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At least 145 records · Page 8

Structural interactions of TLP18.3 and Psb27-H1 to the luminal CP43 and Rubredoxin-ENH1 to the stromal side of Photosystem II in higher plants

TLP18.3 and Psb27 are known proteins on the luminal side of photosystem II. The structural locations of these two proteins are still absent in the currently available higher plant photosystem II cryo-EM structures. We interrogated the structural locations of these proteins using chemical cross-linking followed by liquid chromatography/tandem MS analysis. Structural mass spectrometry results then provided chemical restrains to direct structural modelling to determine the collective binding/stabilization of these two proteins to the luminal PSII CP43 protein. Using this pipeline, we also found the structural location of a Rubredoxin protein on the stromal side of PSII. Discovery of this redox active iron-sulfur protein in the vicinity of PSII subunit D1/D2 proteins, greatly showcases the importance of the redox processes that are potentially involved in PSII assembly or less known steady state functionality or photoprotection. This structural mass spectrometry platform high-lights its powerful applicability in protein complex discovery.

59 BASIC BIOLOGICAL SCIENCES

Cryogenic Vibrational Spectroscopy of the Deprotonated Dimer of Phosphoric Acid

Phosphate-containing molecules are ubiquitous in nature, where they play crucial roles in biochemical processes. Further, they are of technical importance, for example, in certain batteries and in fuel cells, where a unique property of phosphoric acid is exploited its exceptionally high proton conductivity. Proton transport in phosphoric acid is known to involve proton shuttling; however, the elementary steps involved are not clear. To elucidate the hydrogen bonding preferences of phosphoric acid, we investigate the dihydrogen phosphate anion as well as the deprotonated dimer of phosphoric acid (H 3 PO 4 ·H 2 PO 4 − ) in the gas phase using infrared action spectroscopy in helium nanodroplets and infrared D 2 -tagging photodissociation spectroscopy, and the experimental spectra are compared to theoretical ones. Theory finds for H 3 PO 4 ·H 2 PO 4 − two different structures that are predicted to be nearly isoenergetic. The comparison to the experimental spectra, however, allows for a clear assignment and structure identification. The resulting structure has an interesting binding motif, which might be of relevance to interactions of phosphoric acid in the condensed phase and which can serve as a benchmark for quantum chemical calculations.

Chemical structure

Dark matter and galaxy cross-correlations with the Cherenkov Telescope Array Observatory

The Cherenkov Telescope Array Observatory (CTAO) will be a ground-based Cherenkov telescope performing wide-sky surveys, ideal for anisotropy studies such as cross-correlations with tracers of the cosmic large-scale structure. Cross-correlations can shed light on high-energy γ -ray sources and potentially reveal exotic signals from particle dark matter. In this work, we investigate CTAO sensitivity to cross-correlation signals between γ -ray emission and galaxy distributions. We find that by using dense, low-redshift catalogs like 2 MASS, and for integration times around 50 hours, this technique achieves sensitivities to both annihilating and decaying dark matter signals that are competitive with those from dwarf galaxy and cluster analyses.

Pinetti, Elena [CCA, New York; Perimeter Inst. The

Production of protons and light nuclei in Au +Au collisions at $\sqrt{s_{NN}}$ = 3 GeV with the STAR detector

We report the systematic measurement of protons and light nuclei production in Au +Au collisions at $\sqrt{s_{NN}}$ = 3 GeV by the STAR experiment at the Relativistic Heavy Ion Collider (RHIC). The transverse momentum (𝑝 𝑇 ) spectra of protons (𝑝) , deuterons (𝑑) , tritons (𝑡) , 3 He , and 4 He have been measured from midrapidity to target rapidity for different collision centralities. We present the rapidity and centrality dependence of particle yields (𝑑⁢𝑁/𝑑⁢𝑦), average transverse momentum (⟨𝑝 𝑇 ⟩), yield ratios (𝑑/𝑝, 𝑡/𝑝, 3 He/𝑝, 4 He/𝑝), as well as the coalescence parameters (𝐵 2 ,𝐵 3 ). The 4⁢𝜋 yields for various particles are determined by utilizing the measured rapidity distributions, 𝑑⁢𝑁/𝑑⁢𝑦. Furthermore, we present the energy, centrality, and rapidity dependence of the compound yield ratios (𝑁 𝑝 ×𝑁 𝑡 /𝑁$^{2}_{d}$) and compare them with various model calculations. Furthermore, the physics implications of these results on the production mechanism of light nuclei and the QCD phase structure are discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS

Wafer-scale waveguide sidewall roughness scattering loss characterization by image processing

Photonic integrated circuits (PICs) are vital for developing affordable, high-performance optoelectronic devices that can be manufactured at an industrial scale, driving innovation and efficiency in various applications. Optical loss of modes in thin film waveguides and devices is a critical measure of their performance. Thin film growth, lithography, masking, and etching processes are imperfect processes that introduce significant sidewall and top-surface roughness and cause dominating optical losses in waveguides and photonic structures. This roughness, as perturbations couple light from guided to far-field radiation modes, leads to scattering losses that can be estimated from theoretical models. Typically, with UV-based lithography, sidewall roughness is significantly larger than wafer-top surface roughness. Atomic force microscopy (AFM) imaging measurement gives a 3D and high-resolution roughness profile, but the measurement is inconvenient, costly, and unscalable for large-scale PICs and at wafer-scale. Here, we evaluate the sidewall roughness profile based on 2D high-resolution scanning electron microscope (SEM) imaging. We characterized the loss on two homemade nitride and oxide films on 3-inch silicon wafers with 12 waveguide devices on each and correlated the scattering loss estimated from a 2D image-based sidewall profile and theoretical Payne model. The lowest loss of guided fundamental transverse electric (TE 0 ) mode is found at 0.075 dB/cm at 633 nm across 24 devices, a record at visible wavelength. Our work shows 100% success (edge continuity span exceeding 95% of image width/height) in edge detection in image processing of all images to estimate autocorrelation function and optical mode loss. These demonstrations offer valuable insights into waveguide sidewall roughness and a comparison of experimental and 2D SEM image processing based loss estimations with applications in loss characterization at wafer-scale PICs.

Khurana, Mohit (ORCID:0000000207898672)

Optimized Photoemission from Organic Molecules in 2D Layered Halide Perovskites

In recent years, hybrid organic−inorganic metal halides have been at the forefront of materials research. Typically, the functional (e.g., optoelectronic) properties of hybrid halides are derived from the inorganic structural part, whereas the organic structural units can add extra advantages in terms of stability, rigidity, and processability. Here, we report the design, synthesis, and characterization of two new hybrid materials in which the outstanding photophysical properties originate from the organic structural part. The new compounds, (C 15 H 16 N) 2 CdCl 4 and ((Br)C 15 H 15 N) 2 CdCl 4 , have 2D layered Ruddlesden−Poppertype perovskite structures. These hybrids are blue-white light emitters just like their corresponding pure organic salts, but with much improved emission efficiencies. Optical spectroscopy and density functional theory (DFT) studies confirm that photoemission comes from the trans-stilbene organic cations. The photoluminescence quantum yield (PLQY) values of these new materials are among the highest known, 50.83% and 26.60% for (C 15 H 16 N) 2 CdCl 4 and ((Br)C 15 H 15 N) 2 CdCl 4 , respectively. This is up to a 5-fold increase as compared to the light emission efficiency of the precursor salt C 15 H 16 NCl (PLQY of 10.33%). Alongside their outstanding optical properties, their environmental and thermal stability allow their consideration for potential practical applications such as radiation detection. This work shows that hybrid metal halides can be compositionally and structurally engineered to have highly efficient photoemission originating from the organic components for fast scintillation applications.

Halogens

Poincaré beams from a free electron laser

Poincaré beams are light beams that have spatially inhomogeneous polarization structure that spans a finite portion of the Poincaré sphere. This feature bestows the beams with intriguing topological properties and has led to a surge in research on their fundamental characteristics, their controlled generation and on emerging applications. Here we present an experimental demonstration of a Poincaré beam generated in the extreme ultraviolet (16.7 nm) at the FERMI free electron laser (FEL). The ‘star’ type Poincaré beam is generated by exploiting the phase and intensity structure intrinsic to FEL radiation without relying on optical elements. Here, we controlled the spatial polarization distribution through a precise overlap and power balance between two FEL pulses, each with different transverse phase distributions and orthogonal circular polarizations. The spatial polarization structure was mapped in detail and shows extensive coverage of the Poincaré sphere, in agreement with analytic predictions. This method of in situ Poincaré beam production in FELs enables straightforward flexibility in the orientation and balance of polarization states, and can readily be extended to other vector beams and to shorter wavelengths enabling novel science applications in modern light sources.

Morgan, Jenny [SLAC National Accelerator Laborator

Experimental and Computational Insights into the Structural Dynamics of the Fc Fragment of IgG1 Subtype from Biosimilar VEGF‐Trap

The constant fragment (Fc) of the immunoglobulin G1 (IgG1) subtype is increasingly recognized as a crucial scaffold in the development of advanced therapeutics due to its enhanced specificity, efficacy, and extended half‐life. A prime example is VEGF‐Trap (Aflibercept), a recombinant fusion protein that merges the Fc region of the IgG1 subtype with the binding domains of vascular endothelial growth factor receptors (VEGFR)‐1 and VEGFR‐2. The Fc region's role in N‐glycosylation is particularly important, as it significantly influences protein stability. Herein, the first near‐physiological temperature structures of the N‐glycan‐bound Fc fragment of IgG1 subtype from a biosimilar VEGF‐Trap are presented, determined using the SPring‐8 Angstrom Compact free electron LAser (SACLA) and the Turkish Light Source (Turkish DeLight). Comparative analysis with cryogenic structures, including existing data, reveals alternate conformations within the glycan‐binding pocket. Furthermore, molecular dynamics simulations indicate the presence of a high degree of structural plasticity, explaining how the protein adapts its structure through conformational changes. The observed structural fluctuations/conformational changes demonstrate the effect of N‐glycans on protein stability. These findings offer new insights into the molecular basis of Fc‐mediated functions and provide valuable information for the design of next‐generation therapeutics.

60 APPLIED LIFE SCIENCES

Structural Characterization of the Platinum Nanoparticle Hydrogen-Evolving Catalyst Assembled on Photosystem I by Light-Driven Chemistry

Directed assembly of abiotic catalysts onto biological redox protein frameworks is of interest as an approach for the synthesis of biohybrid catalysts that combine features of both synthetic and biological materials. In this report, we provide a multiscale characterization of the platinum nanoparticle (NP) hydrogen-evolving catalysts that are assembled by light-driven reductive precipitation of platinum from an aqueous salt solution onto the photosystem I protein (PSI), isolated from cyanobacteria as trimeric PSI. The resulting PSI-NP assemblies were analyzed using a combination of X-ray energy-dispersive spectroscopy (XEDS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), small-angle X-ray scattering (SAXS), and high-energy X-ray scattering with atomic pair distribution function (PDF) analyses. The results show that the PSI-supported NPs are approximately 1.8 nm diameter disk-shaped particles that assemble at discrete sites with 145 Å separation. This separation is too large to be consistent with NP nucleation and growth at a site adjacent to the F B cofactor site. Instead, we suggest a mechanism for NP growth at hydrophobic sites on the PSI stromal surface. The NPs photoreductively assembled on the PSI stromal surface are found to be analogous to the nanostructures produced by successive cycles of atomic layer deposition (ALD) of platinum onto 40 nm porous anodic alumina oxide supports, although the mechanisms for nucleation appear to differ. In conclusion, this work establishes a foundation for the investigation of the reductive assembly of abiotic metal catalysts at sites connected to photochemically reducing equivalent production in PSI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Mechanistic Studies of a Primitive Homolog of Nitrogenase Involved in Coenzyme F430 Biosynthesis

Methyl-coenzyme M reductase (MCR) is the key enzyme in the biological formation and anaerobic oxidation of methane (AOM). Methane is a potent greenhouse gas and the major component of natural gas. Given the abundance of natural gas reserves in remote areas, there is great current interest in a scalable bio-based process for the conversion of methane to liquid fuel or other high-value commodity chemicals. MCR holds much promise for use in such a methane bioconversion strategy. However, MCR cannot currently be produced in an active form in a heterologous host, due in large part to the lack of genetic and biochemical information about the production of holo MCR. In an effort to overcome this deficiency, our laboratory elucidated the biosynthetic pathway of the unique nickel-containing coenzyme of MCR, F430. The key step in coenzyme F430 biosynthesis (Cfb) was found to involve an unprecedented reductive cyclization reaction that converts Ni-sirohydrochlorin a , c -diamide to 15,17 3 -seco-F430-17 3 -acid. This remarkable transformation, which involves a 6-electron reduction of the isobacteriochlorin ring system, cyclization of the c -acetamide side chain to form a γ-lactam ring, and the formation of 7 stereocenters, is catalyzed by a primitive homolog of nitrogenase (CfbCD). Nitrogenase is a two-component metalloenzyme that catalyzes the ATP-dependent reduction of dinitrogen to ammonia (nitrogen fixation). Homologs of nitrogenase are also involved in the biosynthesis of the photosynthetic pigments chlorophyll and bacteriochlorophyll. Phylogenetic analysis of the CfbCD complex suggests that it is representative of a more ancient lineage of the nitrogenase superfamily, and a thorough investigation of its structure and function is likely to shed light on the mechanisms and evolution of these important metalloenzymes that catalyze multi-electron redox reactions. Moreover, a detailed understanding of the mechanism of the CfbCD complex may aid in the development of specific inhibitors to help reduce natural greenhouse gas emissions and can be exploited for the heterologous production of MCR for methane bioconversion. Towards these goals, the following Specific Aims will be pursued to determine the: 1) Identity of the CfbCD reaction product. The exact reaction catalyzed by CfbCD, including the number of electrons transferred and whether it involves enzymatic cyclization, is unclear. Several approaches, including reaction stoichiometry measurements, spectroelectrochemistry, and magnetic resonance spectroscopy will be applied to elucidate the structure of the reaction product and establish whether CfbCD is a reductase or reductive cyclase. 2) Structure, conformational dynamics, and oligomerization state changes of CfbCD. Significant insight into the mechanism and allosteric regulation of CfbCD can be obtained by assessing changes in the structure and dynamics of the complex during the catalytic cycle. To accomplish this, a combination of size-exclusion chromatography, hydrogen-deuterium exchange mass spectrometry, molecular dynamics simulations, and high-resolution structural methods will be employed. 3) Source, order, and stereochemistry of proton additions during CfbCD catalysis. Details regarding the order and stereochemistry of proton additions during the CfbCD reaction will be uncovered using a combined spectroscopic and computational approach. Complementary mechanistic studies employing site-directed mutagenesis and substrate analogs will establish the identity of active site acid residues and the possible involvement of substrate-assisted catalysis during the CfbCD reaction.

09 BIOMASS FUELS

Improving luminescence response in ZnGeN 2 /GaN superlattices: defect reduction through composition control

Abstract Color-mixed (cm) light-emitting diodes (LEDs) are theoretically the most efficient white light emitters, projected to improve white light luminous efficacy by 34% compared to incumbent phosphor converted LEDs. Since white light technology is pervasive and essential, small improvements in LED technology can result in energy savings. However, cm-LEDs are not yet realized due to poor efficacy in green and amber emitting materials, a spectral region colloquially referred to as the Green Gap. ZnGeN 2 is nearly isostructural and closely lattice-matched to GaN and can be heteroepitaxially integrated with existing GaN devices; ZnGeN 2 /GaN hybrid structures are theorized to emit green (~530 nn) light with a spontaneous emission rate 4.6–4.9 times higher than traditional InGaN LEDs when incorporated into III-N LED structures. In this report we demonstrate the molecular beam epitaxy (MBE) growth of GaN and ZnGeN 2 superlattices, an important step towards realizing multiple quantum well structures required for efficient LEDs. Elemental analysis, including atom probe tomography, shows that Ga and Ge are observed in both ZnGeN 2 and GaN layers, degrading the structural uniformity. The lack of elemental abruptness also leads to increased defect luminescence and reabsorption of band edge luminescence. The source of unintentional Ga distributed throughout the ZnGeN 2 layers was identified as excess flux escaping from around the closed MBE shutter. The source of unintentional Ge, which tended to incorporate as a single delta-doped layer in GaN, was identified as Ge riding along the cyclical metal-rich Ga adlayer used for high quality GaN, incorporating during subsequent nitrogen-rich growth step. Modifying the growth strategy results in improved structural quality, elemental abruptness, and luminescence response. This realization of structurally and elementally abrupt interfaces demonstrates the potential of heteroepitaxially integrated binary and ternary nitrides for energy-relevant devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC

Structural Diversity and Tunable Emission in Hybrid Organic–Inorganic Copper(I) Bromides

Recently, hybrid organic−inorganic copper(I) metal halides have attracted global attention due to their intriguing optical properties and low-cost solution processability. In this work, we report three hybrid organic−inorganic copper(I) bromides, [TMPA] 2 [Cu 2 Br 4 ], [TMPA] 4 [Cu 6 Br 10 ], and [TMPA] 2 [Cu 4 Br 6 ], synthesized through a slow evaporation method using trimethylphenylammonium (TMPA + ) as the organic cation. By precise control of the CuBr and TMPABr precursors, different copper halide [Cu 2 Br 4 ] 2− , [Cu 6 Br 10 ] 4− , and [Cu 4 Br 6 ] 2− structural units can be obtained. [TMPA] 2 [Cu 2 Br 4 ], [TMPA] 4 [Cu 6 Br 10 ], and [TMPA] 2 [Cu 4 Br 6 ] demonstrate distinct blue, orange, and greenish-yellow light emission, respectively. The first two compounds have zero-dimensional (0D) crystal structures in centrosymmetric triclinic space group P-1 and monoclinic space group P2 1 /n. In contrast, [TMPA] 2 [Cu 4 Br 6 ] features a unique one-dimensional (1D) structure and crystallizes in the centrosymmetric monoclinic space group P2 1 /c. Consequently, the observed greenish-yellow emission of [TMPA] 2 [Cu 4 Br 6 ] is also unique, in contrast to the typical orange-red emission of 0D [Cu 4 Br 6 ]-based compounds. This work provides insights into the design of copper halide light emitters and emphasizes the influence of structural dimensionality on photoluminescence. The tunable optical properties suggest the potential of these materials for multicolor photopatterning, information encryption, and anticounterfeiting applications.

Anions

Curvilinear Magnonic Crystal Based on 3D Hierarchical Nanotemplates

Curvilinear magnetic nanostructures enable control of magnetization dynamics through geometry-induced anisotropy and chiral interactions, as well as magnetic field modulation. In this work, we report a curvilinear magnonic crystal based on large-area square arrays of truncated nanospikes fabricated by conformal coating of 3D hierarchical templates with permalloy thin films. Brillouin light scattering spectroscopy reveals an anisotropic band structure with multiple dispersive and folded Bloch-type dispersive spin-wave modes as well as nondispersive modes exhibiting direction-dependent frequency shifts and intensity asymmetries along lattice principal axes. Finite element micromagnetic simulations indicate that curvature-induced variations of the demagnetizing field govern the magnonic response, enabling the identification of modes propagating in nanochannels and others localized on nanospike apexes or along the ridges connecting adjacent nanospikes. The combination of geometric curvature and optical probing asymmetry produces directional dependence of magnonic bands, establishing 3D hierarchical templates as a versatile platform for curvature-engineered magnonics.

3D hierarchical templates

Unique optical excitations in topological insulators (Final Technical Report)

The overall objective of this research is to understand how light interacts with topological insulator (TI) films and layered structures. Unlike normal materials, the electrons in TI films are trapped at the top and bottom surfaces of the film. These electrons have unusual properties, including low mass and high velocity. Light shining on these trapped electrons will excite electron density waves, called plasmons, which inherit the unusual properties of the electrons. This project aims to understand how these plasmons interact with each other and how the plasmon properties change as the film dimensions change. By controlling the physical properties of the films, the optical response of the film can also be controlled. In addition to single TI films, the project will also investigate the properties of stacks of TI films layered with normal insulating films. Stacking these materials results in multiple layers of trapped electrons whose plasmons can interact in ever more complex ways. After these interactions are understood, we can begin to engineer complex TI structures to obtain designer optical phenomena in the far-infrared and THz, wavelength ranges of interest for environmental monitoring and chemical sensing. This research directly addresses DOE Grand Challenges, including understanding how properties of matter emerge from complex electronic correlations and learning how to control these properties as well as the mission of the Basic Energy Sciences program to understand and control matter at the electronic/atomic level.

36 MATERIALS SCIENCE

Unraveling the Nature of Lasing Emission from Hybrid Silicon Nitride and Colloidal Nanocrystal Photonic Crystals with Low Refractive Index Contrast

Silicon nitride is used for its low optical loss and high thermal stability, making it a suitable platform for visible-light applications in integrated photonic devices. However, its application has been limited due to inefficient light emission, a problem addressed by integrating various types of light emitters onto the platform. In particular, the integration of solution-processable colloidal nanocrystals (NCs) as optical gain materials onto the silicon nitride platform is a promising route but requires a more solid theoretical footing. By leveraging 2D surface-emitting photonic crystal structures combined with NCs, we effectively confine and manipulate light to achieve lasing from green to red. Building on this, we model the light–matter interactions of the low index contrast NC/nitride platform, validated by extensive experimental validations through Fourier imaging techniques, revealing the full photonic band structure and showing clear mode congestion. Finally, these comprehensive studies confirm the potential of hybrid NC-based structures for fully integrated on-chip laser applications and indicate routes for further improvement.

BIC Lasing

Iron isotope fractionation between solid and liquid metal in the Fe-P±Ni system: Experimental constraints and implications for meteorites

Iron meteorites record a range of Fe isotope compositions that hold valuable information regarding the evolution of their parent bodies. Interpreting this isotopic variability, however, requires experimental constraints on the equilibrium isotope fractionation between phases. It is thought that the cores of many iron meteorite parent bodies experienced fractional crystallization, during which crystallization of solid iron-nickel occurs from an increasingly non-metal-rich liquid alloy. Phosphorus is one component of this alloy, and this study provides the first constraints on Fe-isotope fractionation between solid and liquid alloys in the Fe-Ni-P system. Experiments comprising Fe and P show a clear enrichment in the light isotopes of Fe in the liquid phase, which increases with the amount of phosphorus. Nickel-bearing samples are offset from the trend defined by Ni-free experiments, which is accounted for by the change in the solid alloy phase from a body-centered cubic to face-centered cubic structure upon the addition of Ni. The increasing light isotope enrichment of the liquid with increasing P content suggests interstitial solution of P, which is known to lengthen Fe-Fe bonds in Fe-P liquids (Waseda and Shiraishi 1977). Results suggest a negligible effect of P on Fe isotope fractionation during planetesimal core crystallization. Iron isotopes may, however, prove useful for identifying the petrogenesis of schreibersite in pallasites and iron meteorites.

58 GEOSCIENCES

Rethinking agrivoltaic incentive programs: A science-based approach to encourage practical design solutions

Agrivoltaic systems are promising solutions to address global food and energy challenges by combining agriculture and solar photovoltaics. However, the lack of appropriate regulations to define and guide their implementation constrains the growth of agrivoltaic systems in the U.S. This study uses a shading and radiation tool to evaluate an existing agrivoltaic incentive program that defines agrivoltaic designs based on shading reduction limits and panel height requirements. Our analysis indicates that structuring policy requirements around shading, and not light availability, may lead to an underestimation of crop suitability by neglecting diffuse radiation. Furthermore, we show that agrivoltaic systems can avoid increasing panel height if policy acknowledges use-case scenarios where farming only occurs between rows. In light of these insights, this study proposes two key policy recommendations: (1) benchmark crop suitability based on daily light integral (DLI) requirements for a shade-intolerant crop selected to represent a prevalent crop in the region, and (2) include an incentive scenario where agriculture is only required between rows. Furthermore, these two recommendations can potentially incentivize designs that are practical and closer in cost to conventional solar farms, thereby accelerating the adoption of cost-effective agrivoltaic systems.

14 SOLAR ENERGY

Mixed lipid bilayers enable enhanced stability and activity retention of Lipase A in low-pH environments

Lipase A (LipA) from Bacillus subtilis is a versatile and industrially relevant enzyme, but its activity is compromised under acidic conditions due to aggregation and deactivation. In this study, we investigated the use of mixed lipid bilayers to stabilize and improve activity retention of LipA at low pH. Attachment to lipid bilayers, particularly those containing cationic lipids, greatly enhanced the long-term stability of LipA in acidic conditions while also leading to improvements in activity. Tethering to cationic bilayers not only shifted the apparent pH activity profile toward more acidic conditions, but also significantly enhanced activity retention upon incubation at pH 6. Notably, this protective effect persisted even without direct tethering, indicating that reversible, non-covalent interactions with the bilayer surface are sufficient for long-term stability. Circular dichroism further revealed that the secondary structure of LipA was retained, while dynamic light scattering suggested that activity loss in solution was primarily due to aggregation of the native state. Together, these findings support a model in which lipid bilayers mitigate aggregation and stabilize LipA through transient interactions and electrostatic modulation of the local surface environment. Furthermore, this approach exemplifies a simple, tether-free strategy for enhancing enzyme performance in acidic or destabilizing conditions, with implications for biocatalysis, biosensing, and therapeutic delivery.

Biocatalysis