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At least 19 records

Characterization of biological materials with soft X-ray scattering

The complex structure of biological assemblies is crucial for function yet challenging to discern given the chemical similarities between constituent components. Hard X-ray techniques, for example, rely on small density differences between domains that lead to modest scattering intensities. Resonant soft X-ray scattering (RSoXS) uses X-rays below 2 keV to access absorption edges of low-Z elements. In this way, RSoXS can enhance scattering contrast between domains of different chemical compositions or bonding motifs, thus providing structural information about specific chemical motifs. RSoXS is emerging as a technique applicable for biological systems, having been used to characterize protein structure in solution and polysaccharide organization in plant cell walls. Sample environment instrumentation, however, is challenging in the current state of the art, particularly with liquid samples. Here, this chapter contains a brief introduction to RSoXS and current beamline capabilities, and provides methods to prepare, store, and mount biological samples for RSoXS characterization. Furthermore, key details during RSoXS and X-ray absorption data acquisition are highlighted and some future opportunities in RSoXS instrumentation for biological systems are discussed.

47 OTHER INSTRUMENTATION↗

Autonomous Aerosol and Plasma Co‐Jet Printing of Metallic Devices at Ambient Temperature

Abstract Additive manufacturing of metallic materials holds the potential to revolutionize the fabrication of functional devices unattainable via traditional methods. Despite recent advancements, printing metallic materials typically requires thermal processing at elevated temperatures to form dense structures with desired properties, which presents a major challenge for direct printing and integration with temperature‐sensitive materials. Herein, a unique co‐jet printing (CJP) method is reported integrating an aerosol jet and a non‐thermal, atmospheric pressure plasma jet to enable concurrent aerosol deposition of metal nanoparticle inks and in situ sintering at ambient temperature. A machine learning algorithm is integrated with the CJP to perform real‐time defect detection and autonomous correction, enhancing the yield of printed films with high electrical conductivity from 44% to 94%. Concurrent printing and sintering eliminate the need for post‐printing processing, reducing the overall manufacturing time by multiple folds depending on product size. CJP enables direct printing of functional devices on a variety of temperature‐sensitive materials including biological materials. Direct printing of hydration sensors on living plant leaves is demonstrated for long‐duration monitoring of hydration level in the plant. The versatile CJP method opens tremendous opportunities to harmoniously integrate abiotic and biotic materials for emerging applications in wearable/implantable devices and biohybrid systems.

Du, Yipu [Department of Aerospace and Mechanical E↗

Principles of Biosafety

Biological safety, or biosafety, means containment principles, technologies and practices that are implemented to prevent unintentional exposure to pathogens and toxins, or their accidental release. This report is a training course for Biosafety with these features and objectives: Topics associated with biological safety, including basic terms, definitions, and approaches to biological safety; regulations, consensus guidance and standards for biological safety; safety requirements for working with biological materials at Los Alamos National Laboratory (LANL); containment requirements for biological materials at LANL; and, emergency response requirements for biological materials at LANL.

99 GENERAL AND MISCELLANEOUS↗

Bioinspired energy absorbing material designs using additive manufacturing

Nature provides many biological materials and structures with exceptional energy absorption capabilities. Few, relatively simple molecular building blocks (e.g., calcium carbonate), which have unremarkable intrinsic mechanical properties individually, are used to produce biopolymer-bioceramic composites with unique hierarchical architectures, thus producing biomaterial-architectures with extraordinary mechanical properties. Several biomaterials have inspired the design and manufacture of novel material architectures to address various engineering problems requiring high energy absorption capabilities. For example, the microarchitecture of seashell nacre has inspired multi-material 3D printed architectures that outperform the energy absorption capabilities of monolithic materials. Using the hierarchical architectural features of biological materials, iterative design approaches using simulation and experimentation are advancing the field of bioinspired material design. However, bioinspired architectures are still challenging to manufacture because of the size scale and architectural hierarchical complexity. Notwithstanding, additive manufacturing technologies are advancing rapidly, continually providing researchers improved abilities to fabricate sophisticated bioinspired, hierarchical designs using multiple materials. This review describes the use of additive manufacturing for producing innovative synthetic materials specifically for energy absorption applications inspired by nacre, conch shell, shrimp shell, horns, hooves, and beetle wings. Potential applications include athletic prosthetics, protective head gear, and automobile crush zones.

36 MATERIALS SCIENCE↗

In vitro investigation of protein assembly by combined microscopy and infrared spectroscopy at the nanometer scale

The nanoscale structure and dynamics of proteins on surfaces has been extensively studied using various imaging techniques, such as transmission electron microscopy and atomic force microscopy (AFM) in liquid environments. These powerful imaging techniques, however, can potentially damage or perturb delicate biological material and do not provide chemical information, which prevents a fundamental understanding of the dynamic processes underlying their evolution under physiological conditions. Here, we use a platform developed in our laboratory that enables acquisition of infrared (IR) spectroscopy and AFM images of biological material in physiological liquids with nanometer resolution in a cell closed by atomically thin graphene membranes transparent to IR photons. In this work, we studied the self-assembly process of S-layer proteins at the graphene-aqueous solution interface. The graphene acts also as the membrane separating the solution containing the proteins and Ca 2+ ions from the AFM tip, thus eliminating sample damage and contamination effects. The formation of S-layer protein lattices and their structural evolution was monitored by AFM and by recording the amide I and II IR absorption bands, which reveal the noncovalent interaction between proteins and their response to the environment, including ionic strength and solvation. Our measurement platform opens unique opportunities to study biological material and soft materials in general.

59 BASIC BIOLOGICAL SCIENCES↗

Controlled Organization of Inorganic Materials Using Biological Molecules for Activating Therapeutic Functionalities

Precise control over the assembly of biocompatible three-dimensional (3D) nanostructures would allow for programmed interactions within the cellular environment. Nucleic acids can be used as programmable crosslinkers to direct the assembly of quantum dots (QDs) and tuned to demonstrate different interparticle binding strategies. In this work, morphologies of self-assembled QDs are evaluated via gel electrophoresis, transmission electron microscopy, small-angle X-ray scattering, and dissipative particle dynamics simulations, with all results being in good agreement. The controlled assembly of 3D QD organizations is demonstrated in cells via the colocalized emission of multiple assembled QDs, and their immunorecognition is assessed via enzyme-linked immunosorbent assays. RNA interference inducers are also embedded into the interparticle binding strategy to be released in human cells only upon QD assembly, which is demonstrated by specific gene silencing. The programmability and intracellular activity of QD assemblies offer a strategy for nucleic acids to imbue the structure and therapeutic function into the formation of complex networks of nanostructures, while the photoluminescent properties of the material allow for optical tracking in cells in vitro.

36 MATERIALS SCIENCE↗

Building a framework to genetically characterize “feather spots” and understand demographic impacts of solar energy sites on migratory bird populations

The lack of data on the impact of utility-scale solar facilities on avian species and populations adds to the cost of siting and operation. As much as 32 percent of the avian biological material (feathers and carcasses) recovered from solar facilities remain unidentified, because they often take the form of “feather spots”. Feather spots are remains of impacted animals that can be separated into two broad categories: 1) those remains that may be visually identified to a species, or 2) those that cannot be visually identified to a species due to degradation from the environment and/or scavenger activity (listed as “unknown”). Even when feather spots can be identified to species, they cannot be visually assigned to particular breeding populations. In some cases, it is unknown whether multiple feather spots represent single or multiple individuals. This project’s objectives were to: 1. Use a developed, genetic-based technique to identify and determine the species, population of origin, and number of individuals found in feather spots recovered from solar facilities. 2. Implement collected data and resulting analyses to develop a publicly accessible web-based decision-making tool that can be used by the solar industry, regulators and other stakeholders to inform siting, mitigation, and conservation management efforts. 3. Establish a not-for-profit fee-for-service center at UCLA to ensure collection and identification of feather spots continue after the project period of performance. During the Project Period, we proposed to establish a pipeline for collecting, transporting, and storing of avian biological material collected at solar facilities and the collection and identification of feather spots to species and individual. We proposed the development of a genetic-based framework that would recover viable DNA from feather spots, amplify this DNA (i.e., make millions of copies of the original DNA), and use it to match the resulting sequences to a national database of known species of birds. The result would be the identification of feathers spots that were previously unidentified, and the incorporation of these samples into a larger database that included all samples recovered from solar facilities. The resulting report (below) details the result of this work and its alignment with proposed activities. We proposed the use of the data collected to assess the comparative risk to specific species or populations of species from solar facilities. For some species, we have already identified genomic markers of specific breeding populations and developed “genoscapes,” maps of unique genetic variation across the full breeding range of a species. We used these (previously and newly developed) genoscapes to probabilistically link a feather spot to the specific breeding populations from which it originated (assignment probabilities range from 75%-100% depending on species and population groups). For those species without genoscapes, we developed a vulnerability and susceptibility estimate that determines the relative local and regional risk to populations that are in geographic proximity to solar facilities, using citizen science data (Breeding Bird Survey (BBS) and eBird). These two feather spot processing pipelines (see Figure 1 below) provide quantitative estimates as to the numbers of individuals from a given population of origin that are affected by solar facilities, and ultimately can reduce costs to the consumer by reducing the industry costs associated with mitigation and siting strategies for future solar energy development.

14 SOLAR ENERGY↗

Microscopic dynamics underlying the stress relaxation of arrested soft materials

Arrested soft materials such as gels and glasses exhibit a slow stress relaxation with a broad distribution of relaxation times in response to linear mechanical perturbations. Although this macroscopic stress relaxation is an essential feature in the application of arrested systems as structural materials, consumer products, foods, and biological materials, the microscopic origins of this relaxation remain poorly understood. Here, we elucidate the microscopic dynamics underlying the stress relaxation of such arrested soft materials under both quiescent and mechanically perturbed conditions through X-ray photon correlation spectroscopy. By studying the dynamics of a model associative gel system that undergoes dynamical arrest in the absence of aging effects, we show that the mean stress relaxation time measured from linear rheometry is directly correlated to the quiescent superdiffusive dynamics of the microscopic clusters, which are governed by a buildup of internal stresses during arrest. We also show that perturbing the system via small mechanical deformations can result in large intermittent fluctuations in the form of avalanches, which give rise to a broad non-Gaussian spectrum of relaxation modes at short times that is observed in stress relaxation measurements. These findings suggest that the linear viscoelastic stress relaxation in arrested soft materials may be governed by nonlinear phenomena involving an interplay of internal stress relaxations and perturbation-induced intermittent avalanches.

36 MATERIALS SCIENCE↗

Thermodynamic Control of Activity Patterns in Cytoskeletal Networks

Biological materials, such as the actin cytoskeleton, exhibit remarkable structural adaptability to various external stimuli by consuming different amounts of energy. In this Letter, we use methods from large deviation theory to identify a thermodynamic control principle for structural transitions in a model cytoskeletal network. Specifically, we demonstrate that biasing the dynamics with respect to the work done by nonequilibrium components effectively renormalizes the interaction strength between such components, which can eventually result in a morphological transition. Further, our work demonstrates how a thermodynamic quantity can be used to renormalize effective interactions, which in turn can tune structure in a predictable manner, suggesting a thermodynamic principle for the control of cytoskeletal structure and dynamics.

59 BASIC BIOLOGICAL SCIENCES↗

Nanolatticed Architecture Mitigates Damage in Shark Egg Cases

Structural versatility and multifunctionality of biological materials have resulted in countless bioinspired strategies seeking to emulate the properties of nature. The nanostructured egg case of swell sharks is one of the toughest permeable membranes known and, thus, presents itself as a model system for materials where the conflicting properties, strength and porosity, are desirable. The egg case possesses an intricately ordered structure that is designed to protect delicate embryos from the external environment while enabling respiratory and metabolic exchange, achieving a tactical balance between conflicting properties. Herein, structural analyses revealed an enabling nanolattice architecture that constitutes a Bouligand-like nanoribbon hierarchical assembly. Three distinct hierarchical architectural adaptations enhance egg case survival: Bouligand-like organization for in-plane isotropic reinforcement, noncylindrical nanoribbons maximizing interfacial stress distribution, and highly ordered nanolattices enabling permeability and lattice-governed toughening mechanisms. Furthermore, these discoveries provide fundamental insights for the improvement of multifunctional membranes, fiber-reinforced soft composites, and mechanical metamaterials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

New high-throughput endstation to accelerate the experimental optimization pipeline for synchrotron X-ray footprinting

Synchrotron X-ray footprinting (XF) is a growing structural biology technique that leverages radiation-induced chemical modifications via X-ray radiolysis of water to produce hydroxyl radicals that probe changes in macromolecular structure and dynamics in solution states of interest. The X-ray Footprinting of Biological Materials (XFP) beamline at the National Synchrotron Light Source II provides the structural biology community with access to instrumentation and expert support in the XF method, and is also a platform for development of new technological capabilities in this field. Hee, the design and implementation of a new high-throughput endstation device based around use of a 96-well PCR plate form factor and supporting diagnostic instrumentation for synchrotron XF is described. This development enables a pipeline for rapid comprehensive screening of the influence of sample chemistry on hydroxyl radical dose using a convenient fluorescent assay, illustrated here with a study of 26 organic compounds. The new high-throughput endstation device and sample evaluation pipeline now available at the XFP beamline provide the worldwide structural biology community with a robust resource for carrying out well optimized synchrotron XF studies of challenging biological systems with complex sample compositions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Fundamentals of bio-electrochemical sensing

The utilization of bio-functionalities such as biorecognition or catalysis derived them their name biosensors. Bio-electrochemical sensing is a new discipline that combines the advantages of biological detection and electrochemical transduction. Bio-electrochemical sensors are devices that use biological materials such as enzymes, antibodies, DNA, or cells as receptors to detect target analytes in a variety of samples. Electrodes convert biological interactions into electrical impulses, which can be studied using various electrochemical techniques. Bio-electrochemical sensors have demonstrated significant promise for use in clinical diagnostics, environmental monitoring, food safety, and biotechnology. Biosensors have received numerous applications in recent years because they are fast, simple, and inexpensive for practical applications. In this article, we cover the basic principles, design strategies, immobilization and regeneration techniques, along with the advantages and applications of bio-electrochemical sensors. Finally, this article discusses the rationale for developing electrochemical biosensors in the context of the various bio-receptors that can be applied.

36 MATERIALS SCIENCE↗

A New Residual Strain Mapping Program Using Energy Dispersive X-Ray Diffraction at the Advanced Photon Source

Here, the ability to non-destructively map the residual strain field inside an engineering component is important for predicting its fatigue life or developing processing methods to prevent failure or enhance performance. In this paper, we describe a new residual strain mapping program at the Advanced Photon Source, Argonne National Laboratory. The new program is based on energy dispersive x-ray diffraction (EDXRD). It is capable of non-destructively penetrating a several- cm thick polycrystalline sample fabricated from engineering alloys using high-energy x-rays and measuring the residual strain field with mm or better spatial resolution and approximately ±1 x 10 -4 strain resolution. A multi-element detector array is employed to measure multiple strain components simultaneously. The residual strain mapping setup is augmented with a high-energy tomography capability, allowing precise alignment of the material volume of interest for residual strain mapping and providing a complementary view of the structure to understand the measured strain field. These measurement capabilities are demonstrated using several strain mapping examples ranging from polycrystalline structural alloys to biological materials. We also provide some guidance for the future users of the program for a successful residual strain mapping experiment. We are expanding the capabilities of the new setup with various in situ capabilities including thermo-mechanical loading.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Methane Consuming Biocatalysts in Gas-Solid Reactor System

Carbon dioxide and methane are the two most abundant greenhouse gases with methane having a higher global warming potential (GWP) than carbon dioxide. Use of methanotrophs as a biocatalyst is a green alternative to chemical conversion of methane. Methanotrophs were immobilized in a 4-arm poly (-ethylene glycol)-tetra-acrylate, PEGTA, hydrogel that is supported by a 3D printed lattice containing micropores. The consumption rate of methane was 2.5 and 42 g CH 4 /L-hr in samples that were at 1 and 3 atm, respectively. A small increase in pressure of the system improves the consumption rate by almost 20x with minimal changes to the reactor system. This system relies on the mass transport of gas through a solid-like material rather than dissolving the gas in a liquid. Immobilization of cells in hydrogel allows for higher cell density and overall increased conversion rates compared to traditional stirred tank reactors. There are many other applications of the use of immobilized biological materials in polymers that require gas-phase reactions.

36 MATERIALS SCIENCE↗

Electron Tomography and Machine Learning for Understanding the Highly Ordered Structure of Leafhopper Brochosomes

Insects known as leafhoppers (Hemiptera: Cicadellidae) produce hierarchically structured nanoparticles known as brochosomes that are exuded and applied to the insect cuticle, thereby providing camouflage and anti-wetting properties to aid insect survival. Although the physical properties of brochosomes are thought to depend on the leafhopper species, the structure–function relationships governing brochosome behavior are not fully understood. Brochosomes have complex hierarchical structures and morphological heterogeneity across species, due to which a multimodal characterization approach is required to effectively elucidate their nanoscale structure and properties. In this work, we study the structural and mechanical properties of brochosomes using a combination of atomic force microscopy (AFM), electron microscopy (EM), electron tomography, and machine learning (ML)-based quantification of large and complex scanning electron microscopy (SEM) image data sets. This suite of techniques allows for the characterization of internal and external brochosome structures, and ML-based image analysis methods of large data sets reveal correlations in the structure across several leafhopper species. Our results show that brochosomes are relatively rigid hollow spheres with characteristic dimensions and morphologies that depend on leafhopper species. Nanomechanical mapping AFM is used to determine a characteristic compression modulus for brochosomes on the order of 1–3 GPa, which is consistent with crystalline proteins. Altogether, this work provides an improved understanding of the structural and mechanical properties of leafhopper brochosomes using a new set of ML-based image classification tools that can be broadly applied to nanostructured biological materials.

Chemical structure↗

Fungal elemental profiling unleashed through rapid laser-induced breakdown spectroscopy (LIBS)

ABSTRACT Elemental profiling of fungal species as a phenotyping tool is an understudied topic and is typically performed to examine plant tissue or non-biological materials. Traditional analytical techniques such as inductively coupled plasma–optical emission spectroscopy (ICP-OES) and inductively coupled plasma–mass spectrometry (ICP-MS) have been used to identify elemental profiles of fungi; however, these techniques can be cumbersome due to the difficulty of preparing samples. Additionally, the instruments used for these techniques can be expensive to procure and operate. Laser-induced breakdown spectroscopy (LIBS) is an alternative elemental analytical technique—one that is sensitive across the periodic table, easy to use on various sample types, and is cost-effective in both procurement and operation. LIBS has not been used on axenic filamentous fungal isolates grown in substrate media. In this work, as a proof of concept, we used LIBS on two genetically distinct fungal species grown on a nutrient-rich and nutrient-poor substrate media to determine whether robust elemental profiles can be detected and whether differences between the fungal isolates can be identified. Our results demonstrate a distinct correlation between fungal species and their elemental profile, regardless of the substrate media, as the same strains shared a similar uptake of carbon, zinc, phosphorus, manganese, and magnesium, which could play a vital role in their survival and propagation. Independently, each fungal species exhibited a unique elemental profile. This work demonstrates a unique and valuable approach to rapidly phenotype fungi through optical spectroscopy, and this approach can be critical in understanding these fungi's behavior and interactions with the environment. IMPORTANCE Historically, ionomics, the elemental profiling of an organism or materials, has been used to understand the elemental composition in waste materials to identify and recycle heavy metals or rare earth elements, identify the soil composition in space exploration on the moon or Mars, or understand human disorders or disease. To our knowledge, ionomic profiling of microbes, particularly fungi, has not been investigated to answer applied and fundamental biological questions. The reason is that current ionomic analytical techniques can be laborious in sample preparation, fail to measure all potential elements accurately, are cost-prohibitive, or provide inconsistent results across replications. In our previous efforts, we explored whether laser-induced breakdown spectroscopy (LIBS) could be used in determining the elemental profiles of poplar tissue, which was successful. In this proof-of-concept endeavor, we undertook a transdisciplinary effort between applied and fundamental mycology and elemental analytical techniques to address the biological question of how LIBS can used for fungi grown axenically in a nutrient-rich and nutrient-poor environment.

59 BASIC BIOLOGICAL SCIENCES↗

Nanophotonics for Chemical Imaging and Spectroscopy

The manipulation of light and light-matter interactions on the nanoscale is enabled by the unique optical properties of plasmonic metal nanostructures and nanoparticles. Indeed, engineered hybrid molecular-plasmonic nanostructures have enabled single molecule detection and identification via surface-enhanced Raman scattering (SERS). Further, the same effect is at the core of visualizing single molecules with sub-nanometer spatial resolution via tip-enhanced Raman scattering (TERS). More generally, modern applications of plasmon-enhanced spectroscopy and microscopy fueled advances in fields as diverse as quantum and semiconductor materials, heterogeneous catalysis, and the health sciences, to name a few. All these exciting developments and many more are touched in this virtual special issue (VSI) on nanophotonics. From ultra-precise chemical imaging measurements performed in a scanning tunneling microscope chamber to single molecule spectroscopic measurements performed at solid-air and solid-liquid interfaces, this VSI includes contributions from active practitioners that are all striving to better-understand increasingly complex interfaces encountered in the biological, materials, and chemical sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗