technique. Both approaches assume that wave‐particle interactions can be described as a probabilistic process that changes electron energy, pitch‐angle, and thus modifies the test particle dynamics. To compare these approaches, we model electron resonant interactions with field‐aligned whistler‐mode waves in dipole magnetic fields. This comparison shows advantages of the mapping technique in simulating the nonlinear resonant effects, but also underlines that more significant computational resources are needed for this technique in comparison with the SDE approach. We further discuss applications of both approaches in improving existing models of energetic electron dynamics.

Experimental Evidence for Millisecond-Timescale Structural Evolution Following the Microsecond-Timescale Folding of a Small Protein.

Prior work has shown that small proteins can fold (i.e., convert from unstructured to structured states) within 10  μs. Here we use time-resolved solid state nuclear magnetic resonance (ssNMR) methods to show that full folding of the 35-residue villin headpiece subdomain (HP35) requires a slow annealing process that has not been previously detected. ^{13}C ssNMR spectra of frozen HP35 solutions, acquired with a variable time τ_{e} at 30 °C after rapid cooling from 95 °C and before rapid freezing, show changes on the 3-10ms timescale, attributable to slow rearrangements of protein sidechains during τ_{e}.

Fast quantum interference of a nanoparticle via optical potential control

We introduce and theoretically analyze a scheme to prepare and detect non-Gaussian quantum states of an optically levitated particle via the interaction with light pulses that generate cubic and inverted potentials. We show that this approach allows to operate on sufficiently short time- and length scales to beat decoherence in a regime accessible in state-of-the-art experiments. Specifically, we predict the observation of single-particle interference of a nanoparticle with a mass above 108 atomic mass units delocalized by several nanometers, on timescales of milliseconds. The proposed experiment uses only optical and electrostatic control, and can be performed at about 10-10 mbar and at room temperature. We discuss the prospect of this method for coherently splitting the wavepacket of massive dielectric objects without using either projective measurements or an internal level structure.

Numerical ellipsometry: Artificial intelligence for real-time, in situ absorbing film process control

Ellipsometry is a material analytical method in which the desired parameters, for example, film thickness and index of refraction, are related to the instrument measurements through Maxwell’s equations, light wavelength, and measurement geometry. Consequently, obtaining the desired parameters has required solving the model equations using a wide variety of methods. A commonly used method is least squares curve fitting, frequently the Levenberg–Marquardt method. This numerical method depends upon not only the model but also the initial estimates of solution, the possible interference of local minima, and the algorithm stopping conditions. Being iterative, it also takes nonzero time. The work here demonstrates the use of artificial intelligence in the form of a multilayer perceptron artificial neural network to avoid these problems and find solutions in the millisecond time scale. This noniterative, stable, and fast performance lends itself to real-time, in situ monitoring of thin film growth. Examples for thin (up to 30 nm) films will be given using a multilayer perceptron configuration consisting of four input and four output neurons with two hidden layers of 40 neurons each. Solutions are predicted by the artificial neural network at each wavelength independently and do not rely on fitting functions which express a relationship between optical properties and wavelength.