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At least 1,153 records · Page 64

The Buckling Spectra of Nanoparticle Surfactant Assemblies

Fine control over the mechanical properties of thin sheets underpins transcytosis, cell shape, and morphogenesis. Applying these principles to artificial, liquid-based systems has led to reconfigurable materials for soft robotics, actuation, and chemical synthesis. However, progress is limited by a lack of synthetic two-dimensional membranes that exhibit tunable mechanical properties over a comparable range to that seen in nature. In this study, we show that the bending modulus, B , of thin assemblies of nanoparticle surfactants (NPSs) at the oil–water interface can be varied continuously from sub- k B T to 10 6 k B T , by varying the ligands and particles that comprise the NPS. We find extensive departure from continuum behavior, including enormous mechanical anisotropy and a power law relation between B and the buckling spectrum width. Our findings provide a platform for shape-changing liquid devices and motivate new theories for the description of thin-film wrinkling.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Battery Capacity Fading Estimation Using a Force-Based Incremental Capacity Analysis

Traditionally health monitoring techniques in lithium-ion batteries rely on voltage and current measurements. A novel method of using a mechanical rather than electrical signal in the incremental capacity analysis (ICA) method is introduced in this paper. This method derives the incremental capacity curves based onmeasured force (ICF) instead of voltage (ICV). The force ismeasured on the surface of a cell under compression in a fixture that replicates a battery pack assembly and preloading. The analysis is performed on data collected from cycling encased prismatic Lithium-ion Nickel-Manganese-Cobalt Oxide (NMC) cells. For the NMC chemistry, the ICF method can complement or replace the ICV method for the following reasons. The identified ICV peaks are centered around 40% of state of charge (SOC) while the peaks of the ICF method are centered around 70% of SOC indicating that the ICF can be used more often because it is more likely that an electric vehicle (EV) or a plug-in hybrid electric vehicle (PHEV) will traverse the 70% SOC range than the 40% SOC. In addition the Signal to Noise ratio (SNR) of the force signal is four times larger than the voltage signal using laboratory grade sensors. The proposed ICF method is shown to achieve 0.42% accuracy in capacity estimation during a low C-rate constant current discharge. Future work will investigate the application of the capacity estimation technique under charging and operation under high C-rates by addressing the transient behavior of force so that an online methodology for capacity estimation is developed.

25 ENERGY STORAGE↗

Engineering Forisome Scaffolds: Elucidating Spatial Self-Assembly Patterning of Bio-inorganic Complexes

Organisms can synthesize biomaterials incorporating an array of naturally occurring elements while overcoming challenges and insults. Although, it is known that most cellular biomaterials are synthesized in specialized cellular compartments, there are knowledge gaps about how organic/inorganic biomaterial synthesis is orchestrated inside cells. In addition, there is great potential in understanding how individual monomers can self-assembly into organized patterns to form responsive biomaterials. Forisomes are a natural responsive biomaterial found in legume plants that serve as a plug sieve element in the plant phloem that undergo anisotropic conformational changes by rapid (<1 s) ATP-independent from condensed spindle to plug-like form, triggered by the influx of Ca 2+ . Addressing principles of forisome synthesis and assembly will determine how biomaterials containing inorganic elements self-assemble and conduct chemical modification to produce biomaterials or undergo biomineralization. We employ transcription and translation (TXTL) using cell-free expression systems for forisome monomer expression, self-assembly, and pattern probing. We conducted experiments to precisely control forisome proteins synthesis of various monomers SEO1, SEO2, SEO3, and SEO4 to explore self- assembly. We demonstrate forisome self-assembly of the SEO monomers is possible and indicate unique monomer fluorescent labeling patterns that require additional analysis. We investigated locations and linkers for adding tetracysteine tag fluorophore probes to determine impacts of self-assembly and anisotropic conformational changes.

42 ENGINEERING↗

Fitness Landscape-Guided Engineering of Locally Supercharged Virus-like Particles with Enhanced Cell Uptake Properties

Protein-based nanoparticles are useful models for the study of self-assembly and attractive candidates for drug delivery. Virus-like particles (VLPs) are especially promising platforms for expanding the repertoire of therapeutics that can be delivered effectively as they can deliver many copies of a molecule per particle for each delivery event. However, their use is often limited due to poor uptake of VLPs into mammalian cells. In this study, we use the fitness landscape of the bacteriophage MS2 VLP as a guide to engineer capsid variants with positively charged surface residues to enhance their uptake into mammalian cells. By combining mutations with positive fitness scores that were likely to produce assembled capsids, we identified two key double mutants with internalization efficiencies as much as 67-fold higher than that of wtMS2. Internalization of these variants with positively charged surface residues depends on interactions with cell surface sulfated proteoglycans, and yet, they are biophysically similar to wtMS2 with low cytotoxicity and an overall negative charge. Additionally, the best-performing engineered MS2 capsids can deliver a potent anticancer small-molecule therapeutic with efficacy levels similar to antibody-drug conjugates. Through this work, we were able to establish fitness landscape-based engineering as a successful method for designing VLPs with improved cell penetration. These findings suggest that VLPs with positive surface charge could be useful in improving the delivery of small-molecule- and nucleic acid-based therapeutics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Light-Modulated Self-Assembly of Synthetic Nanotubes

Artificial biomolecular polymers with the capacity to respond to stimuli are emerging as a key component to the development of living materials and synthetic cells. Here, in this work, we demonstrate artificial DNA tubular nanostructures that form in response to light in a dose-dependent manner. These nanotubes assemble from programmable DNA tile motifs that are engineered to include a UV-responsive domain so that UV irradiation activates nanotube self-assembly. We demonstrate that the nanotube formation speed can be tuned by adjusting the UV dose. We then couple the light-dependent activation of tiles with RNA transcription, making it possible to control nanotube formation via concurrent physical and biochemical stimuli. Finally, we illustrate how UV activation effectively controls nanotube assembly in confinement as a rudimentary stimulus-responsive cytoskeletal system that can achieve various conformations in a minimal synthetic cell. This study contributes new tile designs that are immediately useful to building biomolecular scaffolds with controllable dynamics in response to multiple stimuli.

DNA nanotechnology↗

Decoupling of heat generated from ejected and non-ejected contents of 18650-format lithium-ion cells using statistical methods

Effective thermal management systems, designed to handle the impacts of thermal runaway (TR) and to prevent cell-to-cell propagation, are key to safe operation of lithium-ion (Li-ion) battery assemblies. Critical factors for optimizing these systems include the total energy released during a single cell TR event and the fraction of the total energy that is released through the cell casing versus through the ejecta material. A unique fractional thermal runaway calorimeter (FTRC), designed to characterize said critical factors, was utilized to examine the TR behavior of 18650-format Li-ion cells representing a variety of manufacturers, chemistries, capacities, and safety features. Primarily, the impacts of bottom vent (BV) safety features, varied cell casing thickness, and Dreamweaver cellulose based separators were assessed for select cell types. A subset of cells also had an imbedded internal short circuiting (ISC) device to allow examination of TR behavior initiated at lower temperatures (i.e. closer to field failure conditions). The impact of bottom rupture on TR behavior was also examined for experiments that resulted in this non-standard failure mechanism. Statistical analysis of the results for each cell configuration reveals that a lognormal distribution effectively characterizes the variation of total TR energy release. Typically 20%-30% of the total energy yield is released through the cell casing with the remainder through the ejecta material. Higher energy cells tend to exhibit more violent ejections and less predictable TR events. Inclusion of a BV feature reduces the overall severity of the TR event and can increase the predictability. Results also suggest that the magnitude of the TR event may not be directly proportional to the stored electrical energy, but rather has additional dependence on other design and failure mode factors.

25 ENERGY STORAGE↗

Experimental Evaluation of the Fast-Neutron Passive Collar (FNPC) Performance (Interim Report)

This report represents a deliverable in the Safeguards Technology WBS # Project Title, 24.1.3.1, Task 3 (Report on laboratory-based performance testing of the FNPC). A new, simplified method for the verification of the 235 U mass in fresh LEU fuel assemblies that is relatively independent of burnable poison content is being developed. LWR fresh fuel is currently verified using the uranium neutron coincidence collar (UNCL), which relies on an AmLi source to induce fission in the 235 U. AmLi neutrons are slowed down in polyethylene, so the induced fission is primarily due to thermal neutrons. Burnable poisons, which are added to nuclear fuel assemblies to extend the lifetime of the fuel, absorb neutrons that would otherwise have induced fission in the fuel, thereby reducing the neutron count rate and thus the measured 235 U mass. To remove this bias factor a correction is applied based on the operator’s declared burnable poison content. The new technique uses 238 U spontaneous fission in LWR fresh fuel rods to self-interrogate the 235 U mass. The 238 U spontaneous fission neutrons have a hard neutron energy spectrum, which means that the technique is less sensitive to burnable poisons than the AmLi based systems. This project has continued the work done over the past two years to study this new technique using the optimized 3 He based fastneutron passive collar (FNPC). Fabrication of the FNPC has been completed and measurements are in progress using the LANL mockup PWR fuel assembly. Also, preliminary evaluations of advanced analysis techniques and unattended mode operation have been performed. In FY18, the 3 He tube based detector was compared with a 10 B sealed cell based detector for the same set of PWR fuel assemblies in the Rodeo-II program. The results were that the optimized 3 He detector had higher efficiency and less weight than the 10 B based system where both systems had about the same cost. Thus, the FY19 work continued exclusively with the 3 He based detector; although, either system had the potential for future applications. However, the high efficiency of the FPNC (~24%) is critical for precise measurements of the triples rate necessary in the multiplicity advanced analysis technique which can solve for the burnable poison content.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Statistical Characterization of 18650-Format Lithium-Ion Cell Thermal Runaway Energy Distributions

Effective thermal management systems, designed to handle the impacts of thermal runaway (TR) and to prevent cell-to-cell propagation, are key to safe operation of lithium-ion (Li-ion) battery assemblies. Critical factors for optimizing these systems include the total energy released during a single cell TR event and the fraction of the total energy that is released through the cell casing vs. through the ejecta material. A unique calorimeter was utilized to examine the TR behavior of a statistically significant number of 18650-format Li-ion cells with varying manufacturers, chemistries, and capacities. The calorimeter was designed to contain the TR energy in a format conducive to discerning the fractions of energy released through the cell casing vs. through the ejecta material. Other benefits of this calorimeter included the ability to rapidly test of large quantities of cells and the intentional minimization of secondary combustion effects. High energy (270 Wh/kg) and moderate energy (200 Wh/kg) 18650 cells were tested. Some of the cells had an imbedded short circuit (ISC) device installed to aid in the examination of TR mechanisms under more realistic conditions. Other variations included cells with bottom vent (BV) features and cells with thin casings (0.22 1/4m). After combining the data gathered with the calorimeter, a statistical approach was used to examine the probability of certain TR behavior, and the associated energy distributions, as a function of capacity, venting features, cell casing thickness and temperature.

Thermal Runaway Energy Distribution↗

Solar power satellites - Heat engine or solar cells

A solar power satellite is the energy-converting element of a system that can deliver some 10 GW of power to utilities on the earth's surface. We evaluated heat engines and solar cells for converting sunshine to electric power at the satellite. A potassium Rankine cycle was the best of the heat engines, and 50 microns thick single-crystal silicon cells were the best of the photovoltaic converters. Neither solar cells nor heat engines had a clear advantage when all factors were considered. The potassium-turbine power plant, however, was more difficult to assemble and required a more expensive orbital assembly base. We therefore based our cost analyses on solar-cell energy conversion, concluding that satellite-generated power could be delivered to utilities for around 4 to 5 cents a kWh.

Oman, H.↗

Miniature Oxidizer Ionizer for a Fuel Cell

A proposed miniature device for ionizing the oxygen (or other oxidizing gas) in a fuel cell would consist mostly of a membrane ionizer using the same principles as those of the device described in the earlier article, Miniature Bipolar Electrostatic Ion Thruster (NPO-21057). The oxidizing gas would be completely ionized upon passage through the holes in the membrane ionizer. The resulting positively charged atoms or molecules of oxidizing gas could then, under the influence of the fringe fields of the ionizer, move toward the fuel-cell cathode that would be part of a membrane/electrode assembly comprising the cathode, a solid-electrolyte membrane, and an anode. The electro-oxidized state of the oxidizer atoms and molecules would enhance transfer of them through the cathode, thereby reducing the partial pressure of the oxidizer gas between the ionizer and the fuel-cell cathode, thereby, in turn, causing further inflow of oxidizer gas through the holes in the membrane ionizer. Optionally the ionizer could be maintained at a positive electric potential with respect to the cathode, in which case the resulting electric field would accelerate the ions toward the cathode.

Hartley, Frank↗

Conjugating folate on superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles using click chemistry

Gold-coated magnetic core@shell nanoparticles, which exhibit magneto-optical properties, not only enhance the chemical stability of core and biocompatibility of surface, but also provide a combination of multimodal imaging and therapeutics. The conjugation of these tiny nanoparticles with specific biomolecules allows researchers to target the desired location. In this paper, superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles were synthesized and functionalized with the azide group on the surface by formation of self-assembled monolayers. Folate (FA) molecules, non-immunogenic target ligands for cancer cells, are conjugated with alkyne and then immobilized on the azide-terminated Fe{sub 3}O{sub 4}@Au nanoparticles through copper(I)-catalyzed azide-alkyne cycloaddition (click reaction). Myelogenous leukemia K562 cells were used as a folate receptor (FR) model, which can be targeted and extracted by magnetic field after interaction with the Fe{sub 3}O{sub 4}@Au–FA nanoparticles. - Graphical abstract: Self-assembled azide-terminated group on superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles followed by click reaction with alkyne-functionalized folate, allowing the nanoparticles target folate receptor of cancer cells. - Highlights: • Azidoundecanethiol was coated on the superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles by forming self-assembled monolayers. • Alkyne-terminated folate was synthesized from a reaction between the amine and the carboxylic acid. • Conjugation of Fe{sub 3}O{sub 4}@Au nanoparticles with folate was made by copper-catalyzed azide-alkyne cycloaddition click chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Fabrication Strategy for Reconfigurable Millimeter–Scale Metamaterials

Rather than depending on material composition to primarily dictate performance metrics, metamaterials can leverage geometry to achieve specific properties of interest. For example, reconfigurable metamaterials have enabled programmable shape transformations, tunable mechanical properties, and energy absorption. While several methods exist to fabricate such structures, they often place severe restrictions on manufacturing materials, or require significant manual assembly. Moreover, these arrays are typically composed of unit cells that are either macro–scale or micro–scale in dimension. Here, the fabrication gap is bridged, and laminate manufacturing is used to develop a method for designing reconfigurable metamaterials at the millimeter–scale, that is compatible with a wide range of materials, and that requires minimal manual assembly. In addition to showing the versatility of this fabrication method, how the use of laminate manufacturing affects the behavior of these multi–component arrays is also characterized. To this end, a numerical model that captures the deformations exhibited by the structures is developed, and an analytic model that predicts the strain of the structure under compressive stress is built. Overall, this approach can be leveraged to develop millimeter–scale metamaterials for applications that require reconfigurable materials, such as in the design of tunable acoustics, photonic waveguides, and electromagnetic devices.

36 MATERIALS SCIENCE↗

Rubisco production in maize mesophyll cells through ectopic expression of subunits and chaperones

Abstract C4 plants, such as maize, strictly compartmentalize Rubisco to bundle sheath chloroplasts. The molecular basis for the restriction of Rubisco from the more abundant mesophyll chloroplasts is not fully understood. Mesophyll chloroplasts transcribe the Rubisco large subunit gene and, when normally quiescent transcription of the nuclear Rubisco small subunit gene family is overcome by ectopic expression, mesophyll chloroplasts still do not accumulate measurable Rubisco. Here we show that a combination of five ubiquitin promoter-driven nuclear transgenes expressed in maize leads to mesophyll accumulation of assembled Rubisco. These encode the Rubisco large and small subunits, Rubisco assembly factors 1 and 2, and the assembly factor Bundle sheath defective 2. In these plants, Rubisco large subunit accumulates in mesophyll cells, and appears to be assembled into a holoenzyme capable of binding the substrate analog CABP (carboxyarabinitol bisphosphate). Isotope discrimination assays suggest, however, that mesophyll Rubisco is not participating in carbon assimilation in these plants, most probably due to a lack of the substrate ribulose 1,5-bisphosphate and/or Rubisco activase. Overall, this work defines a minimal set of Rubisco assembly factors in planta and may help lead to methods of regulating the C4 pathway.

Plant Sciences↗

DDX4 (DEAD box polypeptide 4) colocalizes with cancer stem cell marker CD133 in ovarian cancers

Highlights: • Germ cell marker DDX4 was significantly increased in ovarian cancer. • Ovarian cancer stem cell marker CD133 was significantly increased in ovarian cancer. • DDX4 and CD133 were mostly colocalized in various types of ovarian cancer tissues. • CD133 positive ovarian cancer cells also express DDX4 whereas CD133-negative cells did not possess DDX4. • Germ cell marker DDX4 has the potential of ovarian cancer stem cell marker. - Abstract: DDX4 (DEAD box polypeptide 4), characterized by the conserved motif Asp-Glu-Ala-Asp (DEAD), is an RNA helicase which is implicated in various cellular processes involving the alteration of RNA secondary structure, such as translation initiation, nuclear and mitochondrial splicing, and ribosome and spliceosome assembly. DDX4 is known to be a germ cell-specific protein and is used as a sorting marker of germline stem cells for the production of oocytes. A recent report about DDX4 in ovarian cancer showed that DDX4 is overexpressed in epithelial ovarian cancer and disrupts a DNA damage-induced G2 checkpoint. We investigated the relationship between DDX4 and ovarian cancer stem cells by analyzing the expression patterns of DDX4 and the cancer stem cell marker CD133 in ovarian cancers via tissue microarray. Both DDX4 and CD133 were significantly increased in ovarian cancer compared to benign tumors, and showed similar patterns of expression. In addition, DDX4 and CD133 were mostly colocalized in various types of ovarian cancer tissues. Furthermore, almost all CD133 positive ovarian cancer cells also express DDX4 whereas CD133-negative cells did not possess DDX4, suggesting a strong possibility that DDX4 plays an important role in cancer stem cells, and/or can be used as an ovarian cancer stem cell marker.

60 APPLIED LIFE SCIENCES↗

Integral assembly of photovoltaic arrays using glass

For a number of reasons glass is an excellent material for encapsulation of solar cell arrays. Glass can be readily available at relatively low cost. It exhibits excellent stability against degradation by solar ultraviolet illumination and atmospheric pollutants. A superior approach results if glass is employed directly as an integral encapsulant without secondary organic materials. A description is presented of a electrostatic bonding process which is being developed for integral assembly of glass encapsulated arrays. Solar cells are placed in contact with the glass surface, temperature is raised until the glass becomes ionically conductive, and an electric field is applied to initiate the bonding action. Silicon solar cells up to 3 inches in diameter have been integrally bonded without degradation.

Younger, P. R.↗

Focal adhesions, stress fibers and mechanical tension

Stress fibers and focal adhesions are complex protein arrays that produce, transmit and sense mechanical tension. Evidence accumulated over many years led to the conclusion that mechanical tension generated within stress fibers contributes to the assembly of both stress fibers themselves and their associated focal adhesions. However, several lines of evidence have recently been presented against this model. Here we discuss the evidence for and against the role of mechanical tension in driving the assembly of these structures. We also consider how their assembly is influenced by the rigidity of the substratum to which cells are adhering. Finally, we discuss the recently identified connections between stress fibers and the nucleus, and the roles that these may play, both in cell migration and regulating nuclear function. - Highlights: • The different types of stress fiber and focal adhesion are described. • We discuss the controversy about tension and assembly of these structures. • We describe the different models used to investigate assembly of these structures. • The influence of substratum rigidity is discussed. • Stress fiber connections to the nucleus are reviewed.

60 APPLIED LIFE SCIENCES↗

Reduced Graphene Oxide Aerogels with Functionalization-Mediated Disordered Stacking for Sodium-Ion Batteries

Surface modified reduced graphene oxide (rGO) aerogels were synthesized using the hydrothermal method. Ethylene diamine (EDA) and α-cyclodextrin (CD) were used to functionalize the surface of the graphene oxide layers. The oxygen reduction and surface modification occurred in-situ during the hydrothermal self-assembly process. The chemical functionality and structure of the resulting ethylene diamine modified (rGO-EDA) and cyclodextrin modified (rGO-CD) aerogels as well as of the pristine unmodified rGO aerogel were studied using XPS, SEM, XRD, and SANS techniques. The overall surface composition showed a significant decrease in the oxygen content for all synthesized aerogels. The surface modified aerogels were characterized by a disordered stacking of the assembled rGO layers. The surface functionalities resulted in a broad distribution of the interlayer spacing and introduced structural heterogeneities. Such disordered structures can enable a better adsorption mechanism of the sodium ions. Coin cells based on the synthesized aerogels and sodium metal were assembled and tested at several charge and discharge rates. The correlation between the surface functionality of the rGO, the induced structural heterogeneities due to the disordered stacking, and the electrochemical performance of sodium-ion batteries were investigated. Operando XRD measurements were carried out during the battery cycling to investigate the adsorption or intercalation nature of the sodiation mechanism.

25 ENERGY STORAGE↗

Insights into the dynamics between viruses and their hosts in a hot spring microbial mat

Abstract Our current knowledge of host–virus interactions in biofilms is limited to computational predictions based on laboratory experiments with a small number of cultured bacteria. However, natural biofilms are diverse and chiefly composed of uncultured bacteria and archaea with no viral infection patterns and lifestyle predictions described to date. Herein, we predict the first DNA sequence-based host–virus interactions in a natural biofilm. Using single-cell genomics and metagenomics applied to a hot spring mat of the Cone Pool in Mono County, California, we provide insights into virus–host range, lifestyle and distribution across different mat layers. Thirty-four out of 130 single cells contained at least one viral contig (26%), which, together with the metagenome-assembled genomes, resulted in detection of 59 viruses linked to 34 host species. Analysis of single-cell amplification kinetics revealed a lack of active viral replication on the single-cell level. These findings were further supported by mapping metagenomic reads from different mat layers to the obtained host–virus pairs, which indicated a low copy number of viral genomes compared to their hosts. Lastly, the metagenomic data revealed high layer specificity of viruses, suggesting limited diffusion to other mat layers. Taken together, these observations indicate that in low mobility environments with high microbial abundance, lysogeny is the predominant viral lifestyle, in line with the previously proposed “Piggyback-the-Winner” theory.

59 BASIC BIOLOGICAL SCIENCES↗