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At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Decreased Soil Organic Matter in a Long-Term Soil Warming Experiment Lowers Soil Water Holding Capacity and Affects Soil Thermal and Hydrological Buffering

Long-term soil warming can decrease soil organic matter (SOM), resulting in self-reinforcing feedback to the global climate system. We investigated additional consequences of SOM reduction for soil water holding capacity (WHC) and soil thermal and hydrological buffering. At a long-term soil warming experiment in a temperate forest in the northeastern United States, we suspended the warming treatment for 104 days during the summer of 2017. The formerly heated plot remained warmer (+0.39 °C) and drier (-0.024 cm 3 H 2 O cm -3 soil) than the control plot throughout the suspension. We measured decreased SOM content (-0.184 g SOM g -1 for O horizon soil, -0.010 g SOM g -1 for A horizon soil) and WHC (-0.82 g H 2 O g -1 for O horizon soil, -0.18 g H2O g -1 for A horizon soil) in the formerly heated plot relative to the control plot. Reduced SOM content accounted for 62% of the WHC reduction in the O horizon and 22% in the A horizon. We investigated differences in SOM composition as a possible explanation for the remaining reductions with Fourier transform infrared (FTIR) spectra. We found FTIR spectra that correlated more strongly with WHC than SOM, but those particular spectra did not differ between the heated and control plots, suggesting that SOM composition affects WHC but does not explain treatment differences in this study. We conclude that SOM reductions due to soil warming can reduce WHC and hydrological and thermal buffering, further warming soil and decreasing SOM. This feedback may operate in parallel, and perhaps synergistically, with carbon cycle feedbacks to climate change.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

DNA-assembled superconducting 3D nanoscale architectures

Studies of nanoscale superconducting structures have revealed various physical phenomena and led to the development of a wide range of applications. Most of these studies concentrated on one- and two-dimensional structures due to the lack of approaches for creation of fully engineered three-dimensional (3D) nanostructures. Here, we present a ‘bottom-up’ method to create 3D superconducting nanostructures with prescribed multiscale organization using DNA-based self-assembly methods. We assemble 3D DNA superlattices from octahedral DNA frames with incorporated nanoparticles, through connecting frames at their vertices, which result in cubic superlattices with a 48 nm unit cell. The superconductive superlattice is formed by converting a DNA superlattice first into highly-structured 3D silica scaffold, to turn it from a soft and liquid-environment dependent macromolecular construction into a solid structure, following by its coating with superconducting niobium (Nb). Through low-temperature electrical characterization we demonstrate that this process creates 3D arrays of Josephson junctions. This approach may be utilized in development of a variety of applications such as 3D Superconducting Quantum interference Devices (SQUIDs) for measurement of the magnetic field vector, highly sensitive Superconducting Quantum Interference Filters (SQIFs), and parametric amplifiers for quantum information systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2026

Out-of-time-order correlators bridge classical transport and quantum dynamics

The out-of-time-order correlator (OTOC) has emerged as a central tool for quantifying decoherence across wide-ranging physical platforms. Here, we demonstrate its direct measurement in a classical ensemble using nuclear magnetic resonance with a modulated gradient spin echo sequence and extend the method into a multidimensional correlation to track exchange phenomena. Position is encoded through magnetic field gradients and momentum through the velocity autocorrelation function, enabling experimental access to OTOCs for proton motion confined within the self-similar lattice of the metal–organic framework MOF-808. Here, water confined to specified geometries within the MOF pores gives rise to spatially distinct diffusive eigenmodes with characteristic relative entropies. We demonstrate that periodic radio frequency driving combined with gradient modulation yields entropy evolution through the selection of distinct diffusion modes. Frequency-resolved diffusion spectra connect these entropy dynamics to classical heat exchange laws, revealing how operational features of quantum systems are mirrored in confined, macroscopic spin ensembles.

Fricke, Sophia N. [University of California, Berke↗
NASA NTRS1971

Reliability estimation procedures and CARE: The Computer-Aided Reliability Estimation Program

Ultrareliable fault-tolerant onboard digital systems for spacecraft intended for long mission life exploration of the outer planets are under development. The design of systems involving self-repair and fault-tolerance leads to the companion problem of quantifying and evaluating the survival probability of the system for the mission under consideration and the constraints imposed upon the system. Methods have been developed to (1) model self-repair and fault-tolerant organizations; (2) compute survival probability, mean life, and many other reliability predictive functions with respect to various systems and mission parameters; (3) perform sensitivity analysis of the system with respect to mission parameters; and (4) quantitatively compare competitive fault-tolerant systems. Various measures of comparison are offered. To automate the procedures of reliability mathematical modeling and evaluation, the CARE (computer-aided reliability estimation) program was developed. CARE is an interactive program residing on the UNIVAC 1108 system, which makes the above calculations and facilitates report preparation by providing output in tabular form, graphical 2-dimensional plots, and 3-dimensional projections. The reliability estimation of fault-tolerant organization by means of the CARE program is described.

Mathur, F. P.↗
NASA NTRS1972

Automation of reliability evaluation procedures through CARE - The computer-aided reliability estimation program.

Description of an on-line interactive computer program called CARE (Computer-Aided Reliability Estimation) which can model self-repair and fault-tolerant organizations and perform certain other functions. Essentially CARE consists of a repository of mathematical equations defining the various basic redundancy schemes. These equations, under program control, are then interrelated to generate the desired mathematical model to fit the architecture of the system under evaluation. The mathematical model is then supplied with ground instances of its variables and is then evaluated to generate values for the reliability-theoretic functions applied to the model.

Mathur, F. P.↗
NASA NTRS1974

Flow and pressure regulation in the cardiovascular system

Principles and descriptive fragments which may contribute to a model of the regulating chains in the cardiovascular system are presented. Attention is given to the strain sensitivity of blood vessels, the law of the autonomy of the heart beat oscillator, the law of the encapsulation of body fluids, the law of the conservation of protein, the law of minimum 'arterial' pressure, the design of the 'mammalian' kidney, questions of homeokinetic organization, and the development of self-regulatory chains. Details concerning the development program for the heart muscle are considered along with the speed of response of the breathing rate and the significance of the pulmonary vascular pressure-flow characteristics.

Iberall, A.↗
NASA NTRS2019

Chemical Ecosystem Selection on Mineral Surfaces Reveals Long-Term Dynamics Consistent with the Spontaneous Emergence of Mutual Catalysis

How did chemicals first become organized into systems capable of self-propagation and adaptive evolution? One possibility is that the first evolvers were chemical ecosystems localized on mineral surfaces and composed of sets of molecular species that could catalyze each other’s formation. We used a bottom-up experimental framework; chemical ecosystem selection (CES) to evaluate this perspective and search for surface-associated; and mutually catalytic chemical systems based on the changes in chemistry they are expected to induce. Here, we report the results of preliminary CES experiments conducted using a synthetic “prebiotic soup” and pyrite grains, which yield dynamical patterns that are suggestive of the emergence of mutual catalysis. While more research is needed to better understand the specific patterns observed here and determine whether they are reflective of self-propagation, these results illustrate the potential power of CES to test competing hypotheses for the emergence of protobiological chemical systems.

autocatalysis↗
NASA NTRS2006

Stable Carbon Isotopic Signatures of Abiotic Organics from Hydrothermal Synthesis Experiments

Stable carbon isotopes can be powerful biogeochemical markers in the study of life's origins. Biogenic carbon fixation produces organics that are depleted in C-13 by about -20 to -30%0. Less attention has been paid to the isotopic signatures of abiotic processes. The possibility of abiotic processes producing organics with morphologies and isotopic signatures in the biogenic range has been at the center of recent debate over the Earth's earliest microfossils. The abiotic synthesis of organic compounds in hydrothermal environments is one possible source of endogenous organic matter to the prebiotic earth. Simulated hydrothermal settings have been shown to synthesize, among other things, single chain amphiphiles and simple lipids from a mix of CO, CO2, and H2. A key characteristic of these amphiphilic molecules is the ability to self-assemble in aqueous phases into more organized structures called vesicles, which form a selectively permeable boundary and serve the function of containing and concentrating other organic molecules. The ability to form cell like structures also makes these compounds more likely to be mistaken for biogenic. Hydrothermal simulation experiments were conducted from oxalic or formic acid in water at 175 C for 72 hr. The molecular and isotopic composition of the products of these reactions were determined and compared to biogenic fractionations . Preliminary results indicate isotopic fractionation during abiotic hydrocarbon synthesis in hydrothermal environments is on par with biological carbon fixation.

Stern, Jennifer C.↗
NASA NTRS1994

Direct Simulation of a Self-Similar Turbulent Mixing Layer

Three direct numerical simulations of incompressible turbulent plane mixing layers have been performed. All the simulations were initialized with the same two velocity fields obtained from a direct numerical simulation of a turbulent boundary layer with a momentum thickness Reynolds number of 300 computed by Spalart (J. Fluid Mech. 187, 61, 1988). In addition to a baseline case with no additional disturbances, two simulations were begun with two-dimensional disturbances of varying strength in addition to the boundary layer turbulence. After a development stage, the baseline case and the case with weaker additional two-dimensional disturbances evolve self-similarly, reaching visual thickness Reynolds numbers of up to 20 000. This self-similar period is characterized by a lack of large-scale organized pairings, a lack of streamwise vortices in the 'braid' regions, and scalar mixing that is characterized by 'marching' Probability Density Functions (PDFs). The case begun with strong additional two-dimensional disturbances only becomes approximately self-similar, but exhibits sustained organized large-scale pairings, clearly defined braid regions with streamwise vortices that span them, and scalar PDFs that are 'nonmarching.' It is also characterized by much more intense vertical velocity fluctuations than the other two cases. The statistics and structures in several experiments involving turbulent mixing layers are in better agreement with those of the simulations that do not exhibit organized pairings.

Rogers, Michael M.↗
DOE OSTI2024

Self-Powered Circularly Polarized Light Detection Enabled by Chiral Two-Dimensional Perovskites with Mixed Chiral–Achiral Organic Cations

Direct detection of circularly polarized light (CPL) holds great promise for the development of various optical technologies. Chiral 2D organic–inorganic halide perovskites make it possible to fabricate CPL-sensitive photodetectors. However, selectively detecting left-handed circularly polarized (LCP) and right-handed circularly polarized (RCP) light remains a significant challenge. Herein, we demonstrate a greatly enhanced distinguishability of photodiode-type CPL photodetectors based on chiral 2D perovskites with mixed chiral aryl (R)-(+),(S)-(–)-α-methylbenzylammonium (R,S-MBA) and achiral alkyl n-butylammonium (nBA) cations. The (R,S-MBA 0.5 nBA 0.5 ) 2 PbI 4 perovskites exhibit a 10-fold increase in circular dichroism signals compared to (R,S-MBA) 2 PbI 4 perovskites. Here, the CPL photodetectors based on the mixed-cation perovskites exhibit self-powered capabilities with a specific detectivity of 2.45 × 10 12 Jones at a o V bias. Notably, these devices show high distinguishability (gres) factors of –0.58 and +0.54 based on (R,S-MBA 0.5 nBA 0.5 ) 2 PbI 4 perovskites, respectively, surpassing the performance of (R-MBA) 2 PbI 4 -based devices by over 3-fold and setting a record for CPL detectors based on chiral 2D n = 1 perovskites.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Formation and Characterization of Zein-Based Oleogels

Oleogels are interesting as a result of their ability to hold large amounts of oil in a semi-solid gel structure. In the food industry, oleogels are most often investigated as substitutes for saturated and trans fats. In this work, the lyotropic formation of ethanol/zein/oleic acid gels was observed qualitatively and ternary phase diagrams were constructed to map the observations. The viscoelastic parameters G' and G'' were measured to confirm gel formation as observed in phase diagrams. Ultrasmall X-ray scattering was used to study the microstructural organization of ethanol/zein/oleic acid gels. Furthermore, data suggested that the primary unit or building block for gel network structures was the rod-shaped zein molecule. Ultrasmall X-ray data suggested that zein/oleic acid gels have a highly organized microstructure, possibly the result of zein self-assembly. Zein was considered an effective oleogelator in ethanol/zein/oleic acid systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

The evolution of the FIGARO data reduction system

The Figaro data reduction system originated at Caltech around 1983. It was based on concepts being developed in the U.K. by the Starlink organization, particularly the use of hierarchical self-defining data structures and the abstraction of most user-interaction into a set of 'parameter system' routines. Since 1984 it has continued to be developed at AAO, in collaboration with Starlink and Caltech. It was adopted as Starlink's main spectroscopic data reduction package, although it is by no means limited to spectra; it has operations for images and data cubes and even a few (very specialized) for four-dimensional data hypercubes. It continued to be used at Caltech and will be used at the Keck. It is also in use at a variety of other organizations around the world. Figaro was originally a system for VMS Vaxes. Recently it was ported (at Caltech) to run on SUN's, and work is underway at the University of New South Wales on a DecStation version. It is hoped to coordinate all this work into a unified release, but coordination of the development of a system by organizations covering three continents poses a number of interesting administrative problems. The hierarchical data structures used by Figaro allow it to handle a variety of types of data, and to add new items to data structures. Error and data quality information was added to the basic file format used, error information being particularly useful for infrared data. Cooperating sets of programs can add specific sub-structures to data files to carry information that they understand (polarimetry data containing multiple data arrays, for example), without this affecting the way other programs handle the files. Complex instrument-specific ancillary information can be added to data files written at a telescope and can be used by programs that understand the instrumental details in order to produce properly calibrated data files. Once this preliminary data processing was done the resulting files contain 'ordinary' spectra or images that can be processed by programs that are not instrument-specific. The structures holding the instrumental information can then be discarded from the files. Much effort has gone into trying to make it easy to write Figaro programs; data access subroutines are now available to handle access to all the conventional items found in Figaro files (main data arrays, error information, quality information etc), and programs that only need to access such items can be very simple indeed. A large number of Figaro users do indeed write their own Figaro applications using these routines. The fact that Figaro programs are written as callable subroutines getting information from the user through a small set of parameter routines means that they can be invoked in numerous ways; they are normally linked and run as individual programs (called by a small main routine that is generated automatically), but are also available linked to run under the ADAM data acquisition system and there is an interface that lets them be called as part of a user-written Fortran program. The long-term future of Figaro probably depends to a large extent on how successfully it manages the transition from being a VMS-only system to being a multi-platform system.

Shortridge, K.↗
DOE OSTI2020

Programming Amphiphilic Peptoid Oligomers for Hierarchical Assembly and Inorganic Crystallization

Natural organisms make a wide variety of exquisitely complex, nano-, micro-, and macroscale structured materials in an energy-efficient and highly reproducible manner. During these processes, the information-carrying biomolecules (e.g., proteins, peptides, and carbohydrates) enable (1) hierarchical organization to assemble scaffold materials and execute high-level functions and (2) exquisite control over inorganic materials synthesis, generating biominerals whose properties are optimized for their functions. Inspired by nature, significant efforts have been devoted to developing functional materials that can rival those natural molecules by mimicking in vivo functions using engineered proteins, peptides, DNAs, sequence-defined synthetic molecules (e.g., peptoids), and other biomimetic polymers. Among them, peptoids, a new type of synthetic mimetics of peptides and proteins, have received particular attention because they combine the merits of both synthetic polymers (e.g., high chemical stability and efficient synthesis) and biomolecules (e.g., sequence programmability and biocompatibility). The lack of both chirality and hydrogen bonds in their backbone results in a highly designable peptoid-based system with reduced structural complexity and side chain-chemistry-dominated properties. Here in this Account, we present our recent efforts in this field by programming amphiphilic peptoid sequences for (1) the controlled self-assembly into different hierarchically structured nanomaterials with favorable properties and (2) manipulating inorganic (nano)crystal nucleation, growth, and assembly into superstructures. First, we designed a series of amphiphilic peptoids with controlled side chain chemistries that self-assembled into 1D highly stiff and dynamic nanotubes, 2D membrane-mimetic nanosheets, hexagonally patterned nanoribbons, and 3D nanoflowers. These crystalline nanostructures exhibited sequence-dependent properties and showed promise for different applications. The corresponding peptoid self-assembly pathways and mechanisms were also investigated by leveraging in situ atomic force microscopy studies and molecular dynamics simulations, which showed precise sequence dependency. Second, inspired by peptide- and protein-controlled formation of hierarchical inorganic nanostructures in nature, we developed peptoid-based biomimetic approaches for controlled synthesis of inorganic materials (e.g., noble metals and calcite), in which we took advantage of the substantial side chain chemistry of peptoids and investigated the relationship between the peptoid sequences and the morphology and growth kinetics of inorganic materials. For example, to overcome the challenges (e.g., complexity of protein- and peptide-folding, poor thermal and chemical stabilities) facing the area of protein- and peptide-controlled synthesis of inorganic materials, we recently reported the design of sequence-defined peptoids for controlled synthesis of highly branched plasmonic gold particles. Moreover, we developed a rule of thumb for designing peptoids that predictively enabled the morphological evolution from spherical to coral-shaped gold nanoparticles (NPs). With this Account, we hope to stimulate the research interest of chemists and materials scientists and promote the predictive synthesis of functional and robust materials through the design of sequence-defined synthetic molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2018

The Opera Instrument: An Advanced Curation Development for Mars Sample Return Organic Contamination Monitoring

Mars Sample Return (MSR) requires strict organic contamination control (CC) and contamination knowledge (CK) as outlined by the Mars 2020 Organic Contamination Panel (OCP). This includes a need to monitor surficial organic contamination to a ng/sq. cm sensitivity level. Archiving and maintaining this degree of surface cleanliness may be difficult but has been achieved. MSR's CK effort will be very important because all returned samples will be studied thoroughly and in minute detail. Consequently, accurate CK must be collected and characterized to best interpret scientific results from the returned samples. The CK data are not only required to make accurate measurements and interpretations for carbon-depleted martian samples, but also to strengthen the validity of science investigations performed on the samples. The Opera instrument prototype is intended to fulfill a CC/CK role in the assembly, cleaning, and overall contamination history of hardware used in the MSR effort, from initial hardware assembly through post-flight sample curation. Opera is intended to monitor particulate and organic contamination using quartz crystal microbalances (QCMs), in a self-contained portable package that is cleanroom-compliant. The Opera prototype is in initial development capable of approximately 100 ng/sq. cm organic contamination sensitivity, with additional development planned to achieve 1 ng/sq. cm. The Opera prototype was funded by the 2017 NASA Johnson Space Center Innovation Charge Account (ICA), which provides funding for small, short-term projects.

Fries, M. D.↗
DOE OSTI2024

Integration and Optimization of a Waste Heat Driven Organic Rankine Cycle for Power Generation in Wastewater Treatment Plants

The study focuses on achieving energy self-sufficiency in Wastewater Treatment Plants by proposing a comprehensive model for integrating, sizing, and optimizing an Organic Rankine Cycle system. The Organic Rankine Cycle system is designed to utilize waste heat from the gensets at As Samra Wastewater Treatment Plant in Jordan, where it will contribute to the overall electrical energy supply of the plant. Real data from As Samra Wastewater Treatment Plant is used to model and calculate the available waste heat using TRNSYS® software. The Organic Rankine Cycle model is then developed using ASPEN PLUS® software to explore the impact of operational parameters and determine their optimal values for maximizing the plant's energy profile. An economic analysis is conducted to assess the feasibility of the proposed model, considering system components, installation, operation, and maintenance costs. To optimize the Organic Rankine Cycle system, the study employs the Multi-Output Support Vector Regression technique to capture nonlinear relationships between independent variables (fluid type, turbine inlet pressure, turbine inlet temperature, turbine outlet pressure, and mass flow rate) and dependent variables (pump power input, waste heat input, and turbine specific work). The Osprey optimization algorithm is used to address the multi-objective optimization problem, with the proposed Pareto-based Osprey Optimization Algorithm and the Multi-Objective Particle Swarm Optimization technique being employed to evaluate critical performance and economic parameters such as system thermal efficiency, net power output, and the levelized cost of electricity. The results of the optimization strategies indicate that the M-SVR model's prediction accuracy is significantly improved after parameter optimization, with the model returning high R 2 and low Mean Square Error values of 0.991 and 0.00216, respectively. The Pareto-Based Osprey Optimization Algorithm optimizer identifies the best working fluid as Isobutane/Isopentane in a ratio of 66:34, with optimal turbine inlet pressure and temperature of 15 bars and 218 °C, respectively. In conclusion, the Organic Rankine Cycle model at these optimal conditions achieves a cycle efficiency of 19.93% and an Levelized Cost of Electricity value of 0.0353 USD/kWh.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Biomimetic Metal-Free Hydride Donor Catalysts for CO 2 Reduction

The catalytic reduction of carbon dioxide to fuels and value-added chemicals is of significance for the development of carbon recycling technologies. One of the main challenges associated with catalytic CO 2 reduction is product selectivity: the formation of carbon monoxide, molecular hydrogen, formate, methanol, and other products occurs with similar thermodynamic driving forces, making it difficult to selectively reduce CO 2 to the target product. Significant scientific effort has been aimed at the development of catalysts that can suppress the undesired hydrogen evolution reaction and direct the reaction toward the selective formation of the desired products, which are easy to handle and store. Inspired by natural photosynthesis, where the CO 2 reduction is achieved using NADPH cofactors in the Calvin cycle, in this study we explore biomimetic metal-free hydride donors as catalysts for the selective reduction of CO 2 to formate. Here, we outline our recent findings on the thermodynamic and kinetic parameters that control the hydride transfer from metal-free hydrides to CO 2 . By experimentally measuring and theoretically calculating the thermodynamic hydricities of a range of metal-free hydride donors, we derive structural and electronic factors that affect their hydride-donating abilities. Two dominant factors that contribute to the stronger hydride donors are identified to be (i) the stabilization of the positive charge formed upon HT via aromatization or by the presence of electron-donating groups and (ii) the destabilization of hydride donors through the anomeric effect or in the presence of significant structural constrains in the hydride molecule. Hydride donors with appropriate thermodynamic hydricities were reacted with CO 2 , and the formation of the formate ion (the first reduction step in CO 2 reduction to methanol) was confirmed experimentally, providing an important proof of principle that organocatalytic CO 2 reduction is feasible. The kinetics of hydride transfer to CO 2 were found to be slow, and the sluggish kinetics were assigned in part to the large self-exchange reorganization energy associated with the organic hydrides in the DMSO solvent. Finally, we outline our approaches to the closure of the catalytic cycle via the electrochemical and photochemical regeneration of the hydride (R–H) from the conjugate hydride acceptors (R + ). We illustrate how proton-coupled electron transfer can be efficiently utilized not only to lower the electrochemical potential at which the hydride regeneration takes place but also to suppress the unwanted dimerization that neutral radical intermediates tend to undergo. Overall, this account provides a summary of important milestones achieved in organocatalytic CO 2 reduction and provides insights into the future research directions needed for the discovery of inexpensive catalysts for carbon recycling.

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

Interfacing DNA nanotechnology and biomimetic photonic complexes: advances and prospects in energy and biomedicine

Abstract Self-assembled photonic systems with well-organized spatial arrangement and engineered optical properties can be used as efficient energy materials and as effective biomedical agents. The lessons learned from natural light-harvesting antennas have inspired the design and synthesis of a series of biomimetic photonic complexes, including those containing strongly coupled dye aggregates with dense molecular packing and unique spectroscopic features. These photoactive components provide excellent features that could be coupled to multiple applications including light-harvesting, energy transfer, biosensing, bioimaging, and cancer therapy. Meanwhile, nanoscale DNA assemblies have been employed as programmable and addressable templates to guide the formation of DNA-directed multi-pigment complexes, which can be used to enhance the complexity and precision of artificial photonic systems and show the potential for energy and biomedical applications. This review focuses on the interface of DNA nanotechnology and biomimetic photonic systems. We summarized the recent progress in the design, synthesis, and applications of bioinspired photonic systems, highlighted the advantages of the utilization of DNA nanostructures, and discussed the challenges and opportunities they provide. Graphical Abstract

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Role of Protein-Water Interface in the Stacking Interactions of Granum Thylakoid Membranes—As Revealed by the Effects of Hofmeister Salts

The thylakoid membranes of vascular plants are differentiated into stacked granum and unstacked stroma regions. The formation of grana is triggered by the macrodomain formation of photosystem II and light-harvesting complex II (PSII-LHCII) and thus their lateral segregation from the photosystem I—light-harvesting complex I (PSI-LHCI) super-complexes and the ATP-synthase; which is then stabilized by stacking interactions of the adjacent PSII-LHCII enriched regions of the thylakoid membranes. The self-assembly and dynamics of this highly organized membrane system and the nature of forces acting between the PSII-LHCII macrodomains are not well understood. By using circular dichroism (CD) spectroscopy, small-angle neutron scattering (SANS) and transmission electron microscopy (TEM), we investigated the effects of Hofmeister salts on the organization of pigment-protein complexes and on the ultrastructure of thylakoid membranes. We found that the kosmotropic agent (NH 4 ) 2 SO 4 and the Hofmeister-neutral NaCl, up to 2 M concentrations, hardly affected the macro-organization of the protein complexes and the membrane ultrastructure. In contrast, chaotropic salts, NaClO 4 , and NaSCN destroyed the mesoscopic structures, the multilamellar organization of the thylakoid membranes and the chiral macrodomains of the protein complexes but without noticeably affecting the short-range, pigment-pigment excitonic interactions. Comparison of the concentration- and time-dependences of SANS, TEM and CD parameters revealed the main steps of the disassembly of grana in the presence of chaotropes. It begins with a rapid diminishment of the long-range periodic order of the grana membranes, apparently due to an increased stacking disorder of the thylakoid membranes, as reflected by SANS experiments. SANS measurements also allowed discrimination between the cationic and anionic effects—in stacking and disorder, respectively. This step is followed by a somewhat slower disorganization of the TEM ultrastructure, due to the gradual loss of stacked membrane pairs. Occurring last is the stepwise decrease and disappearance of the long-range chiral order of the protein complexes, the rate of which was faster in LHCII-deficient membranes. These data are interpreted in terms of a theory, from our laboratory, according to which Hofmeister salts primarily affect the hydrophylic-hydrophobic interactions of proteins, and the stroma-exposed regions of the intrinsic membrane proteins, in particular—pointing to the role of protein-water interface in the stacking interactions of granum thylakoid membranes.

59 BASIC BIOLOGICAL SCIENCES↗