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At least 1,279 records · Page 71

Time-resolved detectors for quantum ghost imaging

Quantum ghost imaging is a method that utilizes the correlated detection of two photons to generate an image. One photon is detected by an imaging sensor and the other by a single-element bucket detector. The selection of the imaging sensor and its capabilities relative to the bucket detector impact the quality of the ghost images. This work examines a SPAD array and a photocathode detector as imaging sensors for quantum ghost imaging. We discuss how to achieve optimal images using these two technologies. We also demonstrate that these devices are able to generate ghost images at 1Hz frame rates, expanding the technique to biologically relevant time scales.

36 MATERIALS SCIENCE↗

Nonlinear Optical Microscopy with Ultralow Quantum Light

Nonlinear optical (NLO) microscopy relies on multiple light–matter interactions to provide unique contrast mechanisms and imaging capabilities that are inaccessible to traditional linear optical imaging approaches, making them versatile tools to understand a wide range of complex systems. However, the strong excitation fields that are necessary to drive higher-order optical processes efficiently are often responsible for photobleaching, photodegradation, and interruption in many systems of interest. This is especially true for imaging living biological samples over prolonged periods of time or in accessing intrinsic dynamics of electronic excited-state processes in spatially heterogeneous materials. This perspective outlines some of the key limitations of two NLO imaging modalities implemented in our lab and highlights the unique potential afforded by the quantum properties of light, especially entangled two-photon absorption based NLO spectroscopy and microscopy. Here, we further review some of the recent exciting advances in this emerging filed and highlight some major challenges facing the realization of quantum-light-enabled NLO imaging modalities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ablating nanoscale pores in crystalline quartz using laser-induced micro-plasmas in tri-layer structures

We demonstrate a novel approach for achieving rapid, consistent, and controllable micro-pore fabrication in single-crystalline quartz. These micro-pores are essential for applications in biology, i.e., studying ion channels in general and mechano-sensitive channels (MSC) in particular. The fabrication process consists of direct material ablation using pulsed UV light from a 193 nm excimer laser. These pulses ablate single-crystalline quartz chips by burning a laser-induced plasma in a tri-layer structure. Controllable plasma confinement and thus pore size is achieved by sandwiching a thin layer of a selected organic solution between the quartz chip and different substrates. This solution causes the confined micro-plasma to generate special ablation conditions, to create uniformly sized and shaped nanopores.

36 MATERIALS SCIENCE↗

Optimize Electron Beam Energy toward In Situ Imaging of Thick Frozen Bio-Samples with Nanometer Resolution Using MeV-STEM

To optimize electron energy for in situ imaging of large biological samples up to 10 μm in thickness with nanoscale resolutions, we implemented an analytical model based on elastic and inelastic characteristic angles. This model has been benchmarked by Monte Carlo simulations and can be used to predict the transverse beam size broadening as a function of electron energy while the probe beam traverses through the sample. As a result, the optimal choice of the electron beam energy can be realized. In addition, the impact of the dose-limited resolution was analysed. While the sample thickness is less than 10 μm, there exists an optimal electron beam energy below 10 MeV regarding a specific sample thickness. However, for samples thicker than 10 μm, the optimal beam energy is 10 MeV or higher depending on the sample thickness, and the ultimate resolution could become worse with the increase in the sample thickness. Moreover, a MeV-STEM column based on a two-stage lens system can be applied to reduce the beam size from one micron at aperture to one nanometre at the sample with the energy tuning range from 3 to 10 MeV. In conjunction with the state-of-the-art ultralow emittance electron source that we recently implemented, the maximum size of an electron beam when it traverses through an up to 10 μm thick bio-sample can be kept less than 10 nm . This is a critical step toward the in situ imaging of large, thick biological samples with nanometer resolution.

36 MATERIALS SCIENCE↗

Executive Summary: Background

Background information on, and the objectives of, the NASA Global Biology Research Program are given. The following issues were addressed: (1) geographic distribution of wetland parameters, (2) the processes of wetland material fluxes, and (3) the relation of local fluxes with global processes. Wetland inventorying and categorizing, gas-phase exchanges with the atmosphere, material exchange with the aquatic environment, and material storage in wetland sediments were identified as topics requiring further research.

Source record↗

Potential Mars Exploration Rover Landing Sites West and South of Apollinaris Patera

Apollinaris provides an exceptional site for astrobiological, geological, and climatalogical purposes. Fluvial (including ground water sapping) and associated processes were likely pervasive from the late Noachian, through the Hesperian, and into the Amazonian. Long-lived and large scale hydrothermal systems were certainly present throughout much if not all of this period. Thermal springs likely persisted for long periods. Water from the highlands via Ma'adim Valles and other smaller valley networks deposited highland-derived material in the area. In short, Apollinaris provides an excellent variety of rock types and ages and may preserve evidence of biologic or pre-biologic processes in associated thermal spring deposits.

Gulick, Virginia C.↗

Release of somatic embryogenic potential from excised zygotic embryos of carrot and maintenance of proembryonic cultures in hormone-free medium

Excised zygotic embryos, mericarps ("seeds") and hypocotyls of seedlings of cultivated carrot Daucus carota cv. Scarlet Nantes were evaluated for their ability to generate somatic embryos on a semisolid hormone-free nutrient medium. Neither intact zygotic embryos nor hypocotyls ever produced somatic embryos. However, mericarps and broken zygotic embryos were excellent sources for somatic embryo production (response levels as high as 86%). Somatic embryo formation was highest from cotyledons, but was also observed on isolated hypocotyls and root tips of mature zygotic embryos. On media containing unreduced nitrogen, somatic embryo formation led to the generation of vigorous cultures comprised entirely of somatic embryos at various stages of development which in turn proliferated still other somatic embryos. However, a medium was devised which when 1-5 mM NH4+ was the sole nitrogen source, led only to a proliferation of globular proembryos. Sustained subculturing of these proembryos at 2-3 week intervals enabled establishment of highly uniform cultures in which no further development into more mature stages of embryonic development occurred. These have been maintained, without decline, as morphogenetically competent proembryonic globules for over ten months. A basal medium containing from 1-5 mM NH4+ as the sole nitrogen source appears not to be inductive to somatic proembryo formation. Instead, such a medium is best thought of as permissive to the expression of embryogenically determined cells within zygotic embryos. By excising and breaking or wounding zygotic embryos, constituent cells are probably released from positional or chemical restraints and thus are able to express their innate embryogenic potential. Once a proembryonic culture is established, this medium containing 1-5 mM NH4+ as the sole nitrogen source provides a nonpermissive environment to the development and growth of later embryonic stages, but it does allow the continued formation and multiplication of globular somatic proembryos. The sequence of events leading from excised broken zygotic embryos to the formation of somatic embryos and the maintenance of somatic proembryos are demonstrated by scanning electron microscopy and histological preparations. Germination levels from intact zygotic embryos on media with varying levels and ratios of unreduced vs. reduced inorganic nitrogen were determined as well and provided baseline or control data on the type of response obtained from nonwounded material.

Non-NASA Center↗

Mars Sample Receiving Facility Research and Development to Enable Preservation, Safe Containment, and Scientific Research of Martian Samples on Earth

NASA and ESA are working together to plan a joint campaign to potentially bring back the first Martian samples to Earth in the early 2030s. On the surface of Mars, the Mars 2020Perseverance Rover is selecting and packaging samples that could be returned to Earth for careful examination by an international team of scientists. In preparation for this historic sample return, advance planning is underway to design and build a Mars Sample Receiving Facility (SRF) in the mid-2020s. In 2022, a Mars Sample Receiving Facility Assessment Study(MSAS) will be conducted to further define construction modality and capability options for a facility in the conterminous United States. Since Mars Sample Return (MSR) is currently categorized as a planetary protection restricted Earth return, this new facility would feature biosafety level 4 (BSL-4)-like high containment to protect Earth’s biosphere from any potential hazard. In addition, the facility also requires integration of cleanroom technologies to mitigate against terrestrial contamination and preserve sample integrity for science investigations. The integration of both clean handling and high containment requires significant technology research and development (R&D) by the mid-2020s to support the definition and planning of a SRF before commencing the site specific design phase. The SRF project will need to solidify the inorganic, organic, and biological contamination control (CC) requirements for the facility. This could entail a translation of Mars 2020 mission CC requirements for geologic material to engineering requirements for surfaces and airborne molecular contamination inside isolators and cleanrooms. In tandem, the project will need to determine precision cleaning and sterilization approaches for cleanrooms, isolators, equipment, and tools. Initial material selections for the facility construction materials, cleanrooms, isolators, and BSL-4 suits/garments are an important activity. The recent construction of the OSIRIS-REx and Hayabusa2 curation cleanroom laboratories greatly benefited from early materials testing, before the design phase, to reduced organic outgassing and particulate shedding inside the laboratory. While the early biohazard investigations in the SRF may deem the samples safe to release to laboratories throughout the world, sterilization methods need to be defined to safely release Martian samples. One key aspect of enabling simultaneous sample containment and cleanliness is the concept of a Double-Walled Isolator (DWI) that ESA has been pursuing. Further R&D is needed about DWIs, sample handling, and instrumentation interfaces before beginning the SRF site specific design phase. A working isolator/DWI engineering model should be developed and fabricated. Isolator sizes, connections, pass-through antechambers, and configurations and basic interfaces with instruments and tools as well as the use of robotic, mechanical, and/or human manipulation need to be considered. Inert high purity gas supply (one-pass or recirculation) and other isolator utilities must be determined. Special accommodations for large instruments (e.g., XCT,SEM, etc.) need to be developed. Techniques for opening the sample tubes packaged by M2020and extracting the headspace gas while keeping samples pristine will be challenging, requiring additional R&D, and engagement of the M2020 project. In addition, careful micromanipulation for subdivision and packaging of samples will also need to be included. These combined R&D activities are important before commencing the SRF design phase to ensure safe biohazard containment, sample preservation, and science integrity for the samples that would be studied in the SRF and in laboratories around the world.

mars sample return↗

Higher-Order VLP-Based Protein Macromolecular Framework Structures Assembled via Coiled-Coil Interactions

Hierarchical organization is one of the fundamental features observed in biological systems that allows for efficient and effective functioning. Virus-like particles (VLPs) are elegant examples of a hierarchically organized supramolecular structure, where many subunits are self-assembled to generate the functional cage-like architecture. Utilizing VLPs as building blocks to construct two- and three-dimensional (3D) higher-order structures is an emerging research area in developing functional biomimetic materials. VLPs derived from P22 bacteriophages can be repurposed as nanoreactors by encapsulating enzymes and modular units to build higher-order catalytic materials via several techniques. In this study, we have used coiled-coil peptide interactions to mediate the P22 interparticle assembly into a highly stable, amorphous protein macromolecular framework (PMF) material, where the assembly does not depend on the VLP morphology, a limitation observed in previously reported P22 PMF assemblies. Many encapsulated enzymes lose their optimum functionalities under the harsh conditions that are required for the P22 VLP morphology transitions. Therefore, the coiled-coil-based PMF provides a fitting and versatile platform for constructing functional higher-order catalytic materials compatible with sensitive enzymes. Finally, we have characterized the material properties of the PMF and utilized the disordered PMF to construct a biocatalytic 3D material performing single- and multistep catalysis.

59 BASIC BIOLOGICAL SCIENCES↗

Cryo-EM Visualization of Intermolecular π-Electron Interactions within π-Conjugated Peptidic Supramolecular Polymers

The self-assembly of “π-peptides” – molecules with π-electron cores substituted with two or more oligopeptide chains – brings organic electronic function into biologically relevant nanomaterials. π-Peptides assemble into fibrillar nanomaterials as driven by enthalpic peptide-based hydrogen bonding networks and pi-core-based quadrupolar interactions. A large body of spectroscopic, morphological and computational studies informs on the nature of the self-assembly process and the resulting nanostructures, but detailed structural information has remained elusive. Here, inspired by the recent use of cryogenic electron microscopy (cryo-EM) to provide high-resolution structures for synthetic peptide nanomaterials, we present here the use of cryo-EM to offer ca. 3 Å resolution of π-peptide nanomaterial assemblies, visualizing for the first time the nature of the intermolecular π-core electronic interactions responsible for energy transport through these supramolecular materials.

Group theory↗

Plasmonic sensors based on graphene and graphene hybrid materials

Abstract The past decade has witnessed a rapid growth of graphene plasmonics and their applications in different fields. Compared with conventional plasmonic materials, graphene enables highly confined plasmons with much longer lifetimes. Moreover, graphene plasmons work in an extended wavelength range, i.e., mid-infrared and terahertz regime, overlapping with the fingerprints of most organic and biomolecules, and have broadened their applications towards plasmonic biological and chemical sensors. In this review, we discuss intrinsic plasmonic properties of graphene and strategies both for tuning graphene plasmons as well as achieving higher performance by integrating graphene with plasmonic nanostructures. Next, we survey applications of graphene and graphene-hybrid materials in biosensors, chemical sensors, optical sensors, and sensors in other fields. Lastly, we conclude this review by providing a brief outlook and challenges of the field. Through this review, we aim to provide an overall picture of graphene plasmonic sensing and to suggest future trends of development of graphene plasmonics.

Zhang, Zhichao↗

Nanohybrid of Cu2O-Ti3C2Tx as a Silver-Free MXene Sorbent for Iodine Gas Capture from Nuclear Waste

The capture of volatile radioiodine from nuclear fuel reprocessing off-gas streams remains a critical challenge due to the high volatility, long half-life of 129I, and biological uptake of iodide from the environment. Although silver-based sorbents provide strong iodine chemisorption, their high cost and regulatory classification as mixed radioactive-hazardous waste motivate the development of alternative materials. Here, we report a silver-free Cu2O-Ti3C2Tx MXene hybrid for iodine gas capture at 150 °C. Structural and compositional analyses confirm the formation of Cu2O nanoparticles on Ti3C2Tx nanosheets and their subsequent conversion to thermodynamically stable CuI upon static iodine gas exposure, achieving an iodine mass loading of up to 1115 mg/g. These results demonstrate the potential of Cu2O-Ti3C2Tx MXene as a copper-based alternative to silver sorbents for elevated-temperature iodine gas capture.

iodine gas capture↗

Designing Sequence-Defined Peptoids for Biomimetic Control over Inorganic Crystallization

Crystallization defines what the world is all about, ranging from biomineralization in living organisms to various materials in our lives. During these processes, biomineralization set a superexcellent example of the additive-controlled crystallization. However, the high complexity and low stability of peptides and proteins preclude their wide applications in controlling inorganic crystallization beyond the biological systems. Peptoids are one type of sequence-defined biomimetic polymers with a simple structure, high stability, protein-like molecular recognition, and distinctive self-assembly properties. They provide a promising alternative to mimic peptides and proteins for controlling inorganic crystallization and extend its application to predictive materials synthesis. In this review article, we extract the main concepts of peptoid engineering and highlight the recent advances in peptoid-controlled inorganic crystallization. Our focus is to understand the principles of sequence engineering that lead to the predictable physiochemical properties of these substances, which will give insights into other inorganic systems.

36 MATERIALS SCIENCE↗

Heterologous Assembly of Pleomorphic Bacterial Microcompartment Shell Architectures Spanning the Nano- to Microscale

Many bacteria use protein-based organelles known as bacterial microcompartments (BMCs) to organize and sequester sequential enzymatic reactions. Regardless of their specialized metabolic function, all BMCs are delimited by a shell made of multiple structurally redundant, yet functionally diverse, hexameric (BMC-H), pseudohexameric/trimeric (BMC-T), or pentameric (BMC-P) shell protein paralogs. When expressed without their native cargo, shell proteins have been shown to self-assemble into 2D sheets, open-ended nanotubes, and closed shells of ≈40 nm diameter that are being developed as scaffolds and nanocontainers for applications in biotechnology. Here, by leveraging a strategy for affinity-based purification, it is demonstrated that a wide range of empty synthetic shells, many differing in end-cap structures, can be derived from a glycyl radical enzyme-associated microcompartment. The range of pleomorphic shells observed, which span ≈2 orders of magnitude in size from ≈25 nm to ≈1.8 µm, reveal the remarkable plasticity of BMC-based biomaterials. In addition, new capped nanotube and nanocone morphologies are observed that are consistent with a multicomponent geometric model in which architectural principles are shared among asymmetric carbon, viral protein, and BMC-based structures.

36 MATERIALS SCIENCE↗

Hydrogen Bonding Stiffens Peptide Amphiphile Supramolecular Filaments by Aza-Glycine Residues

Peptide amphiphiles (PAs) are a class of molecules comprised of short amino acid sequences conjugated to hydrophobic moieties that may exhibit self-assembly in water into supramolecular structures. Here, we investigate here how mechanical properties of hydrogels formed by PA supramolecular nanofibers are affected by hydrogen bond densities within their internal structure by substituting glycine for aza-glycine (azaG) residues. We found that increasing the number of PA molecules that contain azaG up to 5 mol% in PA supramolecular nanofibers increases their persistence length fivefold and decreases their diffusion coefficients as measured by fluorescence recovery after photobleaching. When these PAs are used to create hydrogels, their bulk storage modulus (G') was found to increase as azaG PA content in the supramolecular assemblies increases up to a value of 10 mol% and beyond this value a decrease was observed, likely due to diminished levels of nanofiber entanglement in the hydrogels as a direct result of increased supramolecular rigidity. Interestingly, we found that the bioactivity of the scaffolds toward dopaminergic neurons derived from induced pluripotent stem cells can be enhanced directly by persistence length independently of storage modulus. We hypothesize that this is due to interactions between the cells and the extracellular environment across different size scales: from filopodia adhering to individual nanofiber bundles to cell adhesion sites that interact with the hydrogel as a bulk substrate. Fine tuning of hydrogen bond density in self-assembling peptide biomaterials such as PAs provides an approach to control nanoscale stiffness as part of an overall strategy to optimize bioactivity in these supramolecular systems. supramolecular biomaterials.

36 MATERIALS SCIENCE↗

Valorization of CO 2 through lithoautotrophic production of sustainable chemicals in Cupriavidus necator

Coupling recent advancements in genetic engineering of diverse microbes and gas-driven fermentation provides a path toward sustainable commodity chemical production. Cupriavidus necator H16 is a suitable species for this task because it effectively utilizes H 2 and CO 2 and is genetically tractable. Here, we demonstrate the versatility of C. necator for chemical production by engineering it to produce three products from CO 2 under lithotrophic conditions: sucrose, polyhydroxyalkanoates (PHAs), and lipochitooligosaccharides (LCOs). We engineered sucrose production in a co-culture system with heterotrophic growth 30 times that of WT C. necator. We engineered PHA production (20-60% DCW) and selectively altered product composition by combining different thioesterases and phaCs to produce copolymers directly from CO 2 . And, we engineered C. necator to convert CO 2 into the LCO, a plant growth enhancer, with titers of ~1.4 mg/L—equivalent to yields in its native source, Bradyrhizobium. Here, we applied the LCOs to germinating seeds as well as corn plants and observed increases in a variety of growth parameters. Taken together, these results expand our understanding of how a gas-utilizing bacteria can promote sustainable production.

09 BIOMASS FUELS↗

The Intermetallic Reactivity Database: Compiling Chemical Pressure and Electronic Metrics toward Materials Design and Discovery

Here, the advent of high-throughput Density Functional Theory (DFT) calculations has supported the creation of large databases containing the quantitative output necessary for constructing theoretical phase diagrams and predicting physical properties. In this Article, we present a complementary resource, the Intermetallic Reactivity Database (IRD), focused on the chemical bonding features of solid-state structures and indicators of potential structural transformations. Each IRD entry augments common features, such as band structures and density of states (DOS) distributions, with chemically motivated information including DFT-Chemical Pressure (CP) schemes and visualizable representations of the atomic charges. Together, these data types enable the rationalization and prediction of potential structural phenomena encountered in intermetallic chemistry, as we illustrate with four examples: the origins of the Y 2 Ni 2 Mg structure in terms of CP features of its parent structures, the anticipation of intergrowth phases from the net atomic CPs collected in Al-containing binary phases, the correlation between trends in the CP schemes of CaCu 5 -type phases and experimentally observed structural variations, and finally, the development of theoretical methodology with the testing of a streamlined method generating DFT-CP schemes. Altogether, these examples highlight how the IRD supports the creation of models of structural chemistry that extend beyond the bounds of its entries.

36 MATERIALS SCIENCE↗