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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Effects of mosaic crystal instrument functions on x-ray Thomson scattering diagnostics

Mosaic crystals, with their high integrated reflectivities, are widely employed in spectrometers used to diagnose high energy density systems. X-ray Thomson scattering (XRTS) has emerged as a powerful diagnostic tool of these systems, providing in principle direct access to important properties such as the temperature via detailed balance. However, the measured XRTS spectrum is broadened by the spectrometer instrument function (IF), and without careful consideration of the IF one risks misdiagnosing system conditions. Here, we consider in detail the IF of 40 and 100 μm mosaic Highly Annealed Pyrolytic Graphite crystals, and how the broadening varies across the spectrometer in an energy range of 6.7–8.6 keV. Notably, we find a strong asymmetry in the shape of the IF toward higher energies. As an example, we consider the effect of the asymmetry in the IF on the temperature inferred via XRTS for simulated 80 eV CH plasmas and find that the temperature can be overestimated if an approximate symmetric IF is used. We, therefore, expect a detailed consideration of the full IF will have an important impact on system properties inferred via XRTS in both forward modeling and model-free approaches.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Comparative determinant quantum Monte Carlo study of the acoustic and optical variants of the Su-Schrieffer-Heeger model

We compare the acoustic Su–Schrieffer–Heeger (SSH) model with two of its optical variants where the phonons are defined on either on the sites or bonds of the system. First, we discuss how to make fair comparisons between these models in any dimension by ensuring their dimensionless coupling λ and relevant phonon energies are the same. We then use determinant quantum Monte Carlo to perform nonperturbative and sign-problem-free simulations of all three models on one-dimensional chains at and away from half-filling. By comparing the results obtained from each model, we demonstrate that the optical and acoustic models produce near identical results within error bars for suitably chosen phonon energies and λ at half-filling. In contrast, the bond model has quantitatively different behavior due to its coupling to the q = 0 phonon mode. These differences also manifest in the total length of the chain, which shrinks for the bond model but not for the acoustic and optical models when λ ≠ 0. Furthermore, our results have important implications for quantum Monte Carlo modeling of SSH-like interactions, where these models are sometimes regarded as being interchangeable.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Large-scale atomistic model construction of subbituminous and bituminous coals for solvent extraction simulations with reactive molecular dynamics

Large-scale atomistic models for complex polycyclic aromatic hydrocarbon systems help understand the chemical properties and behaviors of complex feedstocks such as coal or petroleum. However, the development and utilization of large-scale models remain limited due to the difficulty in achieving the varied structural characteristics necessary to capture stochastic nature of these feedstocks. Here we demonstrate a systematic workflow to construct stochastic molecular systems from a broad analytical suite: high-resolution transmission electron microscopy (HRTEM), carbon-13 nuclear magnetic resonance spectroscopy ( 13 C NMR), laser desorption ionization mass spectroscopy (LDI-MS), and elemental analysis. We present a model construction and analysis utility of a new Python-based module. We selected one subbituminous and three high-volatile bituminous coals to construct large-scale models (~40,000 atoms). The constructed models were utilized to examine the affinity for solvent extraction (naphthalene or tetralin) and the effect of structural properties (e.g., aromatic cluster size, functional groups, and cross-linking) in reactive molecular dynamics simulations. Complex chemical reactions were monitored with bond order transitions, intermediates formation, and mass distributions. Reactive molecular dynamics simulations suggest a plausible chemical extraction process and products for the complex fossil feedstocks. The results indicated that radical formations with bond breaking of bridging oxygens and carbons were required at high temperatures to facilitate hydrogeneration and extraction of gas molecules from radical-free molecules. We observed that aliphatic chains of tetralin were easily decomposed and combined with radicals to form small size of molecules with aryl bonding, mainly increasing molecules in the 500–1000 Da, while naphthalene had little impact on chemical extraction process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Adversarial autoencoder ensemble for fast and probabilistic reconstructions of few-shot photon correlation functions for solid-state quantum emitters

Second-order photon correlation measurements [g (2) (τ) functions] are widely used to classify single-photon emission purity in quantum emitters or to measure the multiexciton quantum yield of emitters that can simultaneously host multiple excitations – such as quantum dots – by evaluating the value of g (2) (τ = 0). Accumulating enough photons to accurately calculate this value is time consuming and could be accelerated by fitting of few-shot photon correlations. Here, we develop an uncertainty-aware, deep adversarial autoencoder ensemble (AAE) that reconstructs noise-free g (2) (τ) functions from noise-dominated, few-shot inputs. The model is trained with simulated g (2) (τ) functions that are facilely generated by Poisson sampling time bins. The AAE reconstructions are performed orders-of-magnitude faster, with reconstruction errors and estimates of g (2) (τ = 0) that are lower in variance and similar in accuracy compared to Maximum likelihood estimation and Levenberg-Marquardt least-squares fitting approaches, for simulated and experimentally measured few-shot g (2) (τ) functions (~100 two-photon events) of InP/ZnS/ZnSe and CdS/CdSe/CdS quantum dots. The deep-ensemble model comprises eight individual autoencoders, allowing for probabilistic reconstructions of noise-free g (2) (τ) functions, and we show that the predicted variance scales inversely with number of shots, with comparable uncertainties to computationally intensive Markov chain Monte Carlo sampling. Furthermore, this work demonstrates the advantage of machine learning models to perform uncertainty-aware, fast, and accurate reconstructions of simple Poisson-distributed photon correlation functions, allowing for on-the-fly reconstructions and accelerated materials characterization of solid-state quantum emitters.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Differential multi-probe thermal transport measurements of multi-walled carbon nanotubes grown by chemical vapor deposition

Carbon nanotubes (CNTs) are quasi-one dimensional nanostructures that display both high thermal conductivity for potential thermal management applications and intriguing low-dimensional phonon transport phenomena. In comparison to the advances made in the theoretical calculation of the lattice thermal conductivity of CNTs, thermal transport measurements of CNTs have been limited by either the poor temperature sensitivity of Raman thermometry technique or the presence of contact thermal resistance errors in sensitive two-probe resistance thermometry measurements. Here we report advances in a multi-probe measurement of the intrinsic thermal conductivity of individual multi-walled CNT samples that are transferred from the growth substrate onto the measurement device. The sample-thermometer thermal interface resistance is directly measured by this multi-probe method and used to model the temperature distribution along the contacted sample segment. The detailed temperature profile helps to eliminate the contact thermal resistance error in the obtained thermal conductivity of the suspended sample segment. A differential electro-thermal bridge measurement method is established to enhance the signal-to-noise ratio and reduce the measurement uncertainty by over 40%. The obtained thermal resistances of multiple suspended segments of the same MWCNT samples increase nearly linearly with increasing length, revealing diffusive phonon transport as a result of phonon-defect scattering in these MWCNT samples. The measured thermal conductivity increases with temperature and reaches up to 390 ± 20 W m –1 K –1 at room temperature for a 9-walled MWCNT. In conclusion, theoretical analysis of the measurement results suggests submicron phonon mean free paths due to extrinsic phonon scattering by extended defects such as grain boundaries. The obtained thermal conductivity is decreased by a factor of 3 upon electron beam damage and surface contamination of the CNT sample.

42 ENGINEERING↗
DOE OSTI2021

Polarization Effects in Water-Mediated Selective Cation Transport across a Narrow Transmembrane Channel

We report despite the progress in modeling complex molecular systems of ever-increasing complexity, a quantitatively accurate computational treatment of ion permeation through narrow membrane channels remains challenging. An important factor to reach this goal is induced electronic polarization, which is likely to impact the permeation rate of small ions through narrow molecular pores. In this work, we extended the recently developed polarizable force field based on the classical Drude oscillators to assess the role of induced polarization effects on the energetics of sodium and potassium ion transport across the gramicidin A (gA) ion channel. The inclusion of induced polarization lowers barriers present in 1D potential of mean force (PMF) for cation permeation by ~50% compared to those obtained with the additive force field. Conductance properties calculated with 1D PMFs from Drude simulations are in better agreement with experimental results. Polarization of single-file water molecules and protein atoms forming the narrow pore has a direct impact on the free-energy barriers and cation-specific solid-state NMR chemical shifts. Sensitivity analysis indicates that small changes to water–channel interactions can alter the free energy barrier for ion permeation. These results, illustrating polarization effects present in the complex electrostatic environment of the gA channel, have broad implications for revising proposed mechanisms of ion permeation and selectivity in a variety of ion channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Molecular Mass Growth Processes to Polycyclic Aromatic Hydrocarbons through Radical–Radical Reactions Exploiting Photoionization Reflectron Time-of-Flight Mass Spectrometry

Polycyclic aromatic hydrocarbons (PAHs) represent critical building blocks in molecular mass growth processes to carbonaceous nanoparticles, referred to as interstellar and circumstellar grains along with soot particles in astrophysical environments and combustion systems, respectively. Recent advancements on elucidating elementary steps to PAHs have utilized reactions of aromatic radicals, resonantly stabilized free radicals, and aliphatic radicals with closed shell hydrocarbons. However, the role of radical–radical reactions (RRRs) leading to PAHs has remained largely unexplored on the molecular level due to preceding experimental challenges in producing sufficiently high number densities of radical reactants for isomer-selective detection of products from bimolecular and termolecular reactions. This Account offers the latest developments in our knowledge on the mechanisms and pathways to PAHs via RRRs probed in a chemical microreactor at temperatures as high as 1600 K. Product preservation in a molecular beam coupled with synchrotron vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry and photoelectron photoion coincidence spectroscopy enabled isomer-selective detection of PAHs of up to three rings by their photoionization efficiency curves, which were fit with a linear combination of reference curves for identification. Experiments were combined with computational fluid dynamics modeling of the physicochemical processes in the microreactor, as well as high-level electronic structure calculations to reveal the reaction pathways of each system. Six distinct reaction mechanisms were discovered in this work: propargyl addition─benzannulation (PABA), methyl addition─ring expansion (MARE), cyclopentadienyl addition─naphthylization (CPAN), fulvenallenyl addition─cyclization─aromatization (FACA), benzyl addition─aromatization (BAA), and phenyl addition─pentacyclization (PAP). By systematically varying the number of carbon atoms in the radical reactants, molecular mass growth processes involving reactions between radicals with odd numbers of carbon atoms access aromatics carrying one, two, or three six-membered rings, whereas reactions between even- and odd-carbon-numbered radicals produce aromatics combining five- and six-membered rings. Our investigations reveal unconventional cycloadditions on excited state triplet surfaces, additions of radicals to low spin density carbon-centered radicals, spiroaromatic and fulvene-type intermediates, and highly strained bicyclic reaction intermediates, challenging current perceptions of PAH molecular mass growth processes. All of the listed mechanisms, except for FACA, feature endoergic reactions or barriers which lie above the separated reactants and therefore might be central to circumstellar environments of carbon-rich stars and planetary nebulae as their descendants, but they play no role in the gas phase of cold molecular clouds where temperatures as low as 10 K dominate. Altogether, this work provides detailed reaction mechanisms of PAH growth processes, advancing our knowledge of the chemistry of carbonaceous matter in the universe.

Addition reactions↗
DOE OSTI2022

Critical role of magnetic moments in heavy-fermion materials: Revisiting mysteries of SmB 6

Heavy-fermion family exhibits fascinating and often puzzling properties due to the presence of open-shell f ions and the complexity of the associated charge, orbital, and spin degrees of freedom. SmB 6 is a prototypical heavy-fermion compound that is electrically insulating but yet it displays quantum oscillations, which are a telltale signature of the metallic state. Adding to the enigma is the possibility that SmB 6 is a topological Kondo insulator. Here, by treating the spin degree of freedom on an equal footing with other degrees of freedom using the parameter-free strongly-constrained and appropriately-normed (SCAN) density functional, we explore the ground-state electronic structure of SmB6. A number of competing magnetic phases lying very closely in energy are found, indicating the key role of spin fluctuations in the material. The computed band structure, crystal-field splittings in the f-electron complex, the heavy effective electron mass at the Fermi energy, and the large specific heat are all in good agreement with the corresponding experimental results. In particular, our predicted FS explains the experimentally observed bulk quantum oscillations as well as the low electrical conductivity of SmB 6 . The topological Kondo state of SmB6 is shown to be robust regardless of its magnetic configuration. The excellent performance of SCAN in heavy-fermion systems is explained in terms of its ability to treat self-interaction errors and symmetry breaking within the framework of the density functional theory. Our study provides a new approach for modeling heavy-fermion materials

36 MATERIALS SCIENCE↗
DOE OSTI2023

A user-friendly plug-and-play cyclic olefin copolymer-based microfluidic chip for room-temperature, fixed-target serial crystallography

Over the past two decades, serial X-ray crystallography has enabled the structure determination of a wide range of proteins. With the advent of X-ray free-electron lasers (XFELs), ever-smaller crystals have yielded high-resolution diffraction and structure determination. A crucial need to continue advancement is the efficient delivery of fragile and micrometre-sized crystals to the X-ray beam intersection. This paper presents an improved design of an all-polymer microfluidic `chip' for room-temperature fixed-target serial crystallography that can be tailored to broadly meet the needs of users at either synchrotron or XFEL light sources. The chips are designed to be customized around different types of crystals and offer users a friendly, quick, convenient, ultra-low-cost and robust sample-delivery platform. Compared with the previous iteration of the chip [Gilbile et al. (2021), Lab Chip , 21 , 4831–4845], the new design eliminates cleanroom fabrication. It has a larger imaging area to volume, while maintaining crystal hydration stability for both in situ crystallization or direct crystal slurry loading. Crystals of two model proteins, lysozyme and thaumatin, were used to validate the effectiveness of the design at both synchrotron (lysozyme and thaumatin) and XFEL (lysozyme only) facilities, yielding complete data sets with resolutions of 1.42, 1.48 and 1.70 Å, respectively. Overall, the improved chip design, ease of fabrication and high modifiability create a powerful, all-around sample-delivery tool that structural biologists can quickly adopt, especially in cases of limited sample volume and small, fragile crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Impact of lanthanide ion complexation and temperature on the chemical reactivity of N , N , N ', N '-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation

The impact of trivalent lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the n-dodecane radical cation (RH˙+) has been measured by electron pulse radiolysis and evaluated by quantum mechanical calculations. Additionally, Arrhenius parameters were determined for the reaction of the non-complexed TODGA ligand with the RH˙ + from 10–40 °C, giving the activation energy (E a = 17.43 ± 1.64 kJ mol –1 ) and pre-exponential factor (A = (2.36 ± 0.05) × 10 13 M –1 s –1 ). The complexation of Nd(III), Gd(III), and Yb(III) ions by TODGA yielded [LnIII(TODGA)3(NO3)3] complexes that exhibited significantly increased reactivity (up to 9.3× faster) with the RH˙ + , relative to the non-complexed ligand: k([Ln III (TODGA) 3 (NO 3 ) 3 ] + RH˙ + ) = (8.99 ± 0.93) × 10 10 , (2.88 ± 0.40) × 10 10 , and (1.53 ± 0.34) × 10 10 M –1 s –1 , for Nd(III), Gd(III), and Yb(III) ions, respectively. The rate coefficient enhancement measured for these complexes exhibited a dependence on atomic number, decreasing as the lanthanide series was traversed. Preliminary reaction free energy calculations—based on a model [Ln III (TOGDA)] 3+ complex system—indicate that both electron/hole and proton transfer reactions are energetically unfavorable for complexed TODGA. Furthermore, complementary average local ionization energy calculations showed that the most reactive region of model N,N,N',N'-tetraethyl diglycolamide (TEDGA) complexes, [Ln III (TEGDA) 3 (NO 3 ) 3 ], toward electrophilic attack is for the coordinated nitrate (NO 3 – ) counter anions. Furthermore, it is possible that radical reactions with the complexed NO 3 – counter anions dominate the differences in rates seen for the [Ln III (TODGA) 3 (NO 3 ) 3 ] complexes, and are likely responsible for the reported radioprotection in the presence of TODGA complexes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Axial magnetic flux amplification in Hall-magnetohydrodynamic simulations of externally magnetized z-pinches

It is shown that externally magnetized gas-puff z-pinches under compression can exhibit robust axial flux amplification under suitable axial boundary conditions. This effect relies upon the Hall term in the generalized Ohm's law to generate azimuthal currents in the presence of a driving axial electric field. Under dynamic compression, the total current tends to flow in a mostly force-free boundary layer, separating the predominately azimuthal field outside the layer and the predominately axial field inside the layer. The effect only appears to occur if the axial boundaries allow for outflow or absorption of electromagnetic energy. The effect is mitigated by imposing either periodic or conducting axial boundary conditions. A semi-analytic equilibrium analysis agrees with steady-state solutions of the time-dependent electron-magnetohydrodynamic equations and provides an estimate of the scaling of the boundary layer as well as suggesting a scenario for the formation of the boundary layer. When operative, the effect can significantly impede plasma compression due to the increase in axial flux that diffuses into the pre-compressed plasma or through the presence of conductors that inhibit movement of the generated axial flux. Several facilities have noted unusual implosion behavior in z-pinch experiments with applied axial fields that does not appear to be explainable within the standard magnetohydrodynamic model. In conclusion, it is suggested that these experiments can be explained by the axial flux amplification and concentration effect

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Superconductivity from Luttinger surfaces: Emergent Sachdev-Ye-Kitaev physics with infinite-body interactions

The pairing of two electrons on a Fermi surface due to an infinitesimal attraction between them always results in a superconducting instability at zero temperature (T = 0). The equivalent question of pairing instability on a Luttinger surface (LS)—190a contour of zeros of the propagator—instead leads to a quantum critical point (QCP) that separates a non-Fermi liquid and superconductor. A surprising and little understood aspect of pair fluctuations at this QCP is that their thermodynamics maps to that of the Sachdev-Ye-Kitaev (SYK) model in the strong coupling limit. Here, we offer a simple justification for this mapping by demonstrating that (i) LS models share the reparametrization symmetry of the q → ∞ SYK model with q-body interactions close to the LS, and (ii) the enforcement of gauge invariance results in a $\frac{1}{√τ}$ (τ ~ T -1 ) behavior of the fluctuation propagator near the QCP, as is the feature of SYK conformal Green functions, but leaves the overall form of the free energy map robust.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Plasma Mirrors For High Power Lasers: A new approach for high repetition rates combined with realistic PIC simulations

We describe a research program to develop high quality plasma mirrors for use with high repetition rate, high power laser facilities to greatly facilitate experiments in high energy density physics, particularly when using solid density targets. A system delivering ultrathin, free standing liquid crystal films that could handle PW class laser pulses was developed that preserved the laser beam image quality and improved pulse contrast by over two orders of magnitude. The pulse contrast improvement was measured using a high dynamic range cross-correlation. The system operated at a repetition rate of several PMs formed in situ per minute. Extension to 1 Hz repetition rates should be possible. As a practical application, a PM system was used to separate laser accelerated electrons from the ultrashort pulse drive laser so that the electron beam emittance could be directly measured. The 20 nm thick PMs did not contribute significantly to emittance degradation. It was also demonstrated that the films could operate in the difficult plasma and laser environment present for GeV laser based electron acceleration. PM operation is still not well understood and much work with PMs is done empirically. Accordingly, we also demonstrated a particle-in-cell based simulation technique that would model PM operation, tracking the PM operation from cold, neutral atoms to a hot dense plasma by accounting for multiphoton ionization, plasma collisionality, and the dynamically changing index of refraction. Simulations in 3D were compared to a 2D based approach that was comparable. Finally, we developed a simpler model that can predict the intensity at which a plasma mirror will have its peak reflectivity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

The Origin of Power-law Spectra in Relativistic Magnetic Reconnection

Abstract Magnetic reconnection is often invoked as a source of high-energy particles, and in relativistic astrophysical systems it is regarded as a prime candidate for powering fast and bright flares. We present a novel analytical model—supported and benchmarked with large-scale three-dimensional kinetic particle-in-cell simulations in electron–positron plasmas—that elucidates the physics governing the generation of power-law energy spectra in relativistic reconnection. Particles with Lorentz factorγ≳ 3σ(here,σis the magnetization) gain most of their energy in the inflow region, while meandering between the two sides of the reconnection layer. Their acceleration time is t acc ∼ γ η rec − 1 ω c − 1 ≃ 20 γ ω c − 1 , whereη rec ≃ 0.06 is the inflow speed in units of the speed of light andω c =eB 0 /mcis the gyrofrequency in the upstream magnetic field. They leave the region of active energization aftert esc , when they get captured by one of the outflowing flux ropes of reconnected plasma. We directly measuret esc in our simulations and find thatt esc ∼t acc forσ≳ few. This leads to a universal (i.e.,σ-independent) power-law spectrum dN free / d γ ∝ γ − 1 for the particles undergoing active acceleration, and dN / d γ ∝ γ − 2 for the overall particle population. Our results help to shed light on the ubiquitous presence of power-law particle and photon spectra in astrophysical nonthermal sources.

Astronomy & Astrophysics↗
DOE OSTI2025

Measurements of the thermal Sunyaev-Zel’dovich effect with ACT and DESI luminous red galaxies

Cosmic Microwave Background (CMB) photons scatter off the free-electron gas in galaxies and clusters, allowing us to use the CMB as a backlight to probe the gas in and around low-redshift galaxies. The thermal Sunyaev-Zel’dovich effect, sourced by hot electrons in high-density environments, measures the thermal pressure of the target objects, shedding light on halo thermodynamics and galaxy formation, and providing a path toward understanding the baryon distribution around cosmic structures. We use a combination of high-resolution CMB maps from the Atacama Cosmology Telescope and photometric luminous red galaxy catalogs from the Dark Energy Spectroscopic Instrument to measure the thermal Sunyaev-Zel’dovich signal in four redshift bins from 𝑧 = 0.4 to 𝑧 = 1.2, with a combined detection significance of 19⁢𝜎 when stacking on the fiducial CMB Compton-𝑦 map. We discuss possible sources of contamination, finding that residual dust emission associated with the target galaxies is important and limits current analyses. We discuss several mitigation strategies and quantify the residual modeling uncertainty. Furthermore, this work complements closely related measurements of the kinematic Sunyaev-Zel’dovich and weak lensing of the same galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Valley splittings in Si/SiGe quantum dots with a germanium spike in the silicon well

Silicon-germanium heterostructures have successfully hosted quantum dot qubits, but the intrinsic near-degeneracy of the two lowest valley states poses an obstacle to high-fidelity quantum computing. Here we present a modification to the Si/SiGe heterostructure by the inclusion of a spike in germanium concentration within the quantum well in order to increase the valley splitting. The heterostructure is grown by chemical vapor deposition and magnetospectroscopy is performed on gate-defined quantum dots to measure the excited state spectrum. We demonstrate a large and widely tunable valley splitting as a function of applied vertical electric field and lateral dot confinement. We further investigate the role of the germanium spike by means of tight-binding simulations in single-electron dots and show a robust doubling of the valley splitting when the spike is present, as compared to a standard (spike-free) heterostructure. This doubling effect is nearly independent of the electric field, germanium content of the spike, and spike location. This experimental evidence of a stable, tunable quantum dot, despite a drastic change to the heterostructure, provides a foundation for future heterostructure modifications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Anti-polyelectrolyte and polyelectrolyte effects on conformations of polyzwitterionic chains in dilute aqueous solutions

Abstract Polyzwitterions (PZs) are considered as model synthetic analogs of intrinsically disordered proteins. Based on this analogy, PZs in dilute aqueous solutions are expected to attain either globular (i.e. molten, compact) or random coil conformations. Addition of salt is expected to open these conformations. To the best of our knowledge, these hypotheses about conformations of PZs have never been verified. In this study, we test these hypotheses by studying effects of added salt [potassium bromide (KBr)] on gyration and hydrodynamic radii of poly(sulfobetaine methacrylate) in dilute aqueous solutions using dynamic light scattering and small-angle X-ray scattering, respectively. Effects of zwitteration are revealed by direct comparisons of the PZs with the polymers of the same backbone but containing (1) no explicit charges on side groups such as poly(2-dimethylaminoethyl methacrylate)s and (2) explicit cationic side groups with tertiary amino bromide pendants. Zeta-potential measurements, transmission electron microscopy, and ab initio molecular dynamics simulations reveal that the PZs acquire net positive charge in near salt-free conditions due to protonation but retain coiled conformations. Added KBr leads to nonmonotonic changes exhibiting an increase followed by a decrease in radius of gyration (and hydrodynamic radius), which are called antipolyelectrolyte and polyelectrolyte effects, respectively. Charge regulation and screening of charge–charge interactions are discussed in relation to the antipolyelectrolyte and polyelectrolyte effects, respectively, which highlight the importance of salt in affecting net charge and conformations of PZs.

36 MATERIALS SCIENCE↗