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At least 73 records · Page 4

Parsed synthesis of pyocyanin via co-culture enables context-dependent intercellular redox communication

Abstract Background Microbial co-cultures and consortia are of interest in cell-based molecular production and even as “smart” therapeutics in that one can take advantage of division of labor and specialization to expand both the range of available functions and mechanisms for control. The development of tools that enable coordination and modulation of consortia will be crucial for future application of multi-population cultures. In particular, these systems would benefit from an expanded toolset that enables orthogonal inter-strain communication. Results We created a co-culture for the synthesis of a redox-active phenazine signaling molecule, pyocyanin (PYO), by dividing its synthesis into the generation of its intermediate, phenazine carboxylic acid (PCA) from the first strain, followed by consumption of PCA and generation of PYO in a second strain. Interestingly, both PCA and PYO can be used to actuate gene expression in cells engineered with the soxRS oxidative stress regulon, although importantly this signaling activity was found to depend on growth media. That is, like other signaling motifs in bacterial systems, the signaling activity is context dependent. We then used this co-culture’s phenazine signals in a tri-culture to modulate gene expression and production of three model products: quorum sensing molecule autoinducer-1 and two fluorescent marker proteins, eGFP and DsRed. We also showed how these redox-based signals could be intermingled with other quorum-sensing (QS) signals which are more commonly used in synthetic biology, to control complex behaviors. To provide control over product synthesis in the tri-cultures, we also showed how a QS-induced growth control module could guide metabolic flux in one population and at the same time guide overall tri-culture function. Specifically, we showed that phenazine signal recognition, enabled through the oxidative stress response regulon soxRS, was dependent on media composition such that signal propagation within our parsed synthetic system could guide different desired outcomes based on the prevailing environment. In doing so, we expanded the range of signaling molecules available for coordination and the modes by which they can be utilized to influence overall function of a multi-population culture. Conclusions Our results show that redox-based signaling can be intermingled with other quorum sensing signaling in ways that enable user-defined control of microbial consortia yielding various outcomes defined by culture medium. Further, we demonstrated the utility of our previously designed growth control module in influencing signal propagation and metabolic activity is unimpeded by orthogonal redox-based signaling. By exploring novel multi-modal strategies for guiding communication and consortia outcome, the concepts introduced here may prove to be useful for coordination of multiple populations within complex microbial systems.

Chun, Kayla↗

Advances in Machine and Deep Learning for Modeling and Real-time Detection of Multi-Messenger Sources

We live in momentous times. The science community is empowered with an arsenal of cosmic messengers to study the universe in unprecedented detail. Gravitational waves, electromagnetic waves, neutrinos, and cosmic rays cover a wide range of wavelengths and timescales. Combining and processing these datasets that vary in volume, speed, and dimensionality requires new modes of instrument coordination, funding, and international collaboration with a specialized human and technological infrastructure. In tandem with the advent of large-scale scientific facilities, the last decade has experienced an unprecedented transformation in computing and signal-processing algorithms. The combination of graphics processing units, deep learning, and the availability of open source, high-quality datasets has powered the rise of artificial intelligence. This digital revolution now powers a multibillion dollar industry, with far-reaching implications in technology and society. In this chapter, we describe pioneering efforts to adapt artificial intelligence algorithms to address computational grand challenges in multi-messenger astrophysics. We review the rapid evolution of these disruptive algorithms, from the first class of algorithms introduced in early 2017 to the sophisticated algorithms that now incorporate domain expertise in their architectural design and optimization schemes. We discuss the importance of scientific visualization and extreme-scale computing in reducing time-to-insight and obtaining new knowledge from the interplay between models and data.

Artificial Intelligence↗

Collective coordinate fix in the path integral

Collective coordinates are frequently employed in path integrals to manage divergences caused by fluctuations around saddle points that align with classical symmetries. These coordinates parametrize a manifold of zero modes and more broadly provide judicious coordinates on the space of fields. However, changing from local coordinates around a saddle point to more global collective coordinates is remarkably subtle. The main complication is that the mapping from local coordinates to collective coordinates is generically multivalued. Consequently one is forced to either restrict the domain of path integral in a delicate way, or otherwise correct for the multivaluedness by dividing the path integral by certain intersection numbers. We provide a careful treatment of how to fix collective coordinates while accounting for these intersection numbers, and then demonstrate the importance of the fix for free theories. We also provide a detailed study of the fix for interacting theories and show that the contributions of higher intersections to the path integral can be nonperturbatively suppressed. Using a variety of examples ranging from single-particle quantum mechanics to quantum field theory, we explain and resolve various pitfalls in the implementation of collective coordinates. Published by the American Physical Society 2024

Bhattacharya, Arindam (ORCID:0000000244578926)↗

Electrolyte Solvation and Ionic Association: Part IX. Structures and Raman Spectroscopic Characterization of LiFSI Solvates

The bis(fluorosulfonyl)imide anion N(SO 2 F) 2 ⁻ (i.e., FSI⁻) (also referred to as bis(fluorosulfonyl)amide (i.e., FSA-) and imidodi(sulphuryl fluoride)) has attracted tremendous interest in recent years for its utility in both lithium salts and ionic liquids for battery electrolyte applications. To facilitate the understanding of the characteristics of this anion, crystal structures are reported here for the uncoordinated anion in LiFSI-based solvates with cryptand CRYPT-222 and tetraglyme (G4). These crystalline solvates were analyzed by Raman spectroscopy to aid in assigning the Raman bands to the modes of ion coordination found in liquid electrolytes. These structures, as well as a thorough review of other relevant crystallographic data, provide insights into the rather remarkable properties of the FSI- anion with regard to solvate formation and electrolyte properties.

25 ENERGY STORAGE↗

Microscopic Mechanisms of Glasslike Lattice Thermal Transport in Cubic Cu 12 Sb 4 S 13 Tetrahedrites

Materials based on cubic tetrahedrites (Cu 12 Sb 4 S 13 ) are useful thermoelectrics with unusual thermal and electrical transport properties, such as very low and nearly temperature-independent lattice thermal conductivity (κ L ). We explain the microscopic origin of the glasslike κ L in Cu 12 Sb 4 S 13 by explicitly treating anharmonicity up to quartic terms for both phonon energies and phonon scattering rates. We show that the strongly unstable phonon modes associated with trigonally coordinated Cu atoms are anharmonically stabilized above approximately 100 K and continue hardening with increasing temperature in accord with experimental data. This temperature-induced hardening effect reduces scattering of heat carrying acoustic modes by reducing the available phase space for three-phonon processes, thereby balancing the conventional ∝ T increase in scattering due to phonon population and yielding nearly temperature independent κ L . Furthermore, we find that very strong phonon broadening leads to a qualitative breakdown of the conventional phonon-gas model and modify the dominant heat transport mechanism from the particlelike phonon wave packet propagation to incoherent contributions described by the off-diagonal terms in the heat-flux operator, which are typically prevailing in glasses and disordered crystals. Furthermore, our work paves the way to a deeper understanding of glasslike thermal conductivity in complex crystals with strong anharmonicity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Excited-state vibronic coherences and intramolecular charge transfer dynamics of the photoinactive cyanobacteriochrome NpF2164g5

We have characterized the excited-state structural dynamics that follow optical excitation of the photoinactive cyanobacteriochrome (CBCR) NpF2164g5 to determine the first events along the photoisomerization reaction coordinate of the phycocyanobilin (PCB) chromophore in red-to-green photoactive CBCRs. Within 25 fs of photoexcitation to the first excited singlet state, S1, a cross peak begins to develop below the diagonal of the broadband two-dimensional electronic spectrum (2DES) owing to the formation of a twisted conformation of the PCB chromophore with an enhanced intramolecular charge-transfer (ICT) character. Excited-state coherent wavepacket motions, including a torsion of the methine bridge between rings C and D and the carbon–hydrogen out-of-plane (HOOP) wagging vibration, are rapidly damped as the cross peak forms. This finding supports an assignment of the torsional and HOOP modes to the reaction coordinate of a coherent nonadiabatic mechanism. The ICT process is accompanied by an ultrafast Stokes shift and rapidly damped oscillations at the torsional mode’s frequency, which are sensed by measurements of the energy gap of the cross peak using its first moment with respect to the detection frequency axis of the 2DES spectrum. Furthermore, these results have the further implication that polar side chains of nearby amino acid residues in the binding site of the PCB chromophore can manipulate the barrier height for photoisomerization in red-to-green photoactive CBCRs and in phytochromes by redistributing the π-electron density along the methine bridge between the C and D rings.

Charge transfer↗

DFT-based investigation of solvation of Nd(III)/Yb(III) cations in room-temperature ionic-liquid

We report a DFT study on the solvation of bare rare-earth (RE) cations [Nd(III) and Yb(III)] in the room-temperature ionic-liquid (RTIL) based on 1,3-dimethyl-imidazolium + , PF 6 - , [MMI][PF 6 ]. In the present article, we aim to investigate whether the chosen RTIL can preferentially solvate any of the RE cations under study. First, the RTIL binding to the RE cation is studied in the gas phase, and then explored with continuum solvation model employing RTIL parameters. First, we considered the formation of the first solvation shell, where the PF 6 - anions directly bond with the Ln(III) cation. We then further surrounded the first solvation shell with [MMI]+ cations to form the second solvation shell. The stability of PF 6 - coordinated complexes is studied by calculating the binding energy values. The number of PF 6 - anions for both Ln(III) cations starts with three ligands and goes until the maximum binding energy in the RTIL medium is reached. The coordination number and binding modes of PF 6 - depend on the size of the RE cation. Comparing the binding energy values between the RE cations for the first solvation shell complexes, it is noticed that Yb-complexes have relatively greater binding energy than Nd-complexes. We have further performed a Boltzmann population analysis to find out the most dominant conformer among each category of PF 6 - coordinated complexes. A study using Natural Population Analysis shows that after complexation with PF 6 - the charge on the Yb-centers lower to a greater extent than Nd-centers, implying stronger bonding between Yb and PF 6 - , which is in harmony with the binding energy analysis. Overall, the computational investigation provides an in-depth understanding of the complexation phenomena of RE cations in RTIL, which can be useful for the practical separation of RE cations using RTIL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MSTor 2023 : A new version of the computer code for multistructural torsional anharmonicity, now with automatic torsional identification using redundant internal coordinates

The MSTor program is a computer program for calculating partition functions and thermodynamic functions of complex gas-phase molecules with multiple torsions; the multi-structural approximation with torsional anharmonicity (MS-T) can be used based on either a coupled torsional potential or an uncoupled torsional potential. The program can also carry out calculations in the multiple-structure local harmonic (MS-LH) approximation or multi-structural local quasiharmonic (MS-LQ) approximation or by the dual-level MS-T method. Furthermore, the program package includes eight utility codes that can be used as stand-alone programs to help the user to generate the input files for the code or to generate comparison results. The 2023 version of MSTor includes a new capability, namely automatic identification of torsional modes with redundant internal coordinates.

97 MATHEMATICS AND COMPUTING↗

Enhancing reactivity of SiO + ions by controlled excitation to extreme rotational states

Optical pumping of molecules provides unique opportunities for control of chemical reactions at a wide range of rotational energies. This work reports a chemical reaction with extreme rotational excitation of a reactant and its kinetic characterization. We investigate the chemical reactivity for the hydrogen abstraction reaction SiO + + H 2 → SiOH + + H in an ion trap. The SiO + cations are prepared in a narrow rotational state distribution, including super-rotor states with rotational quantum number ( j ) as high as 170, using a broad-band optical pumping method. We show that the super-rotor states of SiO + substantially enhance the reaction rate, a trend reproduced by complementary theoretical studies. We reveal the mechanism for the rotational enhancement of the reactivity to be a strong coupling of the SiO + rotational mode with the reaction coordinate at the transition state on the dominant dynamical pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Negative linear compressibility and complex phase behaviour in 7 Li 2 CO 3

We present a combination of neutron powder-diffraction measurements demonstrating negative linear compressibility and irregular thermal expansion in 7 Li 2 CO 3 . This is shown to be due to an interplay between the tilting of the rigid carbonate group and the shear strain in the unit cell, which leads to a first-order transition from monoclinic to hexagonal symmetry. The phase evolution is shown to be highly sensitive to the level of hydrostaticity in the sample. Under hydrostatic conditions, the sample begins transformation at 8.5 GPa leading to a change from tetrahedral to octahedral Li coordination. Symmetry adapted basis mode analysis, combined with density functional theoretical (DFT) calculations and Raman spectroscopy, is used to show that this transition is reverse proper ferroelastic in nature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Proceedings of the 2021 Airborne Wind Energy Workshop

On March 2-3, 2021, the National Renewable Energy Laboratory (NREL) conducted a virtual workshop to evaluate the status, potential development, and technical viability of AWE systems as a source of energy in the United States. Stakeholder input provided at the workshop will contribute to the report to Congress. This report summarizes key workshop findings, current technology research and development activities in the United States, and opportunities and potential modes of collaboration and coordination for future technology research and development activities. The workshop focused on U.S. stakeholders in AWE, with approximately 100 experts and industry stakeholders from AWE technology developers, operators, engineering firms, consultants, government, national laboratories, and university researchers. The workshop began with an explanation from DOE's Wind Energy Technologies Office (WETO) Technology Manager, Ben Hallissy, of the context and purpose of the workshop, including a request from Congress that the U.S. Department of Energy (DOE) deliver a "report on the potential for, and technical viability of, airborne wind energy systems to provide a significant source of energy in the United States, including a summary of research, development, demonstration, and commercialization needs, including an estimate of Federal funding requirements, to further examine and validate the technical and economic viability of airborne wind energy concepts over the 10-year period." The workshop began with brief introductions from attendees who explained their interest in AWE. Nicolas El Hayek of Planair summarized the proceedings from the AWE workshop held in September 2020 by the International Energy Agency (IEA) Wind Task 11. This was followed by a presentation by Roland Schmehl of TU-Delft summarizing European AWE R&D efforts. Chris Vermillion of North Carolina State University and Jason Jonkman of NREL presented an overview of U.S. R&D efforts. Then five panelists discussed AWE markets, sizes of AWE systems, challenges, and opportunities. Panelists included: Cristina Archer, professor at the College of Earth, Ocean, and Environment and associate director at the Center for Research in Wind (CReW) at the University of Delaware; Stephan Brabeck, chief technology officer at SkySails; Thierry Delahave, innovation and technology development lead at Saipem; Rob Creighton, founder and chief executive officer at WindLift; and David Schaefer, founder and chief executive officer at eWind Solutions. The second day of the workshop began with a brief overview of five key topics that are crucial to enabling AWE in the United States. These topics range from estimates of the U.S. wind resource, technical generation potential, economic analysis, environmental challenges, status of current technology and R&D activities, and needed activities to enable commercialization of AWE. This set the stage for a robust discussion in breakout groups where individuals could offer their opinions on the potential opportunities for AWE in the United States. The following topics were discussed in the breakout groups: resource potential and energy output, technical potential, social and environmental impacts, and permitting, techno-economic analysis and markets, technology assessment and upscaling and demonstration and commercialization needs. The second day concluded with reports by the NREL research team, communicating the key themes and outcomes from each of the breakout group discussions.

17 WIND ENERGY↗

Development of High-Fidelity and Efficient Modeling Capabilities for Enabling Co-Optimization of Fuels and Multi-Mode Engines

The objective of this closely coordinated research project is to develop improved physical sub-models and innovative numerical algorithms to enable accurate and efficient predictions of multi-mode combustion to support EERE’s Co-Optima program. To this end, a research pro-gram is proposed that seeks • to develop accurate submodels for predicting multi-mode combustion regimes, wall-heat transfer, non-equilibrium plasma ignition, and combustion-mode transition, • to develop dynamic load-rebalancing algorithms and efficient semi-implicit time-integration schemes for enabling exascale computing, • to validate the computational submodels against experiments and direct numerical simulation (DNS) data in conjunction with sensitivity analysis, and • to support the direct transition of the resulting sub-models into other engine-simulation tools through the development of self-contained modules. All sub-models will be integrated into the open-source exascale engine-simulation platform Nek5000.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Three-Dimensional Electromagnetic High Frequency Concave Cavity Scars

This report examines the localization of high frequency electromagnetic fields in general three-dimensional cavities along periodic paths between opposing sides of the cavity. The focus is on the case where the mirrors at the ends of the orbit are concave and have two different radii of curvature. The cases where these orbits lead to unstable localized modes are known as scars. The ellipsoidal coordinate system is utilized in the construction of the scarred modes. The field at the interior foci is examined as well as trigonometric projections along the periodic scarred ray path.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Analysis of vibronic coupling in a 4f molecular magnet with FIRMS

Vibronic coupling, the interaction between molecular vibrations and electronic states, is a fundamental effect that profoundly affects chemical processes. In the case of molecular magnetic materials, vibronic, or spin-phonon, coupling leads to magnetic relaxation, which equates to loss of magnetic memory and loss of phase coherence in molecular magnets and qubits, respectively. The study of vibronic coupling is challenging, and most experimental evidence is indirect. Here we employ far-infrared magnetospectroscopy to directly probe vibronic transitions in [Yb(trensal)] (where H 3 trensal = 2,2,2-tris(salicylideneimino)trimethylamine). We find intense signals near electronic states, which we show arise due to an “envelope effect” in the vibronic coupling Hamiltonian, which we calculate fully ab initio to simulate the spectra. We subsequently show that vibronic coupling is strongest for vibrational modes that simultaneously distort the first coordination sphere and break the C 3 symmetry of the molecule. With this knowledge, vibrational modes could be identified and engineered to shift their energy towards or away from particular electronic states to alter their impact. Hence, these findings provide new insights towards developing general guidelines for the control of vibronic coupling in molecules.

36 MATERIALS SCIENCE↗

Mode Specificity in the OH + HO 2 → H 2 O + O 2 Reaction: Enhancement of Reactivity by Exciting a Spectator Mode

A reaction usually involves a few active modes while the other modes are largely preserved throughout the reaction as spectators. Excitation of an active mode is expected to promote the reaction, but depositing energy in a spectator mode typically has no effect, because of the differing ability for energy flow to the reaction coordinate. Here, we report a surprising case of mode specificity in a key radical–radical reaction OH + HO 2 → H 2 O + O 2 , where such canonical expectations fail to hold. Despite its spectator nature, the vibrational excitation of the OH reactant is shown at low collision energies to enhance the reactivity significantly. This unique effect can be attributed to the increased attraction with HO 2 due to the larger dipole of the stretched OH. At low collision energies, the stronger attraction increases the chance of capturing the reactants to form a hydrogen-bonded complex, thus of passing through the submerged barrier. The novel mechanism differs from the conventional vibrational enhancement via coupling to the reaction coordinate at the transition state, enriching our understanding of mode specificity in chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Theory of the Tertiary Instability and the Dimits Shift from Reduced Drift-Wave Models

Tertiary modes in electrostatic drift-wave turbulence are localized near extrema of the zonal velocity U(x) with respect to the radial coordinate x. We argue that these modes can be described as quantum harmonic oscillators with complex frequencies, so their spectrum can be readily calculated. The corresponding growth rate $γ$ TI is derived within the modified Hasegawa-Wakatani model. We show that $γ$TI equals the primary-instability growth rate plus a term that depends on the local U''; hence, the instability threshold is shifted compared to that in homogeneous turbulence. This provides a generic explanation of the well-known yet elusive Dimits shift, which we find explicitly in the Terry-Horton limit. Linearly unstable tertiary modes either saturate due to the evolution of the zonal density or generate radially propagating structures when the shear |U'| is sufficiently weakened by viscosity. The Dimits regime ends when such structures are generated continuously.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Theory of the tertiary instability and the Dimits shift from reduced drift-wave models

Tertiary modes in electrostatic drift-wave turbulence are localized near extrema of the zonal velocity $U(x)$ with respect to the radial coordinate $x$. We argue that these modes can be described as quantum harmonic oscillators with complex frequencies, so their spectrum can be readily calculated. The corresponding growth rate $\gamma_{\rm TI}$ is derived within the modified Hasegawa--Wakatani model. We show that $\gamma_{\rm TI}$ equals the primary-instability growth rate plus a term that depends on the local $U''$; hence, the instability threshold is shifted compared to that in homogeneous turbulence. This provides a generic explanation of the well-known yet elusive Dimits shift, which we find explicitly in the Terry--Horton limit. Linearly unstable tertiary modes either saturate due to the evolution of the zonal density or generate radially propagating structures when the shear $|U'|$ is sufficiently weakened by viscosity. The Dimits regime ends when such structures are generated continuously.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Investigating Np(VI) Nitrate Speciation Control through Temperature and Optical Spectroscopy

Numerous areas of nuclear processing, such as radioisotope production, nuclear waste remediation, and separations, depend upon the speciation of f-elements in the solution state. However, fundamental knowledge of the actinides─particularly Np─lags behind most of the elements on the periodic table. Despite the importance of Np(VI) chemistry in separations and nuclear processing, its speciation in HNO 3 remains uncertain. This work addresses some of these gaps by investigating the effect of HNO 3 concentration and temperature on the spectra and speciation of the Np(VI) nitrate system. Six samples of Np in 1 to 10 M HNO 3 were prepared and treated with (NH 4 ) 2 [Ce(NO 3 ) 6 ] to stabilize the hexavalent oxidation state. The absorbance spectrum of the 10 M HNO 3 is drastically different from the spectra of the other samples; the 10 M spectrum indicates coordination of nitrate ligands to the Np(VI)O 2 2+ ion to form a complex with high symmetry. Additionally, absorbance spectra were recorded over the temperature range of 15 to 40 °C, and systematic increases and decreases in certain spectral features of the ultraviolet–visible (UV–vis)–near-infrared (NIR) spectra are present in the spectra. The difference in spectral features suggests that Np(VI) nitrate speciation depends on temperature. Dilution studies of this sample were monitored with UV–vis–NIR and Raman spectroscopies. Spectral data indicate the presence of multiple complexes with different symmetries, including a high-symmetry complex with an inversion center. As samples are diluted and aquo ligands replace nitrate ligands bound to the Np(VI) neptunyl cation, changes in spectroscopic signals indicate a decrease in the high-symmetry nitrate complex and an increase in the lower-symmetry aquo complex. Additionally, the Raman band associated with the Np(VI)O 2 2+ symmetric stretch broadens with dilution and is fitted with two peaks. These peaks are assigned to Np(VI) aquo and nitrato complexes, indicating that this vibrational mode is sensitive to the coordination environment of the Np(VI) neptunyl cation and that contributions from these two Np(VI) complexes can be distinguished. This unique experimental data could be used to advance computational models describing the electronic transitions of complex actinyl ions.

Absorption↗