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DOE OSTI2011

Structural, Dynamical, and Electronic Transport Properties of Modified DNA Duplexes Containing Size-Expanded Nucleobases

Among the distinct strategies proposed to expand the genetic alphabet, sizeexpanded nucleobases are promising for the development of modified DNA duplexes with improved biotechnological properties. In particular, duplexes built up by replacing canonical bases with the corresponding benzo-fused counterparts could be valuable as molecular nanowires. In this context, this study reports the results of classical molecular dynamics simulations carried out to examine the structural and dynamical features of size-expanded DNAs, including both hybrid duplexes containing mixed pairs of natural and benzo-fused bases (xDNA) and pure size-expanded (xxDNA) duplexes. Furthermore, the electronic structure of both natural and size-expanded duplexes is examined by means of density functional computations. The results confirm that the structural and flexibility properties of the canonical DNA are globally little affected by the presence of benzo-fused bases. Themost relevant differences are found in the enhanced size of the grooves, and the reduction in the twist. However, the analysis also reveals subtle structural effects related to the nature and sequence of benzo-fused bases in the duplex. On the other hand, electronic structure calculations performed for xxDNAs confirm the reduction in the HOMOLUMO gap predicted from the analysis of the natural bases and their size-expanded counterparts, which suggests that pure size-expanded DNAs can be good conductors. A more complex situation is found for xDNAs, where fluctuations in the electrostatic interaction between base pairs exerts a decisive influence on the modulation of the energy gap.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2016

Best Bang for the Buck: Part 1 – The Size of Experiments Relative to Design Performance

There are many choices to make, when designing an experiment for a study, such as: what design factors to consider, which levels of the factors to use and which model to focus on. One aspect of design, however, is often left unquestioned: the size of the experiment. When learning about design of experiments, problems are often posed as "select a design for a particular objective with N runs." It’s tempting to consider the design size as a given constraint in the design-selection process. If you think of learning through designed experiments as a sequential process, however, strategically planning for the use of resources at different stages of data collection can be beneficial: Saving experimental runs for later is advantageous if you can efficiently learn with less in the early stages. Alternatively, if you’re too frugal in the early stages, you might not learn enough to proceed confidently with the next stages. Therefore, choosing the right-sized experiment is important—not too large or too small, but with a thoughtful balance to maximize the knowledge gained given the available resources. It can be a great advantage to think about the design size as flexible and include it as an aspect for comparisons. Sometimes you’re asked to provide a small design that is too ambitious for the goals of the study. Finally, if you can show quantitatively how the suggested design size might be inadequate or lead to problems during analysis—and also offer a formal comparison to some alternatives of different (likely larger) sizes—you may have a better chance to ask for additional resources to deliver statistically sound and satisfying results

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2015

Automatic Surface Defect Detection and Sizing for Superconducting Radio Frequency Cavities using Haar cascades

Serious albeit tiny surface defects can remain on the surface of superconducting radio frequency (SRF) cavities after polishing and cleaning. These defects reduce the efficiency of cavities and often limit the maximum attainable fields. We applied a Haar cascade artificial vision technique for automated identification, counting, and sizing of defects induced on niobium surface by Nb-H precipitates formed at cryogenic temperatures. The defects were counted and sized by a computer program and also counted and measured manually to estimate detection rate and accuracy of sizing. The overall detection rate was 53%, and the overall false positive rate was 29%. The technique that was used to automatically size the features was found to oversize the features, but oversize them consistently, resulting in a size histogram that represents the defect size distribution on the sample. After scaling the histogram data, the average defect area was found to be 90 square micrometers with the standard deviation of 70 square micrometers.

Eremeev, Grigory V.↗

DOE OSTI2016

Size Reduction of Contaminated Magnox Pond Skips Using Laser Cutting - 16192

Magnox and TWI Ltd (TWI) have recently developed a first-of-a-kind automated remote laser cutting facility. The facility has been commissioned at Hinkley Point 'A' (HPA) nuclear power station and used to successfully demonstrate the capability of TWI's laser cutting technology to remotely size reduce contaminated Intermediate Level Waste (ILW) Magnox pond skips. The benefits of the facility include reduced cutting times, significantly reduced dose uptake, and significant cost savings. The facility has been designed with a 'plug-and-play' approach such that it could be de-planted and re-mobilised to another nuclear site for other applications. Three contaminated ILW Magnox pond skips with activities of 10.3, 25.1 and 218 GBq/t have been successfully size reduced with this facility; with less than 2.5 hours required to size reduce one skip, and the elapsed laser cutting time being less than 40 minutes. Subsequent radiological assessment showed that the surface contamination and airborne activity were confined within a specifically designed modular containment unit. Continuous real-time air monitoring results indicated a rapid rise and fall of airborne activity. The largest proportion of the airborne activity was removed from the modular containment within 10 minutes by local HEPA ventilation, with the residual activity taking approximately one hour to settle out entirely. The measured dose uptakes were mostly associated with manual handling of the skips to and from the size reduction facility, thus indicating the significance of an automated remote skip size reduction facility. This paper describes the design and performance of the laser skip size reduction facility and presents results of the radiological assessment for three contaminated skips with varying activities. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

Investigating Particle Size‐Dependent Redox Kinetics and Charge Distribution in Disordered Rocksalt Cathodes

Abstract Understanding how various redox activities evolve and distribute in disordered rocksalt oxides (DRX) can advance insights into manipulating materials properties for achieving stable, high‐energy batteries. Herein, the authors present how the reaction kinetics and spatial distribution of redox activities are governed by the particle size of DRX materials. The size‐dependent electrochemical performance is attributed to the distinct cationic and anionic reaction kinetics at different sizes, which can be tailored to achieve optimal capacity and stability. Overall, the local charged domains in DRX particles display random heterogeneity caused by the isotropic delithiation pathways. Owing to the kinetic limitation, the micron‐sized particles exhibit a holistic “core‐shell” charge distribution, whereas sub‐micron particles show more uniform redox reactions throughout the particles and ensembles. Sub‐micron DRX particles exhibit increasing anionic redox activities yet inferior cycling stability. In summary, engineering particle size can effectively modulate how cationic and anionic redox activities evolve and distribute in DRX materials.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Impact of crystalline defects and size on X-ray line broadening: A phenomenological approach for tetragonal SnO{sub 2} nanocrystals

Nanocrystalline tin oxide (SnO{sub 2}) powders with different grain size were prepared by chemical precipitation method. The reaction was carried out by varying the period of hydrolysis and the as-prepared samples were annealed at different temperatures. The samples were characterized using X-ray powder diffractometer and transmission electron microscopy. The microstrain and crystallite size were calculated for all the samples by using Williamson-Hall (W-H) models namely, isotropic strain model (ISM), anisotropic strain model (ASM) and uniform deformation energy density model (UDEDM). The morphology and particle size were determined using TEM micrographs. The directional dependant young’s modulus was modified as an equation relating elastic compliances (s{sub ij}) and Miller indices of the lattice plane (hkl) for tetragonal crystal system and also the equation for elastic compliance in terms of stiffness constants was derived. The changes in crystallite size and microstrain due to lattice defects were observed while varying the hydrolysis time and the annealing temperature. The dependence of crystallite size on lattice strain was studied. The results were correlated with the available studies on electrical properties using impedance spectroscopy.

36 MATERIALS SCIENCE↗

DOE OSTI2015

How chip size impacts steam pretreatment effectiveness for biological conversion of poplar wood into fermentable sugars

We report that woody biomass is highly recalcitrant to enzymatic sugar release and often requires significant size reduction and severe pretreatments to achieve economically viable sugar yields in biological production of sustainable fuels and chemicals. However, because mechanical size reduction of woody biomass can consume significant amounts of energy, it is desirable to minimize size reduction and instead pretreat larger wood chips prior to biological conversion. To date, however, most laboratory research has been performed on materials that are significantly smaller than applicable in a commercial setting. As a result, there is a limited understanding of the effects that larger biomass particle size has on the effectiveness of steam explosion pretreatment and subsequent enzymatic hydrolysis of wood chips. To address these concerns, novel downscaled analysis and high throughput pretreatment and hydrolysis (HTPH) were applied to examine whether differences exist in the composition and digestibility within a single pretreated wood chip due to heterogeneous pretreatment across its thickness. Heat transfer modeling, Simons’ stain testing, magnetic resonance imaging (MRI), and scanning electron microscopy (SEM) were applied to probe the effects of pretreatment within and between pretreated wood samples to shed light on potential causes of variation, pointing to enzyme accessibility (i.e., pore size) distribution being a key factor dictating enzyme digestibility in these samples. Application of these techniques demonstrated that the effectiveness of pretreatment of Populus tremuloides can vary substantially over the chip thickness at short pretreatment times, resulting in spatial digestibility effects and overall lower sugar yields in subsequent enzymatic hydrolysis. Finally, these results indicate that rapid decompression pretreatments (e.g., steam explosion) that specifically alter accessibility at lower temperature conditions are well suited for larger wood chips due to the non-uniformity in temperature and digestibility profiles that can result from high temperature and short pretreatment times. Furthermore, this study also demonstrated that wood chips were hydrated primarily through the natural pore structure during pretreatment, suggesting that preserving the natural grain and transport systems in wood during storage and chipping processes could likely promote pretreatment efficacy and uniformity.

09 BIOMASS FUELS↗

NASA NTRS2024

Advanced Pressure Garment Space Suit Sizing Considerations

Fitting a space suit to a person could be considered an art form. Establishing a repeatable fitcheck process to accommodate the full anthropometric range of test subjects for a single suit design is a critical process to be able to prove suit functionality. Suited test subjects can have different preferences on how they fit inside a suit, and different suited test environments can lead to differences in certain suit sizing accommodations. Throughout this paper, the process of achieving an acceptable suit fit for test subjects will be discussed, along with sizing considerations for changes in suit design and test environments. Lessons learned from the Exploration Extravehicular Mobility Unit (xEMU) will be used to describe specific examples, along with key takeaways from additional NASA prototype mobility space suits. The suit fitcheck process starts with utilizing the anthropometric measurements of a test subject to evaluate their relation to the dimensions of space suit hardware in creating a predicted suit sizing configuration. From here, subjective comments and test team observations drive iterations to the suit sizing configuration to culminate in an acceptable suit fit for performance of further test evaluations. Understanding the relation of subjective comments to their impact on altering suit sizing is critical in establishing an acceptable suit fit.

spacesuit↗

NASA NTRSDate not supplied

Advanced Space Suit Sizing Considerations

spacesuit↗

DOE OSTI2011

Grain size modulation on BaTiO{sub 3} nanoparticles synthesized at room temperature

A new method is developed to synthesize massive BaTiO{sub 3} nanoparticles directly at room temperature. With this method, the synthesis efficiency is improved and mass preparation can be realized. Also, the grain size of the as-prepared nanoparticles can be modulated from several nanometers to 40 nm through proper selection of the content of water and the alkanol chain length of the dispersant. It was found that smaller water content and a larger alkanol chain length of the dispersant will lead to a finer grain size. The mechanisms of the grain size modulation of BaTiO{sub 3} nanoparticles are also discussed. - graphical abstract: This paper offers a direct facile approach to BaTiO{sub 3} nanoparticles at room temperature with a large quantity. The grain size can be modulated purposefully. Highlights: > Room temperature synthesis of BaTiO{sub 3} nanoparticles with large scale is realized. > Grain size can be controlled purposefully. > Effect of content of water on crystallization of BaTiO{sub 3} is revealed. > Influence of alkanol chain length of the dispersant is found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Explaining the Size Dependence in Platinum-Nanoparticle-Catalyzed Hydrogenation Reactions

Hydrogenation reactions are industrially important reactions that typically require unfavorably high H 2 pressure and temperature for many functional groups. Herein we reveal surprisingly strong size-dependent activity of Pt nanoparticles (PtNPs) in catalyzing this reaction. Based on unambiguous spectral analyses, the size effect has been rationalized by the size-dependent d-band electron structure of the PtNPs. This understanding enables production of a catalyst with size of 1.2 nm, which shows a sixfold increase in turnover frequency and 28-fold increase in mass activity in the regioselective hydrogenation of quinoline, compared with PtNPs of 5.3 nm, allowing the reaction to proceed under ambient conditions with unprecedentedly high reaction rates. Finally, the size effect and the synthesis strategy developed herein may provide a general methodology in the design of metal-nanoparticle-based catalysts for a broad range of organic syntheses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Polymer Size–Catalytic Activity Relationships in Solution by Fluorescence Correlation Spectroscopy

Measuring the catalytic activity of specific sizes of polymers with active catalysts in solution is typically challenging, due to limited instrument detection sensitivity and/or dynamic range. Here, a fluorescence correlation spectroscopy (FCS) method is developed to determine the catalytic activity of living polymers of a specific apparent size in solution. Deviation from a single-component FCS data fitting, as assessed by χ2, is also introduced and developed as a “speciation index”—a method to evaluate and track changes in the relative amount of distinct polymer sizes with reaction progress. These methods are enabled by incorporating a selectively reactive fluorescent monomer into growing polydicyclopentadiene or polynorbornene during ring-opening metathesis polymerization (ROMP). Compared to polynorbornene, data showed that catalysts in aggregates of polyDCPD retained higher activity for longer—outcomes not directly inferable from simple diffusional-access predictions. Here, the ability to assign catalytic activity to polymers of specific sizes, and then to determine how this activity evolves with reaction progress, support long-term goals in the development and measurement of nano-objects that possess size-dependent catalytic activity.

Active catalyst↗

DOE OSTI2025

Micron Size NaCrO 2 Particles Enable High‐loading Dry‐processed Electrode for Sodium Ion Batteries

Dry-process fabrication using fibrillatable binder is emerging as a promising method to produce high-loading electrodes for energy storage applications, favored by its cost-efficiency and eco-friendliness. While previous studies have demonstrated the advantages of dry process over the traditional slurry method, there remains a gap in understanding how the particle size of active materials influences the mechanical and electrochemical performance of dry electrodes. In this study, four different particle size NaCrO 2 materials (Average size, S-NCO: 0.6 µm, M1-NCO 1.5 µm, M2-NCO: 4.4 µm, and L-NCO: 9.9 µm) are synthesized to investigate the effect of particle size on dry-processed high-loading electrodes. The findings reveal that the larger micron-sized (>4.4 µm) NCO dry films exhibit significantly improved tensile strength and electrochemical performance, primarily ascribed to the low film porosity, abundant inter-particle connection by the binder, comprehensive carbon coverage, and efficient percolation of the conductive pathway. Notably, a full cell incorporated with a high loading (5.2 mAh cm −2 ) and high active material ratio (96.5 wt.%) L-NCO film electrode demonstrates promising cycling stability and rate capability. Furthermore, these results provide valuable insights regarding the design and fabrication of dry-processed electrodes for future energy storage applications.

25 ENERGY STORAGE↗

DOE OSTI2016

Hybrid SSF/SHF Processing of SO 2 Pretreated Wheat Straw—Tuning Co-fermentation by Yeast Inoculum Size and Hydrolysis Time

Wheat straw is one of the main agricultural residues of interest for bioethanol production. This work examines conversion of steam-pretreated wheat straw (using SO 2 as a catalyst) in a hybrid process consisting of a short enzymatic prehydrolysis step and a subsequent simultaneous saccharification and fermentation (SSF) step with a xylose-fermenting strain of Saccharomyces cerevisiae. A successful process requires a balanced design of reaction time and temperature in the prehydrolysis step and yeast inoculum size and temperature in the SSF step. The pretreated material obtained after steam pretreatment at 210 °C for 5 min using 2.5 % SO 2 (based on moisture content) showed a very good enzymatic digestibility at 45 °C but clearly lower at 30 °C. Furthermore, the pretreatment liquid was found to be rather inhibitory to the yeast, partly due to a furfural content of more than 3 g/L. The effect of varying the yeast inoculum size in this medium was assessed, and at a yeast inoculum size of 4 g/L, a complete conversion of glucose and a 90 % conversion of xylose were obtained within 50 h. An ethanol yield (based on the glucan and xylan in the pretreated material) of 0.39 g/g was achieved for a process with this yeast inoculum size in a hybrid process (10 % water-insoluble solid (WIS)) with 4 h prehydrolysis time and a total process time of 96 h. The obtained xylose conversion was 95 %. A longer prehydrolysis time or a lower yeast inoculum size resulted in incomplete xylose conversion.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2018

Acute and chronic cadmium telluride quantum dots-exposed human bronchial epithelial cells: The effects of particle sizes on their cytotoxicity and carcinogenicity

Highlights: • Human bronchial epithelial cells (BEAS-2B) were dosed with CdTe quantum dots (QDs). • Acute exposure to CdTe QD with • Acute exposure to CdTe QD with >5 nm diameter elicited negligible cytotoxicity. • Notably, chronic exposure to CdTe QDs of all tested sizes induced cell transformation. • CdTe QDs of various particle sizes exert similar carcinogenicity in human lung cells. Quantum dots (QDs) are semiconducting nanocrystals with unique optical properties. When coated with shell/capping, QDs are not deleterious to cells and organisms. However, when QDs are retained in the cellular environment for a certain period of time, their coatings may be degraded, yielding “naked” QDs. Although some studies have documented the acute effects of cadmium telluride (CdTe) QDs in various cell lines, however, to our knowledge, there are no published studies on the chronic effects of CdTe QDs in normal lung cells. In this study, we therefore sought to study the effects of CdTe QDs of various particle sizes on their cytotoxicity and carcinogenicity in normal human bronchial epithelial cells (BEAS-2B). A total of three particle sizes of CdTe QD with emission maximum at 520, 580, and 730 nm were employed (abbreviated as 520Q, 580Q, and 730Q, respectively). Our results indicated that acute exposure to 520Q (∼2.04 nm in diameter) and 580Q (∼3.24 nm in diameter) elicited dose-dependent cytotoxicity; while acute exposure to 730Q (∼5.40 nm in diameter) elicited negligible cytotoxicity in BEAS-2B cells. Notably, chronic exposure to CdTe QD of all three tested particle sizes induced BEAS-2B cell transformation as evidenced by enhanced cell migration and anchorage-independent growth on soft agar. Taken together, our findings suggest that CdTe QDs are potent human lung carcinogens.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2017

Particle size effect in porous film electrodes of ligand-modified graphene for enhanced supercapacitor performance

Graphene-based electrodes for high performance supercapacitors are developed by taking advantage of particle size control, large mass loading, and surface functionalization of reduced graphene oxide (rGO) sheets. Two controlled sizes of graphene sheets (100 nm vs. 45 μm average lateral dimensions) were prepared to study two-electrode system performance. The nano-size graphenes led to the formation of mesoporous films, resulting in higher capacitance, better capacitance retension and lower equivalent series resistance (ESR), indicating better surface usability for diffusion and accessibility of electrolyte ions by shortening transport paths (compared with horizontally stacked films from micro-sized graphenes). For studies using an aqueous electrolyte, the maximum specific capacitance of nano-rGO film was 302 F/g (at 1 A/g with 4.3 mg/cm 2 of mass loading), which was ~2.4 times higher than micro-rGO film, and achieved a ~67% reduced ESR. With an organic electrolyte, the nano-rGO delivered ~4.2 times higher capacitance (115 F/g at 2 A/g with 4.3 mg/cm 2 ), 4.0 times lower IR drops, and an order-of-magnitude lower charge-transfer resistance with an energy density of 18.7 Wh/kg. Finally, the results of this work indicate that the size control of graphene sheet particles for film deposit electrodes can be a simple but effective approach to improve supercapacitor performance.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Machine learning assisted phase and size-controlled synthesis of iron oxide particles

Synthesis of iron oxides with specific phases and particle sizes is a crucial challenge in various fields, including materials science, energy storage, biomedical applications, environmental science, and earth science. However, despite significant advances in this area, much of the current palette of particle outcomes has been based on time-consuming trial-and-error exploration of synthesis conditions. The present study was designed to explore a very different approach to 1) predict the outcome of synthesis from specified reaction parameters based on using machine learning (ML) techniques, and 2) correlate sets of parameters to obtain products with desired outcomes by a newly designed recommendation algorithm. To achieve this, four ML algorithms were tested, namely random forest, logistic regression, support vector machine, and k-nearest neighbor. Among the models, random forest outperformed the others, attaining 96% and 81% accuracy when predicting the phase and size of iron oxide particles in the test dataset. Surprisingly, the permutation feature importance analysis revealed that volume, which may strongly relate to pressure, was one of the important features, along with precursor concentration, pH, temperature, and time, influencing the phase and size of iron oxide particles during synthesis. To verify the robustness of the random forest models, prediction and experimental results were compared based on 24 randomly generated methods in additive and non-additive systems not included in the datasets. The predictions of product phase and particle size from the models agreed well with the experimental results. Furthermore, a searching and ranking algorithm was developed to recommend potential synthesis parameters for obtaining iron oxide products with the desired phase and particle size from previous studies in the dataset. Furthermore, this study lays the foundation for a closed-loop approach in materials synthesis and preparation, beginning with suggesting potential reaction parameters from the dataset and predicting potential outcomes, followed by conducting experiments and analyses, and ultimately enriching the dataset.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Sizing comingled CF/PA 6 fibers with cellulose nanofibrils for enhanced performance properties

Compatibility between the reinforcing phase and the polymer matrix is critical to achieving the desired mechanical and thermal performance of composite materials. Several mechanisms can enhance this interfacial interaction, including surface treatments (e.g., oxidation, plasma, or irradiation), in-situ nanoparticle deposition, and fiber sizing. Here, in this study, cellulose nanofibrils (CNF) were employed as a sustainable sizing agent to modify the interface in commingled carbon fiber (CF)/polyamide 6 (PA 6) yarns, in which CF and PA6 filaments are intimately blended to enable simultaneous consolidation. A 0.25 wt% CNF aqueous suspension was applied under bath sonication to ensure uniform dispersion and minimize agglomeration. CNF-sized and unsized yarns were used to fabricate unidirectional composite plates via filament winding on a flat mandrel, followed by compression molding. Scanning electron microscopy confirmed CNF presence on both CF and PA6 filaments. CNF-sized composites exhibited increments in interlaminar shear strength (ILSS) by 50%, flexural strength by 11%, and tensile strength by 2.5% compared to unsized composites. Thermal analysis showed minimal changes in degradation temperature and crystallinity. These findings demonstrate that CNF sizing enhances interfacial bonding and mechanical performance, offering a scalable and environmentally friendly strategy for thermoplastic composite manufacturing along with yarn/tow handleability.

Cellulose nanofibrils (CNF)↗