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At least 1,441 records · Page 80

Structural and mechanistic basis for redox sensing by the cyanobacterial transcription regulator RexT

Abstract Organisms have a myriad of strategies for sensing, responding to, and combating reactive oxygen species, which are unavoidable consequences of aerobic life. In the heterocystous cyanobacterium Nostoc sp. PCC 7120, one such strategy is the use of an ArsR-SmtB transcriptional regulator RexT that senses H 2 O 2 and upregulates expression of thioredoxin to maintain cellular redox homeostasis. Different from many other members of the ArsR-SmtB family which bind metal ions, RexT has been proposed to use disulfide bond formation as a trigger to bind and release DNA. Here, we present high-resolution crystal structures of RexT in the reduced and H 2 O 2 -treated states. These structures reveal that RexT showcases the ArsR-SmtB winged-helix-turn-helix fold and forms a vicinal disulfide bond to orchestrate a response to H 2 O 2 . The importance of the disulfide-forming Cys residues was corroborated using site-directed mutagenesis, mass spectrometry, and H 2 O 2 -consumption assays. Furthermore, an entrance channel for H 2 O 2 was identified and key residues implicated in H 2 O 2 activation were pinpointed. Finally, bioinformatics analysis of the ArsR-SmtB family indicates that the vicinal disulfide “redox switch” is a unique feature of cyanobacteria in the Nostocales order, presenting an interesting case where an ArsR-SmtB protein scaffold has been evolved to showcase peroxidatic activity and facilitate redox-based regulation.

54 ENVIRONMENTAL SCIENCES↗

Genomewide and Enzymatic Analysis Reveals Efficient D-Galacturonic Acid Metabolism in the Basidiomycete Yeast Rhodosporidium toruloides

Biorefining of renewable feedstocks is one of the most promising routes to replace fossil-based products. Since many common fermentation hosts, such as Saccharomyces cerevisiae , are naturally unable to convert many component plant cell wall polysaccharides, the identification of organisms with broad catabolism capabilities represents an opportunity to expand the range of substrates used in fermentation biorefinery approaches. The red basidiomycete yeast Rhodosporidium toruloides is a promising and robust host for lipid- and terpene-derived chemicals. Previous studies demonstrated assimilation of a range of substrates, from C 5 /C 6 sugars to aromatic molecules similar to lignin monomers. In the current study, we analyzed the potential of R. toruloides to assimilate d -galacturonic acid, a major sugar in many pectin-rich agricultural waste streams, including sugar beet pulp and citrus peels. d -Galacturonic acid is not a preferred substrate for many fungi, but its metabolism was found to be on par with those of d -glucose and d -xylose in R. toruloides . A genomewide analysis by combined transcriptome sequencing (RNA-seq) and RB-TDNA-seq revealed those genes with high relevance for fitness on d -galacturonic acid. While R. toruloides was found to utilize the nonphosphorylative catabolic pathway known from ascomycetes, the maximal velocities of several enzymes exceeded those previously reported. In addition, an efficient downstream glycerol catabolism and a novel transcription factor were found to be important for d -galacturonic acid utilization. These results set the basis for use of R. toruloides as a potential host for pectin-rich waste conversions and demonstrate its suitability as a model for metabolic studies with basidiomycetes. The switch from the traditional fossil-based industry to a green and sustainable bioeconomy demands the complete utilization of renewable feedstocks. Many currently used bioconversion hosts are unable to utilize major components of plant biomass, warranting the identification of microorganisms with broader catabolic capacity and characterization of their unique biochemical pathways. d -Galacturonic acid is a plant component of bioconversion interest and is the major backbone sugar of pectin, a plant cell wall polysaccharide abundant in soft and young plant tissues. The red basidiomycete and oleaginous yeast Rhodosporidium toruloides has been previously shown to utilize a range of sugars and aromatic molecules. Using state-of-the-art functional genomic methods and physiological and biochemical assays, we elucidated the molecular basis underlying the efficient metabolism of d -galacturonic acid. This study identified an efficient pathway for uronic acid conversion to guide future engineering efforts and represents the first detailed metabolic analysis of pectin metabolism in a basidiomycete fungus.

59 BASIC BIOLOGICAL SCIENCES↗

Anisotropic Growth of Otavite on Calcite: Implications for Heteroepitaxial Growth Mechanisms

Elucidating how cation intermixing can affect the mechanisms of heteroepitaxial growth in aqueous media has remained a challenging endeavor. Toward this goal, in situ atomic force microscopy was employed to image the heteroepitaxial growth of otavite (CdCO3) at the (10-14) surface of calcite (CaCO3) single crystals in static aqueous conditions. Heteroepitaxial growth proceeded via spreading of three-dimensional (3D) islands and two-dimensional (2D) atomic layers at low and high initial saturation levels, respectively. Experiments were carried out as a function of applied force and imaging mode thus enabling determination of growth mechanisms unaltered by imaging artifacts. This approach revealed the significant anisotropic nature of heteroepitaxial growth on calcite in both growth modes and its dependence on supersaturation, intermixing, and substrate topography. The 3D islands not only grew preferentially along the [42-1] direction relative to the [010] direction, resulting in rod-like surface precipitates, but also showed clear preference for growth from the island end rich in obtuse/obtuse kink sites. Pinning to step edges was observed to often reverse this tendency. In the 2D growth mode, the relative velocities of acute and obtuse steps were observed to switch between the first and second atomic layers. This phenomenon stemmed from the significant Cd-Ca intermixing in the first layer, despite bulk thermodynamics predicting the formation of almost pure otavite. Composition effects were also responsible for the inability of 3D islands to grow on 2D layers in cases where both modes were observed to occur simultaneously. Overall, the AFM images highlighted the effects of intermixing on heteroepitaxial growth, particularly how it can induce thickness-dependent growth mechanisms at the nanoscale.

Environmental Molecular Sciences Laboratory↗

SPARC: Structural properties associated with residue constraints

SPARC facilitates the generation of plausible hypotheses regarding underlying biochemical mechanisms by structurally characterizing protein sequence constraints. Such constraints appear as residues co-conserved in functionally related subgroups, as subtle pairwise correlations (i.e., direct couplings), and as correlations among these sequence features or with structural features. SPARC performs three types of analyses. First, based on pairwise sequence correlations, it estimates the biological relevance of alternative conformations and of homomeric contacts, as illustrated here for death domains. Second, it estimates the statistical significance of the correspondence between directly coupled residue pairs and interactions at heterodimeric interfaces. Third, given molecular dynamics simulated structures, it characterizes interactions among constrained residues or between such residues and ligands that: (a) are stably maintained during the simulation; (b) undergo correlated formation and/or disruption of interactions with other constrained residues; or (c) switch between alternative interactions. We illustrate this for two homohexameric complexes: the bacterial enhancer binding protein (bEBP) NtrC1, which activates transcription by remodeling RNA polymerase (RNAP) containing σ 54 , and for DnaB helicase, which opens DNA at the bacterial replication fork. Based on the NtrC1 analysis, we hypothesize possible mechanisms for inhibiting ATP hydrolysis until ADP is released from an adjacent subunit and for coupling ATP hydrolysis to restructuring of σ 54 binding loops. Based on the DnaB analysis, we hypothesize that DnaB ‘grabs’ ssDNA by flipping every fourth base and inserting it into cavities between subunits and that flipping of a DnaB-specific glutamine residue triggers ATP hydrolysis.

97 MATHEMATICS AND COMPUTING↗

Microscopy of Electrostatic Field Effect in Novel Quantum Materials (Final Report)

In this DOE Early Career project “Microscopy of Electrostatic Field Effect in Novel Quantum Materials”, the PI’s group explored the nanoscale electronic properties when charge carriers are electrostatically modulated in functional materials. Using a microwave impedance microscope (MIM), the team probed the spatial evolution of local conductivity in various field-effect transistors (FETs) ranging from traditional metal-oxide-semiconductor FETs, sketched oxide-interface FETs, to ferroelectric FETs and electric double-layer transistors (EDLTs). Specifically, the work has led to a deep understanding on the electrical inhomogeneity and conductive edge channels in atomically thin transition metal dichalcogenides and their heterostructures, which is of fundamental importance for their applications in electronics and photonics. The unique sub-surface imaging capability also enables the first-time report of ferroelectric field effect on Ge substrates due to the polarization switching of an epitaxial BaTiO 3 layer, as well as the visualization of sketched nanostructures in the LaAlO 3 /SrTiO 3 interface. Using a cryogenic MIM, the local channel conductance in ion-gel-gated oxide EDLTs has been successfully imaged, resolving a major challenge in the EDLT research to study electronic fluctuations in the devices. Finally, a new tuning-fork-based MIM has been developed to perform quantitative conductivity imaging on back-gated FETs. The research supported by this DOE grant is significant for understanding the nanoscale uniformity in technologically important materials towards energy applications.

2D materials↗

Geometry and growth contributions to cosmic shear observables

We explore the sensitivity of weak-lensing observables to the expansion history of the Universe and to the growth of cosmic structures, as well as the relative contribution of both effects to constraining cosmological parameters. We utilize ray-tracing dark-matter-only N-body simulations and validate our technique by comparing our results for the convergence power spectrum with analytic results from past studies. We then extend our analysis to non-Gaussian observables which cannot be easily treated analytically. We study the convergence (equilateral) bispectrum and two topological observables, lensing peaks and Minkowski functionals, focusing on their sensitivity to the matter density Ω m and the dark energy equation of state w. We find that a cancellation between the geometry and growth effects is a common feature for all observables and exists at the map level. It weakens the overall sensitivity by factors of up to 3 and 1.5 for w and Ω m , respectively, with the bispectrum worst affected. However, combining geometry and growth information alleviates the degeneracy between Ω m and w from either effect alone. As a result, the magnitudes of marginalized errors remain similar to those obtained from growth-only effects, but with the correlation between the two parameters switching sign. Furthermore, these results shed light on the origin of the cosmology sensitivity of non-Gaussian statistics and should be useful in optimizing combinations of observables.

79 ASTRONOMY AND ASTROPHYSICS↗

TREM2 modulates microglia phenotypes in the neuroinflammation of Parkinson's disease

Highlights: • TREM2, Arginase-1 and proinflammatory cytokines increased in the midbrain of PD mice. • Knockdown of TREM2 in BV2 microglia exaggerated M1 microglial inflammatory responses. • TREM2 overexpression promoted M2 polarization and alleviated microglial inflammation. • TREM2 plays a crucial role in altering M1 microglia to M2 phenotype. Neuroinflammation and overactivated microglia underlies the pathogenesis of Parkinson's disease (PD). Furthermore, microglia could polarize into classic inflammatory M1 and immunosuppressive M2 phenotype. Thus, inhibiting the overactivated inflammatory M1 microglia by promoting the transformation of microglia to the protective M2 phenotype provides potential therapy for PD, but the mechanism that modulates microglia polarization remains unknown. Triggering receptor expressed on myeloid cells-2 (TREM2) is a recently identified immune receptor expressed by the microglia in the brain. Emerging evidence indicates that TREM2 enhances the phagocytosis function of microglia and suppress inflammation. Based on these evidence, we hypothesized that TREM2 might play a protective role through regulating microglia polarization. Here, we employ a lentiviral strategy to overexpress or suppress TREM2 on microglia and found that TREM2 was essential for M2 microglia polarization. Knockdown of TREM2 in BV2 microglia inhibited M2 polarization and lead to exaggeration of M1 microglial inflammatory responses, whereas overexpression of TREM2 promoted M2 polarization and alleviated microglial inflammation. We also observed that the TREM2 level was higher in the midbrain of PD mice, which was accompanied by an elevated level of Arginase-1 and increased proinflammatory cytokines, suggesting that TREM2 is an important factor in switching the microglia phenotypes. Taken together, these findings indicate that TREM2 plays a crucial role in altering the proinflammatory M1 microglia to M2 phenotype and has beneficial effects in the immune pathogenesis of PD.

60 APPLIED LIFE SCIENCES↗

Technology requirements for post-1985 communications satellites

The technical and functional requirements for commercial communication satellites are discussed. The need for providing quality service at an acceptable cost is emphasized. Specialized services are postulated in a needs model which forecasts future demands. This needs model is based upon 322 separately identified needs for long distance communication. It is shown that the 1985 demand for satellite communication service for a domestic region such as the United States, and surrounding sea and air lanes, may require on the order of 100,000 MHz of bandwith. This level of demand can be met by means of the presently allocated bandwidths and developing some key technologies. Suggested improvements include: (1) improving antennas so that high speed switching will be possible; (2) development of solid state transponders for 12 GHz and possibly higher frequencies; (3) development of switched or steered beam antennas with 10 db or higher gain for aircraft; and (4) continued development of improved video channel compression techniques and hardware.

Burtt, J. E.↗

A Co-Investigator Project for the Cornell University Cleft Accelerated Plasma Experimental Rocket-CAPER

The CAPER rocket campaign was to follow the SCIFER experiment as a detailed study of the ion acceleration processes in the Cleft Ion Fountain (CIF) above 1000 km altitude. The SCIFER rocket demonstrated that the experiment was feasible and that the CIF acceleration processes on the dayside are different from those observed in the discrete aurora on the nightside. The responsibility of the GI/UAF co-investigator project was to provide the real-time acquisition and display of large-and small-scale ground observations, and satellite solar wind data at the launch control center at Longyearbyen, Svalbard for the determination of the launch conditions and the later interpretation of the rocket observations. The rocket campaign was proposed for January of 1998, but was slipped to January of 1999. The rocket was launched on January 21, 1999 at 06 h 13 m 30 s UT. All of the GI/UAF co-investigator systems functioned well, except the narrow-field TV camera which was to follow the 140 km conjugate of the payload on command from GPS tracking data sent from Andoya. The data were not available during the flight, and the camera tracked the nominal conjugate. Unfortunately, the trajectory was well west of nominal, so no useful narrow-field conjugate data were acquired . In addition, the payload missed the region of more intense precipitation, brighter aurora, stronger currents, and likely large fluxes of transverse ion acceleration. On the other hand, good data were acquired across a region of the ionosphere that appears to have had a double convection boundary because of the IMF switching its z component shortly before launch. These data are important for understanding the reaction of the magnetosphere and ionosphere to changes in the IMF.

Deehr, Charles S.↗

In Situ Analysis of Electron-Induced Chemical Transformations in Vapor-Phase-Synthesized Al-Based Inorganic–Organic Hybrid Thin Films for EUV Resist Platform

The rapid advancement and stringent requirements of extreme ultraviolet (EUV) lithography technology necessitate the development of advanced photoresist systems for next-generation microelectronics. Recent studies have demonstrated that inorganic-based hybrid photoresists offer notable improvements in EUV sensitivity, etch resistance, and greater insusceptibility to pattern collapse compared to their purely organic counterparts. However, variations in the synthesis/coating approaches and chemistry of inorganic–organic photoresists can result in distinct exposure mechanisms. In this work, an Al-based hybrid thin film resist system synthesized via molecular (atomic) layer deposition (MLD or MALD) is explored, focusing on its electron-beam and EUV patterning mechanisms. The Al-based hybrid thin films are deposited using trimethylaluminum (TMA) and the organic precursor hydroquinone, exhibiting a saturated growth rate within the temperature range of 150–200°C. In diluted tetramethylammonium hydroxide (TMAH)-based developer solutions, the electron-irradiated Al-based hybrid thin film system behaves as a negative tone resist, achieving a sensitivity of 10.4 mC/cm 2 at 0.1 kV electron beam lithography (EBL). Chemical changes induced by electron exposure are also analyzed in this study using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and a unique infrared spectroscopy setup, revealing the potential cross-linking pathways. To further correlate the electron-induced chemical transformations with those mediated by EUV irradiations, a combination of X-ray photoemission electron microscopy/low-energy electron microscopy (XPEEM/LEEM) system is also employed. In conclusion, this study provides critical insights into the mechanisms underlying solubility switching and contributes to the design of advanced resist materials for EUV lithography.

36 MATERIALS SCIENCE↗

Solvothermal synthesis and characterization of highly monodisperse organically functionalized vanadium oxide nanocrystals for thermochromic applications

Highlights: • Vanadium oxide nanocrystals is synthesized via an improved solvothermal method. • Vanadium oxide nanocrystals possess a structure of distorted paramontroseite VO{sub 2}(P). • Thermally annealed nanocrystal thin films exhibit good thermochromic properties. - Abstract: We report on the synthesis and characterization of highly monodisperse organically functionalized vanadium oxide (VO{sub x}) nanocrystals with a size of 7–10 nm. We show that how these nanocrystals can be prepared by an improved solvothermal reaction and confirm their composition and structure through various materials characterization techniques. Our results revealed that VO{sub x} nanocrystals have a crystalline structure almost identical to that of paramontroseite VO{sub 2}(P) and the majority of vanadium is in oxidation state of V(IV). VO{sub x} nanocrystal films can be readily prepared via a spin coating technique. Once thermally annealed at ∼350 °C under an air/N{sub 2} flow, the films exhibited good thermochromic properties (luminous transmittance (T{sub lum}) ≈49–66%, infrared switching efficiency (ΔT{sub 2000nm}) ≈28–43%, and solar modulating ability (ΔT{sub sol}) ≈7.4–10.7%), corresponding to a phase transition between monoclinic VO{sub 2}(M) and rutile VO{sub 2}(R).

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Portable Intravenous Fluid Production Device For Ground Use Project

Several medical conditions require the administration of intravenous (IV) fluids,but limitations of mass, volume, shelf-life, transportation, and local resources can restrict the availability of these important fluids. Such limitations are expected in long-duration space exploration missions and in remote or austere places on Earth. This design uses regular drinking water that is pumped through two filters to produce, in minutes, sterile, ultrapure water that meets the stringent quality standards of the United States Pharmacopeia for Water for Injection (Total Bacteria, Conductivity, Endo - toxins, Total Organic Carbon). The device weighs 2.2 lb (1 kg) and is 10 in. long, 5 in. wide, and 3 in. high (≈25, 13, and 7.5 cm, respectively) in its storage configuration. This handheld device produces one liter of medical-grade water in 21 minutes. Total production capacity for this innovation is expected to be in the hundreds of liters. The device contains one battery powered electric mini-pump. Alternatively, a manually powered pump can be attached and used. Drinking water enters the device from a source water bag, flows through two filters, and final sterile production water exits into a sealed, medical-grade collection bag. The collection bag contains pre-placed crystalline salts to mix with product water to form isotonic intravenous medical solutions. Alternatively, a hypertonic salt solution can be injected into a filled bag. The filled collection bag is detached from the device and is ready for use or storage. This device currently contains one collection bag, but a manifold of several pre-attached bags or replacement of single collection bags under sterile needle technique is possible for the production of multiple liters. The entire system will be flushed, sealed, and radiation-sterilized. Operation of the device is easy and requires minimal training. Drinking water is placed into the collection bag. Inline stopcock flow valves at the source and collection bags are opened, and the mini-pump is turned on by a switch to begin fluid flow. When the collection bag is completely filled with the medical- grade water, the pump can be turned off. The pump is designed so it cannot pump air, and overfilling of the collection bag with fluid is avoided by placing an equal amount of water in the source bag. Backflow is avoided by inline check valves. The filled collection bag is disconnected from its tubing and is ready for use. The source bag can be refilled for production of multiple liters, or the source bag can be replaced with an input tube that can be placed in a larger potable water source if the device is attended. The device functions in all orientations independent of any gravity fields. In addition to creating IV fluids, the device produces medical-grade water, which can be used for mixing with medications for injection, reconstituting freeze-dried blood products for injection, or for wound hydration or irrigation. Potential worldwide use is expected with medical activities in environments that have limited resources, storage, or resupply such as in military field operations, humanitarian relief efforts, submarines, commercial cruise ships, etc.

Technology Portfolio System↗

Real-Time Lifetime Prediction of Semiconductor Devices Using Hardware-in-the-Loop

This paper presents a unique approach to enable real-time lifespan prediction of semiconductor power modules using a Hardware-in-the-Loop (HIL) system. By integrating the module's overall loss characteristics-specifically switching and conduction losses-with a thermoelectric model of the thermal management system, this research demonstrates that the model can dynamically estimates the junction temperature profile of the semiconductor devices in response to a changing torque demand profile for the motor drive system. This capability enables continuous monitoring of the module's operational time and cumulative stress induced on the devices to compute accumulated remaining lifetime or time-to-failure (TTF). This study provides an architectural framework for the HIL system with high-fidelity component models of multiple physical domains, allowing simulation of dynamic behaviors of a closely-coupled motor drive system. The advanced real-time computation and measurement functionalities of the HIL system allow for both dynamic lifetime calculations based on simulated data and aggregate lifetime predictions utilizing historical data. Moreover, this paper details an algorithm that not only computes cumulative damage but also synthesizes these data into a comprehensive aggregated lifetime metric. This methodology can enhance the maintenance scheduling strategies and operational reliability of semiconductor devices in critical applications, ultimately extending their service life while optimizing performance.

hardware-in-the-loop (HIL)↗

Experimental evaluation of the concept of supevisory manipulation

A computer-controlled teleoperator system which is based on task-referenced sensor-aided control has been developed to study supervisory manipulation. This system, called SUPERMAN, is capable of performing complicated tasks in real-time by utilizing the operator for high-level functions related to the unpredictable portions of a task, while the subordinate machine performs the more well-defined subtasks under human supervison. To determine whether supervisory control schemes such as these offer any advantage over manual control under real-time conditions, a number of experiments involving both simple and complicated tasks were performed. Six representative tasks were chosen for the study: (1) obtaining a tool from a rack, (2) returning the tool to the rack, (3) removing a nut, (4) placing samples in a storage bin, (5) opening and closing a valve, and (6) digging with a shovel. The experiments were performed under simulated conditions using four forms of manual control (i.e., switch rate, joystick rate, master-slave position control, and master-slave with force feedback), as well as supervisory control. Through these experiments the effectiveness and quality of control were evaluated on the basis of the time required to complete each portion of the task and the type and number of errors which occurred.

Brooks, T. L.↗

Full-Circle Resolver-to-Linear-Analog Converter

A circuit generates sinusoidal excitation signals for a shaft-angle resolver and, like the arctangent circuit described in the preceding article, generates an analog voltage proportional to the shaft angle. The disadvantages of the circuit described in the preceding article arise from the fact that it must be made from precise analog subcircuits, including a functional block capable of implementing some trigonometric identities; this circuitry tends to be expensive, sensitive to noise, and susceptible to errors caused by temperature-induced drifts and imprecise matching of gains and phases. These disadvantages are overcome by the design of the present circuit. The present circuit (see figure) includes an excitation circuit, which generates signals Ksin(Omega(t)) and Kcos(Omega(t)) [where K is an amplitude, Omega denotes 2(pi)x a carrier frequency (the design value of which is 10 kHz), and t denotes time]. These signals are applied to the excitation terminals of a shaft-angle resolver, causing the resolver to put out signals C sin(Omega(t)-Theta) and C cos(Omega(t)-Theta). The cosine excitation signal and the cosine resolver output signal are processed through inverting comparator circuits, which are configured to function as inverting squarers, to obtain logic-level or square-wave signals .-LL[cos(Omega(t)] and -LL[cos(Omega(t)-Theta)], respectively. These signals are fed as inputs to a block containing digital logic circuits that effectively measure the phase difference (which equals Theta between the two logic-level signals). The output of this block is a pulse-width-modulated signal, PWM(Theta), the time-averaged value of which ranges from 0 to 5 VDC as Theta ranges from .180 to +180deg. PWM(Theta) is fed to a block of amplifying and level-shifting circuitry, which converts the input PWM waveform to an output waveform that switches between precise reference voltage levels of +10 and -10 V. This waveform is processed by a two-pole, low-pass filter, which removes the carrier-frequency component. The final output signal is a DC potential, proportional to Theta that ranges continuously from -10 V at Theta = -180deg to +10 V at Theta = +180deg..

Alhorn, Dean C.↗

Switchable client specificity in a dual functional chaperone coordinates light-harvesting complex biogenesis

The proper assembly of light-harvesting complexes (LHCs) is critical for photosynthesis and requires the biogenesis of light-harvesting chlorophylla,b-binding proteins (LHCPs) to be coordinated with chlorophyll (Chl) biosynthesis. The mechanism underlying this coordination is not well understood. Here, we show that a conserved molecular chaperone, chloroplast signal recognition particle 43-kDa protein (cpSRP43), provides a molecular thermostat that helps maintain this coordination. cpSRP43 undergoes a conformational rearrangement between a well-folded closed state and a partially disordered open state. Closed cpSRP43 is dedicated to the biogenesis of LHCPs, whereas open cpSRP43 protects multiple Chl biosynthesis enzymes from heat-induced destabilization. Rising temperature shifts cpSRP43 to the open state, enabling it to protect heat-destabilized Chl biosynthesis enzymes. Our results reveal the molecular basis of a posttranslational mechanism for the thermoadaptation of LHC biogenesis. They also demonstrate how an adenosine triphosphate–independent chaperone uses conformational dynamics to switch its activity and client selectivity, thereby adapting to different proteostatic demands under shifting environmental conditions.

Science & Technology - Other Topics↗

Intersubband Relaxation in CdSe Colloidal Quantum Wells

The dynamics of intersubband relaxation are critical to quantum well technologies such as quantum cascade lasers and quantum well infrared photodetectors. In this work, intersubband relaxation in CdSe colloidal quantum wells, or nanoplatelets, is studied via pump-push-probe transient spectroscopy. An initial interband pump pulse is followed by a secondary infrared push excitation, resonant with intersubband absorption, which promotes electrons from the first conduction band of the quantum well to the second conduction band. A probe pulse monitors subsequent electron cooling to the band edge of the quantum well. Using this technique, intersubband relaxation is studied as a function of critical variables such as colloidal quantum well size and thickness, surface ligand chemistry, temperature, and excitation pulse intensity. Larger quantum well sizes, judicious selection of surface ligand chemistry (e.g., thiolates), low temperatures, and elevated push pulse fluences slow intersubband relaxation. However, compared to resonant intraband relaxation in colloidal quantum dots (up to hundreds of picoseconds), intersubband relaxation in colloidal quantum wells is rapid (<1 ps) under all examined conditions. These experiments indicate that rapid relaxation is driven by both LO phonon and surface scattering. The short time scale of relaxation observed in these materials may hinder intersubband technologies such as mid-infrared detectors, although such rapid relaxation may prove valuable in optical switching.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanism-Resolved PFM of Ferroionic and Ferroelectric Responses in Thickness-Gradient Hf 0.5 Zr 0.5 O 2 Libraries

Resolving growth mechanisms and thickness evolution of functional properties is one of the key tasks in materials discovery and optimization involving thin-film materials, traditionally requiring significant experimental budgets. Here we introduce the combination of thickness-gradient libraries and automated scanning probe microscopy as a systematic pathway to elucidate growth modes and disentangle ferroelectric and electrochemical contributions in ferroelectric thin films. As a model system, we explore the Hf 0.5 Zr 0.5 O 2 (HZO) gradient thin films grown on La x Sr 1-x MnO 3 (LSMO) bottom electrode thin films. Automated piezoresponse force microscopy, spectroscopy, and lithography reveals that irreversible topographic deformation arises from electrochemical activity at the LSMO surface, whereas reversible phase inversion in HZO reflects ferroelectric switching. Automated topography height-map scans are used to further quantify nucleation density, particle-size evolution, and roughness correlations across the thickness-gradient, demonstrating that improved plume stabilization during growth suppresses interfacial reactions and promotes dense, fine-grained HZO conducive to ferroelectric phase formation. This combined materials-engineering and automated-SPM framework establishes a platform for high-throughput, mechanism-resolved characterization of ferroionic and ferroelectric responses in complex oxide films.

FOS: Physical sciences↗