Predicting In-Situ X-ray Diffraction for the SrTiO3/Liquid Interface from First Principles

NASA Astrophysics Data System (ADS)

Letchworth-Weaver, Kendra; Gunceler, Deniz; Sundararaman, Ravishankar; Huang, Xin; Brock, Joel; Arias, T. A.

2013-03-01

Recent advances in experimental techniques, such as in-situ x-ray diffraction, allow researchers to probe the solid-liquid interface in electrochemical systems under operating conditions. These advances offer an unprecedented opportunity for theory to predict properties of electrode materials in aqueous environments and inform the design of energy conversion and storage devices. To compare with experiment, these theoretical studies require microscopic details of both the liquid and the electrode surface. Joint Density Functional Theory (JDFT), a computationally efficient alternative to molecular dynamics, couples a classical density-functional, which captures molecular structure of the liquid, to a quantum-mechanical functional for the electrode surface. We present a JDFT exploration of SrTiO3, which can catalyze solar-driven water splitting, in an electrochemical environment. We determine the geometry of the polar SrTiO3 surface and the equilibrium structure of the contacting liquid, as well as the influence of the liquid upon the electronic structure of the surface. We then predict the effect of the fluid environment on x-ray diffraction patterns and compare our predictions to in-situ measurements performed at the Cornell High Energy Synchrotron Source (CHESS). This material is based upon work supported by the Energy Materials Center at Cornell (EMC2), an Energy Frontier Research Center funded by the U.S. Department of Energy.

An in situ USAXS-SAXS-WAXS study of precipitate size distribution evolution in a model Ni-based alloy.

PubMed

Andrews, Ross N; Serio, Joseph; Muralidharan, Govindarajan; Ilavsky, Jan

2017-06-01

Intermetallic γ' precipitates typically strengthen nickel-based superalloys. The shape, size and spatial distribution of strengthening precipitates critically influence alloy strength, while their temporal evolution characteristics determine the high-temperature alloy stability. Combined ultra-small-, small- and wide-angle X-ray scattering (USAXS-SAXS-WAXS) analysis can be used to evaluate the temporal evolution of an alloy's precipitate size distribution (PSD) and phase structure during in situ heat treatment. Analysis of PSDs from USAXS-SAXS data employs either least-squares fitting of a preordained PSD model or a maximum entropy (MaxEnt) approach, the latter avoiding a priori definition of a functional form of the PSD. However, strong low- q scattering from grain boundaries and/or structure factor effects inhibit MaxEnt analysis of typical alloys. This work describes the extension of Bayesian-MaxEnt analysis methods to data exhibiting structure factor effects and low- q power law slopes and demonstrates their use in an in situ study of precipitate size evolution during heat treatment of a model Ni-Al-Si alloy.

An in situ USAXS–SAXS–WAXS study of precipitate size distribution evolution in a model Ni-based alloy1

PubMed Central

Andrews, Ross N.; Serio, Joseph; Muralidharan, Govindarajan; Ilavsky, Jan

2017-01-01

Intermetallic γ′ precipitates typically strengthen nickel-based superalloys. The shape, size and spatial distribution of strengthening precipitates critically influence alloy strength, while their temporal evolution characteristics determine the high-temperature alloy stability. Combined ultra-small-, small- and wide-angle X-ray scattering (USAXS–SAXS–WAXS) analysis can be used to evaluate the temporal evolution of an alloy’s precipitate size distribution (PSD) and phase structure during in situ heat treatment. Analysis of PSDs from USAXS–SAXS data employs either least-squares fitting of a preordained PSD model or a maximum entropy (MaxEnt) approach, the latter avoiding a priori definition of a functional form of the PSD. However, strong low-q scattering from grain boundaries and/or structure factor effects inhibit MaxEnt analysis of typical alloys. This work describes the extension of Bayesian–MaxEnt analysis methods to data exhibiting structure factor effects and low-q power law slopes and demonstrates their use in an in situ study of precipitate size evolution during heat treatment of a model Ni–Al–Si alloy. PMID:28656039

Tailoring the Electrochemical Properties of Carbon Nanotube Modified Indium Tin Oxide via in Situ Grafting of Aryl Diazonium.

PubMed

Hicks, Jacqueline M; Wong, Zhi Yi; Scurr, David J; Silman, Nigel; Jackson, Simon K; Mendes, Paula M; Aylott, Jonathan W; Rawson, Frankie J

2017-05-23

Our ability to tailor the electronic properties of surfaces by nanomodification is paramount for various applications, including development of sensing, fuel cell, and solar technologies. Moreover, in order to improve the rational design of conducting surfaces, an improved understanding of structure/function relationships of nanomodifications and effect they have on the underlying electronic properties is required. Herein, we report on the tuning and optimization of the electrochemical properties of indium tin oxide (ITO) functionalized with single-walled carbon nanotubes (SWCNTs). This was achieved by controlling in situ grafting of aryl amine diazonium films on the nanoscale which were used to covalently tether SWCNTs. The structure/function relationship of these nanomodifications on the electronic properties of ITO was elucidated via time-of-flight secondary ion mass spectrometry and electrochemical and physical characterization techniques which has led to new mechanistic insights into the in situ grafting of diazonium. We discovered that the connecting bond is a nitro group which is covalently linked to a carbon on the aryl amine. The increased understanding of the surface chemistry gained through these studies enabled us to fabricate surfaces with optimized electron transfer kinetics. The knowledge gained from these studies allows for the rational design and tuning of the electronic properties of ITO-based conducting surfaces important for development of various electronic applications.

In situ single molecule imaging of cell membranes: linking basic nanotechniques to cell biology, immunology and medicine.

PubMed

Pi, Jiang; Jin, Hua; Yang, Fen; Chen, Zheng W; Cai, Jiye

2014-11-07

The cell membrane, which consists of a viscous phospholipid bilayer, different kinds of proteins and various nano/micrometer-sized domains, plays a very important role in ensuring the stability of the intracellular environment and the order of cellular signal transductions. Exploring the precise cell membrane structure and detailed functions of the biomolecules in a cell membrane would be helpful to understand the underlying mechanisms involved in cell membrane signal transductions, which could further benefit research into cell biology, immunology and medicine. The detection of membrane biomolecules at the single molecule level can provide some subtle information about the molecular structure and the functions of the cell membrane. In particular, information obtained about the molecular mechanisms and other information at the single molecule level are significantly different from that detected from a large amount of biomolecules at the large-scale through traditional techniques, and can thus provide a novel perspective for the study of cell membrane structures and functions. However, the precise investigations of membrane biomolecules prompts researchers to explore cell membranes at the single molecule level by the use of in situ imaging methods, as the exact conformation and functions of biomolecules are highly controlled by the native cellular environment. Recently, the in situ single molecule imaging of cell membranes has attracted increasing attention from cell biologists and immunologists. The size of biomolecules and their clusters on the cell surface are set at the nanoscale, which makes it mandatory to use high- and super-resolution imaging techniques to realize the in situ single molecule imaging of cell membranes. In the past few decades, some amazing imaging techniques and instruments with super resolution have been widely developed for molecule imaging, which can also be further employed for the in situ single molecule imaging of cell membranes. In this review, we attempt to summarize the characteristics of these advanced techniques for use in the in situ single molecule imaging of cell membranes. We believe that this work will help to promote the technological and methodological developments of super-resolution techniques for the single molecule imaging of cell membranes and help researchers better understand which technique is most suitable for their future exploring of membrane biomolecules; ultimately promoting further developments in cell biology, immunology and medicine.

In situ single molecule imaging of cell membranes: linking basic nanotechniques to cell biology, immunology and medicine

NASA Astrophysics Data System (ADS)

Pi, Jiang; Jin, Hua; Yang, Fen; Chen, Zheng W.; Cai, Jiye

2014-10-01

The cell membrane, which consists of a viscous phospholipid bilayer, different kinds of proteins and various nano/micrometer-sized domains, plays a very important role in ensuring the stability of the intracellular environment and the order of cellular signal transductions. Exploring the precise cell membrane structure and detailed functions of the biomolecules in a cell membrane would be helpful to understand the underlying mechanisms involved in cell membrane signal transductions, which could further benefit research into cell biology, immunology and medicine. The detection of membrane biomolecules at the single molecule level can provide some subtle information about the molecular structure and the functions of the cell membrane. In particular, information obtained about the molecular mechanisms and other information at the single molecule level are significantly different from that detected from a large amount of biomolecules at the large-scale through traditional techniques, and can thus provide a novel perspective for the study of cell membrane structures and functions. However, the precise investigations of membrane biomolecules prompts researchers to explore cell membranes at the single molecule level by the use of in situ imaging methods, as the exact conformation and functions of biomolecules are highly controlled by the native cellular environment. Recently, the in situ single molecule imaging of cell membranes has attracted increasing attention from cell biologists and immunologists. The size of biomolecules and their clusters on the cell surface are set at the nanoscale, which makes it mandatory to use high- and super-resolution imaging techniques to realize the in situ single molecule imaging of cell membranes. In the past few decades, some amazing imaging techniques and instruments with super resolution have been widely developed for molecule imaging, which can also be further employed for the in situ single molecule imaging of cell membranes. In this review, we attempt to summarize the characteristics of these advanced techniques for use in the in situ single molecule imaging of cell membranes. We believe that this work will help to promote the technological and methodological developments of super-resolution techniques for the single molecule imaging of cell membranes and help researchers better understand which technique is most suitable for their future exploring of membrane biomolecules; ultimately promoting further developments in cell biology, immunology and medicine.

Cellular Electron Cryotomography: Toward Structural Biology In Situ.

PubMed

Oikonomou, Catherine M; Jensen, Grant J

2017-06-20

Electron cryotomography (ECT) provides three-dimensional views of macromolecular complexes inside cells in a native frozen-hydrated state. Over the last two decades, ECT has revealed the ultrastructure of cells in unprecedented detail. It has also allowed us to visualize the structures of macromolecular machines in their native context inside intact cells. In many cases, such machines cannot be purified intact for in vitro study. In other cases, the function of a structure is lost outside the cell, so that the mechanism can be understood only by observation in situ. In this review, we describe the technique and its history and provide examples of its power when applied to cell biology. We also discuss the integration of ECT with other techniques, including lower-resolution fluorescence imaging and higher-resolution atomic structure determination, to cover the full scale of cellular processes.

Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

PubMed

Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

2016-05-04

The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

Evaluation of an in situ chemically crosslinked hydrogel as a long-term vitreous substitute material.

PubMed

Tao, Yong; Tong, Xinming; Zhang, Yan; Lai, Jingjing; Huang, Yanbin; Jiang, Yan-Rong; Guo, Bao-Hua

2013-02-01

Currently there is no material that can be used as a long-term vitreous substitute, and this remains an unmet clinical need in ophthalmology. In this study, we developed an injectable, in situ chemically crosslinked hydrogel system and evaluated it in a rabbit model. The system consisted of two components, both based on multi-functional poly(ethylene glycol) (PEG) but with complementarily reactive end groups of thiol and active vinyl groups, respectively. The two components are mixed and injected as a solution mixture, react in vivo via the Michael addition route and form a chemically crosslinked hydrogel in situ. The linkages between the end groups and the backbone PEG chains are specially designed to ensure that the final network structure is hydrolysis-resistant. In the rabbit study and with an optimized operation protocol, we demonstrated that the hydrogel indeed formed in situ after injection, and remained transparent and stable during the study period of 9 months without significant adverse reactions. In addition, the hydrogel formed in situ showed rheological properties very similar to the natural vitreous. Therefore, our study demonstrated that this in situ chemically crosslinked PEG gel system is suitable as a potential long-term vitreous substitute. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

Form and function in hillslope hydrology: in situ imaging and characterization of flow-relevant structures

NASA Astrophysics Data System (ADS)

Jackisch, Conrad; Angermann, Lisa; Allroggen, Niklas; Sprenger, Matthias; Blume, Theresa; Tronicke, Jens; Zehe, Erwin

2017-07-01

The study deals with the identification and characterization of rapid subsurface flow structures through pedo- and geo-physical measurements and irrigation experiments at the point, plot and hillslope scale. Our investigation of flow-relevant structures and hydrological responses refers to the general interplay of form and function, respectively. To obtain a holistic picture of the subsurface, a large set of different laboratory, exploratory and experimental methods was used at the different scales. For exploration these methods included drilled soil core profiles, in situ measurements of infiltration capacity and saturated hydraulic conductivity, and laboratory analyses of soil water retention and saturated hydraulic conductivity. The irrigation experiments at the plot scale were monitored through a combination of dye tracer, salt tracer, soil moisture dynamics, and 3-D time-lapse ground penetrating radar (GPR) methods. At the hillslope scale the subsurface was explored by a 3-D GPR survey. A natural storm event and an irrigation experiment were monitored by a dense network of soil moisture observations and a cascade of 2-D time-lapse GPR trenches. We show that the shift between activated and non-activated state of the flow paths is needed to distinguish structures from overall heterogeneity. Pedo-physical analyses of point-scale samples are the basis for sub-scale structure inference. At the plot and hillslope scale 3-D and 2-D time-lapse GPR applications are successfully employed as non-invasive means to image subsurface response patterns and to identify flow-relevant paths. Tracer recovery and soil water responses from irrigation experiments deliver a consistent estimate of response velocities. The combined observation of form and function under active conditions provides the means to localize and characterize the structures (this study) and the hydrological processes (companion study Angermann et al., 2017, this issue).

Structure and properties of hybrid composite materials

NASA Astrophysics Data System (ADS)

Chernyshova, T. A.; Kobeleva, L. I.; Bolotova, L. K.; Katin, I. V.

2013-03-01

The structure and interfacial interaction are studied in the hybrid aluminum-matrix composite materials fabricated by reactive casting combined with mechanical mixing of fillers with a metallic melt. The following types of hardening are considered: hardening by ceramic particles and by the phases formed as isolated inclusions or coatings on ceramic particles during in situ reactions. The hardness and tribological properties of the composite materials as functions of their compositions are discussed.

Cytoskeleton and Cytoskeleton-Bound RNA Visualization in Frog and Insect Oocytes.

PubMed

Kloc, Malgorzata; Bilinski, Szczepan; Kubiak, Jacek Z

2016-01-01

The majority of oocyte functions involves and depends on the cytoskeletal elements, which include microtubules and actin and cytokeratin filaments. Various structures and molecules are temporarily or permanently bound to the cytoskeletal elements and their functions rely on cytoskeleton integrity and its timely assembly. Thus the accurate visualization of cytoskeleton is often crucial for studies and analyses of oocyte structure and functions. Here we describe several reliable methods for microtubule and/or microfilaments preservation and visualization in Xenopus oocyte extracts, and in situ in live and fixed insect and frog (Xenopus) oocytes. In addition, we describe visualization of cytoskeleton-bound RNAs using molecular beacons in live Xenopus oocytes.

Spatially Resolved Quantification of Chromatin Condensation through Differential Local Rheology in Cell Nuclei Fluorescence Lifetime Imaging

PubMed Central

Spagnol, Stephen T.; Dahl, Kris Noel

2016-01-01

The linear sequence of DNA encodes access to the complete set of proteins that carry out cellular functions. Yet, much of the functionality appropriate for each cell is nested within layers of dynamic regulation and organization, including a hierarchy of chromatin structural states and spatial arrangement within the nucleus. There remain limitations in our understanding of gene expression within the context of nuclear organization from an inability to characterize hierarchical chromatin organization in situ. Here we demonstrate the use of fluorescence lifetime imaging microscopy (FLIM) to quantify and spatially resolve chromatin condensation state using cell-permeable, DNA-binding dyes (Hoechst 33342 and PicoGreen). Through in vitro and in situ experiments we demonstrate the sensitivity of fluorescence lifetime to condensation state through the mechanical effects that accompany the structural changes and are reflected through altered viscosity. The establishment of FLIM for resolving and quantifying chromatin condensation state opens the door for single-measurement mechanical studies of the nucleus and for characterizing the role of genome structure and organization in nuclear processes that accompany physiological and pathological changes. PMID:26765322

Structural evaluation of reduced graphene oxide in graphene oxide during ion irradiation: X-ray absorption spectroscopy and in-situ sheet resistance studies

NASA Astrophysics Data System (ADS)

Saravanan, K.; Jayalakshmi, G.; Suresh, K.; Sundaravel, B.; Panigrahi, B. K.; Phase, D. M.

2018-03-01

We report the structural evolution of reduced graphene oxide (rGO) in graphene oxide (GO) flakes during 1 MeV Si+ ion irradiation. In-situ electrical resistivity measurements facilitate monitoring the sheet resistance with the increase in the fluence. The electrical sheet resistance of the GO flake shows the exponential decay behaviour with the increasing ion fluence. Raman spectra of the GO flake reveal the increase in the ID/IG ratio, indicating restoration of the sp2 network upon irradiation. The C/O ratio estimated from resonant Rutherford backscattering spectrometry analysis directly evidenced the reduction of oxygen moieties upon irradiation. C K-edge X-ray absorption near edge structure spectra reveal the restoration of C=C sp2-hybridized carbon atoms and the removal of oxygen-containing functional groups in the GO flake. STM data reveal the higher conductance in the rGO regime in comparison with the regime, where the oxygen functional groups are present. The experimental investigation demonstrates that the ion irradiation can be employed for efficient reduction of GO with tunable electrical and structural properties.

Autonomous assembly of ordered metastable DNA nanoarchitecture and in situ visualizing of intracellular microRNAs.

PubMed

Xu, Jianguo; Wu, Zai-Sheng; Wang, Zhenmeng; Le, Jingqing; Zheng, Tingting; Jia, Lee

2017-03-01

Facile assembly of intelligent DNA nanoobjects with the ability to exert in situ visualization of intracellular microRNAs (miRNAs) has long been concerned in the fields of DNA nanotechnology and basic medical study. Here, we present a driving primer (DP)-triggered polymerization-mediated metastable assembly (PMA) strategy to prepare a well-ordered metastable DNA nanoarchitecture composed of only two hairpin probes (HAPs), which has never been explored by assembly methods. Its structural features and functions are characterized by atomic force microscope (AFM) and gel electrophoresis. Even if with a metastable molecular structure, this nanoarchitecture is relatively stable at physiological temperature. The assembly strategy can be expanded to execute microRNA-21 (miRNA-21) in situ imaging inside cancer cells by labelling one of the HAPs with fluorophore and quencher. Compared with the conventional fluorescence probe-based in situ hybridization (FISH) technique, confocal images revealed that the proposed DNA nanoassembly can not only achieve greatly enhanced imaging effect within cancer cells, but also reflect the miRNA-21 expression level sensitively. We believe that the easily constructed DNA nanoarchitecture and in situ profiling strategy are significant progresses in DNA assembly and molecule imaging in cells. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Structural Study of Escherichia coli Cells Using an In Situ Liquid Chamber TEM Technology.

PubMed

Wang, Yibing; Chen, Xin; Cao, Hongliang; Deng, Chao; Cao, Xiaodan; Wang, Ping

2015-01-01

Studying cell microstructures and their behaviors under living conditions has been a challenging subject in microbiology. In this work, in situ liquid chamber TEM was used to study structures of Escherichia coli cells in aqueous solutions at a nanometer-scale resolution. Most of the cells remained intact under electron beam irradiation, and nanoscale structures were observed during the TEM imaging. The analysis revealed structures of pili surrounding the E. coli cells; the movements of the pili in the liquid were also observed during the in situ tests. This technology also allowed the observation of features of the nucleoid in the E. coli cells. Overall, in situ TEM can be applied as a valuable tool to study real-time microscopic structures and processes in microbial cells residing in native aqueous solutions.

In Situ Growth of Mesoporous Silica with Drugs on Titanium Surface and Its Biomedical Applications.

PubMed

Wan, Mimi; Zhang, Jin; Wang, Qi; Zhan, Shuyue; Chen, Xudong; Mao, Chun; Liu, Yuhong; Shen, Jian

2017-06-07

Mesoporous silica has been developed for the modification of titanium surfaces that are used as implant materials. Yet, the traditional modification methods failed to effectively construct mesoporous silica on the titanium surface evenly and firmly, in which the interaction between mesoporous silica and titanium was mainly physical. Here, in situ growth of mesoporous silica on a titanium surface was performed using a simple evaporation-induced self-assembly strategy. Meantime, in situ introduction of drugs (heparin and vancomycin) to mesoporous silica was also adopted to improve the drug-loading amount. Both the above-mentioned processes were completed at the same time. Transmission electron microscopy, N 2 adsorption-desorption isotherms, Fourier transform infrared spectroscopy, scanning electron microscopy, and water contact angle measurements were used to characterize the structure of the mesoporous silica film. Results indicated that the mesoporous silica film that in situ grew on the titanium surface was smooth, thin, transparent, and stable. Cytotoxicity, proliferation performance of osteoblast cells, and in vitro and in vivo studies of the antibacterial activity of the coating were tested. This is the first study to modify the titanium surface by the in situ growth of a mesoporous silica coating with two kinds of drugs. The stability of the mesoporous silica coating can be attributed to the chemical bonding between dopamine and silicon hydroxyl of the mesoporous silica coating, and the smooth surface of mesoporous silica is a result of the method of in situ growth. The large amount of drug-loading also could be ascribed to the in situ introduction of drugs during the synthetic process. The strategy proposed in this work will bring more possibilities for the preparation of advanced functional materials based on the combination of mesoporous structure and metallic materials.

Local structural behavior of PbZr0.5Ti0.5O3 during electric field application via in situ pair distribution function study

NASA Astrophysics Data System (ADS)

Zhao, Changhao; Hou, Dong; Chung, Ching-Chang; Yu, Yingying; Liu, Wenfeng; Li, Shengtao; Jones, Jacob L.

2017-11-01

The local structural behavior of PbZr0.5Ti0.5O3 (PZT 50/50) ceramics during application of an electric field was investigated using pair distribution function (PDF) analysis. In situ synchrotron total scattering was conducted, and the PDFs were calculated from the Fourier transform of the total scattering data. The PDF refinement of the zero-field data suggests a local-structure model with [001] Ti-displacement and negligible Zr-displacement. The directional PDFs at different field amplitudes indicate the bond-length distribution of the nearest Pb-B (B = Zr/Ti) pair changes significantly with the field. The radial distribution functions (RDFs) of a model for polarization rotation were calculated. The calculated and the experimental RDFs are consistent. This result suggests the changes in Pb-B bond-length distribution could be dominantly caused by polarization rotation. Peak fitting of the experimental RDFs was also conducted. The peak position trends with increasing field are mostly in agreement with the calculation result of the polarization rotation model. The area ratio of the peaks in the experimental RDFs also changed with field amplitude, indicating that Zr atoms have a detectable displacement driven by the electric field. Our study provides an experimental observation of the behaviors of PZT 50/50 under field at a local scale which supports the polarization rotation mechanism.

Microbial community succession in alkaline, saline bauxite residue: a cross-refinery study

NASA Astrophysics Data System (ADS)

Santini, T.; Malcolm, L. I.; Tyson, G. W.; Warren, L. A.

2015-12-01

Bauxite residue, a byproduct of the Bayer process for alumina refining, is an alkaline, saline tailings material that is generally considered to be inhospitable to microbial life. In situ remediation strategies promote soil formation in bauxite residue by enhancing leaching of saline, alkaline pore water, and through incorporation of amendments to boost organic matter content, decrease pH, and improve physical structure. The amelioration of chemical and physical conditions in bauxite residue is assumed to support diversification of microbial communities from narrow, poorly functioning microbial communities towards diverse, well-functioning communities. This study aimed to characterise microbial communities in fresh and remediated bauxite residues from refineries worldwide, to identify (a) whether initial microbial communities differed between refineries; (b) major environmental controls on microbial community composition; and (c) whether remediation successfully shifts the composition of microbial communities in bauxite residue towards those found in reference (desired endpoint) soils. Samples were collected from 16 refineries and characterised using 16S amplicon sequencing to examine microbial community composition and structure, in conjunction with physicochemical analyses. Initial microbial community composition was similar across refineries but partitioned into two major groups. Microbial community composition changes slowly over time and indicates that alkalinity and salinity inhibit diversification. Microbially-based strategies for in situ remediation should consider the initial microbial community composition and whether the pre-treatment of chemical properties would optimise subsequent bioremediation outcomes. During in situ remediation, microbial communities become more diverse and develop wider functional capacity, indicating progression towards communities more commonly observed in natural grassland and forest soils.

A multilayered supramolecular self-assembled structure from soybean oil by in situ polymerization and its applications.

PubMed

Kavitha, Varadharajan; Gnanamani, Arumugam

2013-05-01

The present study emphasizes in situ transformation of soybean oil to self-assembled supramolecular multilayered biopolymer material. The said polymer material was characterized and the entrapment efficacy of both hydrophilic and hydrophobic moieties was studied. In brief, soybean oil at varying concentration was mixed with mineral medium and incubated under agitation (200 rpm) at 37 degrees C for 240 h. Physical observations were made till 240 h and the transformed biopolymer was separated and subjected to physical, chemical and functional characterization. The maximum size of the polymer material was measured as 2 cm in diameter and the cross sectional view displayed the multilayered onion rings like structures. SEM analysis illustrated the presence of multilayered honeycomb channeled structures. Thermal analysis demonstrated the thermal stability (200 degrees C) and high heat enthalpy (1999 J/g). Further, this multilayered assembly was able to entrap both hydrophilic and hydrophobic components simultaneously, suggesting the potential industrial application of this material.

In situ dynamic tracking of heterogeneous nanocatalytic processes by shell-isolated nanoparticle-enhanced Raman spectroscopy

PubMed Central

Zhang, Hua; Wang, Chen; Sun, Han-Lei; Fu, Gang; Chen, Shu; Zhang, Yue-Jiao; Chen, Bing-Hui; Anema, Jason R.; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

2017-01-01

Surface molecular information acquired in situ from a catalytic process can greatly promote the rational design of highly efficient catalysts by revealing structure-activity relationships and reaction mechanisms. Raman spectroscopy can provide this rich structural information, but normal Raman is not sensitive enough to detect trace active species adsorbed on the surface of catalysts. Here we develop a general method for in situ monitoring of heterogeneous catalytic processes through shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) satellite nanocomposites (Au-core silica-shell nanocatalyst-satellite structures), which are stable and have extremely high surface Raman sensitivity. By combining operando SHINERS with density functional theory calculations, we identify the working mechanisms for CO oxidation over PtFe and Pd nanocatalysts, which are typical low- and high-temperature catalysts, respectively. Active species, such as surface oxides, superoxide/peroxide species and Pd–C/Pt–C bonds are directly observed during the reactions. We demonstrate that in situ SHINERS can provide a deep understanding of the fundamental concepts of catalysis. PMID:28537269

Reducing Iridium Loading in Oxygen Evolution Reaction Electrocatalysts Using Core–Shell Particles with Nitride Cores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tackett, Brian M.; Sheng, Wenchao; Kattel, Shyam

Here, the oxygen evolution reaction (OER) has broad applications in electrochemical devices, but it often requires expensive and scarce Ir-based catalysts in acid electrolyte. Presented here is a framework to reduce Ir loading by combining core–shell iridium/metal nitride morphologies using in situ experiments and density functional theory (DFT) calculations. Several group VIII transition metal (Fe, Co, and Ni) nitrides are studied as core materials, with Ir/Fe 4N core–shell particles showing enhancement in both OER activity and stability. In situ X-ray absorption fine structure measurements are used to determine the structure and stability of the core–shell catalysts under OER conditions. DFTmore » calculations are used to demonstrate adsorbate binding energies as descriptors of the observed activity trends.« less

Reducing Iridium Loading in Oxygen Evolution Reaction Electrocatalysts Using Core–Shell Particles with Nitride Cores

DOE PAGES

Tackett, Brian M.; Sheng, Wenchao; Kattel, Shyam; ...

2018-02-16

Here, the oxygen evolution reaction (OER) has broad applications in electrochemical devices, but it often requires expensive and scarce Ir-based catalysts in acid electrolyte. Presented here is a framework to reduce Ir loading by combining core–shell iridium/metal nitride morphologies using in situ experiments and density functional theory (DFT) calculations. Several group VIII transition metal (Fe, Co, and Ni) nitrides are studied as core materials, with Ir/Fe 4N core–shell particles showing enhancement in both OER activity and stability. In situ X-ray absorption fine structure measurements are used to determine the structure and stability of the core–shell catalysts under OER conditions. DFTmore » calculations are used to demonstrate adsorbate binding energies as descriptors of the observed activity trends.« less

Hyperbranched polymer functional cotton fabric for its in situ deposition of silver nanoparticles

NASA Astrophysics Data System (ADS)

Zhang, Desuo; Jiao, Chenlu; Xiong, Jiaqing; Lin, Hong; Chen, Yuyue

2015-06-01

This paper describes a strategy of fabricating silver nanoparticles (Ag NPs) finished cotton fabric through in situ synthesis method. In order to endow the cotton fabric with the capability of in situ synthesis of Ag NPs without any other reagents, an amino-terminated hyperbranched polymer (HBP-NH2) was employed to functionalize the cotton fabric. To this end, cotton fabric was oxidized to generate aldehyde groups and then HBP-NH2 was grafted on the oxidized cotton fabric based on the reaction between amino groups and aldehyde groups. Due to numerous imino and amino groups in the polymer and its special three-dimensional structure, the functional cotton fabric could take initiative to capture and reduce silver ions, control the formation of Ag NPs and fix them on the cotton fabric. The sizes of Ag NPs in situ synthesized on cotton fibers range from 4 to 10 nm. The prepared Ag NPs finished cotton fabric has excellent laundering durability.

Synthesis of a polar ordered oxynitride perovskite

NASA Astrophysics Data System (ADS)

Vadapoo, Rajasekarakumar; Ahart, Muhtar; Somayazulu, Maddury; Holtgrewe, Nicholas; Meng, Yue; Konopkova, Zuzana; Hemley, Russell J.; Cohen, R. E.

2017-06-01

For decades, numerous attempts have been made to produce polar oxynitride perovskites, where some of the oxygen is replaced by nitrogen, but a polar ordered oxynitride has never been demonstrated. Caracas and Cohen [Appl. Phys. Lett. 91, 092902 (2007), 10.1063/1.2776370] studied possible ordered polar oxynitrides within density-functional theory (DFT) and found a few candidates that were predicted to be insulating and at least metastable. YSi O2N stood out with huge predicted polarization and nonlinear optic coefficients. In this study, we demonstrate the synthesis of perovskite-structured YSi O2N by using a combination of a diamond-anvil cell and in situ laser-heating techniques. Subsequent in situ x-ray diffraction, second-harmonic generation, and Raman-scattering measurements confirm that it is polar and a strong nonlinear optical material, with structure and properties similar to those predicted by DFT.

Synthesis of a polar ordered oxynitride perovskite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vadapoo, Rajasekarakumar; Ahart, Muhtar; Somayazulu, Maddury

For decades, numerous attempts have been made to produce polar oxynitride perovskites, where some of the oxygen is replaced by nitrogen, but a polar ordered oxynitride has never been demonstrated. Caracas and Cohen [Appl. Phys. Lett. 91, 092902 (2007)] studied possible ordered polar oxynitrides within density-functional theory (DFT) and found a few candidates that were predicted to be insulating and at least metastable. YSi O 2 N stood out with huge predicted polarization and nonlinear optic coefficients. In this study, we demonstrate the synthesis of perovskite-structured YSi O 2 N by using a combination of a diamond-anvil cell and inmore » situ laser-heating techniques. Subsequent in situ x-ray diffraction, second-harmonic generation, and Raman-scattering measurements confirm that it is polar and a strong nonlinear optical material, with structure and properties similar to those predicted by DFT.« less

Structure and Electronic Properties of Crystalline and Amorphous Zinc Indium Tin Oxide Thin Films

NASA Astrophysics Data System (ADS)

Proffit, Diana Elizabeth

The local structures and surface electronic properties of crystalline (c-) and amorphous (a-) Zn and Sn codoped In2O3 (ZITO) films were studied. X-ray absorption spectroscopy (XAS) measurements confirm that Zn and Sn dopants occupy In sites in the bixbyite structure of c-ZITO. Also, Zn dopants are generally under-coordinated and some compensated Sn dopants are over-coordinated, as demonstrated by the trend in coordination numbers (CN) of CNSn>CNIn>CNZn. Aliovalent Sn dopants form Frank-Kostlin clusters, (2Sn•InO'' i)x , which can act as donors when reduced. XAS and anomalous X-ray scattering studies on a-ZITO show that the local structure in a-ZITO is somewhat different than that in c-ZITO, particularly around Zn. The Zn-O bond length is significantly smaller than in c-ZITO and Zn is 4-fold coordinated. The smaller coordination numbers in a-ZITO follow the same trend as in c-ZITO. Unlike in c-ZITO, variations in the Sn/Zn ratio do not alter the electrical properties of a-ZITO, although variations in deposition oxygen pressure do. The 3-D geometrical arrangement linking local structure units seems to play a key role in charge balancing ZITO. As measured by in situ grazing incidence wide angle X-ray scattering, ZITO crystallizes at a higher temperature than In2 O3 and Sn-doped In2O3. The difference is attributed to a higher activation energy, which may result from the unique structure around Zn in a-ZITO. Increasing the codoping level consistently increases crystallization temperature. For a given codoping level, the crystallization temperature during deposition is lower than that during post-deposition annealing. X-ray and ultraviolet photoelectron spectroscopy measurements show that a-ZITO and c-ZITO thin films have similar surface electronic properties. In situ a-ZITO and c-ZITO films have low ionization potentials that are similar to In2O3. However, dry-air-annealed in situ films, ex situ films, and bulk ceramics have higher ionization potentials that are similar to ITO and match well with previous results on air-exposed surfaces. Lastly, a parallelogram plot of work function versus Fermi level shows that a wider range of work functions is achievable in ZITO materials than in Sb-doped SnO2, Al-doped ZnO, and Sn-doped In2O3.

Architecture engineering of supercapacitor electrode materials

NASA Astrophysics Data System (ADS)

Chen, Kunfeng; Li, Gong; Xue, Dongfeng

2016-02-01

The biggest challenge for today’s supercapacitor systems readily possessing high power density is their low energy density. Their electrode materials with controllable structure, specific surface area, electronic conductivity, and oxidation state, have long been highlighted. Architecture engineering of functional electrode materials toward powerful supercapacitor systems is becoming a big fashion in the community. The construction of ion-accessible tunnel structures can microscopically increase the specific capacitance and materials utilization; stiff 3D structures with high specific surface area can macroscopically assure high specific capacitance. Many exciting findings in electrode materials mainly focus on the construction of ice-folded graphene paper, in situ functionalized graphene, in situ crystallizing colloidal ionic particles and polymorphic metal oxides. This feature paper highlights some recent architecture engineering strategies toward high-energy supercapacitor electrode systems, including electric double-layer capacitance (EDLC) and pseudocapacitance.

Fabrication and electric measurements of nanostructures inside transmission electron microscope.

PubMed

Chen, Qing; Peng, Lian-Mao

2011-06-01

Using manipulation holders specially designed for transmission electron microscope (TEM), nanostructures can be characterized, measured, modified and even fabricated in-situ. In-situ TEM techniques not only enable real-time study of structure-property relationships of materials at atomic scale, but also provide the ability to control and manipulate materials and structures at nanoscale. This review highlights in-situ electric measurements and in-situ fabrication and structure modification using manipulation holder inside TEM. Copyright © 2011 Elsevier B.V. All rights reserved.

Atoms in Action: Observing Atomic Motion with Dynamic in situ X-ray Diffraction

NASA Astrophysics Data System (ADS)

Cox, Jordan Michael

Metal-organic framework (MOF) materials are rich in both structural diversity and application. These materials are comprised of metal atoms or clusters which are connected in a three-dimensional polymer-like network by bridging organic linker molecules. One of the major attractive features in MOFs is their permanent pore space which can potentially be used to adsorb or exchange foreign molecules from/with the surrounding environment. While MOFs are an active area of scientific interest, MOF materials are still relatively new, only 20 years old. As such, there is still much that needs to be understood about these materials before they can be effectively applied to widespread chemical problems like CO2 sequestration or low-pressure hydrogen fuel storage. One of the most important facets of MOF chemistry to understand in order to rationally design MOF materials with tailor-made properties is the relationship between the structural features in a MOF and the chemical and physical properties of that material. By examining in detail the atomic structure of a MOF with known properties under a variety of conditions, scientists can begin to unravel the guiding principles which govern these relationships. X-ray diffraction remains one of the most effective tools for determining the structure of a crystalline material with atomic resolution, and has been applied to the determination of MOF structures for years. Typically these experiments have been carried out using powder X-ray diffraction, but this technique lacks the high-resolution structural information found in single-crystal methods. Some studies have been reported which use specialized devices, sometimes called Environmental Control Cells, to study single crystalline MOFs under non-ambient chemical conditions in situ . However, these in situ studies are performed under static conditions. Even in cases where the ECC provides continued access to the local chemical environment during diffraction data collections, the environment is left static or data is not collected until after the material has equilibrated to its new environment. First, a unique ECC has been designed and constructed which allows continuous access to the local chemical environment of a single-crystal sample while maintaining ease of use, minimizing size, and which is easily adaptable to a wide variety of gaseous and liquid chemical stimuli. Novel methods have been developed and are herein described for utilizing this ECC and in situ X-ray diffraction methods in a dynamic manner for monitoring the structural responses of single crystals to changes in their local chemical environment. These methods provide the opportunity for the determination of changes in unit cell parameters and even complete crystal structures during adsorption, desorption, and exchange processes in MOF materials. The application of these methods to the determination of the dehydration process of a previously reported cobalt-based MOF have revealed surprising structural and dynamics data. Several new intermediate structures have been determined in this process, including one metastable species and several actively transitioning species during the dehydration process. Applying these methods to the ethanol solvation process in the same material again yielded results which were richer in structural information than the previously reported ex situ structures. A computational study of rotational potential energy surfaces in a family of photochromic MOF linkers revealed the important role rotational stereoisomers can play in maintaining light-activated functionality when these linkers are incorporated into next-generation functional MOF materials. Finally, the application of novel photocrystallography techniques were used in conjunction with spectroscopic methods to determine the nature of the anomalous behavior of a photochromic diarylethene single-crystal.

Early stage structural development of prototypical zeolitic imidazolate framework (ZIF) in solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Terban, Maxwell W.; Banerjee, Debasis; Ghose, Sanjit

Given the wide-ranging potential applications of metal organic frameworks (MOFs), an emerging imperative is to understand their formation with atomic scale precision. This will aid in designing syntheses for next-generation MOFs with enhanced properties and functionalities. Major challenges are to characterize the early-stage seeds, and the pathways to framework growth, which require synthesis coupled with in situ structural characterization sensitive to nanoscale structures in solution. Here we report measurements of an in situ synthesis of a prototypical MOF, ZIF-8, utilizing synchrotron X-ray atomic pair distribution function (PDF) analysis optimized for sensitivity to dilute species, complemented by mass spectrometry, electron microscopy,more » and density functional theory calculations. We observe that despite rapid formation of the crystalline product, a high concentration of Zn(2-MeIm) 4(2-MeIm=2-methylimidazolate) initially forms and persists as stable clusters over long times. A secondary, amorphous phase also pervades during the synthesis, which has a structural similarity to the final ZIF-8 and may act as an intermediate to the final product.« less

Early stage structural development of prototypical zeolitic imidazolate framework (ZIF) in solution

DOE PAGES

Terban, Maxwell W.; Banerjee, Debasis; Ghose, Sanjit; ...

2018-02-05

Given the wide-ranging potential applications of metal organic frameworks (MOFs), an emerging imperative is to understand their formation with atomic scale precision. This will aid in designing syntheses for next-generation MOFs with enhanced properties and functionalities. Major challenges are to characterize the early-stage seeds, and the pathways to framework growth, which require synthesis coupled with in situ structural characterization sensitive to nanoscale structures in solution. Here we report measurements of an in situ synthesis of a prototypical MOF, ZIF-8, utilizing synchrotron X-ray atomic pair distribution function (PDF) analysis optimized for sensitivity to dilute species, complemented by mass spectrometry, electron microscopy,more » and density functional theory calculations. We observe that despite rapid formation of the crystalline product, a high concentration of Zn(2-MeIm) 4(2-MeIm=2-methylimidazolate) initially forms and persists as stable clusters over long times. A secondary, amorphous phase also pervades during the synthesis, which has a structural similarity to the final ZIF-8 and may act as an intermediate to the final product.« less

Cluster Tool for In Situ Processing and Comprehensive Characterization of Thin Films at High Temperatures.

PubMed

Wenisch, Robert; Lungwitz, Frank; Hanf, Daniel; Heller, René; Zscharschuch, Jens; Hübner, René; von Borany, Johannes; Abrasonis, Gintautas; Gemming, Sibylle; Escobar-Galindo, Ramon; Krause, Matthias

2018-06-13

A new cluster tool for in situ real-time processing and depth-resolved compositional, structural and optical characterization of thin films at temperatures from -100 to 800 °C is described. The implemented techniques comprise magnetron sputtering, ion irradiation, Rutherford backscattering spectrometry, Raman spectroscopy, and spectroscopic ellipsometry. The capability of the cluster tool is demonstrated for a layer stack MgO/amorphous Si (∼60 nm)/Ag (∼30 nm), deposited at room temperature and crystallized with partial layer exchange by heating up to 650 °C. Its initial and final composition, stacking order, and structure were monitored in situ in real time and a reaction progress was defined as a function of time and temperature.

Recent Advances on In Situ SEM Mechanical and Electrical Characterization of Low-Dimensional Nanomaterials.

PubMed

Jiang, Chenchen; Lu, Haojian; Zhang, Hongti; Shen, Yajing; Lu, Yang

2017-01-01

In the past decades, in situ scanning electron microscopy (SEM) has become a powerful technique for the experimental study of low-dimensional (1D/2D) nanomaterials, since it can provide unprecedented details for individual nanostructures upon mechanical and electrical stimulus and thus uncover the fundamental deformation and failure mechanisms for their device applications. In this overview, we summarized recent developments on in situ SEM-based mechanical and electrical characterization techniques including tensile, compression, bending, and electrical property probing on individual nanostructures, as well as the state-of-the-art electromechanical coupling analysis. In addition, the advantages and disadvantages of in situ SEM tests were also discussed with some possible solutions to address the challenges. Furthermore, critical challenges were also discussed for the development and design of robust in situ SEM characterization platform with higher resolution and wider range of samples. These experimental efforts have offered in-depth understanding on the mechanical and electrical properties of low-dimensional nanomaterial components and given guidelines for their further structural and functional applications.

Recent Advances on In Situ SEM Mechanical and Electrical Characterization of Low-Dimensional Nanomaterials

PubMed Central

Jiang, Chenchen; Lu, Haojian; Zhang, Hongti

2017-01-01

In the past decades, in situ scanning electron microscopy (SEM) has become a powerful technique for the experimental study of low-dimensional (1D/2D) nanomaterials, since it can provide unprecedented details for individual nanostructures upon mechanical and electrical stimulus and thus uncover the fundamental deformation and failure mechanisms for their device applications. In this overview, we summarized recent developments on in situ SEM-based mechanical and electrical characterization techniques including tensile, compression, bending, and electrical property probing on individual nanostructures, as well as the state-of-the-art electromechanical coupling analysis. In addition, the advantages and disadvantages of in situ SEM tests were also discussed with some possible solutions to address the challenges. Furthermore, critical challenges were also discussed for the development and design of robust in situ SEM characterization platform with higher resolution and wider range of samples. These experimental efforts have offered in-depth understanding on the mechanical and electrical properties of low-dimensional nanomaterial components and given guidelines for their further structural and functional applications. PMID:29209445

Evolution of Active Sites in Pt-Based Nanoalloy Catalysts for the Oxidation of Carbonaceous Species by Combined in Situ Infrared Spectroscopy and Total X-ray Scattering.

PubMed

Petkov, Valeri; Maswadeh, Yazan; Lu, Aolin; Shan, Shiyao; Kareem, Haval; Zhao, Yinguang; Luo, Jin; Zhong, Chuan-Jian; Beyer, Kevin; Chapman, Karena

2018-04-04

We present results from combined in situ infrared spectroscopy and total X-ray scattering studies on the evolution of catalytically active sites in exemplary binary and ternary Pt-based nanoalloys during a sequence of CO oxidation-reactivation-CO oxidation reactions. We find that when within a particular compositional range, the fresh nanoalloys may exhibit high catalytic activity for low-temperature CO oxidation. Using surface-specific atomic pair distribution functions (PDFs) extracted from the in situ total X-ray scattering data, we find that, regardless of their chemical composition and initial catalytic activity, the fresh nanoalloys suffer a significant surface structural disorder during CO oxidation. Upon reactivation in oxygen atmosphere, the surface of used nanoalloy catalysts both partially oxidizes and orders. Remarkably, it largely retains its structural state when the nanoalloys are reused as CO oxidation catalysts. The seemingly inverse structural changes of studied nanoalloy catalysts occurring under CO oxidation and reactivation conditions affect the active sites on their surface significantly. In particular, through different mechanisms, both appear to reduce the CO binding strength to the nanoalloy's surface and thus increase the catalytic stability of the nanoalloys. The findings provide clues for further optimization of nanoalloy catalysts for the oxidation of carbonaceous species through optimizing their composition, activation, and reactivation. Besides, the findings demonstrate the usefulness of combined in situ infrared spectroscopy and total X-ray scattering coupled to surface-specific atomic PDF analysis to the ongoing effort to produce advanced catalysts for environmentally and technologically important applications.

Determination of the Effects of Magnesium on the Structural Order of Amorphous Calcium Phosphate

NASA Astrophysics Data System (ADS)

Hoeher, A.; Michel, F. M.; Rakovan, J. F.; Borkiewicz, O.; Klysubun, W.

2016-12-01

Determining the pathways and mechanisms of calcium phosphate formation is important for understanding bone mineralization and advancing potential biological applications such as coatings on internal prosthetics. Studies show that amorphous calcium phosphate (ACP) is a precursor phase in the low temperature crystallization of hydroxylapatite, the primary mineral component found in bone and teeth of most modern vertebrates. ACP has been shown to have a structural order out to about 1 nm. Our recent extended x-ray absorption fine structure (EXAFS) spectroscopy analysis of synthetic ACP showed that the local structure of calcium in ACP differed from that in hydroxylapatite. Phosphorus EXAFS, however, indicated that the local structure in ACP is similar to hydroxylapatite (i.e., tetrahedrally coordinated with oxygen). EXAFS results were limited to only the first and second nearest neighbors in these samples, so the intermediate range order in ACP is yet unexplored. Furthermore, it remains unclear how ACP structure varies as a function of initial solution chemistry, how common impurities such as Mg are incorporated, and what role they play in determining the structural and physical characteristics of the final crystalline solid. We are using synchrotron x-ray total scattering for pair distribution function (PDF) analysis to investigate the influence of initial solution chemistry and Mg content on the structure of ACP. Magnesium is commonly used to stabilize the amorphous nature of the material, preventing crystallization. Ex situ samples synthesized at pH 10, with Ca:Mg ratios of 2:1, and freeze-dried are structurally similar to hydroxylapatite. Samples synthesized in identical conditions without Mg are structurally similar to another calcium phosphate mineral, brushite. In situ PDF measurements done at similar conditions in a custom mixed-flow reactor reveal that the short range order of ACP after 10 minutes of reacting is structurally different from ACP formed ex situ in the laboratory. Future analysis is aimed at quantifying the influence of these differences and to determine the validity of competing structural models proposed for ACP. This information is essential to further develop our understanding of the ACP transformation process into hydroxylapatite.

Liquid metal-organic frameworks

NASA Astrophysics Data System (ADS)

Gaillac, Romain; Pullumbi, Pluton; Beyer, Kevin A.; Chapman, Karena W.; Keen, David A.; Bennett, Thomas D.; Coudert, François-Xavier

2017-11-01

Metal-organic frameworks (MOFs) are a family of chemically diverse materials, with applications in a wide range of fields, covering engineering, physics, chemistry, biology and medicine. Until recently, research has focused almost entirely on crystalline structures, yet now a clear trend is emerging, shifting the emphasis onto disordered states, including `defective by design’ crystals, as well as amorphous phases such as glasses and gels. Here we introduce a strongly associated MOF liquid, obtained by melting a zeolitic imidazolate framework. We combine in situ variable temperature X-ray, ex situ neutron pair distribution function experiments, and first-principles molecular dynamics simulations to study the melting phenomenon and the nature of the liquid obtained. We demonstrate from structural, dynamical, and thermodynamical information that the chemical configuration, coordinative bonding, and porosity of the parent crystalline framework survive upon formation of the MOF liquid.

Liquid metal-organic frameworks.

PubMed

Gaillac, Romain; Pullumbi, Pluton; Beyer, Kevin A; Chapman, Karena W; Keen, David A; Bennett, Thomas D; Coudert, François-Xavier

2017-11-01

Metal-organic frameworks (MOFs) are a family of chemically diverse materials, with applications in a wide range of fields, covering engineering, physics, chemistry, biology and medicine. Until recently, research has focused almost entirely on crystalline structures, yet now a clear trend is emerging, shifting the emphasis onto disordered states, including 'defective by design' crystals, as well as amorphous phases such as glasses and gels. Here we introduce a strongly associated MOF liquid, obtained by melting a zeolitic imidazolate framework. We combine in situ variable temperature X-ray, ex situ neutron pair distribution function experiments, and first-principles molecular dynamics simulations to study the melting phenomenon and the nature of the liquid obtained. We demonstrate from structural, dynamical, and thermodynamical information that the chemical configuration, coordinative bonding, and porosity of the parent crystalline framework survive upon formation of the MOF liquid.

Liquid metal–organic frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaillac, Romain; Pullumbi, Pluton; Beyer, Kevin A.

Metal–organic frameworks (MOFs) are a family of chemically diverse materials, with applications in a wide range of fields, covering engineering, physics, chemistry, biology and medicine. Until recently, research has focused almost entirely on crystalline structures, yet now a clear trend is emerging, shifting the emphasis onto disordered states, including ‘defective by design’ crystals, as well as amorphous phases such as glasses and gels. Here we introduce a strongly associated MOF liquid, obtained by melting a zeolitic imidazolate framework. We combine in situ variable temperature X-ray, ex situ neutron pair distribution function experiments, and first-principles molecular dynamics simulations to study themore » melting phenomenon and the nature of the liquid obtained. We demonstrate from structural, dynamical, and thermodynamical information that the chemical configuration, coordinative bonding, and porosity of the parent crystalline framework survive upon formation of the MOF liquid.« less

Testing the Chemical/Structural Stability of Proton Conducting Perovskite Ceramic Membranes by in Situ/ex Situ Autoclave Raman Microscopy.

PubMed

Slodczyk, Aneta; Zaafrani, Oumaya; Sharp, Matthew D; Kilner, John A; Dabrowski, Bogdan; Lacroix, Olivier; Colomban, Philippe

2013-10-25

Ceramics, which exhibit high proton conductivity at moderate temperatures, are studied as electrolyte membranes or electrode components of fuel cells, electrolysers or CO2 converters. In severe operating conditions (high gas pressure/high temperature), the chemical activity towards potentially reactive atmospheres (water, CO2, etc.) is enhanced. This can lead to mechanical, chemical, and structural instability of the membranes and premature efficiency loss. Since the lifetime duration of a device determines its economical interest, stability/aging tests are essential. Consequently, we have developed autoclaves equipped with a sapphire window, allowing in situ Raman study in the 25-620 °C temperature region under 1-50 bar of water vapor/gas pressure, both with and without the application of an electric field. Taking examples of four widely investigated perovskites (BaZr0.9Yb0.1O3-δ, SrZr0.9Yb0.1O3-δ, BaZr0.25In0.75O3-δ, BaCe0.5Zr0.3Y0.16Zn0.04O3-δ), we demonstrate the high potential of our unique set-up to discriminate between good/stable and instable electrolytes as well as the ability to detect and monitor in situ: (i) the sample surface reaction with surrounding atmospheres and the formation of crystalline or amorphous secondary phases (carbonates, hydroxides, hydrates, etc.); and (ii) the structural modifications as a function of operating conditions. The results of these studies allow us to compare quantitatively the chemical stability versus water (corrosion rate from ~150 µm/day to less than 0.25 µm/day under 200-500 °C/15-80 bar PH2O) and to go further in comprehension of the aging mechanism of the membrane.

New in-situ neutron diffraction cell for electrode materials

NASA Astrophysics Data System (ADS)

Biendicho, Jordi Jacas; Roberts, Matthew; Offer, Colin; Noréus, Dag; Widenkvist, Erika; Smith, Ronald I.; Svensson, Gunnar; Edström, Kristina; Norberg, Stefan T.; Eriksson, Sten G.; Hull, Stephen

2014-02-01

A novel neutron diffraction cell has been constructed to allow in-situ studies of the structural changes in materials of relevance to battery applications during charge/discharge cycling. The new design is based on the coin cell geometry, but has larger dimensions compared to typical commercial batteries in order to maximize the amount of electrode material and thus, collect diffraction data of good statistical quality within the shortest possible time. An important aspect of the design is its modular nature, allowing flexibility in both the materials studied and the battery configuration. This paper reports electrochemical tests using a Nickel-metal-hydride battery (Ni-MH), which show that the cell is able to deliver 90% of its theoretical capacity when using deuterated components. Neutron diffraction studies performed on the Polaris diffractometer using nickel metal and a hydrogen-absorbing alloy (MH) clearly show observable changes in the neutron diffraction patterns as a function of the discharge state. Due to the high quality of the diffraction patterns collected in-situ (i.e. good peak-to-background ratio), phase analysis and peak indexing can be performed successfully using data collected in around 30 min. In addition to this, structural parameters for the β-phase (charged) MH electrode obtained by Rietveld refinement are presented.

Vascular Mechanobiology: Towards Control of In Situ Regeneration

PubMed Central

van Haaften, Eline E.; Bouten, Carlijn V. C.; Kurniawan, Nicholas A.

2017-01-01

The paradigm of regenerative medicine has recently shifted from in vitro to in situ tissue engineering: implanting a cell-free, biodegradable, off-the-shelf available scaffold and inducing the development of functional tissue by utilizing the regenerative potential of the body itself. This approach offers a prospect of not only alleviating the clinical demand for autologous vessels but also circumventing the current challenges with synthetic grafts. In order to move towards a hypothesis-driven engineering approach, we review three crucial aspects that need to be taken into account when regenerating vessels: (1) the structure-function relation for attaining mechanical homeostasis of vascular tissues; (2) the environmental cues governing cell function; and (3) the available experimental platforms to test instructive scaffolds for in situ tissue engineering. The understanding of cellular responses to environmental cues leads to the development of computational models to predict tissue formation and maturation, which are validated using experimental platforms recapitulating the (patho)physiological micro-environment. With the current advances, a progressive shift is anticipated towards a rational and effective approach of building instructive scaffolds for in situ vascular tissue regeneration. PMID:28671618

Vascular Mechanobiology: Towards Control of In Situ Regeneration.

PubMed

van Haaften, Eline E; Bouten, Carlijn V C; Kurniawan, Nicholas A

2017-07-03

The paradigm of regenerative medicine has recently shifted from in vitro to in situ tissue engineering: implanting a cell-free, biodegradable, off-the-shelf available scaffold and inducing the development of functional tissue by utilizing the regenerative potential of the body itself. This approach offers a prospect of not only alleviating the clinical demand for autologous vessels but also circumventing the current challenges with synthetic grafts. In order to move towards a hypothesis-driven engineering approach, we review three crucial aspects that need to be taken into account when regenerating vessels: (1) the structure-function relation for attaining mechanical homeostasis of vascular tissues, (2) the environmental cues governing cell function, and (3) the available experimental platforms to test instructive scaffolds for in situ tissue engineering. The understanding of cellular responses to environmental cues leads to the development of computational models to predict tissue formation and maturation, which are validated using experimental platforms recapitulating the (patho)physiological micro-environment. With the current advances, a progressive shift is anticipated towards a rational and effective approach of building instructive scaffolds for in situ vascular tissue regeneration.

A Facile Strategy for In Situ Core-Template-Functionalizing Siliceous Hollow Nanospheres for Guest Species Entrapment

PubMed Central

2009-01-01

The shell wall-functionalized siliceous hollow nanospheres (SHNs) with functional molecules represent an important class of nanocarriers for a rich range of potential applications. Herein, a self-templated approach has been developed for the synthesis of in situ functionalized SHNs, in which the biocompatible long-chain polycarboxylates (i.e., polyacrylate, polyaspartate, gelatin) provide the framework for silica precursor deposition by simply controlling chain conformation with divalent metal ions (i.e., Ca2+, Sr2+), without the intervention of any external templates. Metal ions play crucial roles in the formation of organic vesicle templates by modulating the long chains of polymers and preventing them from separation by washing process. We also show that, by in situ functionalizing the shell wall of SHNs, it is capable of entrapping nearly an eightfold quantity of vitamin Bc in comparison to the bare bulk silica nanospheres. These results confirm the feasibility of guest species entrapment in the functionalized shell wall, and SHNs are effective carriers of guest (bio-)molecules potentially for a variety of biomedical applications. By rationally choosing the functional (self-templating) molecules, this concept may represent a general strategy for the production of functionalized silica hollow structures. PMID:20596316

Fabrication of Nanocarbon Composites Using In Situ Chemical Vapor Deposition and Their Applications.

PubMed

He, Chunnian; Zhao, Naiqin; Shi, Chunsheng; Liu, Enzuo; Li, Jiajun

2015-09-23

Nanocarbon (carbon nanotubes (CNTs) and graphene (GN)) composites attract considerable research interest due to their fascinating applications in many fields. Here, recent developments in the field of in situ chemical vapor deposition (CVD) for the design and controlled preparation of advanced nanocarbon composites are highlighted, specifically, CNT-reinforced bulk structural composites, as well as CNT, GN, and CNT/GN functional composites, together with their practical and potential applications. In situ CVD is a very attractive approach for the fabrication of composites because of its engaging features, such as its simplicity, low-cost, versatility, and tunability. The morphologies, structures, dispersion, and interface of the resulting nanocarbon composites can be easily modulated by varying the experimental parameters (such as temperature, catalysts, carbon sources, templates or template catalysts, etc.), which enables a great potential for the in situ synthesis of high-quality nanocarbons with tailored size and dimension for constructing high-performance composites, which has not yet been achieved by conventional methods. In addition, new trends of the in situ CVD toward nanocarbon composites are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Drying-induced atomic structural rearrangements in sodium-based calcium-alumino-silicate-hydrate gel and the mitigating effects of ZrO 2 nanoparticles

DOE PAGES

Yang, Kengran; Özçelik, V. Ongun; Garg, Nishant; ...

2018-01-01

Drying-induced nanoscopic alterations to the local atomic structure of silicate-activated slag and the mitigated effects of nano-ZrO2 are elucidated using in situ X-ray pair distribution function analysis.

Drying-induced atomic structural rearrangements in sodium-based calcium-alumino-silicate-hydrate gel and the mitigating effects of ZrO 2 nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Kengran; Özçelik, V. Ongun; Garg, Nishant

Drying-induced nanoscopic alterations to the local atomic structure of silicate-activated slag and the mitigated effects of nano-ZrO2 are elucidated using in situ X-ray pair distribution function analysis.

Assessing morphology and function of the semicircular duct system: introducing new in-situ visualization and software toolbox

PubMed Central

David, R.; Stoessel, A.; Berthoz, A.; Spoor, F.; Bennequin, D.

2016-01-01

The semicircular duct system is part of the sensory organ of balance and essential for navigation and spatial awareness in vertebrates. Its function in detecting head rotations has been modelled with increasing sophistication, but the biomechanics of actual semicircular duct systems has rarely been analyzed, foremost because the fragile membranous structures in the inner ear are hard to visualize undistorted and in full. Here we present a new, easy-to-apply and non-invasive method for three-dimensional in-situ visualization and quantification of the semicircular duct system, using X-ray micro tomography and tissue staining with phosphotungstic acid. Moreover, we introduce Ariadne, a software toolbox which provides comprehensive and improved morphological and functional analysis of any visualized duct system. We demonstrate the potential of these methods by presenting results for the duct system of humans, the squirrel monkey and the rhesus macaque, making comparisons with past results from neurophysiological, oculometric and biomechanical studies. Ariadne is freely available at http://www.earbank.org. PMID:27604473

Quantitative depth profiling of Ce(3+) in Pt/CeO2 by in situ high-energy XPS in a hydrogen atmosphere.

PubMed

Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas; Paun, Cristina; Lampimäki, Markus; Lee, Ming-Tao; Rothensteiner, Matthäus; van Bokhoven, Jeroen A

2015-02-21

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

Functional response of an adapted subtidal macrobenthic community to an oil spill: macrobenthic structure and bioturbation activity over time throughout an 18-month field experiment.

PubMed

Gilbert, Franck; Stora, Georges; Cuny, Philippe

2015-10-01

An experimental oil spill was carried out in order to assess in situ responses of a macrobenthic community of shallow subtidal sediments historically exposed to petroleum contamination. Both structural and functional (bioturbation activity) parameters of the community, subjected or not to a pulse acute contamination (25,000 ppm), were studied for 18 months. No difference in the community structure was detected between contaminated and control sediments, from 6 to 18 months of experimentation. Vertical distributions of organisms, however, were affected by the presence of oil contamination leading to a deeper burial of some polychaete species. In the same time, changes in sediment-reworking activity and more especially a deeper particle burying in sediments subjected to acute oil contamination were shown. These results highlight the need to complete the analysis of community structure by assessing functional aspects, such as bioturbation activity, a process integrating various aspects of benthic behaviour (e.g. feeding, locomotion, burrow building) in order to estimate real (structural and functional) and long-term effects of oil contamination on benthic communities.

Assesment of hydraulics properties of technosoil constructed with waste material using Beerkan infiltration

NASA Astrophysics Data System (ADS)

Yilmaz, Deniz; Peyneau, Pierre-Emmanuel; Beaudet, Laure; Cannavo, Patrice; Sere, Geoffroy

2017-04-01

For the characterization of hydraulics soils functions, in situ infiltration experiments are commonly used. The BEST method based on the infiltration through a single ring is well suited for soils containing coarse material. Technosols built from Civil engineering waste material such as brick waste, concrete waste, track ballast and demolition rubble wastes contain large part of coarse material. In this work, different materials made of civil engineering wastes mixed with organic wastes are tested for greening applications in an urban environment using in situ lysimeters. Beerkan infiltrations experiments were performed on these technosols. Experimental data are used to estimate hydraulics properties through the BEST method. The results shows from a hydraulic point of view that studied technosols can achieve the role of urban soil for greening application. Five combinations of artefacts were tested either as "growing material" (one combination) or "structural material" (4 combinations) - as support for traffic. Structural materials consisted in 27 wt.% earth material, 60 wt.% mineral coarse material and 3 wt.% organic material. These constructed technosols were studied in situ using lysimeters under two contrasted climatic conditions in two sites in France (Angers, in northwestern France and Homécourt, in northeastern France). Constructed technosols exhibited high porosities (31-48 vol% for structural materials, 70 vol% for the growing material). The dry bulk density of the growing material is estimated to 0.66 kg/m3 and 1.59 kg/m3 for structural material. The particle size distribution analysis, involving manual sieving (> 2 mm) and complemented by a grain size analysis (< 2 mm) were used as described in the BEST method (2006) for the estimation of the shape parameter n of hydraulics functions (Van-Genuchten -Mualem, 1980). This n parameter was estimated to 2.23 for growing materials and 2.29 for structural materials. Beerkan infiltrations experiments data were inversed using the BEST method, the results exhibited high saturated hydraulic conductivities 10.7 cm/h for structural materials and 14,8 cm/h for the growing material. Beerkan infiltration experiements are well suited for assesment of hydraulic properties of technosol constructed with civil engineering wastes. According to the estimated hydraulics functions, the studied technosols can be classified between a sand and a loam soil. It shows that these materials can achieve the role of alternative to the consumption of natural arable earth for urban greening applications such as gardens, parks and trees lines.

Unravel the submesoscale dynamics of the phytoplanktonic community in the NW Mediterranean Sea by in situ observations: the 2015 OSCAHR cruise

NASA Astrophysics Data System (ADS)

Marrec, Pierre; Doglioli, Andrea M.; Grégori, Gérald; Della Penna, Alice; Wagener, Thibaut; Rougier, Gille; Bhairy, Nagib; Dugenne, Mathilde; Lahbib, Soumaya; Thyssen, Melilotus

2017-04-01

Submesoscale phenomena have been recently recognized as a key factor in physical-biological-biogeochemical interactions, even if it remains unclear how these processes affect the global state of the ocean. Significant large-scale impacts of submesoscale structures on primary production and influence on the phytoplankton community structure and diversity have also been reported. In the past decade submesoscale dynamics have been predominately studied through the analysis of numerical simulations. Observing the coupled physical and biogeochemical variability at this scale remains challenging due to the ephemeral nature of submesoscale structures. The in-situ study of such structures necessitates multidisciplinary approaches involving in situ observations, remote sensing and modeling. Last progresses in biogeochemical sensor development and advanced methodology including Lagrangian real-time adaptative strategies represent outstanding opportunities. The OSCAHR (Observing Submesoscale Coupling At High Resolution) campaign has been conducted thanks to a multidisciplinary approach in order to improve the understanding of submesoscale processes. An ephemeral submesoscale structure was first identified in the Ligurian Sea in fall 2015 using both satellite and numerical modeling data before the campaign. Afterwards, advanced observing systems for the physical, biological and biogeochemical characterization of the sea surface layer at a high spatial and temporal frequency were deployed during a 10-days cruise. A MVP (Moving Vessel Profiler) was used to obtain high resolution CTD profiles associated to a new pumping system with 1-m vertical resolution. Moreover, along the ship track, in addition to the standard measurements of seawater surface samples (Chl-a, nutrients, O2, SST, SSS …), we deployed an automated flow cytometer for near real-time characterization of phytoplankton functional groups (from micro-phytoplankton down to cyanobacteria). The observed submesoscale feature presented a cyclonic structure with a relatively cold core surrounded by warmer waters. Six phytoplankton groups were identified across the structure with an unprecedented spatial and temporal resolution. According to our observations, we could quantify the influence of the fast established physical structure on the spatial distribution of the phytoplankton functional groups, giving coherence to the observed community structuration. Moreover, the high resolution of our observations allows us to estimate the growth rate of the main phytoplankton groups. Our innovative adaptative strategy with a multidisciplinary and transversal approach provides a deeper understanding of the marine biogeochemical dynamics through the first trophic levels.

Analysis of sintered polymer scaffolds using concomitant synchrotron computed tomography and in situ mechanical testing.

PubMed

Dhillon, A; Schneider, P; Kuhn, G; Reinwald, Y; White, L J; Levchuk, A; Rose, F R A J; Müller, R; Shakesheff, K M; Rahman, C V

2011-12-01

The mechanical behaviour of polymer scaffolds plays a vital role in their successful use in bone tissue engineering. The present study utilised novel sintered polymer scaffolds prepared using temperature-sensitive poly(DL-lactic acid-co-glycolic acid)/poly(ethylene glycol) particles. The microstructure of these scaffolds was monitored under compressive strain by image-guided failure assessment (IGFA), which combined synchrotron radiation computed tomography (SR CT) and in situ micro-compression. Three-dimensional CT data sets of scaffolds subjected to a strain rate of 0.01%/s illustrated particle movement within the scaffolds with no deformation or cracking. When compressed using a higher strain rate of 0.02%/s particle movement was more pronounced and cracks between sintered particles were observed. The results from this study demonstrate that IGFA based on simultaneous SR CT imaging and micro-compression testing is a useful tool for assessing structural and mechanical scaffold properties, leading to further insight into structure-function relationships in scaffolds for bone tissue engineering applications.

Application of Genomic In Situ Hybridization in Horticultural Science

PubMed Central

Ramzan, Fahad; Lim, Ki-Byung

2017-01-01

Molecular cytogenetic techniques, such as in situ hybridization methods, are admirable tools to analyze the genomic structure and function, chromosome constituents, recombination patterns, alien gene introgression, genome evolution, aneuploidy, and polyploidy and also genome constitution visualization and chromosome discrimination from different genomes in allopolyploids of various horticultural crops. Using GISH advancement as multicolor detection is a significant approach to analyze the small and numerous chromosomes in fruit species, for example, Diospyros hybrids. This analytical technique has proved to be the most exact and effective way for hybrid status confirmation and helps remarkably to distinguish donor parental genomes in hybrids such as Clivia, Rhododendron, and Lycoris ornamental hybrids. The genome characterization facilitates in hybrid selection having potential desirable characteristics during the early hybridization breeding, as this technique expedites to detect introgressed sequence chromosomes. This review study epitomizes applications and advancements of genomic in situ hybridization (GISH) techniques in horticultural plants. PMID:28459054

Aminosilane functionalizations of mesoporous oxidized silicon for oligonucleotide synthesis and detection

PubMed Central

De Stefano, Luca; Oliviero, Giorgia; Amato, Jussara; Borbone, Nicola; Piccialli, Gennaro; Mayol, Luciano; Rendina, Ivo; Terracciano, Monica; Rea, Ilaria

2013-01-01

Direct solid phase synthesis of peptides and oligonucleotides (ONs) requires high chemical stability of the support material. In this work, we have investigated the passivation ability of porous oxidized silicon multilayered structures by two aminosilane compounds, 3-aminopropyltriethoxysilane and 3-aminopropyldimethylethoxysilane (APDMES), for optical label-free ON biosensor fabrication. We have also studied by spectroscopic reflectometry the hybridization between a 13 bases ON, directly grown on the aminosilane modified porous oxidized silicon by in situ synthesis, and its complementary sequence. Even if the results show that both devices are stable to the chemicals (carbonate/methanol) used, the porous silica structure passivated by APDMES reveals higher functionalization degree due to less steric hindrance of pores. PMID:23536541

In Situ Live-Cell Nucleus Fluorescence Labeling with Bioinspired Fluorescent Probes.

PubMed

Ding, Pan; Wang, Houyu; Song, Bin; Ji, Xiaoyuan; Su, Yuanyuan; He, Yao

2017-08-01

Fluorescent imaging techniques for visualization of nuclear structure and function in live cells are fundamentally important for exploring major cellular events. The ideal cellular labeling method is capable of realizing label-free, in situ, real-time, and long-term nucleus labeling in live cells, which can fully obtain the nucleus-relative information and effectively alleviate negative effects of alien probes on cellular metabolism. However, current established fluorescent probes-based strategies (e.g., fluorescent proteins-, organic dyes-, fluorescent organic/inorganic nanoparticles-based imaging techniques) are unable to simultaneously realize label-free, in situ, long-term, and real-time nucleus labeling, resulting in inevitable difficulties in fully visualizing nuclear structure and function in live cells. To this end, we present a type of bioinspired fluorescent probes, which are highly efficacious for in situ and label-free tracking of nucleus in long-term and real-time manners. Typically, the bioinspired polydopamine (PDA) nanoparticles, served as fluorescent probes, can be readily synthesized in situ within live cell nucleus without any further modifications under physiological conditions (37 °C, pH ∼7.4). Compared with other conventional nuclear dyes (e.g., propidium iodide (PI), Hoechst), superior spectroscopic properties (e.g., quantum yield of ∼35.8% and high photostability) and low cytotoxicity of PDA-based probes enable long-term (e.g., 3 h) fluorescence tracking of nucleus. We also demonstrate the generality of this type of bioinspired fluorescent probes in different cell lines and complex biological samples.

Prediction of gene expression in embryonic structures of Drosophila melanogaster.

PubMed

Samsonova, Anastasia A; Niranjan, Mahesan; Russell, Steven; Brazma, Alvis

2007-07-01

Understanding how sets of genes are coordinately regulated in space and time to generate the diversity of cell types that characterise complex metazoans is a major challenge in modern biology. The use of high-throughput approaches, such as large-scale in situ hybridisation and genome-wide expression profiling via DNA microarrays, is beginning to provide insights into the complexities of development. However, in many organisms the collection and annotation of comprehensive in situ localisation data is a difficult and time-consuming task. Here, we present a widely applicable computational approach, integrating developmental time-course microarray data with annotated in situ hybridisation studies, that facilitates the de novo prediction of tissue-specific expression for genes that have no in vivo gene expression localisation data available. Using a classification approach, trained with data from microarray and in situ hybridisation studies of gene expression during Drosophila embryonic development, we made a set of predictions on the tissue-specific expression of Drosophila genes that have not been systematically characterised by in situ hybridisation experiments. The reliability of our predictions is confirmed by literature-derived annotations in FlyBase, by overrepresentation of Gene Ontology biological process annotations, and, in a selected set, by detailed gene-specific studies from the literature. Our novel organism-independent method will be of considerable utility in enriching the annotation of gene function and expression in complex multicellular organisms.

Prediction of Gene Expression in Embryonic Structures of Drosophila melanogaster

PubMed Central

Samsonova, Anastasia A; Niranjan, Mahesan; Russell, Steven; Brazma, Alvis

2007-01-01

Understanding how sets of genes are coordinately regulated in space and time to generate the diversity of cell types that characterise complex metazoans is a major challenge in modern biology. The use of high-throughput approaches, such as large-scale in situ hybridisation and genome-wide expression profiling via DNA microarrays, is beginning to provide insights into the complexities of development. However, in many organisms the collection and annotation of comprehensive in situ localisation data is a difficult and time-consuming task. Here, we present a widely applicable computational approach, integrating developmental time-course microarray data with annotated in situ hybridisation studies, that facilitates the de novo prediction of tissue-specific expression for genes that have no in vivo gene expression localisation data available. Using a classification approach, trained with data from microarray and in situ hybridisation studies of gene expression during Drosophila embryonic development, we made a set of predictions on the tissue-specific expression of Drosophila genes that have not been systematically characterised by in situ hybridisation experiments. The reliability of our predictions is confirmed by literature-derived annotations in FlyBase, by overrepresentation of Gene Ontology biological process annotations, and, in a selected set, by detailed gene-specific studies from the literature. Our novel organism-independent method will be of considerable utility in enriching the annotation of gene function and expression in complex multicellular organisms. PMID:17658945

Unraveling the Hydrogenation of TiO 2 and Graphene Oxide/TiO 2 Composites in Real Time by in Situ Synchrotron X-ray Powder Diffraction and Pair Distribution Function Analysis

DOE PAGES

Nguyen-Phan, Thuy-Duong; Liu, Zongyuan; Luo, Si; ...

2016-02-18

The functionalization of graphene oxide (GO) and graphene by TiO 2 and other metal oxides has attracted considerable attention due to numerous promising applications in catalysis, energy conversion, and storage. We propose hydrogenation of this class of materials as a promising way to tune catalytic properties by altering the structural and chemical transformations that occur upon H incorporation. We also investigate the structural changes that occur during the hydrogenation process using in situ powder X-ray diffraction and pair distribution function analysis of GO–TiO 2 and TiO 2 under H 2 reduction. Sequential Rietveld refinement was employed to gain insight intomore » the evolution of crystal growth of TiO 2 nanoparticles in the presence of two-dimensional (2D) GO nanosheets. GO sheets not only significantly retarded the nucleation and growth of rutile impurities, stabilizing the anatase structure, but was also partially reduced to hydrogenated graphene by the introduction of atomic hydrogen into the honeycomb lattice. We discuss the hydrogenation processes and the resulting composite structure that occurs during the incorporation of atomic H and the dynamic structural transformations that leads to a highly active photocatalyst.« less

The power of in situ pulsed laser deposition synchrotron characterization for the detection of domain formation during growth of Ba0.5Sr0.5TiO3 on MgO.

PubMed

Bauer, Sondes; Lazarev, Sergey; Molinari, Alan; Breitenstein, Andreas; Leufke, Philipp; Kruk, Robert; Hahn, Horst; Baumbach, Tilo

2014-03-01

A highly sophisticated pulsed laser deposition (PLD) chamber has recently been installed at the NANO beamline at the synchrotron facility ANKA (Karlsruhe, Germany), which allows for comprehensive studies on the PLD growth process of dielectric, ferroelectric and ferromagnetic thin films in epitaxial oxide heterostructures or even multilayer systems by combining in situ reflective high-energy diffraction with the in situ synchrotron high-resolution X-ray diffraction and surface diffraction methods. The modularity of the in situ PLD chamber offers the opportunity to explore the microstructure of the grown thin films as a function of the substrate temperature, gas pressure, laser fluence and target-substrate separation distance. Ba0.5Sr0.5TiO3 grown on MgO represents the first system that is grown in this in situ PLD chamber and studied by in situ X-ray reflectivity, in situ two-dimensional reciprocal space mapping of symmetric X-ray diffraction and acquisition of time-resolved diffraction profiles during the ablation process. In situ PLD synchrotron investigation has revealed the occurrence of structural distortion as well as domain formation and misfit dislocation which all depend strongly on the film thickness. The microstructure transformation has been accurately detected with a time resolution of 1 s. The acquisition of two-dimensional reciprocal space maps during the PLD growth has the advantage of simultaneously monitoring the changes of the crystalline structure as well as the formation of defects. The stability of the morphology during the PLD growth is demonstrated to be remarkably affected by the film thickness. A critical thickness for the domain formation in Ba0.5Sr0.5TiO3 grown on MgO could be determined from the acquisition of time-resolved diffraction profiles during the PLD growth. A splitting of the diffraction peak into two distinguishable peaks has revealed a morphology change due to modification of the internal strain during growth.

Advances in the Use of In Situ Flux Tower Measures of Canopy Structure and Function for Evaluation of MODIS and VIIRS Vegetation Indices and Phenology

NASA Astrophysics Data System (ADS)

Huete, A. R.; Ma, X.; Devadas, R.; Miura, T.; Obata, K.; Restrepo-Coupe, N.; Kato, A.

2016-12-01

Prior studies have linked tower-based measures of ecosystem productivity (GEP) and satellite vegetation indices (VIs) over primarily phenologically driven ecosystems. In situ flux towers are advantageous for satellite product assessments due to their comparable footprints and finer temporal resolution measurements. However, weaker relationships have been reported in meteorological driven ecosystems in which satellite and flux tower measures of productivity are asynchronous. This suggests that satellite derived biophysical measures are not a measure of GEP, but rather a proxy for ecosystem structure (e.g. LAI) and function. Here we investigate the use of flux tower measures of photosynthetic infrastructure, including photosynthetic capacity and light use efficiency, as more appropriate measures for the evaluation of satellite VI products and phenology. We related MODIS and VIIRS VIs (NDVI, EVI, EVI2) and phenology over a series of flux tower sites located across a climatically-diverse north to south gradient in central Australia, encompassing wet and dry subtropcal savannas, semi-arid shrub/grass, and temperate broadleaf evergreen forests. These represented environmental conditions where phenology and meteorology are not always synchronized. Our objectives were to (1) advance the use of in situ tower data for more accurate evaluation of satellite products and assess challenges and limitations of in situ tower networks; (2) intercompare cross-sensor VI products and derived phenology with tower measures across biomes to assess consistencies; and (3) better understand satellite and tower relationships to improve upon interpretation of satellite VI and phenology data. Our results show, that in contrast to measures of GEP, our measures of photosynthetic infrastructure were much better related to satellite VIs; they removed strong hysteresis influences on VI- productivity relationships across phenologic green-up and brown-down phases; and thus were better related to satellite phenology profiles. We conclude that flux tower networks offer a valuable source of in situ and consistent data that can be used for satellite time series continuity and cross sensor studies. This can also bring forward the validation of vegetation indices beyond simple reflectance-based accuracy assessments.

Probing the Li Insertion Mechanism of ZnFe 2O 4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe 2O 4 in Li ion batteries: A combined XRD, EXAFS, and DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe 2O 4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn 2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Limore » + ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn 2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe 2O 3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe 2O 4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.« less

Probing the Li Insertion Mechanism of ZnFe 2O 4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe 2O 4 in Li ion batteries: A combined XRD, EXAFS, and DFT study

DOE PAGES

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2017-04-24

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe 2O 4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn 2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Limore » + ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn 2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe 2O 3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe 2O 4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.« less

Nucleation and phase transformation pathways in electrolyte solutions investigated by in situ microscopy techniques

DOE PAGES

Tao, Jinhui; Nielsen, Michael H.; De Yoreo, James J.

2018-04-27

Identification of crystal nucleation and growth pathways is of fundamental importance for synthesis of functional materials, which requires control over size, orientation, polymorph, and hierarchical structure, often in the presence of additives used to tune the energy landscape defining these pathways. Furthermore we summarize the recent progress in application of in situ TEM and AFM techniques to monitor or even tune the pathway of crystal nucleation and growth.

Nucleation and phase transformation pathways in electrolyte solutions investigated by in situ microscopy techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, Jinhui; Nielsen, Michael H.; De Yoreo, James J.

Identification of crystal nucleation and growth pathways is of fundamental importance for synthesis of functional materials, which requires control over size, orientation, polymorph, and hierarchical structure, often in the presence of additives used to tune the energy landscape defining these pathways. Furthermore we summarize the recent progress in application of in situ TEM and AFM techniques to monitor or even tune the pathway of crystal nucleation and growth.

Kinetics of methane-ethane gas replacement in clathrate-hydrates studied by time-resolved neutron diffraction and Raman spectroscopy.

PubMed

Murshed, M Mangir; Schmidt, Burkhard C; Kuhs, Werner F

2010-01-14

The kinetics of CH(4)-C(2)H(6) replacement in gas hydrates has been studied by in situ neutron diffraction and Raman spectroscopy. Deuterated ethane structure type I (C(2)H(6) sI) hydrates were transformed in a closed volume into methane-ethane mixed structure type II (CH(4)-C(2)H(6) sII) hydrates at 5 MPa and various temperatures in the vicinity of 0 degrees C while followed by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. The role of available surface area of the sI starting material on the formation kinetics of sII hydrates was studied. Ex situ Raman spectroscopic investigations were carried out to crosscheck the gas composition and the distribution of the gas species over the cages as a function of structure type and compared to the in situ neutron results. Raman micromapping on single hydrate grains showed compositional and structural gradients between the surface and core of the transformed hydrates. Moreover, the observed methane-ethane ratio is very far from the one expected for a formation from a constantly equilibrated gas phase. The results also prove that gas replacement in CH(4)-C(2)H(6) hydrates is a regrowth process involving the nucleation of new crystallites commencing at the surface of the parent C(2)H(6) sI hydrate with a progressively shrinking core of unreacted material. The time-resolved neutron diffraction results clearly indicate an increasing diffusion limitation of the exchange process. This diffusion limitation leads to a progressive slowing down of the exchange reaction and is likely to be responsible for the incomplete exchange of the gases.

Genetic Distinctiveness of Rye In situ Accessions from Portugal Unveils a New Hotspot of Unexplored Genetic Resources

PubMed Central

Monteiro, Filipa; Vidigal, Patrícia; Barros, André B.; Monteiro, Ana; Oliveira, Hugo R.; Viegas, Wanda

2016-01-01

Rye (Secale cereale L.) is a cereal crop of major importance in many parts of Europe and rye breeders are presently very concerned with the restrict pool of rye genetic resources available. Such narrowing of rye genetic diversity results from the presence of “Petkus” pool in most modern rye varieties as well as “Petkus” × “Carsten” heterotic pool in hybrid rye breeding programs. Previous studies on rye's genetic diversity revealed moreover a common genetic background on landraces (ex situ) and cultivars, regardless of breeding level or geographical origin. Thus evaluation of in situ populations is of utmost importance to unveil “on farm” diversity, which is largely undervalued. Here, we perform the first comprehensive assessment of rye's genetic diversity and population structuring using cultivars, ex situ landraces along a comprehensive sampling of in situ accessions from Portugal, through a molecular-directed analysis using SSRs markers. Rye genetic diversity and population structure analysis does not present any geographical trend but disclosed marked differences between genetic backgrounds of in situ accessions and those of cultivars/ex situ collections. Such genetic distinctiveness of in situ accessions highlights their unexplored potential as new genetic resources, which can be used to boost rye breeding strategies and the production of new varieties. Overall, our study successfully demonstrates the high prospective impact of comparing genetic diversity and structure of cultivars, ex situ, and in situ samples in ascertaining the status of plant genetic resources (PGR). PMID:27630658

Universal mechanism of thermo-mechanical deformation in metallic glasses

DOE PAGES

Dmowski, W.; Tong, Y.; Iwashita, T.; ...

2015-02-11

Here we investigated the atomistic structure of metallic glasses subjected to thermo-mechanical creep deformation using high energy x-ray diffraction and molecular dynamics simulation. The experiments were performed in-situ, at high temperatures as a time dependent deformation in the elastic regime, and ex-situ on samples quenched under stress. We show that all the anisotropic structure functions of the samples undergone thermo-mechanical creep can be scaled into a single curve, regardless of the magnitude of anelastic strain, stress level and the sign of the stress, demonstrating universal behavior and pointing to unique atomistic unit of anelastic deformation. The structural changes due tomore » creep are strongly localized within the second nearest neighbors, involving only a small group of atoms.« less

In Vitro Maturation and In Vivo Integration and Function of an Engineered Cell-Seeded Disc-like Angle Ply Structure (DAPS) for Total Disc Arthroplasty.

PubMed

Martin, J T; Gullbrand, S E; Kim, D H; Ikuta, K; Pfeifer, C G; Ashinsky, B G; Smith, L J; Elliott, D M; Smith, H E; Mauck, R L

2017-11-17

Total disc replacement with an engineered substitute is a promising avenue for treating advanced intervertebral disc disease. Toward this goal, we developed cell-seeded disc-like angle ply structures (DAPS) and showed through in vitro studies that these constructs mature to match native disc composition, structure, and function with long-term culture. We then evaluated DAPS performance in an in vivo rat model of total disc replacement; over 5 weeks in vivo, DAPS maintained their structure, prevented intervertebral bony fusion, and matched native disc mechanical function at physiologic loads in situ. However, DAPS rapidly lost proteoglycan post-implantation and did not integrate into adjacent vertebrae. To address this, we modified the design to include polymer endplates to interface the DAPS with adjacent vertebrae, and showed that this modification mitigated in vivo proteoglycan loss while maintaining mechanical function and promoting integration. Together, these data demonstrate that cell-seeded engineered discs can replicate many characteristics of the native disc and are a viable option for total disc arthroplasty.

The Dual Origin Of Stellar Halos

NASA Astrophysics Data System (ADS)

Zolotov, Adi

In the dominant Lambda+Cold Dark Matter cosmological paradigm, galaxy stellar halos are thought to form hierarchically from multiple accretion events, starting from the first structures to collapse in the Universe. This dissertation aims to make the first detailed theoretical predictions for the origin of galactic stellar halos. We focus on understanding the physical processes involved in halo formation using high-resolution, N-body + Smooth Particle Hydrodynamic simulations of disk galaxies in a cosmological context. These self-consistent simulations are used to study the competing importance of dissipative processes and dissipationless mergers in the formation of stellar halos. The relative contribution of each mechanism, and its specific role in assembling the inner and outer regions of halos is explored, as a function of galaxy mass and merging history. We show that the presence of both accreted and in situ stars in halos is a generic feature of galaxy formation. For L* galaxies, the relative contribution of each stellar population to a halo is shown to be a function of a galaxy's accretion history. Galaxies with recent mergers, like M31, will host relatively few in situ stars, while galaxies with more quiescent recent histories, like the Milky Way, will likely have a larger relative contribution from an in situ population. We show that in situ halo stars are more [alpha/Fe]-rich than accreted stars at the high [Fe/H] end of a halo's metallicity distribution function. In lower mass galaxies, M ˜ 1010 M, in situ stars dominate the stellarmass of halos. In these galaxies, in situ halo stars are, on average, younger and more metal-rich than accreted halo stars. Because in situ stars are dominant, these trends result in halos that are more metal-rich than simple accretion models predict. The halos of low mass galaxies do not extend out to the virial radii of the primary, as they do in more massive galaxies. We find that the ratio of luminous-halo mass to total galaxy mass decreases from ˜ 1% in L* galaxies to ˜ 0.2% in 1010 M mass galaxies.

Functional materials analysis using in situ and in operando X-ray and neutron scattering

PubMed Central

Peterson, Vanessa K.; Papadakis, Christine M.

2015-01-01

In situ and in operando studies are commonplace and necessary in functional materials research. This review highlights recent developments in the analysis of functional materials using state-of-the-art in situ and in operando X-ray and neutron scattering and analysis. Examples are given covering a number of important materials areas, alongside a description of the types of information that can be obtained and the experimental setups used to acquire them. PMID:25866665

Correlations between Transition Metal Chemistry, Local Structure and Global Structure in Li 2Ru 0.5Mn 0.5O 3 Investigated in a Wide Voltage Window

DOE PAGES

Lyu, Yingchun; Hu, Enyuan; Xiao, Dongdong; ...

2017-10-20

Li 2Ru 0.5Mn 0.5O 3, a high capacity lithium rich layered cathode material for lithium-ion batteries, was subject to comprehen-sive diagnostic studies including in situ/ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), pair distribu-tion function (PDF) and high resolution scanning transmission electron microscopy (STEM) analysis, to understand the cor-relations between transition metal chemistry, structure and lithium storage electrochemical behavior. Ru-Ru dimers have been identified in the as-prepared sample and found to be preserved upon prolonged cycling. Presence of these dimers, which are likely caused by the delocalized nature of 4d electrons, is found to favor the stabilization of themore » structure in a lay-ered phase. The in situ XAS results confirm the participation of oxygen redox into the charge compensation at high charge voltage, and the great flexibility of the covalent bond between Ru and O may provide great reversibility of the global struc-ture despite of the significant local distortion around Ru. In contrast, the local distortion around Mn occurs at low discharge voltage and is accompanied by a “layered to 1T” phase transformation, which is found to be detrimental to the cycle per-formances. It is clear that the changes of local structure around individual transition metal cations respond separately and differently to lithium intercalation/deintercalation. Here, cations with the capability to tolerate the lattice distortion will benefit for maintaining the integrality of the crystal structure and therefore is able to enhance the long-term cycling performance of the electrode materials.« less

Correlations between Transition Metal Chemistry, Local Structure and Global Structure in Li 2Ru 0.5Mn 0.5O 3 Investigated in a Wide Voltage Window

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lyu, Yingchun; Hu, Enyuan; Xiao, Dongdong

Li 2Ru 0.5Mn 0.5O 3, a high capacity lithium rich layered cathode material for lithium-ion batteries, was subject to comprehen-sive diagnostic studies including in situ/ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), pair distribu-tion function (PDF) and high resolution scanning transmission electron microscopy (STEM) analysis, to understand the cor-relations between transition metal chemistry, structure and lithium storage electrochemical behavior. Ru-Ru dimers have been identified in the as-prepared sample and found to be preserved upon prolonged cycling. Presence of these dimers, which are likely caused by the delocalized nature of 4d electrons, is found to favor the stabilization of themore » structure in a lay-ered phase. The in situ XAS results confirm the participation of oxygen redox into the charge compensation at high charge voltage, and the great flexibility of the covalent bond between Ru and O may provide great reversibility of the global struc-ture despite of the significant local distortion around Ru. In contrast, the local distortion around Mn occurs at low discharge voltage and is accompanied by a “layered to 1T” phase transformation, which is found to be detrimental to the cycle per-formances. It is clear that the changes of local structure around individual transition metal cations respond separately and differently to lithium intercalation/deintercalation. Here, cations with the capability to tolerate the lattice distortion will benefit for maintaining the integrality of the crystal structure and therefore is able to enhance the long-term cycling performance of the electrode materials.« less

Programmable gradational micropatterning of functional materials using maskless lithography controlling absorption.

PubMed

Jung, Yushin; Lee, Howon; Park, Tae-Joon; Kim, Sungsik; Kwon, Sunghoon

2015-10-22

The demand for patterning functional materials precisely on surfaces of stimuli-responsive devices has increased in many research fields. In situ polymerization technology is one of the most convenient ways to place the functional materials on a desired location with micron-scale accuracy. To fabricate stimuli-responsive surfaces, controlling concentration of the functional material is much as important as micropatterning them. However, patterning and controlling concentration of the functional materials simultaneously requires an additional process, such as preparing multiple co-flow microfluidic structures and numbers of solutions with various concentrations. Despite applying these processes, fabricating heterogeneous patterns in large scale (millimeter scale) is still impossible. In this study, we propose an advanced in situ polymerization technique to pattern the surface in micron scale in a concentration-controlled manner. Because the concentration of the functional materials is manipulated by self-assembly on the surface, a complex pattern could be easily fabricated without any additional procedure. The complex pattern is pre-designed with absorption amount of the functional material, which is pre-determined by the duration of UV exposure. We show that the resolution reaches up to 2.5 μm and demonstrate mm-scale objects, maintaining the same resolution. We also fabricated Multi-bit barcoded micro particles verify the flexibility of our system.

Observing and modeling dynamics in terrestrial gross primary productivity and phenology from remote sensing: An assessment using in-situ measurements

NASA Astrophysics Data System (ADS)

Verma, Manish K.

Terrestrial gross primary productivity (GPP) is the largest and most variable component of the carbon cycle and is strongly influenced by phenology. Realistic characterization of spatio-temporal variation in GPP and phenology is therefore crucial for understanding dynamics in the global carbon cycle. In the last two decades, remote sensing has become a widely-used tool for this purpose. However, no study has comprehensively examined how well remote sensing models capture spatiotemporal patterns in GPP, and validation of remote sensing-based phenology models is limited. Using in-situ data from 144 eddy covariance towers located in all major biomes, I assessed the ability of 10 remote sensing-based methods to capture spatio-temporal variation in GPP at annual and seasonal scales. The models are based on different hypotheses regarding ecophysiological controls on GPP and span a range of structural and computational complexity. The results lead to four main conclusions: (i) at annual time scale, models were more successful capturing spatial variability than temporal variability; (ii) at seasonal scale, models were more successful in capturing average seasonal variability than interannual variability; (iii) simpler models performed as well or better than complex models; and (iv) models that were best at explaining seasonal variability in GPP were different from those that were best able to explain variability in annual scale GPP. Seasonal phenology of vegetation follows bounded growth and decay, and is widely modeled using growth functions. However, the specific form of the growth function affects how phenological dynamics are represented in ecosystem and remote sensing-base models. To examine this, four different growth functions (the logistic, Gompertz, Mirror-Gompertz and Richards function) were assessed using remotely sensed and in-situ data collected at several deciduous forest sites. All of the growth functions provided good statistical representation of in-situ and remote sensing time series. However, the Richards function captured observed asymmetric dynamics that were not captured by the other functions. The timing of key phenophase transitions derived using the Richards function therefore agreed best with observations. This suggests that ecosystem models and remote-sensing algorithms would benefit from using the Richards function to represent phenological dynamics.

Development of micro-four-point probe in a scanning tunneling microscope for in situ electrical transport measurement.

PubMed

Ge, Jian-Feng; Liu, Zhi-Long; Gao, Chun-Lei; Qian, Dong; Liu, Canhua; Jia, Jin-Feng

2015-05-01

Electrons at surface may behave differently from those in bulk of a material. Multi-functional tools are essential in comprehensive studies on a crystal surface. Here, we developed an in situ microscopic four-point probe (4PP) transport measurement system on the basis of a scanning tunneling microscope (STM). In particular, convenient replacement between STM tips and micro-4PPs enables systematic investigations of surface morphology, electronic structure, and electrical transport property of a same sample surface. Performances of the instrument are demonstrated with high-quality STM images, tunneling spectra, and low-noise electrical I-V characteristic curves of a single-layer FeSe film grown on a conductive SrTiO3 surface.

Testing the Chemical/Structural Stability of Proton Conducting Perovskite Ceramic Membranes by in Situ/ex Situ Autoclave Raman Microscopy

PubMed Central

Slodczyk, Aneta; Zaafrani, Oumaya; Sharp, Matthew D.; Kilner, John A.; Dabrowski, Bogdan; Lacroix, Olivier; Colomban, Philippe

2013-01-01

Ceramics, which exhibit high proton conductivity at moderate temperatures, are studied as electrolyte membranes or electrode components of fuel cells, electrolysers or CO2 converters. In severe operating conditions (high gas pressure/high temperature), the chemical activity towards potentially reactive atmospheres (water, CO2, etc.) is enhanced. This can lead to mechanical, chemical, and structural instability of the membranes and premature efficiency loss. Since the lifetime duration of a device determines its economical interest, stability/aging tests are essential. Consequently, we have developed autoclaves equipped with a sapphire window, allowing in situ Raman study in the 25–620 °C temperature region under 1–50 bar of water vapor/gas pressure, both with and without the application of an electric field. Taking examples of four widely investigated perovskites (BaZr0.9Yb0.1O3−δ, SrZr0.9Yb0.1O3−δ, BaZr0.25In0.75O3−δ, BaCe0.5Zr0.3Y0.16Zn0.04O3−δ), we demonstrate the high potential of our unique set-up to discriminate between good/stable and instable electrolytes as well as the ability to detect and monitor in situ: (i) the sample surface reaction with surrounding atmospheres and the formation of crystalline or amorphous secondary phases (carbonates, hydroxides, hydrates, etc.); and (ii) the structural modifications as a function of operating conditions. The results of these studies allow us to compare quantitatively the chemical stability versus water (corrosion rate from ~150 µm/day to less than 0.25 µm/day under 200–500 °C/15–80 bar PH2O) and to go further in comprehension of the aging mechanism of the membrane. PMID:24957060

I-SonReb: an improved NDT method to evaluate the in situ strength of carbonated concrete

NASA Astrophysics Data System (ADS)

Breccolotti, Marco; Bonfigli, Massimo F.

2015-10-01

Concrete strength evaluated in situ by means of the conventional SonReb method can be highly overestimated in presence of carbonation. This latter, in fact, is responsible for the physical and chemical alteration of the outer layer of concrete. As most of the existing concrete structures are subjected to carbonation, it is of high importance to overcome this problem. In this paper, an Improved SonReb method (I-SonReb) for carbonated concretes is proposed. It relies on the definition of a correction coefficient of the measured Rebound index as a function of the carbonated concrete cover thickness, an additional parameter to be measured during in situ testing campaigns. The usefulness of the method has been validated showing the improvement in the accuracy of concrete strength estimation from two sets of NDT experimental data collected from investigations on real structures.

Direct observation of twin deformation in YBa2Cu3O7-x thin films by in situ nanoindentation in TEM

NASA Astrophysics Data System (ADS)

Lee, Joon Hwan; Zhang, Xinghang; Wang, Haiyan

2011-04-01

The deformation behaviors of YBa2Cu3O7-x (YBCO) thin films with twinning structures were studied via in situ nanoindentation experiments in a transmission electron microscope. The YBCO films were grown on SrTiO3 (001) substrates by pulsed laser deposition. Both ex situ (conventional) and in situ nanoindentation were conducted to reveal the deformation of the YBCO films from the directions perpendicular and parallel to the twin interfaces. The hardness measured perpendicular to the twin interfaces is ˜50% and 40% higher than that measured parallel to the twin interfaces ex situ and in situ, respectively. Detailed in situ movie analysis reveals that the twin structures play an important role in deformation and strengthening mechanisms in YBCO thin films.

Correlating molecular spectroscopy and molecular chemometrics to explore carbohydrate functional groups and utilization of coproducts from biofuel and biobrewing processing.

PubMed

Chen, Limei; Zhang, Xuewei; Yu, Peiqiang

2014-06-04

Dried distillers grains with solubles (DDGS) was coproducts from bioethanol and biobrewing industry. It was an excellent resource of protein and energy feedstuff in China. Conventional studies often focus on traditional nutritional profiles. To data, there is little research on molecular structure-nutrition interaction of carbohydrate in coproducts. In this study, five kinds of corn-grain based DDGS and two kinds of barley-grain based DDGS were collected from different manufactures in the north of China. They were coded as "1, 2, 3, 4, 5, 6, and 7", respectively. The primary purposes of this project were to investigate the molecular structure-nutrition interaction of carbohydrate in coproducts, in terms of (1) carbohydrate-related chemical composition and nutrient profiles, (2) predicted values for energy in coproducts for animal, and (3) in situ digestion of dry matter. The result showed that acid detergent fiber content in corn DDGS and barley DDGS had negative correlation with structural carbohydrate peak area, cellulose compounds, and carbohydrate component peaks (first, second, and total peak area), which were measured with molecular spectroscopy. The correlation between carbohydrate peak area (second and total) and digestible fiber (tdNDF) were negative. There were no correlation between carbohydrate spectral intensities and energy values, carbohydrate subfractions partitioned by CNCPS system, and in situ rumen degradation. The results indicate that carbohydrate spectral profiles (functional groups) are associated with the carbohydrate nutritive values in coproducts from biofuel and biobrewing processing.

In situ characterization of charge rate dependent stress and structure changes in V2O5 cathode prepared by atomic layer deposition

NASA Astrophysics Data System (ADS)

Jung, Hyun; Gerasopoulos, Konstantinos; Talin, A. Alec; Ghodssi, Reza

2017-02-01

The insertion/extraction of lithium into/from various host materials is the basic process by which lithium-ion batteries reversible store charge. This process is generally accompanied by strain in the host material, inducing stress which can lead to capacity loss. Therefore, understanding of both the structural changes and the associated stress - investigated almost exclusively separate to date - is a critical factor for developing high-performance batteries. Here, we report an in situ method, which utilizes Raman spectroscopy in parallel with optical interferometry to study effects of varying charging rates (C-rates) on the structure and stress in a V2O5 thin film cathode. Abrupt stress changes at specific crystal phase transitions in the Lisbnd Vsbnd O system are observed and the magnitude of the stress changes with the amount of lithium inserted into the electrode are correlated. A linear increase in the stress as a function of x in LixV2O5 is observed, indicating that C-rate does not directly contribute to larger intercalation stress. However, a more rapid increase in disorder within the LixV2O5 layers is correlated with higher C-rate. Ultimately, these experiments demonstrate how the simultaneous stress/Raman in situ approach can be utilized as a characterization platform for investigating various critical factors affecting lithium-ion battery performance.

Heavy ion composition in the inner heliosphere: Predictions for Solar Orbiter

NASA Astrophysics Data System (ADS)

Lepri, S. T.; Livi, S. A.; Galvin, A. B.; Kistler, L. M.; Raines, J. M.; Allegrini, F.; Collier, M. R.; Zurbuchen, T.

2014-12-01

The Heavy Ion Sensor (HIS) on SO, with its high time resolution, will provide the first ever solar wind and surpathermal heavy ion composition and 3D velocity distribution function measurements inside the orbit of Mercury. These measurements will provide us the most in depth examination of the origin, structure and evolution of the solar wind. The near co-rotation phases of the orbiter will enable the most accurate mapping of in-situ structures back to their solar sources. Measurements of solar wind composition and heavy ion kinetic properties enable characterization of the sources, transport mechanisms and acceleration processes of the solar wind. This presentation will focus on the current state of in-situ studies of heavy ions in the solar wind and their implications for the sources of the solar wind, the nature of structure and variability in the solar wind, and the acceleration of particles. Additionally, we will also discuss opportunities for coordinated measurements across the payloads of Solar Orbiter and Solar Probe in order to answer key outstanding science questions of central interest to the Solar and Heliophysics communities.

Influence of Magnesium Content on the Local Structure of Amorphous Calcium Carbonate (ACC): Real Time Determination by In Situ PDF Analysis

NASA Astrophysics Data System (ADS)

Mergelsberg, S. T.; Ulrich, R. N.; Michel, F. M.; Dove, P. M.

2016-12-01

Calcium carbonate minerals are an essential component in the exoskeletons of crustaceans and mollusks. The onset of exoskeleton mineralization includes the precipitation of amorphous calcium carbonate (ACC) as a reactive intermediate that later transforms to produce diverse structures. Despite the importance of ACC as a critical phase during skeleton formation, the chemical and physical properties are not well characterized at conditions that approximate biological environments. Of particular interest are the solubility of ACC, the short-range structure at the time of formation, and the evolution of ACC structure to final products. Recent advances showing the widespread occurrence of multistep pathways to mineralization in biological and geological settings (De Yoreo et al., 2015) underline the importance of understanding amorphous intermediates. Using quantitative laboratory techniques developed by our research group (Blue et al., 2013; Blue and Dove, 2015; Blue et al., in press), this experimental study quantifies the solubility of ACC in parallel with the physical characterization of the corresponding structure. We measured ACC solubility at specific time points during the precipitation and during its subsequent evolution under the mild pH conditions that approximate biological and environmental conditions. In parallel experiments, structural data were collected from in situ pair distribution function (PDF) analyses were conducted to follow the evolution of individual samples from initial precipitation to final product. The measurements are leading to a quantitative solubility function for ACC with variable Mg contents and an x-ray based understanding of ACC structure in the same particles. We are also finding temporal changes in the short-range order of ACC after precipitation and this order is dependent upon Mg content. Moreover, the data show Mg distribution through the ACC particles is dependent upon total alkalinity. Insights from this study hold promise for better understanding the nature of the initial ACC that forms and factors that influence its structural evolution to final products.

Number density structures in the inner heliosphere

NASA Astrophysics Data System (ADS)

Stansby, D.; Horbury, T. S.

2018-06-01

Aims: The origins and generation mechanisms of the slow solar wind are still unclear. Part of the slow solar wind is populated by number density structures, discrete patches of increased number density that are frozen in to and move with the bulk solar wind. In this paper we aimed to provide the first in-situ statistical study of number density structures in the inner heliosphere. Methods: We reprocessed in-situ ion distribution functions measured by Helios in the inner heliosphere to provide a new reliable set of proton plasma moments for the entire mission. From this new data set we looked for number density structures measured within 0.5 AU of the Sun and studied their properties. Results: We identified 140 discrete areas of enhanced number density. The structures occurred exclusively in the slow solar wind and spanned a wide range of length scales from 50 Mm to 2000 Mm, which includes smaller scales than have been previously observed. They were also consistently denser and hotter that the surrounding plasma, but had lower magnetic field strengths, and therefore remained in pressure balance. Conclusions: Our observations show that these structures are present in the slow solar wind at a wide range of scales, some of which are too small to be detected by remote sensing instruments. These structures are rare, accounting for only 1% of the slow solar wind measured by Helios, and are not a significant contribution to the mass flux of the solar wind.

The in situ transverse lamina strength of composite laminates

NASA Technical Reports Server (NTRS)

Flaggs, D. L.

1983-01-01

The objective of the work reported in this presentation is to determine the in situ transverse strength of a lamina within a composite laminate. From a fracture mechanics standpoint, in situ strength may be viewed as constrained cracking that has been shown to be a function of both lamina thickness and the stiffness of adjacent plies that serve to constrain the cracking process. From an engineering point of view, however, constrained cracking can be perceived as an apparent increase in lamina strength. With the growing need to design more highly loaded composite structures, the concept of in situ strength may prove to be a viable means of increasing the design allowables of current and future composite material systems. A simplified one dimensional analytical model is presented that is used to predict the strain at onset of transverse cracking. While it is accurate only for the most constrained cases, the model is important in that the predicted failure strain is seen to be a function of a lamina's thickness d and of the extensional stiffness bE theta of the adjacent laminae that constrain crack propagation in the 90 deg laminae.

A generalized method for high throughput in-situ experiment data analysis: An example of battery materials exploration

NASA Astrophysics Data System (ADS)

Aoun, Bachir; Yu, Cun; Fan, Longlong; Chen, Zonghai; Amine, Khalil; Ren, Yang

2015-04-01

A generalized method is introduced to extract critical information from series of ranked correlated data. The method is generally applicable to all types of spectra evolving as a function of any arbitrary parameter. This approach is based on correlation functions and statistical scedasticity formalism. Numerous challenges in analyzing high throughput experimental data can be tackled using the herein proposed method. We applied this method to understand the reactivity pathway and formation mechanism of a Li-ion battery cathode material during high temperature synthesis using in-situ high-energy X-ray diffraction. We demonstrate that Pearson's correlation function can easily unravel all major phase transition and, more importantly, the minor structural changes which cannot be revealed by conventionally inspecting the series of diffraction patterns. Furthermore, a two-dimensional (2D) reactivity pattern calculated as the scedasticity along all measured reciprocal space of all successive diffraction pattern pairs unveils clearly the structural evolution path and the active areas of interest during the synthesis. The methods described here can be readily used for on-the-fly data analysis during various in-situ operando experiments in order to quickly evaluate and optimize experimental conditions, as well as for post data analysis and large data mining where considerable amount of data hinders the feasibility of the investigation through point-by-point inspection.

A generalized method for high throughput in-situ experiment data analysis: An example of battery materials exploration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aoun, Bachir; Yu, Cun; Fan, Longlong

A generalized method is introduced to extract critical information from series of ranked correlated data. The method is generally applicable to all types of spectra evolving as a function of any arbitrary parameter. This approach is based on correlation functions and statistical scedasticity formalism. Numerous challenges in analyzing high throughput experimental data can be tackled using the herein proposed method. We applied this method to understand the reactivity pathway and formation mechanism of a Li-ion battery cathode material during high temperature synthesis using in-situ highenergy X-ray diffraction. We demonstrate that Pearson's correlation function can easily unravel all major phase transitionmore » and, more importantly, the minor structural changes which cannot be revealed by conventionally inspecting the series of diffraction patterns. Furthermore, a two-dimensional (2D) reactivity pattern calculated as the scedasticity along all measured reciprocal space of all successive diffraction pattern pairs unveils clearly the structural evolution path and the active areas of interest during the synthesis. The methods described here can be readily used for on-the-fly data analysis during various in-situ operando experiments in order to quickly evaluate and optimize experimental conditions, as well as for post data analysis and large data mining where considerable amount of data hinders the feasibility of the investigation through point-by-point inspection.« less

Orientation determination of interfacial beta-sheet structures in situ.

PubMed

Nguyen, Khoi Tan; King, John Thomas; Chen, Zhan

2010-07-01

Structural information such as orientations of interfacial proteins and peptides is important for understanding properties and functions of such biological molecules, which play crucial roles in biological applications and processes such as antimicrobial selectivity, membrane protein activity, biocompatibility, and biosensing performance. The alpha-helical and beta-sheet structures are the most widely encountered secondary structures in peptides and proteins. In this paper, for the first time, a method to quantify the orientation of the interfacial beta-sheet structure using a combined attenuated total reflectance Fourier transformation infrared spectroscopic (ATR-FTIR) and sum frequency generation (SFG) vibrational spectroscopic study was developed. As an illustration of the methodology, the orientation of tachyplesin I, a 17 amino acid peptide with an antiparallel beta-sheet, adsorbed to polymer surfaces as well as associated with a lipid bilayer was determined using the regular and chiral SFG spectra, together with polarized ATR-FTIR amide I signals. Both the tilt angle (theta) and the twist angle (psi) of the beta-sheet at interfaces are determined. The developed method in this paper can be used to obtain in situ structural information of beta-sheet components in complex molecules. The combination of this method and the existing methodology that is currently used to investigate alpha-helical structures will greatly broaden the application of optical spectroscopy in physical chemistry, biochemistry, biophysics, and structural biology.

Characterization of SWNT based Polystyrene Nanocomposites

NASA Astrophysics Data System (ADS)

Mitchell, Cynthia; Bahr, Jeffrey; Tour, James; Arepalli, Sivaram; Krishnamoorti, Ramanan

2003-03-01

Polystyrene nanocomposites with functionalized single walled carbon nanotubes (SWNTs), prepared by the in-situ generation and addition of organic diazonium compounds, were characterized using a range of structural and dynamic methods. These were contrasted to the properties of polystyrene composites prepared with unfunctionalized SWNTs at the same loadings. The functionalized nanocomposites demonstrated a percolated SWNT network structure at concentrations of 1 vol SWNT based composites at similar loadings of SWNT exhibited behavior comparable to that of the unfilled polymer. This formation of the SWNT network structure is because of the improved compatibility between the SWNTs and the polymer matrix due to the functionalization. Further structural evidence for the compatibility of the modified SWNTs and the polymer matrix will be discussed in the presentation.

Growth and characterization of Al2O3 films on fluorine functionalized epitaxial graphene

NASA Astrophysics Data System (ADS)

Robinson, Zachary R.; Jernigan, Glenn G.; Wheeler, Virginia D.; Hernández, Sandra C.; Eddy, Charles R.; Mowll, Tyler R.; Ong, Eng Wen; Ventrice, Carl A.; Geisler, Heike; Pletikosic, Ivo; Yang, Hongbo; Valla, Tonica

2016-08-01

Intelligent engineering of graphene-based electronic devices on SiC(0001) requires a better understanding of processes used to deposit gate-dielectric materials on graphene. Recently, Al2O3 dielectrics have been shown to form conformal, pinhole-free thin films by functionalizing the top surface of the graphene with fluorine prior to atomic layer deposition (ALD) of the Al2O3 using a trimethylaluminum (TMA) precursor. In this work, the functionalization and ALD-precursor adsorption processes have been studied with angle-resolved photoelectron spectroscopy, low energy electron diffraction, and X-ray photoelectron spectroscopy. It has been found that the functionalization process has a negligible effect on the electronic structure of the graphene, and that it results in a twofold increase in the adsorption of the ALD-precursor. In situ TMA-dosing and XPS studies were also performed on three different Si(100) substrates that were terminated with H, OH, or dangling Si-bonds. This dosing experiment revealed that OH is required for TMA adsorption. Based on those data along with supportive in situ measurements that showed F-functionalization increases the amount of oxygen (in the form of adsorbed H2O) on the surface of the graphene, a model for TMA-adsorption on graphene is proposed that is based on a reaction of a TMA molecule with OH.

Synthesis, Structure, and Electrochemical Performance of High Capacity Li 2Cu 0.5Ni 0.5O 2 Cathodes

DOE PAGES

Ruther, Rose E; Zhou, Hui; Dhital, Chetan; ...

2015-09-08

Orthorhombic Li 2NiO 2, Li 2CuO 2, and solid solutions thereof have been studied as potential cathode materials for lithium-ion batteries due to their high theoretical capacity and relatively low cost. While neither endmember shows good cycling stability, the intermediate composition, Li 2Cu 0.5Ni 0.5O 2, yields reasonably high reversible capacities. A new synthetic approach and detailed characterization of this phase and the parent Li 2CuO 2 are presented. The cycle life of Li 2Cu 0.5Ni 0.5O 2 is shown to depend critically on the voltage window. The formation of Cu 1+ at low voltage and oxygen evolution at highmore » voltage limit the electrochemical reversibility. In situ X-ray absorption spectroscopy (XAS), in situ Raman spectroscopy, and gas evolution measurements are used to follow the chemical and structural changes that occur as a function of cell voltage.« less

In situ studies of oxide nucleation, growth, and transformation using slow electrons

NASA Astrophysics Data System (ADS)

Flege, Jan Ingo; Grinter, David C.

2018-05-01

Surface processes such as metal oxidation and metal oxide growth invariably influence the physical and chemical properties of materials and determine their interaction with their surroundings and hence their functionality in many technical applications. On a fundamental level, these processes are found to be governed by a complex interplay of thermodynamic variables and kinetic constraints, resulting in a rich variety of material-specific phenomena. In this review article, we discuss recent results and insights on transition metal oxidation and rare-earth oxide growth acquired by low-energy electron microscopy and related techniques. We demonstrate that the use of in situ surface sensitive methods is a prerequisite to gaining a deeper understanding of the underlying concepts and the mechanisms responsible for the emerging oxide structure and morphology. Furthermore, examples will be provided on how structural and chemical modifications of the oxide films and nanostructures can be followed in real-time and analyzed in terms of local reactivity and cooperative effects relevant for heterogeneous model catalysis.

Dynamic Succession of Groundwater Functional Microbial Communities in Response to Emulsified Vegetable Oil Amendment during Sustained In Situ U(VI) Reduction.

PubMed

Zhang, Ping; Wu, Wei-Min; Van Nostrand, Joy D; Deng, Ye; He, Zhili; Gihring, Thomas; Zhang, Gengxin; Schadt, Chris W; Watson, David; Jardine, Phil; Criddle, Craig S; Brooks, Scott; Marsh, Terence L; Tiedje, James M; Arkin, Adam P; Zhou, Jizhong

2015-06-15

A pilot-scale field experiment demonstrated that a one-time amendment of emulsified vegetable oil (EVO) reduced groundwater U(VI) concentrations for 1 year in a fast-flowing aquifer. However, little is known about how EVO amendment stimulates the functional gene composition, structure, and dynamics of groundwater microbial communities toward prolonged U(VI) reduction. In this study, we hypothesized that EVO amendment would shift the functional gene composition and structure of groundwater microbial communities and stimulate key functional genes/groups involved in EVO biodegradation and reduction of electron acceptors in the aquifer. To test these hypotheses, groundwater microbial communities after EVO amendment were analyzed using a comprehensive functional gene microarray. Our results showed that EVO amendment stimulated sequential shifts in the functional composition and structure of groundwater microbial communities. Particularly, the relative abundance of key functional genes/groups involved in EVO biodegradation and the reduction of NO3 (-), Mn(IV), Fe(III), U(VI), and SO4 (2-) significantly increased, especially during the active U(VI) reduction period. The relative abundance for some of these key functional genes/groups remained elevated over 9 months. Montel tests suggested that the dynamics in the abundance, composition, and structure of these key functional genes/groups were significantly correlated with groundwater concentrations of acetate, NO3 (-), Mn(II), Fe(II), U(VI), and SO4 (2-). Our results suggest that EVO amendment stimulated dynamic succession of key functional microbial communities. This study improves our understanding of the composition, structure, and function changes needed for groundwater microbial communities to sustain a long-term U(VI) reduction. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Dynamic Succession of Groundwater Functional Microbial Communities in Response to Emulsified Vegetable Oil Amendment during Sustained In Situ U(VI) Reduction

PubMed Central

Zhang, Ping; Wu, Wei-Min; Van Nostrand, Joy D.; Deng, Ye; He, Zhili; Gihring, Thomas; Zhang, Gengxin; Schadt, Chris W.; Watson, David; Jardine, Phil; Criddle, Craig S.; Brooks, Scott; Marsh, Terence L.; Tiedje, James M.; Arkin, Adam P.

2015-01-01

A pilot-scale field experiment demonstrated that a one-time amendment of emulsified vegetable oil (EVO) reduced groundwater U(VI) concentrations for 1 year in a fast-flowing aquifer. However, little is known about how EVO amendment stimulates the functional gene composition, structure, and dynamics of groundwater microbial communities toward prolonged U(VI) reduction. In this study, we hypothesized that EVO amendment would shift the functional gene composition and structure of groundwater microbial communities and stimulate key functional genes/groups involved in EVO biodegradation and reduction of electron acceptors in the aquifer. To test these hypotheses, groundwater microbial communities after EVO amendment were analyzed using a comprehensive functional gene microarray. Our results showed that EVO amendment stimulated sequential shifts in the functional composition and structure of groundwater microbial communities. Particularly, the relative abundance of key functional genes/groups involved in EVO biodegradation and the reduction of NO3−, Mn(IV), Fe(III), U(VI), and SO42− significantly increased, especially during the active U(VI) reduction period. The relative abundance for some of these key functional genes/groups remained elevated over 9 months. Montel tests suggested that the dynamics in the abundance, composition, and structure of these key functional genes/groups were significantly correlated with groundwater concentrations of acetate, NO3−, Mn(II), Fe(II), U(VI), and SO42−. Our results suggest that EVO amendment stimulated dynamic succession of key functional microbial communities. This study improves our understanding of the composition, structure, and function changes needed for groundwater microbial communities to sustain a long-term U(VI) reduction. PMID:25862231

Si{sub 3}N{sub 4} layers for the in-situ passivation of GaN-based HEMT structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yunin, P. A., E-mail: yunin@ipmras.ru; Drozdov, Yu. N.; Drozdov, M. N.

2015-11-15

A method for the in situ passivation of GaN-based structures with silicon nitride in the growth chamber of a metal organic vapor phase epitaxy (MOVPE) reactor is described. The structural and electrical properties of the obtained layers are investigated. The in situ and ex situ passivation of transistor structures with silicon nitride in an electron-beam-evaporation device are compared. It is shown that ex situ passivation changes neither the initial carrier concentration nor the mobility. In situ passivation makes it possible to protect the structure surface against uncontrollable degradation upon the finishing of growth and extraction to atmosphere. In the inmore » situ passivated structure, the carrier concentration increases and the mobility decreases. This effect should be taken into account when manufacturing passivated GaN-based transistor structures.« less

Fundamental Understanding of Crack Growth in Structural Components of Generation IV Supercritical Light Water Reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iouri I. Balachov; Takao Kobayashi; Francis Tanzella

2004-11-17

This work contributes to the design of safe and economical Generation-IV Super-Critical Water Reactors (SCWRs) by providing a basis for selecting structural materials to ensure the functionality of in-vessel components during the entire service life. During the second year of the project, we completed electrochemical characterization of the oxide film properties and investigation of crack initiation and propagation for candidate structural materials steels under supercritical conditions. We ranked candidate alloys against their susceptibility to environmentally assisted degradation based on the in situ data measure with an SRI-designed controlled distance electrochemistry (CDE) arrangement. A correlation between measurable oxide film properties andmore » susceptibility of austenitic steels to environmentally assisted degradation was observed experimentally. One of the major practical results of the present work is the experimentally proven ability of the economical CDE technique to supply in situ data for ranking candidate structural materials for Generation-IV SCRs. A potential use of the CDE arrangement developed ar SRI for building in situ sensors monitoring water chemistry in the heat transport circuit of Generation-IV SCWRs was evaluated and proved to be feasible.« less

Post-Fire Spatial Patterns of Soil Nitrogen Mineralization and Microbial Abundance

PubMed Central

Smithwick, Erica A. H.; Naithani, Kusum J.; Balser, Teri C.; Romme, William H.; Turner, Monica G.

2012-01-01

Stand-replacing fires influence soil nitrogen availability and microbial community composition, which may in turn mediate post-fire successional dynamics and nutrient cycling. However, fires create patchiness at both local and landscape scales and do not result in consistent patterns of ecological dynamics. The objectives of this study were to (1) quantify the spatial structure of microbial communities in forest stands recently affected by stand-replacing fire and (2) determine whether microbial variables aid predictions of in situ net nitrogen mineralization rates in recently burned stands. The study was conducted in lodgepole pine (Pinus contorta var. latifolia) and Engelmann spruce/subalpine fir (Picea engelmannii/Abies lasiocarpa) forest stands that burned during summer 2000 in Greater Yellowstone (Wyoming, USA). Using a fully probabilistic spatial process model and Bayesian kriging, the spatial structure of microbial lipid abundance and fungi-to-bacteria ratios were found to be spatially structured within plots two years following fire (for most plots, autocorrelation range varied from 1.5 to 10.5 m). Congruence of spatial patterns among microbial variables, in situ net N mineralization, and cover variables was evident. Stepwise regression resulted in significant models of in situ net N mineralization and included variables describing fungal and bacterial abundance, although explained variance was low (R2<0.29). Unraveling complex spatial patterns of nutrient cycling and the biotic factors that regulate it remains challenging but is critical for explaining post-fire ecosystem function, especially in Greater Yellowstone, which is projected to experience increased fire frequencies by mid 21st Century. PMID:23226324

Acoustic actuation of in situ fabricated artificial cilia

NASA Astrophysics Data System (ADS)

Orbay, Sinem; Ozcelik, Adem; Bachman, Hunter; Huang, Tony Jun

2018-02-01

We present on-chip acoustic actuation of in situ fabricated artificial cilia. Arrays of cilia structures are UV polymerized inside a microfluidic channel using a photocurable polyethylene glycol (PEG) polymer solution and photomasks. During polymerization, cilia structures are attached to a silane treated glass surface inside the microchannel. Then, the cilia structures are actuated using acoustic vibrations at 4.6 kHz generated by piezo transducers. As a demonstration of a practical application, DI water and fluorescein dye solutions are mixed inside a microfluidic channel. Using pulses of acoustic excitations, and locally fabricated cilia structures within a certain region of the microchannel, a waveform of mixing behavior is obtained. This result illustrates one potential application wherein researchers can achieve spatiotemporal control of biological microenvironments in cell stimulation studies. These acoustically actuated, in situ fabricated, cilia structures can be used in many on-chip applications in biological, chemical and engineering studies.

An in situ polymerization approach for the synthesis of superhydrophobic and superoleophilic nanofibrous membranes for oil-water separation

NASA Astrophysics Data System (ADS)

Shang, Yanwei; Si, Yang; Raza, Aikifa; Yang, Liping; Mao, Xue; Ding, Bin; Yu, Jianyong

2012-11-01

Superhydrophobic and superoleophilic nanofibrous membranes exhibiting robust oil-water separation performance were prepared by a facile combination of electrospun cellulose acetate (CA) nanofibers and a novel in situ polymerized fluorinated polybenzoxazine (F-PBZ) functional layer that incorporated silica nanoparticles (SiO2 NPs). By employing the F-PBZ/SiO2 NPs modification, the pristine hydrophilic CA nanofibrous membranes were endowed with a superhydrophobicity with the water contact angle of 161° and a superoleophilicity with the oil contact angle of 3°. Surface morphological studies have indicated that the wettability of resultant membranes could be manipulated by tuning the surface composition as well as the hierarchical structures. The quantitative hierarchical roughness analysis using the N2 adsorption method has confirmed the major contribution of SiO2 NPs on enhancing the porous structure, and a detailed correlation between roughness and solid-liquid interface pinning is proposed. Furthermore, the as-prepared membranes exhibited fast and efficient separation for oil-water mixtures and excellent stability over a wide range of pH conditions, which would make them a good candidate in industrial oil-polluted water treatments and oil spill cleanup, and also provided a new insight into the design and development of functional nanofibrous membranes through F-PBZ modification.Superhydrophobic and superoleophilic nanofibrous membranes exhibiting robust oil-water separation performance were prepared by a facile combination of electrospun cellulose acetate (CA) nanofibers and a novel in situ polymerized fluorinated polybenzoxazine (F-PBZ) functional layer that incorporated silica nanoparticles (SiO2 NPs). By employing the F-PBZ/SiO2 NPs modification, the pristine hydrophilic CA nanofibrous membranes were endowed with a superhydrophobicity with the water contact angle of 161° and a superoleophilicity with the oil contact angle of 3°. Surface morphological studies have indicated that the wettability of resultant membranes could be manipulated by tuning the surface composition as well as the hierarchical structures. The quantitative hierarchical roughness analysis using the N2 adsorption method has confirmed the major contribution of SiO2 NPs on enhancing the porous structure, and a detailed correlation between roughness and solid-liquid interface pinning is proposed. Furthermore, the as-prepared membranes exhibited fast and efficient separation for oil-water mixtures and excellent stability over a wide range of pH conditions, which would make them a good candidate in industrial oil-polluted water treatments and oil spill cleanup, and also provided a new insight into the design and development of functional nanofibrous membranes through F-PBZ modification. Electronic supplementary information (ESI) available: Detailed synthesis and structural confirmation of BAF-tfa, FT-IR results, OCA results and Movie S1. See DOI: 10.1039/c2nr33063f

[Mechanisms of immune deposit formation in glomerulonephritis].

PubMed

Bussolati, B; Camussi, G

1996-03-01

Recent experimental studies allowed the identification of several mechanisms of immune deposit formation, which are able to reproduce the morphological and clinical pattern of human glomerulonephritis. Moreover, it was shown that most of the lesions considered, in the past, as due to circulating immune complexes (IC), are instead caused by the "in situ" formation of IC. As a result of these studies, the following schematic classification was proposed: 1) immune deposits formed by glomerular localization of IC primarily formed in the circulation; 2) immune deposits formed "in situ" by reaction of circulating antibodies with fixed structural antigens; 3) immune deposits formed "in situ" by antibodies reactive with movable structural antigens; 4) immune deposits formed "in situ" by antibodies reactive with sequestered antigens leaking out of tissues; 5) IC formed "in situ" by antibodies reactive with exogenous or non-glomerular endogenous antigens planted in the glomeruli; 6) ANCA-associated glomerular disease.

Clinical, radiological, and morphological evaluations of posterior horn tears of the lateral meniscus left in situ during anterior cruciate ligament reconstruction.

PubMed

Lee, Dhong Won; Jang, Hyoung Won; Lee, Sung Rak; Park, Jung Ho; Ha, Jeong Ku; Kim, Jin Goo

2014-02-01

Recent studies have shown that lateral menisci have a higher healing potential and that they can be treated successfully without symptoms by being left in situ during anterior cruciate ligament (ACL) reconstruction. However, few studies have reported morphological results. Stable posterior horn tears of the lateral meniscus left in situ during ACL reconstruction could be healed spontaneously and would result in not only successful clinical outcomes but also morphological restoration. Cohort study; Level of evidence, 3. Among 367 patients who underwent primary ACL reconstruction between 2008 and 2010, 53 patients who had lateral meniscus tears that were left in situ were analyzed. These patients were evaluated subjectively and radiologically and compared with a matched control group that underwent ACL reconstruction without any other structural disorders. Of the 53 patients with stable posterior horn tears of the lateral meniscus left in situ, 28 patients were assessed by second-look arthroscopic surgery and magnetic resonance imaging (MRI). The mean follow-up of the study group and the control group was 36.47 and 37.26 months, respectively. There were no statistical differences in postoperative clinical outcomes between the 2 groups. Clinical results of both groups including the Lysholm score, Tegner activity score, and International Knee Documentation Committee (IKDC) score significantly improved. In the subgroup composed of 28 patients, follow-up MRI showed 25 (89%) and 24 (86%) healed menisci in sagittal and coronal views, respectively. Twenty-one (75%) were considered to be completely healed, and 5 (18%) were incompletely healed on second-look arthroscopic surgery. Stable posterior horn tears of the lateral meniscus left in situ at the time of ACL reconstruction revealed successful clinical outcomes compared with isolated ACL injuries and showed considerable healing and functional restoration of tears with repeat MRI and second-look arthroscopic surgery. Therefore, leaving stable posterior horn tears of the lateral meniscus in situ during ACL reconstruction should be considered.

Electrochemical and in situ spectroscopic studies of materials of relevance to energy storage and electrocatalysis

NASA Astrophysics Data System (ADS)

Mo, Yibo

In situ X-ray absorption (XAS), surface enhanced Raman spectroscopy (SERS) and rotating ring disk electrode techniques have been employed for the characterization of materials of relevance to electrochemical energy storage and electrocatalysis. In particular, analysis of in situ Ir LIII-edge extended X-ray absorption fine structure (EXAFS) of IrO2 films electrodeposited on Au substrates yielded Ir-O bond lengths decreasing in the sequence 2.02, 1.97 and 1.93 A, for Ir3+, Ir4+ and Ir5+ sites, respectively. Although features consistent with the presence of crystalline IrO2 in the highly hydrated films were found from in situ SERS, the lack of intense shells in the FT of the EXAFS function beyond the nearest oxygen neighbors indicates that the films by and large do not display long range order. In similar studies, the Fourier transform of the k3-weighted Ru K-edge EXAFS of electrodeposited RuO2 films recorded in situ were characterized by two shells attributed to Ru-O and Ru-Ru interactions at 1.94(1) and 3.12(2) A, in agreement with results obtained ex situ for Ru4+ in hydrous RuO2, whereas films in the reduced state yielded a single Ru-O interaction shell at 2.02(1) A. Extensions of these in situ XAS to the study of electrocatalysts for the nitrite reduction made it possible to identify and characterize the electronic and structural properties of a nitrosyl iron porphyrin adduct adsorbed on an electrode surface via the analysis of Fe K-edge XAS data. The effects of Se and S ad-atoms on the electrocatalytic activity of Pt electrodes have been examined using RRDE techniques. In acid, within a rather narrow range of coverages, both S- and Se-modified Pt surfaces promote the 2-electron reduction of dioxygen to hydrogen peroxide at ca. 100% faradaic efficiency over a wide potential region. Also developed were methods for immobilizing unsupported dispersed high area Pt particles a glassy carbon (GC) disk of a rotating Pt(ring)/GC(disk) electrode assembly allowing electrochemical measurements to be performed under forced convection with only minimal losses of Pt from the surface.

Electric-field-induced structural modulation of epitaxial BiFeO3 multiferroic thin films as studied using x-ray microdiffraction

NASA Astrophysics Data System (ADS)

Bark, Chung W.; Ryu, Sangwoo; Koo, Yang M.; Jang, Hyun M.; Youn, Hwa S.

2007-01-01

An in situ method, called synchrotron x-ray microdiffraction, was introduced to examine the electric-field-induced structural modulation of the epitaxially grown pseudotetragonal BiFeO3 thin film. To evaluate the d spacing (d001) from the measured intensity contour in the 2θ-χ space, the peak position in each diffraction profile was determined by applying two-dimensional Lorentzian fitting. By tracing the change of d spacing as a function of the applied electric field and by examining the Landau free energy function for P4mm symmetry, the authors were able to estimate the two important parameters that characterize the field-induced structural modulation. The estimated linear piezoelectric coefficient (d33) at zero-field limit is 15pm /V, and the effective nonlinear electrostrictive coefficient (Qeff) is as low as ˜8.0×10-3m4/C2.

In situ Raman cell for high pressure and temperature studies of metal and complex hydrides.

PubMed

Domènech-Ferrer, Roger; Ziegs, Frank; Klod, Sabrina; Lindemann, Inge; Voigtländer, Ralf; Dunsch, Lothar; Gutfleisch, Oliver

2011-04-15

A novel cell for in situ Raman studies at hydrogen pressures up to 200 bar and at temperatures as high as 400 °C is presented. This device permits in situ monitoring of the formation and decomposition of chemical structures under high pressure via Raman scattering. The performance of the cell under extreme conditions is stable as the design of this device compensates much of the thermal expansion during heating which avoids defocusing of the laser beam. Several complex and metal hydrides were analyzed to demonstrate the advantageous use of this in situ cell. Temperature calibration was performed by monitoring the structural phase transformation and melting point of LiBH(4). The feasibility of the cell in hydrogen atmosphere was confirmed by in situ studies of the decomposition of NaAlH(4) with added TiCl(3) at different hydrogen pressures and the decomposition and rehydrogenation of MgH(2) and LiNH(2). © 2011 American Chemical Society

Cytochemical features common to nucleoli and cytoplasmic nucleoloids of Olea europaea meiocytes: detection of rRNA by in situ hybridization.

PubMed

Alché, J D; Fernández, M C; Rodríguez-García, M I

1994-02-01

We used light and electron microscopic techniques to study the composition of cytoplasmic nucleoloids during meiotic division in Olea europaea. Nucleoloids were found in two clearly distinguishable morphological varieties: one similar in morphology to the nucleolus, and composed mainly of dense fibrillar component, and another surrounded by many ribosome-like particles. Cytochemical and immunocytochemical techniques showed similar reactivities in nucleoloids and the nucleolus: both are ribonucleoproteic in nature, and possess argyrophillic, argentaffinic and highly phosphorylated proteins. Immunohistochemical techniques failed to detect DNA in either structure. In situ hybridization to a 18 S rRNA probe demonstrated the presence of ribosomal transcripts in both the nucleolus and nucleoloids. These similarities in morphology and composition may reflect similar functionalities.

In-situ preparation of functionalized molecular sieve material and a methodology to remove template

NASA Astrophysics Data System (ADS)

Yadav, Rekha; Ahmed, Maqsood; Singh, Arvind Kumar; Sakthivel, Ayyamperumal

2016-03-01

A series of diaminosilane-functionalized silicoaluminophosphate molecular sieve (SAPO-37) was prepared by in-situ synthesis, and a novel method was developed for the selective removal of structure directing agent (SDA)/template from the functionalized SAPO-37.The complete removal of the SDA was evident according to FT-IR, TGA, 13C MAS-NMR and elemental analysis. The developed method was found to be efficient for removal of template from microporous molecular sieve viz., SAPO-37 and can be applied for other microporous molecular sieves such as SAPO-5, SAPO-40, etc. The powder XRD pattern of the template-removed samples showed a highly crystalline SAPO-37 phase. Argentometric titration revealed that more than 90% of diamine functionality exposed on the surface was accessible for catalytic applications. The resultant materials showed promising activity for ring opening of epoxide with aniline to yield β-amino-alcohol.

In-situ preparation of functionalized molecular sieve material and a methodology to remove template.

PubMed

Yadav, Rekha; Ahmed, Maqsood; Singh, Arvind Kumar; Sakthivel, Ayyamperumal

2016-03-10

A series of diaminosilane-functionalized silicoaluminophosphate molecular sieve (SAPO-37) was prepared by in-situ synthesis, and a novel method was developed for the selective removal of structure directing agent (SDA)/template from the functionalized SAPO-37.The complete removal of the SDA was evident according to FT-IR, TGA, (13)C MAS-NMR and elemental analysis. The developed method was found to be efficient for removal of template from microporous molecular sieve viz., SAPO-37 and can be applied for other microporous molecular sieves such as SAPO-5, SAPO-40, etc. The powder XRD pattern of the template-removed samples showed a highly crystalline SAPO-37 phase. Argentometric titration revealed that more than 90% of diamine functionality exposed on the surface was accessible for catalytic applications. The resultant materials showed promising activity for ring opening of epoxide with aniline to yield β-amino-alcohol.

Characterisation of cuticular nanostructures on surfaces of insects by atomic force microscopy: mining evolution for smart structures

NASA Astrophysics Data System (ADS)

Watson, Gregory S.; Blach, Jolanta A.

2002-11-01

The optical properties of insect nano-structures have been extensively studied. In particular, nano-scale ordered arrays have been reported from studies of the corneal surfaces of some insects and of insect wings showing anti-reflective properties. These arrays have been ascribed to evolutionary adaptation and survival value arising from increased visual capacity and better camouflage against predators. In this study we show that the Atomic Force Microscope (AFM) can effectively reveal and quantify the three dimensional structures of nano-arrays on moth eyes and cicada wings. It is also shown that the arrays present an ideal surface for in situ characterisation of the AFM probe/tip. In addition, a new structure is presented which has been discovered on a termite wing. The structure is similar to that found on the cicada wing, but has a much larger 'lattice parameter' for the ordered array. The function(s) of the array is unknown at present. It could be effective as an anti-reflective coating, but would then be active in the infra-red region of the light spectrum. Alternatively, it may confer evolutionary advantage by virtue of its mechanical strength, or it may improve the aerodynamics of flying. The study demonstrates that natural selection may be a rich source of 'smart' structures.

Advances in functional X-ray imaging techniques and contrast agents

PubMed Central

Chen, Hongyu; Rogalski, Melissa M.

2012-01-01

X-rays have been used for non-invasive high-resolution imaging of thick biological specimens since their discovery in 1895. They are widely used for structural imaging of bone, metal implants, and cavities in soft tissue. Recently, a number of new contrast methodologies have emerged which are expanding X-ray’s biomedical applications to functional as well as structural imaging. These techniques are promising to dramatically improve our ability to study in situ biochemistry and disease pathology. In this review, we discuss how X-ray absorption, X-ray fluorescence, and X-ray excited optical luminescence can be used for physiological, elemental, and molecular imaging of vasculature, tumours, pharmaceutical distribution, and the surface of implants. Imaging of endogenous elements, exogenous labels, and analytes detected with optical indicators will be discussed. PMID:22962667

In situ and ex situ spectroscopic monitoring of biochar's surface functional groups

USDA-ARS?s Scientific Manuscript database

A number of studies described the higher heating temperature (HHT) as the primary pyrolysis parameter dictating the biochar property: surface functional group and fixed carbon contents, O/C, H/C ratios, and Brunauer-Emmett-Teller (BET) surface area. In order to produce desirable biochar properties ...

DeepPIV: Measuring in situ Biological-Fluid Interactions from the Surface to Benthos

NASA Astrophysics Data System (ADS)

Katija, K.; Sherman, A.; Graves, D.; Kecy, C. D.; Klimov, D.; Robison, B. H.

2015-12-01

The midwater region of the ocean (below the euphotic zone and above the benthos) is one of the largest ecosystems on our planet, yet it remains one of the least explored. Little known marine organisms that inhabit midwater have developed strategies for swimming and feeding that ultimately contributes to their evolutionary success, and may inspire engineering solutions for societally relevant challenges. Fluid mechanics governs the interactions that midwater organisms have with their physical environment, but limited access to midwater depths and lack of non-invasive methods to measure in situ small-scale fluid motions prevent these interactions from being better understood. Significant advances in underwater vehicle technologies have only recently improved access to midwater. Unfortunately, in situ small-scale fluid mechanics measurement methods are still lacking in the oceanographic community. Here we present DeepPIV, an instrumentation package that can be affixed to remotely operated underwater vehicles that quantifies small-scale fluid motions from the surface of the ocean down to 4000 m depths. Utilizing ambient, suspended particulate in the coastal regions of Monterey Bay, fluid-structure interactions are evaluated on a range of marine organisms in midwater. Initial science targets include larvaceans, biological equivalents of flapping flexible foils, that create mucus houses to filter food. Little is known about the structure of these mucus houses and the function they play in selectively filtering particles, and these dynamics can serve as particle-mucus models for human health. Using DeepPIV, we reveal the complex structures and flows generated within larvacean mucus houses, and elucidate how these structures function.

Chemical bath deposition of semiconductor thin films & nanostructures in novel microreactors

NASA Astrophysics Data System (ADS)

McPeak, Kevin M.

Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures and thin films, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. CBD is traditionally performed in a batch reactor, requiring only a substrate to be immersed in a supersaturated solution of aqueous precursors such as metal salts, complexing agents, and pH buffers. Highlights of CBD include low cost, operation at low temperature and atmospheric pressure, and scalability to large area substrates. In this dissertation, I explore CBD of semiconductor thin films and nanowire arrays in batch and continuous flow microreactors. Microreactors offer many advantages over traditional reactor designs including a reduction in mass transport limitations, precise temperature control and ease of production scale-up by "numbering up". Continuous flow micoreactors offer the unique advantage of providing reaction conditions that are time-invariant but change smoothly as a function of distance down the reaction channel. Growth from a bath whose composition changes along the reactor length results in deposited materials whose properties vary as a function of position on the substrate, essentially creating a combinatorial library. These substrates can be rapidly characterized to identify relationships between growth conditions and material properties or growth mechanisms. I have used CBD in a continuous flow microreactor to deposit ZnO nanowire arrays and CdZnS films whose optoelectronic properties vary as a function of position. The spatially-dependent optoelectronic properties of these materials have been correlated to changes in the composition, structure or growth mechanisms of the materials and ultimately their growth conditions by rigorous spatial characterization. CBD in a continuous flow microreactor, coupled with spatial characterization, provides a new route to understanding the connection between CBD growth conditions and the resulting optoelectronic properties of the film. The high surface-to-volume ratio of a microreactor also lends itself to in situ characterization studies. I demonstrated the first in situ x-ray absorption fine-structure spectroscopy (XAFS) study of CBD. The high sensitivity and ability to characterize liquid, amorphous and crystalline materials simultaneously make in situ XAFS spectroscopy an ideal tool to study the CBD of inorganic nanomaterials.

In situ AFM imaging of apolipoprotein A-I directly derived from plasma HDL.

PubMed

Gan, Chaoye; Wang, Zhexuan; Chen, Yong

2017-04-01

The major apolipoproteins of plasma lipoproteins play vital roles in the structural integrity and physiological functions of lipoproteins. More than ten structural models of apolipoprotein A-I (apoA-I), the major apolipoprotein of high-density lipoprotein (HDL), have been developed successively. In these models, apoA-I was supposed to organize in a ring-shaped form. To date, however, there is no direct evidence under physiological condition. Here, atomic force microscopy (AFM) was used to in situ visualize the organization of apoA-I, which was exposed via depletion of the lipid component of plasma HDL pre-immobilized on functionalized mica sheets. For the first time, the ring-shaped coarse structure and three detailed structures (crescent-shaped, gapped "O"-shaped, and parentheses-shaped structures, respectively) of apoA-I in plasma HDL, which have the ability of binding scavenger receptors, were directly observed and quantitatively measured by AFM. The three detailed structures probably represent the different extents to which the lipid component of HDL was depleted. Data on lipid depletion of HDL may provide clues to understand lipid insertion of HDL. These data provide important information for the understanding of the structure/maturation of plasma HDL. Moreover, they suggest a powerful method for directly visualizing the major apolipoproteins of plasma lipoproteins or the protein component of lipoprotein-like lipid-protein complexes. Copyright © 2017 Elsevier B.V. All rights reserved.

28 CFR 79.61 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

.... The term includes in situ lung cancers. (m) Readily available documentation means documents in the... injury means structural or functional damage to the kidney tubules that results in renal disease and... resulting in chronic renal dysfunction. (j) Nonmalignant respiratory disease means fibrosis of the lung...

ADHESION AND REPULSION MOLECULES IN DEVELOPMENTAL NEUROTOXIC INJURY

EPA Science Inventory

Work during the next year will focus on establishing structural and functional correlations between the changes in Eph/ephrin expression and MeHg exposure. We have begun to characterize the cellular expression of the specific molecules using in situ hybridization ...

X-ray diffraction of solid tin to 1.2 TPa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lazicki, A.; Rygg, J. R.; Coppari, F.

2015-08-12

In this study, we report direct in situ measurements of the crystal structure of tin between 0.12 and 1.2 TPa, the highest stress at which a crystal structure has ever been observed. Using angle-dispersive powder x-ray diffraction, we find that dynamically compressed Sn transforms to the body-centered-cubic (bcc) structure previously identified by ambient-temperature quasistatic-compression studies and by zero-kelvin density-functional theory predictions between 0.06 and 0.16 TPa. However, we observe no evidence for the hexagonal close-packed (hcp) phase found by those studies to be stable above 0.16 TPa. Instead, our results are consistent with bcc up to 1.2 TPa. We conjecturemore » that at high temperature bcc is stabilized relative to hcp due to differences in vibrational free energy.« less

Structural and functional organization of ribosomal genes within the mammalian cell nucleolus.

PubMed

Derenzini, Massimo; Pasquinelli, Gianandrea; O'Donohue, Marie-Françoise; Ploton, Dominique; Thiry, Marc

2006-02-01

Data on the in situ structural-functional organization of ribosomal genes in the mammalian cell nucleolus are reviewed here. Major findings on chromatin structure in situ come from investigations carried out using the Feulgen-like osmium ammine reaction as a highly specific electron-opaque DNA tracer. Intranucleolar chromatin shows three different levels of organization: compact clumps, fibers ranging from 11 to 30 nm, and loose agglomerates of extended DNA filaments. Both clumps and fibers of chromatin exhibit a nucleosomal organization that is lacking in the loose agglomerates of extended DNA filaments. In fact, these filaments constantly show a thickness of 2-3 nm, the same as a DNA double-helix molecule. The loose agglomerates of DNA filaments are located in the fibrillar centers, the interphase counterpart of metaphase NORs, therefore being constituted by ribosomal DNA. The extended, non-nucleosomal configuration of this rDNA has been shown to be independent of transcriptional activity and characterizes ribosome genes that are either transcribed or transcriptionally silent. Data reviewed are consistent with a model of control for ribosome gene activity that is not mediated by changes in chromatin structure. The presence of rDNA in mammalian cells always structurally ready for transcription might facilitate a more rapid adjustment of the ribosome production in response to the metabolic needs of the cell.

An in situ polymerization approach for the synthesis of superhydrophobic and superoleophilic nanofibrous membranes for oil-water separation.

PubMed

Shang, Yanwei; Si, Yang; Raza, Aikifa; Yang, Liping; Mao, Xue; Ding, Bin; Yu, Jianyong

2012-12-21

Superhydrophobic and superoleophilic nanofibrous membranes exhibiting robust oil-water separation performance were prepared by a facile combination of electrospun cellulose acetate (CA) nanofibers and a novel in situ polymerized fluorinated polybenzoxazine (F-PBZ) functional layer that incorporated silica nanoparticles (SiO(2) NPs). By employing the F-PBZ/SiO(2) NPs modification, the pristine hydrophilic CA nanofibrous membranes were endowed with a superhydrophobicity with the water contact angle of 161° and a superoleophilicity with the oil contact angle of 3°. Surface morphological studies have indicated that the wettability of resultant membranes could be manipulated by tuning the surface composition as well as the hierarchical structures. The quantitative hierarchical roughness analysis using the N(2) adsorption method has confirmed the major contribution of SiO(2) NPs on enhancing the porous structure, and a detailed correlation between roughness and solid-liquid interface pinning is proposed. Furthermore, the as-prepared membranes exhibited fast and efficient separation for oil-water mixtures and excellent stability over a wide range of pH conditions, which would make them a good candidate in industrial oil-polluted water treatments and oil spill cleanup, and also provided a new insight into the design and development of functional nanofibrous membranes through F-PBZ modification.

New Pyrazole-Hydrazone Derivatives: X-ray Analysis, Molecular Structure Investigation via Density Functional Theory (DFT) and Their High In-Situ Catecholase Activity.

PubMed

Karrouchi, Khalid; Yousfi, El Bekkaye; Sebbar, Nada Kheira; Ramli, Youssef; Taoufik, Jamal; Ouzidan, Younes; Ansar, M'hammed; Mabkhot, Yahia N; Ghabbour, Hazem A; Radi, Smaail

2017-10-25

The development of low-cost catalytic systems that mimic the activity of tyrosinase enzymes (Catechol oxidase) is of great promise for future biochemistry technologic demands. Herein, we report the synthesis of new biomolecules systems based on hydrazone derivatives containing a pyrazole moiety ( L1 - L6 ) with superior catecholase activity. Crystal structures of L1 and L2 biomolecules were determined by X-ray single crystal diffraction (XRD). Optimized geometrical parameters were calculated by density functional theory (DFT) at B3LYP/6-31G (d, p) level and were found to be in good agreement with single crystal XRD data. Copper (II) complexes of the compounds ( L1 - L6 ), generated in-situ, were investigated for their catalytic activities towards the oxidation reaction of catechol to ortho -quinone with the atmospheric dioxygen, in an attempt to model the activity of the copper containing enzyme tyrosinase. The studies showed that the activities depend on four parameters: the nature of the ligand, the nature of counter anion, the nature of solvent and the concentration of ligand. The Cu(II)-ligands, given here, present the highest catalytic activity (72.920 μmol·L -1 ·min -1 ) among the catalysts recently reported in the existing literature.

In-Situ Studies of Structure Transformation and Al Coordination of KAl(MoO4)2 during Heating by High Temperature Raman and 27Al NMR Spectroscopies

PubMed Central

Wang, Min; You, Jinglin; Sobol, Alexander; Lu, Liming; Wang, Jian; Xie, Yingfang

2017-01-01

Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family MIMIII(MVIO4)2 (MI = alkali metal, MIII = Al, In, Sc, Fe, Bi, lanthanide; MVI = Mo, W). The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO4)2 have been investigated by in-situ high temperature Raman scattering and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO6] octahedra in both KAl(MoO4)2 glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K+, from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples. PMID:28772669

In-Situ Studies of Structure Transformation and Al Coordination of KAl(MoO₄)₂ during Heating by High Temperature Raman and 27Al NMR Spectroscopies.

PubMed

Wang, Min; You, Jinglin; Sobol, Alexander; Lu, Liming; Wang, Jian; Xie, Yingfang

2017-03-17

Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family M I M III (M VI O₄)₂ (M I = alkali metal, M III = Al, In, Sc, Fe, Bi, lanthanide; M VI = Mo, W). The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO₄)₂ have been investigated by in-situ high temperature Raman scattering and 27 Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO₆] octahedra in both KAl(MoO₄)₂ glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K⁺, from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples.

Development of an arthroscopically compatible polymer additive layer manufacture technique.

PubMed

Partridge, Simon W; Benning, Matthew J; German, Matthew J; Dalgarno, Kenneth W

2017-06-01

This article describes a proof of concept study designed to evaluate the potential of an in vivo three-dimensional printing route to support minimally invasive repair of the musculoskeletal system. The study uses a photocurable material to additively manufacture in situ a model implant and demonstrates that this can be achieved effectively within a clinically relevant timescale. The approach has the potential to be applied with a wide range of light-curable materials and with development could be applied to create functionally gradient structures in vivo.

In situ characterization of charge rate dependent stress and structure changes in V 2O 5 cathode prepared by atomic layer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jung, Hyun; Gerasopoulos, Konstantinos; Talin, Albert Alec

Here, the insertion/extraction of lithium into/from various host materials is the basic process by which lithium-ion batteries reversible store charge. This process is generally accompanied by strain in the host material, inducing stress which can lead to capacity loss. Therefore, understanding of both the structural changes and the associated stress – investigated almost exclusively separate to date – is a critical factor for developing high-performance batteries. Here, we report an in situ method, which utilizes Raman spectroscopy in parallel with optical interferometry to study effects of varying charging rates (C-rates) on the structure and stress in a V 2O 5more » thin film cathode. Abrupt stress changes at specific crystal phase transitions in the Li—V—O system are observed and the magnitude of the stress changes with the amount of lithium inserted into the electrode are correlated. A linear increase in the stress as a function of x in Li xV 2O 5 is observed, indicating that C-rate does not directly contribute to larger intercalation stress. However, a more rapid increase in disorder within the Li xV 2O 5 layers is correlated with higher C-rate. Ultimately, these experiments demonstrate how the simultaneous stress/Raman in situ approach can be utilized as a characterization platform for investigating various critical factors affecting lithium-ion battery performance.« less

In situ characterization of charge rate dependent stress and structure changes in V 2O 5 cathode prepared by atomic layer deposition

DOE PAGES

Jung, Hyun; Gerasopoulos, Konstantinos; Talin, Albert Alec; ...

2016-11-22

Here, the insertion/extraction of lithium into/from various host materials is the basic process by which lithium-ion batteries reversible store charge. This process is generally accompanied by strain in the host material, inducing stress which can lead to capacity loss. Therefore, understanding of both the structural changes and the associated stress – investigated almost exclusively separate to date – is a critical factor for developing high-performance batteries. Here, we report an in situ method, which utilizes Raman spectroscopy in parallel with optical interferometry to study effects of varying charging rates (C-rates) on the structure and stress in a V 2O 5more » thin film cathode. Abrupt stress changes at specific crystal phase transitions in the Li—V—O system are observed and the magnitude of the stress changes with the amount of lithium inserted into the electrode are correlated. A linear increase in the stress as a function of x in Li xV 2O 5 is observed, indicating that C-rate does not directly contribute to larger intercalation stress. However, a more rapid increase in disorder within the Li xV 2O 5 layers is correlated with higher C-rate. Ultimately, these experiments demonstrate how the simultaneous stress/Raman in situ approach can be utilized as a characterization platform for investigating various critical factors affecting lithium-ion battery performance.« less

Spectroscopic Ellipsometry Studies of Thin Film a-Si:H Solar Cell Fabrication by Multichamber Deposition in the n-i-p Substrate Configuration

NASA Astrophysics Data System (ADS)

Dahal, Lila Raj

Real time spectroscopic ellipsometry (RTSE), and ex-situ mapping spectroscopic ellipsometry (SE) are powerful characterization techniques capable of performance optimization and scale-up evaluation of thin film solar cells used in various photovoltaics technologies. These non-invasive optical probes employ multichannel spectral detection for high speed and provide high precision parameters that describe (i) thin film structure, such as layer thicknesses, and (ii) thin film optical properties, such as oscillator variables in analytical expressions for the complex dielectric function. These parameters are critical for evaluating the electronic performance of materials in thin film solar cells and also can be used as inputs for simulating their multilayer optical performance. In this Thesis, the component layers of thin film hydrogenated silicon (Si:H) solar cells in the n-i-p or substrate configuration on rigid and flexible substrate materials have been studied by RTSE and ex-situ mapping SE. Depositions were performed by magnetron sputtering for the metal and transparent conducting oxide contacts and by plasma enhanced chemical vapor deposition (PECVD) for the semiconductor doped contacts and intrinsic absorber layers. The motivations are first to optimize the thin film Si:H solar cell in n-i-p substrate configuration for single-junction small-area dot cells and ultimately to scale-up the optimized process to larger areas with minimum loss in device performance. Deposition phase diagrams for both i- and p -layers on 2" x 2" rigid borosilicate glass substrate were developed as functions of the hydrogen-to-silane flow ratio in PECVD. These phase diagrams were correlated with the performance parameters of the corresponding solar cells, fabricated in the Cr/Ag/ZnO/n/i/ p/ITO structure. In both cases, optimization was achieved when the layers were deposited in the protocrystalline phase. Identical solar cell structures were fabricated on 6" x 6" borosilicate glass with 256 cells followed by ex-situ mapping SE on each cell to achieve better statistics for solar cell optimization by correlating local structural parameters with solar cell parameters. Solar cells of similar structure were also fabricated on flexible polymer substrates in the roll-to-roll configuration. In this configuration as well, RTSE was demonstrated as an effective process monitoring and control tool for thin film photovoltaics.

Frontiers of in situ electron microscopy

DOE PAGES

Zheng, Haimei; Zhu, Yimei; Meng, Shirley Ying

2015-01-01

In situ transmission electron microscopy (TEM) has become an increasingly important tool for materials characterization. It provides key information on the structural dynamics of a material during transformations and the correlation between structure and properties of materials. With the recent advances in instrumentation, including aberration corrected optics, sample environment control, the sample stage, and fast and sensitive data acquisition, in situ TEM characterization has become more and more powerful. In this article, a brief review of the current status and future opportunities of in situ TEM is included. It also provides an introduction to the six articles covered by inmore » this issue of MRS Bulletin explore the frontiers of in situ electron microscopy, including liquid and gas environmental TEM, dynamic four-dimensional TEM, nanomechanics, ferroelectric domain switching studied by in situ TEM, and state-of-the-art atomic imaging of light elements (i.e., carbon atoms) and individual defects.« less

Interfacial ionic 'liquids': connecting static and dynamic structures

DOE PAGES

Uysal, Ahmet; Zhou, Hua; Feng, Guang; ...

2014-12-05

It is well known that room temperature ionic liquids (RTILs) often adopt a charge-separated layered structure, i.e. with alternating cation- and anion-rich layers, at electrified interfaces. However, the dynamic response of the layered structure to temporal variations in applied potential is not well understood. For this research, we used in situ, real-time x-ray reflectivity to study the potential-dependent electric double layer (EDL) structure of an imidazolium-based RTIL on charged epitaxial graphene during potential cycling as a function of temperature. The results suggest that the graphene–RTIL interfacial structure is bistable in which the EDL structure at any intermediate potential can bemore » described by the combination of two extreme-potential structures whose proportions vary depending on the polarity and magnitude of the applied potential. This picture is supported by the EDL structures obtained by fully atomistic molecular dynamics simulations at various static potentials. Lastly, the potential-driven transition between the two structures is characterized by an increasing width but with an approximately fixed hysteresis magnitude as a function of temperature. The results are consistent with the coexistence of distinct anion- and cation-adsorbed structures separated by an energy barrier (~0.15 eV).« less

Interfacial ionic 'liquids': connecting static and dynamic structures.

PubMed

Uysal, Ahmet; Zhou, Hua; Feng, Guang; Lee, Sang Soo; Li, Song; Cummings, Peter T; Fulvio, Pasquale F; Dai, Sheng; McDonough, John K; Gogotsi, Yury; Fenter, Paul

2015-01-28

It is well known that room temperature ionic liquids (RTILs) often adopt a charge-separated layered structure, i.e. with alternating cation- and anion-rich layers, at electrified interfaces. However, the dynamic response of the layered structure to temporal variations in applied potential is not well understood. We used in situ, real-time x-ray reflectivity to study the potential-dependent electric double layer (EDL) structure of an imidazolium-based RTIL on charged epitaxial graphene during potential cycling as a function of temperature. The results suggest that the graphene-RTIL interfacial structure is bistable in which the EDL structure at any intermediate potential can be described by the combination of two extreme-potential structures whose proportions vary depending on the polarity and magnitude of the applied potential. This picture is supported by the EDL structures obtained by fully atomistic molecular dynamics simulations at various static potentials. The potential-driven transition between the two structures is characterized by an increasing width but with an approximately fixed hysteresis magnitude as a function of temperature. The results are consistent with the coexistence of distinct anion- and cation-adsorbed structures separated by an energy barrier (∼0.15 eV).

In Situ Generation of Two-Dimensional Au–Pt Core–Shell Nanoparticle Assemblies

PubMed Central

2010-01-01

Two-dimensional assemblies of Au–Pt bimetallic nanoparticles are generated in situ on polyethyleneimmine (PEI) silane functionalized silicon and indium tin oxide (ITO) coated glass surfaces. Atomic force microscopy (AFM), UV–Visible spectroscopy, and electrochemical measurements reveal the formation of core–shell structure with Au as core and Pt as shell. The core–shell structure is further supported by comparing with the corresponding data of Au nanoparticle assemblies. Static contact angle measurements with water show an increase in hydrophilic character due to bimetallic nanoparticle generation on different surfaces. It is further observed that these Au–Pt core–shell bimetallic nanoparticle assemblies are catalytically active towards methanol electro-oxidation, which is the key reaction for direct methanol fuel cells (DMFCs). PMID:20651923

Using ATR-FT/IR to detect carbohydrate-related molecular structure features of carinata meal and their in situ residues of ruminal fermentation in comparison with canola meal

NASA Astrophysics Data System (ADS)

Xin, Hangshu; Yu, Peiqiang

2013-10-01

There is no information on the co-products from carinata bio-fuel and bio-oil processing (carinata meal) in molecular structural profiles mainly related to carbohydrate biopolymers in relation to ruminant nutrition. Molecular analyses with Fourier transform infrared spectroscopy (FT/IR) technique with attenuated total reflectance (ATR) and chemometrics enable to detect structural features on a molecular basis. The objectives of this study were to: (1) determine carbohydrate conformation spectral features in original carinata meal, co-products from bio-fuel/bio-oil processing; and (2) investigate differences in carbohydrate molecular composition and functional group spectral intensities after in situ ruminal fermentation at 0, 12, 24 and 48 h compared to canola meal as a reference. The molecular spectroscopic parameters of carbohydrate profiles detected were structural carbohydrates (STCHO, mainly associated with hemi-cellulosic and cellulosic compounds; region and baseline ca. 1483-1184 cm-1), cellulosic compounds (CELC, region and baseline ca. 1304-1184 cm-1), total carbohydrates (CHO, region and baseline ca. 1193-889 cm-1) as well as the spectral ratios calculated based on respective spectral intensity data. The results showed that the spectral profiles of carinata meal were significantly different from that of canola meal in CHO 2nd peak area (center at ca. 1091 cm-1, region: 1102-1083 cm-1) and functional group peak intensity ratios such as STCHO 1st peak (ca. 1415 cm-1) to 2nd peak (ca. 1374 cm-1) height ratio, CHO 1st peak (ca. 1149 cm-1) to 3rd peak (ca. 1032 cm-1) height ratio, CELC to total CHO area ratio and STCHO to CELC area ratio, indicating that carinata meal may not in full accord with canola meal in carbohydrate utilization and availability in ruminants. Carbohydrate conformation and spectral features were changed by significant interaction of meal type and incubation time and almost all the spectral parameters were significantly decreased (P < 0.05) during 48 h ruminal degradation in both carinata meal and canola meal. Although carinata meal differed from canola meal in some carbohydrate spectral parameters, multivariate results from agglomerative hierarchical cluster analysis and principal component analysis showed that both original and in situ residues of two meals were not fully distinguished from each other within carbohydrate spectral regions. It was concluded that carbohydrate structural conformation could be detected in carinata meal by using ATR-FT/IR techniques and further study is needed to explore more information on molecular spectral features of other functional group such as protein structure profile and their association with potential nutrient supply and availability of carinata meal in animals.

Using ATR-FT/IR to detect carbohydrate-related molecular structure features of carinata meal and their in situ residues of ruminal fermentation in comparison with canola meal.

PubMed

Xin, Hangshu; Yu, Peiqiang

2013-10-01

There is no information on the co-products from carinata bio-fuel and bio-oil processing (carinata meal) in molecular structural profiles mainly related to carbohydrate biopolymers in relation to ruminant nutrition. Molecular analyses with Fourier transform infrared spectroscopy (FT/IR) technique with attenuated total reflectance (ATR) and chemometrics enable to detect structural features on a molecular basis. The objectives of this study were to: (1) determine carbohydrate conformation spectral features in original carinata meal, co-products from bio-fuel/bio-oil processing; and (2) investigate differences in carbohydrate molecular composition and functional group spectral intensities after in situ ruminal fermentation at 0, 12, 24 and 48 h compared to canola meal as a reference. The molecular spectroscopic parameters of carbohydrate profiles detected were structural carbohydrates (STCHO, mainly associated with hemi-cellulosic and cellulosic compounds; region and baseline ca. 1483-1184 cm(-1)), cellulosic compounds (CELC, region and baseline ca. 1304-1184 cm(-1)), total carbohydrates (CHO, region and baseline ca. 1193-889cm(-1)) as well as the spectral ratios calculated based on respective spectral intensity data. The results showed that the spectral profiles of carinata meal were significantly different from that of canola meal in CHO 2nd peak area (center at ca. 1091 cm(-1), region: 1102-1083 cm(-1)) and functional group peak intensity ratios such as STCHO 1st peak (ca. 1415 cm(-1)) to 2nd peak (ca. 1374 cm(-1)) height ratio, CHO 1st peak (ca. 1149 cm(-1)) to 3rd peak (ca. 1032 cm(-1)) height ratio, CELC to total CHO area ratio and STCHO to CELC area ratio, indicating that carinata meal may not in full accord with canola meal in carbohydrate utilization and availability in ruminants. Carbohydrate conformation and spectral features were changed by significant interaction of meal type and incubation time and almost all the spectral parameters were significantly decreased (P<0.05) during 48 h ruminal degradation in both carinata meal and canola meal. Although carinata meal differed from canola meal in some carbohydrate spectral parameters, multivariate results from agglomerative hierarchical cluster analysis and principal component analysis showed that both original and in situ residues of two meals were not fully distinguished from each other within carbohydrate spectral regions. It was concluded that carbohydrate structural conformation could be detected in carinata meal by using ATR-FT/IR techniques and further study is needed to explore more information on molecular spectral features of other functional group such as protein structure profile and their association with potential nutrient supply and availability of carinata meal in animals. Copyright © 2013 Elsevier B.V. All rights reserved.

Intracellular degradation of chemically functionalized carbon nanotubes using a long-term primary microglial culture model

NASA Astrophysics Data System (ADS)

Bussy, Cyrill; Hadad, Caroline; Prato, Maurizio; Bianco, Alberto; Kostarelos, Kostas

2015-12-01

Chemically functionalized carbon nanotubes (f-CNTs) have been used in proof-of-concept studies to alleviate debilitating neurological conditions. Previous in vivo observations in brain tissue have suggested that microglia - acting as resident macrophages of the brain - play a critical role in the internalization of f-CNTs and their partial in situ biodegradation following a stereotactic administration in the cortex. At the same time, several reports have indicated that immune cells such as neutrophils, eosinophils and even macrophages could participate in the processing of carbon nanomaterials via oxidation processes leading to degradation, with surface properties acting as modulators of CNT biodegradability. In this study we questioned whether degradability of f-CNTs within microglia could be modulated depending on the type of surface functionalization used. We investigated the kinetics of degradation of multi-walled carbon nanotubes (MWNTs) functionalized via different chemical strategies that were internalized within isolated primary microglia over three months. A cellular model of rat primary microglia that can be maintained in cell culture for a long period of time was first developed. The Raman structural signature of the internalized f-CNTs was then studied directly in cells over a period of up to three months, following a single exposure to a non-cytotoxic concentration of three different f-CNTs (carboxylated, aminated and both carboxylated and aminated). Structural modifications suggesting partial but continuous degradation were observed for all nanotubes irrespective of their surface functionalization. Carboxylation was shown to promote more pronounced structural changes inside microglia over the first two weeks of the study.Chemically functionalized carbon nanotubes (f-CNTs) have been used in proof-of-concept studies to alleviate debilitating neurological conditions. Previous in vivo observations in brain tissue have suggested that microglia - acting as resident macrophages of the brain - play a critical role in the internalization of f-CNTs and their partial in situ biodegradation following a stereotactic administration in the cortex. At the same time, several reports have indicated that immune cells such as neutrophils, eosinophils and even macrophages could participate in the processing of carbon nanomaterials via oxidation processes leading to degradation, with surface properties acting as modulators of CNT biodegradability. In this study we questioned whether degradability of f-CNTs within microglia could be modulated depending on the type of surface functionalization used. We investigated the kinetics of degradation of multi-walled carbon nanotubes (MWNTs) functionalized via different chemical strategies that were internalized within isolated primary microglia over three months. A cellular model of rat primary microglia that can be maintained in cell culture for a long period of time was first developed. The Raman structural signature of the internalized f-CNTs was then studied directly in cells over a period of up to three months, following a single exposure to a non-cytotoxic concentration of three different f-CNTs (carboxylated, aminated and both carboxylated and aminated). Structural modifications suggesting partial but continuous degradation were observed for all nanotubes irrespective of their surface functionalization. Carboxylation was shown to promote more pronounced structural changes inside microglia over the first two weeks of the study. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06625e

In situ real-time imaging of self-sorted supramolecular nanofibres

NASA Astrophysics Data System (ADS)

Onogi, Shoji; Shigemitsu, Hajime; Yoshii, Tatsuyuki; Tanida, Tatsuya; Ikeda, Masato; Kubota, Ryou; Hamachi, Itaru

2016-08-01

Self-sorted supramolecular nanofibres—a multicomponent system that consists of several types of fibre, each composed of distinct building units—play a crucial role in complex, well-organized systems with sophisticated functions, such as living cells. Designing and controlling self-sorting events in synthetic materials and understanding their structures and dynamics in detail are important elements in developing functional artificial systems. Here, we describe the in situ real-time imaging of self-sorted supramolecular nanofibre hydrogels consisting of a peptide gelator and an amphiphilic phosphate. The use of appropriate fluorescent probes enabled the visualization of self-sorted fibres entangled in two and three dimensions through confocal laser scanning microscopy and super-resolution imaging, with 80 nm resolution. In situ time-lapse imaging showed that the two types of fibre have different formation rates and that their respective physicochemical properties remain intact in the gel. Moreover, we directly visualized stochastic non-synchronous fibre formation and observed a cooperative mechanism.

Hydrodynamic fractionation of finite size gold nanoparticle clusters.

PubMed

Tsai, De-Hao; Cho, Tae Joon; DelRio, Frank W; Taurozzi, Julian; Zachariah, Michael R; Hackley, Vincent A

2011-06-15

We demonstrate a high-resolution in situ experimental method for performing simultaneous size classification and characterization of functional gold nanoparticle clusters (GNCs) based on asymmetric-flow field flow fractionation (AFFF). Field emission scanning electron microscopy, atomic force microscopy, multi-angle light scattering (MALS), and in situ ultraviolet-visible optical spectroscopy provide complementary data and imagery confirming the cluster state (e.g., dimer, trimer, tetramer), packing structure, and purity of fractionated populations. An orthogonal analysis of GNC size distributions is obtained using electrospray-differential mobility analysis (ES-DMA). We find a linear correlation between the normalized MALS intensity (measured during AFFF elution) and the corresponding number concentration (measured by ES-DMA), establishing the capacity for AFFF to quantify the absolute number concentration of GNCs. The results and corresponding methodology summarized here provide the proof of concept for general applications involving the formation, isolation, and in situ analysis of both functional and adventitious nanoparticle clusters of finite size. © 2011 American Chemical Society

In Situ Gold Nanoparticle Gradient Formation in a 3D Meso- and Macroporous Polymer Matrix.

PubMed

Penders, Jelle; Rajasekharan, Anand K; Hulander, Mats; Andersson, Martin

2017-08-01

Herein, the development and characterization of a 3D gradient structure of gold nanoparticles is described. The gradient of gold nanoparticles is made in situ in a macroporous nonionic block copolymer hydrogel matrix, through gold ion diffusion control. The polymer provides a matrix for diffusion of gold ions, acts as a template for controlling nanoparticle growth, and facilitates the in situ reduction of gold ions to gold nanoparticles. A clear gradient in gold nanoparticles is observed across the 3D space of the polymer matrix using scanning electron microscopy, fluorescence microscopy, atomic force microscopy, and thermogravimetric analysis. The particle gradient is further functionalized with both hydrophobic and hydrophilic groups via thiol-gold linkage to demonstrate the ability to form gradients with different chemical functionalities. Using additive manufacturing, the polymer can also be printed as a porous network with possible applications for 3D cell culturing in, e.g., biomaterials research. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modification of conductive polyaniline with carbon nanomaterials

NASA Astrophysics Data System (ADS)

Sedaghat, Sajjad; Alavijeh, Mahdi Soleimani

2014-08-01

The synthesis of polyaniline/single-wall nanotube, polyaniline/multi-wall nanotube and polyaniline/single-wall nanotube/graphen nanosheets nanocomposites by in situ polymerization are reported in this study. The substrates were treated with a mixture of concentrated sulfuric acid and concentrated nitric acid before usage to functionalize with carboxylic and hydroxyl groups. Aniline monomers are adsorbed and polymerized on the surface of these fillers. Structural analysis using scanning electron microscopy showed that nanomaterials dispersed into polymer matrix and made tubular structures with diameters several tens to hundreds nanometers depending on the polyaniline content. These nanocomposites can be used for production of excellent electrode materials applications in high-performance supercapacitors.

Facile fabrication of BiVO4 nanofilms with controlled pore size and their photoelectrochemical performances

NASA Astrophysics Data System (ADS)

Feng, Chenchen; Jiao, Zhengbo; Li, Shaopeng; Zhang, Yan; Bi, Yingpu

2015-12-01

We demonstrate a facile method for the rational fabrication of pore-size controlled nanoporous BiVO4 photoanodes, and confirmed that the optimum pore-size distributions could effectively absorb visible light through light diffraction and confinement functions. Furthermore, in situ X-ray photoelectron spectroscopy (XPS) reveals more efficient photoexcited electron-hole separation than conventional particle films, induced by light confinement and rapid charge transfer in the inter-crossed worm-like structures.We demonstrate a facile method for the rational fabrication of pore-size controlled nanoporous BiVO4 photoanodes, and confirmed that the optimum pore-size distributions could effectively absorb visible light through light diffraction and confinement functions. Furthermore, in situ X-ray photoelectron spectroscopy (XPS) reveals more efficient photoexcited electron-hole separation than conventional particle films, induced by light confinement and rapid charge transfer in the inter-crossed worm-like structures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06584d

In situ Low-temperature Pair Distribution Function (PDF) Analysis of CH4 and CO2 Hydrates

NASA Astrophysics Data System (ADS)

Cladek, B.; Everett, M.; McDonnell, M.; Tucker, M.; Keffer, D.; Rawn, C.

2017-12-01

Gas hydrates occur in ocean floor and sub-surface permafrost deposits and are stable at moderate to high pressures and low temperatures. They are a clathrate structure composed of hydrogen bonded water cages that accommodate a wide variety of guest molecules. CO2 and CH4 hydrates both crystallize as the cubic sI hydrate and can form a solid solution. Natural gas hydrates are interesting as a potential methane source and for CO2 sequestration. Long-range diffraction studies on gas hydrates give valuable structural information but do not provide a detailed understanding of the disordered gas molecule interactions with the host lattice. In-situ low temperature total scattering experiments combined with pair distribution function (PDF) analysis are used to investigate the gas molecule motions and guest-cage interactions. CO2 and methane hydrates exhibit different decomposition behavior, and CO2 hydrate has a smaller lattice parameter despite it being a relatively larger molecule. Total scattering studies characterizing both the short- and long-range order simultaneously help to elucidate the structural source of these phenomena. Low temperature neutron total scattering data were collected using the Nanoscale Ordered MAterials Diffractometer (NOMAD) beamline at the Spallation Neutron Source (SNS) on CO2 and CH4 hydrates synthesized with D2O. Guest molecule motion within cages and interactions between gases and cages are investigated through the hydrate stability and decomposition regions. Data were collected from 2-80 K at a pressure of 55 mbar on CO2 and CH4 hydrates, and from 80-270 K at 25 bar on CH4 hydrate. The hydrate systems were modeled with classical molecular dynamic (MD) simulations to provide an analysis of the total energy into guest-guest, guest-host and host-host contributions. Combined Reitveld and Reverse Monte Carlo (RMC) structure refinement were used to fit models of the data. This combined modeling and simulation characterizes the effects of CO2 and CH4 as guest molecules on the structure and decomposition of gas hydrates. Structure and thermodynamic studies will provide a more comprehensive understanding of CO2-CH4 solid solutions, exchange kinetics, and implications on hydrate structure.

Polyurethane nanofiber strain sensors via in situ polymerization of polypyrrole and application to monitoring joint flexion

NASA Astrophysics Data System (ADS)

Kim, Inhwan; Cho, Gilsoo

2018-07-01

Strain sensors made of intrinsically conductive polymers (ICPs) and nanofibers were fabricated and tested for suitability for use in wearable technology. The sensors were fabricated and evaluated based on their surface appearances, and electrical, tensile, and chemical/thermal properties. Polypyrrole (PPy) was in situ polymerized onto polyurethane (PU) nanofiber substrates by exposing pyrrole monomers to ammonium persulfate as oxidant and 2,6-naphthalenedisulfonic acid disodium salt as doping agents in an aqueous bath. The PPy treated PU nanofibers were then coated with polydimethylsiloxane (PDMS). Both pyrrole concentrations and layer numbers were significantly related to change in electrical conductivity. Specimen treated with 0.1 M of PPy and having three layered structure showed the best electrical conductivity. Regarding tensile strength, the in situ polymerization process decreased tensile strength because the oxidant chemically degraded the PU fibers. Adding layers and PDMS treatment generally improved tensile properties while adding layers created fracture parts in the stress–strain curves. The treatment condition of 0.1 M of PPy, two layered, and PDMS treated specimen showed the best tensile properties as a strain sensor. The chemical property evaluation with Fourier transform infrared and x-ray photoelectron spectroscopy tests showed successful PPy polymerization and PDMS treatments. The functional groups and chemical bonds in polyol, urethane linkage, backbone ring structure in PPy, silicon-based functional groups in PDMS, and elemental content changes by treatment at each stage were characterized. The real-time data acquired from the dummy and five human subjects with repetition of motion at three different speeds of 0.16, 0.25 and 0.5 Hz generated similar trends and tendencies. The PU nanofiber sensors based on PPy and PDMS treatments in this study point to the possibility of developing textiles based wearable strain sensors developed using ICPs.

3D structure of eukaryotic flagella in a quiescent state revealed by cryo-electron tomography

PubMed Central

Nicastro, Daniela; McIntosh, J. Richard; Baumeister, Wolfgang

2005-01-01

We have used cryo-electron tomography to investigate the 3D structure and macromolecular organization of intact, frozen-hydrated sea urchin sperm flagella in a quiescent state. The tomographic reconstructions provide information at a resolution better than 6 nm about the in situ arrangements of macromolecules that are key for flagellar motility. We have visualized the heptameric rings of the motor domains in the outer dynein arm complex and determined that they lie parallel to the plane that contains the axes of neighboring flagellar microtubules. Both the material associated with the central pair of microtubules and the radial spokes display a plane of symmetry that helps to explain the planar beat pattern of these flagella. Cryo-electron tomography has proven to be a powerful technique for helping us understand the relationships between flagellar structure and function and the design of macromolecular machines in situ. PMID:16246999

Efficient direct solar-to-hydrogen conversion by in situ interface transformation of a tandem structure

NASA Astrophysics Data System (ADS)

May, Matthias M.; Lewerenz, Hans-Joachim; Lackner, David; Dimroth, Frank; Hannappel, Thomas

2015-09-01

Photosynthesis is nature's route to convert intermittent solar irradiation into storable energy, while its use for an industrial energy supply is impaired by low efficiency. Artificial photosynthesis provides a promising alternative for efficient robust carbon-neutral renewable energy generation. The approach of direct hydrogen generation by photoelectrochemical water splitting utilizes customized tandem absorber structures to mimic the Z-scheme of natural photosynthesis. Here a combined chemical surface transformation of a tandem structure and catalyst deposition at ambient temperature yields photocurrents approaching the theoretical limit of the absorber and results in a solar-to-hydrogen efficiency of 14%. The potentiostatically assisted photoelectrode efficiency is 17%. Present benchmarks for integrated systems are clearly exceeded. Details of the in situ interface transformation, the electronic improvement and chemical passivation are presented. The surface functionalization procedure is widely applicable and can be precisely controlled, allowing further developments of high-efficiency robust hydrogen generators.

Efficient direct solar-to-hydrogen conversion by in situ interface transformation of a tandem structure

PubMed Central

May, Matthias M.; Lewerenz, Hans-Joachim; Lackner, David; Dimroth, Frank; Hannappel, Thomas

2015-01-01

Photosynthesis is nature's route to convert intermittent solar irradiation into storable energy, while its use for an industrial energy supply is impaired by low efficiency. Artificial photosynthesis provides a promising alternative for efficient robust carbon-neutral renewable energy generation. The approach of direct hydrogen generation by photoelectrochemical water splitting utilizes customized tandem absorber structures to mimic the Z-scheme of natural photosynthesis. Here a combined chemical surface transformation of a tandem structure and catalyst deposition at ambient temperature yields photocurrents approaching the theoretical limit of the absorber and results in a solar-to-hydrogen efficiency of 14%. The potentiostatically assisted photoelectrode efficiency is 17%. Present benchmarks for integrated systems are clearly exceeded. Details of the in situ interface transformation, the electronic improvement and chemical passivation are presented. The surface functionalization procedure is widely applicable and can be precisely controlled, allowing further developments of high-efficiency robust hydrogen generators. PMID:26369620

It is all about location: how to pinpoint microorganisms and their functions in multispecies biofilms.

PubMed

Costa, Angela M; Mergulhão, Filipe J; Briandet, Romain; Azevedo, Nuno F

2017-09-01

Multispecies biofilms represent the dominant mode of life for the vast majority of microorganisms. Bacterial spatial localization in such biostructures governs ecological interactions between different populations and triggers the overall community functions. Here, we discuss the pros and cons of fluorescence-based techniques used to decipher bacterial species patterns in biofilms at single cell level, including fluorescence in situ hybridization and the use of genetically modified bacteria that express fluorescent proteins, reporting the significant improvements of those techniques. The development of tools for spatial and temporal study of multispecies biofilms will allow live imaging and spatial localization of cells in naturally occurring biofilms coupled with metabolic information, increasing insight of microbial community and the relation between its structure and functions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aden, Bethany; Kite, Camille M.; Hopkins, Benjamin W.

Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize these layers in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends onmore » the size of the amine, the grafting density of brush chains, and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. In addition, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. In conclusion, these findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aden, Bethany; Kite, Camille M.; Hopkins, Benjamin W.

Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize the layer in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends on themore » size of the amine, the grafting density of brush chains and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale, shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. Additionally, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. These findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.« less

Hexavalent chromium reduction under fermentative conditions with lactate stimulated native microbial communities.

PubMed

Somenahally, Anil C; Mosher, Jennifer J; Yuan, Tong; Podar, Mircea; Phelps, Tommy J; Brown, Steven D; Yang, Zamin K; Hazen, Terry C; Arkin, Adam P; Palumbo, Anthony V; Van Nostrand, Joy D; Zhou, Jizhong; Elias, Dwayne A

2013-01-01

Microbial reduction of toxic hexavalent chromium (Cr(VI)) in-situ is a plausible bioremediation strategy in electron-acceptor limited environments. However, higher [Cr(VI)] may impose stress on syntrophic communities and impact community structure and function. The study objectives were to understand the impacts of Cr(VI) concentrations on community structure and on the Cr(VI)-reduction potential of groundwater communities at Hanford, WA. Steady state continuous flow bioreactors were used to grow native communities enriched with lactate (30 mM) and continuously amended with Cr(VI) at 0.0 (No-Cr), 0.1 (Low-Cr) and 3.0 (High-Cr) mg/L. Microbial growth, metabolites, Cr(VI), 16S rRNA gene sequences and GeoChip based functional gene composition were monitored for 15 weeks. Temporal trends and differences in growth, metabolite profiles, and community composition were observed, largely between Low-Cr and High-Cr bioreactors. In both High-Cr and Low-Cr bioreactors, Cr(VI) levels were below detection from week 1 until week 15. With lactate enrichment, native bacterial diversity substantially decreased as Pelosinus spp., and Sporotalea spp., became the dominant groups, but did not significantly differ between Cr concentrations. The Archaea diversity also substantially decreased after lactate enrichment from Methanosaeta (35%), Methanosarcina (17%) and others, to mostly Methanosarcina spp. (95%). Methane production was lower in High-Cr reactors suggesting some inhibition of methanogens. Several key functional genes were distinct in Low-Cr bioreactors compared to High-Cr. Among the Cr resistant microbes, Burkholderia vietnamiensis, Comamonas testosterone and Ralstonia pickettii proliferated in Cr amended bioreactors. In-situ fermentative conditions facilitated Cr(VI) reduction, and as a result 3.0 mg/L Cr(VI) did not impact the overall bacterial community structure.

Spatio-Temporal Cellular Imaging of Polymer-pDNA Nanocomplexes Affords In Situ Morphology and Trafficking Trends

PubMed Central

Ingle, Nilesh P.; Lian, Xue; Reineke, Theresa M.

2013-01-01

Synthetic polymers are ubiquitous in the development of drug and polynucleotide delivery vehicles, offering promise for personalized medicine. However, the polymer structure plays a central yet elusive role in dictating the efficacy, safety, mechanisms, and kinetics of therapeutic transport in a spatial and temporal manner. Here, we decipher the intracellular evolutionary pathways pertaining to shape, size, location, and mechanism of four structurally-divergent polymer vehicles (Tr455, Tr477, jetPEI™ and Glycofect™) that create colloidal nanoparticles (polyplexes) when complexed with fluorescently-labeled plasmid DNA (pDNA). Multiple high resolution tomographic images of whole HeLa (human cervical adenocarcinoma) cells were captured via confocal microscopy at 4, 8, 12 and 24 hours. The images were reconstructed to visualize and quantify trends in situ in a four-dimensional spatio-temporal manner. The data revealed heretofore-unseen images of polyplexes in situ and structure-function relationships, i.e., Glycofect™ polyplexes are trafficked as the smallest polyplex complexes and Tr455 polyplexes have expedited translocation to the perinuclear region. Also, all of the polyplex types appeared to be preferentially internalized and trafficked via early endosomes affiliated with caveolae, a Rab-5-dependent pathway, actin, and microtubules. PMID:24007201

Visualizing Redox Dynamics of a Single Ag/AgCl Heterogeneous Nanocatalyst at Atomic Resolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yimin A.; Li, Liang; Li, Zheng

Operando characterization of gas solid reactions at the atomic scale is of great importance for determining the mechanism of catalysis. This is especially true in the study of heterostructures because of structural correlation between the different parts. However, such experiments are challenging and have rarely been accomplished. In this work, atomic scale redox dynamics of Ag/AgCl heterostructures have been studied using in situ environmental transmission electron microscopy (ETEM) in combination with density function theory (DFT) calculations. The reduction of Ag/AgCl to Ag is likely a result of the formation of Cl vacancies while Ag+ ions accept electrons. The oxidation processmore » of Ag/AgCl has been observed: rather than direct replacement of Cl by O, the Ag/AgCl nanocatalyst was first reduced to Ag, and then Ag was oxidized to different phases of silver oxide under different O-2 partial pressures. Ag2O formed at low O-2 partial pressure, whereas AgO formed at atmospheric pressure. By combining in situ ETEM observation and DFT calculations, this structural evolution is characterized in a distinct nanoscale environment.« less

Utilizing In Situ Directional Hyperspectral Measurements to Validate Bio-Indicator Simulations for a Corn Crop Canopy

NASA Technical Reports Server (NTRS)

Cheng, Yen-Ben; Middleton, Elizabeth M.; Huemmrich, Karl F.; Zhang, Qingyuan; Campbell, Petya K. E.; Corp, Lawrence A.; Russ, Andrew L.; Kustas, William P.

2010-01-01

Two radiative transfer canopy models, SAIL and the two-layer Markov-Chain Canopy Reflectance Model (MCRM), were coupled with in situ leaf optical properties to simulate canopy-level spectral band ratio vegetation indices with the focus on the photochemical reflectance index in a cornfield. In situ hyperspectral measurements were made at both leaf and canopy levels. Leaf optical properties were obtained from both sunlit and shaded leaves. Canopy reflectance was acquired for eight different relative azimuth angles (psi) at three different view zenith angles (Theta (sub v)), and later used to validate model outputs. Field observations of photochemical reflectance index (PRI) for sunlit leaves exhibited lower values than shaded leaves, indicating higher light stress. Canopy PRI expressed obvious sensitivity to viewing geometry, as a function of both Theta (sub v) and psi . Overall, simulations from MCRM exhibited better agreements with in situ values than SAIL. When using only sunlit leaves as input, the MCRM-simulated PRI values showed satisfactory correlation and RMSE, as compared to in situ values. However, the performance of the MCRM model was significantly improved after defining a lower canopy layer comprised of shaded leaves beneath the upper sunlit leaf layer. Four other widely used band ratio vegetation indices were also studied and compared with the PRI results. MCRM simulations were able to generate satisfactory simulations for these other four indices when using only sunlit leaves as input; but unlike PRI, adding shaded leaves did not improve the performance of MCRM. These results support the hypothesis that the PRI is sensitive to physiological dynamics while the others detect static factors related to canopy structure. Sensitivity analysis was performed on MCRM in order to better understand the effects of structure related parameters on the PRI simulations. Leaf area index (LAI) showed the most significant impact on MCRM-simulated PRI among the parameters studied. This research shows the importance of hyperspectral and narrow band sensor studies, and especially the necessity of including the green wavelengths (e.g., 531 nm) on satellites proposing to monitor carbon dynamics of terrestrial ecosystems.

Oxygen Passivation Mediated Tunability of Trion and Excitons in MoS2

NASA Astrophysics Data System (ADS)

Gogoi, Pranjal Kumar; Hu, Zhenliang; Wang, Qixing; Carvalho, Alexandra; Schmidt, Daniel; Yin, Xinmao; Chang, Yung-Huang; Li, Lain-Jong; Sow, Chorng Haur; Neto, A. H. Castro; Breese, Mark B. H.; Rusydi, Andrivo; Wee, Andrew T. S.

2017-08-01

Using wide spectral range in situ spectroscopic ellipsometry with systematic ultrahigh vacuum annealing and in situ exposure to oxygen, we report the complex dielectric function of MoS2 isolating the environmental effects and revealing the crucial role of unpassivated and passivated sulphur vacancies. The spectral weights of the A (1.92 eV) and B (2.02 eV) exciton peaks in the dielectric function reduce significantly upon annealing, accompanied by spectral weight transfer in a broad energy range. Interestingly, the original spectral weights are recovered upon controlled oxygen exposure. This tunability of the excitonic effects is likely due to passivation and reemergence of the gap states in the band structure during oxygen adsorption and desorption, respectively, as indicated by ab initio density functional theory calculation results. This Letter unravels and emphasizes the important role of adsorbed oxygen in the optical spectra and many-body interactions of MoS2 .

In situ synthesis of silver nanoparticles uniformly distributed on polydopamine-coated silk fibers for antibacterial application.

PubMed

Lu, Zhisong; Xiao, Jing; Wang, Ying; Meng, Mei

2015-08-15

Fabrication of silver nanoparticles (AgNPs)-modified silk for antibacterial application is one of the hottest topics in the textile material research. However, the utilization of a polymer as both 3-dimensional matrix and reductant for the in-situ synthesis of AgNPs on silk fibers has not been realized. In this work, a facile, efficient and green approach was developed to in-situ grow AgNPs on the polydopamine (PDA)-functionalized silk. AgNPs with the size of 30-90 nm were uniformly deposited on the silk fiber surface with the PDA coating layer as a reduction reagent. The AgNPs exhibit excellent face-centered cubic crystalline structures. The bacterial growth curve and inhibition zone assays clearly demonstrate the antibacterial properties of the functionalized silk. Both high Ag(+) release level and long-time release profile were observed for the as-prepared AgNPs-PDA-coated silk, indicating the high-density loading of AgNPs and the possible long-term antibacterial effects. This work may provide a new method for the preparation of AgNPs-functionalized silk with antibacterial activity for the clothing and textile industry. Copyright © 2015 Elsevier Inc. All rights reserved.

Functionalization of textiles with silver and zinc oxide nanoparticles

NASA Astrophysics Data System (ADS)

Pulit-Prociak, Jolanta; Chwastowski, Jarosław; Kucharski, Arkadiusz; Banach, Marcin

2016-11-01

The paper presents a method for functionalization of textile materials using fabric dyes modified with silver or zinc oxide nanoparticles. Embedding of these nanoparticles into the structure of other materials makes that the final product is characterized by antimicrobial properties. Indigo and commercially available dye were involved in studies. It is worth to note that silver nanoparticles were obtained in-situ in the reaction of preparing indigo dye and in the process of preparing commercial dye baths. Such a method allows reducing technological steps. The modified dyes were used for dyeing of cotton fibers. The antimicrobial properties of final textile materials were studied. Saccharomyces cerevisiae strain was used in microbiological test. The results confirmed biocidal activity of prepared materials.

The effect of carbon nanotubes functionalization on the band-gap energy of TiO2-CNT nanocomposite

NASA Astrophysics Data System (ADS)

Shahbazi, Hessam; Shafei, Alireza; Sheibani, Saeed

2018-01-01

In this paper the morphology and structure of TiO2-CNT nanocomposite powder obtained by an in situ sol-gel process were investigated. The synthesized nanocomposite powders were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and diffuse reflectance spectroscopy (DRS). The effect of functionalizing of CNT on the properties was studied. XRD results showed amorphous structure before calcination. Also, anatase phase TiO2 was formed after calcination at 400 °C. The SEM results indicate different distributions of TiO2 on CNTs. As a result, well dispersed TiO2 microstructure on the surface of CNTs was observed after functionalizing, while compact and large aggregated particles were found without functionalizing. The average thickness of uniform and well-defined coated TiO2 layer was in the range of 30-40 nm. The DRS results have determined the reflective properties and band gap energies of nanocomposite powders and have shown that functionalizing of CNTs caused the change of band-gap energy from 2.98 to 2.87 eV.

Smart multifunctional core-shell nanospheres with drug and gene co-loaded for enhancing the therapeutic effect in a rat intracranial tumor model

NASA Astrophysics Data System (ADS)

Wang, Hanjie; Su, Wenya; Wang, Sheng; Wang, Xiaomin; Liao, Zhenyu; Kang, Chunsheng; Han, Lei; Chang, Jin; Wang, Guangxiu; Pu, Peiyu

2012-09-01

Glioblastoma with high mortality has been one of the most serious cancers threatening human health. Because of the present treatment limitations, there is an urgent need to construct a multifunctional vesicle for enhancing the treatment of in situ malignant glioblastoma. In our study, drug and gene co-loaded magnetic PLGA/multifunctional polymeric liposome (magnetic PLGA/MPLs) core-shell nanospheres were constructed. They were mainly self-assembled from two parts: hydrophobic PLGA cores that can load drugs and magnetic nanocrystals; and polymeric lipid shells anchored with functional molecules such as PEG chains, TAT peptides and RGD peptides that can help the vectors to condense the gene, prolong the circulation time, cross the blood brain barrier and target delivery to the cancer tissue. The results showed that the magnetic PLGA/MPLs nanosphere has a nanosized core-shell structure, can achieve sustained drug release and has good DNA binding abilities. Importantly, compared with the control group and other groups with single functionality, it can co-deliver the drug and gene into the same cell in vitro and show the strongest inhibiting effect on the growth of the in situ malignant glioblastoma in vivo. All of these results indicated that the different functional components of magnetic PLGA/MPLs, can form an organic whole and none of them can be dispensed with. The magnetic PLGA/MPLs nanosphere may be another option for treatment of glioblastoma.Glioblastoma with high mortality has been one of the most serious cancers threatening human health. Because of the present treatment limitations, there is an urgent need to construct a multifunctional vesicle for enhancing the treatment of in situ malignant glioblastoma. In our study, drug and gene co-loaded magnetic PLGA/multifunctional polymeric liposome (magnetic PLGA/MPLs) core-shell nanospheres were constructed. They were mainly self-assembled from two parts: hydrophobic PLGA cores that can load drugs and magnetic nanocrystals; and polymeric lipid shells anchored with functional molecules such as PEG chains, TAT peptides and RGD peptides that can help the vectors to condense the gene, prolong the circulation time, cross the blood brain barrier and target delivery to the cancer tissue. The results showed that the magnetic PLGA/MPLs nanosphere has a nanosized core-shell structure, can achieve sustained drug release and has good DNA binding abilities. Importantly, compared with the control group and other groups with single functionality, it can co-deliver the drug and gene into the same cell in vitro and show the strongest inhibiting effect on the growth of the in situ malignant glioblastoma in vivo. All of these results indicated that the different functional components of magnetic PLGA/MPLs, can form an organic whole and none of them can be dispensed with. The magnetic PLGA/MPLs nanosphere may be another option for treatment of glioblastoma. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr31263h

Porous Pt-Ni Nanowires within In Situ Generated Metal-Organic Frameworks for Highly Chemoselective Cinnamaldehyde Hydrogenation.

PubMed

Zhang, Nan; Shao, Qi; Wang, Pengtang; Zhu, Xing; Huang, Xiaoqing

2018-05-01

Although chemoselective hydrogenation of unsaturated aldehydes is the major route to highly valuable industrially demanded unsaturated alcohols, it is still challenging, as the production of saturated aldehydes is more favorable over unsaturated alcohols from the view of thermodynamics. By combining the structural features of porous nanowires (NWs) and metal-organic frameworks (MOFs), a unique class of porous Pt-Ni NWs in situ encapsuled by MOFs (Pt-Ni NWs@Ni/Fex-MOFs) is designed to enhance the unsaturated alcohols selectivity in the cinnamaldehyde (CAL) hydrogenation. A detailed catalytic study shows that the porous Pt-Ni NWs@Ni/Fe x -MOFs exhibit volcano-type activity and selectivity in CAL hydrogenation as a function of Fe content. The optimized porous PtNi 2.20 NWs@Ni/Fe 4 -MOF is highly active and selective with 99.5% CAL conversion and 83.3% cinnamyl alcohol selectivity due to the confinement effect, appropriate thickness of MOF and its optimized electronic structure, and excellent durability with negligible activity and selectivity loss after five runs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale Ex-Situ Thermal Impulse Sensors for Structural Fire Forensics.

PubMed

Anderson, Benjamin R; Gese, Natalie; Gunawidjaja, Ray; Eilers, Hergen

2017-01-01

We develop nanoscale ex situ thermal impulse (i.e., the temperature and duration of a heating event) sensors for structural fire forensics using a mixture of two lanthanide-doped oxide precursors (precursor Eu:ZrO 2 and precursor Dy:Y 2 O 3 ) that undergo irreversible phase changes when heated. These changes are probed using photoluminescence (PL) spectroscopy with the PL spectra being dependent on the thermal impulse (TI) experienced by the sensors. By correlating the PL spectra to different in-lab TIs, we are able to produce a spectroscopic calibration for our sensors. This calibration allows us to determine an unknown TI of a heating event using only the PL spectrum of the heated TI sensors. In this study, we report on the calibration of these sensors for isothermal heating durations up to 600 s and isothermal temperatures up to 1273 K. Using this calibration, we also demonstrate their ability to determine an unknown TI and demonstrate their functionality when dispersed into paint, which is heated in the presence of drywall.

Manufacturing technology of integrated textile-based sensor networks for in situ monitoring applications of composite wind turbine blades

NASA Astrophysics Data System (ADS)

Haentzsche, Eric; Mueller, Ralf; Huebner, Matthias; Ruder, Tristan; Unger, Reimar; Nocke, Andreas; Cherif, Chokri

2016-10-01

Based on in situ strain sensors consisting of piezo-resistive carbon filament yarns (CFYs), which have been successfully integrated into textile reinforcement structures during their textile-technological manufacturing process, a continuous load of fibre-reinforced plastic (FRP) components has been realised. These sensors are also suitable for structural health monitoring (SHM) applications. The two-dimensional sensor layout is made feasible by the usage of a modular warp yarn path manipulation unit. Using a functional model of a small wind turbine blade in thermoset composite design, the sensor function for basic SHM applications (e.g. static load monitoring) are demonstrated. Any mechanical loads along the pressure or suction side of the wind turbine blade can be measured and calculated via a correlative change in resistance of the CFYs within the textile reinforcement plies. Performing quasi-static load tests on both tensile specimen and full-scale wind turbine blade, elementary results have been obtained concerning electro-mechanical behaviour and spatial resolution of global and even local static stresses according to the CFY sensor integration length. This paper demonstrates the great potential of textile-based and textile-technological integrated sensors in reinforcement structures for future SHM applications of FRPs.

In situ characterization of N-carboxy anhydride polymerization in nanoporous anodic alumina.

PubMed

Lau, K H Aaron; Duran, Hatice; Knoll, Wolfgang

2009-03-12

Poly(gamma-benzyl-L-glutamate) (PBLG) has been a popular model polypeptide for a range of physicochemical studies, and its modifiable ester side chains make it an attractive platform for various potential applications. Thin films of Poly(gamma-benzyl-L-glutamate) PBLG were surface grafted within nanoporous anodic alumina (AAO) by surface-initiated polymerization of the N-carboxy anhydride of benzyl-L-glutamate (BLG-NCA). The grafting process was characterized by optical waveguide spectroscopy (OWS), infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). OWS was able to track the PBLG layer thickness increase in situ, and ex situ FT-IR gave complementary information on the PBLG chain's secondary structure. Transitions in the PBLG growth rate could be correlated with transitions in the polypeptide secondary structure. The emergence of a three-dimensional, anisotropic PBLG morphology within the cylindrical pores of the AAO membrane was also identified as the grafted PBLG average layer thickness increased. Comparison of the PBLG/AAO results with those on a planar silicon dioxide surface indicated that both the conformational transitions and the PBLG nanostructure development could be attributed to the confining geometry within the pores of the nanoporous AAO matrix. The use of a nanoporous AAO matrix, combined with the surface grafting of a thin film of PBLG chains with multiple modifiable side chains, could potentially offer a nanoporous platform with a very high density of functional sites.

Crustal seismic anisotropy and structure from textural and seismic investigations in the Cycladic region, Greece

NASA Astrophysics Data System (ADS)

Cossette, Élise; Schneider, David; Audet, Pascal; Grasemann, Bernhard

2016-04-01

Seismic anisotropy data are often used to resolve rock structures and deformation styles in the crust based on compilations of rock properties that may not be representative of the exposed geology. We use teleseismic receiver functions jointly with in situ rock property data to constrain the seismic structure and anisotropy of the crust in the Cyclades, Greece, located in the back arc region of the Hellenic subduction zone. Crystallographic preferred orientations (CPOs) via electron backscatter diffraction (EBSD) analyses were measured on a suite of samples representative of different structural depths along the West Cycladic Detachment System; average seismic properties of the rocks were calculated with the Voigt-Reuss-Hill average of the single minerals' elastic stiffness tensor. The calcitic and quartzitic rocks have P- and S-wave velocity anisotropies (AVp, AVs) averaging 8.1% and 7.1%, respectively. The anisotropy increases with depth represented by blueschist assemblages, with AVp averaging 20.3% and AVs averaging 14.5% due to the content of aligned glaucophane and mica, which strongly control the seismic properties of the rocks. Localized anisotropies of very high magnitude are caused by the presence of mica schists as they possess the strongest anisotropies, with values of ~25% for AVp and AVs. The direction of the fast and slow P-wave velocities occur parallel and perpendicular to the foliation, respectively, for most samples. The fast propagation has the same NE-SW orientation as the lithospheric stretching direction present in the Cyclades since the Late Oligocene. The maximum shear wave anisotropy is subhorizontal, similarly concordant with mineral alignment that developed during back-arc extension. Our results strongly favor radial anisotropy in the Aegean mid-crust over azimuthal anisotropy. The receiver function data indicate that the Moho is relatively flat at 25 km depth in the south and deepens to 33 km in the north, consistent with previous studies, and reveal an intra-crustal discontinuity at depth varying from 3 to 11 km, mostly observed in the south-central Aegean. Harmonic decomposition of the receiver functions further indicates layering of both shallow and deep crustal anisotropy related to crustal structures. We model synthetic receiver functions based on constraints from the in situ rock properties that we measured using the EBSD technique. Our results indicate that the shallow upper crustal layer is characterized by metapelites with ~5% anisotropy, underlain by a 20 km thick and anisotropic layer of possible high-pressure rocks comprising blueschist and eclogite and/or restitic crust as a consequence of Miocene magmatism. Seismic anisotropy models require a sub-vertical axis of hexagonal symmetry in the upper crust (i.e. radial anisotropy), consistent with in situ rock data. Finally, a thinned crust is likely caused by back-arc extension associated with elevated sub-crustal temperatures, in agreement with thermal isostasy models of back arcs. This study demonstrates the importance of integrating rock textural data with seismic velocity profiles in the interpretation of crustal architecture.

Sample environment for in situ synchrotron corrosion studies of materials in extreme environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elbakhshwan, Mohamed S.; Gill, Simerjeet K.; Motta, Arthur T.

A new in situ sample environment has been designed and developed to study the interfacial interactions of nuclear cladding alloys with high temperature steam. The sample environment is particularly optimized for synchrotron X-ray diffraction (XRD) studies for in situ structural analysis. The sample environment is highly corrosion resistant and can be readily adapted for steam environments. The in situ sample environment design complies with G2 ASTM standards for studying corrosion in zirconium and its alloys and offers remote temperature and pressure monitoring during the in situ data collection. The use of the in situ sample environment is exemplified by monitoringmore » the oxidation of metallic zirconium during exposure to steam at 350°C. Finally, the in situ sample environment provides a powerful tool for fundamental understanding of corrosion mechanisms by elucidating the substoichiometric oxide phases formed during early stages of corrosion, which can provide a better understanding the oxidation process.« less

Sample environment for in situ synchrotron corrosion studies of materials in extreme environments

DOE PAGES

Elbakhshwan, Mohamed S.; Gill, Simerjeet K.; Motta, Arthur T.; ...

2016-10-25

A new in situ sample environment has been designed and developed to study the interfacial interactions of nuclear cladding alloys with high temperature steam. The sample environment is particularly optimized for synchrotron X-ray diffraction (XRD) studies for in situ structural analysis. The sample environment is highly corrosion resistant and can be readily adapted for steam environments. The in situ sample environment design complies with G2 ASTM standards for studying corrosion in zirconium and its alloys and offers remote temperature and pressure monitoring during the in situ data collection. The use of the in situ sample environment is exemplified by monitoringmore » the oxidation of metallic zirconium during exposure to steam at 350°C. Finally, the in situ sample environment provides a powerful tool for fundamental understanding of corrosion mechanisms by elucidating the substoichiometric oxide phases formed during early stages of corrosion, which can provide a better understanding the oxidation process.« less

Dynamic Succession of Groundwater Functional Microbial Communities in Response to Emulsified Vegetable Oil Amendment during Sustained In Situ U(VI) Reduction

DOE PAGES

Zhang, Ping; Wu, Wei-Min; Van Nostrand, Joy D.; ...

2015-04-10

A pilot-scale field experiment demonstrated that a one-time amendment of emulsified vegetable oil (EVO) reduced groundwater U(VI) concentrations for 1 year in a fast-flowing aquifer. However, little is known about how EVO amendment stimulates the functional gene composition, structure, and dynamics of groundwater microbial communities toward prolonged U(VI) reduction. In this paper, we hypothesized that EVO amendment would shift the functional gene composition and structure of groundwater microbial communities and stimulate key functional genes/groups involved in EVO biodegradation and reduction of electron acceptors in the aquifer. To test these hypotheses, groundwater microbial communities after EVO amendment were analyzed using amore » comprehensive functional gene microarray. Our results showed that EVO amendment stimulated sequential shifts in the functional composition and structure of groundwater microbial communities. Particularly, the relative abundance of key functional genes/groups involved in EVO biodegradation and the reduction of NO 3 -, Mn(IV), Fe(III), U(VI), and SO 4 2- significantly increased, especially during the active U(VI) reduction period. The relative abundance for some of these key functional genes/groups remained elevated over 9 months. Montel tests suggested that the dynamics in the abundance, composition, and structure of these key functional genes/groups were significantly correlated with groundwater concentrations of acetate, NO 3 -, Mn(II), Fe(II), U(VI), and SO 4 2-. Our results suggest that EVO amendment stimulated dynamic succession of key functional microbial communities. Finally, this study improves our understanding of the composition, structure, and function changes needed for groundwater microbial communities to sustain a long-term U(VI) reduction.« less

Dynamic Succession of Groundwater Functional Microbial Communities in Response to Emulsified Vegetable Oil Amendment during Sustained In Situ U(VI) Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Ping; Wu, Wei-Min; Van Nostrand, Joy D.

A pilot-scale field experiment demonstrated that a one-time amendment of emulsified vegetable oil (EVO) reduced groundwater U(VI) concentrations for 1 year in a fast-flowing aquifer. However, little is known about how EVO amendment stimulates the functional gene composition, structure, and dynamics of groundwater microbial communities toward prolonged U(VI) reduction. In this paper, we hypothesized that EVO amendment would shift the functional gene composition and structure of groundwater microbial communities and stimulate key functional genes/groups involved in EVO biodegradation and reduction of electron acceptors in the aquifer. To test these hypotheses, groundwater microbial communities after EVO amendment were analyzed using amore » comprehensive functional gene microarray. Our results showed that EVO amendment stimulated sequential shifts in the functional composition and structure of groundwater microbial communities. Particularly, the relative abundance of key functional genes/groups involved in EVO biodegradation and the reduction of NO 3 -, Mn(IV), Fe(III), U(VI), and SO 4 2- significantly increased, especially during the active U(VI) reduction period. The relative abundance for some of these key functional genes/groups remained elevated over 9 months. Montel tests suggested that the dynamics in the abundance, composition, and structure of these key functional genes/groups were significantly correlated with groundwater concentrations of acetate, NO 3 -, Mn(II), Fe(II), U(VI), and SO 4 2-. Our results suggest that EVO amendment stimulated dynamic succession of key functional microbial communities. Finally, this study improves our understanding of the composition, structure, and function changes needed for groundwater microbial communities to sustain a long-term U(VI) reduction.« less

Biomimetic cellular metals-using hierarchical structuring for energy absorption.

PubMed

Bührig-Polaczek, A; Fleck, C; Speck, T; Schüler, P; Fischer, S F; Caliaro, M; Thielen, M

2016-07-19

Fruit walls as well as nut and seed shells typically perform a multitude of functions. One of the biologically most important functions consists in the direct or indirect protection of the seeds from mechanical damage or other negative environmental influences. This qualifies such biological structures as role models for the development of new materials and components that protect commodities and/or persons from damage caused for example by impacts due to rough handling or crashes. We were able to show how the mechanical properties of metal foam based components can be improved by altering their structure on various hierarchical levels inspired by features and principles important for the impact and/or puncture resistance of the biological role models, rather than by tuning the properties of the bulk material. For this various investigation methods have been established which combine mechanical testing with different imaging methods, as well as with in situ and ex situ mechanical testing methods. Different structural hierarchies especially important for the mechanical deformation and failure behaviour of the biological role models, pomelo fruit (Citrus maxima) and Macadamia integrifolia, were identified. They were abstracted and transferred into corresponding structural principles and thus hierarchically structured bio-inspired metal foams have been designed. A production route for metal based bio-inspired structures by investment casting was successfully established. This allows the production of complex and reliable structures, by implementing and combining different hierarchical structural elements found in the biological concept generators, such as strut design and integration of fibres, as well as by minimising casting defects. To evaluate the structural effects, similar investigation methods and mechanical tests were applied to both the biological role models and the metallic foams. As a result an even deeper quantitative understanding of the form-structure-function relationship of the biological concept generators as well as the bio-inspired metal foams was achieved, on deeper hierarchical levels and overarching different levels.

Hierarchically structured transparent hybrid membranes by in situ growth of mesostructured organosilica in host polymer

NASA Astrophysics Data System (ADS)

Vallé, Karine; Belleville, Philippe; Pereira, Franck; Sanchez, Clément

2006-02-01

The elaborate performances characterizing natural materials result from functional hierarchical constructions at scales ranging from nanometres to millimetres, each construction allowing the material to fit the physical or chemical demands occurring at these different levels. Hierarchically structured materials start to demonstrate a high input in numerous promising applied domains such as sensors, catalysis, optics, fuel cells, smart biologic and cosmetic vectors. In particular, hierarchical hybrid materials permit the accommodation of a maximum of elementary functions in a small volume, thereby optimizing complementary possibilities and properties between inorganic and organic components. The reported strategies combine sol-gel chemistry, self-assembly routes using templates that tune the material's architecture and texture with the use of larger inorganic, organic or biological templates such as latex, organogelator-derived fibres, nanolithographic techniques or controlled phase separation. We propose an approach to forming transparent hierarchical hybrid functionalized membranes using in situ generation of mesostructured hybrid phases inside a non-porogenic hydrophobic polymeric host matrix. We demonstrate that the control of the multiple affinities existing between organic and inorganic components allows us to design the length-scale partitioning of hybrid nanomaterials with tuned functionalities and desirable size organization from ångström to centimetre. After functionalization of the mesoporous hybrid silica component, the resulting membranes have good ionic conductivity offering interesting perspectives for the design of solid electrolytes, fuel cells and other ion-transport microdevices.

In-situ determination of amine/epoxy and carboxylic/epoxy exothermic heat of reaction on surface of modified carbon nanotubes and structural verification of covalent bond formation

NASA Astrophysics Data System (ADS)

Neves, Juliana C.; de Castro, Vinícius G.; Assis, Ana L. S.; Veiga, Amanda G.; Rocco, Maria Luiza M.; Silva, Glaura G.

2018-04-01

An effective nanofiller-matrix interaction is considered crucial to produce enhanced nanocomposites. Nevertheless, there is lack of experiments focused in the direct measurement of possible filler-matrix covalent linkage, which was the main goal of this work for a carbon nanotube (CNT)/epoxy system. CNT were functionalized with oxygenated (ox) functions and further with triethylenetetramine (TETA). An in-situ determination methodology of epoxy-CNTs heat of reaction was developed by Differential Scanning Calorimetry (DSC). Values of -(8.7 ± 0.4) and -(6.0 ± 0.6) J/g were observed for epoxy with CNT-ox and CNT-TETA, respectively. These results confirm the occurrence of covalent bonds for both functionalized CNTs, a very important information due to the literature generally disregard this possibility for oxygenated functions. The higher value obtained for CNT-ox can be attributed to a not complete amidation and to steric impediments in the CNT-TETA structure. The modified CNTs produced by DSC experiments were then characterized by X-Ray Photoelectron Spectroscopy, Transmission Electron Microscopy and Thermogravimetry, which confirmed the covalent linkage. This characterization methodology can be used to verify the occurrence of covalent bonds in various nanocomposites with a quantitative evaluation, providing data for better understanding of the role of CNT functional groups and for tailoring its interface with polymers.

Neuroanatomy of the killer whale (Orcinus orca): a magnetic resonance imaging investigation of structure with insights on function and evolution.

PubMed

Wright, Alexandra; Scadeng, Miriam; Stec, Dominik; Dubowitz, Rebecca; Ridgway, Sam; Leger, Judy St

2017-01-01

The evolutionary process of adaptation to an obligatory aquatic existence dramatically modified cetacean brain structure and function. The brain of the killer whale (Orcinus orca) may be the largest of all taxa supporting a panoply of cognitive, sensory, and sensorimotor abilities. Despite this, examination of the O. orca brain has been limited in scope resulting in significant deficits in knowledge concerning its structure and function. The present study aims to describe the neural organization and potential function of the O. orca brain while linking these traits to potential evolutionary drivers. Magnetic resonance imaging was used for volumetric analysis and three-dimensional reconstruction of an in situ postmortem O. orca brain. Measurements were determined for cortical gray and cerebral white matter, subcortical nuclei, cerebellar gray and white matter, corpus callosum, hippocampi, superior and inferior colliculi, and neuroendocrine structures. With cerebral volume comprising 81.51 % of the total brain volume, this O. orca brain is one of the most corticalized mammalian brains studied to date. O. orca and other delphinoid cetaceans exhibit isometric scaling of cerebral white matter with increasing brain size, a trait that violates an otherwise evolutionarily conserved cerebral scaling law. Using comparative neurobiology, it is argued that the divergent cerebral morphology of delphinoid cetaceans compared to other mammalian taxa may have evolved in response to the sensorimotor demands of the aquatic environment. Furthermore, selective pressures associated with the evolution of echolocation and unihemispheric sleep are implicated in substructure morphology and function. This neuroanatomical dataset, heretofore absent from the literature, provides important quantitative data to test hypotheses regarding brain structure, function, and evolution within Cetacea and across Mammalia.

Understanding the Thermal Stability of Palladium–Platinum Core–Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vara, Madeline; Roling, Luke T.; Wang, Xue

Core–shell nanocrystals offer many advantages for heterogeneous catalysis, including precise control over both the surface structure and composition, as well as reduction in loading for rare and costly metals. Although many catalytic processes are operated at elevated temperatures, the adverse impacts of heating on the shape and structure of core–shell nanocrystals are yet to be understood. In this work, we used ex situ heating experiments to demonstrate that Pd@Pt 4L core–shell nanoscale cubes and octahedra are promising for catalytic applications at temperatures up to 400 °C. We also used in situ transmission electron microscopy to monitor the thermal stability ofmore » the core–shell nanocrystals in real time. Our results demonstrate a facet dependence for the thermal stability in terms of shape and composition. Specifically, the cubes enclosed by {100} facets readily deform shape at a temperature 300 °C lower than that of the octahedral counterparts enclosed by {111} facets. A reversed trend is observed for composition, as alloying between the Pd core and the Pt shell of an octahedron occurs at a temperature 200 °C lower than that for the cubic counterpart. Density functional theory calculations provide atomic-level explanations for the experimentally observed behaviors, demonstrating that the barriers for edge reconstruction determine the relative ease of shape deformation for cubes compared to octahedra. Furthermore, the opposite trend for alloying of the core–shell structure can be attributed to a higher propensity for subsurface Pt vacancy formation in octahedra than in cubes.« less

Understanding the Thermal Stability of Palladium–Platinum Core–Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory

DOE PAGES

Vara, Madeline; Roling, Luke T.; Wang, Xue; ...

2017-05-09

Core–shell nanocrystals offer many advantages for heterogeneous catalysis, including precise control over both the surface structure and composition, as well as reduction in loading for rare and costly metals. Although many catalytic processes are operated at elevated temperatures, the adverse impacts of heating on the shape and structure of core–shell nanocrystals are yet to be understood. In this work, we used ex situ heating experiments to demonstrate that Pd@Pt 4L core–shell nanoscale cubes and octahedra are promising for catalytic applications at temperatures up to 400 °C. We also used in situ transmission electron microscopy to monitor the thermal stability ofmore » the core–shell nanocrystals in real time. Our results demonstrate a facet dependence for the thermal stability in terms of shape and composition. Specifically, the cubes enclosed by {100} facets readily deform shape at a temperature 300 °C lower than that of the octahedral counterparts enclosed by {111} facets. A reversed trend is observed for composition, as alloying between the Pd core and the Pt shell of an octahedron occurs at a temperature 200 °C lower than that for the cubic counterpart. Density functional theory calculations provide atomic-level explanations for the experimentally observed behaviors, demonstrating that the barriers for edge reconstruction determine the relative ease of shape deformation for cubes compared to octahedra. Furthermore, the opposite trend for alloying of the core–shell structure can be attributed to a higher propensity for subsurface Pt vacancy formation in octahedra than in cubes.« less

Understanding the Thermal Stability of Palladium-Platinum Core-Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory.

PubMed

Vara, Madeline; Roling, Luke T; Wang, Xue; Elnabawy, Ahmed O; Hood, Zachary D; Chi, Miaofang; Mavrikakis, Manos; Xia, Younan

2017-05-23

Core-shell nanocrystals offer many advantages for heterogeneous catalysis, including precise control over both the surface structure and composition, as well as reduction in loading for rare and costly metals. Although many catalytic processes are operated at elevated temperatures, the adverse impacts of heating on the shape and structure of core-shell nanocrystals are yet to be understood. In this work, we used ex situ heating experiments to demonstrate that Pd@Pt 4L core-shell nanoscale cubes and octahedra are promising for catalytic applications at temperatures up to 400 °C. We also used in situ transmission electron microscopy to monitor the thermal stability of the core-shell nanocrystals in real time. Our results demonstrate a facet dependence for the thermal stability in terms of shape and composition. Specifically, the cubes enclosed by {100} facets readily deform shape at a temperature 300 °C lower than that of the octahedral counterparts enclosed by {111} facets. A reversed trend is observed for composition, as alloying between the Pd core and the Pt shell of an octahedron occurs at a temperature 200 °C lower than that for the cubic counterpart. Density functional theory calculations provide atomic-level explanations for the experimentally observed behaviors, demonstrating that the barriers for edge reconstruction determine the relative ease of shape deformation for cubes compared to octahedra. The opposite trend for alloying of the core-shell structure can be attributed to a higher propensity for subsurface Pt vacancy formation in octahedra than in cubes.

Lab on a Biomembrane: Rapid prototyping and manipulation of 2D fluidic lipid bilayers circuits

PubMed Central

Ainla, Alar; Gözen, Irep; Hakonen, Bodil; Jesorka, Aldo

2013-01-01

Lipid bilayer membranes are among the most ubiquitous structures in the living world, with intricate structural features and a multitude of biological functions. It is attractive to recreate these structures in the laboratory, as this allows mimicking and studying the properties of biomembranes and their constituents, and to specifically exploit the intrinsic two-dimensional fluidity. Even though diverse strategies for membrane fabrication have been reported, the development of related applications and technologies has been hindered by the unavailability of both versatile and simple methods. Here we report a rapid prototyping technology for two-dimensional fluidic devices, based on in-situ generated circuits of phospholipid films. In this “lab on a molecularly thin membrane”, various chemical and physical operations, such as writing, erasing, functionalization, and molecular transport, can be applied to user-defined regions of a membrane circuit. This concept is an enabling technology for research on molecular membranes and their technological use. PMID:24067786

Effect of dissolved LiCl on the ionic liquid-Au(111) interface: an in situ STM study

NASA Astrophysics Data System (ADS)

Borisenko, Natalia; Atkin, Rob; Lahiri, Abhishek; Zein El Abedin, Sherif; Endres, Frank

2014-07-01

The structure of the electrolyte/electrode interface plays a significant role in electrochemical processes. To date, most studies are focusing on understanding the interfacial structure in pure ionic liquids. In this paper in situ scanning tunnelling microscopy (STM) has been employed to elucidate the structure of the charged Au(111)-ionic liquid (1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, [Py1,4]FAP) interface in the presence of 0.1 M LiCl. The addition of the Li salt to the ionic liquid has a strong influence on the interfacial structure. In the first STM scan in situ measurements reveal that Au(111) undergoes the (22 \\times \\surd 3) ‘herringbone’ reconstruction in a certain potential regime, and there is strong evidence that the gold surface dissolves at negative electrode potentials in [Py1,4]FAP containing LiCl. Bulk deposition of Li is obtained at -2.9 V in the second STM scan.

In situ study of the growth and degradation processes in tetragonal lysozyme crystals on a silicon substrate by high-resolution X-ray diffractometry

NASA Astrophysics Data System (ADS)

Kovalchuk, M. V.; Prosekov, P. A.; Marchenkova, M. A.; Blagov, A. E.; D'yakova, Yu. A.; Tereshchenko, E. Yu.; Pisarevskii, Yu. V.; Kondratev, O. A.

2014-09-01

The results of an in situ study of the growth of tetragonal lysozyme crystals by high-resolution X-ray diffractometry are considered. The crystals are grown by the sitting-drop method on crystalline silicon substrates of different types: both on smooth substrates and substrates with artificial surface-relief structures using graphoepitaxy. The crystals are grown in a special hermetically closed crystallization cell, which enables one to obtain images with an optical microscope and perform in situ X-ray diffraction studies in the course of crystal growth. Measurements for lysozyme crystals were carried out in different stages of the crystallization process, including crystal nucleation and growth, developed crystals, the degradation of the crystal structure, and complete destruction.

Toward correlating structure and mechanics of platelets.

PubMed

Sorrentino, Simona; Studt, Jan-Dirk; Horev, Melanie Bokstad; Medalia, Ohad; Sapra, K Tanuj

2016-09-02

The primary physiological function of blood platelets is to seal vascular lesions after injury and form hemostatic thrombi in order to prevent blood loss. This task relies on the formation of strong cellular-extracellular matrix interactions in the subendothelial lesions. The cytoskeleton of a platelet is key to all of its functions: its ability to spread, adhere and contract. Despite the medical significance of platelets, there is still no high-resolution structural information of their cytoskeleton. Here, we discuss and present 3-dimensional (3D) structural analysis of intact platelets by using cryo-electron tomography (cryo-ET) and atomic force microscopy (AFM). Cryo-ET provides in situ structural analysis and AFM gives stiffness maps of the platelets. In the future, combining high-resolution structural and mechanical techniques will bring new understanding of how structural changes modulate platelet stiffness during activation and adhesion.

Effective adsorption and collection of cesium from aqueous solution using graphene oxide grown on porous alumina

NASA Astrophysics Data System (ADS)

Entani, Shiro; Honda, Mitsunori; Shimoyama, Iwao; Li, Songtian; Naramoto, Hiroshi; Yaita, Tsuyoshi; Sakai, Seiji

2018-04-01

Graphene oxide (GO) with a large surface area was synthesized by the direct growth of GO on porous alumina using chemical vapor deposition to study the Cs adsorption mechanism in aqueous solutions. Electronic structure analysis employing in situ near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy measurements clarifies the Cs atoms bond via oxygen functional groups on GO in the aqueous solution. The Cs adsorption capacity was found to be as high as 650-850 mg g-1, which indicates that the GO/porous alumina acts as an effective adsorbent with high adsorption efficiency for radioactive nuclides in aqueous solutions.

Influence of Steel Reinforcement on In-Situ Stress Evaluation in Concrete Structures by the Core-Drilling Method

NASA Astrophysics Data System (ADS)

McGinnis, M. J.; Pessiki, S.

2006-03-01

The core-drilling method is an emerging technique for evaluating in-situ stress in a concrete structure. A small hole is drilled into the structure, and the deformations in the vicinity of the hole are measured and related via elasticity theory to the stress. The method is similar to the ASTM hole-drilling strain-gauge method excepting that displacements rather than strains are the measured quantities. The technique may be considered nondestructive since the ability of the structure to perform its function is unaffected, and the hole is easily repaired. Displacement measurements in the current work are performed using 3D digital image correlation and industrial photogrammetry. The current paper addresses perturbations in the method caused by steel reinforcement within the concrete. The reinforcement is significantly stiffer than the surrounding concrete, altering the expected displacement field. A numerical investigation performed indicates an under-prediction of stress by as much as 18 percent in a heavily reinforced structure, although the effect is significantly smaller for more common amounts of reinforcement.

Influence of Steel Reinforcement on In-Situ Stress Evaluation in Concrete Structures by the Core-Drilling Method

DOE Office of Scientific and Technical Information (OSTI.GOV)

McGinnis, M. J.; Pessiki, S.

2006-03-06

The core-drilling method is an emerging technique for evaluating in-situ stress in a concrete structure. A small hole is drilled into the structure, and the deformations in the vicinity of the hole are measured and related via elasticity theory to the stress. The method is similar to the ASTM hole-drilling strain-gauge method excepting that displacements rather than strains are the measured quantities. The technique may be considered nondestructive since the ability of the structure to perform its function is unaffected, and the hole is easily repaired. Displacement measurements in the current work are performed using 3D digital image correlation andmore » industrial photogrammetry. The current paper addresses perturbations in the method caused by steel reinforcement within the concrete. The reinforcement is significantly stiffer than the surrounding concrete, altering the expected displacement field. A numerical investigation performed indicates an under-prediction of stress by as much as 18 percent in a heavily reinforced structure, although the effect is significantly smaller for more common amounts of reinforcement.« less

Structure of Carbon Nanotube Porins in Lipid Bilayers: An in Situ Small-Angle X-ray Scattering (SAXS) Study [Atomic-level structure of carbon nanotube porins in lipid bilayers: an in-situ small-angle x-ray scattering (SAXS) study

DOE PAGES

Tran, Ich C.; Tunuguntla, Ramya H.; Kim, Kyunghoon; ...

2016-06-20

Carbon nanotube porins (CNTPs), small segments of carbon nanotubes capable of forming defined pores in lipid membranes, are important future components for bionanoelectronic devices as they could provide a robust analog of biological membrane channels. Furthermore, in order to control the incorporation of these CNT channels into lipid bilayers, it is important to understand the structure of the CNTPs before and after insertion into the lipid bilayer as well as the impact of such insertion on the bilayer structure. Here we employed a noninvasive in situ probe, small-angle X-ray scattering, to study the integration of CNT porins into dioleoylphosphatidylcholine bilayers.more » These results show that CNTPs in solution are stabilized by a monolayer of lipid molecules wrapped around their outer surface. We also demonstrate that insertion of CNTPs into the lipid bilayer results in decreased bilayer thickness with the magnitude of this effect increasing with the concentration of CNTPs.« less

Molecular commonality detection using an artificial enzyme membrane for in situ one-stop biosurveillance.

PubMed

Ikeno, Shinya; Asakawa, Hitoshi; Haruyama, Tetsuya

2007-08-01

Biodetection and biosensing have been developed based on the concept of sensitivity toward specific molecules. However, current demand may require more levelheaded or far-sighted methods, especially in the field of biological safety and security. In the fields of hygiene, public safety, and security including fighting bioterrorism, the detection of biological contaminants, e.g., microorganisms, spores, and viruses, is a constant challenge. However, there is as yet no sophisticated method of detecting such contaminants in situ without oversight. The authors focused their attention on diphosphoric acid anhydride, which is a structure common to all biological phosphoric substances. Interestingly, biological phosphoric substances are peculiar substances present in all living things and include many different substances, e.g., ATP, ADP, dNTP, pyrophosphate, and so forth, all of which have a diphosphoric acid anhydride structure. The authors took this common structure as the basis of their development of an artificial enzyme membrane with selectivity for the structure common to all biological phosphoric substances and studied the possibility of its application to in situ biosurveillance sensors. The artificial enzyme membrane-based amperometric biosensor developed by the authors can detect various biological phosphoric substances, because it has a comprehensive molecular selectivity for the structure of these biological phosphoric substances. This in situ detection method of the common diphosphoric acid anhydride structure brings a unique advantage to the fabrication of in situ biosurveillance sensors for monitoring biological contaminants, e.g., microorganism, spores, and viruses, without an oversight, even if they were transformed.

Microbial community structure and function on sinking particles in the North Pacific Subtropical Gyre

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fontanez, Kristina M.; Eppley, John M.; Samo, Ty J.

Sinking particles mediate the transport of carbon and energy to the deep-sea, yet the specific microbes associated with sedimenting particles in the ocean's interior remain largely uncharacterized. In this study, we used particle interceptor traps (PITs) to assess the nature of particle-associated microbial communities collected at a variety of depths in the North Pacific Subtropical Gyre. Comparative metagenomics was used to assess differences in microbial taxa and functional gene repertoires in PITs containing a preservative (poisoned traps) compared to preservative-free traps where growth was allowed to continue in situ (live traps). Live trap microbial communities shared taxonomic and functional similaritiesmore » with bacteria previously reported to be enriched in dissolved organic matter (DOM) microcosms (e.g., Alteromonas and Methylophaga), in addition to other particle and eukaryote-associated bacteria (e.g., Flavobacteriales and Pseudoalteromonas). Poisoned trap microbial assemblages were enriched in Vibrio and Campylobacterales likely associated with eukaryotic surfaces and intestinal tracts as symbionts, pathogens, or saprophytes. The functional gene content of microbial assemblages in poisoned traps included a variety of genes involved in virulence, anaerobic metabolism, attachment to chitinaceaous surfaces, and chitin degradation. The presence of chitinaceaous surfaces was also accompanied by the co-existence of bacteria which encoded the capacity to attach to, transport and metabolize chitin and its derivatives. Distinctly different microbial assemblages predominated in live traps, which were largely represented by copiotrophs and eukaryote-associated bacterial communities. Predominant sediment trap-assocaited eukaryotic phyla included Dinoflagellata, Metazoa (mostly copepods), Protalveolata, Retaria, and Stramenopiles. In conclusion, these data indicate the central role of eukaryotic taxa in structuring sinking particle microbial assemblages, as well as the rapid responses of indigenous microbial species in the degradation of marine particulate organic matter (POM) in situ in the ocean's interior.« less

Microbial community structure and function on sinking particles in the North Pacific Subtropical Gyre

DOE PAGES

Fontanez, Kristina M.; Eppley, John M.; Samo, Ty J.; ...

2015-05-19

Sinking particles mediate the transport of carbon and energy to the deep-sea, yet the specific microbes associated with sedimenting particles in the ocean's interior remain largely uncharacterized. In this study, we used particle interceptor traps (PITs) to assess the nature of particle-associated microbial communities collected at a variety of depths in the North Pacific Subtropical Gyre. Comparative metagenomics was used to assess differences in microbial taxa and functional gene repertoires in PITs containing a preservative (poisoned traps) compared to preservative-free traps where growth was allowed to continue in situ (live traps). Live trap microbial communities shared taxonomic and functional similaritiesmore » with bacteria previously reported to be enriched in dissolved organic matter (DOM) microcosms (e.g., Alteromonas and Methylophaga), in addition to other particle and eukaryote-associated bacteria (e.g., Flavobacteriales and Pseudoalteromonas). Poisoned trap microbial assemblages were enriched in Vibrio and Campylobacterales likely associated with eukaryotic surfaces and intestinal tracts as symbionts, pathogens, or saprophytes. The functional gene content of microbial assemblages in poisoned traps included a variety of genes involved in virulence, anaerobic metabolism, attachment to chitinaceaous surfaces, and chitin degradation. The presence of chitinaceaous surfaces was also accompanied by the co-existence of bacteria which encoded the capacity to attach to, transport and metabolize chitin and its derivatives. Distinctly different microbial assemblages predominated in live traps, which were largely represented by copiotrophs and eukaryote-associated bacterial communities. Predominant sediment trap-assocaited eukaryotic phyla included Dinoflagellata, Metazoa (mostly copepods), Protalveolata, Retaria, and Stramenopiles. In conclusion, these data indicate the central role of eukaryotic taxa in structuring sinking particle microbial assemblages, as well as the rapid responses of indigenous microbial species in the degradation of marine particulate organic matter (POM) in situ in the ocean's interior.« less

A neutron-X-ray, NMR and calorimetric study of glassy Probucol synthesized using containerless techniques

NASA Astrophysics Data System (ADS)

Weber, J. K. R.; Benmore, C. J.; Tailor, A. N.; Tumber, S. K.; Neuefeind, J.; Cherry, B.; Yarger, J. L.; Mou, Q.; Weber, W.; Byrn, S. R.

2013-10-01

Acoustic levitation was used to trap 1-3 mm diameter drops of Probucol and other pharmaceutical materials in containerless conditions. Samples were studied in situ using X-ray diffraction and ex situ using neutron diffraction, NMR and DSC techniques. The materials were brought into non-equilibrium states by supersaturating solutions or by supercooling melts. The glass transition and crystallization temperatures of glassy Probucol were 29 ± 1 and 71 ± 1 °C respectively. The glassy form was stable with a shelf life of at least 8 months. A neutron/X-ray difference function of the glass showed that while molecular sub-groups remain rigid, many of the hydrogen correlations observed in the crystal become smeared out in the disordered material. The glass is principally comprised of slightly distorted Form I Probucol molecules with disordered packing rather than large changes in the individual molecular structure. Avoiding surface contact-induced nucleation provided access to highly non-equilibrium phases and enabled synthesis of phase-pure glasses.

Thermal expansion behavior study of Co nanowire array with in situ x-ray diffraction and x-ray absorption fine structure techniques

NASA Astrophysics Data System (ADS)

Mo, Guang; Cai, Quan; Jiang, Longsheng; Wang, Wei; Zhang, Kunhao; Cheng, Weidong; Xing, Xueqing; Chen, Zhongjun; Wu, Zhonghua

2008-10-01

In situ x-ray diffraction and x-ray absorption fine structure techniques were used to study the structural change of ordered Co nanowire array with temperature. The results show that the Co nanowires are polycrystalline with hexagonal close packed structure without phase change up until 700 °C. A nonlinear thermal expansion behavior has been found and can be well described by a quadratic equation with the first-order thermal expansion coefficient of 4.3×10-6/°C and the second-order thermal expansion coefficient of 5.9×10-9/°C. The mechanism of this nonlinear thermal expansion behavior is discussed.

{ital In-situ} x-ray investigation of hydrogen charging in thin film bimetallic electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jisrawi, N.M.; Wiesmann, H.; Ruckman, M.W.

Hydrogen uptake and discharge by thin metallic films under potentiostatic control was studied using x-ray diffraction at the National Synchrotron Light Source (NSLS). The formation of metal-hydrogen phases in Pd, Pd-capped Nb and Pd/Nb multilayer electrode structures was deduced from x-ray diffraction data and correlated with the cyclic voltammetry (CV) peaks. The x-ray data was also used to construct a plot of the hydrogen concentration as a function of cell potential for a multilayered thin film. {copyright} {ital 1997 Materials Research Society.}

Synthesis and application of in-situ molecularly imprinted silica monolithic in pipette-tip solid-phase microextraction for the separation and determination of gallic acid in orange juice samples.

PubMed

Arabi, Maryam; Ghaedi, Mehrorang; Ostovan, Abbas

2017-03-24

A novel strategy was presented for the synthesis and application of functionalized silica monolithic as artificial receptor of gallic acid at micro-pipette tip. A sol-gel process was used to prepare the sorbent. In this in-situ polymerization reaction, tetraethyl orthosilicate (TEOS), 3-aminopropyl trimethoxysilane (APTMS), gallic acid and thiourea were used, respectively, as cross-linker, functionalized monomer, template and precursor to make crack-free and non-fragile structure. Such durable and inexpensive in-situ monolithic was successfully employed as useful tool for highly efficient extraction of gallic acid from orange juice samples. The effective parameters in extraction recovery were investigated and optimum conditions were obtained using experimental design methodology. Applying HPLC-UV for separation quantification at optimal conditions, the gallic acid was efficiently extracted without significant matrix interference. Good linearity for gallic acid in the range of 0.02-5.0mgL -1 with correlation coefficients of R 2 >0.999 revealed well applicability of the method for trace analysis. Copyright © 2017. Published by Elsevier B.V.

Visualizing Viral Protein Structures in Cells Using Genetic Probes for Correlated Light and Electron Microscopy

PubMed Central

Ou, Horng D.; Deerinck, Thomas J.; Bushong, Eric; Ellisman, Mark H.; O’Shea, Clodagh C.

2015-01-01

Structural studies of viral proteins most often use high-resolution techniques such as X-ray crystallography, nuclear magnetic resonance, single particle negative stain, or cryo-electron microscopy (EM) to reveal atomic interactions of soluble, homogeneous viral proteins or viral protein complexes. Once viral proteins or complexes are separated from their host’s cellular environment, their natural in-situ structure and details of how they interact with other cellular components may be lost. EM has been an invaluable tool in virology since its introduction in the late 1940’s and subsequent application to cells in the 1950’s. EM studies have expanded our knowledge of viral entry, viral replication, alteration of cellular components, and viral lysis. Most of these early studies were focused on conspicuous morphological cellular changes, because classic EM metal stains were designed to highlight classes of cellular structures rather than specific molecular structures. Much later, to identify viral proteins inducing specific structural configurations at the cellular level, immunostaining with a primary antibody followed by colloidal gold secondary antibody was employed to mark the location of specific viral proteins. This technique can suffer from artifacts in cellular ultrastructure due to compromises required to provide access to the immuno-reagents. Immunolocalization methods also require the generation of highly specific antibodies, which may not be available for every viral protein. Here we discuss new methods to visualize viral proteins and structures at high resolutions in-situ using correlated light and electron microscopy (CLEM). We discuss the use of genetically encoded protein fusions that oxidize diaminobenzidine (DAB) into an osmiophilic polymer that can be visualized by EM. Detailed protocols for applying the genetically encoded photo-oxidizing protein MiniSOG to a viral protein, photo-oxidation of the fusion protein to yield DAB polymer staining, and preparation of photo-oxidized samples for TEM and serial block-face scanning EM (SBEM) for large-scale volume EM data acquisition are also presented. As an example, we discuss the recent multi-scale analysis of Adenoviral protein E4-ORF3 that reveals a new type of multi-functional polymer that disrupts multiple cellular proteins. This new capability to visualize unambiguously specific viral protein structures at high resolutions in the native cellular environment is revealing new insights into how they usurp host proteins and functions to drive pathological viral replication. PMID:26066760

Visualizing viral protein structures in cells using genetic probes for correlated light and electron microscopy.

PubMed

Ou, Horng D; Deerinck, Thomas J; Bushong, Eric; Ellisman, Mark H; O'Shea, Clodagh C

2015-11-15

Structural studies of viral proteins most often use high-resolution techniques such as X-ray crystallography, nuclear magnetic resonance, single particle negative stain, or cryo-electron microscopy (EM) to reveal atomic interactions of soluble, homogeneous viral proteins or viral protein complexes. Once viral proteins or complexes are separated from their host's cellular environment, their natural in situ structure and details of how they interact with other cellular components may be lost. EM has been an invaluable tool in virology since its introduction in the late 1940's and subsequent application to cells in the 1950's. EM studies have expanded our knowledge of viral entry, viral replication, alteration of cellular components, and viral lysis. Most of these early studies were focused on conspicuous morphological cellular changes, because classic EM metal stains were designed to highlight classes of cellular structures rather than specific molecular structures. Much later, to identify viral proteins inducing specific structural configurations at the cellular level, immunostaining with a primary antibody followed by colloidal gold secondary antibody was employed to mark the location of specific viral proteins. This technique can suffer from artifacts in cellular ultrastructure due to compromises required to provide access to the immuno-reagents. Immunolocalization methods also require the generation of highly specific antibodies, which may not be available for every viral protein. Here we discuss new methods to visualize viral proteins and structures at high resolutions in situ using correlated light and electron microscopy (CLEM). We discuss the use of genetically encoded protein fusions that oxidize diaminobenzidine (DAB) into an osmiophilic polymer that can be visualized by EM. Detailed protocols for applying the genetically encoded photo-oxidizing protein MiniSOG to a viral protein, photo-oxidation of the fusion protein to yield DAB polymer staining, and preparation of photo-oxidized samples for TEM and serial block-face scanning EM (SBEM) for large-scale volume EM data acquisition are also presented. As an example, we discuss the recent multi-scale analysis of Adenoviral protein E4-ORF3 that reveals a new type of multi-functional polymer that disrupts multiple cellular proteins. This new capability to visualize unambiguously specific viral protein structures at high resolutions in the native cellular environment is revealing new insights into how they usurp host proteins and functions to drive pathological viral replication. Copyright © 2015 Elsevier Inc. All rights reserved.

Mechanical properties of in situ consolidated nanocrystalline multi-phase Al-Pb-W alloy studied by nanoindentation

NASA Astrophysics Data System (ADS)

Varam, Sreedevi; Prasad, Muvva D.; Rao, K. Bhanu Sankara; Rajulapati, Koteswararao V.

2016-12-01

Formation of chunks of various sizes ranging between 2 and 6 mm was achieved using high-energy ball milling in Al-1at.%Pb-1at.%W alloy system at room temperature during milling itself, aiding in in situ consolidation. X-ray diffraction and transmission electron microscopy (TEM) studies indicate the formation of multi-phase structure with nanocrystalline structural features. From TEM data, an average grain size of 23 nm was obtained for Al matrix and the second-phase particles were around 5 nm. A high strain rate sensitivity (SRS) of 0.071 ± 0.004 and an activation volume of 4.71b3 were measured using nanoindentation. Modulus mapping studies were carried out using Berkovich tip in dynamic mechanical analysis mode coupled with in situ scanning probe microscopy imaging. The salient feature of this investigation is highlighting the role of different phases, their crystal structures and the resultant interfaces on the overall SRS and activation volume of a multi-phase nc material.

Assessing Chemical Transformation of Reactive, Interfacial Thin Films Made of End-Tethered Poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) Chains

DOE PAGES

Aden, Bethany; Kite, Camille M.; Hopkins, Benjamin W.; ...

2017-01-24

Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize these layers in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends onmore » the size of the amine, the grafting density of brush chains, and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. In addition, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. In conclusion, these findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.« less

An in situ approach to study trace element partitioning in the laser heated diamond anvil cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petitgirard, S.; Mezouar, M.; Borchert, M.

2012-01-15

Data on partitioning behavior of elements between different phases at in situ conditions are crucial for the understanding of element mobility especially for geochemical studies. Here, we present results of in situ partitioning of trace elements (Zr, Pd, and Ru) between silicate and iron melts, up to 50 GPa and 4200 K, using a modified laser heated diamond anvil cell (DAC). This new experimental set up allows simultaneous collection of x-ray fluorescence (XRF) and x-ray diffraction (XRD) data as a function of time using the high pressure beamline ID27 (ESRF, France). The technique enables the simultaneous detection of sample meltingmore » based to the appearance of diffuse scattering in the XRD pattern, characteristic of the structure factor of liquids, and measurements of elemental partitioning of the sample using XRF, before, during and after laser heating in the DAC. We were able to detect elements concentrations as low as a few ppm level (2-5 ppm) on standard solutions. In situ measurements are complimented by mapping of the chemical partitions of the trace elements after laser heating on the quenched samples to constrain the partitioning data. Our first results indicate a strong partitioning of Pd and Ru into the metallic phase, while Zr remains clearly incompatible with iron. This novel approach extends the pressure and temperature range of partitioning experiments derived from quenched samples from the large volume presses and could bring new insight to the early history of Earth.« less

Probing Local Ionic Dynamics in Functional Oxides: From Nanometer to Atomic Scale

NASA Astrophysics Data System (ADS)

Kalinin, Sergei

2014-03-01

Vacancy-mediated electrochemical reactions in oxides underpin multiple applications ranging from electroresistive memories, to chemical sensors to energy conversion systems such as fuel cells. Understanding the functionality in these systems requires probing reversible (oxygen reduction/evolution reaction) and irreversible (cathode degradation and activation, formation of conductive filaments) electrochemical processes. In this talk, I summarize recent advances in probing and controlling these transformations locally on nanometer level using scanning probe microscopy. The localized tip concentrates the electric field in the nanometer scale volume of material, inducing local transition. Measured simultaneously electromechanical response (piezoresponse) or current (conductive AFM) provides the information on the bias-induced changes in material. Here, I illustrate how these methods can be extended to study local electrochemical transformations, including vacancy dynamics in oxides such as titanates, LaxSr1-xCoO3, BiFeO3, and YxZr1-xO2. The formation of electromechanical hysteresis loops and their bias-, temperature- and environment dependences provide insight into local electrochemical mechanisms. In materials such as lanthanum-strontium cobaltite, mapping both reversible vacancy motion and vacancy ordering and static deformation is possible, and can be corroborated by post mortem STEM/EELS studies. In ceria, a broad gamut of electrochemical behaviors is observed as a function of temperature and humidity. The possible strategies for elucidation ionic motion at the electroactive interfaces in oxides using high-resolution electron microscopy and combined ex-situ and in-situ STEM-SPM studies are discussed. In the second part of the talk, probing electrochemical phenomena on in-situ grown surfaces with atomic resolution is illustrated. I present an approach based on the multivariate statistical analysis of the coordination spheres of individual atoms to reveal preferential structures and symmetries. The relevant statistical techniques including k-means clustering, principal component analysis, and Baesian unmixing are briefly intriduced. This approach is illustrated for several systems, including chemical phase identification, mapping ferroic variants, and probing topological and structural defects, and provides real space view on surface atomic processes. Research supported (SVK) by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division and partially performed at the Center for Nanophase Materials Sciences (AK, SJ), a DOE-BES user facility.

Intracellular degradation of chemically functionalized carbon nanotubes using a long-term primary microglial culture model.

PubMed

Bussy, Cyrill; Hadad, Caroline; Prato, Maurizio; Bianco, Alberto; Kostarelos, Kostas

2016-01-07

Chemically functionalized carbon nanotubes (f-CNTs) have been used in proof-of-concept studies to alleviate debilitating neurological conditions. Previous in vivo observations in brain tissue have suggested that microglia - acting as resident macrophages of the brain - play a critical role in the internalization of f-CNTs and their partial in situ biodegradation following a stereotactic administration in the cortex. At the same time, several reports have indicated that immune cells such as neutrophils, eosinophils and even macrophages could participate in the processing of carbon nanomaterials via oxidation processes leading to degradation, with surface properties acting as modulators of CNT biodegradability. In this study we questioned whether degradability of f-CNTs within microglia could be modulated depending on the type of surface functionalization used. We investigated the kinetics of degradation of multi-walled carbon nanotubes (MWNTs) functionalized via different chemical strategies that were internalized within isolated primary microglia over three months. A cellular model of rat primary microglia that can be maintained in cell culture for a long period of time was first developed. The Raman structural signature of the internalized f-CNTs was then studied directly in cells over a period of up to three months, following a single exposure to a non-cytotoxic concentration of three different f-CNTs (carboxylated, aminated and both carboxylated and aminated). Structural modifications suggesting partial but continuous degradation were observed for all nanotubes irrespective of their surface functionalization. Carboxylation was shown to promote more pronounced structural changes inside microglia over the first two weeks of the study.

Directional Carrier Transfer in Strongly Coupled Binary Nanocrystal Superlattice Films Formed by Assembly and in Situ Ligand Exchange at a Liquid–Air Interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yaoting; Li, Siming; Gogotsi, Natalie

Two species of monodisperse nanocrystals (NCs) can self-assemble into a variety of complex 2D and 3D periodic structures, or binary NC superlattice (BNSL) films, based on the relative number and size of the NCs. BNSL films offer great promise for both fundamental scientific studies and optoelectronic applications; however, the utility of as-assembled structures has been limited by the insulating ligands that originate from the synthesis of NCs. Here we report the application of an in situ ligand exchange strategy at a liquid–air interface to replace the long synthesis ligands with short ligands while preserving the long-range order of BNSL films.more » This approach is demonstrated for BNSL structures consisting of PbSe NCs of different size combinations and ligands of interest for photovoltaic devices, infrared detectors, and light-emitting diodes. To confirm enhanced coupling introduced by ligand exchange, we show ultrafast (~1 ps) directional carrier transfer across the type-I heterojunction formed by NCs of different sizes within ligand-exchanged BNSL films. In conclusion, this approach shows the potential promise of functional BNSL films, where the local and long-range energy landscape and electronic coupling can be adjusted by tuning NC composition, size, and interparticle spacing.« less

In Situ FTIR Microspectroscopy of Brain Tissue from a Transgenic Mouse Model of Alzheimer Disease

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rak,M.; Del Bigio, M.; Mai, S.

2007-01-01

Plaques composed of the A{beta} peptide are the main pathological feature of Alzheimer's disease. Dense-core plaques are fibrillar deposits of A{beta}, showing all the classical properties of amyloid including {beta}-sheet secondary structure, while diffuse plaques are amorphous deposits. We studied both plaque types, using synchrotron infrared (IR) microspectroscopy, a technique that allows the chemical composition and average protein secondary structure to be investigated in situ. We examined plaques in hippocampal, cortical and caudal tissue from 5- to 21-month-old TgCRND8 mice, a transgenic model expressing doubly mutant amyloid precursor protein, and displaying impaired hippocampal function and robust pathology from an earlymore » age. Spectral analysis confirmed that the congophilic plaque cores were composed of protein in a {beta}-sheet conformation. The amide I maximum of plaque cores was at 1623 cm-1, and unlike for in vitro A{beta} fibrils, the high-frequency (1680-1690 cm-1) component attributed to antiparallel {beta}-sheet was not observed. A significant elevation in phospholipids was found around dense-core plaques in TgCRND8 mice ranging in age from 5 to 21 months. In contrast, diffuse plaques were not associated with IR detectable changes in protein secondary structure or relative concentrations of any other tissue components.« less

BUILDING LATE-TYPE SPIRAL GALAXIES BY IN-SITU AND EX-SITU STAR FORMATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pillepich, Annalisa; Madau, Piero; Mayer, Lucio

We analyze the formation and evolution of the stellar components in ''Eris'', a 120 pc resolution cosmological hydrodynamic simulation of a late-type spiral galaxy. The simulation includes the effects of a uniform UV background, a delayed-radiative-cooling scheme for supernova feedback, and a star formation recipe based on a high gas density threshold. It allows a detailed study of the relative contributions of ''in-situ'' (within the main host) and ''ex-situ'' (within satellite galaxies) star formation to each major Galactic component in a close Milky Way analog. We investigate these two star-formation channels as a function of galactocentric distance, along different lines ofmore » sight above and along the disk plane, and as a function of cosmic time. We find that: (1) approximately 70% of today's stars formed in-situ; (2) more than two thirds of the ex-situ stars formed within satellites after infall; (3) the majority of ex-situ stars are found today in the disk and in the bulge; (4) the stellar halo is dominated by ex-situ stars, whereas in-situ stars dominate the mass profile at distances ≲ 5 kpc from the center at high latitudes; and (5) approximately 25% of the inner, r ≲ 20 kpc, halo is composed of in-situ stars that have been displaced from their original birth sites during Eris' early assembly history.« less

In situ data collection and structure refinement from microcapillary protein crystallization

PubMed Central

Yadav, Maneesh K.; Gerdts, Cory J.; Sanishvili, Ruslan; Smith, Ward W.; Roach, L. Spencer; Ismagilov, Rustem F.; Kuhn, Peter; Stevens, Raymond C.

2007-01-01

In situ X-ray data collection has the potential to eliminate the challenging task of mounting and cryocooling often fragile protein crystals, reducing a major bottleneck in the structure determination process. An apparatus used to grow protein crystals in capillaries and to compare the background X-ray scattering of the components, including thin-walled glass capillaries against Teflon, and various fluorocarbon oils against each other, is described. Using thaumatin as a test case at 1.8 Å resolution, this study demonstrates that high-resolution electron density maps and refined models can be obtained from in situ diffraction of crystals grown in microcapillaries. PMID:17468785

In situ X-ray polymerization: from swollen lamellae to polymer-surfactant complexes.

PubMed

Agzenai, Yahya; Lindman, Björn; Alfredsson, Viveka; Topgaard, Daniel; Renamayor, Carmen S; Pacios, Isabel E

2014-01-30

The influence of the monomer diallyldimethylammonium chloride (D) on the lamellar liquid crystal formed by the anionic surfactant aerosol OT (AOT) and water is investigated, determining the lamellar spacings by SAXS and the quadrupolar splittings by deuterium NMR, as a function of the D or AOT concentrations. The cationic monomer D induces a destabilization of the AOT lamellar structure such that, at a critical concentration higher than 5 wt %, macroscopic phase separation takes place. When the monomer, which is dissolved in the AOT lamellae, is polymerized in situ by X-ray initiation, a new collapsed lamellar phase appears, corresponding to the complexation of the surfactant with the resulting polymer. A theoretical model is employed to analyze the variation of the interactions between the AOT bilayers and the stability of the lamellar structure.

Micro-scale in situ characterisation of the organic and mineral composition of modern, hypersaline, photosynthetic microbial mats

NASA Astrophysics Data System (ADS)

Gautret, P.; Ramboz, C.; de Wit, R.; Delarue, F.; Orange, F.; Sorieul, S.; Westall, F.

2012-04-01

Physico-chemical and biological micro-scale environmental parameters within microbial mats formed in hypersaline conditions favour the precipitation of minerals, such as carbonates. We used optical microscopy and the technique "Fluorescence Induction Relaxation » (FIRe) to differentiate the photosynthetic activity of oxygenic photosynthesisers (cyanobacteria) from anoxygenic photosynthesisers (Chloroflexus-like bacteria, CFB) in samples obtained in 2011. After this preliminary investigation, we characterised the elemental composition of the different species of microorganisms, their extracellular substances (EPS), and the minerals precipitated on their surface. This study was made in-situ by µ-PIXE using the nuclear microprobe of the AIFIRA platform (CEN Bordeaux-Gradignan ; protons of 1.5 or 3MeV). With this microprobe it is possible to map the distribution of elements occurring in quantities down to several ppm, a resolution that is particularly favourable for studying microorganisms. SEM observation of the same zones allowed us to localise exactly the microbial structures (cells, EPS) and minerals analysed by nuclear probe. We were thus able to document the differential S and P concentrations in the different microbial species, the CLB being richer in P. Note that the CLB filaments are < 1 µm in diameter. We were also able to demonstrate the anti-correlation of Ca and Mg in the minerals precipitated directly on the microorganisms and on their EPS. Thus we have shown the utility of these in situ, nano-scale methods in studying microbial structures consisting of different species with different metabolic activitie, and different functional groups on their cell walls and EPS implicated in the bioprecipitation of different kinds of minerals. Such features in ancient microbial mats could aid their interpretation and possibly the distinction between ancient oxygenic and anoxygenic mats.

Physical deoxygenation of graphene oxide paper surface and facile in situ synthesis of graphene based ZnO films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Jijun; Wang, Minqiang, E-mail: mqwang@mail.xjtu.edu.cn; Zhang, Xiangyu

2014-12-08

In-situ sputtering ZnO films on graphene oxide (GO) paper are used to fabricate graphene based ZnO films. Crystal structure and surface chemical states are investigated. Results indicated that GO paper can be effectively deoxygenated by in-situ sputtering ZnO on them without adding any reducing agent. Based on the principle of radio frequency magnetron sputtering, we propose that during magnetron sputtering process, plasma streams contain large numbers of electrons. These electrons not only collide with argon atoms to produce secondary electrons but also they are accelerated to bombard the substrates (GO paper) resulting in effective deoxygenation of oxygen-containing functional groups. In-situmore » sputtering ZnO films on GO paper provide an approach to design graphene-semiconductor nanocomposites.« less

Low-Temperature (75 To 400°C) Oxidation Study Of Coal By Diffuse Reflectance Infrared Fourier Transform (DRIFT) Spectroscopy

NASA Astrophysics Data System (ADS)

Smyrl, Norman R.; Fuller, E. L.

1989-12-01

In situ low-temperature air oxidation studies of subbituminous coal have been performed at 77, 125, 200, 300, and 400°C by diffuse reflectance Fourier transform (DRIFT) spectroscopy. The oxidation reaction proceeds via oxygen insertion at aliphatic sites in the coal structure, which progressively produces aldo/keto groups, acid groups, and acid anhydride entities with the simultaneous consumption of hydrogen at these sites. The production of anhydrides occurs even at the lowest temperature (77?°C), but only above 200°C is there sufficient mobility of the acid functionalities for major quantities of the anhydride species to be formed. Above 400C, the anhydro groups predominate in the steady-state production of carbon dioxide and water vapor. In addition to the detailed information concerning the carbonyl species, the spectra of the oxidized coal reveal some new information regarding the aromatic C-H stretching bands, which can be studied in some detail unencumbered by interference from the aliphatic bands that have been removed in the oxidation process. Further details related to the aromatic bands are revealed by deuterium exchange of the remaining 0-H groups (primarily phenolic type 0-H) in the oxidized coal structure. This exchange removes these bands from overlap with the broad 0-H stretching band resulting from hydrogen bonding of the 0-H groups. The present study reveals further merits of in situ DRIFT analysis in extending the knowledge of coal structure and reactions. The study also indicates much potential for further work.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, Jinhui; Buchko, Garry W.; Shaw, Wendy J.

The interactions between proteins and surfaces are critical to a number of important processes including biomineralization, the biocompatibility of biomaterials, and the function of biosensors. Although many proteins exist as monomers or small oligomers, amelogenin is a unique protein that self-assembles into supramolecular structures called “nanospheres,” aggregates of 100’s of monomers that are 20-60 nm in diameter. The nanosphere quaternary structure is observed in solution, however, the quaternary structure of amelogenin adsorbed onto hydroxyapatite (HAP) surfaces is not known even though it may be important to amelogenin’s function in forming highly elongated and intricately assembled HAP crystallites during enamel formation.more » We report studies of the interactions of the enamel protein, amelogenin (rpM179), with a well-defined (100) face prepared by synthesis of large crystals of HAP. High resolution, in-situ atomic force microscopy (AFM) was used to directly observe protein adsorption onto HAP at the molecular level within an aqueous solution environment. Our study shows that the amelogenin nanospheres disassemble onto the HAP surface, breaking down into oligomeric (25-mer) subunits of the larger nanosphere. In some cases, the disassembly event is directly observed by in situ imaging for the first time. Quantification of the adsorbate amounts by size analysis led to the determination of a protein binding energy (17.1 kbT) to a specific face of HAP (100). The kinetics of disassembly are greatly slowed in aged solutions, indicating there are time-dependent increases in oligomer-oligomer binding interactions within the nanosphere. A small change in the sequence of amelogenin by the attachment of a histidine tag to the N-terminus of rpM179 to form rp(H)M180 results in the adsorption of a complete second layer on top of the underlying first layer. Our research elucidates how supramolecular protein structures interact and break down at surfaces and how small changes in the primary sequence of amelogenin can affect the disassembly process.« less

Sexual Functioning After Treatment of In Situ Vulvar Cancer: Preliminary Report

PubMed Central

Andersen, Barbara L.; Turnquist, Dawn; LaPolla, James; Turner, Deborah

2010-01-01

Forty-two patients treated for in situ vulvar cancer at two institutions participated in structured assessment interviews and completed questionnaires to examine postoperative sexual, marital, and psychological adjustment. Patient responses were compared with a matched sample of gynecologically healthy women. The results indicated a specific pattern of sexual disruption for the women treated for preinvasive disease. Sexual behavior patterns appeared to be maintained, as was the desire phase of the sexual response cycle. However, there was specific disruption of the phases of excitement and resolution and, to a lesser extent, orgasm. In addition to a two- to threefold increase in the frequency of sexual dysfunction, 30% of the sample was sexually inactive at follow-up. Although replication of these findings is necessary, this investigation suggests that sexual functioning correlates with the magnitude of treatment. PMID:3336539

In Situ Monitoring of Ni-based Catalysts during the Synthesis of Propylene Carbonate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramin, Michael; Reimann, Sven; Grunwaldt, Jan-Dierk

2007-02-02

Three different nickel complexes were catalytically tested in the synthesis of propylene carbonate by carbon dioxide insertion. XAS measurements of the as prepared catalysts confirmed the differences in the structure which led to the varying catalytic activity. The structure of one of the active nickel-based catalysts was followed in situ by X-ray absorption spectroscopy using a specially designed batch reactor cell. The novel batch reactor allows in situ studies in dense carbon dioxide at elevated temperature and high pressure (up to 200 bar) even at the low energy of the nickel K-edge. Hence, important information on the fate of themore » ligands and structural changes under reaction conditions could be gained providing new insight into the reaction mechanism.« less

An Atomic-Scale X-ray View of Functional Oxide Films

NASA Astrophysics Data System (ADS)

Tung, I.-Cheng

Complex oxides are a class of materials that exhibit a wide variety of physical functionalities, such as ferroelectricity, colossal magnetoresistance, mulitferroicity and superconductivity, with outstanding potential for meeting many of our technological demands. The primary objective of this dissertation is to understand the structural and electronic behavior of complex oxide ultrathin films subjected to confinement, lattice misfit and broken symmetry at the interface. In complex oxide ultrathin films, heteroepitaxial synthesis has evolved into a reliable strategy to engineer orbital-lattice interactions in correlated materials and led to new and entirely unexpected phenomena at their interfaces. I experimentally demonstrated that the bulk crystal symmetry directs the atomic and orbital responses adopted by coherently strained ultrathin films of RNiO3 (R = La, Nd) with detailed X-ray scattering, polarization-dependent X-ray absorption spectroscopy (XAS) and supported by a mathematical point group symmetry analysis, found that strain-stabilized phases maintain a ``memory'' of their bulk state. This topic, however, touched only upon the properties of such films. A fundamental challenge in this research area occurs before this and centers around the understanding of how to create high-quality films with arbitrary configurations. A longstanding challenge in the oxide thin film community has been the growth of An+1BnO3 n+1 Ruddlesden-Popper (RP) compounds. To understand this problem, we have utilized a newly constructed oxide MBE with in situ synchrotron X-ray scattering capability to study the initial growth of such layered oxides and track the dynamic evolution. X-ray results are supported by theoretical calculations that demonstrated the layered oxide films dynamically rearrange during growth, leading to structures that are highly unexpected, and suggest a general approach that may be essential for the construction of metastable RP phases with performing the first atomically controlled synthesis of single-crystalline La3Ni2O7. By building upon this knowledge, I have completed the first to date study of in situ surface X-ray scattering during homoepitaxial MBE growth of SrTiO3, which demonstrates codeposition is consistent with a 2D island growth mode with SrTiO3 islands, but shuttered deposition proceeds by the growth of SrO islands which then restructure into atomically flat SrTiO3 layer during the deposition of the TiO2. From this point, we have conducted a detailed microscopic study of epitaxial LaNiO3 ultrathin films grown on SrTiO3 (001) by using reactive MBE with in situ surface X-ray diffraction and ex situ soft XAS to explore the influence of polar mismatch on the resulting structural and electronic properties. Overall, this thesis highlights the power of artificial confinement to harness control over competing phases in complex oxides with atomic-scale precision.

In Situ and Ex Situ TEM Study of Lithiation Behaviours of Porous Silicon Nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Chenfei; Ge, Mingyuan; Luo, Langli

Here in this work, we study the lithiation behaviours of both porous silicon (Si) nanoparticles and porous Si nanowires by in situ and ex situ transmission electron microscopy (TEM) and compare them with solid Si nanoparticles and nanowires. The in situ TEM observation reveals that the critical fracture diameter of porous Si particles reaches up to 1.52 μm, which is much larger than the previously reported 150 nm for crystalline Si nanoparticles and 870 nm for amorphous Si nanoparticles. After full lithiation, solid Si nanoparticles and nanowires transform to crystalline Li 15Si 4 phase while porous Si nanoparticles and nanowiresmore » transform to amorphous Li xSi phase, which is due to the effect of domain size on the stability of Li 15Si 4 as revealed by the first-principle molecular dynamic simulation. Ex situ TEM characterization is conducted to further investigate the structural evolution of porous and solid Si nanoparticles during the cycling process, which confirms that the porous Si nanoparticles exhibit better capability to suppress pore evolution than solid Si nanoparticles. The investigation of structural evolution and phase transition of porous Si nanoparticles and nanowires during the lithiation process reveal that they are more desirable as lithium-ion battery anode materials than solid Si nanoparticles and nanowires.« less

In Situ and Ex Situ TEM Study of Lithiation Behaviours of Porous Silicon Nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Chenfei; Ge, Mingyuan; Luo, Langli

In this work, we study the lithiation behaviours of both porous silicon (Si) nanoparticles and porous Si nanowires by in situ and ex situ transmission electron microscopy (TEM) and compare them with solid Si nanoparticles and nanowires. The in situ TEM observation reveals that the critical fracture diameter of porous Si particles reaches up to 1.52 μm, which is much larger than the previously reported 150 nm for crystalline Si nanoparticles and 870 nm for amorphous Si nanoparticles. After full lithiation, solid Si nanoparticles and nanowires transform to crystalline Li15Si4 phase while porous Si nanoparticles and nanowires transform to amorphousmore » LixSi phase, which is due to the effect of domain size on the stability of Li15Si4 as revealed by the first-principle molecular dynamic simulation. Ex situ TEM characterization is conducted to further investigate the structural evolution of porous and solid Si nanoparticles during the cycling process, which confirms that the porous Si nanoparticles exhibit better capability to suppress pore evolution than solid Si nanoparticles. The investigation of structural evolution and phase transition of porous Si nanoparticles and nanowires during the lithiation process reveal that they are more desirable as lithium-ion battery anode materials than solid Si nanoparticles and nanowires.« less

In Situ and Ex Situ TEM Study of Lithiation Behaviours of Porous Silicon Nanostructures

NASA Astrophysics Data System (ADS)

Shen, Chenfei; Ge, Mingyuan; Luo, Langli; Fang, Xin; Liu, Yihang; Zhang, Anyi; Rong, Jiepeng; Wang, Chongmin; Zhou, Chongwu

2016-08-01

In this work, we study the lithiation behaviours of both porous silicon (Si) nanoparticles and porous Si nanowires by in situ and ex situ transmission electron microscopy (TEM) and compare them with solid Si nanoparticles and nanowires. The in situ TEM observation reveals that the critical fracture diameter of porous Si particles reaches up to 1.52 μm, which is much larger than the previously reported 150 nm for crystalline Si nanoparticles and 870 nm for amorphous Si nanoparticles. After full lithiation, solid Si nanoparticles and nanowires transform to crystalline Li15Si4 phase while porous Si nanoparticles and nanowires transform to amorphous LixSi phase, which is due to the effect of domain size on the stability of Li15Si4 as revealed by the first-principle molecular dynamic simulation. Ex situ TEM characterization is conducted to further investigate the structural evolution of porous and solid Si nanoparticles during the cycling process, which confirms that the porous Si nanoparticles exhibit better capability to suppress pore evolution than solid Si nanoparticles. The investigation of structural evolution and phase transition of porous Si nanoparticles and nanowires during the lithiation process reveal that they are more desirable as lithium-ion battery anode materials than solid Si nanoparticles and nanowires.

In Situ and Ex Situ TEM Study of Lithiation Behaviours of Porous Silicon Nanostructures

PubMed Central

Shen, Chenfei; Ge, Mingyuan; Luo, Langli; Fang, Xin; Liu, Yihang; Zhang, Anyi; Rong, Jiepeng; Wang, Chongmin; Zhou, Chongwu

2016-01-01

In this work, we study the lithiation behaviours of both porous silicon (Si) nanoparticles and porous Si nanowires by in situ and ex situ transmission electron microscopy (TEM) and compare them with solid Si nanoparticles and nanowires. The in situ TEM observation reveals that the critical fracture diameter of porous Si particles reaches up to 1.52 μm, which is much larger than the previously reported 150 nm for crystalline Si nanoparticles and 870 nm for amorphous Si nanoparticles. After full lithiation, solid Si nanoparticles and nanowires transform to crystalline Li15Si4 phase while porous Si nanoparticles and nanowires transform to amorphous LixSi phase, which is due to the effect of domain size on the stability of Li15Si4 as revealed by the first-principle molecular dynamic simulation. Ex situ TEM characterization is conducted to further investigate the structural evolution of porous and solid Si nanoparticles during the cycling process, which confirms that the porous Si nanoparticles exhibit better capability to suppress pore evolution than solid Si nanoparticles. The investigation of structural evolution and phase transition of porous Si nanoparticles and nanowires during the lithiation process reveal that they are more desirable as lithium-ion battery anode materials than solid Si nanoparticles and nanowires. PMID:27571919

In Situ and Ex Situ TEM Study of Lithiation Behaviours of Porous Silicon Nanostructures

DOE PAGES

Shen, Chenfei; Ge, Mingyuan; Luo, Langli; ...

2016-08-30

Here in this work, we study the lithiation behaviours of both porous silicon (Si) nanoparticles and porous Si nanowires by in situ and ex situ transmission electron microscopy (TEM) and compare them with solid Si nanoparticles and nanowires. The in situ TEM observation reveals that the critical fracture diameter of porous Si particles reaches up to 1.52 μm, which is much larger than the previously reported 150 nm for crystalline Si nanoparticles and 870 nm for amorphous Si nanoparticles. After full lithiation, solid Si nanoparticles and nanowires transform to crystalline Li 15Si 4 phase while porous Si nanoparticles and nanowiresmore » transform to amorphous Li xSi phase, which is due to the effect of domain size on the stability of Li 15Si 4 as revealed by the first-principle molecular dynamic simulation. Ex situ TEM characterization is conducted to further investigate the structural evolution of porous and solid Si nanoparticles during the cycling process, which confirms that the porous Si nanoparticles exhibit better capability to suppress pore evolution than solid Si nanoparticles. The investigation of structural evolution and phase transition of porous Si nanoparticles and nanowires during the lithiation process reveal that they are more desirable as lithium-ion battery anode materials than solid Si nanoparticles and nanowires.« less

In Situ Fabrication of 3D Ag@ZnO Nanostructures for Microfluidic Surface-Enhanced Raman Scattering Systems

PubMed Central

2015-01-01

In this work, we develop an in situ method to grow highly controllable, sensitive, three-dimensional (3D) surface-enhanced Raman scattering (SERS) substrates via an optothermal effect within microfluidic devices. Implementing this approach, we fabricate SERS substrates composed of Ag@ZnO structures at prescribed locations inside microfluidic channels, sites within which current fabrication of SERS structures has been arduous. Conveniently, properties of the 3D Ag@ZnO nanostructures such as length, packing density, and coverage can also be adjusted by tuning laser irradiation parameters. After exploring the fabrication of the 3D nanostructures, we demonstrate a SERS enhancement factor of up to ∼2 × 106 and investigate the optical properties of the 3D Ag@ZnO structures through finite-difference time-domain simulations. To illustrate the potential value of our technique, low concentrations of biomolecules in the liquid state are detected. Moreover, an integrated cell-trapping function of the 3D Ag@ZnO structures records the surface chemical fingerprint of a living cell. Overall, our optothermal-effect-based fabrication technique offers an effective combination of microfluidics with SERS, resolving problems associated with the fabrication of SERS substrates in microfluidic channels. With its advantages in functionality, simplicity, and sensitivity, the microfluidic-SERS platform presented should be valuable in many biological, biochemical, and biomedical applications. PMID:25402207

In-situ and Ex-situ Observations of Lithium De-intercalation from LiCoO2: Atomic Force Microscopy and Transmission Electron Microscopy Studies

DTIC Science & Technology

2005-06-01

has a layered structure consisting of lithium and cobalt sheets stacked alternatively between oxygen sheets. Li and Co occupy octahedral sites in...cobalt sheets stacked alternatively between ABCABC close-packed oxygen arrays. Li and Co occupy octahedral sites in alternating layers between the oxygen... Co 4.- o 4 Li Figure 1: Crystal structure of LiCoO2. LiCoO2 has a layered structure consisting of lithium and cobalt sheets stacked alternatively

Maize Germplasm Conservation in Southern California's Urban Gardens: Introduced Diversity Beyond ex situ and in situ Management.

PubMed

Heraty, Joanne M; Ellstrand, Norman C

Contemporary germplasm conservation studies largely focus on ex situ and in situ management of diversity within centers of genetic diversity. Transnational migrants who transport and introduce landraces to new locations may catalyze a third type of conservation that combines both approaches. Resulting populations may support reduced diversity as a result of evolutionary forces such as genetic drift, selection, and gene flow, yet they may also be more diverse as a result of multiple introductions, selective breeding and cross pollination among multiple introduced varietals. In this study, we measured the amount and structure of maize molecular genetic diversity in samples collected from home gardens and community gardens maintained by immigrant farmers in Southern California. We used the same markers to measure the genetic diversity and structure of commercially available maize varieties and compared our data to previously reported genetic diversity statistics of Mesoamerican landraces. Our results reveal that transnational dispersal creates an opportunity for the maintenance of maize genetic diversity beyond its recognized centers of diversity.

Layer-by-layer epitaxial growth of defect-engineered strontium cobaltites

DOE PAGES

Andersen, Tassie K.; Cook, Seyoung; Wan, Gang; ...

2018-01-18

Here, control over structure and composition of (ABO 3) perovskite oxides offers exciting opportunities since these materials possess unique, tunable properties. Perovskite oxides with cobalt B-site cations are particularly promising, as the range of the cation’s stable oxidation states leads to many possible structural frameworks. Here, we report growth of strontium cobalt oxide thin films by molecular beam epitaxy, and conditions necessary to stabilize different defect concentration phases. In situ X-ray scattering is used to monitor structural evolution during growth, while in situ X-ray absorption near-edge spectroscopy is used to probe oxidation state and measure changes to oxygen vacancy concentrationmore » as a function of film thickness. Experimental results are compared to kinetically-limited thermodynamic predictions, in particular, solute trapping, with semi-quantitative agreement. Agreement between observations of dependence of cobaltite phase on oxidation activity and deposition rate, and predictions indicates that a combined experimental/theoretical approach is key to understanding phase behavior in the strontium cobalt oxide system.« less

Layer-by-layer epitaxial growth of defect-engineered strontium cobaltites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersen, Tassie K.; Cook, Seyoung; Wan, Gang

Here, control over structure and composition of (ABO 3) perovskite oxides offers exciting opportunities since these materials possess unique, tunable properties. Perovskite oxides with cobalt B-site cations are particularly promising, as the range of the cation’s stable oxidation states leads to many possible structural frameworks. Here, we report growth of strontium cobalt oxide thin films by molecular beam epitaxy, and conditions necessary to stabilize different defect concentration phases. In situ X-ray scattering is used to monitor structural evolution during growth, while in situ X-ray absorption near-edge spectroscopy is used to probe oxidation state and measure changes to oxygen vacancy concentrationmore » as a function of film thickness. Experimental results are compared to kinetically-limited thermodynamic predictions, in particular, solute trapping, with semi-quantitative agreement. Agreement between observations of dependence of cobaltite phase on oxidation activity and deposition rate, and predictions indicates that a combined experimental/theoretical approach is key to understanding phase behavior in the strontium cobalt oxide system.« less

Layer-by-Layer Epitaxial Growth of Defect-Engineered Strontium Cobaltites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersen, Tassie K.; Cook, Seyoung; Wan, Gang

Control over structure and composition of (ABO(3)) perovskite oxides offers exciting opportunities since these materials possess unique, tunable properties. Perovskite oxides with cobalt B-site cations are particularly promising, as the range of the cations stable oxidation states leads to many possible structural frameworks. Here, we report growth of strontium cobalt oxide thin films by molecular beam epitaxy, and conditions necessary to stabilize different defect concentration phases. In situ X-ray scattering is used to monitor structural evolution during growth, while in situ X-ray absorption near-edge spectroscopy is used to probe oxidation state and measure changes to oxygen vacancy concentration as amore » function of film thickness. Experimental results are compared to kinetically limited thermodynamic predictions, in particular, solute trapping, with semiquantitative agreement. Agreement between observations of dependence of cobaltite phase on oxidation activity and deposition rate, and predictions indicates that a combined experimental/theoretical approach is key to understanding phase behavior in the strontium cobalt oxide system.« less

Correlative live and super-resolution imaging reveals the dynamic structure of replication domains.

PubMed

Xiang, Wanqing; Roberti, M Julia; Hériché, Jean-Karim; Huet, Sébastien; Alexander, Stephanie; Ellenberg, Jan

2018-06-04

Chromosome organization in higher eukaryotes controls gene expression, DNA replication, and DNA repair. Genome mapping has revealed the functional units of chromatin at the submegabase scale as self-interacting regions called topologically associating domains (TADs) and showed they correspond to replication domains (RDs). A quantitative structural and dynamic description of RD behavior in the nucleus is, however, missing because visualization of dynamic subdiffraction-sized RDs remains challenging. Using fluorescence labeling of RDs combined with correlative live and super-resolution microscopy in situ, we determined biophysical parameters to characterize the internal organization, spacing, and mechanical coupling of RDs. We found that RDs are typically 150 nm in size and contain four co-replicating regions spaced 60 nm apart. Spatially neighboring RDs are spaced 300 nm apart and connected by highly flexible linker regions that couple their motion only <550 nm. Our pipeline allows a robust quantitative characterization of chromosome structure in situ and provides important biophysical parameters to understand general principles of chromatin organization. © 2018 Xiang et al.

Mechanical Anisotropy and Pressure Induced Structural Changes in Piroxicam Crystals Probed by In Situ Indentation and Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Manimunda, Praveena; Hintsala, Eric; Asif, Syed; Mishra, Manish Kumar

2017-01-01

The ability to correlate mechanical and chemical characterization techniques in real time is both lacking and powerful tool for gaining insights into material behavior. This is demonstrated through use of a novel nanoindentation device equipped with Raman spectroscopy to explore the deformation-induced structural changes in piroxicam crystals. Mechanical anisotropy was observed in two major faces ( 0bar{1}1 ) and (011), which are correlated to changes in the interlayer interaction from in situ Raman spectra recorded during indentation. The results of this study demonstrate the considerable potential of an in situ Raman nanoindentation instrument for studying a variety of topics, including stress-induced phase transformation mechanisms, mechanochemistry, and solid state reactivity under mechanical forces that occur in molecular and pharmaceutical solids.

Multifunctional 3D printing of heterogeneous hydrogel structures

NASA Astrophysics Data System (ADS)

Nadernezhad, Ali; Khani, Navid; Skvortsov, Gözde Akdeniz; Toprakhisar, Burak; Bakirci, Ezgi; Menceloglu, Yusuf; Unal, Serkan; Koc, Bahattin

2016-09-01

Multimaterial additive manufacturing or three-dimensional (3D) printing of hydrogel structures provides the opportunity to engineer geometrically dependent functionalities. However, current fabrication methods are mostly limited to one type of material or only provide one type of functionality. In this paper, we report a novel method of multimaterial deposition of hydrogel structures based on an aspiration-on-demand protocol, in which the constitutive multimaterial segments of extruded filaments were first assembled in liquid state by sequential aspiration of inks into a glass capillary, followed by in situ gel formation. We printed different patterned objects with varying chemical, electrical, mechanical, and biological properties by tuning process and material related parameters, to demonstrate the abilities of this method in producing heterogeneous and multi-functional hydrogel structures. Our results show the potential of proposed method in producing heterogeneous objects with spatially controlled functionalities while preserving structural integrity at the switching interface between different segments. We anticipate that this method would introduce new opportunities in multimaterial additive manufacturing of hydrogels for diverse applications such as biosensors, flexible electronics, tissue engineering and organ printing.

Multifunctional 3D printing of heterogeneous hydrogel structures

PubMed Central

Nadernezhad, Ali; Khani, Navid; Skvortsov, Gözde Akdeniz; Toprakhisar, Burak; Bakirci, Ezgi; Menceloglu, Yusuf; Unal, Serkan; Koc, Bahattin

2016-01-01

Multimaterial additive manufacturing or three-dimensional (3D) printing of hydrogel structures provides the opportunity to engineer geometrically dependent functionalities. However, current fabrication methods are mostly limited to one type of material or only provide one type of functionality. In this paper, we report a novel method of multimaterial deposition of hydrogel structures based on an aspiration-on-demand protocol, in which the constitutive multimaterial segments of extruded filaments were first assembled in liquid state by sequential aspiration of inks into a glass capillary, followed by in situ gel formation. We printed different patterned objects with varying chemical, electrical, mechanical, and biological properties by tuning process and material related parameters, to demonstrate the abilities of this method in producing heterogeneous and multi-functional hydrogel structures. Our results show the potential of proposed method in producing heterogeneous objects with spatially controlled functionalities while preserving structural integrity at the switching interface between different segments. We anticipate that this method would introduce new opportunities in multimaterial additive manufacturing of hydrogels for diverse applications such as biosensors, flexible electronics, tissue engineering and organ printing. PMID:27630079

"In situ preparation": new surgical procedure indicated for soft-tissue sarcoma of a lower limb in close proximity to major neurovascular structures.

PubMed

Matsumoto, Seiichi; Kawaguchi, Noriyoshi; Manabe, Jun; Matsushita, Yasushi

2002-02-01

When soft-tissue sarcomas occur near neurovascular structures, preoperative images cannot always reveal the accurate relationship between the tumor and these structures. Therefore, in some patients, neurovascular structures are sacrificed unnecessarily. In other patients, neurovascular structures are preserved with an inappropriate margin, followed by local recurrence. The objective of this study was to evaluate a new surgical method, "in situ preparation" (ISP), which enables the preparation of neurovascular bundles and the intraoperative evaluation of the surgical margin without contamination by tumor cells. With this method, additional procedures, including pasteurization, alcohol soaking, and distilled water soaking of the preserved neurovascular bundle can also be performed to preserve the continuity of vessels. Between April 1992 and December 1998, 18 patients with soft-tissue sarcoma were operated on using ISP. The tumor and neurovascular structure were lifted en bloc from the surgical bed and separated from the field by the use of a vinyl sheet. The consistency of the neurovascular structures was preserved. The tissue block could be freely turned around and the neurovascular structure was separated from the block through the nearest approach. The margin between the tumor and neurovascular structure was evaluated, and an additional procedure, such as pasteurization, alcohol soaking or distilled water soaking, was performed, according to the safety of the surgical margin. Only one patient showed recurrence after ISP. Complications after ISP were arterial occlusion in two patients and nerve palsy in three patients. The main cause of these complications was the long period of pasteurization; modified additional procedures could prevent such complications. ISP is a useful method with which to ensure a safe surgical margin and good functional results.

In situ population structure and ex situ representation of the endangered Amur tiger.

PubMed

Henry, P; Miquelle, D; Sugimoto, T; McCullough, D R; Caccone, A; Russello, M A

2009-08-01

The Amur tiger (Panthera tigris altaica) is a critically endangered felid that suffered a severe demographic contraction in the 1940s. In this study, we sampled 95 individuals collected throughout their native range to investigate questions relative to population genetic structure and demographic history. Additionally, we sampled targeted individuals from the North American ex situ population to assess the genetic representation found in captivity. Population genetic and Bayesian structure analyses clearly identified two populations separated by a development corridor in Russia. Despite their well-documented 20th century decline, we failed to find evidence of a recent population bottleneck, although genetic signatures of a historical contraction were detected. This disparity in signal may be due to several reasons, including historical paucity in population genetic variation associated with postglacial colonization and potential gene flow from a now extirpated Chinese population. Despite conflicting signatures of a bottleneck, our estimates of effective population size (N(e) = 27-35) and N(e)/N ratio (0.07-0.054) were substantially lower than the only other values reported for a wild tiger population. Lastly, the extent and distribution of genetic variation in captive and wild populations were similar, yet gene variants persisted ex situ that were lost in situ. Overall, our results indicate the need to secure ecological connectivity between the two Russian populations to minimize loss of genetic diversity and overall susceptibility to stochastic events, and support a previous study suggesting that the captive population may be a reservoir of gene variants lost in situ.

Titration of submonolayer Au growth on Si(111)

NASA Astrophysics Data System (ADS)

Kautz, J.; Copel, M. W.; Gordon, M. S.; Tromp, R. M.; van der Molen, S. J.

2014-01-01

We study and analyze the growth of submonolayers of Au on Si(111) by a complementary set of surface techniques. Specifically, we focus on the 5×2 and the α√3 ×√3 structures. We determine the gold coverage of these structures as a function of temperature by means of low energy electron diffraction (LEED) and low energy electron microscopy (LEEM). These results are independently calibrated by ex-situ ion scattering experiments. This allows us to present a phase diagram for this system. Remarkably, for all temperatures considered (820-1040 K), we find a coverage for the 5×2 phase that is significantly (≈10%) higher than the value of 0.6 monolayers which is assumed in the latest structural models. Therefore, a further refinement of the present picture of the quasi-one-dimensional 5×2 structure is required.

The interplay between the paracetamol polymorphism and its molecular structures dissolved in supercritical CO2 in contact with the solid phase: In situ vibration spectroscopy and molecular dynamics simulation analysis.

PubMed

Oparin, Roman D; Moreau, Myriam; De Walle, Isabelle; Paolantoni, Marco; Idrissi, Abdenacer; Kiselev, Michael G

2015-09-18

The aim of this paper is to characterize the distribution of paracetamol conformers which are dissolved in a supercritical CO2 phase being in equilibrium with their corresponding crystalline form. The quantum calculations and molecular dynamics simulations were used in order to characterize the structure and analyze the vibration spectra of the paracetamol conformers in vacuum and in a mixture with CO2 at various thermodynamic state parameters (p,T). The metadynamics approach was applied to efficiently sample the various conformers of paracetamol. Furthermore, using in situ IR spectroscopy, the conformers that are dissolved in supercritical CO2 were identified and the evolution of the probability of their presence as a functions of thermodynamic condition was quantified while the change in the crystalline form of paracetamol have been monitored by DSC, micro IR and Raman techniques. The DSC analysis as well as micro IR and Raman spectroscopic studies of the crystalline paracetamol show that the subsequent heating up above the melting temperature of the polymorph I of paracetamol and the cooling down to room temperature in the presence of supercritical CO2 induces the formation of polymorph II. The in situ IR investigation shows that two conformers (Conf. 1 and Conf. 2) are present in the phase of CO2 while conformer 3 (Conf. 3) has a high probability to be present after re-crystallization. Copyright © 2015. Published by Elsevier B.V.

Elucidation of structure and nature of the PdO-Pd transformation using in situ PDF and XAS techniques.

PubMed

Keating, Jonathan; Sankar, Gopinathan; Hyde, Timothy I; Kohara, Shinji; Ohara, Koji

2013-06-14

The PdO-Pd phase transformation in a 4 wt% Pd/Al2O3 catalyst has been investigated using in situ X-ray absorption spectroscopy (XAS) and in situ X-ray total scattering (also known as high-energy X-ray diffraction) techniques. Both the partial and total pair distribution functions (PDF) from these respective techniques have been analysed in depth. New information from PDF analysis of total scattering data has been garnered using the differential PDF (d-PDF) approach where only correlations orginating from PdO and metallic Pd are extracted. This method circumvents problems encountered in characerising the catalytically active components due to the diffuse scattering from the disordered γ-Al2O3 support phase. Quantitative analysis of the palladium components within the catalyst allowed for the phase composition to be established at various temperatures. Above 850 °C it was found that PdO had converted to metallic Pd, however, the extent of reduction was of the order ca. 70% Pd metal and 30% PdO. Complementary in situ XANES and EXAFS were performed, with heating to high temperature and subsequent cooling in air, and the results of the analyses support the observations, that residual PdO is detected at elevated temperatures. Hysteresis in the transformation upon cooling is confirmed from XAS studies where reoxidation occurs below 680 °C.

Manipulation of Microenvironment with a Built-in Electrochemical Actuator in Proximity of a Dissolved Oxygen Microsensor

NASA Technical Reports Server (NTRS)

Kim, Chang-Soo; Lee, Cae-Hyang; Fiering, Jason O.; Ufer, Stefan; Scarantino, Charles W.; Nagle, H. Troy; Fiering, Jason O.; Ufer, Stefan; Nagle, H. Troy; Scarantino, Charles W.

2004-01-01

Abstract - Biochemical sensors for continuous monitoring require dependable periodic self- diagnosis with acceptable simplicity to check its functionality during operation. An in situ self- diagnostic technique for a dissolved oxygen microsensor is proposed in an effort to devise an intelligent microsensor system with an integrated electrochemical actuation electrode. With a built- in platinum microelectrode that surrounds the microsensor, two kinds of microenvironments, called the oxygen-saturated or oxygen-depleted phases, can be created by water electrolysis depending on the polarity. The functionality of the microsensor can be checked during these microenvironment phases. The polarographic oxygen microsensor is fabricated on a flexible polyimide substrate (Kapton) and the feasibility of the proposed concept is demonstrated in a physiological solution. The sensor responds properly during the oxygen-generating and oxygen- depleting phases. The use of these microenvironments for in situ self-calibration is discussed to achieve functional integration as well as structural integration of the microsensor system.

Analysis of biosurfaces by neutron reflectometry: From simple to complex interfaces

DOE PAGES

Junghans, Ann; Watkins, Erik B.; Barker, Robert D.; ...

2015-03-16

Because of its high sensitivity for light elements and the scattering contrast manipulation via isotopic substitutions, neutron reflectometry (NR) is an excellent tool for studying the structure of soft-condensed material. These materials include model biophysical systems as well as in situ living tissue at the solid–liquid interface. The penetrability of neutrons makes NR suitable for probing thin films with thicknesses of 5–5000 Å at various buried, for example, solid–liquid, interfaces [J. Daillant and A. Gibaud, Lect. Notes Phys. 770, 133 (2009); G. Fragneto-Cusani, J. Phys.: Condens. Matter 13, 4973 (2001); J. Penfold, Curr. Opin. Colloid Interface Sci. 7, 139 (2002)].more » Over the past two decades, NR has evolved to become a key tool in the characterization of biological and biomimetic thin films. Highlighted In the current report are some of the authors' recent accomplishments in utilizing NR to study highly complex systems, including in-situ experiments. Such studies will result in a much better understanding of complex biological problems, have significant medical impact by suggesting innovative treatment, and advance the development of highly functionalized biomimetic materials.« less

Growth of Nanoparticles with Desired Catalytic Functions by Controlled Doping-Segregation of Metal in Oxide

DOE PAGES

Wu, Qiyuan; Yan, Binhang; Cen, Jiajie; ...

2018-02-05

Here, the size and morphology of metal nanoparticles (NPs) often play a critical role in defining the catalytic performance of supported metal nanocatalysts. However, common synthetic methods struggle to produce metal NPs of appropriate size and morphological control. Thus, facile synthetic methods that offer controlled catalytic functions are highly desired. Here we have identified a new pathway to synthesize supported Rh nanocatalysts with finely tuned spatial dimensions and controlled morphology using a doping-segregation method. We have analyzed their structure evolutions during both the segregation process and catalytic reaction using a variety of in situ spectroscopic and microscopic techniques. A correlationmore » between the catalytic functional sites and activity in CO 2 hydrogenation over supported Rh nanocatalysts is then established. This study demonstrates a facile strategy to design and synthesize nanocatalysts with desired catalytic functions.« less

Growth of Nanoparticles with Desired Catalytic Functions by Controlled Doping-Segregation of Metal in Oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Qiyuan; Yan, Binhang; Cen, Jiajie

Here, the size and morphology of metal nanoparticles (NPs) often play a critical role in defining the catalytic performance of supported metal nanocatalysts. However, common synthetic methods struggle to produce metal NPs of appropriate size and morphological control. Thus, facile synthetic methods that offer controlled catalytic functions are highly desired. Here we have identified a new pathway to synthesize supported Rh nanocatalysts with finely tuned spatial dimensions and controlled morphology using a doping-segregation method. We have analyzed their structure evolutions during both the segregation process and catalytic reaction using a variety of in situ spectroscopic and microscopic techniques. A correlationmore » between the catalytic functional sites and activity in CO 2 hydrogenation over supported Rh nanocatalysts is then established. This study demonstrates a facile strategy to design and synthesize nanocatalysts with desired catalytic functions.« less

[Study of the phase transformation of TiO2 with in-situ XRD in different gas].

PubMed

Ma, Li-Jing; Guo, Lie-Jin

2011-04-01

TiO2 sample was prepared by sol-gel method from chloride titanium. The phase transformation of the prepared TiO2 sample was studied by in-situ XRD and normal XRD in different gas. The experimental results showed that the phase transformation temperatures of TiO2 were different under in-situ or normal XRD in different kinds of gas. The transformation of amorphous TiO2 to anatase was controlled by kinetics before 500 degrees C. In-situ XRD showed that the growth of anatase was inhibited, but the transformation of anatase to rutile was accelerated under inactive nitrogen in contrast to air. Also better crystal was obtained under hydrogen than in argon. These all showed that external oxygen might accelerate the growth of TiO2, but reduced gas might partly counteract the negative influence of lack of external oxygen. The mechanism of phase transformation of TiO2 was studied by in-situ XRD in order to control the structure in situ.

In situ MEMS testing: correlation of high-resolution X-ray diffraction with mechanical experiments and finite element analysis

NASA Astrophysics Data System (ADS)

Schifferle, Andreas; Dommann, Alex; Neels, Antonia

2017-12-01

New methods are needed in microsystems technology for evaluating microelectromechanical systems (MEMS) because of their reduced size. The assessment and characterization of mechanical and structural relations of MEMS are essential to assure the long-term functioning of devices, and have a significant impact on design and fabrication.

Development of Additive Construction Technologies for Application to Development of Lunar/Martian Surface Structures Using In-Situ Materials

NASA Technical Reports Server (NTRS)

Werkheiser, Niki J.; Fiske, Michael R.; Edmunson, Jennifer E.; Khoshnevis, Berokh

2015-01-01

For long-duration missions on other planetary bodies, the use of in situ materials will become increasingly critical. As human presence on these bodies expands, so must the breadth of the structures required to accommodate them including habitats, laboratories, berms, radiation shielding for natural radiation and surface reactors, garages, solar storm shelters, greenhouses, etc. Planetary surface structure manufacturing and assembly technologies that incorporate in situ resources provide options for autonomous, affordable, pre-positioned environments with radiation shielding features and protection from micrometeorites, exhaust plume debris, and other hazards. The ability to use in-situ materials to construct these structures will provide a benefit in the reduction of up-mass that would otherwise make long-term Moon or Mars structures cost prohibitive. The ability to fabricate structures in situ brings with it the ability to repair these structures, which allows for the self-sufficiency and sustainability necessary for long-duration habitation. Previously, under the auspices of the MSFC In-Situ Fabrication and Repair (ISFR) project and more recently, under the jointly-managed MSFC/KSC Additive Construction with Mobile Emplacement (ACME) project, the MSFC Surface Structures Group has been developing materials and construction technologies to support future planetary habitats with in-situ resources. One such additive construction technology is known as Contour Crafting. This paper presents the results to date of these efforts, including development of novel nozzle concepts for advanced layer deposition using this process. Conceived initially for rapid development of cementitious structures on Earth, it also lends itself exceptionally well to the automated fabrication of planetary surface structures using minimally processed regolith as aggregate, and binders developed from in situ materials as well. This process has been used successfully in the fabrication of construction elements using lunar regolith simulant and Mars regolith simulant, both with various binder materials. Future planned activities will be discussed as well.

X-ray induced chemical reaction revealed by in-situ X-ray diffraction and scanning X-ray microscopy in 15 nm resolution (Conference Presentation)

NASA Astrophysics Data System (ADS)

Ge, Mingyuan; Liu, Wenjun; Bock, David; De Andrade, Vincent; Yan, Hanfei; Huang, Xiaojing; Marschilok, Amy; Takeuchi, Esther; Xin, Huolin; Chu, Yong S.

2016-09-01

The detection sensitivity of synchrotron-based X-ray techniques has been largely improved due to the ever increasing source brightness, which have significantly advanced ex-situ and in-situ research for energy materials, such as lithium-ion batteries. However, the strong beam-matter interaction arisen from the high beam flux can significantly modify the material structure. The parasitic beam-induced effect inevitably interferes with the intrinsic material property, which brings difficulties in interpreting experimental results, and therefore requires comprehensive evaluation. Here we present a quantitative in-situ study of the beam-effect on one electrode material Ag2VO2PO4 using four different X-ray probes with different radiation dose rate. The material system we reported exhibits interesting and reversible radiation-induced thermal and chemical reactions, which was further evaluated under electron microscopy to illustrate the underlying mechanism. The work we presented here will provide a guideline in using synchrotron X-rays to distinguish the materials' intrinsic behavior from extrinsic structure changed induced by X-rays, especially in the case of in-situ and operando study where the materials are under external field of either temperature or electric field.

In situ study of heavy ion irradiation response of immiscible Cu/Fe multilayers

DOE PAGES

Chen, Youxing; Li, Nan; Bufford, Daniel Charles; ...

2016-04-09

By providing active defect sinks that capture and annihilate radiation induced defect clusters immiscible metallic multilayers with incoherent interfaces can effectively reduce defect density in ion irradiated metals. Although it is anticipated that defect density within the layers should vary as a function of distance to the layer interface, there is, to date, little in situ TEM evidence to validate this hypothesis. In our study monolithic Cu films and Cu/Fe multilayers with individual layer thickness, h, of 100 and 5 nm were subjected to in situ Cu ion irradiation at room temperature to nominally 1 displacement-per-atom inside a transmission electronmore » microscope. Rapid formation and propagation of defect clusters were observed in monolithic Cu, whereas fewer defects with smaller dimensions were generated in Cu/Fe multilayers with smaller h. Moreover, in situ video shows that the cumulative defect density in Cu/Fe 100 nm multilayers indeed varies, as a function of distance to the layer interfaces, supporting a long postulated hypothesis.« less

In Situ Resource-Based Lunar and Martian Habitat Structures Development at NASA/MSFC

NASA Technical Reports Server (NTRS)

Bodiford, Melanie P.; Fiske, Michael R.; McGregory, Walter; Pope, Regina D.

2005-01-01

As the nation prepares to return to the Moon and subsequently to Mars, it is apparent that the viability of long duration visits with appropriate radiation shielding/crew protection, hinges on the development of habitat structures, preferably in advance of a manned landing, and preferably utilizing in-situ resources. A relatively large number of habitat structure configurations can be developed from a relatively small set of in-situ resource-based construction products, including, blocks, raw regolith, reinforced concrete, and glass products. A much larger group of habitat designs can be developed when "imported" material are brought from Earth, including thin films and liners, and foldable, or expandable metal structures. These, and other technologies have been identified, and subjected to a rigorous trade study evaluation with respect to exploration and other performance criteria. In this paper, results of this trade study will be presented, as well as various habitat structure design concepts and concepts for construction automation. Results of initial tests aimed at concrete, block and glass production using Lunar regolith simulants will also be presented. Key issues and concerns will be discussed, as well as design concepts for a Lunar environment testbed to be developed at MSFC's Microgravity Development Laboratory. (MDL).

In-situ Resource-based Lunar and Martian Habitat Structures Development at NASA/MSFC

NASA Technical Reports Server (NTRS)

Bodiford, Melanie P.; Burks, Kevin H.; Fiske, Michael R.; Strong, Janet D.; McGregor, Walter

2005-01-01

As the nation prepares to return to the Moon and subsequently to Mars, it is apparent that the viability of long duration visits with appropriate radiation shielding/crew protection, hinges on the development of habitat structures, preferably in advance of a manned landing, and preferably utilizing in-situ resources. A relatively large number of habitat structure configurations can be developed from a relatively small set of in-situ resource-based construction products, including, blocks, raw regolith, reinforced concrete, and glass products. A much larger group of habitat designs can be developed when "imported" material are brought from Earth, including thin films and liners, and foldable, or expandable metal structures. These, and other technologies have been identified, and subjected to a rigorous trade study evaluation with respect to exploration and other performance criteria. In this paper, results of this trade study will be presented, as well as various habitat structure design concepts and concepts for construction automation. Results of initial tests aimed at concrete, block and glass production using Lunar regolith simulants will also be presented. Key issues and concerns will be discussed, as well as design concepts for a Lunar environment testbed to be developed at MSFC's Microgravity Development Laboratory (MDL).

Structural evolution of Li{sub x}Mn{sub 2}O{sub 4} in lithium-ion battery cells measured in situ using synchrotron X-ray diffraction techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukerjee, S.; Thurston, T.R.; Jisrawi, N.M.

The authors describe synchrotron based X-ray diffraction techniques and issues related to in situ studies of intercalation processes in battery electrodes. They then demonstrate the utility of this technique, through a study of two batches of Li{sub x}Mn{sub 2}O{sub 4} cathode materials. The structural evolution of these spinel materials was monitored in situ during the initial charge of these electrodes in actual battery cells. Significant differences were observed in the two batches, particularly in the intercalation range of x = 0.45 to 0.20. The first-order structural transitions in this region indicated coexistence of two cubic phases in the batch 2more » material, whereas the batch 1 material showed suppressed two-phase coexistence. Batch 2 cells also indicated structural evolution in the low-potential region below 3.0 V in contrast to the batch 1 material. Differences in structural evolution between batches of Li{sub x}Mn{sub 2}O{sub 4} could have important ramifications in their cycle life and stability characteristics.« less

Structural and spectroscopic analysis of ex-situ annealed RF sputtered aluminium doped zinc oxide thin films

NASA Astrophysics Data System (ADS)

Otieno, Francis; Airo, Mildred; Erasmus, Rudolph M.; Billing, David G.; Quandt, Alexander; Wamwangi, Daniel

2017-08-01

Aluminium doped zinc oxide thin films are prepared by Radio Frequency magnetron sputtering in pure argon atmosphere at 100 W. The structural results reveal good film adhesion on a silicon substrate (001). The thin films were then subjected to heat treatment in a furnace under ambient air. The structural, morphological, and optical properties of the thin films as a function of deposition time and annealing temperatures have been investigated using Grazing incidence X-Ray Diffraction (GIXRD), Atomic Force Microscopy, and Scanning Electronic Microscopy. The photoluminescence properties of the annealed films showed significant changes in the optical properties attributed to mid gap defects. Annealing increases the crystallite size and the roughness of the film. The crystallinity of the films also improved as evident from the Raman and XRD studies.

Enhanced functional connectivity properties of human brains during in-situ nature experience

PubMed Central

2016-01-01

In this study, we investigated the impacts of in-situ nature and urban exposure on human brain activities and their dynamics. We randomly assigned 32 healthy right-handed college students (mean age = 20.6 years, SD = 1.6; 16 males) to a 20 min in-situ sitting exposure in either a nature (n = 16) or urban environment (n = 16) and measured their Electroencephalography (EEG) signals. Analyses revealed that a brief in-situ restorative nature experience may induce more efficient and stronger brain connectivity with enhanced small-world properties compared with a stressful urban experience. The enhanced small-world properties were found to be correlated with “coherent” experience measured by Perceived Restorativeness Scale (PRS). Exposure to nature also induces stronger long-term correlated activity across different brain regions with a right lateralization. These findings may advance our understanding of the functional activities during in-situ environmental exposures and imply that a nature or nature-like environment may potentially benefit cognitive processes and mental well-being. PMID:27547533

In situ visualization of domain structure evolution during field cooling in 0.67PMN-0.33PT single crystal

NASA Astrophysics Data System (ADS)

Ushakov, A. D.; Esin, A. A.; Chezganov, D. S.; Turygin, A. P.; Akhmatkhanov, A. R.; Hu, Q.; Sun, L.; Wei, X.; Shur, V. Ya

2017-10-01

The evolution of the domain structure during in-field cooling was in situ studied in [001]-cut single crystals of relaxor ferroelectric (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT) with x = 0.33 with maximum of dielectric permittivity at 150°C. The main stages of domain evolution have been separated. The visualization of the static as-grown and polarized domain structures with high spatial resolution by piezoresponse force microscopy and scanning electron microscopy allowed measuring the characteristic features of maze and needle-like domain structures.

Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry.

PubMed

Durham, Jessica L; Poyraz, Altug S; Takeuchi, Esther S; Marschilok, Amy C; Takeuchi, Kenneth J

2016-09-20

Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and mass of the final system. Material multifunctionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cations can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multimechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM'O) or phosphorus oxides (MM'PO) where M = Ag and M' = V or Fe. One discharge process can be described as reduction-displacement where Ag(+) is reduced to Ag(0) and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity, determining the kinetically and thermodynamically preferred reduction processes at various states of discharge is critical to elucidating the mechanism. Specific advanced in situ and ex situ characterization techniques are conducive to gaining insight regarding the electrochemical behavior of these multifunctional materials over multiple length scales. At the material level, optical microscopy, scanning electron microscopy, and local conductivity measurement via a nanoprobe can track the discharge mechanism of an isolated single particle. At the mesoscale electrode level, in situ data from synchrotron based energy dispersive X-ray diffraction (EDXRD) within fully intact steel batteries can be used to spatially map the distribution of silver metal generated through reduction displacement as a function of discharge depth and discharge rate. As illustrated here, appropriate design of materials with multiple electrochemically active metal centers and properties tuned through strategically conceptualized materials synthesis may provide a path toward the next generation of high energy content electroactive materials and systems. Full understanding of the multiple electrochemical mechanisms can be achieved only by utilizing advanced characterization tools over multiple length scales.

In Situ Transformation of MOFs into Layered Double Hydroxide Embedded Metal Sulfides for Improved Electrocatalytic and Supercapacitive Performance.

PubMed

Yilmaz, Gamze; Yam, Kah Meng; Zhang, Chun; Fan, Hong Jin; Ho, Ghim Wei

2017-07-01

Direct adoption of metal-organic frameworks (MOFs) as electrode materials shows impoverished electrochemical performance owing to low electrical conductivity and poor chemical stability. In this study, we demonstrate self-templated pseudomorphic transformation of MOF into surface chemistry rich hollow framework that delivers highly reactive, durable, and universal electrochemically active energy conversion and storage functionalities. In situ pseudomorphic transformation of MOF-derived hollow rhombic dodecahedron template and sulfurization of nickel cobalt layered double hydroxides (NiCo-LDHs) lead to the construction of interlayered metal sulfides (NiCo-LDH/Co 9 S 8 ) system. The embedment of metal sulfide species (Co 9 S 8 ) at the LDH intergalleries offers optimal interfacing of the hybrid constituent elements and materials stability. The hybrid NiCo-LDH/Co 9 S 8 system collectively presents an ideal porous structure, rich redox chemistry, and high electrical conductivity matrix. This leads to a significant enhancement in its complementary electrocatalytic hydrogen evolution and supercapacitive energy storage properties. This work establishes the potential of MOF derived scaffold for designing of novel class hybrid inorganic-organic functional materials for electrochemical applications and beyond. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Markers for the identification of tendon-derived stem cells in vitro and tendon stem cells in situ - update and future development.

PubMed

Lui, Pauline Po Yee

2015-06-02

The efficacy of tendon-derived stem cells (TDSCs) for the promotion of tendon and tendon-bone junction repair has been reported in animal studies. Modulation of the tendon stem cell niche in vivo has also been reported to influence tendon structure. There is a need to have specific and reliable markers that can define TDSCs in vitro and tendon stem cells in situ for several reasons: to understand the basic biology of TDSCs and their subpopulations in vitro; to understand the identity, niches and functions of tendon/progenitor stem cells in vivo; to meet the governmental regulatory requirements for quality of TDSCs when translating the exciting preclinical findings into clinical trial/practice; and to develop new treatment strategies for mobilizing endogenous stem/progenitor cells in tendon. TDSCs were reported to express the common mesenchymal stem cell (MSC) markers and some embryonic stem cell (ESC) markers, and there were attempts to use these markers to label tendon stem cells in situ. Are these stem cell markers useful for the identification of TDSCs in vitro and tracking of tendon stem cells in situ? This review aims to discuss the values of the panel of MSC, ESC and tendon-related markers for the identification of TDSCs in vitro. Important factors influencing marker expression by TDSCs are discussed. The usefulness and limitations of the panel of MSC, ESC and tendon-related markers for tracking stem cells in tendon, especially tendon stem cells, in situ are then reviewed. Future research directions are proposed.

A Protein Structure Initiative Approach to Expression, Purification, and In Situ Delivery of Human Cytochrome b5 to Membrane Vesicles†

PubMed Central

Sobrado, Pablo; Goren, Michael A.; James, Declan; Amundson, Carissa K.; Fox, Brian G.

2008-01-01

A specialized vector backbone from the Protein Structure Initiative was used to express full-length human cytochrome b5 as a C-terminal fusion to His8-maltose binding protein in Escherichia coli. The fusion protein could be completely cleaved by tobacco etch virus protease, and a yield of ~18 mg of purified full-length human cytochrome b5 per liter of culture medium was obtained (2.3 mg per]of wet weight bacterial cells). In situ proteolysis of the fusion protein in the presence of chemically defined synthetic liposomes allowed facile spontaneous delivery of the functional peripheral membrane protein into a defined membrane environment without prior exposure to detergents or other lipids. The utility of this approach as a delivery method for production and incorporation of monotopic (peripheral) membrane proteins is discussed. PMID:18226920

A Protein Structure Initiative approach to expression, purification, and in situ delivery of human cytochrome b5 to membrane vesicles.

PubMed

Sobrado, Pablo; Goren, Michael A; James, Declan; Amundson, Carissa K; Fox, Brian G

2008-04-01

A specialized vector backbone from the Protein Structure Initiative was used to express full-length human cytochrome b5 as a C-terminal fusion to His8-maltose binding protein in Escherichia coli. The fusion protein could be completely cleaved by tobacco etch virus protease, and a yield of approximately 18 mg of purified full-length human cytochrome b5 per liter of culture medium was obtained (2.3mg per g of wet weight bacterial cells). In situ proteolysis of the fusion protein in the presence of chemically defined synthetic liposomes allowed facile spontaneous delivery of the functional peripheral membrane protein into a defined membrane environment without prior exposure to detergents or other lipids. The utility of this approach as a delivery method for production and incorporation of monotopic (peripheral) membrane proteins is discussed.

Correlation of In Situ Measurements of Plasma Irregularities with Ground-Based Scintillation Observations

DTIC Science & Technology

2010-06-01

extensive case study of the relationships between the observation of in situ irregularities, UHF scintillation observed by the Scin - tillation Decision...use these space-based measurements, however, the correlation between the structures and the resulting scin - tillation must be quantified. [10] As a

In-situ poling and structurization of piezoelectric particulate composites.

PubMed

Khanbareh, H; van der Zwaag, S; Groen, W A

2017-11-01

Composites of lead zirconate titanate particles in an epoxy matrix are prepared in the form of 0-3 and quasi 1-3 with different ceramic volume contents from 10% to 50%. Two different processing routes are tested. Firstly a conventional dielectrophoretic structuring is used to induce a chain-like particle configuration, followed by curing the matrix and poling at a high temperature and under a high voltage. Secondly a simultaneous combination of dielectrophoresis and poling is applied at room temperature while the polymer is in the liquid state followed by subsequent curing. This new processing route is practiced in an uncured thermoset system while the polymer matrix still possess a relatively high electrical conductivity. Composites with different degrees of alignment are produced by altering the magnitude of the applied electric field. A significant improvement in piezoelectric properties of quasi 1-3 composites can be achieved by a combination of dielectrophoretic alignment of the ceramic particles and poling process. It has been observed that the degree of structuring as well as the functional properties of the in-situ structured and poled composites enhance significantly compared to those of the conventionally manufactured structured composites. Improving the alignment quality enhances the piezoelectric properties of the particulate composites.

AFM Structural Characterization of Drinking Water Biofilm ...

EPA Pesticide Factsheets

Due to the complexity of mixed culture drinking water biofilm, direct visual observation under in situ conditions has been challenging. In this study, atomic force microscopy (AFM) revealed the three dimensional morphology and arrangement of drinking water relevant biofilm in air and aqueous solution. Operating parameters were optimized to improve imaging of structural details for a mature biofilm in liquid. By using a soft cantilever (0.03 N/m) and slow scan rate (0.5 Hz), biofilm and individual bacterial cell’s structural topography were resolved and continuously imaged in liquid without loss of spatial resolution or sample damage. The developed methodology will allow future in situ investigations to temporally monitor mixed culture drinking water biofilm structural changes during disinfection treatments. Due to the complexity of mixed culture drinking water biofilm, direct visual observation under in situ conditions has been challenging. In this study, atomic force microscopy (AFM) revealed the three dimensional morphology and arrangement of drinking water relevant biofilm in air and aqueous solution. Operating parameters were optimized to improve imaging of structural details for a mature biofilm in liquid. By using a soft cantilever (0.03 N/m) and slow scan rate (0.5 Hz), biofilm and individual bacterial cell’s structural topography were resolved and continuously imaged in liquid without loss of spatial resolution or sample damage. The developed methodo

In-situ spectroscopic analysis of the traditional dyeing pigment Turkey red inside textile matrix

NASA Astrophysics Data System (ADS)

Meyer, M.; Huthwelker, T.; Borca, C. N.; Meßlinger, K.; Bieber, M.; Fink, R. H.; Späth, A.

2018-03-01

Turkey red is a traditional pigment for textile dyeing and its use has been proven for various cultures within the last three millennia. The pigment is a dye-mordant complex consisting of Al and an extract from R. tinctorum that contains mainly the anthraquinone derivative alizarin. The chemical structure of the complex has been analyzed by various spectroscopic and crystallographic techniques for extractions from textiles or directly in solution. We present an in-situ study of Turkey red by means of μ-XRF mapping and NEXAFS spectroscopy on textile fibres dyed according to a traditional process to gain insight into the coordination chemistry of the pigment in realistic matrix. We find an octahedral coordination of Al that corresponds well to the commonly accepted structure of the Al alizarin complex derived from ex-situ studies.

Intercellular communication via gap junctions affected by mechanical load in the bovine annulus fibrosus.

PubMed

Desrochers, Jane; Duncan, Neil A

2014-01-01

Cells in the intervertebral disc, as in other connective tissues including tendon, ligament and bone, form interconnected cellular networks that are linked via functional gap junctions. These cellular networks may be necessary to affect a coordinated response to mechanical and environmental stimuli. Using confocal microscopy with fluorescence recovery after photobleaching methods, we explored the in situ strain environment of the outer annulus of an intact bovine disc and the effect of high-level flexion on gap junction signalling. The in situ strain environment in the extracellular matrix of the outer annulus under high flexion load was observed to be non-uniform with the extensive cellular processes remaining crimped sometimes at flexion angles greater than 25°. A significant transient disruption of intercellular communication via functional gap junctions was measured after 10 and 20 min under high flexion load. This study illustrates that in healthy annulus fibrosus tissue, high mechanical loads can impede the functioning of the gap junctions. Future studies will explore more complex loading conditions to determine whether losses in intercellular communication can be permanent and whether gap junctions in aged and degenerated tissues become more susceptible to load. The current research suggests that cellular structures such as gap junctions and intercellular networks, as well as other cell-cell and cell-matrix interconnections, need to be considered in computational models in order to fully understand how macroscale mechanical signals are transmitted across scales to the microscale and ultimately into a cellular biosynthetic response in collagenous tissues.

Analysis of the C. elegans Nucleolus by Immuno-DNA FISH.

PubMed

Lanctôt, Christian

2016-01-01

Caenorhabditis elegans is a well-established model organism which allows, among others, to investigate the link between nucleolar structure/function on the one hand and cell fate choices and cellular differentiation on the other. In addition, C. elegans can be used to study the role of the nucleolus in processes that can be difficult to faithfully reproduce in vitro, such as gametogenesis, disease development, and aging. Here I present two complementary techniques, immunofluorescent staining and DNA fluorescence in situ hybridization, that have been adapted to label nucleolar components at various stages of the life cycle of the worm.

Delithiated states of layered cathode materials: doping and dispersion interaction effects on the structure

NASA Astrophysics Data System (ADS)

Eremin, Roman; Zolotarev, Pavel; Bobrikov, Ivan

2018-04-01

Here we present results of density functional theory (DFT) study of delithiated structures of layered LiNiO2 (LNO, Li12Ni12O24 model) cathode material and its doped analogue LiNi0.833Co0.083Al0.083O2 (N10C1A1, Li12Ni10CoAlO24 model). The paper is aimed at independent elucidation of doping and dispersion interaction effects on the structural stability of cathode materials studied. For this purpose, the LNO and N10C1A1 configurational spaces consisting of 87 and 4512 crystallographically independent configurations (obtained starting from 2×2×1 supercell of R-3m structure of LNO) are optimized within a number of DFT models. Based on a comparison of the calculated dependencies for the lattice parameters with the results of in situ neutron diffraction experiments, the most pronounced effect of cathode material stabilization is due to the dispersion interaction. In turn, the doping effect is found to affect cathode structure behavior at the latest stages of delithiation only.

Materials, structures, and devices for high-speed electronics

NASA Technical Reports Server (NTRS)

Woollam, John A.; Snyder, Paul G.

1992-01-01

Advances in materials, devices, and instrumentation made under this grant began with ex-situ null ellipsometric measurements of simple dielectric films on bulk substrates. Today highly automated and rapid spectroscopic ellipsometers are used for ex-situ characterization of very complex multilayer epitaxial structures. Even more impressive is the in-situ capability, not only for characterization but also for the actual control of the growth and etching of epitaxial layers. Spectroscopic ellipsometry has expanded from the research lab to become an integral part of the production of materials and structures for state of the art high speed devices. Along the way, it has contributed much to our understanding of the growth characteristics and material properties. The following areas of research are summarized: Si3N4 on GaAs, null ellipsometry; diamondlike carbon films; variable angle spectroscopic ellipsometry (VASE) development; GaAs-AlGaAs heterostructures; Ta-Cu diffusion barrier films on GaAs; GaAs-AlGaAs superlattices and multiple quantum wells; superconductivity; in situ elevated temperature measurements of III-V's; optical constants of thermodynamically stable InGaAs; doping dependence of optical constants of GaAs; in situ ellipsometric studies of III-V epitaxial growth; photothermal spectroscopy; microellipsometry; and Si passivation and Si/SiGe strained-layer superlattices.

Ab initio structure search and in situ 7Li NMR studies of discharge products in the Li–S battery system

DOE PAGES

See, Kimberly A.; Leskes, Michal; Griffin, John M.; ...

2014-11-10

The high theoretical gravimetric capacity of the Li–S battery system makes it an attractive candidate for numerous energy storage applications. In practice, cell performance is plagued by low practical capacity and poor cycling. In an effort to explore the mechanism of the discharge with the goal of better understanding performance, we examine the Li–S phase diagram using computational techniques and complement this with an in situ 7Li NMR study of the cell during discharge. Both the computational and experimental studies are consistent with the suggestion that the only solid product formed in the cell is Li 2S, formed soon aftermore » cell discharge is initiated. In situ NMR spectroscopy also allows the direct observation of soluble Li +-species during cell discharge; species that are known to be highly detrimental to capacity retention. We suggest that during the first discharge plateau, S is reduced to soluble polysulfide species concurrently with the formation of a solid component (Li 2S) which forms near the beginning of the first plateau, in the cell configuration studied here. The NMR data suggest that the second plateau is defined by the reduction of the residual soluble species to solid product (Li 2S). Lastly, a ternary diagram is presented to rationalize the phases observed with NMR during the discharge pathway and provide thermodynamic underpinnings for the shape of the discharge profile as a function of cell composition.« less

The Exotic Legume Tree Species Acacia holosericea Alters Microbial Soil Functionalities and the Structure of the Arbuscular Mycorrhizal Community▿

PubMed Central

Remigi, P.; Faye, A.; Kane, A.; Deruaz, M.; Thioulouse, J.; Cissoko, M.; Prin, Y.; Galiana, A.; Dreyfus, B.; Duponnois, R.

2008-01-01

The response of microbial functional diversity as well as its resistance to stress or disturbances caused by the introduction of an exotic tree species, Acacia holosericea, ectomycorrhized or not with Pisolithus albus, was examined. The results show that this ectomycorrhizal fungus promotes drastically the growth of this fast-growing tree species in field conditions after 7 years of plantation. Compared to the crop soil surrounding the A. holosericea plantation, this exotic tree species, associated or not with the ectomycorrhizal symbiont, induced strong modifications in soil microbial functionalities (assessed by measuring the patterns of in situ catabolic potential of microbial communities) and reduced soil resistance in response to increasing stress or disturbance (salinity, temperature, and freeze-thaw and wet-dry cycles). In addition, A. holosericea strongly modified the structure of arbuscular mycorrhizal fungus communities. These results show clearly that exotic plants may be responsible for important changes in soil microbiota affecting the structure and functions of microbial communities. PMID:18203858

Uriniferous tubule: structural and functional organization.

PubMed

Christensen, Erik Ilsø; Wagner, Carsten A; Kaissling, Brigitte

2012-04-01

The uriniferous tubule is divided into the proximal tubule, the intermediate (thin) tubule, the distal tubule and the collecting duct. The present chapter is based on the chapters by Maunsbach and Christensen on the proximal tubule, and by Kaissling and Kriz on the distal tubule and collecting duct in the 1992 edition of the Handbook of Physiology, Renal Physiology. It describes the fine structure (light and electron microscopy) of the entire mammalian uriniferous tubule, mainly in rats, mice, and rabbits. The structural data are complemented by recent data on the location of the major transport- and transport-regulating proteins, revealed by morphological means(immunohistochemistry, immunofluorescence, and/or mRNA in situ hybridization). The structural differences along the uriniferous tubule strictly coincide with the distribution of the major luminal and basolateral transport proteins and receptors and both together provide the basis for the subdivision of the uriniferous tubule into functional subunits. Data on structural adaptation to defined functional changes in vivo and to genetical alterations of specified proteins involved in transepithelial transport importantly deepen our comprehension of the correlation of structure and function in the kidney, of the role of each segment or cell type in the overall renal function,and our understanding of renal pathophysiology. © 2012 American Physiological Society. Compr Physiol 2:933-996, 2012.

In situ spectroscopic monitoring of CO2 reduction at copper oxide electrode.

PubMed

Wang, Liying; Gupta, Kalyani; Goodall, Josephine B M; Darr, Jawwad A; Holt, Katherine B

2017-04-28

Copper oxide modified electrodes were investigated as a function of applied electrode potential using in situ infrared spectroscopy and ex situ Raman and X-ray photoelectron spectroscopy. In deoxygenated KHCO 3 electrolyte bicarbonate and carbonate species were found to adsorb to the electrode during reduction and the CuO was reduced to Cu(i) or Cu(0) species. Carbonate was incorporated into the structure and the CuO starting material was not regenerated on cycling to positive potentials. In contrast, in CO 2 saturated KHCO 3 solution, surface adsorption of bicarbonate and carbonate was not observed and adsorption of a carbonato-species was observed with in situ infrared spectroscopy. This species is believed to be activated, bent CO 2 . On cycling to negative potentials, larger reduction currents were observed in the presence of CO 2 ; however, less of the charge could be attributed to the reduction of CuO. In the presence of CO 2 CuO underwent reduction to Cu 2 O and potentially Cu, with no incorporation of carbonate. Under these conditions the CuO starting material could be regenerated by cycling to positive potentials.

Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durham, Jessica L.; Poyraz, Altug S.; Takeuchi, Esther S.

Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and massmore » of the final system. Material multi-functionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cation can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multi-mechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM’O) or phosphorous oxides (MM’PO) where M = Ag and M’ = V or Fe. One discharge process can be described as reduction-displacement where Ag + is reduced to Ag 0 and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in-situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity, determining the kinetically and thermodynamically preferred reduction processes at various states of discharge is critical to elucidating the mechanism. Specific advanced in-situ and ex-situ characterization techniques are conducive to gaining insight regarding the electrochemical behavior of these multifunctional materials over multiple length scales. At the material level, optical microscopy, scanning electron microscopy, and local conductivity measurement via a nanoprobe can track the discharge mechanism of an isolated single particle. At the mesoscale electrode level, in-situ data from synchrotron based energy dispersive X-ray diffraction (EDXRD) within fully intact steel batteries can be used to spatially map the distribution of silver metal generated through reduction displacement as a function of discharge depth and discharge rate. As illustrated here, appropriate design of materials with multiple electrochemically active metal centers and properties tuned through strategically conceptualized materials synthesis may provide a path toward the next generation of high energy content electroactive materials and systems. In conclusion, full understanding of the multiple electrochemical mechanisms can be achieved only by utilizing advanced characterization tools over multiple length scales.« less

Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry

DOE PAGES

Durham, Jessica L.; Poyraz, Altug S.; Takeuchi, Esther S.; ...

2016-08-26

Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and massmore » of the final system. Material multi-functionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cation can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multi-mechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM’O) or phosphorous oxides (MM’PO) where M = Ag and M’ = V or Fe. One discharge process can be described as reduction-displacement where Ag + is reduced to Ag 0 and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in-situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity, determining the kinetically and thermodynamically preferred reduction processes at various states of discharge is critical to elucidating the mechanism. Specific advanced in-situ and ex-situ characterization techniques are conducive to gaining insight regarding the electrochemical behavior of these multifunctional materials over multiple length scales. At the material level, optical microscopy, scanning electron microscopy, and local conductivity measurement via a nanoprobe can track the discharge mechanism of an isolated single particle. At the mesoscale electrode level, in-situ data from synchrotron based energy dispersive X-ray diffraction (EDXRD) within fully intact steel batteries can be used to spatially map the distribution of silver metal generated through reduction displacement as a function of discharge depth and discharge rate. As illustrated here, appropriate design of materials with multiple electrochemically active metal centers and properties tuned through strategically conceptualized materials synthesis may provide a path toward the next generation of high energy content electroactive materials and systems. In conclusion, full understanding of the multiple electrochemical mechanisms can be achieved only by utilizing advanced characterization tools over multiple length scales.« less

Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Seung-Yong; Wu, Lijun; Poyraz, Altug S.

Manganese oxide (α-MnO 2) has been considered as a promising energy material, including as a lithium-based battery electrode candidate, due to its environmental friendliness. Thanks to its unique 1D [2 × 2] tunnel structure, α-MnO 2 can be applied to a cathode by insertion reaction and to an anode by conversion reaction in corresponding voltage ranges, in a lithium-based battery. Numerous reports have attributed its remarkable performance to its unique tunnel structure; however, the precise electrochemical reaction mechanism remains unknown. In this study, finding of the lithiation mechanism of α-MnO 2 nanowire by in situ transmission electron microscopy (TEM) ismore » reported. By elaborately modifying the existing in situ TEM experimental technique, rapid lithium-ion diffusion through the tunnels is verified. Furthermore, by tracing the full lithiation procedure, the evolution of the MnO intermediate phase and the development of the MnO and Li 2O phases with preferred orientations is demonstrated, which explains how the conversion reaction occurs in α-MnO 2 material. This study provides a comprehensive understanding of the electrochemical lithiation process and mechanism of α-MnO 2 material, in addition to the introduction of an improved in situ TEM biasing technique.« less

Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy

DOE PAGES

Lee, Seung-Yong; Wu, Lijun; Poyraz, Altug S.; ...

2017-10-06

Manganese oxide (α-MnO 2) has been considered as a promising energy material, including as a lithium-based battery electrode candidate, due to its environmental friendliness. Thanks to its unique 1D [2 × 2] tunnel structure, α-MnO 2 can be applied to a cathode by insertion reaction and to an anode by conversion reaction in corresponding voltage ranges, in a lithium-based battery. Numerous reports have attributed its remarkable performance to its unique tunnel structure; however, the precise electrochemical reaction mechanism remains unknown. In this study, finding of the lithiation mechanism of α-MnO 2 nanowire by in situ transmission electron microscopy (TEM) ismore » reported. By elaborately modifying the existing in situ TEM experimental technique, rapid lithium-ion diffusion through the tunnels is verified. Furthermore, by tracing the full lithiation procedure, the evolution of the MnO intermediate phase and the development of the MnO and Li 2O phases with preferred orientations is demonstrated, which explains how the conversion reaction occurs in α-MnO 2 material. This study provides a comprehensive understanding of the electrochemical lithiation process and mechanism of α-MnO 2 material, in addition to the introduction of an improved in situ TEM biasing technique.« less

Direct 3D Printing of Catalytically Active Structures

DOE PAGES

Manzano, J. Sebastian; Weinstein, Zachary B.; Sadow, Aaron D.; ...

2017-09-22

3D printing of materials with active functional groups can provide custom-designed structures that promote chemical conversions. Catalytically active architectures were produced by photopolymerizing bifunctional molecules using a commercial stereolithographic 3D printer. Functionalities in the monomers included a polymerizable vinyl group to assemble the 3D structures and a secondary group to provide them with active sites. The 3D-printed architectures containing accessible carboxylic acid, amine, and copper carboxylate functionalities were catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions, respectively. The functional groups in the 3D-printed structures were also amenable to post-printing chemical modification. And as proof of principle, chemically activemore » cuvette adaptors were 3D printed and used to measure in situ the kinetics of a heterogeneously catalyzed Mannich reaction in a conventional solution spectrophotometer. In addition, 3D-printed millifluidic devices with catalytically active copper carboxylate complexes were used to promote azide-alkyne cycloaddition under flow conditions. The importance of controlling the 3D architecture of the millifluidic devices was evidenced by enhancing reaction conversion upon increasing the complexity of the 3D prints.« less

Direct 3D Printing of Catalytically Active Structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manzano, J. Sebastian; Weinstein, Zachary B.; Sadow, Aaron D.

3D printing of materials with active functional groups can provide custom-designed structures that promote chemical conversions. Catalytically active architectures were produced by photopolymerizing bifunctional molecules using a commercial stereolithographic 3D printer. Functionalities in the monomers included a polymerizable vinyl group to assemble the 3D structures and a secondary group to provide them with active sites. The 3D-printed architectures containing accessible carboxylic acid, amine, and copper carboxylate functionalities were catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions, respectively. The functional groups in the 3D-printed structures were also amenable to post-printing chemical modification. And as proof of principle, chemically activemore » cuvette adaptors were 3D printed and used to measure in situ the kinetics of a heterogeneously catalyzed Mannich reaction in a conventional solution spectrophotometer. In addition, 3D-printed millifluidic devices with catalytically active copper carboxylate complexes were used to promote azide-alkyne cycloaddition under flow conditions. The importance of controlling the 3D architecture of the millifluidic devices was evidenced by enhancing reaction conversion upon increasing the complexity of the 3D prints.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roy, Surajit; Ladpli, Purim; Chang, Fu-Kuo

Accurate interpretation of in-situ piezoelectric sensor signals is a challenging task. This article presents the development of a numerical compensation model based on physical insight to address the influence of structural loads on piezo-sensor signals. The model requires knowledge of in-situ strain and temperature distribution in a structure while acquiring sensor signals. The parameters of the numerical model are obtained using experiments on flat aluminum plate under uniaxial tensile loading. It is shown that the model parameters obtained experimentally can be used for different structures, and sensor layout. Furthermore, the combined effects of load and temperature on the piezo-sensor responsemore » are also investigated and it is observed that both of these factors have a coupled effect on the sensor signals. It is proposed to obtain compensation model parameters under a range of operating temperatures to address this coupling effect. An important outcome of this study is a new load monitoring concept using in-situ piezoelectric sensor signals to track changes in the load paths in a structure.« less

Solvent exchange in a metal–organic framework single crystal monitored by dynamic in situ X-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cox, Jordan M.; Walton, Ian M.; Bateman, Gage

2017-07-25

Understanding the processes by which porous solid-state materials adsorb and release guest molecules would represent a significant step towards developing rational design principles for functional porous materials. To elucidate the process of liquid exchange in these materials, dynamicin situX-ray diffraction techniques have been developed which utilize liquid-phase chemical stimuli. Using these time-resolved diffraction techniques, the ethanol solvation process in a flexible metal–organic framework [Co(AIP)(bpy) 0.5(H 2O)]·2H 2O was examined. The measurements provide important insight into the nature of the chemical transformation in this system including the presence of a previously unreported neat ethanol solvate structure.

Ordering in bio-inorganic hybrid nanomaterials probed by in situ scanning transmission X-ray microscopy

DOE PAGES

Lee, Jonathan R. I.; Bagge-Hansen, Michael; Tunuguntla, Ramya; ...

2015-04-15

Here, phospholipid bilayer coated Si nanowires are one-dimensional (1D) composites that provide versatile bio-nanoelectronic functionality via incorporation of a wide variety of biomolecules into the phospholipid matrix. The physiochemical behaviour of the phospholipid bilayer is strongly dependent on its structure and, as a consequence, substantial modelling and experimental efforts have been directed at the structural characterization of supported bilayers and unsupported phospholipid vesicles; nonetheless, the experimental studies conducted to date have exclusively involved volume-averaged techniques, which do not allow for the assignment of spatially resolved structural variations that could critically impact the performance of the 1D phospholipid-Si NW composites. Inmore » this manuscript, we use scanning transmission X-ray microscopy (STXM) to probe bond orientation and bilayer thickness as a function of position with a spatial resolution of ~30 nm for Δ9-cis 1,2-dioleoyl-sn-glycero-3-phosphocholine layers prepared Si NWs. When coupled with small angle X-ray scattering measurements, the STXM data reveal structural motifs of the Si NWs that give rise to multi-bilayer formation and enable assignment of the orientation of specific bonds known to affect the order and rigidity of phospholipid bilayers.« less

Electric-field-induced local and mesoscale structural changes in polycrystalline dielectrics and ferroelectrics

DOE PAGES

Usher, Tedi -Marie; Levin, Igor; Daniels, John E.; ...

2015-10-01

In this study, the atomic-scale response of dielectrics/ferroelectrics to electric fields is central to their functionality. Here we introduce an in situ characterization method that reveals changes in the local atomic structure in polycrystalline materials under fields. The method employs atomic pair distribution functions (PDFs), determined from X-ray total scattering that depends on orientation relative to the applied field, to probe structural changes over length scales from sub-Ångstrom to several nanometres. The PDF is sensitive to local ionic displacements and their short-range order, a key uniqueness relative to other techniques. The method is applied to representative ferroelectrics, BaTiO 3 andmore » Na ½Bi ½TiO 3, and dielectric SrTiO 3. For Na ½Bi ½TiO 3, the results reveal an abrupt field-induced monoclinic to rhombohedral phase transition, accompanied by ordering of the local Bi displacements and reorientation of the nanoscale ferroelectric domains. For BaTiO 3 and SrTiO 3, the local/nanoscale structural changes observed in the PDFs are dominated by piezoelectric lattice strain and ionic polarizability, respectively.« less

Real Time Fatigue Damage Growth Assessment of a Composite Three-Stringer Panel Using Passive Thermography

NASA Technical Reports Server (NTRS)

Zalameda, Joseph N.; Burke, Eric R.; Horne, Michael R.; Bly, James B.

2015-01-01

Fatigue testing of advanced composite structures is critical to validate both structural designs and damage prediction models. In-situ inspection methods are necessary to track damage onset and growth as a function of load cycles. Passive thermography is a large area, noncontact inspection technique that is used to detect composite damage onset and growth in real time as a function of fatigue cycles. The thermal images are acquired in synchronicity to the applied compressive load using a dual infrared camera acquisition system for full (front and back) coverage. Image processing algorithms are investigated to increase defect contrast areas. The thermal results are compared to non-immersion ultrasound inspections and acoustic emission data.

Structure and optical properties of silica-supported Ag-Au nanoparticles.

PubMed

Barreca, Davide; Gasparotto, Alberto; Maragno, Cinzia; Tondello, Eugenio; Gialanella, Stefano

2007-07-01

Bimetallic Ag-Au nanoparticles are synthesized by sequential deposition of Au and Ag on amorphous silica by Radio Frequency (RF)-sputtering under mild conditions. Specimens are thoroughly characterized by a multi-technique approach, aimed at investigating the system properties as a function of the Ag/Au content, as well as the evolution induced by ex-situ annealing under inert (N2) or reducing (4% H2/N2) atmospheres. The obtained results demonstrate the possibility to obtain Ag-Au alloyed nanoparticles with controllable size, shape, structure, and dispersion under mild conditions, so that the optical properties can be finely tuned as a function of the synthesis and thermal treatment conditions.

In-situ crystallization of GeTe\\GaSb phase change memory stacked films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Velea, A., E-mail: alin.velea@psi.ch; National Institute of Materials Physics, RO-077125 Magurele, Ilfov; Borca, C. N.

2014-12-21

Single and double layer phase change memory structures based on GeTe and GaSb thin films were deposited by pulsed laser deposition (PLD). Their crystallization behavior was studied using in-situ synchrotron techniques. Electrical resistance vs. temperature investigations, using the four points probe method, showed transition temperatures of 138 °C and 198 °C for GeTe and GaSb single films, respectively. It was found that after GeTe crystallization in the stacked films, Ga atoms from the GaSb layer diffused in the vacancies of the GeTe crystalline structure. Therefore, the crystallization temperature of the Sb-rich GaSb layer is decreased by more than 30 °C. Furthermore, at 210 °C,more » the antimony excess from GaSb films crystallizes as a secondary phase. At higher annealing temperatures, the crystalline Sb phase increased on the expense of GaSb crystalline phase which was reduced. Extended X-ray absorption fine structure (EXAFS) measurements at the Ga and Ge K-edges revealed changes in their local atomic environments as a function of the annealing temperature. Simulations unveil a tetrahedral configuration in the amorphous state and octahedral configuration in the crystalline state for Ge atoms, while Ga is four-fold coordinated in both as-deposited and annealed samples.« less

Observation of electromigration in a Cu thin line by in situ coherent x-ray diffraction microscopy

NASA Astrophysics Data System (ADS)

Takahashi, Yukio; Nishino, Yoshinori; Furukawa, Hayato; Kubo, Hideto; Yamauchi, Kazuto; Ishikawa, Tetsuya; Matsubara, Eiichiro

2009-06-01

Electromigration (EM) in a 1-μm-thick Cu thin line was investigated by in situ coherent x-ray diffraction microscopy (CXDM). Characteristic x-ray speckle patterns due to both EM-induced voids and thermal deformation in the thin line were observed in the coherent x-ray diffraction patterns. Both parts of the voids and the deformation were successfully visualized in the images reconstructed from the diffraction patterns. This result not only represents the first demonstration of the visualization of structural changes in metallic materials by in situ CXDM but is also an important step toward studying the structural dynamics of nanomaterials using x-ray free-electron lasers in the near future.

The development of in situ fracture toughness evaluation techniques in hydrogen environment

DOE PAGES

Wang, John Jy-An; Ren, Fei; Tan, Tin; ...

2014-12-19

Reliability of hydrogen pipelines and storage tanks is significantly influenced by the mechanical performance of the structural materials exposed in the hydrogen environment. Fracture behavior and fracture toughness are of specific interest since they are relevant to many catastrophic failures. However, many conventional fracture testing techniques are difficult to be realized under the presence of hydrogen. Thus it is desired to develop novel in situ techniques to study the fracture behavior of structural materials in hydrogen environments. In this study, special testing apparatus were designed to facilitate in situ fracture testing in H 2. A torsional fixture was developed tomore » utilize an emerging fracture testing technique, Spiral Notch Torsion Test (SNTT). The design concepts will be discussed. Preliminary in situ testing results indicated that the exposure to H 2 significantly reduces the fracture toughness of 4340 high strength steels by up to 50 percent. Furthermore, SNTT tests conducted in air demonstrated a significant fracture toughness reduction in samples subject to simulated welding heat treatment using Gleeble, which illustrated the effect of welding on the fracture toughness of this material.« less

Active damage interrogation system for structural health monitoring

NASA Astrophysics Data System (ADS)

Lichtenwalner, Peter F.; Dunne, James P.; Becker, Ronald S.; Baumann, Erwin W.

1997-05-01

An integrated and automated smart structures approach for in situ damage assessment has been implemented and evaluated in a laboratory environment for health monitoring of a realistic aerospace structural component. This approach, called Active Damage Interrogation (ADI), utilizes an array of piezoelectric transducers attached to or embedded within the structure for both actuation and sensing. The ADI system, which is model independent, actively interrogates the structure through broadband excitation of multiple actuators across the desired frequency range. Statistical analysis of the changes in transfer functions between actuator/sensor pairs is used to detect, localize, and assess the severity of damage in the structure. This paper presents the overall concept of the ADI system and provides experimental results of damage assessment studies conducted for a composite structural component of the MD-900 Explorer helicopter rotor system. The potential advantages of this approach include simplicity (no need for a model), sensitivity, and low cost implementation. The results obtained thus far indicate considerably promise for integrated structural health monitoring of aerospace vehicles, leading to the practice of condition-based maintenance and consequent reduction in life cycle costs.

Improving Attachments of Remotely-Deployed Dorsal Fin-Mounted Tags: Tissue Structure, Hydrodynamics, In Situ Performance, and Tagged-Animal Follow-Up

DTIC Science & Technology

2013-09-30

in situ performance of our current attachment devices and then design and test improved retention systems 4. Conduct follow-up studies of tagged... retention system operates when first implanted, we do not fully understand the mechanics in a living fin. Therefore, we will use non-invasive imaging of...carcass tissue to determine how the retention elements behave in situ. These results, along with those from the analysis of dorsal fin histology

In-situ X-ray diffraction studies of the phase transformations and structural states of B2, R and B19′ phases in Ti{sub 49.5}Ni{sub 50.5} alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ostapenko, Marina G., E-mail: artifakt@ispms.tsc.ru; National Research Tomsk Polytechnic University, Tomsk, 634050; Meisner, Ludmila L., E-mail: llm@ispms.tsc.ru

2015-10-27

The martensitic transformation, Debye–Waller factor, mean-square atomic displacements and the coefficient of thermal expansion on cooling of the Ti{sub 49.5}Ni{sub 50.5} shape memory alloy were examined using in-situ X-ray diffraction. It was revealed B2→R (T{sub R} ≡ T = 273 ± 10 K) along with B2→B19’ (M{sub s} ≡ T = 273 ± 10 K) transitions occur. It was found that Debye–Waller factor and mean-square displacement of B2 phase undergo significant increase as functions of temperature when phase transition B2→R and B2→B19’ take place. The analysis of the thermal expansion coefficient of the B2 phase indicates that the value of a increasesmore » almost linearly while cooling.« less

A global database of lake surface temperatures collected by in situ and satellite methods from 1985–2009

PubMed Central

Sharma, Sapna; Gray, Derek K; Read, Jordan S; O’Reilly, Catherine M; Schneider, Philipp; Qudrat, Anam; Gries, Corinna; Stefanoff, Samantha; Hampton, Stephanie E; Hook, Simon; Lenters, John D; Livingstone, David M; McIntyre, Peter B; Adrian, Rita; Allan, Mathew G; Anneville, Orlane; Arvola, Lauri; Austin, Jay; Bailey, John; Baron, Jill S; Brookes, Justin; Chen, Yuwei; Daly, Robert; Dokulil, Martin; Dong, Bo; Ewing, Kye; de Eyto, Elvira; Hamilton, David; Havens, Karl; Haydon, Shane; Hetzenauer, Harald; Heneberry, Jocelyne; Hetherington, Amy L; Higgins, Scott N; Hixson, Eric; Izmest’eva, Lyubov R; Jones, Benjamin M; Kangur, Külli; Kasprzak, Peter; Köster, Olivier; Kraemer, Benjamin M; Kumagai, Michio; Kuusisto, Esko; Leshkevich, George; May, Linda; MacIntyre, Sally; Müller-Navarra, Dörthe; Naumenko, Mikhail; Noges, Peeter; Noges, Tiina; Niederhauser, Pius; North, Ryan P; Paterson, Andrew M; Plisnier, Pierre-Denis; Rigosi, Anna; Rimmer, Alon; Rogora, Michela; Rudstam, Lars; Rusak, James A; Salmaso, Nico; Samal, Nihar R; Schindler, Daniel E; Schladow, Geoffrey; Schmidt, Silke R; Schultz, Tracey; Silow, Eugene A; Straile, Dietmar; Teubner, Katrin; Verburg, Piet; Voutilainen, Ari; Watkinson, Andrew; Weyhenmeyer, Gesa A; Williamson, Craig E; Woo, Kara H

2015-01-01

Global environmental change has influenced lake surface temperatures, a key driver of ecosystem structure and function. Recent studies have suggested significant warming of water temperatures in individual lakes across many different regions around the world. However, the spatial and temporal coherence associated with the magnitude of these trends remains unclear. Thus, a global data set of water temperature is required to understand and synthesize global, long-term trends in surface water temperatures of inland bodies of water. We assembled a database of summer lake surface temperatures for 291 lakes collected in situ and/or by satellites for the period 1985–2009. In addition, corresponding climatic drivers (air temperatures, solar radiation, and cloud cover) and geomorphometric characteristics (latitude, longitude, elevation, lake surface area, maximum depth, mean depth, and volume) that influence lake surface temperatures were compiled for each lake. This unique dataset offers an invaluable baseline perspective on global-scale lake thermal conditions as environmental change continues. PMID:25977814

A global database of lake surface temperatures collected by in situ and satellite methods from 1985-2009.

PubMed

Sharma, Sapna; Gray, Derek K; Read, Jordan S; O'Reilly, Catherine M; Schneider, Philipp; Qudrat, Anam; Gries, Corinna; Stefanoff, Samantha; Hampton, Stephanie E; Hook, Simon; Lenters, John D; Livingstone, David M; McIntyre, Peter B; Adrian, Rita; Allan, Mathew G; Anneville, Orlane; Arvola, Lauri; Austin, Jay; Bailey, John; Baron, Jill S; Brookes, Justin; Chen, Yuwei; Daly, Robert; Dokulil, Martin; Dong, Bo; Ewing, Kye; de Eyto, Elvira; Hamilton, David; Havens, Karl; Haydon, Shane; Hetzenauer, Harald; Heneberry, Jocelyne; Hetherington, Amy L; Higgins, Scott N; Hixson, Eric; Izmest'eva, Lyubov R; Jones, Benjamin M; Kangur, Külli; Kasprzak, Peter; Köster, Olivier; Kraemer, Benjamin M; Kumagai, Michio; Kuusisto, Esko; Leshkevich, George; May, Linda; MacIntyre, Sally; Müller-Navarra, Dörthe; Naumenko, Mikhail; Noges, Peeter; Noges, Tiina; Niederhauser, Pius; North, Ryan P; Paterson, Andrew M; Plisnier, Pierre-Denis; Rigosi, Anna; Rimmer, Alon; Rogora, Michela; Rudstam, Lars; Rusak, James A; Salmaso, Nico; Samal, Nihar R; Schindler, Daniel E; Schladow, Geoffrey; Schmidt, Silke R; Schultz, Tracey; Silow, Eugene A; Straile, Dietmar; Teubner, Katrin; Verburg, Piet; Voutilainen, Ari; Watkinson, Andrew; Weyhenmeyer, Gesa A; Williamson, Craig E; Woo, Kara H

2015-01-01

Global environmental change has influenced lake surface temperatures, a key driver of ecosystem structure and function. Recent studies have suggested significant warming of water temperatures in individual lakes across many different regions around the world. However, the spatial and temporal coherence associated with the magnitude of these trends remains unclear. Thus, a global data set of water temperature is required to understand and synthesize global, long-term trends in surface water temperatures of inland bodies of water. We assembled a database of summer lake surface temperatures for 291 lakes collected in situ and/or by satellites for the period 1985-2009. In addition, corresponding climatic drivers (air temperatures, solar radiation, and cloud cover) and geomorphometric characteristics (latitude, longitude, elevation, lake surface area, maximum depth, mean depth, and volume) that influence lake surface temperatures were compiled for each lake. This unique dataset offers an invaluable baseline perspective on global-scale lake thermal conditions as environmental change continues.

A global database of lake surface temperatures collected by in situ and satellite methods from 1985–2009

USGS Publications Warehouse

Sharma, Sapna; Gray, Derek; Read, Jordan S.; O'Reilly, Catherine; Schneider, Philipp; Qudrat, Anam; Gries, Corinna; Stefanoff, Samantha; Hampton, Stephanie; Hook, Simon; Lenters, John; Livingstone, David M.; McIntyre, Peter B.; Adrian, Rita; Allan, Mathew; Anneville, Orlane; Arvola, Lauri; Austin, Jay; Bailey, John E.; Baron, Jill S.; Brookes, Justin D; Chen, Yuwei; Daly, Robert; Ewing, Kye; de Eyto, Elvira; Dokulil, Martin; Hamilton, David B.; Havens, Karl; Haydon, Shane; Hetzenaeur, Harald; Heneberry, Jocelyn; Hetherington, Amy; Higgins, Scott; Hixson, Eric; Izmest'eva, Lyubov; Jones, Benjamin M.; Kangur, Kulli; Kasprzak, Peter; Kraemer, Benjamin; Kumagai, Michio; Kuusisto, Esko; Leshkevich, George; May, Linda; MacIntyre, Sally; Dörthe Müller-Navarra,; Naumenko, Mikhail; Noges, Peeter; Noges, Tiina; Pius Niederhauser,; North, Ryan P.; Andrew Paterson,; Plisnier, Pierre-Denis; Rigosi, Anna; Rimmer, Alon; Rogora, Michela; Rudstam, Lars G.; Rusak, James A.; Salmaso, Nico; Samal, Nihar R.; Daniel E. Schindler,; Geoffrey Schladow,; Schmidt, Silke R.; Tracey Schultz,; Silow, Eugene A.; Straile, Dietmar; Teubner, Katrin; Verburg, Piet; Voutilainen, Ari; Watkinson, Andrew; Weyhenmeyer, Gesa A.; Craig E. Williamson,; Kara H. Woo,

2015-01-01

Global environmental change has influenced lake surface temperatures, a key driver of ecosystem structure and function. Recent studies have suggested significant warming of water temperatures in individual lakes across many different regions around the world. However, the spatial and temporal coherence associated with the magnitude of these trends remains unclear. Thus, a global data set of water temperature is required to understand and synthesize global, long-term trends in surface water temperatures of inland bodies of water. We assembled a database of summer lake surface temperatures for 291 lakes collected in situ and/or by satellites for the period 1985–2009. In addition, corresponding climatic drivers (air temperatures, solar radiation, and cloud cover) and geomorphometric characteristics (latitude, longitude, elevation, lake surface area, maximum depth, mean depth, and volume) that influence lake surface temperatures were compiled for each lake. This unique dataset offers an invaluable baseline perspective on global-scale lake thermal conditions as environmental change continues.

Observing and modelling phytoplankton community structure in the North Sea

NASA Astrophysics Data System (ADS)

Ford, David A.; van der Molen, Johan; Hyder, Kieran; Bacon, John; Barciela, Rosa; Creach, Veronique; McEwan, Robert; Ruardij, Piet; Forster, Rodney

2017-03-01

Phytoplankton form the base of the marine food chain, and knowledge of phytoplankton community structure is fundamental when assessing marine biodiversity. Policy makers and other users require information on marine biodiversity and other aspects of the marine environment for the North Sea, a highly productive European shelf sea. This information must come from a combination of observations and models, but currently the coastal ocean is greatly under-sampled for phytoplankton data, and outputs of phytoplankton community structure from models are therefore not yet frequently validated. This study presents a novel set of in situ observations of phytoplankton community structure for the North Sea using accessory pigment analysis. The observations allow a good understanding of the patterns of surface phytoplankton biomass and community structure in the North Sea for the observed months of August 2010 and 2011. Two physical-biogeochemical ocean models, the biogeochemical components of which are different variants of the widely used European Regional Seas Ecosystem Model (ERSEM), were then validated against these and other observations. Both models were a good match for sea surface temperature observations, and a reasonable match for remotely sensed ocean colour observations. However, the two models displayed very different phytoplankton community structures, with one better matching the in situ observations than the other. Nonetheless, both models shared some similarities with the observations in terms of spatial features and inter-annual variability. An initial comparison of the formulations and parameterizations of the two models suggests that diversity between the parameter settings of model phytoplankton functional types, along with formulations which promote a greater sensitivity to changes in light and nutrients, is key to capturing the observed phytoplankton community structure. These findings will help inform future model development, which should be coupled with detailed validation studies, in order to help facilitate the wider application of marine biogeochemical modelling to user and policy needs.

Lunar Contour Crafting: A Novel Technique for ISRU-Based Habitat Development

NASA Technical Reports Server (NTRS)

Khoshnevis, Behrokh; Bodiford, Melanie P.; Burks, Kevin H.; Ethridge, Ed; Tucker, Dennis; Kim, Won; Toutanji, Houssam; Fiske, Michael R.

2005-01-01

1. Habitat Structures at MSFC is one element of the In-Situ Fabrication and Repair (ISFR) Program: ISFR develops technologies for fabrication, repair and recycling of tools, parts, and habitats/structures using in-situ resources. ISRU - based habitat structures are considered Class III. 2. Habitat Structure Purpose: Develop Lunar and/or Martian habitat structures for manned missions that maximize the use of in-situ resources to address the following agency topics: bioastronautics critical path roadmap; strategic technical challenges defined in H&RT formulation plan: margins and redundancy; modularity, robotic network, space resource utilization; autonomy, affordable logistics pre-positioning.

Lithium storage in structurally tunable carbon anode derived from sustainable source

DOE PAGES

Lim, Daw Gen; Kim, Kyungho; Razdan, Mayuri; ...

2017-09-01

Here, a meticulous solid state chemistry approach has been developed for the synthesis of carbon anode from a sustainable source. The reaction mechanism of carbon formation during pyrolysis of sustainable feed-stock was studied in situ by employing Raman microspectroscopy. No Raman spectral changes observed below 160°C (thermally stable precursor) followed by color change, however above 280°C characteristic D and G bands of graphitic carbon are recorded. Derived carbon particles exhibited high specific surface area with low structural ordering (active carbons) to low specific surface area with high graphitic ordering as a function of increasing reaction temperature. Carbons synthesized at 600°Cmore » demonstrated enhanced reversible lithiation capacity (390 mAh g -1), high charge-discharge rate capability, and stable cycle life. On the contrary, carbons synthesized at higher temperatures (>1200°C) produced more graphite-like structure yielding longer specific capacity retention with lower reversible capacity.« less

An Organotypic 3D Assay for Primary Human Mammary Epithelial Cells that Recapitulates Branching Morphogenesis.

PubMed

Linnemann, Jelena R; Meixner, Lisa K; Miura, Haruko; Scheel, Christina H

2017-01-01

We have developed a three-dimensional organotypic culture system for primary human mammary epithelial cells (HMECs) in which the cells are cultured in free floating collagen type I gels. In this assay, luminal cells predominantly form multicellular spheres, while basal/myoepithelial cells form complex branched structures resembling terminal ductal lobular units (TDLUs), the functional units of the human mammary gland in situ. The TDLU-like organoids can be cultured for at least 3 weeks and can then be passaged multiple times. Subsequently, collagen gels can be stained with carmine or by immunofluorescence to allow for the analysis of morphology, protein expression and polarization, and to facilitate quantification of structures. In addition, structures can be isolated for gene expression analysis. In summary, this technique is suitable for studying branching morphogenesis, regeneration, and differentiation of HMECs as well as their dependence on the physical environment.

Identification of intermediates in zeolite-catalyzed reactions by in situ UV/Vis microspectroscopy and a complementary set of molecular simulations.

PubMed

Hemelsoet, Karen; Qian, Qingyun; De Meyer, Thierry; De Wispelaere, Kristof; De Sterck, Bart; Weckhuysen, Bert M; Waroquier, Michel; Van Speybroeck, Veronique

2013-12-02

The optical absorption properties of (poly)aromatic hydrocarbons occluded in a nanoporous environment were investigated by theoretical and experimental methods. The carbonaceous species are an essential part of a working catalyst for the methanol-to-olefins (MTO) process. In situ UV/Vis microscopy measurements on methanol conversion over the acidic solid catalysts H-SAPO-34 and H-SSZ-13 revealed the growth of various broad absorption bands around 400, 480, and 580 nm. The cationic nature of the involved species was determined by interaction of ammonia with the methanol-treated samples. To determine which organic species contribute to the various bands, a systematic series of aromatics was analyzed by means of time-dependent density functional theory (TDDFT) calculations. Static gas-phase simulations revealed the influence of structurally different hydrocarbons on the absorption spectra, whereas the influence of the zeolitic framework was examined by using supramolecular models within a quantum mechanics/molecular mechanics framework. To fully understand the origin of the main absorption peaks, a molecular dynamics (MD) study on the organic species trapped in the inorganic host was essential. During such simulation the flexibility is fully taken into account and the effect on the UV/Vis spectra is determined by performing TDDFT calculations on various snapshots of the MD run. This procedure allows an energy absorption scale to be provided and the various absorption bands determined from in situ UV/Vis spectra to be assigned to structurally different species. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, Structure, and Pressure-Induced Polymerization of Li3Fe(CN)6 Accompanied with Enhanced Conductivity.

PubMed

Li, Kuo; Zheng, Haiyan; Hattori, Takanori; Sano-Furukawa, Asami; Tulk, Christopher A; Molaison, Jamie; Feygenson, Mikhail; Ivanov, Ilia N; Yang, Wenge; Mao, Ho-Kwang

2015-12-07

Pressure-induced polymerization of charged triple-bond monomers like acetylide and cyanide could lead to formation of a conductive metal-carbon network composite, thus providing a new route to synthesize inorganic/organic conductors with tunable composition and properties. The industry application of this promising synthetic method is mainly limited by the reaction pressure needed, which is often too high to be reached for gram amounts of sample. Here we successfully synthesized highly conductive Li3Fe(CN)6 at maximum pressure around 5 GPa and used in situ diagnostic tools to follow the structural and functional transformations of the sample, including in situ X-ray and neutron diffraction and Raman and impedance spectroscopy, along with the neutron pair distribution function measurement on the recovered sample. The cyanide anions start to react around 1 GPa and bond to each other irreversibly at around 5 GPa, which are the lowest reaction pressures in all known metal cyanides and within the technologically achievable pressure range for industrial production. The conductivity of the polymer is above 10(-3) S · cm(-1), which reaches the range of conductive polymers. This investigation suggests that the pressure-induced polymerization route is practicable for synthesizing some types of functional conductive materials for industrial use, and further research like doping and heating can hence be motivated to synthesize novel materials under lower pressure and with better performances.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Mingyi; Xu, Xiaoyang, E-mail: xiaoyangxu2012@163.com; Wu, Tao

Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-raymore » photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide.« less

In situ SUMOylation analysis reveals a modulatory role of RanBP2 in the nuclear rim and PML bodies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saitoh, Noriko; Uchimura, Yasuhiro; The 21st Century Center of Excellence, Kumamoto University, 2-2-1 Honjo, Kumamoto 860-0811

2006-05-01

SUMO modification plays a critical role in a number of cellular functions including nucleocytoplasmic transport, gene expression, cell cycle and formation of subnuclear structures such as promyelocytic leukemia (PML) bodies. In order to identify the sites where SUMOylation takes place in the cell, we developed an in situ SUMOylation assay using a semi-intact cell system and subsequently combined it with siRNA-based knockdown of nucleoporin RanBP2, also known as Nup358, which is one of the known SUMO E3 proteins. With the in situ SUMOylation assay, we found that both nuclear rim and PML bodies, besides mitotic apparatuses, are major targets formore » active SUMOylation. The ability to analyze possible SUMO conjugation sites would be a valuable tool to investigate where SUMO E3-like activities and/or SUMO substrates exist in the cell. Specific knockdown of RanBP2 completely abolished SUMOylation along the nuclear rim and dislocated RanGAP1 from the nuclear pore complexes. Interestingly, the loss of RanBP2 markedly reduced the number of PML bodies, in contrast to other, normal-appearing nuclear compartments including the nuclear lamina, nucleolus and chromatin, suggesting a novel link between RanBP2 and PML bodies. SUMOylation facilitated by RanBP2 at the nuclear rim may be a key step for the formation of a particular subnuclear organization. Our data imply that SUMO E3 proteins like RanBP2 facilitate spatio-temporal SUMOylation for certain nuclear structure and function.« less

Rotator side chains trigger cooperative transition for shape and function memory effect in organic semiconductors.

PubMed

Chung, Hyunjoong; Dudenko, Dmytro; Zhang, Fengjiao; D'Avino, Gabriele; Ruzié, Christian; Richard, Audrey; Schweicher, Guillaume; Cornil, Jérôme; Beljonne, David; Geerts, Yves; Diao, Ying

2018-01-18

Martensitic transition is a solid-state phase transition involving cooperative movement of atoms, mostly studied in metallurgy. The main characteristics are low transition barrier, ultrafast kinetics, and structural reversibility. They are rarely observed in molecular crystals, and hence the origin and mechanism are largely unexplored. Here we report the discovery of martensitic transition in single crystals of two different organic semiconductors. In situ microscopy, single-crystal X-ray diffraction, Raman and nuclear magnetic resonance spectroscopy, and molecular simulations combined indicate that the rotating bulky side chains trigger cooperative transition. Cooperativity enables shape memory effect in single crystals and function memory effect in thin film transistors. We establish a molecular design rule to trigger martensitic transition in organic semiconductors, showing promise for designing next-generation smart multifunctional materials.

Expression and distribution of octopus gonadotropin-releasing hormone in the central nervous system and peripheral organs of the octopus (Octopus vulgaris) by in situ hybridization and immunohistochemistry.

PubMed

Iwakoshi-Ukena, Eiko; Ukena, Kazuyoshi; Takuwa-Kuroda, Kyoko; Kanda, Atshuhiro; Tsutsui, Kazuyoshi; Minakata, Hiroyuki

2004-09-20

We recently purified a peptide with structural features similar to vertebrate gonadotropin-releasing hormone (GnRH) from the brain of Octopus vulgaris, cloned a cDNA encoding the precursor protein, and named it oct-GnRH. In the current study, we investigated the expression and distribution of oct-GnRH throughout the central nervous system (CNS) and peripheral organs of Octopus by in situ hybridization on the basis of the cDNA sequence and by immunohistochemistry using a specific antiserum against oct-GnRH. Oct-GnRH mRNA-expressing cell bodies were located in 10 of 19 lobes in the supraesophageal and subesophageal parts of the CNS. Several oct-GnRH-like immunoreactive fibers were seen in all the neuropils of the CNS lobes. The sites of oct-GnRH mRNA expression and the mature peptide distribution were consistent with each other as judged by in situ hybridization and immunohistochemistry. In addition, many immunoreactive fibers were distributed in peripheral organs such as the heart, the oviduct, and the oviducal gland. Modulatory effects of oct-GnRH on the contractions of the heart and the oviduct were demonstrated. The results suggested that, in the context of reproduction, oct-GnRH is a key peptide in the subpedunculate lobe and/or posterior olfactory lobe-optic gland-gonadal axis, an octopus analogue of the hypothalamo-hypophysial-gonadal axis. It may also act as a modulatory factor in controlling higher brain functions such as feeding, memory, movement, maturation, and autonomic functions

Effect of in situ exopolysaccharide production on physicochemical, rheological, sensory, and microstructural properties of the yogurt drink ayran: an optimization study based on fermentation kinetics.

PubMed

Yilmaz, M T; Dertli, E; Toker, O S; Tatlisu, N B; Sagdic, O; Arici, M

2015-03-01

Exopolysaccharide (EPS)-producing starter cultures are preferred for the manufacture of fermented milk products to improve rheological and technological properties. However, no clear correlation exists between EPS production and the rheological and technological properties of fermented milk products such as the yogurt drink ayran. In this study, 4 different strain conditions (EPS- and EPS+ Streptococcus thermophilus strains) were tested as a function of incubation temperature (32, 37, or 42°C) and time (2, 3, or 4 h) to determine the effect of culture type and in situ EPS production on physicochemical, rheological, sensory, and microstructural properties of ayran. Furthermore, we assessed the effect of fermentation conditions on amounts of EPS production by different EPS-producing strains during ayran production. A multifactorial design of response surface methodology was used to model linear, interaction, and quadratic effects of these variables on steady shear rheological properties of ayran samples and in situ EPS production levels. The physicochemical and microbiological characteristics of ayran samples altered depending on incubation conditions and strain selection. Steady shear tests showed that ayran samples inoculated with EPS+ strains exhibited pseudoplastic flow behavior. Production of ayran with EPS- strain (control sample) resulted in the lowest apparent viscosity values (η50), whereas those produced with the combination of 2 EPS+ strains yielded ayran with notably increased η50 values. We concluded that incubation time was the variable with the greatest effect on η50, consistency coefficient (K), and flow behavior index (n) values. In situ EPS production was also affected by these conditions during ayran fermentation in which strain-specific metabolism conditions were found to be the most important factor for EPS production. In addition, these findings correlated the amount of in situ EPS produced with the rheological properties of ayran. Scanning electron microscopy images of the samples showed differences in structural features, revealing a prominent network strand structure in the ayran samples inoculated with the admixture of 2 EPS-producing strains incubated at 37°C for 3 h. These results provide useful information for large-scale production of ayran by the dairy industry. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Respiratory analysis of coupled mitochondria in cryopreserved liver biopsies.

PubMed

García-Roche, Mercedes; Casal, Alberto; Carriquiry, Mariana; Radi, Rafael; Quijano, Celia; Cassina, Adriana

2018-07-01

The aim of this work was to develop a cryopreservation method of small liver biopsies for in situ mitochondrial function assessment. Herein we describe a detailed protocol for tissue collection, cryopreservation, high-resolution respirometry using complex I and II substrates, calculation and interpretation of respiratory parameters. Liver biopsies from cow and rat were sequentially frozen in a medium containing dimethylsulfoxide as cryoprotectant and stored for up to 3 months at -80 °C. Oxygen consumption rate studies of fresh and cryopreserved samples revealed that most respiratory parameters remained unchanged. Additionally, outer mitochondrial membrane integrity was assessed adding cytochrome c, proving that our cryopreservation method does not harm mitochondrial structure. In sum, we present a reliable way to cryopreserve small liver biopsies without affecting mitochondrial function. Our protocol will enable the transport and storage of samples, extending and facilitating mitochondrial function analysis of liver biopsies. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Bottom-up formation of robust gold carbide

PubMed Central

Westenfelder, Benedikt; Biskupek, Johannes; Meyer, Jannik C.; Kurasch, Simon; Lin, Xiaohang; Scholz, Ferdinand; Gross, Axel; Kaiser, Ute

2015-01-01

A new phenomenon of structural reorganization is discovered and characterized for a gold-carbon system by in-situ atomic-resolution imaging at temperatures up to 1300 K. Here, a graphene sheet serves in three ways, as a quasi transparent substrate for aberration-corrected high-resolution transmission electron microscopy, as an in-situ heater, and as carbon supplier. The sheet has been decorated with gold nanoislands beforehand. During electron irradiation at 80 kV and at elevated temperatures, the accumulation of gold atoms has been observed on defective graphene sites or edges as well as at the facets of gold nanocrystals. Both resulted in clustering, forming unusual crystalline structures. Their lattice parameters and surface termination differ significantly from standard gold nanocrystals. The experimental data, supported by electron energy loss spectroscopy and density-functional theory calculations, suggests that isolated gold and carbon atoms form – under conditions of heat and electron irradiation – a novel type of compound crystal, Au-C in zincblende structure. The novel material is metastable, but surprisingly robust, even under annealing condition. PMID:25772348

Planarian myosin essential light chain is involved in the formation of brain lateral branches during regeneration.

PubMed

Yu, Shuying; Chen, Xuhui; Yuan, Zuoqing; Zhou, Luming; Pang, Qiuxiang; Mao, Bingyu; Zhao, Bosheng

2015-08-01

The myosin essential light chain (ELC) is a structure component of the actomyosin cross-bridge, however, the functions in the central nervous system (CNS) development and regeneration remain poorly understood. Planarian Dugesia japonica has revealed fundamental mechanisms and unique aspects of neuroscience and neuroregeneration. In this study, the cDNA DjElc, encoding a planarian essential light chain of myosin, was identified from the planarian Dugesia japonica cDNA library. It encodes a deduced protein with highly conserved functionally domains EF-Hand and Ca(2+) binding sites that shares significant similarity with other members of ELC. Whole mount in situ hybridization studies show that DjElc expressed in CNS during embryonic development and regeneration of adult planarians. Loss of function of DjElc by RNA interference during planarian regeneration inhibits brain lateral branches regeneration completely. In conclusion, these results demonstrated that DjElc is required for maintenance of neurons and neurite outgrowth, particularly for involving the brain later branch regeneration.

Critical role of the coupling between the octahedral rotation and A -site ionic displacements in PbZr O3 -based antiferroelectric materials investigated by in situ neutron diffraction

NASA Astrophysics Data System (ADS)

Lu, Teng; Studer, Andrew J.; Yu, Dehong; Withers, Ray L.; Feng, Yujun; Chen, Hua; Islam, S. S.; Xu, Zhuo; Liu, Yun

2017-12-01

This in situ neutron-diffraction study on antiferroelectric (AFE) P b0.99(N b0.02Z r0.65S n0.28T i0.05 ) O3 polycrystalline materials describes systematic structural and associated preferred orientation changes as a function of applied electric field and temperature. It is found that the pristine AFE phase can be poled into the metastable ferroelectric (FE) phase at room temperature. At this stage, both AFE and FE phases consist of modes associated with octahedral rotation and A -site ionic displacements. The temperature-induced phase transition indicates that the octahedral rotation and ionic displacements are weakly coupled in the room-temperature FE phase and decoupled in the high-temperature FE phase. However, both temperature and E -field-induced phase transitions between the AFE and high-temperature FE phase demonstrate the critical role of coupling between octahedral rotation and A -site ionic displacements in stabilizing the AFE structure, which provides not only experimental evidence to support previous theoretical calculations, but also an insight into the design and development of AFE materials. Moreover, the associated preferred orientation evolution in both AFE and FE phases is studied during the phase transitions. It is found that the formation of the preferred orientation can be controlled to tune the samples' FE and AFE properties.

In situ determination of crystal structure and chemistry of minerals at Earth's deep lower mantle conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Hongsheng; Zhang, Li

Recent advances in experimental techniques and data processing allow in situ determination of mineral crystal structure and chemistry up to Mbar pressures in a laser-heated diamond anvil cell (DAC), providing the fundamental information of the mineralogical constitution of our Earth's interior. This work highlights several recent breakthroughs in the field of high-pressure mineral crystallography, including the stability of bridgmanite, the single-crystal structure studies of post-perovskite and H-phase as well as the identification of hydrous minerals and iron oxides in the deep lower mantle. The future development of high-pressure crystallography is also discussed.

In situ SAXS study on cationic and non-ionic surfactant liquid crystals using synchrotron radiation.

PubMed

Fritscher, C; Hüsing, N; Bernstorff, S; Brandhuber, D; Koch, T; Seidler, S; Lichtenegger, H C

2005-11-01

In situ synchrotron small-angle X-ray scattering was used to investigate various surfactant/water systems with hexagonal and lamellar structures regarding their structural behaviour upon heating and cooling. Measurements of the non-ionic surfactant Triton X-45 (polyethylene glycol 4-tert-octylphenyl ether) at different surfactant concentrations show an alignment of the lamellar liquid-crystalline structure close to the wall of the glass capillaries and also a decrease in d-spacing following subsequent heating/cooling cycles. Additionally, samples were subjected to a weak magnetic field (0.3-0.7 T) during heating and cooling, but no influence of the magnetic field was observed.

First results from the in-situ temperature measurements by the newly developed downhole tool during the drilling cruise in the hydrothermal fields of the mid-Okinawa Trough

NASA Astrophysics Data System (ADS)

Kitada, K.; Wu, H. Y.; Miyazaki, J.; Akiyama, K.; Nozaki, T.; Ishibashi, J. I.; Kumagai, H.; Maeda, L.

2016-12-01

The Okinawa trough is an active backarc basin behind the Ryukyu subduction zone and exhibits active rifting associated with extension of the continental margin. The temperature measurement in this area is essential for understanding hydrothermal system and hydraulic structure. During the CK16-01 cruise this March, we have conducted the in-situ temperature measurements by the newly developed downhole tool, TRDT (Thermo-Resistant Downhole Thermometer) in hydrothermal fields of the mid-Okinawa Trough. The purpose of this measurement is to investigate the in-situ temperature structure in deep-hot zones and its variation after coring and/or drilling. TRDT was designed by JAMSTEC as a memory downhole tool to measure in-situ borehole temperature under the extreme high temperature environment. First trial was conducted in the CK14-04 cruise by the free fall deployment to reduce the operation time. However, there was no temperature data recorded due to the strong vibration during the operation. After CK14-04 cruise, TRDT was modified to improve the function against vibration and shock. The improved TRDT passed the high temperature, vibration and shock tests to ensure the data acquisition of borehole logging. During the CK16-01 cruise, we have first successfully collected the in-situ temperature data from hydrothermal borehole in the Iheya North Knoll with wireline system. The temperature at depth of 187mbsf continued to increase almost linearly from 220 to 245°C during the 20 minute measurements time. This suggests that the inside borehole was cooled down by pumping seawater through drill pipes during the coring and lowering down the TRDT tool to the bottom hole. The in-situ temperature were extrapolated with exponential curve using nonlinear least squares fitting and the estimated equilibrium temperature was 278°C. To recover the in-situ temperature more precisely, the measurement time should kept as long as possible by considering the temperature rating. The operational procedure is also important to succeed in temperature logging. TRDT was deployed by wireline system to avoid damage from the strong vibration and shock. In order to get in-situ temperature data, the key factors are: 1) keeping the borehole for recovering the in-situ temperature after the coring; 2) TRDT sensor deployment without pumping seawater.

[Laser Raman Spectroscopy and Its Application in Gas Hydrate Studies].

PubMed

Fu, Juan; Wu, Neng-you; Lu, Hai-long; Wu, Dai-dai; Su, Qiu-cheng

2015-11-01

Gas hydrates are important potential energy resources. Microstructural characterization of gas hydrate can provide information to study the mechanism of gas hydrate formation and to support the exploitation and application of gas hydrate technology. This article systemly introduces the basic principle of laser Raman spectroscopy and summarizes its application in gas hydrate studies. Based on Raman results, not only can the information about gas composition and structural type be deduced, but also the occupancies of large and small cages and even hydration number can be calculated from the relative intensities of Raman peaks. By using the in-situ analytical technology, laser Raman specstropy can be applied to characterize the formation and decomposition processes of gas hydrate at microscale, for example the enclathration and leaving of gas molecules into/from its cages, to monitor the changes in gas concentration and gas solubility during hydrate formation and decomposition, and to identify phase changes in the study system. Laser Raman in-situ analytical technology has also been used in determination of hydrate structure and understanding its changing process under the conditions of ultra high pressure. Deep-sea in-situ Raman spectrometer can be employed for the in-situ analysis of the structures of natural gas hydrate and their formation environment. Raman imaging technology can be applied to specify the characteristics of crystallization and gas distribution over hydrate surface. With the development of laser Raman technology and its combination with other instruments, it will become more powerful and play a more significant role in the microscopic study of gas hydrate.

Size really does matter: effects of filter fractionation on microbial community structure in a model oxygen minimum zone.

NASA Astrophysics Data System (ADS)

Torres Beltran, M.

2016-02-01

The Scientific Committee on Oceanographic Research (SCOR) Working Group 144 "Microbial Community Responses to Ocean Deoxygenation" workshop held in Vancouver, British Columbia in July 2014 had the primary objective of kick-starting the establishment of a minimal core of technologies, techniques and standard operating procedures (SOPs) to enable compatible process rate and multi-molecular data (DNA, RNA and protein) collection in marine oxygen minimum zones (OMZs) and other oxygen starved waters. Experimental activities conducted in Saanich Inlet, a seasonally anoxic fjord on Vancouver Island British Columbia, were designed to compare and cross-calibrate in situ sampling devices (McLane PPS system) with conventional bottle sampling and incubation methods. Bottle effects on microbial community composition, and activity were tested using different filter combinations and sample volumes to compare PPS/IPS (0.4 µm) versus Sterivex (0.22 µm) filtration methods with and without prefilters (2.7 µm). Resulting biomass was processed for small subunit ribosomal RNA gene sequencing across all three domains of life on the 454 platform followed by downstream community structure analyses. Significant community shifts occurred within and between filter fractions for in situ versus on-ship processed samples. For instance, the relative abundance of several bacterial phyla including Bacteroidetes, Delta and Gammaproteobacteria decreased five-fold on-ship when compared to in situ filtration. Similarly, experimental mesocosms showed similar community structure and activity to in situ filtered samples indicating the need to cross-calibrate incubations to constrain bottle effects. In addition, alpha and beta diversity significantly changed as function of filter size and volume, as well as the operational taxonomic units identified using indicator species analysis for each filter size. Our results provide statistical support that microbial community structure is systematically biased by filter fraction methods and highlight the need for establishing compatible techniques among researchers that facilitate comparative and reproducible science for the whole community.

Model for the analysis of sun radiation structures exposed to open air: consideration of its validity and usefulness based on its experimentation in situ

NASA Astrophysics Data System (ADS)

Bottoni, Mario; Fabretti, Giuseppe

2001-03-01

The definition of the thermal dynamics of a structure-work of cultural interest is important both from the microclimatic point of view and from the structural one. Elastic and plastic deformations, due to phenomena of heat exchange, influence, in a significant way, the mechanical behavior of the structure. Dealing with objects exposed to open air, one of the main sources of heat radiation is, obviously, the sun. Consequently, it is significant to evaluate the importance that solar radiation has in the global heating dynamics of the structure. Therefore, while studying the system Marcus Aurelius- Capitolium square, it was decided to support the investigations in situ (carried out by using thermovision and thermocouples) with the realization, on computer, of a system that could define the theoretical relationship existing between solar dynamics and the bronze monument. Correlation between information deduced from such a model and data obtained in situ, gave useful results and constituted a significant instrument for the analysis of the concrete thermal model of the investigated structure. The opportunity to deepen and improve such an experience arose when the Soprintendenza per i Beni Architettonici ed Ambientali di Firenze e Pistoia asked for a contribution to the studies and investigations aimed to define the thermal model of the Dome of Santa Maria del Fiore.

Examination of an aloe vera galacturonate polysaccharide capable of in situ gelation for the controlled release of protein therapeutics

NASA Astrophysics Data System (ADS)

McConaughy, Shawn David

A therapeutic delivery platform has been investigated with the ultimate goal of designing a sustained protein release matrix utilizing an in-situ gelling, acidic polysaccharide derived from the Aloe vera plant. The Aloe vera polysaccharide (AvP) has been examined in order to determine how chemical composition, structure, molecular weight and solution behavior affect gelation and protein/peptide delivery. Correlations are drawn between structural characteristics and solution behavior in order to determine the impact of polymer conformation and solvation on gel formation under conditions designed to simulate nasal applications. Steady state and dynamic rheology, classic and dynamic light scattering, zeta potential, pulse field gradient nuclear magnetic resonance and fluorescence spectroscopy have been employed to gain insight into the effects of galacturonic acid content, degree of methylation, entanglement and ionic strength on both solution behavior and the hydrogel state which ultimately governs protein/peptide release. This dissertation is divided into two sections. In the first section, a series of Aloe vera polysaccharides (AvP), from the pectin family have been structurally characterized indicating high galacturonic acid (GalA) content, low degree of methylester substitution (DM), low numbers of rhamnose residues and high molecular weight with respect to pectins extracted from traditional sources. The behavior of AvP was examined utilizing dilute solution, low-shear rheological techniques for specific molecular weight samples at selected conditions of ionic strength. From these dilute aqueous solution studies, the Mark-Houwink-Sakurada (MHS) constants (K and alpha), persistence length (Lp) and inherent chain stiffness (B parameter) were determined, indicating an expanded random coil in aqueous salt solutions. The critical concentration for transition from dilute to concentrated solution, C e, was determined by measuring both the zero shear viscosity and fluorescence emission of the probe molecule 1,8-anilino-1-naphthalene sulphonic acid (1,8-ANS) as a function of polymer concentration. Correlations are drawn between viscosity experiments and measurement of zeta potential. Increased degrees of intermolecular interactions are responsible for a shift of Ce to lower polymer concentrations with increasing ionic strength. Additionally, dynamic rheology data are presented highlighting the ability of AvP to form gels at low polymer and calcium ion concentrations, exemplifying the technological potential of this polysaccharide for in-situ drug delivery. In the second section, properties of Aloe vera galacturonate hydrogels formed via Ca2+ crosslinking have been studied in regard to key parameters influencing gel formation including molecular weight, ionic strength and molar ratio of Ca2+ to COO- functionality. Dynamic oscillatory rheology and pulsed field gradient NMR (PFG-NMR) studies have been conducted on hydrogels formed at specified Ca2+ concentrations in the presence and absence of Na+ and K+ ions, in order to assess the feasibility of in situ gelation for controlled delivery of therapeutics. Aqueous Ca2+ concentrations similar to those present in nasal and subcutaneous fluids induce the formation of elastic Aloe vera polysaccharide (AvP) hydrogel networks. By altering the ratio of Ca2+ to COO- functionality, networks may be tailored to provide elastic modulus (G') values between 20 and 20,000 Pa. The Aloe vera polysaccharide exhibits time dependent phase separation in the presence of monovalent electrolytes. Thus the relative rates of calcium induced gelation and phase separation become major considerations when designing a system for in situ delivery applications where both monovalent (Na+, K+) and divalent (Ca2+) ions are present. PFG-NMR and fluorescence microscopy confirm that distinctly different morphologies are present in gels formed in the presence and absence 0.15 M NaCl. Curve fitting of theoretical models to experimental release profiles of fluorescein labeled dextrans indicate diffusion rates are related to hydrogel morphology. These studies suggest that for efficient in situ release of therapeutic agents, polymer concentrations should be maintained above the critical entanglement concentration (Ce, 0.60 wt%) when [Ca2+]/[COO -] ratios are less than 1. Additionally, the monovalent electrolyte concentration in AvP solutions should not exceed 0.10 M prior to Ca 2+ crosslinking.

Investigation of Thermally Induced Degradation in CH3NH3PbI3 Perovskite Solar Cells using In-situ Synchrotron Radiation Analysis.

PubMed

Kim, Nam-Koo; Min, Young Hwan; Noh, Seokhwan; Cho, Eunkyung; Jeong, Gitaeg; Joo, Minho; Ahn, Seh-Won; Lee, Jeong Soo; Kim, Seongtak; Ihm, Kyuwook; Ahn, Hyungju; Kang, Yoonmook; Lee, Hae-Seok; Kim, Donghwan

2017-07-05

In this study, we employ a combination of various in-situ surface analysis techniques to investigate the thermally induced degradation processes in MAPbI 3 perovskite solar cells (PeSCs) as a function of temperature under air-free conditions (no moisture and oxygen). Through a comprehensive approach that combines in-situ grazing-incidence wide-angle X-ray diffraction (GIWAXD) and high-resolution X-ray photoelectron spectroscopy (HR-XPS) measurements, we confirm that the surface structure of MAPbI 3 perovskite film changes to an intermediate phase and decomposes to CH 3 I, NH 3 , and PbI 2 after both a short (20 min) exposure to heat stress at 100 °C and a long exposure (>1 hour) at 80 °C. Moreover, we observe clearly the changes in the orientation of CH 3 NH 3 + organic cations with respect to the substrate in the intermediate phase, which might be linked directly to the thermal degradation processes in MAPbI 3 perovskites. These results provide important progress towards improved understanding of the thermal degradation mechanisms in perovskite materials and will facilitate improvements in the design and fabrication of perovskite solar cells with better thermal stability.

In-situ XRD vs ex-situ vacuum annealing of tantalum oxynitride thin films: Assessments on the structural evolution

NASA Astrophysics Data System (ADS)

Cunha, L.; Apreutesei, M.; Moura, C.; Alves, E.; Barradas, N. P.; Cristea, D.

2018-04-01

The purpose of this work is to discuss the main structural characteristics of a group of tantalum oxynitride (TaNxOy) thin films, with different compositions, prepared by magnetron sputtering, and to interpret and compare the structural changes, by X-ray diffraction (XRD), when the samples are vacuum annealed under two different conditions: i) annealing, followed by ex-situ XRD: one sample of each deposition run was annealed at a different temperature, until a maximum of 800 °C, and the XRD patterns were obtained, at room temperature, after each annealing process; ii) annealing with in-situ XRD: the diffraction patterns are obtained, at certain temperatures, during the annealing process, using always the same sample. In-situ XRD annealing could be an interesting process to perform annealing, and analysing the evolution of the structure with the temperature, when compared to the classical process. A higher structural stability was observed in some of the samples, particularly on those with highest oxygen content, but also on the sample with non-metal (O + N) to metal (Ta) ratio around 0.5.

Tannin structural elucidation and quantitative ³¹P NMR analysis. 2. Hydrolyzable tannins and proanthocyanidins.

PubMed

Melone, Federica; Saladino, Raffaele; Lange, Heiko; Crestini, Claudia

2013-10-02

An unprecedented analytical method that allows simultaneous structural and quantitative characterization of all functional groups present in tannins is reported. In situ labeling of all labile H groups (aliphatic and phenolic hydroxyls and carboxylic acids) with a phosphorus-containing reagent (Cl-TMDP) followed by quantitative ³¹P NMR acquisition constitutes a novel fast and reliable analytical tool for the analysis of tannins and proanthocyanidins with significant implications for the fields of food and feed analyses, tannery, and the development of natural polyphenolics containing products.

Lunar In Situ Materials-Based Surface Structure Technology Development Efforts at NASA/MSFC

NASA Technical Reports Server (NTRS)

Fiske, M. R.; McGregor, W.; Pope, R.; McLemore, C. A.; Kaul, R.; Smithers, G.; Ethridge, E.; Toutanji, H.

2007-01-01

For long-duration missions on other planetary bodies, the use of in situ materials will become increasingly critical. As man's presence on these bodies expands, so must the structures to accommodate them, including habitats, laboratories, berms, radiation shielding for surface reactors, garages, solar storm shelters, greenhouses, etc. The use of in situ materials will significantly offset required launch upmass and volume issues. Under the auspices of the In Situ Fabrication & Repair (ISFR) Program at NASA/Marshall Space Flight Center (MSFC), the Surface Structures project has been developing materials and construction technologies to support development of these in situ structures. This paper will report on the development of several of these technologies at MSFC's Prototype Development Laboratory (PDL). These technologies include, but are not limited to, development of extruded concrete and inflatable concrete dome technologies based on waterless and water-based concretes, development of regolith-based blocks with potential radiation shielding binders including polyurethane and polyethylene, pressure regulation systems for inflatable structures, production of glass fibers and rebar derived from molten lunar regolith simulant, development of regolithbag structures, and others, including automation design issues. Results to date and lessons learned will be presented, along with recommendations for future activities.

Fixation of CO 2 by chrysotile in low-pressure dry and moist carbonation: Ex-situ and in-situ characterizations

NASA Astrophysics Data System (ADS)

Larachi, Faïçal; Daldoul, Insaf; Beaudoin, Georges

2010-06-01

A detailed study of low-pressure gas-solid carbonation of chrysotile in dry and humid environments has been carried out. The evolving structure of chrysotile and its reactivity as a function of temperature (300-1200 °C), humidity (0-10 mol %) and CO 2 partial pressure (20-67 mol %), thermal preconditioning, and alkali metal doping (Li, Na, K, Cs) have been monitored through in-situ X-ray photoelectron spectroscopy, isothermal thermogravimetry/mass spectrometry, ex-situ X-ray powder diffraction, and water and nitrogen adsorption/desorption. Based on chrysotile crystalline structure and its nanofibrilar orderliness, a multistep carbonation mechanism was elaborated to explain the role of water during chrysotile partial amorphisation, formation of periclase, brucite, and hydromagnesite crystalline phases, and surface passivation thereof, during humid carbonation. The weak carbonation reactivity was rationalized in terms of incongruent CO 2 van der Waals molecular diameters with the octahedral-tetrahedral lattice constants of chrysotile. This lack of reactivity appeared to be relatively indifferent to the facilitated water crisscrossing during chrysotile core dehydroxylation/pseudo-amorphisation and surface hydroxylation induced product stabilization during humid carbonation. Thermodynamic stability domains of the species observed at low pressure have been thoroughly discussed on the basis of X-ray powder diffraction patterns and X-ray photoelectron spectroscopy evidence. The highest carbon dioxide uptake occurred at 375 °C in moist atmospheres. On the basis of chrysotile fresh N 2 BET area, nearly 15 atoms out of 100 of the surface chrysotile brucitic Mg moiety have been carbonated at this temperature which was tantamount to the carbonation of about 2.5 at. % of the total brucitic Mg moiety in chrysotile. The carbonation of brucite (Mg(OH) 2) impurities coexisting in chrysotile was minor and estimated to contribute by less than 17.6 at. % of the total converted magnesium. The presence of cesium traces (3 Cs atoms per 100 Mg atoms) was found to boost chrysotile carbonation capacity by a factor 2.7.

Detection of amide I signals of interfacial proteins in situ using SFG.

PubMed

Wang, Jie; Even, Mark A; Chen, Xiaoyun; Schmaier, Alvin H; Waite, J Herbert; Chen, Zhan

2003-08-20

In this Communication, we demonstrate the novel observation that it is feasible to collect amide signals from polymer/protein solution interfaces in situ using sum frequency generation (SFG) vibrational spectroscopy. Such SFG amide signals allow for acquisition of more detailed molecular level information of entire interfacial protein structures. Proteins investigated include bovine serum albumin, mussel protein mefp-2, factor XIIa, and ubiquitin. Our studies indicate that different proteins generate different SFG amide signals at the polystyrene/protein solution interface, showing that they have different interfacial coverage, secondary structure, or orientation.

Desmin Cytoskeleton Linked to Muscle Mitochondrial Distribution and Respiratory Function

PubMed Central

Milner, Derek J.; Mavroidis, Manolis; Weisleder, Noah; Capetanaki, Yassemi

2000-01-01

Ultrastructural studies have previously suggested potential association of intermediate filaments (IFs) with mitochondria. Thus, we have investigated mitochondrial distribution and function in muscle lacking the IF protein desmin. Immunostaining of skeletal muscle tissue sections, as well as histochemical staining for the mitochondrial marker enzymes cytochrome C oxidase and succinate dehydrogenase, demonstrate abnormal accumulation of subsarcolemmal clumps of mitochondria in predominantly slow twitch skeletal muscle of desmin-null mice. Ultrastructural observation of desmin-null cardiac muscle demonstrates in addition to clumping, extensive mitochondrial proliferation in a significant fraction of the myocytes, particularly after work overload. These alterations are frequently associated with swelling and degeneration of the mitochondrial matrix. Mitochondrial abnormalities can be detected very early, before other structural defects become obvious. To investigate related changes in mitochondrial function, we have analyzed ADP-stimulated respiration of isolated muscle mitochondria, and ADP-stimulated mitochondrial respiration in situ using saponin skinned muscle fibers. The in vitro maximal rates of respiration in isolated cardiac mitochondria from desmin-null and wild-type mice were similar. However, mitochondrial respiration in situ is significantly altered in desmin-null muscle. Both the maximal rate of ADP-stimulated oxygen consumption and the dissociation constant (K m) for ADP are significantly reduced in desmin-null cardiac and soleus muscle compared with controls. Respiratory parameters for desmin-null fast twitch gastrocnemius muscle were unaffected. Additionally, respiratory measurements in the presence of creatine indicate that coupling of creatine kinase and the adenine translocator is lost in desmin-null soleus muscle. This coupling is unaffected in cardiac muscle from desmin-null animals. All of these studies indicate that desmin IFs play a significant role in mitochondrial positioning and respiratory function in cardiac and skeletal muscle. PMID:10995435

True-triaxial experimental seismic velocities linked to an in situ 3D seismic velocity structure

NASA Astrophysics Data System (ADS)

Tibbo, M.; Young, R. P.

2017-12-01

Upscaling from laboratory seismic velocities to in situ field seismic velocities is a fundamental problem in rock physics. This study presents a unique situation where a 3D velocity structure of comparable frequency ranges is available both in situ and experimentally. The in situ data comes from the Underground Research Laboratory (URL) located in Manitoba, Canada. The velocity survey and oriented, cubic rock sample, are from the 420m level of the mine, where the geology is a homogeneous and isotropic granite. The triaxial in situ stress field at this level was determined and the Mine-by tunnel was excavated horizontally to maximize borehole break out. Ultrasonic velocity measurements for P-, S1-,and S2-waves were done in the tunnel sidewall, ceiling and far-field rock mass.The geophysical imaging cell (GIC) used in this study allows for true triaxial stress (σ1 > σ2 > σ3). Velocity surveys for P-, S1-, and S2-wave can be acquired along all three axes, and therefore the effects of σ1, σ2, σ3 on the velocity-stress relationship is obtained along all 3 axes. The cubic (80 mm) granite sample was prepared oriented to the in situ principle stress axis in the field. The stress path of the sample extraction from in situ stress was modeled in FLAC 3D (by Itasca inc ), and then reapplied in the GIC to obtain the laboratory velocities at in situ stress. Both laboratory and field velocities conclude the same maximum velocity axis, within error, to be along σ2 at 5880±60 m/s for P-wave. This deviation from the expected fast axis being σ1, is believed to be caused by an aligned microcrack fabric. The theory of acoustoelasticity, the dependence of acoustic wave velocity on stresses in the propagating isotropic medium, is applied to the borehole hoop and radial stresses produced by the Mine-by tunnel. The acoustoelastic effect involves determining the linear (second-order) and nonlinear (third-order) elastic constants, which are derived from the velocity-stress slopes obtained from both uniaxial and hydrostatic stress tests performed on the granite. The acoustoelastic model produces the in situ far field P-wave velocity, as well as similar near borehole field velocities. In summary, this study compares a 3D field and laboratory velocity structure, and shows the potential of the theory of acoustoelasticity for velocity-stress inversion.

Spectroscopic Ellipsometry Studies of Ag and ZnO Thin Films and Their Interfaces for Thin Film Photovoltaics

NASA Astrophysics Data System (ADS)

Sainju, Deepak

Many modern optical and electronic devices, including photovoltaic devices, consist of multilayered thin film structures. Spectroscopic ellipsometry (SE) is a critically important characterization technique for such multilayers. SE can be applied to measure key parameters related to the structural, optical, and electrical properties of the components of multilayers with high accuracy and precision. One of the key advantages of this non-destructive technique is its capability of monitoring the growth dynamics of thin films in-situ and in real time with monolayer level precision. In this dissertation, the techniques of SE have been applied to study the component layer materials and structures used as back-reflectors and as the transparent contact layers in thin film photovoltaic technologies, including hydrogenated silicon (Si:H), copper indium-gallium diselenide (CIGS), and cadmium telluride (CdTe). The component layer materials, including silver and both intrinsic and doped zinc oxide, are fabricated on crystalline silicon and glass substrates using magnetron sputtering techniques. These thin films are measured in-situ and in real time as well as ex-situ by spectroscopic ellipsometry in order to extract parameters related to the structural properties, such as bulk layer thickness and surface roughness layer thickness and their time evolution, the latter information specific to real time measurements. The index of refraction and extinction coefficient or complex dielectric function of a single unknown layer can also be obtained from the measurement versus photon energy. Applying analytical expressions for these optical properties versus photon energy, parameters that describe electronic transport, such as electrical resistivity and electron scattering time, can be extracted. The SE technique is also performed as the sample is heated in order to derive the effects of annealing on the optical properties and derived electrical transport parameters, as well as the intrinsic temperature dependence of these properties and parameters. One of the major achievements of this dissertation research is the characterization of the thickness and optical properties of the interface layer formed between the silver and zinc oxide layers in a back-reflector structure used in thin film photovoltaics. An understanding of the impact of these thin film material properties on solar cell device performance has been complemented by applying reflectance and transmittance spectroscopy as well as simulations of cell performance.

Mechanisms Determining the Structure of Gold-Catalyzed GaAs Nanowires Studied by in Situ X-ray Diffraction

DOE PAGES

Takahasi, Masamitu; Kozu, Miwa; Sasaki, Takuo; ...

2015-09-02

The evolution of polytypism during GaAs nanowire growth was investigated with in situ X-ray diffraction. The growth of nanowires was found to start with the formation of zincblende structure, followed by the growth of wurtzite structure. The growth process was well reproduced by a simulation based on a layer-by-layer nucleation model. The good agreement between the measured and simulated results confirms that nucleation costs higher energy for the stackings changing the crystal structure than for those conserving the preceding structure. The transition in prevalent structure can be accounted for by the change of local growth conditions related to the shapemore » of triple phase line rather than by the change in supersaturation level, which quickly reaches steady state after starting growth.« less

Selected Topics on the Synthesis, Properties and Applications of Multiwalled Carbon Nanotubes

PubMed Central

Stoner, B.R.; Brown, B.; Glass, J.T.

2014-01-01

Summary In summary, MWCNTs have been examined for a variety of electronic applications due to their unique structure and chemistry. Electrodes for field emission, energy and sensor applications hold particular interest. MWCNTs provide a very high surface area, relatively easy methods of surface modification, controllable and high concentration of reactive surface sites, and high specific capacitance. Combining MWCNTs with graphene structures, oxide and metal nanoparticles and certain polymers extends their performance and functionality. Such hybrid structures have been produced in situ during CNT growth and in two-step processes. Excellent progress on understanding the mechanisms of CNT growth has enabled numerous growth methods to all yield MWCNT structures in a variety of morphologies. PMID:24910503

Applications of x ray absorption fine structure to the in situ study of the effect of cobalt in nickel hydrous oxide electrodes for fuel cells and rechargeable batteries

NASA Technical Reports Server (NTRS)

Kim, Sunghyun; Tryk, Donald A.; Scherson, Daniel A.; Antonio, Mark R.

1993-01-01

Electronic and structural aspects of composite nickel-cobalt hydrous oxides have been examined in alkaline solutions using in situ X-ray absorption fine structure (XAFS). The results obtained have indicated that cobalt in this material is present as cobaltic ions regardless of the oxidation state of nickel in the lattice. Furthermore, careful analysis of the Co K-edge Extended X-ray absorption fine structure data reveals that the co-electrodeposition procedure generates a single phase, mixed metal hydrous oxide, in which cobaltic ions occupy nickel sites in the NiO2 sheet-like layers and not two intermixed phases each consisting of a single metal hydrous oxide.

A multifaceted FISH approach to study endogenous RNAs and DNAs in native nuclear and cell structures.

PubMed

Byron, Meg; Hall, Lisa L; Lawrence, Jeanne B

2013-01-01

Fluorescence in situ hybridization (FISH) is not a singular technique, but a battery of powerful and versatile tools for examining the distribution of endogenous genes and RNAs in precise context with each other and in relation to specific proteins or cell structures. This unit offers the details of highly sensitive and successful protocols that were initially developed largely in our lab and honed over a number of years. Our emphasis is on analysis of nuclear RNAs and DNA to address specific biological questions about nuclear structure, pre-mRNA metabolism, or the role of noncoding RNAs; however, cytoplasmic RNA detection is also discussed. Multifaceted molecular cytological approaches bring precise resolution and sensitive multicolor detection to illuminate the organization and functional roles of endogenous genes and their RNAs within the native structure of fixed cells. Solutions to several common technical pitfalls are discussed, as are cautions regarding the judicious use of digital imaging and the rigors of analyzing and interpreting complex molecular cytological results.

Facet-Dependent Cr(VI) Adsorption of Hematite Nanocrystals.

PubMed

Huang, Xiaopeng; Hou, Xiaojing; Song, Fahui; Zhao, Jincai; Zhang, Lizhi

2016-02-16

In this study, the adsorption process of Cr(VI) on the hematite facets was systematically investigated with synchrotron-based Cr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, density-functional theory calculation, and surface complexation models. Structural model fitting of EXAFS spectroscopy suggested that the interatomic distances of Cr-Fe were, respectively, 3.61 Å for the chromate coordinated hematite nanoplates with exposed {001} facets, 3.60 and 3.30 Å for the chromate coordinated hematite nanorods with exposed {001} and {110} facets, which were characteristic of inner-sphere complexation. In situ ATR-FTIR spectroscopy analysis confirmed the presence of two inner-sphere surface complexes with C3ν and C2ν symmetry, while the C3ν and C2ν species were assigned to monodentate and bidentate inner-sphere surface complexes with average Cr-Fe interatomic distances of 3.60 and 3.30 Å, respectively. On the basis of these experimental and theoretical results, we concluded that HCrO4(-) as dominated Cr(VI) species was adsorbed on {001} and {110} facets in inner-sphere monodentate mononuclear and bidentate binuclear configurations, respectively. Moreover, the Cr(VI) adsorption performance of hematite facets was strongly dependent on the chromate complexes formed on the hematite facets.

Photodissolution of ferrihydrite in the presence of oxalic acid: an in situ ATR-FTIR/DFT study.

PubMed

Bhandari, Narayan; Hausner, Douglas B; Kubicki, James D; Strongin, Daniel R

2010-11-02

The photodissolution of the iron oxyhydroxide, ferrihydrite, in the presence of oxalic acid was investigated with vibrational spectroscopy, density functional theory (DFT) calculations, and batch geochemical techniques that determined the composition of the solution phase during the dissolution process. Specifically, in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR- FTIR) was used to determine the structure of the adsorbed layer during the dissolution process at a solution pH of 4.5. DFT based computations were used to interpret the vibrational data associated with the surface monolayer in order to help determine the structure of the adsorbed complexes. Results showed that at pH 4.5, oxalate adsorbed on ferrihydrite adopted a mononuclear bidentate (MNBD) binding geometry. Photodissolution at pH 4.5 exhibited an induction period where the rate of Fe(II) release was limited by a low concentration of adsorbed oxalate due to the site-blocking of carbonate that was intrinsic to the surface of the ferrihydrite starting material. Oxalate displaced this initial carbonate over time, and the dissolution rate showed a corresponding increase. Irradiation of oxalate/ferrihydrite at pH 4.5 also ultimately led to the appearance of carbonate reaction product (distinct from carbonate intrinsic to the starting material) on the surface.

Radial Growth of Self-Catalyzed GaAs Nanowires and the Evolution of the Liquid Ga-Droplet Studied by Time-Resolved in Situ X-ray Diffraction.

PubMed

Schroth, Philipp; Jakob, Julian; Feigl, Ludwig; Mostafavi Kashani, Seyed Mohammad; Vogel, Jonas; Strempfer, Jörg; Keller, Thomas F; Pietsch, Ullrich; Baumbach, Tilo

2018-01-10

We report on a growth study of self-catalyzed GaAs nanowires based on time-resolved in situ X-ray structure characterization during molecular-beam-epitaxy in combination with ex situ scanning-electron-microscopy. We reveal the evolution of nanowire radius and polytypism and distinguish radial growth processes responsible for tapering and side-wall growth. We interpret our results using a model for diameter self-stabilization processes during growth of self-catalyzed GaAs nanowires including the shape of the liquid Ga-droplet and its evolution during growth.

In situ deformation and mechanical properties of bismuth telluride prepared via zone melting

NASA Astrophysics Data System (ADS)

Lai, Tang-Yu; Hsiao, Yu-Jen; Fang, Te-Hua

2018-03-01

In this study, we prepared Bi2Te3 nanostructures via zone melting and characterized their mechanical properties by nanoindentation and in situ transmission electron microscopy (TEM). The nanoindentation results revealed that a significant ‘pop-in’ phenomenon occurs under high-loading conditions with multiple dislocations and phase transitions in the material structure. Young’s modulus of the nanostructures was found to be 42.7 ± 2.56 GPa from nanoindentation measurements and 12.3 ± 0.1 GPa from in situ TEM measurements. The results of this study may be useful for the future development of Bi2Te3 thermoelectric devices via printing processes.

In situ probing of doping- and stress-mediated phase transitions in a single-crystalline VO2 nanobeam by spatially resolved Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chang, Sung-Jin; Park, Jong Bae; Lee, Gaehang; Kim, Hae Jin; Lee, Jin-Bae; Bae, Tae-Sung; Han, Young-Kyu; Park, Tae Jung; Huh, Yun Suk; Hong, Woong-Ki

2014-06-01

We demonstrate an experimental in situ observation of the temperature-dependent evolution of doping- and stress-mediated structural phase transitions in an individual single-crystalline VO2 nanobeam on a Au-coated substrate under exposure to hydrogen gas using spatially resolved Raman spectroscopy. The nucleation temperature of the rutile R structural phase in the VO2 nanobeam upon heating under hydrogen gas was lower than that under air. The spatial structural phase evolution behavior along the length of the VO2 nanobeam under hydrogen gas upon heating was much more inhomogeneous than that along the length of the same nanobeam under air. The triclinic T phase of the VO2 nanobeam upon heating under hydrogen gas transformed to the R phase and this R phase was stabilized even at room temperature in air after sample cooling. In particular, after the VO2 nanobeam with the R phase was annealed at approximately 250 °C in air, it exhibited the monoclinic M1 phase (not the T phase) at room temperature during heating and cooling cycles. These results were attributed to the interplay between hydrogen doping and stress associated with nanobeam-substrate interactions. Our study has important implications for engineering metal-insulator transition properties and developing functional devices based on VO2 nanostructures through doping and stress.We demonstrate an experimental in situ observation of the temperature-dependent evolution of doping- and stress-mediated structural phase transitions in an individual single-crystalline VO2 nanobeam on a Au-coated substrate under exposure to hydrogen gas using spatially resolved Raman spectroscopy. The nucleation temperature of the rutile R structural phase in the VO2 nanobeam upon heating under hydrogen gas was lower than that under air. The spatial structural phase evolution behavior along the length of the VO2 nanobeam under hydrogen gas upon heating was much more inhomogeneous than that along the length of the same nanobeam under air. The triclinic T phase of the VO2 nanobeam upon heating under hydrogen gas transformed to the R phase and this R phase was stabilized even at room temperature in air after sample cooling. In particular, after the VO2 nanobeam with the R phase was annealed at approximately 250 °C in air, it exhibited the monoclinic M1 phase (not the T phase) at room temperature during heating and cooling cycles. These results were attributed to the interplay between hydrogen doping and stress associated with nanobeam-substrate interactions. Our study has important implications for engineering metal-insulator transition properties and developing functional devices based on VO2 nanostructures through doping and stress. Electronic supplementary information (ESI) available: Illustration, photograph, Raman data, and EDX spectra. See DOI: 10.1039/c4nr01118j

In-Situ TEM-STM Observations of SWCNT Ropes/Tubular Transformations

NASA Technical Reports Server (NTRS)

Sola, F.; Lebron-Colon, M.; Ferreira, P. J.; Fonseca, L. F.; Meador, M. A.; Marin, C.

2010-01-01

Single-walled carbon nanotubes (SWCNTs) prepared by the HiPco process were purified using a modified gas phase purification technique. A TEM-STM holder was used to study the morphological changes of SWCNT ropes as a function of applied voltage. Kink formation, buckling behavior, tubular transformation and eventual breakdown of the system were observed. The tubular formation was attributed to a transformation from SWCNT ropes to multi-walled carbon nanotube (MWCNT) structures. It is likely mediated by the patching and tearing mechanism which is promoted primarily by the mobile vacancies generated due to current-induced heating and, to some extent, by electron irradiation.

Function of bacterial community dynamics in the formation of cadaveric semiochemicals during in situ carcass decomposition.

PubMed

Pascual, Javier; von Hoermann, Christian; Rottler-Hoermann, Ann-Marie; Nevo, Omer; Geppert, Alicia; Sikorski, Johannes; Huber, Katharina J; Steiger, Sandra; Ayasse, Manfred; Overmann, Jörg

2017-08-01

The decomposition of dead mammalian tissue involves a complex temporal succession of epinecrotic bacteria. Microbial activity may release different cadaveric volatile organic compounds which in turn attract other key players of carcass decomposition such as scavenger insects. To elucidate the dynamics and potential functions of epinecrotic bacteria on carcasses, we monitored bacterial communities developing on still-born piglets incubated in different forest ecosystems by combining high-throughput Illumina 16S rRNA sequencing with gas chromatography-mass spectrometry of volatiles. Our results show that the community structure of epinecrotic bacteria and the types of cadaveric volatile compounds released over the time course of decomposition are driven by deterministic rather than stochastic processes. Individual cadaveric volatile organic compounds were correlated with specific taxa during the first stages of decomposition which are dominated by bacteria. Through best-fitting multiple linear regression models, the synthesis of acetic acid, indole and phenol could be linked to the activity of Enterobacteriaceae, Tissierellaceae and Xanthomonadaceae, respectively. These conclusions are also commensurate with the metabolism described for the dominant taxa identified for these families. The predictable nature of in situ synthesis of cadaveric volatile organic compounds by epinecrotic bacteria provides a new basis for future chemical ecology and forensic studies. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

Pressure tuning the lattice and optical response of silver sulfide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Zhao, E-mail: zhaozhao@stanford.edu; Wei, Hua; Mao, Wendy L.

2016-06-27

Binary transition metal chalcogenides have attracted increasing attention for their unique structural and electronic properties. High pressure is a powerful tool for tuning the lattice and electronic structure of transition metal chalcogenides away from their pristine states. In this work, we systematically studied the in situ structural and optical behavior of silver sulfide (Ag{sub 2}S) under pressure by synchrotron X-ray diffraction and infrared spectroscopy measurements in a diamond anvil cell. Upon compression, Ag{sub 2}S undergoes structural symmetrization accompanied by a series of structural transitions while the crystallographic inequivalence of the two Ag sites is maintained. Electronically, pressure effectively tunes themore » ambient semiconducting Ag{sub 2}S into a metal at ∼22 GPa. Drude model analysis shows that the optical conductivity evolves significantly, reaching the highest value of 100 Ω{sup −1} cm{sup −1} at ∼40 GPa. Our results highlight the structural and electronic tunability of silver chalcogenides as a function of pressure and suggest the potential of Ag{sub 2}S as a platform for developing optical and opto-electronic applications.« less

In situ structural analysis of the Yersinia enterocolitica injectisome

PubMed Central

Kudryashev, Mikhail; Stenta, Marco; Schmelz, Stefan; Amstutz, Marlise; Wiesand, Ulrich; Castaño-Díez, Daniel; Degiacomi, Matteo T; Münnich, Stefan; Bleck, Christopher KE; Kowal, Julia; Diepold, Andreas; Heinz, Dirk W; Dal Peraro, Matteo; Cornelis, Guy R; Stahlberg, Henning

2013-01-01

Injectisomes are multi-protein transmembrane machines allowing pathogenic bacteria to inject effector proteins into eukaryotic host cells, a process called type III secretion. Here we present the first three-dimensional structure of Yersinia enterocolitica and Shigella flexneri injectisomes in situ and the first structural analysis of the Yersinia injectisome. Unexpectedly, basal bodies of injectisomes inside the bacterial cells showed length variations of 20%. The in situ structures of the Y. enterocolitica and S. flexneri injectisomes had similar dimensions and were significantly longer than the isolated structures of related injectisomes. The crystal structure of the inner membrane injectisome component YscD appeared elongated compared to a homologous protein, and molecular dynamics simulations documented its elongation elasticity. The ring-shaped secretin YscC at the outer membrane was stretched by 30–40% in situ, compared to its isolated liposome-embedded conformation. We suggest that elasticity is critical for some two-membrane spanning protein complexes to cope with variations in the intermembrane distance. DOI: http://dx.doi.org/10.7554/eLife.00792.001 PMID:23908767

Structure determination of an integral membrane protein at room temperature from crystals in situ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Axford, Danny; Foadi, James; Imperial College London, London SW7 2AZ

2015-05-14

The X-ray structure determination of an integral membrane protein using synchrotron diffraction data measured in situ at room temperature is demonstrated. The structure determination of an integral membrane protein using synchrotron X-ray diffraction data collected at room temperature directly in vapour-diffusion crystallization plates (in situ) is demonstrated. Exposing the crystals in situ eliminates manual sample handling and, since it is performed at room temperature, removes the complication of cryoprotection and potential structural anomalies induced by sample cryocooling. Essential to the method is the ability to limit radiation damage by recording a small amount of data per sample from many samplesmore » and subsequently assembling the resulting data sets using specialized software. The validity of this procedure is established by the structure determination of Haemophilus influenza TehA at 2.3 Å resolution. The method presented offers an effective protocol for the fast and efficient determination of membrane-protein structures at room temperature using third-generation synchrotron beamlines.« less

Use of In Situ Cloud Condensation Nuclei, Extinction, and Aerosol Size Distribution Measurements to Test a Method for Retrieving Cloud Condensation Nuclei Profiles From Surface Measurements

NASA Technical Reports Server (NTRS)

Ghan, Stephen J.; Rissman, Tracey A.; Ellman, Robert; Ferrare, Richard A.; Turner, David; Flynn, Connor; Wang, Jian; Ogren, John; Hudson, James; Jonsson, Haflidi H.;

Structural studies of the crystallisation of microporous materials

NASA Astrophysics Data System (ADS)

Davies, Andrew Treharne

A range of powerful synchrotron radiation characterisation techniques have been used to study fundamental aspects of the fonnation of microporous solids, specifically alumi nosilicates, heteroatom substituted aluminophosphates and titanosilicates. This work has been performed with the aim of investigating in situ the structural changes occurring during crystallisation and post synthetic treatment. In situ EDXRD was used to follow the crystallisation of these materials under a wide range of synthesis conditions using a hydrothermal cell and a solid-state detector array. A quantitative analysis of the crystallisation kinetics was performed for the large pore aluminosilicate, zeolite A, using a simple mathematical model to calculate the activation energy of formation. The results obtained were found to closely agree with both the experimental results and theoretical models of others. A qualitative study of the effect of altering the synthesis conditions was also investigated for this material. Similar kinetic studies were then performed for a range of microporous aluminophosphates and their cobalt substituted derivatives in order to follow the effects of varying synthesis conditions such as the synthesis temperature, organic template type, and cobalt concentration. Distinct trends were noted in the formation times, stability and nature of the resulting crystalline phases as conditions were varied. The relationship between the cobalt and organic template molecules during crystallisation was considered in some detail with reference to other experimental data and theoretical models. The alumi nophosphate studies were subsequently extended to a range of other heteroatom substituted aluminophosphates, using in situ EDXRD, complimented by EXAFS, which allowed investigation of the local environments around the heteroatoms within the microporous structure. EDXRD and EXAFS studies have been performed on the microporous titanosilicate, ETS-10, while the thermal stability of this material has also been investigated in situ using synchrotron X-ray diffraction in conjunction with a high temperature environmental cell.

Neural network approach for characterizing structural transformations by X-ray absorption fine structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Timoshenko, Janis; Frenkel, Anatoly I.; Cintins, Arturs

The knowledge of coordination environment around various atomic species in many functional materials provides a key for explaining their properties and working mechanisms. Many structural motifs and their transformations are difficult to detect and quantify in the process of work (operando conditions), due to their local nature, small changes, low dimensionality of the material, and/or extreme conditions. Here we use artificial neural network approach to extract the information on the local structure and its in-situ changes directly from the X-ray absorption fine structure spectra. We illustrate this capability by extracting the radial distribution function (RDF) of atoms in ferritic andmore » austenitic phases of bulk iron across the temperature-induced transition. Integration of RDFs allows us to quantify the changes in the iron coordination and material density, and to observe the transition from body-centered to face-centered cubic arrangement of iron atoms. Furthermore, this method is attractive for a broad range of materials and experimental conditions« less

Neural network approach for characterizing structural transformations by X-ray absorption fine structure

DOE PAGES

Timoshenko, Janis; Frenkel, Anatoly I.; Cintins, Arturs; ...

2018-05-25

The knowledge of coordination environment around various atomic species in many functional materials provides a key for explaining their properties and working mechanisms. Many structural motifs and their transformations are difficult to detect and quantify in the process of work (operando conditions), due to their local nature, small changes, low dimensionality of the material, and/or extreme conditions. Here we use artificial neural network approach to extract the information on the local structure and its in-situ changes directly from the X-ray absorption fine structure spectra. We illustrate this capability by extracting the radial distribution function (RDF) of atoms in ferritic andmore » austenitic phases of bulk iron across the temperature-induced transition. Integration of RDFs allows us to quantify the changes in the iron coordination and material density, and to observe the transition from body-centered to face-centered cubic arrangement of iron atoms. Furthermore, this method is attractive for a broad range of materials and experimental conditions« less

Neural Network Approach for Characterizing Structural Transformations by X-Ray Absorption Fine Structure Spectroscopy

NASA Astrophysics Data System (ADS)

Timoshenko, Janis; Anspoks, Andris; Cintins, Arturs; Kuzmin, Alexei; Purans, Juris; Frenkel, Anatoly I.

2018-06-01

The knowledge of the coordination environment around various atomic species in many functional materials provides a key for explaining their properties and working mechanisms. Many structural motifs and their transformations are difficult to detect and quantify in the process of work (operando conditions), due to their local nature, small changes, low dimensionality of the material, and/or extreme conditions. Here we use an artificial neural network approach to extract the information on the local structure and its in situ changes directly from the x-ray absorption fine structure spectra. We illustrate this capability by extracting the radial distribution function (RDF) of atoms in ferritic and austenitic phases of bulk iron across the temperature-induced transition. Integration of RDFs allows us to quantify the changes in the iron coordination and material density, and to observe the transition from a body-centered to a face-centered cubic arrangement of iron atoms. This method is attractive for a broad range of materials and experimental conditions.

In situ microscopy of the self-assembly of branched nanocrystals in solution

DOE PAGES

Sutter, Eli; Tkachenko, Alexei V.; Sutter, Peter; ...

2016-04-04

Here, solution-phase self-assembly of nanocrystals into mesoscale structures is a promising strategy for constructing functional materials from nanoscale components. Liquid environments are key to self-assembly since they allow suspended nanocrystals to diffuse and interact freely, but they also complicate experiments. Real-time observations with single-particle resolution could have transformative impact on our understanding of nanocrystal self-assembly. Here we use real-time in situ imaging by liquid-cell electron microscopy to elucidate the nucleation and growth mechanism and properties of linear chains of octapod-shaped nanocrystals in their native solution environment. Statistical mechanics modelling based on these observations and using the measured chain-length distribution clarifiesmore » the relative importance of dipolar and entropic forces in the assembly process and gives direct access to the interparticle interaction. Our results suggest that monomer-resolved in situ imaging combined with modelling can provide unprecedented quantitative insight into the microscopic processes and interactions that govern nanocrystal self-assembly in solution.« less

Resistive switching mechanism in the one diode-one resistor memory based on p+-Si/n-ZnO heterostructure revealed by in-situ TEM

NASA Astrophysics Data System (ADS)

Zhang, Lei; Zhu, Liang; Li, Xiaomei; Xu, Zhi; Wang, Wenlong; Bai, Xuedong

2017-03-01

One diode-one resistor (1D1R) memory is an effective architecture to suppress the crosstalk interference, realizing the crossbar network integration of resistive random access memory (RRAM). Herein, we designed a p+-Si/n-ZnO heterostructure with 1D1R function. Compared with the conventional multilayer 1D1R devices, the structure and fabrication technique can be largely simplified. The real-time imaging of formation/rupture process of conductive filament (CF) process demonstrated the RS mechanism by in-situ transmission electron microscopy (TEM). Meanwhile, we observed that the formed CF is only confined to the outside of depletion region of Si/ZnO pn junction, and the formation of CF does not degrade the diode performance, which allows the coexistence of RS and rectifying behaviors, revealing the 1D1R switching model. Furthermore, it has been confirmed that the CF is consisting of the oxygen vacancy by in-situ TEM characterization.

In situ microscopy of the self-assembly of branched nanocrystals in solution

NASA Astrophysics Data System (ADS)

Sutter, Eli; Sutter, Peter; Tkachenko, Alexei V.; Krahne, Roman; de Graaf, Joost; Arciniegas, Milena; Manna, Liberato

2016-04-01

Solution-phase self-assembly of nanocrystals into mesoscale structures is a promising strategy for constructing functional materials from nanoscale components. Liquid environments are key to self-assembly since they allow suspended nanocrystals to diffuse and interact freely, but they also complicate experiments. Real-time observations with single-particle resolution could have transformative impact on our understanding of nanocrystal self-assembly. Here we use real-time in situ imaging by liquid-cell electron microscopy to elucidate the nucleation and growth mechanism and properties of linear chains of octapod-shaped nanocrystals in their native solution environment. Statistical mechanics modelling based on these observations and using the measured chain-length distribution clarifies the relative importance of dipolar and entropic forces in the assembly process and gives direct access to the interparticle interaction. Our results suggest that monomer-resolved in situ imaging combined with modelling can provide unprecedented quantitative insight into the microscopic processes and interactions that govern nanocrystal self-assembly in solution.

Bi-functional Au/FeS (Au/Co3O4) composite for in situ SERS monitoring and degradation of organic pollutants

NASA Astrophysics Data System (ADS)

Ma, Shuzhen; Cai, Qian; Lu, Kailing; Liao, Fan; Shao, Mingwang

2016-01-01

The bi-functional Au/FeS (Au/Co3O4) composite was fabricated by in situ reducing Au nanoparticles onto the surface of FeS (Co3O4). The as-prepared FeS possessed a multi-structure composed of plenty of nanoplates, which were coated by Au nanoparticles with an average size of 47.5 nm. While the Co3O4 showed a thin hexagonal sheet containing Au nanoparticles on its surface with an average size of 79.0 nm. Both the as-prepared Au/FeS and Au/Co3O4 composites exhibited excellent SERS performance, capable of enhancing the Raman signals of R6G molecules with the enhancement factor up to 1.81 × 106 and 7.60 × 104, respectively. Moreover, Au/FeS (Au/Co3O4) composite also has been verified to have intrinsic peroxidase-like activity, which could decompose H2O2 into hydroxyl radicals and then degrade organic pollutants into small molecules. Therefore, SERS can be used to real-time and in situ monitoring the degradation process of R6G molecules, employing the Au/FeS (Au/Co3O4) composite both as SERS substrate and catalyst.

Dynamics of barite growth in porous media quantified by in situ synchrotron X-ray tomography

NASA Astrophysics Data System (ADS)

Godinho, jose; Gerke, kirill

2016-04-01

Current models used to formulate mineral sequestration strategies of dissolved contaminants in the bedrock often neglect the effect of confinement and the variation of reactive surface area with time. In this work, in situ synchrotron X-ray micro-tomography is used to quantify barite growth rates in a micro-porous structure as a function of time during 13.5 hours with a resolution of 1 μm. Additionally, the 3D porous network at different time frames are used to simulate the flow velocities and calculate the permeability evolution during the experiment. The kinetics of barite growth under porous confinement is compared with the kinetics of barite growth on free surfaces in the same fluid composition. Results are discussed in terms of surface area normalization and the evolution of flow velocities as crystals fill the porous structure. During the initial hours the growth rate measured in porous media is similar to the growth rate on free surfaces. However, as the thinner flow paths clog the growth rate progressively decreases, which is correlated to a decrease of local flow velocity. The largest pores remain open, enabling growth to continue throughout the structure. Quantifying the dynamics of mineral precipitation kinetics in situ in 4D, has revealed the importance of using a time dependent reactive surface area and accounting for the local properties of the porous network, when formulating predictive models of mineral precipitation in porous media.

Probing hydrogen positions in hydrous compounds: information from parametric neutron powder diffraction studies.

PubMed

Ting, Valeska P; Henry, Paul F; Schmidtmann, Marc; Wilson, Chick C; Weller, Mark T

2012-05-21

We demonstrate the extent to which modern detector technology, coupled with a high flux constant wavelength neutron source, can be used to obtain high quality diffraction data from short data collections, allowing the refinement of the full structures (including hydrogen positions) of hydrous compounds from in situ neutron powder diffraction measurements. The in situ thermodiffractometry and controlled humidity studies reported here reveal that important information on the reorientations of structural water molecules with changing conditions can be easily extracted, providing insight into the effects of hydrogen bonding on bulk physical properties. Using crystalline BaCl2·2H2O as an example system, we analyse the structural changes in the compound and its dehydration intermediates with changing temperature and humidity levels to demonstrate the quality of the dynamic structural information on the hydrogen atoms and associated hydrogen bonding that can be obtained without resorting to sample deuteration.

Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhu-Jun; Dong, Jichen; Cui, Yi

In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy andmore » density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.« less

An in situ self-assembly template strategy for the preparation of hierarchical-pore metal-organic frameworks

PubMed Central

Huang, Hongliang; Li, Jian-Rong; Wang, Keke; Han, Tongtong; Tong, Minman; Li, Liangsha; Xie, Yabo; Yang, Qingyuan; Liu, Dahuan; Zhong, Chongli

2015-01-01

Metal-organic frameworks (MOFs) have recently emerged as a new type of nanoporous materials with tailorable structures and functions. Usually, MOFs have uniform pores smaller than 2 nm in size, limiting their practical applications in some cases. Although a few approaches have been adopted to prepare MOFs with larger pores, it is still challenging to synthesize hierarchical-pore MOFs (H-MOFs) with high structural controllability and good stability. Here we demonstrate a facile and versatile method, an in situ self-assembly template strategy for fabricating stable H-MOFs, in which multi-scale soluble and/or acid-sensitive metal-organic assembly (MOA) fragments form during the reactions between metal ions and organic ligands (to construct MOFs), and act as removable dynamic chemical templates. This general strategy was successfully used to prepare various H-MOFs that show rich porous properties and potential applications, such as in large molecule adsorption. Notably, the mesopore sizes of the H-MOFs can be tuned by varying the amount of templates. PMID:26548441

Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

DOE PAGES

Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; ...

2016-10-19

In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy andmore » density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.« less

Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

PubMed Central

Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Schloegl, R.; Willinger, Marc-Georg

2016-01-01

In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene–graphene and graphene–substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite. PMID:27759024

In situ fabrication of quasi-free-standing epitaxial graphene nanoflakes on gold.

PubMed

Leicht, Philipp; Zielke, Lukas; Bouvron, Samuel; Moroni, Riko; Voloshina, Elena; Hammerschmidt, Lukas; Dedkov, Yuriy S; Fonin, Mikhail

2014-04-22

Addressing the multitude of electronic phenomena theoretically predicted for confined graphene structures requires appropriate in situ fabrication procedures yielding graphene nanoflakes (GNFs) with well-defined geometries and accessible electronic properties. Here, we present a simple strategy to fabricate quasi-free-standing GNFs of variable sizes, performing temperature programmed growth of graphene flakes on the Ir(111) surface and subsequent intercalation of gold. Using scanning tunneling microscopy (STM), we show that epitaxial GNFs on a perfectly ordered Au(111) surface are formed while maintaining an unreconstructed, singly hydrogen-terminated edge structure, as confirmed by the accompanying density functional theory (DFT) calculations. Using tip-induced lateral displacement of GNFs, we demonstrate that GNFs on Au(111) are to a large extent decoupled from the Au(111) substrate. The direct accessibility of the electronic states of a single GNF is demonstrated upon analysis of the quasiparticle interference patterns obtained by low-temperature STM. These findings open up an interesting playground for diverse investigations of graphene nanostructures with possible implications for device fabrication.

In-situ fabrication of halloysite nanotubes/silica nano hybrid and its application in unsaturated polyester resin

NASA Astrophysics Data System (ADS)

Lin, Jing; Zhong, Bangchao; Jia, Zhixin; Hu, Dechao; Ding, Yong; Luo, Yuanfang; Jia, Demin

2017-06-01

Silica nanoparticles was in-situ grown on the surface of halloysite nanotubes (HNTs) by a facile one-step approach to prepare a unique nano-structured hybrid (HNTs-g-Silica). The structure, morphology and composition of HNTs-g-Silica were investigated. It was confirmed that silica nanoparticles with the diameter of 10-20 nm were chemically grafted through Sisbnd O bonds and uniformly dispersed onto the surface of HNTs, leading to the formation of nano-protrusions on the nanotube surface. Due to the significantly improved interface strength between HNTs-g-Silica and polymer matrix, HNTs-g-Silica effectively toughened unsaturated polyester resin (UPE) and endowed UPE with superior thermal stability compared to HNTs. Based on the unique hybrid architecture and the improved properties of UPE nanocomposites, it is envisioned that HNTs-g-Silica may be a promising filler for more high performance and functional polymers composites and the fabrication method may have implications in the synthesis of nano hybrid materials.

Relationships between the decoupled and coupled transfer functions: Theoretical studies and experimental validation

NASA Astrophysics Data System (ADS)

Wang, Zengwei; Zhu, Ping; Liu, Zhao

2018-01-01

A generalized method for predicting the decoupled transfer functions based on in-situ transfer functions is proposed. The method allows predicting the decoupled transfer functions using coupled transfer functions, without disassembling the system. Two ways to derive relationships between the decoupled and coupled transfer functions are presented. Issues related to immeasurability of coupled transfer functions are also discussed. The proposed method is validated by numerical and experimental case studies.

Beamline Electrostatic Levitator (BESL) for in-situ High Energy K-Ray Diffraction Studies of Levitated Solids and Liquids at High Temperature

NASA Technical Reports Server (NTRS)

Gangopadhyay, A. K.; Lee, G. W.; Kelton, K. F.; Rogers, J. R.; Goldman, A. I.; Robinson, D. S.; Rathz, T. J.; Hyers, R. W.

2005-01-01

Determinations of the phase formation sequence, the crystal structures and the thermodynamic properties of materials at high temperatures are difficult because of contamination from the sample container and environment. Containerless processing techniques, such as electrostatic (ESL), electromagnetic (EML), aerodynamic, and acoustic levitation, are most suitable these studies. An adaptation of ESL for in-situ structural studies of a wide range of materials, including metals, semiconductors, insulators using high energy (125 keV) synchrotron x-rays is described here. This beamline ESL (BESL) allows the in-situ determination of the atomic structures of equilibrium solid and liquid phases, including undercooled liquids, as well as real-time studies of solid-solid and liquid-solid phase transformations. The use of image plate (MAR345) or GE-Angio detectors enables fast (30 ms - 1s) acquisition of complete diffraction patterns over a wide q-range (4 - 140/mm). The wide temperature range (300 - 2500 K), containerless processing under high vacuum (10(exp -7) - 10(exp -8) torr), and fast data acquisition, make BESL particularly suitable for phase diagram studies of high temperature materials. An additional, critically important, feature of BESL is the ability to also make simultaneous measurement of a host of thermo-physical properties, including the specific heat, enthalpy of transformation, solidus and liquidus temperatures, density, viscosity, and surface tension; all on the same sample and simultaneous with the structural measurements.

Controllable in situ synthesis of silver nanoparticles on multilayered film-coated silk fibers for antibacterial application.

PubMed

Meng, Mei; He, Huawei; Xiao, Jing; Zhao, Ping; Xie, Jiale; Lu, Zhisong

2016-01-01

Layer-by-layer (LbL) assembly is a versatile technique for the preparation of multilayered polymeric films. However, fabrication of LbL polymetic film on silk for the in situ growth of high-density silver nanoparticles (AgNPs) has not been realized. Herein poly(acrylic acid) (PAA)/poly(dimethyldiallylammonium chloride) (PDDA) multilayers are constructed on silk via the LbL approach, subsequently serving as a 3-dimensional matrix for in situ synthesis of AgNPs. After 8 rounds of LbL assembly, the silk is fully covered with a layer of polymeric film. AgNPs with good crystalline structures could be in-situ generated in the silk-coated multilayers and their amount could be tailored by adjusting the bilayer numbers. The as-prepared silk could effectively kill the existing bacteria and inhibit the bacterial growth, demonstrating the antimicrobial activity. Moreover, the release of Ag(+) from the modified silk can last for 120 h, rendering the modified silk sustainable antimicrobial activity. This work may provide a novel method to prepare AgNPs-functionalized antimicrobial silk for potential applications in textile industry. Copyright © 2015 Elsevier Inc. All rights reserved.

In-situ observation for growth of hierarchical metal-organic frameworks and their self-sequestering mechanism for gas storage

NASA Astrophysics Data System (ADS)

Hyo Park, Jung; Min Choi, Kyung; Joon Jeon, Hyung; Jung Choi, Yoon; Ku Kang, Jeung

2015-07-01

Although structures with the single functional constructions and micropores were demonstrated to capture many different molecules such as carbon dioxide, methane, and hydrogen with high capacities at low temperatures, their feeble interactions still limit practical applications at room temperature. Herein, we report in-situ growth observation of hierarchical pores in pomegranate metal-organic frameworks (pmg-MOFs) and their self-sequestering storage mechanism, not observed for pristine MOFs. Direct observation of hierarchical pores inside the pmg-MOF was evident by in-situ growth X-ray measurements while self-sequestering storage mechanism was revealed by in-situ gas sorption X-ray analysis and molecular dynamics simulations. The results show that meso/macropores are created at the early stage of crystal growth and then enclosed by micropore crystalline shells, where hierarchical pores are networking under self-sequestering mechanism to give enhanced gas storage. This pmg-MOF gives higher CO2 (39%) and CH4 (14%) storage capacity than pristine MOF at room temperature, in addition to fast kinetics with robust capacity retention during gas sorption cycles, thus giving the clue to control dynamic behaviors of gas adsorption.

In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Jianqing; Zhang, Wei; Huq, Ashfia

Ni-rich layered oxides (LiNi1-xMxO2; M = Co, Mn, ...) are appealing alternatives to conventional LiCoO2 as cathodes in Li-ion batteries for automobile and other large-scale applications due to their high theoretical capacity and low cost. However, preparing stoichiometric LiNi1-xMxO2 with ordered layer structure and high reversible capacity, has proven difficult due to cation mixing in octahedral sites. Herein, in situ studies of synthesis reactions and the associated structural ordering in preparing LiNiO2 and the Co-substituted variant, LiNi0.8Co0.2O2, are made, to gain insights into synthetic control of the structure and electrochemical properties of Ni-rich layered oxides. Results from this study indicatemore » a direct transformation of the intermediate from the rock salt structure into hexagonal phase, and during the process, Co substitution facilities the nucleation of a Co-rich layered phase at low temperatures and subsequent growth and stabilization of solid solution Li(Ni, Co)O-2 upon further heat treatment. Optimal conditions are identified from the in situ studies and utilized to obtain stoichiometric LiNi0.8Co0.2O2 that exhibits high capacity (up to 200 mA h g(-1) ) with excellent retention. The findings shed light on designing high performance Ni-rich layered oxide cathodes through synthetic control of the structural ordering in the materials.« less

A Hydrogel of Ultrathin Pure Polyaniline Nanofibers: Oxidant-Templating Preparation and Supercapacitor Application.

PubMed

Zhou, Kun; He, Yuan; Xu, Qingchi; Zhang, Qin'e; Zhou, An'an; Lu, Zihao; Yang, Li-Kun; Jiang, Yuan; Ge, Dongtao; Liu, Xiang Yang; Bai, Hua

2018-05-15

Although challenging, fabrication of porous conducting polymeric materials with excellent electronic properties is crucial for many applications. We developed a fast in situ polymerization approach to pure polyaniline (PANI) hydrogels, with vanadium pentoxide hydrate nanowires as both the oxidant and sacrifice template. A network comprised of ultrathin PANI nanofibers was generated during the in situ polymerization, and the large aspect ratio of these PANI nanofibers allowed the formation of hydrogels at a low solid content of 1.03 wt %. Owing to the ultrathin fibril structure, PANI hydrogels functioning as a supercapacitor electrode display a high specific capacitance of 636 F g -1 , a rate capability, and good cycling stability (∼83% capacitance retention after 10,000 cycles). This method was also extended to the preparation of polypyrrole and poly(3,4-ethylenedioxythiophene) hydrogels. This template polymerization method represents a rational strategy for design of conducing polymer networks, which can be readily integrated in high-performance devices or a further platform for functional composites.

Flow behaviour and structure of heterogeneous particles-water mixture in horizontal and inclined pipes

NASA Astrophysics Data System (ADS)

Vlasák, Pavel; Chára, Zdeněk; Konfršt, Jiří

2018-06-01

The effect of slurry velocity and mean concentration of heterogeneous particle-water mixture on flow behaviour and structure in the turbulent regime was studied in horizontal and inclined pipe sections of inner diameter D = 100 mm. The stratified flow pattern of heterogeneous particle-water mixture in the inclined pipe sections was revealed. The particles moved mostly near to the pipe invert. Concentration distribution in ascending and descending vertical pipe sections confirmed the effect of fall velocity on particle-carrier liquid slip velocity and increase of in situ concentration in the ascending pipe section. Slip velocity in two-phase flow, which is defined as the velocity difference between the solid and liquid phase, is one of mechanism of particle movement in two-phase flow. Due to the slip velocity, there is difference between transport and in situ concentrations, and the slip velocity can be determined from comparison of the in situ and transport concentration. For heterogeneous particle-water mixture flow the slip velocity depends on the flow structure.

Role of the H-containing groups on the structural dynamics of Ti3C2Tx MXene

NASA Astrophysics Data System (ADS)

Wen, Jing; Zhang, Xitian; Gao, Hong

2018-05-01

It is a confused problem in the literature that the c-axis value of Ti3C2 MXene changes with the synthesis procedure, but the part of the surface structures that plays the role of pillar to support the Ti3C2 layers and their variation rules remain controversial. In this work, we develop the structure models and formation mechanisms of Ti3C2Tx based on the density functional theory calculations and experimental results. While the c-axis values of the samples vary from about 1.9 to 2.9 nm, the corresponding pillars are determined by different distributions and proportions of the H-containing groups. The proportions of the H-containing groups that determine the c-axis value are formulated as the functions of the interlayer space, which can be used to quantitatively clarify the changes of the surface functional groups after the samples experiencing different treatments. The results can facilitate the in situ detections of the surface structures of MXenes during different treatments or electrochemical processes.

Modular in situ-Functionalization Strategy: Multicomponent Polymerization via Palladium/Norbornene Cooperative Catalysis.

PubMed

Yoon, Ki-Young; Dong, Guangbin

2018-05-23

Herein, we report the palladium/norbornene cooperatively catalyzed polymerization, which simplifies synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A2B2C-type multicomponent polymerization is developed using ortho-amination/ipso-alkynylation reaction for preparing various amine-functionalized arylacetylene-containing polymers. Within a single catalytic cycle, the amine side-chains are site-selectively installed in situ via C-H activation during the polymerization process, which represents a major difference from conventional cross-coupling polymerizations. This in situ-functionalization strategy enables modular incorporation of functional side-chains from simple monomers, thereby conveniently affording a diverse range of functional polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functional gene diversity of soil microbial communities from five oil-contaminated fields in China.

PubMed

Liang, Yuting; Van Nostrand, Joy D; Deng, Ye; He, Zhili; Wu, Liyou; Zhang, Xu; Li, Guanghe; Zhou, Jizhong

2011-03-01

To compare microbial functional diversity in different oil-contaminated fields and to know the effects of oil contaminant and environmental factors, soil samples were taken from typical oil-contaminated fields located in five geographic regions of China. GeoChip, a high-throughput functional gene array, was used to evaluate the microbial functional genes involved in contaminant degradation and in other major biogeochemical/metabolic processes. Our results indicated that the overall microbial community structures were distinct in each oil-contaminated field, and samples were clustered by geographic locations. The organic contaminant degradation genes were most abundant in all samples and presented a similar pattern under oil contaminant stress among the five fields. In addition, alkane and aromatic hydrocarbon degradation genes such as monooxygenase and dioxygenase were detected in high abundance in the oil-contaminated fields. Canonical correspondence analysis indicated that the microbial functional patterns were highly correlated to the local environmental variables, such as oil contaminant concentration, nitrogen and phosphorus contents, salt and pH. Finally, a total of 59% of microbial community variation from GeoChip data can be explained by oil contamination, geographic location and soil geochemical parameters. This study provided insights into the in situ microbial functional structures in oil-contaminated fields and discerned the linkages between microbial communities and environmental variables, which is important to the application of bioremediation in oil-contaminated sites.

Functional gene diversity of soil microbial communities from five oil-contaminated fields in China

PubMed Central

Liang, Yuting; Van Nostrand, Joy D; Deng, Ye; He, Zhili; Wu, Liyou; Zhang, Xu; Li, Guanghe; Zhou, Jizhong

2011-01-01

To compare microbial functional diversity in different oil-contaminated fields and to know the effects of oil contaminant and environmental factors, soil samples were taken from typical oil-contaminated fields located in five geographic regions of China. GeoChip, a high-throughput functional gene array, was used to evaluate the microbial functional genes involved in contaminant degradation and in other major biogeochemical/metabolic processes. Our results indicated that the overall microbial community structures were distinct in each oil-contaminated field, and samples were clustered by geographic locations. The organic contaminant degradation genes were most abundant in all samples and presented a similar pattern under oil contaminant stress among the five fields. In addition, alkane and aromatic hydrocarbon degradation genes such as monooxygenase and dioxygenase were detected in high abundance in the oil-contaminated fields. Canonical correspondence analysis indicated that the microbial functional patterns were highly correlated to the local environmental variables, such as oil contaminant concentration, nitrogen and phosphorus contents, salt and pH. Finally, a total of 59% of microbial community variation from GeoChip data can be explained by oil contamination, geographic location and soil geochemical parameters. This study provided insights into the in situ microbial functional structures in oil-contaminated fields and discerned the linkages between microbial communities and environmental variables, which is important to the application of bioremediation in oil-contaminated sites. PMID:20861922

Insights into the Effects of Zinc Doping on Structural Phase Transition of P2-Type Sodium Nickel Manganese Oxide Cathodes for High-Energy Sodium Ion Batteries.

PubMed

Wu, Xuehang; Xu, Gui-Liang; Zhong, Guiming; Gong, Zhengliang; McDonald, Matthew J; Zheng, Shiyao; Fu, Riqiang; Chen, Zonghai; Amine, Khalil; Yang, Yong

2016-08-31

P2-type sodium nickel manganese oxide-based cathode materials with higher energy densities are prime candidates for applications in rechargeable sodium ion batteries. A systematic study combining in situ high energy X-ray diffraction (HEXRD), ex situ X-ray absorption fine spectroscopy (XAFS), transmission electron microscopy (TEM), and solid-state nuclear magnetic resonance (SS-NMR) techniques was carried out to gain a deep insight into the structural evolution of P2-Na0.66Ni0.33-xZnxMn0.67O2 (x = 0, 0.07) during cycling. In situ HEXRD and ex situ TEM measurements indicate that an irreversible phase transition occurs upon sodium insertion-extraction of Na0.66Ni0.33Mn0.67O2. Zinc doping of this system results in a high structural reversibility. XAFS measurements indicate that both materials are almost completely dependent on the Ni(4+)/Ni(3+)/Ni(2+) redox couple to provide charge/discharge capacity. SS-NMR measurements indicate that both reversible and irreversible migration of transition metal ions into the sodium layer occurs in the material at the fully charged state. The irreversible migration of transition metal ions triggers a structural distortion, leading to the observed capacity and voltage fading. Our results allow a new understanding of the importance of improving the stability of transition metal layers.

Quantitative Analysis Of Three-dimensional Branching Systems From X-ray Computed Microtomography Data

DOE Office of Scientific and Technical Information (OSTI.GOV)

McKinney, Adriana L.; Varga, Tamas

Branching structures such as lungs, blood vessels and plant roots play a critical role in life. Growth, structure, and function of these branching structures have an immense effect on our lives. Therefore, quantitative size information on such structures in their native environment is invaluable for studying their growth and the effect of the environment on them. X-ray computed tomography (XCT) has been an effective tool for in situ imaging and analysis of branching structures. We developed a costless tool that approximates the surface and volume of branching structures. Our methodology of noninvasive imaging, segmentation and extraction of quantitative information ismore » demonstrated through the analysis of a plant root in its soil medium from 3D tomography data. XCT data collected on a grass specimen was used to visualize its root structure. A suite of open-source software was employed to segment the root from the soil and determine its isosurface, which was used to calculate its volume and surface. This methodology of processing 3D data is applicable to other branching structures even when the structure of interest is of similar x-ray attenuation to its environment and difficulties arise with sample segmentation.« less

Small-scale structure and turbulence observed in MAP/WINE)

NASA Technical Reports Server (NTRS)

Blix, T. A.

1989-01-01

During MAP/WINE small scale structure and turbulence in the mesosphere and lower thermosphere was studied in situ by rocket-borne instruments as well as from the ground by remote sensing techniques. The eight salvoes launched during the campaign resulted in a wealth of information on the dynamical structure of these regions. The experimental results are reviewed and their interpretation is discussed in terms of gravity waves and turbulence. It is shown that eddy diffusion coefficients and turbulent energy dissipation rates may be derived from the in situ measurements in a consistent manner. The observations are also shown to be consistent with the hypothesis that turbulence can be created by a process of gravity wave saturation.

In Situ Three-Dimensional Reciprocal-Space Mapping of Diffuse Scattering Intensity Distribution and Data Analysis for Precursor Phenomenon in Shape-Memory Alloy

NASA Astrophysics Data System (ADS)

Cheng, Tian-Le; Ma, Fengde D.; Zhou, Jie E.; Jennings, Guy; Ren, Yang; Jin, Yongmei M.; Wang, Yu U.

2012-01-01

Diffuse scattering contains rich information on various structural disorders, thus providing a useful means to study the nanoscale structural deviations from the average crystal structures determined by Bragg peak analysis. Extraction of maximal information from diffuse scattering requires concerted efforts in high-quality three-dimensional (3D) data measurement, quantitative data analysis and visualization, theoretical interpretation, and computer simulations. Such an endeavor is undertaken to study the correlated dynamic atomic position fluctuations caused by thermal vibrations (phonons) in precursor state of shape-memory alloys. High-quality 3D diffuse scattering intensity data around representative Bragg peaks are collected by using in situ high-energy synchrotron x-ray diffraction and two-dimensional digital x-ray detector (image plate). Computational algorithms and codes are developed to construct the 3D reciprocal-space map of diffuse scattering intensity distribution from the measured data, which are further visualized and quantitatively analyzed to reveal in situ physical behaviors. Diffuse scattering intensity distribution is explicitly formulated in terms of atomic position fluctuations to interpret the experimental observations and identify the most relevant physical mechanisms, which help set up reduced structural models with minimal parameters to be efficiently determined by computer simulations. Such combined procedures are demonstrated by a study of phonon softening phenomenon in precursor state and premartensitic transformation of Ni-Mn-Ga shape-memory alloy.

Multi-Stage Structural Transformations in Zero-Strain Lithium Titanate Unveiled by in Situ X-ray Absorption Fingerprints

DOE PAGES

Zhang, Wei; Topsakal, Mehmet; Cama, Christina; ...

2017-10-13

Zero-strain electrodes, such as spinel lithium titanate (Li 4/3Ti 5/3O 4), are appealing for application in batteries due to their negligible volume change and extraordinary stability upon repeated charge/discharge cycles. On the other hand, this same property makes it challenging to probe their structural changes during the electrochemical reaction. In this paper, we report in situ studies of lithiation-driven structural transformations in Li 4/3Ti 5/3O 4 via a combination of X-ray absorption spectroscopy and ab initio calculations. Based on excellent agreement between computational and experimental spectra of Ti K-edge, we identified key spectral features as fingerprints for quantitative assessment ofmore » structural evolution at different length scales. Results from this study indicate that, despite the small variation in the crystal lattice during lithiation, pronounced structural transformations occur in Li 4/3Ti 5/3O 4, both locally and globally, giving rise to a multi-stage kinetic process involving mixed quasi-solid solution/macroscopic two-phase transformations over a wide range of Li concentrations. Finally, this work highlights the unique capability of combining in situ core-level spectroscopy and first-principles calculations for probing Li-ion intercalation in zero-strain electrodes, which is crucial to designing high-performance electrode materials for long-life batteries.« less

Multi-Stage Structural Transformations in Zero-Strain Lithium Titanate Unveiled by in Situ X-ray Absorption Fingerprints

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Wei; Topsakal, Mehmet; Cama, Christina

Zero-strain electrodes, such as spinel lithium titanate (Li 4/3Ti 5/3O 4), are appealing for application in batteries due to their negligible volume change and extraordinary stability upon repeated charge/discharge cycles. On the other hand, this same property makes it challenging to probe their structural changes during the electrochemical reaction. In this paper, we report in situ studies of lithiation-driven structural transformations in Li 4/3Ti 5/3O 4 via a combination of X-ray absorption spectroscopy and ab initio calculations. Based on excellent agreement between computational and experimental spectra of Ti K-edge, we identified key spectral features as fingerprints for quantitative assessment ofmore » structural evolution at different length scales. Results from this study indicate that, despite the small variation in the crystal lattice during lithiation, pronounced structural transformations occur in Li 4/3Ti 5/3O 4, both locally and globally, giving rise to a multi-stage kinetic process involving mixed quasi-solid solution/macroscopic two-phase transformations over a wide range of Li concentrations. Finally, this work highlights the unique capability of combining in situ core-level spectroscopy and first-principles calculations for probing Li-ion intercalation in zero-strain electrodes, which is crucial to designing high-performance electrode materials for long-life batteries.« less

Sphingomyelinase D activity in model membranes: structural effects of in situ generation of ceramide-1-phosphate.

PubMed

Stock, Roberto P; Brewer, Jonathan; Wagner, Kerstin; Ramos-Cerrillo, Blanca; Duelund, Lars; Jernshøj, Kit Drescher; Olsen, Lars Folke; Bagatolli, Luis A

2012-01-01

The toxicity of Loxosceles spider venom has been attributed to a rare enzyme, sphingomyelinase D, which transforms sphingomyelin to ceramide-1-phosphate. The bases of its inflammatory and dermonecrotic activity, however, remain unclear. In this work the effects of ceramide-1-phosphate on model membranes were studied both by in situ generation of this lipid using a recombinant sphingomyelinase D from the spider Loxosceles laeta and by pre-mixing it with sphingomyelin and cholesterol. The systems of choice were large unilamellar vesicles for bulk studies (enzyme kinetics, fluorescence spectroscopy and dynamic light scattering) and giant unilamellar vesicles for fluorescence microscopy examination using a variety of fluorescent probes. The influence of membrane lateral structure on the kinetics of enzyme activity and the consequences of enzyme activity on the structure of target membranes containing sphingomyelin were examined. The findings indicate that: 1) ceramide-1-phosphate (particularly lauroyl ceramide-1-phosphate) can be incorporated into sphingomyelin bilayers in a concentration-dependent manner and generates coexistence of liquid disordered/solid ordered domains, 2) the activity of sphingomyelinase D is clearly influenced by the supramolecular organization of its substrate in membranes and, 3) in situ ceramide-1-phosphate generation by enzymatic activity profoundly alters the lateral structure and morphology of the target membranes.

In-situ small-angle x-ray scattering study of nanoparticles in the plasma plume induced by pulsed laser irradiation of metallic targets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lavisse, L.; Jouvard, J.-M.; Girault, M.

2012-04-16

Small angle x-ray scattering was used to probe in-situ the formation of nanoparticles in the plasma plume generated by pulsed laser irradiation of a titanium metal surface under atmospheric conditions. The size and morphology of the nanoparticles were characterized as function of laser irradiance. Two families of nanoparticles were identified with sizes on the order of 10 and 70 nm, respectively. These results were confirmed by ex-situ transmission electron microscopy experiments.

Computational genetic neuroanatomy of the developing mouse brain: dimensionality reduction, visualization, and clustering.

PubMed

Ji, Shuiwang

2013-07-11

The structured organization of cells in the brain plays a key role in its functional efficiency. This delicate organization is the consequence of unique molecular identity of each cell gradually established by precise spatiotemporal gene expression control during development. Currently, studies on the molecular-structural association are beginning to reveal how the spatiotemporal gene expression patterns are related to cellular differentiation and structural development. In this article, we aim at a global, data-driven study of the relationship between gene expressions and neuroanatomy in the developing mouse brain. To enable visual explorations of the high-dimensional data, we map the in situ hybridization gene expression data to a two-dimensional space by preserving both the global and the local structures. Our results show that the developing brain anatomy is largely preserved in the reduced gene expression space. To provide a quantitative analysis, we cluster the reduced data into groups and measure the consistency with neuroanatomy at multiple levels. Our results show that the clusters in the low-dimensional space are more consistent with neuroanatomy than those in the original space. Gene expression patterns and developing brain anatomy are closely related. Dimensionality reduction and visual exploration facilitate the study of this relationship.

Structure of ribose 5-phosphate isomerase from the probiotic bacterium Lactobacillus salivarius UCC118.

PubMed

Lobley, Carina M C; Aller, Pierre; Douangamath, Alice; Reddivari, Yamini; Bumann, Mario; Bird, Louise E; Nettleship, Joanne E; Brandao-Neto, Jose; Owens, Raymond J; O'Toole, Paul W; Walsh, Martin A

2012-12-01

The structure of ribose 5-phosphate isomerase from the probiotic bacterium Lactobacillus salivarius UCC188 has been determined at 1.72 Å resolution. The structure was solved by molecular replacement, which identified the functional homodimer in the asymmetric unit. Despite only showing 57% sequence identity to its closest homologue, the structure adopted the typical α and β D-ribose 5-phosphate isomerase fold. Comparison to other related structures revealed high homology in the active site, allowing a model of the substrate-bound protein to be proposed. The determination of the structure was expedited by the use of in situ crystallization-plate screening on beamline I04-1 at Diamond Light Source to identify well diffracting protein crystals prior to routine cryocrystallography.

Spectroscopic Ellipsometry Studies of n-i-p Hydrogenated Amorphous Silicon Based Photovoltaic Devices

PubMed Central

Karki Gautam, Laxmi; Junda, Maxwell M.; Haneef, Hamna F.; Collins, Robert W.; Podraza, Nikolas J.

2016-01-01

Optimization of thin film photovoltaics (PV) relies on characterizing the optoelectronic and structural properties of each layer and correlating these properties with device performance. Growth evolution diagrams have been used to guide production of materials with good optoelectronic properties in the full hydrogenated amorphous silicon (a-Si:H) PV device configuration. The nucleation and evolution of crystallites forming from the amorphous phase were studied using in situ near-infrared to ultraviolet spectroscopic ellipsometry during growth of films prepared as a function of hydrogen to reactive gas flow ratio R = [H2]/[SiH4]. In conjunction with higher photon energy measurements, the presence and relative absorption strength of silicon-hydrogen infrared modes were measured by infrared extended ellipsometry measurements to gain insight into chemical bonding. Structural and optical models have been developed for the back reflector (BR) structure consisting of sputtered undoped zinc oxide (ZnO) on top of silver (Ag) coated glass substrates. Characterization of the free-carrier absorption properties in Ag and the ZnO + Ag interface as well as phonon modes in ZnO were also studied by spectroscopic ellipsometry. Measurements ranging from 0.04 to 5 eV were used to extract layer thicknesses, composition, and optical response in the form of complex dielectric function spectra (ε = ε1 + iε2) for Ag, ZnO, the ZnO + Ag interface, and undoped a-Si:H layer in a substrate n-i-p a-Si:H based PV device structure. PMID:28773255

Method for analyzing soil structure according to the size of structural elements

NASA Astrophysics Data System (ADS)

Wieland, Ralf; Rogasik, Helmut

2015-02-01

The soil structure in situ is the result of cropping history and soil development over time. It can be assessed by the size distribution of soil structural elements such as air-filled macro-pores, aggregates and stones, which are responsible for important water and solute transport processes, gas exchange, and the stability of the soil against compacting and shearing forces exerted by agricultural machinery. A method was developed to detect structural elements of the soil in selected horizontal slices of soil core samples with different soil structures in order for them to be implemented accordingly. In the second step, a fitting tool (Eureqa) based on artificial programming was used to find a general function to describe ordered sets of detected structural elements. It was shown that all the samples obey a hyperbolic function: Y(k) = A /(B + k) , k ∈ { 0 , 1 , 2 , … }. This general behavior can be used to develop a classification method based on parameters {A and B}. An open source software program in Python was developed, which can be downloaded together with a selection of soil samples.

In situ synthesis studies of silicon clathrates

NASA Astrophysics Data System (ADS)

Hutchins, Peter Thomas

Solid state clathrates have shown considerable potential as a new class of materials over the past 30 years. Experimental and theoretical studies have shown that precise tuning and synthetic control of these materials, may lead to desirable properties. Very little is known about the mechanism of formation of the clathrates and so the desire to have accurate synthetic control was, until now, unrealistic. This thesis address the problem using in situ synchrotron x-ray techniques. In this study, experiments were designed to utilise time-resolved in situ diffraction techniques and high temperature 23Na NMR, in efforts to understand the mechanism of formation for this class of expanded framework materials. A complex high vacuum capillary synthesis cell was designed for loading under inert conditions and operation under high vacuum at station 6.2 of the SRS Daresbury. The cell was designed to operate in conjunction with a custom made furnace capable of temperatures in excess of 1000 C, as well as a vacuum system capable of 10"5 bar. The clathrate system was studied in situ, using rapid data collection to elucidate the mechanism of formation. The data were analysed using Rietveld methods and showed a structural link between the monoclinic, C2/c, Zintl precursors and the cubic, Pm3n, clathrate I phase. The phases were found to be linked by relation of the sodium planes in the silicide and the sodium atoms resident at cages centres in the clathrate system. This evidence suggests the guest species is instrumental in formation of the clathrate structure by templating the formation of the cages in the structure. Solid state 23Na NMR was utilised to complete specially design experiments, similar to those complete in situ using synchrotron x-ray techniques. The experiments showed increased spherical symmetry of the alkali metal sites and suggested increased mobility of the guest atoms during heating. In addition, cyclic heating experiments using in situ diffraction showed reversible reintroduction of the guest species on heating and cooling, during formation and subsequent dissipation of the clathrate structure. The realisation of the synthesis of a guest free type II clathrate and the theoretical prediction of negative thermal expansion behaviour at low temperature prompted the use of laboratory x-ray diffraction and a liquid helium cryostat to test the prediction. Careful study of the region from 20 to 200 K showed a region of zero or negative thermal expansion in the predicted region the effect observed showed good agreement with theory.

Reactor for nano-focused x-ray diffraction and imaging under catalytic in situ conditions

NASA Astrophysics Data System (ADS)

Richard, M.-I.; Fernández, S.; Hofmann, J. P.; Gao, L.; Chahine, G. A.; Leake, S. J.; Djazouli, H.; De Bortoli, Y.; Petit, L.; Boesecke, P.; Labat, S.; Hensen, E. J. M.; Thomas, O.; Schülli, T.

2017-09-01

A reactor cell for in situ studies of individual catalyst nanoparticles or surfaces by nano-focused (coherent) x-ray diffraction has been developed. Catalytic reactions can be studied in flow mode in a pressure range of 10-2-103 mbar and temperatures up to 900 °C. This instrument bridges the pressure and materials gap at the same time within one experimental setup. It allows us to probe in situ the structure (e.g., shape, size, strain, faceting, composition, and defects) of individual nanoparticles using a nano-focused x-ray beam. Here, the setup was used to observe strain and facet evolution of individual model Pt catalysts during in situ experiments. It can be used for heating other (non-catalytically active) nanoparticles (e.g., nanowires) in inert or reactive gas atmospheres or vacuum as well.

Reactor for nano-focused x-ray diffraction and imaging under catalytic in situ conditions.

PubMed

Richard, M-I; Fernández, S; Hofmann, J P; Gao, L; Chahine, G A; Leake, S J; Djazouli, H; De Bortoli, Y; Petit, L; Boesecke, P; Labat, S; Hensen, E J M; Thomas, O; Schülli, T

2017-09-01

A reactor cell for in situ studies of individual catalyst nanoparticles or surfaces by nano-focused (coherent) x-ray diffraction has been developed. Catalytic reactions can be studied in flow mode in a pressure range of 10 -2 -10 3 mbar and temperatures up to 900 °C. This instrument bridges the pressure and materials gap at the same time within one experimental setup. It allows us to probe in situ the structure (e.g., shape, size, strain, faceting, composition, and defects) of individual nanoparticles using a nano-focused x-ray beam. Here, the setup was used to observe strain and facet evolution of individual model Pt catalysts during in situ experiments. It can be used for heating other (non-catalytically active) nanoparticles (e.g., nanowires) in inert or reactive gas atmospheres or vacuum as well.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taguchi, Takahiro; Testa, J.R.; Mitcham, J.L.

This report describes the localization of the the TIL gene to human chromosome 4p14 using fluorescence in situ hybridization. This gene encodes a protein which is related to the Drosophila transmembrane receptor Toll and the mammalian interleukin-1 receptor, which share similarities in structure and function. The Drosophila gene is also important during embryonic development, which makes TIL a candidate locus for human congenital malformations that are genetically linked to human chromosome 4. 17 refs., 1 fig.

Lunar In Situ Materials-Based Habitat Technology Development Efforts at NASA/MSFC

NASA Technical Reports Server (NTRS)

Bodiford, Melanie P.; Burks, K. H.; Perry M. R.; Cooper, R. W.; Fiske, M. R.

2006-01-01

For long duration missions on other planetary bodies, the use of in situ materials will become increasingly critical. As man's presence on these bodies expands, so must the structures to accommodate them including habitats, laboratories, berms, garages, solar storm shelters, greenhouses, etc. The use of in situ materials will significantly offset required launch upmass and volume issues. Under the auspices of the In Situ Fabrication & Repair (ISFR) Program at NASA/Marshall Space Flight Center (MSFC), the Habitat Structures project has been developing materials and construction technologies to support development of these in situ structures. This paper will report on the development of several of these technologies at MSFC's Prototype Development Laboratory (PDL). These technologies include, but are not limited to, development of extruded concrete and inflatable concrete dome technologies based on waterless and water-based concretes, development of regolith-based blocks with potential radiation shielding binders including polyurethane and polyethylene, pressure regulation systems for inflatable structures, production of glass fibers and rebar derived from molten lunar regolith simulant, development of regolithbag structures, and others, including automation design issues. Results to date and planned efforts for FY06 will also be presented.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neelgund, Gururaj M.; Oki, Aderemi, E-mail: aroki@pvamu.edu; Luo, Zhiping

Graphical abstract: A facile chemical precipitation method is reported for effective in situ deposition of hydroxyapatite on graphene nanosheets. Prior to grafting of hydroxyapatite, chemically modified graphene nanosheets were obtained by the reduction of graphene oxide in presence of ethylenediamine. Display Omitted Highlights: ► It is a facile and effective method for deposition of HA on GR nanosheets. ► It avoids the use of harmful reducing agents like hydrazine, NaBH{sub 4} etc. ► GR nanosheets were produced using bio-compatible, ethylenediamine. ► The graphitic structure of synthesized GR nanosheets was high ordered. ► The ratio of Ca to P in HAmore » was 1.64, which is close to ratio in natural bone. -- Abstract: Graphene nanosheets were effectively functionalized by in situ deposition of hydroxyapatite through a facile chemical precipitation method. Prior to grafting of hydroxyapatite, chemically modified graphene nanosheets were obtained by the reduction of graphene oxide in presence of ethylenediamine. The resulting hydroxyapatite functionalized graphene nanosheets were characterized by attenuated total reflection IR spectroscopy, X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, Raman spectroscopy and thermogravimetric analysis. These characterization techniques revealed the successful grafting of hydroxyapatite over well exfoliated graphene nanosheets without destroying their structure.« less

Towards identifying the active sites on RuO 2 (110) in catalyzing oxygen evolution

DOE PAGES

Rao, Reshma R.; Kolb, Manuel J.; Halck, Niels Bendtsen; ...

2017-11-17

While the surface atomic structure of RuO 2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO 2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used to determine the surface structural changes on single-crystal RuO2(110) as a function of potential in acidic electrolyte. The redox peaks at 0.7, 1.1 and 1.4 V vs. reversible hydrogen electrode (RHE) could be attributed to surface transitions associated with the successive deprotonation of –H 2O on the coordinatively unsaturated Ru sites (CUS)more » and hydrogen adsorbed to the bridging oxygen sites. At potentials relevant to the oxygen evolution reaction (OER), an –OO species on the Ru CUS sites was detected, which was stabilized by a neighboring –OH group on the Ru CUS or bridge site. Combining potential-dependent surface structures with their energetics from DFT led to a new OER pathway, where the deprotonation of the –OH group used to stabilize –OO was found to be rate-limiting.« less

Towards identifying the active sites on RuO 2 (110) in catalyzing oxygen evolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rao, Reshma R.; Kolb, Manuel J.; Halck, Niels Bendtsen

While the surface atomic structure of RuO 2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO 2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used to determine the surface structural changes on single-crystal RuO2(110) as a function of potential in acidic electrolyte. The redox peaks at 0.7, 1.1 and 1.4 V vs. reversible hydrogen electrode (RHE) could be attributed to surface transitions associated with the successive deprotonation of –H 2O on the coordinatively unsaturated Ru sites (CUS)more » and hydrogen adsorbed to the bridging oxygen sites. At potentials relevant to the oxygen evolution reaction (OER), an –OO species on the Ru CUS sites was detected, which was stabilized by a neighboring –OH group on the Ru CUS or bridge site. Combining potential-dependent surface structures with their energetics from DFT led to a new OER pathway, where the deprotonation of the –OH group used to stabilize –OO was found to be rate-limiting.« less

Painting Supramolecular Polymers in Organic Solvents by Super-resolution Microscopy

PubMed Central

2018-01-01

Despite the rapid development of complex functional supramolecular systems, visualization of these architectures under native conditions at high resolution has remained a challenging endeavor. Super-resolution microscopy was recently proposed as an effective tool to unveil one-dimensional nanoscale structures in aqueous media upon chemical functionalization with suitable fluorescent probes. Building upon our previous work, which enabled photoactivation localization microscopy in organic solvents, herein, we present the imaging of one-dimensional supramolecular polymers in their native environment by interface point accumulation for imaging in nanoscale topography (iPAINT). The noncovalent staining, typical of iPAINT, allows the investigation of supramolecular polymers’ structure in situ without any chemical modification. The quasi-permanent adsorption of the dye to the polymer is exploited to identify block-like arrangements within supramolecular fibers, which were obtained upon mixing homopolymers that were prestained with different colors. The staining of the blocks, maintained by the lack of exchange of the dyes, permits the imaging of complex structures for multiple days. This study showcases the potential of PAINT-like strategies such as iPAINT to visualize multicomponent dynamic systems in their native environment with an easy, synthesis-free approach and high spatial resolution. PMID:29697958

In situ electrochemical high-energy X-ray diffraction using a capillary working electrode cell geometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Matthias J.; Bedford, Nicholas M.; Jiang, Naisheng

The ability to generate new electrochemically active materials for energy generation and storage with improved properties will likely be derived from an understanding of atomic-scale structure/function relationships during electrochemical events. Here, the design and implementation of a new capillary electrochemical cell designed specifically forin situhigh-energy X-ray diffraction measurements is described. By increasing the amount of electrochemically active material in the X-ray path while implementing low-Zcell materials with anisotropic scattering profiles, an order of magnitude enhancement in diffracted X-ray signal over traditional cell geometries for multiple electrochemically active materials is demonstrated. This signal improvement is crucial for high-energy X-ray diffraction measurementsmore » and subsequent Fourier transformation into atomic pair distribution functions for atomic-scale structural analysis. As an example, clear structural changes in LiCoO 2under reductive and oxidative conditions using the capillary cell are demonstrated, which agree with prior studies. Accurate modeling of the LiCoO 2diffraction data using reverse Monte Carlo simulations further verifies accurate background subtraction and strong signal from the electrochemically active material, enabled by the capillary working electrode geometry.« less

Geometry of electromechanically active structures in Gadolinium - doped Cerium oxides

DOE PAGES

Li, Yuanyuan; Kraynis, Olga; Kas, Joshua; ...

2016-05-20

Local distortions from average structure are important in many functional materials, such as electrostrictors or piezoelectrics, and contain clues about their mechanism of work. However, the geometric attributes of these distortions are exceedingly difficult to measure, leading to a gap in knowledge regarding their roles in electromechanical response. This task is particularly challenging in the case of recently reported non-classical electrostriction in Cerium-Gadolinium oxides (CGO), where only a small population of Ce-O bonds that are located near oxygen ion vacancies responds to external electric field. In this study, we used high-energy resolution fluorescence detection (HERFD) technique to collect X-ray absorptionmore » spectra in CGO in situ, with and without an external electric field, coupled with theoretical modeling to characterize three-dimensional geometry of electromechanically active units.« less

In situ synchrotron X-ray diffraction study on epitaxial-growth dynamics of III–V semiconductors

NASA Astrophysics Data System (ADS)

Takahasi, Masamitu

2018-05-01

The application of in situ synchrotron X-ray diffraction (XRD) to the molecular-beam epitaxial (MBE) growth of III–V semiconductors is overviewed along with backgrounds of the diffraction theory and instrumentation. X-rays are sensitive not only to the surface of growing films but also to buried interfacial structures because of their large penetration depth. Moreover, a spatial coherence length up to µm order makes X-rays widely applicable to the characterization of low-dimensional structures, such as quantum dots and wires. In situ XRD studies during growth were performed using an X-ray diffractometer, which was combined with an MBE chamber. X-ray reciprocal space mapping at a speed matching a typical growth rate was achieved using intense X-rays available from a synchrotron light source and an area detector. The importance of measuring the three-dimensional distribution of XRD intensity in a reciprocal space map is demonstrated for the MBE growth of two-, one-, and zero-dimensional structures. A large amount of information about the growth process of two-dimensional InGaAs/GaAs(001) epitaxial films has been provided by three-dimensional X-ray reciprocal mappings, including the anisotropic strain relaxation, the compositional inhomogeneity, and the evolution of surface and interfacial roughness. For one-dimensional GaAs nanowires grown in a Au-catalyzed vapor-liquid–solid mode, the relationship between the diameter of the nanowires and the formation of polytypes has been suggested on the basis of in situ XRD measurements. In situ three-dimensional X-ray reciprocal space mapping is also shown to be useful for determining the lateral and vertical sizes of self-assembled InAs/GaAs(001) quantum dots as well as their internal strain distributions during growth.

Kinetics and fracture resistance of lithiated silicon nanostructure pairs controlled by their mechanical interaction

DOE PAGES

Lee, Seok Woo; Lee, Hyun -Wook; Ryu, Ill; ...

2015-06-26

Following an explosion of studies of silicon as a negative electrode for Li-ion batteries, the anomalous volumetric changes and fracture of lithiated single Si particles have attracted significant attention in various fields, including mechanics. However, in real batteries, lithiation occurs simultaneously in clusters of Si in a confined medium. Hence, understanding how the individual Si structures interact during lithiation in a closed space is necessary. Here, we demonstrate physical and mechanical interactions of swelling Si structures during lithiation using well-defined Si nanopillar pairs. Ex situ SEM and in situ TEM studies reveal that compressive stresses change the reaction kinetics somore » that preferential lithiation occurs at free surfaces when the pillars are mechanically clamped. Such mechanical interactions enhance the fracture resistance of lithiated Si by lessening the tensile stress concentrations in Si structures. Lastly, this study will contribute to improved design of Si structures at the electrode level for high-performance Li-ion batteries.« less

Correlation between the microstructures of graphite oxides and their catalytic behaviors in air oxidation of benzyl alcohol.

PubMed

Geng, Longlong; Wu, Shujie; Zou, Yongcun; Jia, Mingjun; Zhang, Wenxiang; Yan, Wenfu; Liu, Gang

2014-05-01

A series of graphite oxide (GO) materials were obtained by thermal treatment of oxidized natural graphite powder at different temperatures (from 100 to 200 °C). The microstructure evolution (i.e., layer structure and surface functional groups) of the graphite oxide during the heating process is studied by various characterization means, including XRD, N2 adsorption, TG-DTA, in situ DRIFT, XPS, Raman, TEM and Boehm titration. The characterization results show that the structures of GO materials change gradually from multilayer sheets to a transparent ultrathin 2D structure of the carbon sheets. The concentration of surface COH and HOCO groups decrease significantly upon treating temperature increasing. Benzyl alcohol oxidation with air as oxidant source was carried out to detect the catalytic behaviors of different GO materials. The activities of GO materials decrease with the increase of treating temperatures. It shows that the structure properties, including ultrathin sheets and high specific surface area, are not crucial factors affecting the catalytic activity. The type and amount of surface oxygen-containing functional groups of GO materials tightly correlates with the catalytic performance. Carboxylic groups on the surface of GO should act as oxidative sites for benzyl alcohol and the reduced form could be reoxidized by molecular oxygen. Copyright © 2014 Elsevier Inc. All rights reserved.

New Textile Sensors for In Situ Structural Health Monitoring of Textile Reinforced Thermoplastic Composites Based on the Conductive Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) Polymer Complex

PubMed Central

Jerkovic, Ivona; Koncar, Vladan; Grancaric, Ana Marija

2017-01-01

Many metallic structural and non-structural parts used in the transportation industry can be replaced by textile-reinforced composites. Composites made from a polymeric matrix and fibrous reinforcement have been increasingly studied during the last decade. On the other hand, the fast development of smart textile structures seems to be a very promising solution for in situ structural health monitoring of composite parts. In order to optimize composites’ quality and their lifetime all the production steps have to be monitored in real time. Textile sensors embedded in the composite reinforcement and having the same mechanical properties as the yarns used to make the reinforcement exhibit actuating and sensing capabilities. This paper presents a new generation of textile fibrous sensors based on the conductive polymer complex poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) developed by an original roll to roll coating method. Conductive coating for yarn treatment was defined according to the preliminary study of percolation threshold of this polymer complex. The percolation threshold determination was based on conductive dry films’ electrical properties analysis, in order to develop highly sensitive sensors. A novel laboratory equipment was designed and produced for yarn coating to ensure effective and equally distributed coating of electroconductive polymer without distortion of textile properties. The electromechanical properties of the textile fibrous sensors confirmed their suitability for in situ structural damages detection of textile reinforced thermoplastic composites in real time. PMID:28994733

New Textile Sensors for In Situ Structural Health Monitoring of Textile Reinforced Thermoplastic Composites Based on the Conductive Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) Polymer Complex.

PubMed

Jerkovic, Ivona; Koncar, Vladan; Grancaric, Ana Marija

2017-10-10

Many metallic structural and non-structural parts used in the transportation industry can be replaced by textile-reinforced composites. Composites made from a polymeric matrix and fibrous reinforcement have been increasingly studied during the last decade. On the other hand, the fast development of smart textile structures seems to be a very promising solution for in situ structural health monitoring of composite parts. In order to optimize composites' quality and their lifetime all the production steps have to be monitored in real time. Textile sensors embedded in the composite reinforcement and having the same mechanical properties as the yarns used to make the reinforcement exhibit actuating and sensing capabilities. This paper presents a new generation of textile fibrous sensors based on the conductive polymer complex poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) developed by an original roll to roll coating method. Conductive coating for yarn treatment was defined according to the preliminary study of percolation threshold of this polymer complex. The percolation threshold determination was based on conductive dry films' electrical properties analysis, in order to develop highly sensitive sensors. A novel laboratory equipment was designed and produced for yarn coating to ensure effective and equally distributed coating of electroconductive polymer without distortion of textile properties. The electromechanical properties of the textile fibrous sensors confirmed their suitability for in situ structural damages detection of textile reinforced thermoplastic composites in real time.

A patient with myelodysplastic syndrome studied by GTG-banding and fluorescent in situ hybridization (FISH).

PubMed

Mark, H F; Mark, Y; Sotomayor, E; Sambandam, S

1998-01-01

Molecular cytogenetics using fluorescent in situ hybridization (FISH) is an extremely useful adjunct technique to conventional cytogenetics via GTG-banding. The present paper illustrates the utility of FISH by describing a patient with myelodysplastic syndrome (MDS) who was initially studied using GTG-banding and whose bone marrow was found to be populated with hyperdiploid cells. FISH was used to delineate the numerical and structural chromosomal abnormalities. It revealed the presence of trisomy 8 and determined that the previously unidentifiable marker chromosome was of chromosome 10 origin. Although trisomy 8 is a frequent finding in MDS, the structural chromosomal abnormality of chromosome 10 as reported here is not a common finding.

Imaging stem cell distribution, growth, migration, and differentiation in 3-D scaffolds for bone tissue engineering using mesoscopic fluorescence tomography.

PubMed

Tang, Qinggong; Piard, Charlotte; Lin, Jonathan; Nan, Kai; Guo, Ting; Caccamese, John; Fisher, John; Chen, Yu

2018-01-01

Regenerative medicine has emerged as an important discipline that aims to repair injury or replace damaged tissues or organs by introducing living cells or functioning tissues. Successful regenerative medicine strategies will likely depend upon a simultaneous optimization strategy for the design of biomaterials, cell-seeding methods, cell-biomaterial interactions, and molecular signaling within the engineered tissues. It remains a challenge to image three-dimensional (3-D) structures and functions of the cell-seeded scaffold in mesoscopic scale (>2 ∼ 3 mm). In this study, we utilized angled fluorescence laminar optical tomography (aFLOT), which allows depth-resolved molecular characterization of engineered tissues in 3-D to investigate cell viability, migration, and bone mineralization within bone tissue engineering scaffolds in situ. © 2017 Wiley Periodicals, Inc.

Substituent effects on the redox states of locally functionalized single-walled carbon nanotubes revealed by in situ photoluminescence spectroelectrochemistry.

PubMed

Shiraishi, Tomonari; Shiraki, Tomohiro; Nakashima, Naotoshi

2017-11-09

Single-walled carbon nanotubes (SWNTs) with local chemical modification have been recognized as a novel near infrared (NIR) photoluminescent nanomaterial due to the emergence of a new red-shifted photoluminescence (PL) with enhanced quantum yields. As a characteristic feature of the locally functionalized SWNTs (lf-SWNTs), PL wavelength changes occur with the structural dependence of the substituent structures in the modified aryl groups, showing up to a 60 nm peak shift according to an electronic property difference of the aryl groups. Up to now, however, the structural effect on the electronic states of the lf-SWNTs has been discussed only on the basis of theoretical calculations due to the very limited amount of modifications. Herein, we describe the successfully-determined electronic states of the aryl-modified lf-SWNTs with different substituents (Ar-X SWNTs) using an in situ PL spectroelectrochemical method based on electrochemical quenching of the PL intensities analyzed by the Nernst equation. In particular, we reveal that the local functionalization of (6,5)SWNTs induced potential changes in the energy levels of the HOMO and the LUMO by -23 to -38 meV and +20 to +22 meV, respectively, compared to those of the pristine SWNTs, which generates exciton trapping sites with narrower band gaps. Moreover, the HOMO levels of the Ar-X SWNTs specifically shift in a negative potential direction by 15 meV according to an enhancement of the electron-accepting property of the substituents in the aryl groups that corresponds to an increase in the Hammet substituent constants, suggesting the importance of the dipole effect from the aryl groups on the lf-SWNTs to the level shift of the frontier orbitals. Our method is a promising way to characterize the electronic features of the lf-SWNTs.

Visualizing the chemistry and structure dynamics in lithium-ion batteries by in-situ neutron diffraction

PubMed Central

Wang, Xun-Li; An, Ke; Cai, Lu; Feng, Zhili; Nagler, Stephen E.; Daniel, Claus; Rhodes, Kevin J.; Stoica, Alexandru D.; Skorpenske, Harley D.; Liang, Chengdu; Zhang, Wei; Kim, Joon; Qi, Yue; Harris, Stephen J.

2012-01-01

We report an in-situ neutron diffraction study of a large format pouch battery cell. The succession of Li-Graphite intercalation phases was fully captured under an 1C charge-discharge condition (i.e., charge to full capacity in 1 hour). However, the lithiation and dilithiation pathways are distinctively different and, unlike in slowing charging experiments with which the Li-Graphite phase diagram was established, no LiC24 phase was found during charge at 1C rate. Approximately 75 mol. % of the graphite converts to LiC6 at full charge, and a lattice dilation as large as 4% was observed during a charge-discharge cycle. Our work demonstrates the potential of in-situ, time and spatially resolved neutron diffraction study of the dynamic chemical and structural changes in “real-world” batteries under realistic cycling conditions, which should provide microscopic insights on degradation and the important role of diffusion kinetics in energy storage materials. PMID:23087812

Small-scale Pressure-balanced Structures Driven by Oblique Slow Mode Waves Measured in the Solar Wind

NASA Astrophysics Data System (ADS)

Yao, Shuo; He, J.-S.; Tu, C.-Y.; Wang, L.-H.; Marsch, E.

2013-09-01

Recently, small-scale pressure-balanced structures (PBSs) were identified in the solar wind, but their formation mechanism remains unclear. This work aims to reveal the dependence of the properties of small-scale PBSs on the background magnetic field (B 0) direction and thus to corroborate the in situ mechanism that forms them. We analyze the plasma and magnetic field data obtained by WIND in the quiet solar wind at 1 AU. First, we use a developed moving-average method to obtain B 0(s, t) for every temporal scale (s) at each time moment (t). By wavelet cross-coherence analysis, we obtain the correlation coefficients between the thermal pressure P th and the magnetic pressure P B, distributing against the temporal scale and the angle θxB between B 0(s, t) and Geocentric Solar Ecliptic coordinates (GSE)-x. We note that the angle coverage of a PBS decreases with shorter temporal scale, but the occurrence of the PBSs is independent of θxB. Suspecting that the isolated small PBSs are formed by compressive waves in situ, we continue this study by testing the wave modes forming a small-scale PBS with B 0(s, t) quasi-parallel to GSE-x. As a result, we identify that the cross-helicity and the compressibility attain values for a slow mode from theoretical calculations. The wave vector is derived from minimum variance analysis. Besides, the proton temperatures obey T < T ∥ derived from the velocity distribution functions, excluding a mirror mode, which is the other candidate for the formation of PBSs in situ. Thus, a small-scale PBS is shown to be driven by oblique, slow-mode waves in the solar wind.

Inhibition of the cellular function of perforin by 1-amino-2,4-dicyanopyrido[1,2-a]benzimidazoles.

PubMed

Lyons, Dani M; Huttunen, Kristiina M; Browne, Kylie A; Ciccone, Annette; Trapani, Joseph A; Denny, William A; Spicer, Julie A

2011-07-01

A high throughput screen showed the ability of a 1-amino-2,4-dicyanopyrido[1,2-a]benzimidazole analogue to directly inhibit the lytic activity of the pore-forming protein perforin. A series of analogues were prepared to study structure-activity relationships (SAR) for the this activity, either directly added to cells or released in situ by KHYG-1 NK cells, at non-toxic concentrations. These studies showed that the pyridobenzimidazole moiety was required for effective activity, with strongly basic centres disfavoured. This class of compounds was relatively unaffected by the addition of serum, which was not the case for a previous class of direct inhibitors. Copyright © 2011 Elsevier Ltd. All rights reserved.

Structural properties of zirconia - in-situ high temperature XRD characterization

NASA Astrophysics Data System (ADS)

Kurpaska, Lukasz

2018-07-01

In this work, the effect of high temperature on structural properties of pure zirconium have been investigated. In-situ X-ray diffraction analysis of the oxide layer formed at temperature window 25-600 °C on pure zirconium were performed. Conducted experiment aimed at investigation of the zirconia phases developed on surface of the metallic substrate. Based on the conducted studies, possible stress state (during heating, continuous oxidation and cooling), cell parameters and HWHM factor were analyzed. A tetragonal and monoclinic phases peak shifts and intensities change were observed, suggesting that different phases react in different way upon temperature effect.

In Situ Flow MAS NMR Spectroscopy and Synchrotron PDF Analyses of the Local Response of the Brønsted Acidic Site in SAPO-34 during Hydration at Elevated Temperatures.

PubMed

Kalantzopoulos, Georgios N; Lundvall, Fredrik; Checchia, Stefano; Lind, Anna; Wragg, David S; Fjellvåg, Helmer; Arstad, Bjørnar

2018-02-19

In situ flow magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and synchrotron-based pair distribution function (PDF) analyses were applied to study water's interactions with the Brønsted acidic site and the surrounding framework in the SAPO-34 catalyst at temperatures up to 300 °C for NMR spectroscopy and 700 °C for PDF. 29 Si enrichment of the sample enabled detailed NMR spectroscopy investigations of the T-atom generating the Brønsted site. By NMR spectroscopy, we observed dehydration above 100 °C and a coalescence of Si peaks due to local framework adjustments. Towards 300 °C, the NMR spectroscopy data indicated highly mobile acidic protons. In situ total X-ray scattering measurements analyzed by PDF showed clear changes in the Al local environment in the 250-300 °C region, as the Al-O bond lengths showed a sudden change. This fell within the same temperature range as the increased Brønsted proton mobility. We suggest that the active site in this catalyst under industrial conditions comprises not only the Brønsted proton but also SiO 4 . To the best of our knowledge, this is the first work proposing a structural model of a SAPO catalyst by atomic PDF analysis. The combination of synchrotron PDF analysis with in situ NMR spectroscopy is promising in revealing the dynamic features of a working catalyst. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses.

PubMed

Miglierini, Marcel B; Procházka, Vít; Vrba, Vlastimil; Švec, Peter; Janičkovič, Dušan; Matúš, Peter

2018-06-07

We demonstrate the use of two nuclear-based analytical methods that can follow the modifications of microstructural arrangement of iron-based metallic glasses (MGs). Despite their amorphous nature, the identification of hyperfine interactions unveils faint structural modifications. For this purpose, we have employed two techniques that utilize nuclear resonance among nuclear levels of a stable 57 Fe isotope, namely Mössbauer spectrometry and nuclear forward scattering (NFS) of synchrotron radiation. The effects of heat treatment upon (Fe2.85Co1)77Mo8Cu1B14 MG are discussed using the results of ex situ and in situ experiments, respectively. As both methods are sensitive to hyperfine interactions, information on structural arrangement as well as on magnetic microstructure is readily available. Mössbauer spectrometry performed ex situ describes how the structural arrangement and magnetic microstructure appears at room temperature after the annealing under certain conditions (temperature, time), and thus this technique inspects steady states. On the other hand, NFS data are recorded in situ during dynamically changing temperature and NFS examines transient states. The use of both techniques provides complementary information. In general, they can be applied to any suitable system in which it is important to know its steady state but also transient states.

Recent Advances and Applications in Synchrotron X-Ray Protein Footprinting for Protein Structure and Dynamics Elucidation.

PubMed

Gupta, Sayan; Feng, Jun; Chance, Mark; Ralston, Corie

2016-01-01

Synchrotron X-ray Footprinting is a powerful in situ hydroxyl radical labeling method for analysis of protein structure, interactions, folding and conformation change in solution. In this method, water is ionized by high flux density broad band synchrotron X-rays to produce a steady-state concentration of hydroxyl radicals, which then react with solvent accessible side-chains. The resulting stable modification products are analyzed by liquid chromatography coupled to mass spectrometry. A comparative reactivity rate between known and unknown states of a protein provides local as well as global information on structural changes, which is then used to develop structural models for protein function and dynamics. In this review we describe the XF-MS method, its unique capabilities and its recent technical advances at the Advanced Light Source. We provide a comparison of other hydroxyl radical and mass spectrometry based methods with XFMS. We also discuss some of the latest developments in its usage for studying bound water, transmembrane proteins and photosynthetic protein components, and the synergy of the method with other synchrotron based structural biology methods.

Restructuring of an Ir(210) electrode surface by potential cycling

PubMed Central

Soliman, Khaled A; Kolb, Dieter M; Jacob, Timo

2014-01-01

Summary This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s−1 between −0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation. PMID:25247118

Restructuring of an Ir(210) electrode surface by potential cycling.

PubMed

Soliman, Khaled A; Kolb, Dieter M; Kibler, Ludwig A; Jacob, Timo

2014-01-01

This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s(-1) between -0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation.

Synthesis, Structure, and Pressure-Induced Polymerization of Li 3 Fe(CN) 6 Accompanied with Enhanced Conductivity

DOE PAGES

Li, Kuo; Zheng, Haiyan; Hattori, Takanori; ...

2015-11-17

By providing a new route to synthesize inorganic/organic conductors with tunable composition and properties, pressure-induced polymerization of charged triple-bond monomers like acetylide and cyanide could lead to formation of a conductive metal–carbon network composite. The industry application of this promising synthetic method is mainly limited by the reaction pressure needed, which is often too high to be reached for gram amounts of sample. Here we successfully synthesized highly conductive Li 3Fe(CN) 6 at maximum pressure around 5 GPa and used in situ diagnostic tools to follow the structural and functional transformations of the sample, including in situ X-ray and neutronmore » diffraction and Raman and impedance spectroscopy, along with the neutron pair distribution function measurement on the recovered sample. The cyanide anions start to react around 1 GPa and bond to each other irreversibly at around 5 GPa, which are the lowest reaction pressures in all known metal cyanides and within the technologically achievable pressure range for industrial production. Moreover, the conductivity of the polymer is above 10 –3 S·cm –1, which reaches the range of conductive polymers. Our investigation suggests that the pressure-induced polymerization route is practicable for synthesizing some types of functional conductive materials for industrial use, and further research like doping and heating can hence be motivated to synthesize novel materials under lower pressure and with better performances.« less

Identification of prominence ejecta by the proton distribution function and magnetic fine structure in ICMEs in the inner heliosphere

NASA Astrophysics Data System (ADS)

Marsch, Eckart; Yao, Shuo; Tu, Chuanyi; Schwenn, Rainer

This work presents in-situ solar wind observations of three magnetic clouds that contain certain cold high-density material, when Helios 2 was located at 0.3 AU, on 9 May 1979, 0.5 AU on 30 March 1976, and 0.7 AU on 24 December 1978, respectively. In the cold high-density regions embedded in the ICMEs we find that (1) the number density of protons is higher than in other regions inside the magnetic cloud (MC), (2)the possible existence of He+, (3) the thermal velocity distribution functions (VDFs) are more isotropic and appear to be colder than in the other regions of the MC, and the proton temperature is lower than that of the ambient plasma, (4) the associated magnetic field configuration can for all three MC events be identified as a flux rope. This cold high-density region is located at the polarity inversion line in the center of the bipolar structure of the MC magnetic field (consistent with previous work of solar observation that a prominence lies over the neutral line of the related bipolar solar magnetic field ). It is the first time that prominence ejecta are identified by both the plasma and magnetic field features inside 1 AU, and that thermal ion velocity distribution functions are used to investigate the microstate of the prominence material. Overall, our in situ observations are consistent with the three-part CME models.

Comparative Study of Two Different TiO2 Film Sensors on Response to H2 under UV Light and Room Temperature

PubMed Central

Peng, Xiaoying; Wang, Zhongming; Huang, Pan; Chen, Xun; Fu, Xianzhi; Dai, Wenxin

2016-01-01

An anatase TiO2 film sensor was prepared by a facile in-situ method on the interdigitated Au electrode deposited on the alumina substrate. The structure, morphology and the optical properties of the in-situ TiO2 film sensor were characterized by X-ray diffraction, Scanning Electron Microscopy, and UV-vis diffuse reflectance spectra. The photo-assisted gas sensitivities of the prepared film towards H2 gas were evaluated at room temperature in N2 and synthetic air atmospheres. As compared to TiO2 film sensor prepared by drop-coating method, this in-situ TiO2 film sensor exhibited a more compact structure composed of uniform TiO2 microspheres as well as a better gas sensitivity towards H2 under UV irradiation, especially in synthetic air. The photo-electrochemical measurements suggest that these improvements may be associated with the efficient charge transfer in the TiO2 interface induced by the TiO2 microsphere structure. This study might offer a feasible approach to develop photo-assisted gas sensors at ambient temperature. PMID:27509502

In situ synthesis of fluorescent magnetosomes using an organic membrane as a soft template.

PubMed

Ke, Wenjing; Zhang, Juhua; An, Xueqin; Zhang, Bo

2017-05-04

A novel approach was presented for the in situ synthesis of fluorescent magnetosomes by biological mineralization and carbonization processes for the first time. The surface structures, magnetism and fluorescence were studied, and the cytotoxicity tests and fluorescent trace in liposomes were probed. The fluorescent magnetosomes exhibit not only unique fluorescence and ferromagnetic properties but also low toxicity and superior imaging capability.

Functional and structural responses to marine urbanisation

NASA Astrophysics Data System (ADS)

Mayer-Pinto, M.; Cole, V. J.; Johnston, E. L.; Bugnot, A.; Hurst, H.; Airoldi, L.; Glasby, T. M.; Dafforn, K. A.

2018-01-01

Urban areas have broad ecological footprints with complex impacts on natural systems. In coastal areas, growing populations are advancing their urban footprint into the ocean through the construction of seawalls and other built infrastructure. While we have some understanding of how urbanisation might drive functional change in terrestrial ecosystems, coastal systems have been largely overlooked. This study is one of the first to directly assess how changes in diversity relate to changes in ecosystem properties and functions (e.g. productivity, filtration rates) of artificial and natural habitats in one of the largest urbanised estuaries in the world, Sydney Harbour. We complemented our surveys with an extensive literature search. We found large and important differences in the community structure and function between artificial and natural coastal habitats. However, differences in diversity and abundance of organisms do not necessarily match observed functional changes. The abundance and composition of important functional groups differed among habitats with rocky shores having 40% and 70% more grazers than seawalls or pilings, respectively. In contrast, scavengers were approximately 8 times more abundant on seawalls than on pilings or rocky shores and algae were more diverse on natural rocky shores and seawalls than on pilings. Our results confirm previous findings in the literature. Oysters were more abundant on pilings than on rocky shores, but were also smaller. Interestingly, these differences in oyster populations did not affect in situ filtration rates between habitats. Seawalls were the most invaded habitats while pilings supported greater secondary productivity than other habitats. This study highlights the complexity of the diversity-function relationship and responses to ocean sprawl in coastal systems. Importantly, we showed that functional properties should be considered independently from structural change if we are to design and manage artificial habitats in ways to maximise the services provided by urban coastal systems and minimise their ecological impacts.

Spectroscopic ellipsometry for analysis of polycrystalline thin-film photovoltaic devices and prediction of external quantum efficiency

NASA Astrophysics Data System (ADS)

Ibdah, Abdel-Rahman; Koirala, Prakash; Aryal, Puruswottam; Pradhan, Puja; Marsillac, Sylvain; Rockett, Angus A.; Podraza, Nikolas J.; Collins, Robert W.

2017-11-01

Complete polycrystalline thin-film photovoltaic (PV) devices employing CuIn1-xGaxSe2/CdS and CdS/CdTe heterojunctions have been studied by ex situ spectroscopic ellipsometry (SE). In this study, layer thicknesses have been extracted along with photon energy independent parameters such as compositions that describe the dielectric function spectra ε(E) of the individual layers. For accurate ex situ SE analysis of these PV devices, a database of ε(E) spectra is required for all thin film component materials used in each of the two absorber technologies. When possible, database measurements are performed by applying SE in situ immediately after deposition of the thin film materials and after cooling to room temperature in order to avoid oxidation and surface contamination. Determination of ε(E) from the resulting in situ SE data requires structural information that can be obtained from analysis of SE data acquired in real time during the deposition process. From the results of ex situ analysis of the complete CuIn1-xGaxSe2 (CIGS) and CdTe PV devices, the deduced layer thicknesses in combination with the parameters describing ε(E) can be employed in further studies that simulate the external quantum efficiency (EQE) spectra of the devices. These simulations have been performed here by assuming that all electron-hole pairs generated within the active layers, i.e. layers incorporating a dominant absorber component (either CIGS or CdTe), are separated and collected. The active layers may include not only the bulk absorber but also window and back contact interface layers, and individual current contributions from these layers have been determined in the simulations. In addition, the ex situ SE analysis results enable calculation of the absorbance spectra for the inactive layers and the overall reflectance spectra, which lead to quantification of all optical losses in terms of a current density deficit. Mapping SE can be performed given the high speed of multichannel ellipsometers employing array detection, and the resulting EQE simulation capability has wide applications in predicting large area PV module output. The ultimate goal is an on-line capability that enables prediction of PV sub-cell current output as early as possible in the production process.

Automated batch fiducial-less tilt-series alignment in Appion using Protomo

PubMed Central

Noble, Alex J.; Stagg, Scott M.

2015-01-01

The field of electron tomography has benefited greatly from manual and semi-automated approaches to marker-based tilt-series alignment that have allowed for the structural determination of multitudes of in situ cellular structures as well as macromolecular structures of individual protein complexes. The emergence of complementary metal-oxide semiconductor detectors capable of detecting individual electrons has enabled the collection of low dose, high contrast images, opening the door for reliable correlation-based tilt-series alignment. Here we present a set of automated, correlation-based tilt-series alignment, contrast transfer function (CTF) correction, and reconstruction workflows for use in conjunction with the Appion/Leginon package that are primarily targeted at automating structure determination with cryogenic electron microscopy. PMID:26455557

Fluid density and concentration measurement using noninvasive in situ ultrasonic resonance interferometry

DOEpatents

Pope, Noah G.; Veirs, Douglas K.; Claytor, Thomas N.

1994-01-01

The specific gravity or solute concentration of a process fluid solution located in a selected structure is determined by obtaining a resonance response spectrum of the fluid/structure over a range of frequencies that are outside the response of the structure itself. A fast fourier transform (FFT) of the resonance response spectrum is performed to form a set of FFT values. A peak value for the FFT values is determined, e.g., by curve fitting, to output a process parameter that is functionally related to the specific gravity and solute concentration of the process fluid solution. Calibration curves are required to correlate the peak FFT value over the range of expected specific gravities and solute concentrations in the selected structure.

Fluid density and concentration measurement using noninvasive in situ ultrasonic resonance interferometry

DOEpatents

Pope, N.G.; Veirs, D.K.; Claytor, T.N.

1994-10-25

The specific gravity or solute concentration of a process fluid solution located in a selected structure is determined by obtaining a resonance response spectrum of the fluid/structure over a range of frequencies that are outside the response of the structure itself. A fast Fourier transform (FFT) of the resonance response spectrum is performed to form a set of FFT values. A peak value for the FFT values is determined, e.g., by curve fitting, to output a process parameter that is functionally related to the specific gravity and solute concentration of the process fluid solution. Calibration curves are required to correlate the peak FFT value over the range of expected specific gravities and solute concentrations in the selected structure. 7 figs.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eilert, Andre; Cavalca, Filippo; Roberts, F. Sloan

Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO 2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy-loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stablemore » under the strongly reducing conditions found in CO 2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.« less

In-situ measurement system

DOEpatents

Lord, David E.

1983-01-01

A multipurpose in situ underground measurement system comprising a plurality of long electrical resistance elements in the form of rigid reinforcing bars, each having an open loop "hairpin" configuration of shorter length than the other resistance elements. The resistance elements are arranged in pairs in a unitized structure, and grouted in place in the underground volume. The electrical resistance of each element and the difference in electrical resistance of the paired elements are obtained, which difference values may be used in analytical methods involving resistance as a function of temperature. A scanner sequentially connects the resistance-measuring apparatus to each individual pair of elements. A source of heating current is also selectively connectable for heating the elements to an initial predetermined temperature prior to electrical resistance measurements when used as an anemometer.

Theoretical study of mixing in liquid clouds – Part 1: Classical concepts

DOE PAGES

Korolev, Alexei; Khain, Alex; Pinsky, Mark; ...

2016-07-28

The present study considers final stages of in-cloud mixing in the framework of classical concept of homogeneous and extreme inhomogeneous mixing. Simple analytical relationships between basic microphysical parameters were obtained for homogeneous and extreme inhomogeneous mixing based on the adiabatic consideration. It was demonstrated that during homogeneous mixing the functional relationships between the moments of the droplets size distribution hold only during the primary stage of mixing. Subsequent random mixing between already mixed parcels and undiluted cloud parcels breaks these relationships. However, during extreme inhomogeneous mixing the functional relationships between the microphysical parameters hold both for primary and subsequent mixing.more » The obtained relationships can be used to identify the type of mixing from in situ observations. The effectiveness of the developed method was demonstrated using in situ data collected in convective clouds. It was found that for the specific set of in situ measurements the interaction between cloudy and entrained environments was dominated by extreme inhomogeneous mixing.« less

Advanced Metal Foam Structures for Outer Space

NASA Technical Reports Server (NTRS)

Hanan, Jay; Johnson, William; Peker, Atakan

2005-01-01

A document discusses a proposal to use advanced materials especially bulk metallic glass (BMG) foams in structural components of spacecraft, lunar habitats, and the like. BMG foams, which are already used on Earth in some consumer products, are superior to conventional metal foams: BMG foams have exceptionally low mass densities and high strength-to-weight ratios and are more readily processable into strong, lightweight objects of various sizes and shapes. These and other attractive properties of BMG foams would be exploited, according to the proposal, to enable in situ processing of BMG foams for erecting and repairing panels, shells, containers, and other objects. The in situ processing could include (1) generation of BMG foams inside prefabricated deployable skins that would define the sizes and shapes of the objects thus formed and (2) thermoplastic deformation of BMG foams. Typically, the generation of BMG foams would involve mixtures of precursor chemicals that would be subjected to suitable pressure and temperature schedules. In addition to serving as structural components, objects containing or consisting of BMG foams could perform such functions as thermal management, shielding against radiation, and shielding against hypervelocity impacts of micrometeors and small debris particles.

From chloroplasts to photosystems: in situ scanning force microscopy on intact thylakoid membranes

PubMed Central

Kaftan, David; Brumfeld, Vlad; Nevo, Reinat; Scherz, Avigdor; Reich, Ziv

2002-01-01

Envelope-free chloroplasts were imaged in situ by contact and tapping mode scanning force microscopy at a lateral resolution of 3–5 nm and vertical resolution of ∼0.3 nm. The images of the intact thylakoids revealed detailed structural features of their surface, including individual protein complexes over stroma, grana margin and grana-end membrane domains. Structural and immunogold-assisted assignment of two of these complexes, photosystem I (PS I) and ATP synthase, allowed direct determination of their surface density, which, for both, was found to be highest in grana margins. Surface rearrangements and pigment– protein complex redistribution associated with salt-induced membrane unstacking were followed on native, hydrated specimens. Unstacking was accompanied by a substantial increase in grana diameter and, eventually, led to their merging with the stroma lamellae. Concomitantly, PS IIα effective antenna size decreased by 21% and the mean size of membrane particles increased substantially, consistent with attachment of mobile light-harvesting complex II to PS I. The ability to image intact photosynthetic membranes at molecular resolution, as demonstrated here, opens up new vistas to investigate thylakoid structure and function. PMID:12426386

Long-term carbon exclusion alters soil microbial function but not community structure across forests of contrasting productivity

NASA Astrophysics Data System (ADS)

Hart, S. C.; Dove, N. C.; Stark, J.

2017-12-01

While it is well-documented that distinct heterotrophic microbial communities emerge under different conditions of carbon (C) availability, the response of soil microbial communities and their function to long-term conditions of C exclusion in situ has yet to be investigated. We evaluated the role of C in controlling soil microbial communities and function by experimentally excluding plant C inputs for nine years at four forest sites along a productivity gradient in Oregon, USA. Carbon exclusion treatments were implemented by root trenching to a depth of 30 cm using 25-cm diameter steel pipe, and minimizing aboveground inputs as plant litter by covering the pipe with a 1-mm mesh screen. After nine years, we measured rates of gross and net nitrogen (N) transformations and microbial respiration in situ in the upper 15-cm of mineral soil in both C excluded plots and undisturbed control soils. We measured the soil total C and N concentration and potential extracellular enzyme activities. We used phospholipid fatty acid (PLFA) analysis to determine potential changes in the microbial community structure. Nine years of C exclusion reduced soil total C by about 20%, except at the highest productivity site where no statistically significant change was observed. Although PLFA community structure and microbial C were unchanged, microbial respiration was reduced by 15-45% at all sites. Similarly, specific extracellular enzyme activities for all enzymes increased at these sites with C exclusion, suggesting that the microbial communities were substrate-limited. Although gross N mineralization decreased under C exclusion, decreases in gross N immobilization were greater, resulting in increased net N mineralization rates in all but the lowest productivity site. Furthermore, C exclusion only increased net nitrification in the highest productivity site. Although these field-based results are largely consistent with previous laboratory studies indicating a strong coupling between C and N biogeochemical cycles, they build upon this earlier research by suggesting that the "C connection" to the N cycle depends on the rate of C cycling within the ecosystem.

Glucose- and Cellulose-Derived Ni/C-SO3H Catalysts for Liquid Phase Phenol Hydrodeoxygenation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kasakov, Stanislav; Zhao, Chen; Barath, Eszter

2015-01-19

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalyzed the reduction of phenol to cyclohexanolmore » in water. The state of 3 – 5 nm grafted Ni particles was analyzed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt.% C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.« less

Glucose- and cellulose-derived Ni/C-SO3H catalysts for liquid phase phenol hydrodeoxygenation.

PubMed

Kasakov, Stanislav; Zhao, Chen; Baráth, Eszter; Chase, Zizwe A; Fulton, John L; Camaioni, Donald M; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A

2015-01-19

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalysed the reduction of phenol to cyclohexanol in water. The state of 3-5 nm grafted Ni particles was analysed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in the presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt % C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural and molecular interrogation of intact biological systems

PubMed Central

Chung, Kwanghun; Wallace, Jenelle; Kim, Sung-Yon; Kalyanasundaram, Sandhiya; Andalman, Aaron S.; Davidson, Thomas J.; Mirzabekov, Julie J.; Zalocusky, Kelly A.; Mattis, Joanna; Denisin, Aleksandra K.; Pak, Sally; Bernstein, Hannah; Ramakrishnan, Charu; Grosenick, Logan; Gradinaru, Viviana; Deisseroth, Karl

2014-01-01

Obtaining high-resolution information from a complex system, while maintaining the global perspective needed to understand system function, represents a key challenge in biology. Here we address this challenge with a method (termed CLARITY) for the transformation of intact tissue into a nanoporous hydrogel-hybridized form (crosslinked to a three-dimensional network of hydrophilic polymers) that is fully assembled but optically transparent and macromolecule-permeable. Using mouse brains, we show intact-tissue imaging of long-range projections, local circuit wiring, cellular relationships, subcellular structures, protein complexes, nucleic acids and neurotransmitters. CLARITY also enables intact-tissue in situ hybridization, immunohistochemistry with multiple rounds of staining and de-staining in non-sectioned tissue, and antibody labelling throughout the intact adult mouse brain. Finally, we show that CLARITY enables fine structural analysis of clinical samples, including non-sectioned human tissue from a neuropsychiatric-disease setting, establishing a path for the transmutation of human tissue into a stable, intact and accessible form suitable for probing structural and molecular underpinnings of physiological function and disease. PMID:23575631

In Situ Industrial Bimetallic Catalyst Characterization using Scanning Transmission Electron Microscopy and X-ray Absorption Spectroscopy at One Atmosphere and Elevated Temperature.

PubMed

Prestat, Eric; Kulzick, Matthew A; Dietrich, Paul J; Smith, Mr Matthew; Tien, Mr Eu-Pin; Burke, M Grace; Haigh, Sarah J; Zaluzec, Nestor J

2017-08-18

We have developed a new experimental platform for in situ scanning transmission electron microscope (STEM) energy dispersive X-ray spectroscopy (EDS) which allows real time, nanoscale, elemental and structural changes to be studied at elevated temperature (up to 1000 °C) and pressure (up to 1 atm). Here we demonstrate the first application of this approach to understand complex structural changes occurring during reduction of a bimetallic catalyst, PdCu supported on TiO 2 , synthesized by wet impregnation. We reveal a heterogeneous evolution of nanoparticle size, distribution, and composition with large differences in reduction behavior for the two metals. We show that the data obtained is complementary to in situ STEM electron energy loss spectroscopy (EELS) and when combined with in situ X-ray absorption spectroscopy (XAS) allows correlation of bulk chemical state with nanoscale changes in elemental distribution during reduction, facilitating new understanding of the catalytic behavior for this important class of materials. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

In-situ spectro-microscopy on organic films: Mn-Phthalocyanine on Ag(100)

NASA Astrophysics Data System (ADS)

Al-Mahboob, Abdullah; Sadowski, Jerzy T.; Vescovo, Elio

2013-03-01

Metal phthalocyanines are attracting significant attention, owing to their potential for applications in chemical sensors, solar cells and organic magnets. As the electronic properties of molecular films are determined by their crystallinity and molecular packing, the optimization of film quality is important for improving the performance of organic devices. Here, we present the results of in situ low-energy electron microscopy / photoemission electron microscopy (LEEM/PEEM) studies of incorporation-limited growth of manganese-phthalocyanine (MnPc) on Ag(100) surfaces. MnPc thin films were grown on both, bulk Ag(100) surface and thin Ag(100)/Fe(100) films, where substrate spin-polarized electronic states can be modified through tuning the thickness of the Ag film. We also discuss the electronic structure and magnetic ordering in MnPc thin films, investigated by angle- and spin-resolved photoemission spectroscopy. Research carried out at the Center for Functional Nanomaterials and National Synchrotron Light Source, Brookhaven National Laboratory, which are supported by the U.S. Dept. of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

Time-Resolved Chemical Mapping in Light-Emitting Electrochemical Cells.

PubMed

Jafari, Mohammad Javad; Liu, Jiang; Engquist, Isak; Ederth, Thomas

2017-01-25

An understanding of the doping and ion distributions in light-emitting electrochemical cells (LECs) is required to approach a realistic conduction model which can precisely explain the electrochemical reactions, p-n junction formation, and ion dynamics in the active layer and to provide relevant information about LECs for systematic improvement of function and manufacture. Here, Fourier-transform infrared (FTIR) microscopy is used to monitor anion density profile and polymer structure in situ and for time-resolved mapping of electrochemical doping in an LEC under bias. The results are in very good agreement with the electrochemical doping model with respect to ion redistribution and formation of a dynamic p-n junction in the active layer. We also physically slow ions by decreasing the working temperature and study frozen-junction formation and immobilization of ions in a fixed-junction LEC device by FTIR imaging. The obtained results show irreversibility of the ion redistribution and polymer doping in a fixed-junction device. In addition, we demonstrate that infrared microscopy is a useful tool for in situ characterization of electroactive organic materials.

Concepts and Relations in Neurally Inspired In Situ Concept-Based Computing

PubMed Central

van der Velde, Frank

2016-01-01

In situ concept-based computing is based on the notion that conceptual representations in the human brain are “in situ.” In this way, they are grounded in perception and action. Examples are neuronal assemblies, whose connection structures develop over time and are distributed over different brain areas. In situ concepts representations cannot be copied or duplicated because that will disrupt their connection structure, and thus the meaning of these concepts. Higher-level cognitive processes, as found in language and reasoning, can be performed with in situ concepts by embedding them in specialized neurally inspired “blackboards.” The interactions between the in situ concepts and the blackboards form the basis for in situ concept computing architectures. In these architectures, memory (concepts) and processing are interwoven, in contrast with the separation between memory and processing found in Von Neumann architectures. Because the further development of Von Neumann computing (more, faster, yet power limited) is questionable, in situ concept computing might be an alternative for concept-based computing. In situ concept computing will be illustrated with a recently developed BABI reasoning task. Neurorobotics can play an important role in the development of in situ concept computing because of the development of in situ concept representations derived in scenarios as needed for reasoning tasks. Neurorobotics would also benefit from power limited and in situ concept computing. PMID:27242504

Concepts and Relations in Neurally Inspired In Situ Concept-Based Computing.

PubMed

van der Velde, Frank

2016-01-01

In situ concept-based computing is based on the notion that conceptual representations in the human brain are "in situ." In this way, they are grounded in perception and action. Examples are neuronal assemblies, whose connection structures develop over time and are distributed over different brain areas. In situ concepts representations cannot be copied or duplicated because that will disrupt their connection structure, and thus the meaning of these concepts. Higher-level cognitive processes, as found in language and reasoning, can be performed with in situ concepts by embedding them in specialized neurally inspired "blackboards." The interactions between the in situ concepts and the blackboards form the basis for in situ concept computing architectures. In these architectures, memory (concepts) and processing are interwoven, in contrast with the separation between memory and processing found in Von Neumann architectures. Because the further development of Von Neumann computing (more, faster, yet power limited) is questionable, in situ concept computing might be an alternative for concept-based computing. In situ concept computing will be illustrated with a recently developed BABI reasoning task. Neurorobotics can play an important role in the development of in situ concept computing because of the development of in situ concept representations derived in scenarios as needed for reasoning tasks. Neurorobotics would also benefit from power limited and in situ concept computing.

In situ studies of surface of NiFe 2O 4 catalyst during complete oxidation of methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Shiran; Shan, Junjun; Nie, Longhui

2015-12-21

Here, NiFe 2O 4 with an inverse spinel structure exhibits high activity for a complete oxidation of methane at 400 °C–425 °C and a higher temperature. The surface of the catalyst and its adsorbates were well characterized with ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ infrared spectroscopy (IR). In situ studies of the surface of NiFe 2O 4 using AP-XPS suggest the formation of methoxy-like and formate-like intermediates at a temperature lower than 200 °C, supported by the observed vibrational signatures in in situ IR studies. Evolutions of C1s photoemission features and the nominal atomic ratios of C/(Nimore » + Fe) of the catalyst surface suggest that the formate-like intermediate is transformed to product molecules CO 2 and H 2O in the temperature range of 250–300 °C. In situ studies suggest the formation of a spectator, – O lattice – CH 2 – O lattice –. It strongly bonds to surface through C–O bonds and cannot be activated even at 400 °C.« less

Analysis of leaf surfaces using scanning ion conductance microscopy.

PubMed

Walker, Shaun C; Allen, Stephanie; Bell, Gordon; Roberts, Clive J

2015-05-01

Leaf surfaces are highly complex functional systems with well defined chemistry and structure dictating the barrier and transport properties of the leaf cuticle. It is a significant imaging challenge to analyse the very thin and often complex wax-like leaf cuticle morphology in their natural state. Scanning electron microscopy (SEM) and to a lesser extent Atomic force microscopy are techniques that have been used to study the leaf surface but their remains information that is difficult to obtain via these approaches. SEM is able to produce highly detailed and high-resolution images needed to study leaf structures at the submicron level. It typically operates in a vacuum or low pressure environment and as a consequence is generally unable to deal with the in situ analysis of dynamic surface events at submicron scales. Atomic force microscopy also possess the high-resolution imaging required and can follow dynamic events in ambient and liquid environments, but can over exaggerate small features and cannot image most leaf surfaces due to their inherent roughness at the micron scale. Scanning ion conductance microscopy (SICM), which operates in a liquid environment, provides a potential complementary analytical approach able to address these issues and which is yet to be explored for studying leaf surfaces. Here we illustrate the potential of SICM on various leaf surfaces and compare the data to SEM and atomic force microscopy images on the same samples. In achieving successful imaging we also show that SICM can be used to study the wetting of hydrophobic surfaces in situ. This has potentially wider implications than the study of leaves alone as surface wetting phenomena are important in a range of fundamental and applied studies. © 2015 The Authors Journal of Microscopy © 2015 Royal Microscopical Society.

Identification of a preferred substrate peptide for transglutaminase 3 and detection of in situ activity in skin and hair follicles.

PubMed

Yamane, Asaka; Fukui, Mina; Sugimura, Yoshiaki; Itoh, Miho; Alea, Mileidys Perez; Thomas, Vincent; El Alaoui, Said; Akiyama, Masashi; Hitomi, Kiyotaka

2010-09-01

Transglutaminases (TGases) are a family of enzymes that catalyze cross-linking reactions between proteins. During epidermal differentiation, these enzymatic reactions are essential for formation of the cornified envelope, which consists of cross-linked structural proteins. Two main transglutaminases isoforms, epidermal-type (TGase 3) and keratinocyte-type (TGase 1), are cooperatively involved in this process of differentiating keratinocytes. Information regarding their substrate preference is of great importance to determine the functional role of these isozymes and clarify their possible co-operative action. Thus far, we have identified highly reactive peptide sequences specifically recognized by TGases isozymes such as TGase 1, TGase 2 (tissue-type isozyme) and the blood coagulation isozyme, Factor XIII. In this study, several substrate peptide sequences for human TGase 3 were screened from a phage-displayed peptide library. The preferred substrate sequences for TGase 3 were selected and evaluated as fusion proteins with mutated glutathione S-transferase. From these studies, a highly reactive and isozyme-specific sequence (E51) was identified. Furthermore, this sequence was found to be a prominent substrate in the peptide form and was suitable for detection of in situ TGase 3 activity in the mouse epidermis. TGase 3 enzymatic activity was detected in the layers of differentiating keratinocytes and hair follicles with patterns distinct from those of TGase 1. Our findings provide new information on the specific distribution of TGase 3 and constitute a useful tool to clarify its functional role in the epidermis.

In situ and ex situ modifications of bacterial cellulose for applications in tissue engineering.

PubMed

Stumpf, Taisa Regina; Yang, Xiuying; Zhang, Jingchang; Cao, Xudong

2018-01-01

Bacterial cellulose (BC) is secreted by a few strains of bacteria and consists of a cellulose nanofiber network with unique characteristics. Because of its excellent mechanical properties, outstanding biocompatibilities, and abilities to form porous structures, BC has been studied for a variety of applications in different fields, including the use as a biomaterial for scaffolds in tissue engineering. To extend its applications in tissue engineering, native BC is normally modified to enhance its properties. Generally, BC modifications can be made by either in situ modification during cell culture or ex situ modification of existing BC microfibers. In this review we will first provide a brief introduction of BC and its attributes; this will set the stage for in-depth and up-to-date discussions on modified BC. Finally, the review will focus on in situ and ex situ modifications of BC and its applications in tissue engineering, particularly in bone regeneration and wound dressing. Copyright © 2016. Published by Elsevier B.V.

An In-Situ XAS Study of the Structural Changes in a CuO-CeO2/Al2O3 Catalyst during Total Oxidation of Propane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silversmith, Geert; Poelman, Hilde; Poelman, Dirk

2007-02-02

A CuOx-CeOx/Al2O3 catalyst was studied with in-situ transmission Cu K XAS for the total oxidation of propane as model reaction for the catalytic elimination of volatile organic compounds. The local Cu structure was determined for the catalyst as such, after pre-oxidation and after reduction with propane. The catalyst as such has a local CuO structure. No structural effect was observed upon heating in He up to 600 deg. C or after pre-oxidation at 150 deg. C. A full reduction of the Cu2+ towards metallic Cu0 occurred, when propane was fed to the catalyst. The change in local Cu structure duringmore » propane reduction was followed with a time resolution of 1 min. The {chi}(k) scans appeared as linear combinations of start and end spectra, CuO and Cu structure, respectively. However, careful examination of the XANES edge spectra indicates the presence of a small amount of additional Cu1+ species.« less

In situ electron microscope study of the phase transformation, structure and growth of thin Te1-xSex films

NASA Astrophysics Data System (ADS)

Vermaak, J. S.; Raubenheimer, D.

1988-01-01

An in-situ electron microscope technique was utilized to observe directly the amorphous-to-crystalline phase transformation, the isothermal growth rates, as well as the orientation and structure of the recrystallized films for the Te1-xSex alloy system for x=0.2, 0.3 and 0.4. Activation energies of E=0.91, 0.93 and 0.96 eV and crystallization temperatures of Tc=-14, 81.5 and 85°C for the three alloys, respectively, were found. In all three cases the crystallization process originated from single crystalline nuclei with a hexagonal structure and with the c-axis in general parallel to the substrate surface.

Common Prairie feeds with different soluble and insoluble fractions used for CPM diet formulation in dairy cattle: impact of carbohydrate-protein matrix structure on protein and other primary nutrient digestion.

PubMed

Peng, Quanhui; Wang, Zhisheng; Zhang, Xuewei; Yu, Peiqiang

2014-01-01

An experiment was conducted to investigate the relationship of carbohydrates molecular spectral characteristics to rumen degradability of primary nutrients in Prairie feeds in dairy cattle. In total, 12 different types of feeds were selected, each type of feed was from three different source with total 37 samples. Six types of them were energy-sourced feeds and the others were protein-sourced feeds. The carbohydrates molecular spectral intensity of various functional groups were collected using Fourier transform infrared attenuated total reflectance (ATR-FT/IR) spectroscopy. In the in situ study, the results showed that the rumen digestibility and digestible fractions of primary nutrients (DM, OM, NCP, and CP) were significantly different (P<0.05) among the feeds. The spectral bands features were significantly different (P<0.05) among the feeds. Spectral intensities of A_Cell, H_1415 and H_1370 were weakly positively correlated with in situ rumen digestibility and digestible fractions of DM, OM and NCP. Spectral intensities of H_1150, H_1015, A_1, and A_3 were weakly negatively associated with in situ rumen degradation of CP. Spectral intensities of A_1240 and H_1240, mainly associated with cellulosic compounds, were correlated with rumen CP degradation. The multiple regression analysis demonstrated that the spectral intensities of A_3 and H_1415 played the most important role and could be used as a potential tool to predict rumen protein degradation of feeds in dairy cattle. In conclusion, this study showed that the carbohydrates as a whole have an effect on protein rumen degradation, rather than cellulose alone, indicating carbohydrate-protein matrix structure impact protein utilization in dairy cattle. The non-invasive molecular spectral technique (ATR-FT/IR) could be used as a rapid potential tool to predict rumen protein degradation of feedstuffs by using molecular spectral bands intensities in carbohydrate fingerprint region. Copyright © 2013 Elsevier B.V. All rights reserved.

Common Prairie feeds with different soluble and insoluble fractions used for CPM diet formulation in dairy cattle: Impact of carbohydrate-protein matrix structure on protein and other primary nutrient digestion

NASA Astrophysics Data System (ADS)

Peng, Quanhui; Wang, Zhisheng; Zhang, Xuewei; Yu, Peiqiang

2014-03-01

An experiment was conducted to investigate the relationship of carbohydrates molecular spectral characteristics to rumen degradability of primary nutrients in Prairie feeds in dairy cattle. In total, 12 different types of feeds were selected, each type of feed was from three different source with total 37 samples. Six types of them were energy-sourced feeds and the others were protein-sourced feeds. The carbohydrates molecular spectral intensity of various functional groups were collected using Fourier transform infrared attenuated total reflectance (ATR-FT/IR) spectroscopy. In the in situ study, the results showed that the rumen digestibility and digestible fractions of primary nutrients (DM, OM, NCP, and CP) were significantly different (P < 0.05) among the feeds. The spectral bands features were significantly different (P < 0.05) among the feeds. Spectral intensities of A_Cell, H_1415 and H_1370 were weakly positively correlated with in situ rumen digestibility and digestible fractions of DM, OM and NCP. Spectral intensities of H_1150, H_1015, A_1, and A_3 were weakly negatively associated with in situ rumen degradation of CP. Spectral intensities of A_1240 and H_1240, mainly associated with cellulosic compounds, were correlated with rumen CP degradation. The multiple regression analysis demonstrated that the spectral intensities of A_3 and H_1415 played the most important role and could be used as a potential tool to predict rumen protein degradation of feeds in dairy cattle. In conclusion, this study showed that the carbohydrates as a whole have an effect on protein rumen degradation, rather than cellulose alone, indicating carbohydrate-protein matrix structure impact protein utilization in dairy cattle. The non-invasive molecular spectral technique (ATR-FT/IR) could be used as a rapid potential tool to predict rumen protein degradation of feedstuffs by using molecular spectral bands intensities in carbohydrate fingerprint region.

Formation of atomically ordered and chemically selective Si-O-Ti monolayer on Si0.5Ge0.5(110) for a MIS structure via H2O2(g) functionalization.

PubMed

Park, Sang Wook; Choi, Jong Youn; Siddiqui, Shariq; Sahu, Bhagawan; Galatage, Rohit; Yoshida, Naomi; Kachian, Jessica; Kummel, Andrew C

2017-02-07

Si 0.5 Ge 0.5 (110) surfaces were passivated and functionalized using atomic H, hydrogen peroxide (H 2 O 2 ), and either tetrakis(dimethylamino)titanium (TDMAT) or titanium tetrachloride (TiCl 4 ) and studied in situ with multiple spectroscopic techniques. To passivate the dangling bonds, atomic H and H 2 O 2 (g) were utilized and scanning tunneling spectroscopy (STS) demonstrated unpinning of the surface Fermi level. The H 2 O 2 (g) could also be used to functionalize the surface for metal atomic layer deposition. After subsequent TDMAT or TiCl 4 dosing followed by a post-deposition annealing, scanning tunneling microscopy demonstrated that a thermally stable and well-ordered monolayer of TiO x was deposited on Si 0.5 Ge 0.5 (110), and X-ray photoelectron spectroscopy verified that the interfaces only contained Si-O-Ti bonds and a complete absence of GeO x . STS measurements confirmed a TiO x monolayer without mid-gap and conduction band edge states, which should be an ideal ultrathin insulating layer in a metal-insulator-semiconductor structure. Regardless of the Ti precursors, the final Ti density and electronic structure were identical since the Ti bonding is limited by the high coordination of Ti to O.

UV-induced reaction kinetics of dilinoleoylphosphatidylethanolamine monolayers.

PubMed Central

Viitala, T; Peltonen, J

1999-01-01

The UV-induced reactivity of dilinoleoylphosphatidylethanolamine (DLiPE) Langmuir and Langmuir-Blodgett films has been studied by in situ measurements of the changes in the mean molecular area, UV-vis and Fourier transform infrared spectroscopy, and atomic force microscopy (AFM). Optimum orientation and packing density of the DLiPE molecules in the monolayer were achieved by adding uranyl acetate to the subphase. A first-order reaction kinetic model was successfully fitted to the experimental reaction kinetics data obtained at a surface pressure of 30 mN/m. Topographical studies of LB films by AFM were performed on bilayer structures as a function of subphase composition and UV irradiation time. The orientational effect of the uranyl ions on the monolayer molecules was observed as an enhanced homogeneity of the freshly prepared monomeric LB films. However, the long-term stability of these films proved to be bad; clear reorganization and loss of a true monolayer structure were evidenced by the AFM images. This instability was inhibited for the UV-irradiated films, indicating that the UV irradiation gave rise to a cross-linked structure. PMID:10233096

Kinetically-Driven Phase Transformation during Lithiation in Copper Sulfide Nanoflakes

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Kai; Yao, Zhenpeng; Hwang, Sooyeon

Two-dimensional (2D) transition metal chalcogenides have been widely studied and utilized as electrode materials for lithium ion batteries due to their unique layered structures to accommodate reversible lithium insertion. Real-time observation and mechanistic understanding of the phase transformations during lithiation of these materials are critically important for improving battery performance by controlling structures and reaction pathways. Here, we use in situ transmission electron microscopy methods to study the structural, morphological, and chemical evolutions in individual copper sulfide (CuS) nanoflakes during lithiation. We report a highly kinetically driven phase transformation in which lithium ions rapidly intercalate into the 2D van dermore » Waals-stacked interlayers in the initial stage, and further lithiation induces the Cu extrusion via a displacement reaction mechanism that is different from the typical conversion reactions. Density functional theory calculations have confirmed both the thermodynamically favored and the kinetically driven reaction pathways. Lastly, our findings elucidate the reaction pathways of the Li/CuS system under nonequilibrium conditions and provide valuable insight into the atomistic lithiation mechanisms of transition metal sulfides in general.« less

Kinetically-Driven Phase Transformation during Lithiation in Copper Sulfide Nanoflakes

DOE PAGES

He, Kai; Yao, Zhenpeng; Hwang, Sooyeon; ...

2017-08-11

Two-dimensional (2D) transition metal chalcogenides have been widely studied and utilized as electrode materials for lithium ion batteries due to their unique layered structures to accommodate reversible lithium insertion. Real-time observation and mechanistic understanding of the phase transformations during lithiation of these materials are critically important for improving battery performance by controlling structures and reaction pathways. Here, we use in situ transmission electron microscopy methods to study the structural, morphological, and chemical evolutions in individual copper sulfide (CuS) nanoflakes during lithiation. We report a highly kinetically driven phase transformation in which lithium ions rapidly intercalate into the 2D van dermore » Waals-stacked interlayers in the initial stage, and further lithiation induces the Cu extrusion via a displacement reaction mechanism that is different from the typical conversion reactions. Density functional theory calculations have confirmed both the thermodynamically favored and the kinetically driven reaction pathways. Lastly, our findings elucidate the reaction pathways of the Li/CuS system under nonequilibrium conditions and provide valuable insight into the atomistic lithiation mechanisms of transition metal sulfides in general.« less

Functional copolymer/organo-MMT nanoarchitectures. VI. Synthesis and characterization of novel nanocomposites by interlamellar controlled/living radical copolymerization via preintercalated RAFT-agent/organoclay complexes.

PubMed

Rzayev, Zakir M O; Söylemez, A Ernur

2011-04-01

We have developed a new approach for the synthesis of polymer nanocomposites using a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent, two types of organo-montmorillonites, such as a non-reactive dimethyldodecyl ammonium (DMDA)-MMT and a reactive octadecylamine (ODA)-MMT organoclays, and a radical initiator. The method includes the following stages: (1) synthesis of RAFT intercalated O-MMTs by a physical or chemical interaction of the RAFT agent having two pendant carboxylic groups [S,S-bis(alpha,alpha'-dimethyl-alpha"-acetic acid)trithiocarbonate] with surface alkyl amines of O-MMT containing tertiary ammonium cation or primary amine groups through strong H-bonding and complexing/amidization reactions, respectively, and (2) utilization of these well-dispersed and intercalated RAFT ... O-MMT complexes and their amide derivatives as new modified RAFT agents in radical-initiated interlamellar controlled/living copolymerization of itaconic acid (IA)-n-butylmethacrylate (BMA) monomer pair. The structure and compositions of the synthesized RAFT ... O-MMT complexes and functional copolymer/O-MMT hybrids were confirmed by FTIR, XRD, thermal (DSC-TGA), SEM and TEM morphology analyses. It was demonstrated that the degree of interaction/exfoliation, morphology and thermal behavior of nanocomposites significantly depended on the type of organoclay and in situ interaction, as well as on the content of flexible butyl-ester linkages as a internal plasticizer. The results of the comparative analysis of the nanocomposites structure-composition-property relations show that the functional copolymer-organoclay hybrids prepared with reactive RAFT ... ODA-MMT complex and containing a combination of partially intercalated and predominantly exfoliated nano-structures exhibit relatively higher thermal stability and fine dispersed morphology. These effects were explained by in situ interfacial chemical reactions through amidization of RAFT with surface alkyl amine of MMT clay in interlamellar copolymerization. This simple and versatile method can be applied to a wide range of functional monomer/comonomer systems and mono- and bifunctional RAFT compounds for preparation new generation of nanomaterials.

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

PubMed Central

Johnson, Grant E.; Gunaratne, K. Don Dasitha; Laskin, Julia

2014-01-01

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3]2+ (bpy = bipyridine), onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivity of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces. PMID:24961913

In Situ SIMS and IR Spectroscopy of Well-Defined Surfaces Prepared by Soft Landing of Mass-Selected Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Grant E.; Gunaratne, Kalupathirannehelage Don D.; Laskin, Julia

2014-06-16

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3]2+, onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivitymore » of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces.« less

In Situ Thermal Generation of Silver Nanoparticles in 3D Printed Polymeric Structures.

PubMed

Fantino, Erika; Chiappone, Annalisa; Calignano, Flaviana; Fontana, Marco; Pirri, Fabrizio; Roppolo, Ignazio

2016-07-19

Polymer nanocomposites have always attracted the interest of researchers and industry because of their potential combination of properties from both the nanofillers and the hosting matrix. Gathering nanomaterials and 3D printing could offer clear advantages and numerous new opportunities in several application fields. Embedding nanofillers in a polymeric matrix could improve the final material properties but usually the printing process gets more difficult. Considering this drawback, in this paper we propose a method to obtain polymer nanocomposites by in situ generation of nanoparticles after the printing process. 3D structures were fabricated through a Digital Light Processing (DLP) system by disolving metal salts in the starting liquid formulation. The 3D fabrication is followed by a thermal treatment in order to induce in situ generation of metal nanoparticles (NPs) in the polymer matrix. Comprehensive studies were systematically performed on the thermo-mechanical characteristics, morphology and electrical properties of the 3D printed nanocomposites.

In Situ X-ray Absorption Near-Edge Structure Spectroscopy of ZnO Nanowire Growth During Chemical Bath Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.

2010-12-03

Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. Here we report the first use of in situ X-ray absorption spectroscopy during CBD, enabling detailed investigation of both reaction mechanisms and kinetics of ZnO nanowire growth from zinc nitrate and hexamethylenetetramine (HMTA) precursors. Time-resolved X-ray absorption near-edge structure (XANES) spectra were used to quantify Zn(II) speciation in both solution and solid phases. ZnO crystallizes directly from [Zn(H{sub 2}O){sub 6}]{sup 2+} without long-lived intermediates. Using ZnO nanowire deposition as an example,more » this study establishes in situ XANES spectroscopy as an excellent quantitative tool to understand CBD of nanomaterials.« less

Ultraviolet GaN photodetectors on Si via oxide buffer heterostructures with integrated short period oxide-based distributed Bragg reflectors and leakage suppressing metal-oxide-semiconductor contacts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szyszka, A., E-mail: szyszka@ihp-microelectronics.com, E-mail: adam.szyszka@pwr.wroc.pl; Faculty of Microsystem Electronics and Photonics, Wroclaw University of Technology, Janiszewskiego 11/17, 50-372 Wroclaw; Lupina, L.

2014-08-28

Based on a novel double step oxide buffer heterostructure approach for GaN integration on Si, we present an optimized Metal-Semiconductor-Metal (MSM)-based Ultraviolet (UV) GaN photodetector system with integrated short-period (oxide/Si) Distributed Bragg Reflector (DBR) and leakage suppressing Metal-Oxide-Semiconductor (MOS) electrode contacts. In terms of structural properties, it is demonstrated by in-situ reflection high energy electron diffraction and transmission electron microscopy-energy dispersive x-ray studies that the DBR heterostructure layers grow with high thickness homogeneity and sharp interface structures sufficient for UV applications; only minor Si diffusion into the Y{sub 2}O{sub 3} films is detected under the applied thermal growth budget. Asmore » revealed by comparative high resolution x-ray diffraction studies on GaN/oxide buffer/Si systems with and without DBR systems, the final GaN layer structure quality is not significantly influenced by the growth of the integrated DBR heterostructure. In terms of optoelectronic properties, it is demonstrated that—with respect to the basic GaN/oxide/Si system without DBR—the insertion of (a) the DBR heterostructures and (b) dark current suppressing MOS contacts enhances the photoresponsivity below the GaN band-gap related UV cut-off energy by almost up to two orders of magnitude. Given the in-situ oxide passivation capability of grown GaN surfaces and the one order of magnitude lower number of superlattice layers in case of higher refractive index contrast (oxide/Si) systems with respect to classical III-N DBR superlattices, virtual GaN substrates on Si via functional oxide buffer systems are thus a promising robust approach for future GaN-based UV detector technologies.« less

Influence of human fibroblasts on development and quality of multilayered composite grafts in athymic nude mice.

PubMed

Cedidi, C Can; Wilkens, L; Berger, A; Ingianni, G

2007-11-05

In patients after extensive burn injury the lack of split thickness skin graft donor sites, and consecutive delay in wound closure are critical factors of morbidity and mortality. In addition limited functional and aesthetic results after transplantation of split thickness skin grafts present a socioeconomic problem. For improved wound closure the aim of this study was the development of a one stage technique for the establishment of a multi layer composite graft, existing of a collagen-GAG-matrix with silicon layer of a two layer synthetic dermal equivalent (DE) with integrated fibroblasts, and ceratinocytes. - In 64 athymic nude mice the evaluation of the multi layer skin grafts potential to re-establish a human epidermis, and high quality dermal structure was performed. In addition to clinical investigations we measured wound contraction, and analyzed histomorphologic, immunohistologic, "in situ hybridisation", and electro microscopic data. - Our results show, that the seeding of DE with human fibroblasts and ceratinocytes as a composite skin graft reproducible enabled a wound healing with an organised human dermis and epidermis within 10 - 15 days. The histological studies of the grafted composite skin grafts in this model showed morphologically a characteristic dermal-epidermal skin structure with a cornifying epithelium, being of human origin ("in situ hybridisation"). Through the co-cultivation of fibroblasts and ceratinocytes in the DE the generation and structural morphology of collagen fibres, and inflammatory reaction in the neodermis is positively influenced, and as a consequence wound contraction significantly reduced. In regard to the early preparation of composite grafts, and the minimal requirements for donor sites - with dependable stable reconstruction of the integument - this technique may present a step forward in the treatment of patients with extensive burns.

Three-dimensional culture of sebaceous gland cells revealing the role of prostaglandin E{sub 2}-induced activation of canonical Wnt signaling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoshida, Go J., E-mail: medical21go@yahoo.co.jp; Saya, Hideyuki

Highlights: •Three-dimensional culture generates “semi-vivo” sebaceous glands. •Xenograft model failed to mimic the biology of sebaceous glands in vivo. •Proinflammatory cytokine PGE{sub 2} enhances Wnt signal activity in the organoids. •PGE{sub 2} influences on the mitochondrial and lipid metabolism in the organoids. •Considering 3R agenda, “semi-vivo” sebaceous glands are useful for research. -- Abstract: Background: Prostaglandin E{sub 2} (PGE{sub 2}) is a proinflammatory mediator and activates the canonical Wnt–β-catenin signaling pathway in hematopoietic stem cells. The SZ95 cell line was established from human sebaceous gland cells and is studied as a model system for these cells. Given that 2D culturemore » of SZ95 cells does not recapitulate the organization of sebaceous glands in situ, we developed a 3D culture system for these cells and examined the effects of PGE{sub 2} on cell morphology and function. Results: SZ95 cells maintained in 3D culture formed organoids that mimicked the organization of sebaceous glands in situ, including the establishment of a basement membrane. Organoids exposed to PGE{sub 2} were larger and adopted a more complex organization compared with control organoids. PGE{sub 2} activated the canonical Wnt signaling pathway as well as increased cell viability and proliferation, mitochondrial metabolism, and lipid synthesis in the organoids. Conclusions: Culture of SZ95 cells in 3D culture system recapitulates the structure and susceptibility to PGE{sub 2} of sebaceous glands in situ and should prove useful for studies of the response of these glands to inflammation and other environmental stressors. Our results also implicate PGE{sub 2}-induced activation of canonical Wnt signaling pathway in regulation of the morphology,proliferation, and function of “semi-vivo” sebaceous glands.« less

Insights into the Effects of Zinc Doping on Structural Phase Transition of P2-Type Sodium Nickel Manganese Oxide Cathodes for High-Energy Sodium Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Xuehang; Xu, Gui-Liang; Zhong, Guiming

P2-type sodium nickel manganese oxide-based cathode materials with higher energy densities are prime candidates for applications in rechargeable sodium ion batteries. A systematic study combining in situ high energy X-ray diffraction (HEXRD), ex situ Xray absorption fine spectroscopy (XAFS), transmission electron microscopy (TEM), and solid-state nuclear magnetic resonance (SSNMR) techniques was carried out to gain a deep insight into the structural evolution of P2-Na 0.66Ni 0.33-xZn xMn 0.67O 2 (x = 0, 0.07) during cycling. In situ HEXRD and ex situ TEM measurements indicate that an irreversible phase transition occurs upon sodium insertion-extraction of Na 0.66Ni 0.33Mn 0.67O 2. Zincmore » doping of this system results in a high structural reversibility. XAFS measurements indicate that both materials are almost completely dependent on the Ni 4+/Ni 3+/ Ni 2+ redox couple to provide charge/discharge capacity. SS-NMR measurements indicate that both reversible and irreversible migration of transition metal ions into the sodium layer occurs in the material at the fully charged state. The irreversible migration of transition metal ions triggers a structural distortion, leading to the observed capacity and voltage fading. Our results allow a new understanding of the importance of improving the stability of transition metal layers.« less

Irradiation effects in UO2 and CeO2

NASA Astrophysics Data System (ADS)

Ye, Bei; Oaks, Aaron; Kirk, Mark; Yun, Di; Chen, Wei-Ying; Holtzman, Benjamin; Stubbins, James F.

2013-10-01

Single crystal CeO2, as a surrogate material to UO2, was irradiated with 500 keV xenon ions at 800 °C while being observed using in situ transmission electron microscopy (TEM). Experimental results show the formation and growth of defect clusters including dislocation loops and cavities as a function of increasing atomic displacement dose. At high dose, the dislocation loop structure evolves into an extended dislocation line structure, which appears to remain stable to the high dose levels examined in this study. A high concentration of cavities was also present in the microstructure. Despite high atomic displacement doses, the specimen remained crystalline to a cumulated dose of 5 × 1015 ions/cm2, which is consistent with the known stability of the fluorite structure under high dose irradiation. Kinetic Monte Carlo calculations show that oxygen mobility is substantially higher in hypo-stoichiometric UO2/CeO2 than hyper-stoichiometric systems. This result is consistent with the ability of irradiation damage to recover even at intermediate irradiation temperatures.

Pressure/temperature fluid cell apparatus for the neutron powder diffractometer instrument: probing atomic structure in situ.

PubMed

Wang, Hsiu-Wen; Fanelli, Victor R; Reiche, Helmut M; Larson, Eric; Taylor, Mark A; Xu, Hongwu; Zhu, Jinlong; Siewenie, Joan; Page, Katharine

2014-12-01

This contribution describes a new local structure compatible gas/liquid cell apparatus for probing disordered materials at high pressures and variable temperatures in the Neutron Powder Diffraction instrument at the Lujan Neutron Scattering Center, Los Alamos National Laboratory. The new sample environment offers choices for sample canister thickness and canister material type. Finite element modeling is utilized to establish maximum allowable working pressures of 414 MPa at 15 K and 121 MPa at 600 K. High quality atomic pair distribution function data extraction and modeling have been demonstrated for a calibration standard (Si powder) and for supercritical and subcritical CO2 measurements. The new sample environment was designed to specifically target experimental studies of the local atomic structures involved in geologic CO2 sequestration, but will be equally applicable to a wide variety of energy applications, including sorption of fluids on nano/meso-porous solids, clathrate hydrate formation, catalysis, carbon capture, and H2 and natural gas uptake/storage.

Gene encoding the collagen type I and thrombospondin receptor CD36 is located on chromosome 7q11. 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fernandez-Ruiz, E.; Armesilla, A.L.; Sanchez-Madrid, F.

The human CD36 is a member of a gene family of structurally related glycoproteins and functions as a receptor for collagen type I and thrombospondin. CD36 also binds to red blood cells infected with the human malaria parasite Plasmodium falciparum. In the present study, the CD36 gene was assigned to chromosome 7 by using the polymerase chain reaction with DNA from human-hamster somatic cell hybrids. Furthermore, the use of a CD36 genomic probe has allowed the localization of the CD36 locus to the 7q11.2 band by fluorescence in situ hybridization coupled with GTG-banding. 14 refs., 2 figs.

Investigation of the Spectroscopic Information on Functional Groups Related to Carbohydrates in Different Morphological Fractions of Corn Stover and Their Relationship to Nutrient Supply and Biodegradation Characteristics.

PubMed

Xin, Hangshu; Ding, Xue; Zhang, Liyang; Sun, Fang; Wang, Xiaofan; Zhang, Yonggen

2017-05-24

The objectives of this study were to investigate (1) nutritive values and biodegradation characteristics and (2) mid-IR spectroscopic features within the regions associated with carbohydrate functional groups (including cellulosic component (CELC), structural carbohydrate (STCHO), and total carbohydrate (CHO)) in different morphological fractions of corn stover. Furthermore, correlation and regression analyses were also applied to determine the relationship between nutritional values and spectroscopic parameters. The results showed that different morphological sections of corn stover had different nutrient supplies, in situ biodegradation characteristics, and spectral structural features within carbohydrate regions. The stem rind and ear husk were both high in fibrous content, which led to the lowest effective degradabilities (ED) among these stalk fractions. The ED values of NDF were ranked ear husk > stem pith > leaf blade > leaf sheath > whole plant > stem rind. Intensities of peak height and area within carbohydrate regions were relatively more stable compared with spectral ratio profiles. Significant difference was found only in peak area intensity of CELC, which was at the highest level for stem rind, followed by stem pith, leaf sheath, whole plant, leaf blade, and ear husk. Correlation results showed that changes in some carbohydrate spectral ratios were highly associated with carbohydrate chemical profiles and in situ rumen degradation kinetics. Among the various carbohydrate molecular spectral parameters that were tested in multiple regression analysis, CHO height ratios, and area ratios of CELC:CHO and CELC:STCHO as well as CELC area were mostly sensitive to nutrient supply and biodegradation characteristics in different morphological fractions of corn stover.

Spatial and Temporal Variability of Carbon Dioxide Using Structure Functions in Urban Areas: Insights for Future Active Remote CO2 Sensors

NASA Technical Reports Server (NTRS)

Choi, Yonghoon; Yang, Melissa; Kooi, Susan A.; Browell, Edward V.; DiGangi, Joshua P.

2015-01-01

High resolution in-situ CO2 measurements were recorded onboard the NASA P-3B during the DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) Field Campaigns during July 2011 over Washington DC/Baltimore, MD; January-February 2013 over the San Joaquin Valley, CA; September 2013 over Houston, TX; and July-August 2014 over Denver, CO. Each of these campaigns have approximately two hundred vertical soundings of CO2 within the lower troposphere (surface to about 5 kilometers) at 6-8 different sites in each of the urban areas. In this study, we used structure function analysis, which is a useful way to quantify spatial and temporal variability, by displaying differences with average observations, to evaluate the variability of CO2 in the 0-2 kilometers range (representative of the planetary boundary layer). These results can then be used to provide guidance in the development of science requirements for the future ASCENDS (Active Sensing of CO2 Emissions over Nights, Days, and Seasons) mission to measure near-surface CO2 variability in different urban areas. We also compare the observed in-situ CO2 variability with the variability of the CO2 column-averaged optical depths in the 0-1 kilometer and 0-3.5 kilometers altitude ranges in the four geographically different urban areas, using vertical weighting functions for potential future ASCENDS lidar CO2 sensors operating in the 1.57 and 2.05 millimeter measurement regions. In addition to determining the natural variability of CO2 near the surface and in the column, radiocarbon method using continuous CO2 and CO measurements are used to examine the variation of emission quantification between anthropogenic and biogenic sources in the DC/Maryland urban site.

A propagation tool to connect remote-sensing observations with in-situ measurements of heliospheric structures

NASA Astrophysics Data System (ADS)

Rouillard, A. P.; Lavraud, B.; Génot, V.; Bouchemit, M.; Dufourg, N.; Plotnikov, I.; Pinto, R. F.; Sanchez-Diaz, E.; Lavarra, M.; Penou, M.; Jacquey, C.; André, N.; Caussarieu, S.; Toniutti, J.-P.; Popescu, D.; Buchlin, E.; Caminade, S.; Alingery, P.; Davies, J. A.; Odstrcil, D.; Mays, L.

2017-11-01

The remoteness of the Sun and the harsh conditions prevailing in the solar corona have so far limited the observational data used in the study of solar physics to remote-sensing observations taken either from the ground or from space. In contrast, the 'solar wind laboratory' is directly measured in situ by a fleet of spacecraft measuring the properties of the plasma and magnetic fields at specific points in space. Since 2007, the solar-terrestrial relations observatory (STEREO) has been providing images of the solar wind that flows between the solar corona and spacecraft making in-situ measurements. This has allowed scientists to directly connect processes imaged near the Sun with the subsequent effects measured in the solar wind. This new capability prompted the development of a series of tools and techniques to track heliospheric structures through space. This article presents one of these tools, a web-based interface called the 'Propagation Tool' that offers an integrated research environment to study the evolution of coronal and solar wind structures, such as Coronal Mass Ejections (CMEs), Corotating Interaction Regions (CIRs) and Solar Energetic Particles (SEPs). These structures can be propagated from the Sun outwards to or alternatively inwards from planets and spacecraft situated in the inner and outer heliosphere. In this paper, we present the global architecture of the tool, discuss some of the assumptions made to simulate the evolution of the structures and show how the tool connects to different databases.

Controlling effects of mesoscale eddies on thermohaline structure and in situ chlorophyll distribution in the western North Pacific

NASA Astrophysics Data System (ADS)

Gao, Wei; Wang, Zhenyan; Zhang, Kainan

2017-11-01

Based on the conductivity, temperature and depth (CTD) data collected at 93 hydrographic stations during a marine cruise and on contemporary satellite altimeter observations, a series of eddies have been observed passing over the stratified upper water of the Parece Vela Basin. The results from hydrographic measurements and in situ chlorophyll fluorescence measurements have revealed that these eddies exerted significant controlling effects on the thermohaline structure and chlorophyll distribution, especially on the prevalent subsurface chlorophyll maximum layer (SCML). Based on these observations and particulate beam attenuation coefficient (cp) data, the in situ phytoplankton bloom around the pycnocline can be largely attributable to the formation of a well-developed SCML in the studied system. The uplift of the cold subsurface water within the cyclone, shoaling the pycnocline to a shallower layer, resulted in a low-temperature anomaly and different salinity anomalies at different depths. This uplift in the cyclone further caused the SCML to appear at a shallower depth with a higher in situ chlorophyll concentration than that in the normal domain. Conversely, the sinking of the warm surface water to the subsurface layer within the anticyclone depressed the pycnocline to a deeper layer and generated a high-temperature anomaly and opposite salinity anomalies compared with the cyclone. The sinking of the pycnocline within the anticyclone considerably influenced the characteristics of the SCML, which had a deeper depth and a lower in situ chlorophyll concentration than that of the normal sea. This study contributes rare quasi-synchronous CTD observations capturing mesoscale eddies and provides valuable descriptions of the variations in the SCML under the influence of mesoscale eddies based on in situ optical measurements from the seldom-discussed western North Pacific.

Non-ionic block copolymers leading to a highly ordered organosilica material

NASA Astrophysics Data System (ADS)

Rebbin, V.; Rothkirch, A.; Vainio, U.; Funari, S. S.

2012-03-01

Phenylene-bridged periodic mesoporous organosilica (PMO) materials with hexaethylene glycol mono hexadecylether (C16(EO)6) as structure directing agent (SDA) in acidic solution were synthesised and the reaction was studied in different conditions, including in situ small angle X-ray scattering at room temperature and at 60 °C. The in situ SAXS investigations at 60 °C show the formation of a 2D hexagonal mesostructure after 3 hours reaction time. In contrast to these results the same reaction performed in the laboratory produced a powder that, after drying at room temperature, shows a large number of diffraction peaks, allowing identifying a lamellar structure, possibly in coexistence of a micellar cubic structure (space group Pm3n). Aposteriori removal of the surfactant from the powder synthesised in the laboratory led to the collapse of the lamellar structure.

Polymer biomaterial constructs for regenerative medicine and functional biological systems

NASA Astrophysics Data System (ADS)

Meng, Linghui

The use of collagen as a biomaterial is currently undergoing a renaissance in the tissue engineering field. The excellent biocompatibility and safety due to its biological characteristics, such as biodegradability and weak antigenicity, make collagen a primary material resource in medical applications. Described herein is work towards the development of novel collagen-based matrices, with additional multi-functionality imparted through a novel in-situ crosslinking approach. The process of electrospinning has become a widely used technique for the creation of fibrous scaffolds for tissue engineering applications due to its ability to rapidly create structures composed of nano-scale polymer fibers closely resembling the architecture of the extracellular matrix (ECM). Collagen-PCL sheath-core bicomponent fibrous scaffolds were fabricated using a novel variation on traditional electrospinning, known as co-axial electrospinning. The results showed that the addition of a synthetic polymer core into collagen nanofibers remarkably increased the mechanical strength of collagen matrices spun from the benign solvent system. A novel single-step, in-situ collagen crosslink approach was developed in order to solve the problems dominating traditional collagen crosslinking methods, such as dimensional shrinking and loss of porous morphology, and to simplify the crosslinking procedure for electrospun collagen scaffolds. The excess amount of NHS present in the crosslinking mixture was found to delay the EDC/collagen coupling reaction in a controlled fashion. Fundamental investigations into the development and characterization of in-situ crosslinked collagen matrices such as fibrous scaffolds, gels and sponges, as well as their biomedical applications including cell culture substrates, wound dressings, drug delivery matrices and bone regeneration substitutes, were performed. The preliminary mice studies indicated that the in-situ crosslinked collagen matrices could be good candidates for wound healing and skin regeneration. Polyelectrolyte fibrous tubes of highly-crosslinked poly (acrylic acid) were fabricated by means of electrospinning as polymer models for functional biological systems, with special attention to the axon cortical layer and its cation-exchange properties. The processing parameters of fiber formation and the reversible phase transitions of PAA tubes according to monovalent-divalent ion exchange in solution were systematically investigated. The results showed that the neutralized PAA tubes were responsive to calcium ions, exhibiting significant shrinkage that could be reversed with a chelator such as citrate. Study of such phase transitions may help to better understand the electrophysiological processes known as nerve excitation and conduction in the nervous system, and the resulting PAA tubes might be used as polymer models of artificial axons for potential tissue engineering and nerve repair applications.

Rapid and sensitive analysis of polychlorinated biphenyls and acrylamide in food samples using ionic liquid-based in situ dispersive liquid-liquid microextraction coupled to headspace gas chromatography.

PubMed

Zhang, Cheng; Cagliero, Cecilia; Pierson, Stephen A; Anderson, Jared L

2017-01-20

A simple and rapid ionic liquid (IL)-based in situ dispersive liquid-liquid microextraction (DLLME) method was developed and coupled to headspace gas chromatography (HS-GC) employing electron capture (ECD) and mass spectrometry (MS) detection for the analysis of polychlorinated biphenyls (PCBs) and acrylamide at trace levels from milk and coffee samples. The chemical structures of the halide-based ILs were tailored by introducing various functional groups to the cations to evaluate the effect of different structural features on the extraction efficiency of the target analytes. Extraction parameters including the molar ratio of IL to metathesis reagent and IL mass were optimized. The effects of HS oven temperature and the HS sample vial volume on the analyte response were also evaluated. The optimized in situ DLLME method exhibited good analytical precision, good linearity, and provided detection limits down to the low ppt level for PCBs and the low ppb level for acrylamide in aqueous samples. The matrix-compatibility of the developed method was also established by quantifying acrylamide in brewed coffee samples. This method is much simpler and faster compared to previously reported GC-MS methods using solid-phase microextraction (SPME) for the extraction/preconcentration of PCBs and acrylamide from complex food samples. Copyright © 2016 Elsevier B.V. All rights reserved.

In Situ and Real-Time SFG Measurements Revealing Organization and Transport of Cholesterol Analogue 6-Ketocholestanol in a Cell Membrane.

PubMed

Ma, Sulan; Li, Hongchun; Tian, Kangzhen; Ye, Shuji; Luo, Yi

2014-02-06

Cholesterol organization and transport within a cell membrane are essential for human health and many cellular functions yet remain elusive so far. Using cholesterol analogue 6-ketocholestanol (6-KC) as a model, we have successfully exploited sum frequency generation vibrational spectroscopy (SFG-VS) to track the organization and transport of cholesterol in a membrane by combining achiral-sensitive ssp (ppp) and chiral-sensitive psp polarization measurements. It is found that 6-KC molecules are aligned at the outer leaflet of the DMPC lipid bilayer with a tilt angle of about 10°. 6-KC organizes itself by forming an α-β structure at low 6-KC concentration and most likely a β-β structure at high 6-KC concentration. Among all proposed models, our results favor the so-called umbrella model with formation of a 6-KC cluster. Moreover, we have found that the long anticipated flip-flop motion of 6-KC in the membrane takes time to occur, at least much longer than previously thought. All of these interesting findings indicate that it is critical to explore in situ, real-time, and label-free methodologies to obtain a precise molecular description of cholesterol's behavior in membranes. This study represents the first application of SFG to reveal the cholesterol-lipid interaction mechanism at the molecular level.

In situ MEMS testing: correlation of high-resolution X-ray diffraction with mechanical experiments and finite element analysis.

PubMed

Schifferle, Andreas; Dommann, Alex; Neels, Antonia

2017-01-01

New methods are needed in microsystems technology for evaluating microelectromechanical systems (MEMS) because of their reduced size. The assessment and characterization of mechanical and structural relations of MEMS are essential to assure the long-term functioning of devices, and have a significant impact on design and fabrication. Within this study a concept for the investigation of mechanically loaded MEMS materials on an atomic level is introduced, combining high-resolution X-ray diffraction (HRXRD) measurements with finite element analysis (FEA) and mechanical testing. In situ HRXRD measurements were performed on tensile loaded single crystal silicon (SCSi) specimens by means of profile scans and reciprocal space mapping (RSM) on symmetrical (004) and (440) reflections. A comprehensive evaluation of the rather complex XRD patterns and features was enabled by the correlation of measured with simulated, 'theoretical' patterns. Latter were calculated by a specifically developed, simple and fast approach on the basis of continuum mechanical relations. Qualitative and quantitative analysis confirmed the admissibility and accuracy of the presented method. In this context [001] Poisson's ratio was determined providing an error of less than 1.5% with respect to analytical prediction. Consequently, the introduced procedure contributes to further going investigations of weak scattering being related to strain and defects in crystalline structures and therefore supports investigations on materials and devices failure mechanisms.

In situ MEMS testing: correlation of high-resolution X-ray diffraction with mechanical experiments and finite element analysis

PubMed Central

Schifferle, Andreas; Dommann, Alex; Neels, Antonia

2017-01-01

Abstract New methods are needed in microsystems technology for evaluating microelectromechanical systems (MEMS) because of their reduced size. The assessment and characterization of mechanical and structural relations of MEMS are essential to assure the long-term functioning of devices, and have a significant impact on design and fabrication. Within this study a concept for the investigation of mechanically loaded MEMS materials on an atomic level is introduced, combining high-resolution X-ray diffraction (HRXRD) measurements with finite element analysis (FEA) and mechanical testing. In situ HRXRD measurements were performed on tensile loaded single crystal silicon (SCSi) specimens by means of profile scans and reciprocal space mapping (RSM) on symmetrical (004) and (440) reflections. A comprehensive evaluation of the rather complex XRD patterns and features was enabled by the correlation of measured with simulated, ‘theoretical’ patterns. Latter were calculated by a specifically developed, simple and fast approach on the basis of continuum mechanical relations. Qualitative and quantitative analysis confirmed the admissibility and accuracy of the presented method. In this context [001] Poisson’s ratio was determined providing an error of less than 1.5% with respect to analytical prediction. Consequently, the introduced procedure contributes to further going investigations of weak scattering being related to strain and defects in crystalline structures and therefore supports investigations on materials and devices failure mechanisms. PMID:28533825

K 3 Fe(CN) 6 under External Pressure: Dimerization of CN – Coupled with Electron Transfer to Fe(III)

DOE PAGES

Li, Kuo; Zheng, Haiyan; Wang, Lijuan; ...

2015-09-14

The addition polymerization of charged monomers like C≡C 2– and C≡N– is scarcely seen at ambient conditions but can progress under external pressure with their conductivity significantly enhanced, which expands the research field of polymer science to inorganic salts. Moreover, the reaction pressures of transition metal cyanides like Prussian blue and K 3Fe(CN) 6 are much lower than that of alkali cyanides. To figure out the effect of the transition metal on the reaction, the crystal structure and electronic structure of K 3Fe(CN) 6 under external pressure are investigated by in situ neutron diffraction, in situ X-ray absorption fine structuremore » (XAFS), and neutron pair distribution functions (PDF) up to ~15 GPa. The cyanide anions react following a sequence of approaching–bonding–stabilizing. The Fe(III) brings the cyanides closer which makes the bonding progress at a low pressure (2–4 GPa). At ~8 GPa, an electron transfers from the CN to Fe(III), reduces the charge density on cyanide ions, and stabilizes the reaction product of cyanide. Finally, from this study we can conclude that bringing the monomers closer and reducing their charge density are two effective routes to decrease the reaction pressure, which is important for designing novel pressure induced conductor and excellent electrode materials.« less

Rapid and Facile Formation of P3HT Organogels via Spin Coating: Tuning Functional Properties of Organic Electronic Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Cameron S.; Yin, Wen; Holt, Adam P.

Poly(3-hexyl thiophene) (P3HT) is widely regarded as the benchmark polymer when studying the physics of conjugated polymers used in organic electronic devices. P3HT can self-assemble via stacking of its backbone, leading to an assembly and growth of P3HT fi brils into 3D percolating organogels. These structures are capable of bridging the electrodes, providing multiple pathways for charge transport throughout the active layer. Here, a novel set of conditions is identified and discussed for P3HT organogel network formation via spin coating by monitoring the spin-coating process from various solvents. The development of organogel formation is detected by in situ static lightmore » scattering, which measures both the thinning rate by refl ectance and structural development in the fi lm via off-specular scattering during fi lm formation. Optical microscopy and thermal annealing experiments provide ex situ confi rmation of organogel fabrication. The role of solution characteristics, including solvent boiling point, P3HT solubility, and initial P3HT solution concentration on organogel formation, is examined to correlate these parameters to the rate of film formation, organogel-onset concentration, and overall network size. The correlation of film properties to the fabrication parameters is also analyzed within the context of the hole mobility and density-of-states measured by impedance spectroscopy.« less

Iron oxide nanoparticle layer templated by polydopamine spheres: a novel scaffold toward hollow-mesoporous magnetic nanoreactors

NASA Astrophysics Data System (ADS)

Huang, Liang; Ao, Lijiao; Xie, Xiaobin; Gao, Guanhui; Foda, Mohamed F.; Su, Wu

2014-12-01

Superparamagnetic iron oxide nanoparticle layers with high packing density and controlled thickness were in situ deposited on metal-affinity organic templates (polydopamine spheres), via one-pot thermal decomposition. The as synthesized hybrid structure served as a facile nano-scaffold toward hollow-mesoporous magnetic carriers, through surfactant-assisted silica encapsulation and its subsequent calcination. Confined but accessible gold nanoparticles were successfully incorporated into these carriers to form a recyclable catalyst, showing quick magnetic response and a large surface area (642.5 m2 g-1). Current nano-reactors exhibit excellent catalytic performance and high stability in reduction of 4-nitrophenol, together with convenient magnetic separability and good reusability. The integration of compact iron oxide nanoparticle layers with programmable polydopamine templates paves the way to fabricate magnetic-response hollow structures, with high permeability and multi-functionality.Superparamagnetic iron oxide nanoparticle layers with high packing density and controlled thickness were in situ deposited on metal-affinity organic templates (polydopamine spheres), via one-pot thermal decomposition. The as synthesized hybrid structure served as a facile nano-scaffold toward hollow-mesoporous magnetic carriers, through surfactant-assisted silica encapsulation and its subsequent calcination. Confined but accessible gold nanoparticles were successfully incorporated into these carriers to form a recyclable catalyst, showing quick magnetic response and a large surface area (642.5 m2 g-1). Current nano-reactors exhibit excellent catalytic performance and high stability in reduction of 4-nitrophenol, together with convenient magnetic separability and good reusability. The integration of compact iron oxide nanoparticle layers with programmable polydopamine templates paves the way to fabricate magnetic-response hollow structures, with high permeability and multi-functionality. Electronic supplementary information (ESI) available: Fig. S1-S5. See DOI: 10.1039/c4nr05931j

Application of Sub-Bottom Profiler to Study Riverbed Structure and Sediment Density

NASA Astrophysics Data System (ADS)

Rui, Wang; Changzheng, Li; Xiaofei, Yan

2018-03-01

In this pater, we present a study on the riverbed structure and sediment density in-situ test by using sub-bottom profiler. Compared with traditional direct observation methods, the sub-bottom profiler method based on sonar technology is non-contact, low-disturbance and high-efficient. We finish the investigation of several sections in Sanmenxia and Xiaolangdi reservoirs, which located on the main channel of lower reaches of Yellow River. Collected data show a detailed layered structure of the riverbed sediment which believed caused by sedimentary processes in different periods. Further more, we analyse the reflection coefficient of water-sediment interface and inverse the sediment density data from the raw wave record. The inversion method is based on the effective density fluid model and Kozeny-Carman formula. The comparison of the inversion results and sample tests shows that the in-situ test is reliable and useable.

Study of the mechanical behavior of the hydride blister/rim structure in Zircaloy-4 using in-situ synchrotron X-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Jun-li; Han, Xiaochun; Heuser, Brent J.

2016-04-01

High-energy synchrotron X-ray diffraction was utilized to study the mechanical response of the f.c.c delta hydride phase, the intermetallic precipitation with hexagonal C14 lave phase and the alpha-Zr phase in the Zircaloy-4 materials with a hydride rim/blister structure near one surface of the material during in-situ uniaxial tension experiment at 200 degrees C. The f.c.c delta was the only hydride phase observed in the rim/blister structure. The conventional Rietveld refinement was applied to measure the macro-strain equivalent response of the three phases. Two regions were delineated in the applied load versus lattice strain measurement: a linear elastic strain region andmore » region that exhibited load partitioning. Load partitioning was quantified by von Mises analysis. The three phases were observed to have similar elastic modulus at 200 degrees C.« less

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

PubMed

Baier, Sina; Damsgaard, Christian D; Klumpp, Michael; Reinhardt, Juliane; Sheppard, Thomas; Balogh, Zoltan; Kasama, Takeshi; Benzi, Federico; Wagner, Jakob B; Schwieger, Wilhelm; Schroer, Christian G; Grunwaldt, Jan-Dierk

2017-06-01

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

In situ/operando studies for the production of hydrogen through the water-gas shift on metal oxide catalysts.

PubMed

Rodriguez, José A; Hanson, Jonathan C; Stacchiola, Dario; Senanayake, Sanjaya D

2013-08-07

In this perspective article, we show how a series of in situ techniques {X-ray diffraction (XRD), pair-distribution-function analysis (PDF), X-ray absorption fine structure (XAFS), environmental transmission electron microscopy (ETEM), infrared spectroscopy (IR), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)} can be combined to perform detailed studies of the structural, electronic and chemical properties of metal oxide catalysts used for the production of hydrogen through the water-gas shift reaction (WGS, CO + H2O → H2 + CO2). Under reaction conditions most WGS catalysts undergo chemical transformations that drastically modify their composition with respect to that obtained during the synthesis process. Experiments of time-resolved in situ XRD, XAFS, and PDF indicate that the active phase of catalysts which combine Cu, Au or Pt with oxides such as ZnO, CeO2, TiO2, CeOx/TiO2 and Fe2O3 essentially involves nanoparticles of the reduced noble metals. The oxide support undergoes partial reduction and is not a simple spectator, facilitating the dissociation of water and in some cases modifying the chemical properties of the supported metal. Therefore, to optimize the performance of these catalysts one must take into consideration the properties of the metal and oxide phases. IR and AP-XPS have been used to study the reaction mechanism for the WGS on metal oxide catalysts. Data of IR spectroscopy indicate that formate species are not necessarily involved in the main reaction path for the water-gas shift on Cu-, Au- and Pt-based catalysts. Thus, a pure redox mechanism or associative mechanisms that involve either carbonate-like (CO3, HCO3) or carboxyl (HOCO) species should be considered. In the last two decades, there have been tremendous advances in our ability to study catalytic materials under reaction conditions and we are moving towards the major goal of fully understanding how the active sites for the production of hydrogen through the WGS actually work.

The Structure of Resting Bacterial Populations in Soil and Subsoil Permafrost

NASA Astrophysics Data System (ADS)

Soina, Vera S.; Mulyukin, Andrei L.; Demkina, Elena V.; Vorobyova, Elena A.; El-Registan, Galina I.

2004-09-01

The structure of individual cells in microbial populations in situ of the Arctic and Antarctic permafrost was studied by scanning and transmission electron microscopy methods and compared with that of cyst-like resting forms generated under special conditions by the non-sporeforming bacteria Arthrobacter and Micrococcus isolated from the permafrost. Electron microscopy examination of microorganisms in situ revealed several types of bacterial cells having no signs of damage, including "dwarf" curved forms similar to nanoforms. Intact bacterial cells in situ and frozen cultures of the permafrost isolates differed from vegetative cells by thickened cell walls, the altered structure of cytoplasm, and the compact nucleoid, and were similar in these features to cyst-like resting forms of non-spore-forming "permafrost" bacterial strains of Arthrobacter and Micrococcus spp. Cyst-like cells, being resistant to adverse external factors, are regarded as being responsible for survival of the non-spore-formers under prolonged exposure to subzero temperatures and can be a target to search for living microorganisms in natural environments both on the Earth and on extraterrestrial bodies.

Linking soil biology and chemistry in biological soil crust using isolate exometabolomics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swenson, Tami L.; Karaoz, Ulas; Swenson, Joel M.

Metagenomic sequencing provides a window into microbial community structure and metabolic potential; however, linking these data to exogenous metabolites that microorganisms process and produce (the exometabolome) remains challenging. Previously, we observed strong exometabolite niche partitioning among bacterial isolates from biological soil crust (biocrust). For this study, we examine native biocrust to determine if these patterns are reproduced in the environment. Overall, most soil metabolites display the expected relationship (positive or negative correlation) with four dominant bacteria following a wetting event and across biocrust developmental stages. For metabolites that were previously found to be consumed by an isolate, 70% are negativelymore » correlated with the abundance of the isolate's closest matching environmental relative in situ, whereas for released metabolites, 67% were positively correlated. Our results demonstrate that metabolite profiling, shotgun sequencing and exometabolomics may be successfully integrated to functionally link microbial community structure with environmental chemistry in biocrust.« less

Linking soil biology and chemistry in biological soil crust using isolate exometabolomics

DOE PAGES

Swenson, Tami L.; Karaoz, Ulas; Swenson, Joel M.; ...

2018-01-02

Metagenomic sequencing provides a window into microbial community structure and metabolic potential; however, linking these data to exogenous metabolites that microorganisms process and produce (the exometabolome) remains challenging. Previously, we observed strong exometabolite niche partitioning among bacterial isolates from biological soil crust (biocrust). For this study, we examine native biocrust to determine if these patterns are reproduced in the environment. Overall, most soil metabolites display the expected relationship (positive or negative correlation) with four dominant bacteria following a wetting event and across biocrust developmental stages. For metabolites that were previously found to be consumed by an isolate, 70% are negativelymore » correlated with the abundance of the isolate's closest matching environmental relative in situ, whereas for released metabolites, 67% were positively correlated. Our results demonstrate that metabolite profiling, shotgun sequencing and exometabolomics may be successfully integrated to functionally link microbial community structure with environmental chemistry in biocrust.« less

High-pressure structural, elastic, and electronic properties of the scintillator host material KMgF3

NASA Astrophysics Data System (ADS)

Vaitheeswaran, G.; Kanchana, V.; Kumar, Ravhi S.; Cornelius, A. L.; Nicol, M. F.; Svane, A.; Delin, A.; Johansson, B.

2007-07-01

The high-pressure structural behavior of the fluoroperovskite KMgF3 is investigated by theory and experiment. Density functional calculations were performed within the local density approximation and the generalized gradient approximation for exchange and correlation effects, as implemented within the full-potential linear muffin-tin orbital method. In situ high-pressure powder x-ray diffraction experiments were performed up to a maximum pressure of 40GPa using synchrotron radiation. We find that the cubic Pm3¯m crystal symmetry persists throughout the pressure range studied. The calculated ground state properties—the equilibrium lattice constant, bulk modulus, and elastic constants—are in good agreement with experimental results. By analyzing the ratio between the bulk and shear moduli, we conclude that KMgF3 is brittle in nature. Under ambient conditions, KMgF3 is found to be an indirect gap insulator, with the gap increasing under pressure.

Complex biomembrane mimetics on the sub-nanometer scale

DOE PAGES

Heberle, Frederick A.; Pabst, Georg

2017-07-17

Biomimetic lipid vesicles are indispensable tools for gaining insight into the biophysics of cell physiology on the molecular level. The level of complexity of these model systems has steadily increased, and now spans from domain forming lipid mixtures to asymmetric lipid bilayers. We review recent progress in the development and application of elastic neutron and X-ray scattering techniques for studying these systems in situ and under physiologically relevant conditions on the nanometer to sub-nanometer length scales. Particularly we focus on: (i) structural details of coexisting liquid-ordered and liquid-disordered domains, including their thickness and lipid packing mismatch as a function ofmore » a size transition from nanoscopic to macroscopic domains; (ii) membrane-mediated protein partitioning into lipid domains; (iii) the role of the aqueous medium in tuning interactions between membranes and domains; and (iv) leaflet specific structure in asymmetric bilayers and passive lipid flip-flop.« less

Influence of controlled surface oxidation on the magnetic anisotropy of Co ultrathin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Di, N.; Maroun, F., E-mail: fouad.maroun@polytechnique.fr; Allongue, P.

2015-03-23

We studied the influence of controlled surface-limited oxidation of electrodeposited epitaxial Co(0001)/Au(111) films on their magnetic anisotropy energy using real time in situ magneto optical Kerr effect and density functional theory (DFT) calculations. We investigated the Co first electrochemical oxidation step which we demonstrate to be completely reversible and determined the structure of this oxide layer. We show that the interface magnetic anisotropy of the Co film increases by 0.36 erg/cm{sup 2} upon Co surface oxidation. We performed DFT calculations to determine the different surface structures in a wide potential range as well as the charge transfer at the Co surface.more » Our results suggest that the magnetic anisotropy change is correlated with a positive charge increase of 0.54 e{sup −} for the Co surface atom upon oxidation.« less

Complex biomembrane mimetics on the sub-nanometer scale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heberle, Frederick A.; Pabst, Georg

Biomimetic lipid vesicles are indispensable tools for gaining insight into the biophysics of cell physiology on the molecular level. The level of complexity of these model systems has steadily increased, and now spans from domain forming lipid mixtures to asymmetric lipid bilayers. We review recent progress in the development and application of elastic neutron and X-ray scattering techniques for studying these systems in situ and under physiologically relevant conditions on the nanometer to sub-nanometer length scales. Particularly we focus on: (i) structural details of coexisting liquid-ordered and liquid-disordered domains, including their thickness and lipid packing mismatch as a function ofmore » a size transition from nanoscopic to macroscopic domains; (ii) membrane-mediated protein partitioning into lipid domains; (iii) the role of the aqueous medium in tuning interactions between membranes and domains; and (iv) leaflet specific structure in asymmetric bilayers and passive lipid flip-flop.« less

Synergistic Enhancement of Microwave Absorption Using Hybridized Polyaniline@helical CNTs with Dual Chirality.

PubMed

Tian, Xin; Meng, Fanbin; Meng, Fanchen; Chen, Xiangnan; Guo, Yifan; Wang, Ying; Zhu, Wenjun; Zhou, Zuowan

2017-05-10

In this study, we designed a dual-chirality hierarchical structure to achieve a synergistically enhanced effect in microwave absorption via the hybridization of nanomaterials. Herein, polyaniline (PANi) nanorods with tunable chirality are grown on helical carbon nanotubes (HCNTs), a typical nanoscale chiral structure, through in situ polymerization. The experimental results show that the hierarchical hybrids (PANi@HCNTs) exhibit distinctly dual chirality and a significant enhancement in electromagnetic (EM) losses compared to those of either pure PANi or HCNTs. The maximum reflection loss of the as-prepared hybrids can reach -32.5 dB at 8.9 GHz. Further analysis demonstrates that combinations of chiral acid-doped PANi and coiled HCNTs with molecular and nanoscale chirality lead to synergistic effects resulting from the dual chirality. The so-called cross-polarization may result in additional interactions with induced EM waves in addition to multiscaled relaxations from functional groups and interfacial polarizations, which can benefit EM absorption.

High-energy X-ray powder diffraction and atomic-pair distribution-function studies of charged/discharged structures in carbon-hybridized Li2MnSiO4 nanoparticles as a cathode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Moriya, Maki; Miyahara, Masahiko; Hokazono, Mana; Sasaki, Hirokazu; Nemoto, Atsushi; Katayama, Shingo; Akimoto, Yuji; Hirano, Shin-ichi; Ren, Yang

2014-10-01

The stable cycling performance with a high discharge capacity of ∼190 mAh g-1 in a carbon-hybridized Li2MnSiO4 nanostructured powder has prompted an experimental investigation of the charged/discharged structures using synchrotron-based and laboratory-based X-rays and atomic-pair distribution-function (PDF) analyses. A novel method of in-situ spray pyrolysis of a precursor solution with glucose as a carbon source enabled the successful synthesis of the carbon-hybridized Li2MnSiO4 nanoparticles. The XRD patters of the discharged (lithiated) samples exhibit a long-range ordered structure characteristic of the (β) Li2MnSiO4 crystalline phase (space group Pmn21) which dissipates in the charged (delithiated) samples. However, upon discharging the long-range ordered structure recovers in each cycle. The disordered structure, according to the PDF analysis, is mainly due to local distortions of the MnO4 tetrahedra which show a mean Mn-O nearest neighbor distance shorter than that of the long-range ordered phase. These results corroborate the notion of the smaller Mn3+/Mn4+ ionic radii in the Li extracted phase versus the larger Mn2+ ionic radius in Li inserted phase. Thus Li extraction/insertion drives the fluctuation between the disordered and the long-range ordered structures.

Hydrophobic Coatings on Cotton Obtained by in Situ Plasma Polymerization of a Fluorinated Monomer in Ethanol Solutions.

PubMed

Molina, Ricardo; Teixidó, Josep Maria; Kan, Chi-Wai; Jovančić, Petar

2017-02-15

Plasma polymerization using hydrophobic monomers in the gas phase is a well-known technology to generate hydrophobic coatings. However, synthesis of functional hydrophobic coatings using plasma technology in liquids has not yet been accomplished. This work is consequently focused on polymerization of a liquid fluorinated monomer on cotton fabric initiated by atmospheric plasma in a dielectric barrier discharge configuration. Functional hydrophobic coatings on cotton were successfully achieved using in situ atmospheric plasma-initiated polymerization of fluorinated monomer dissolved in ethanol. Gravimetric measurements reveal that the amount of polymer deposited on cotton substrates can be modulated with the concentration of monomer in ethanol solution, and cross-linking reactions occur during plasma polymerization of a fluorinated monomer even without the presence of a cross-linking agent. FTIR and XPS analysis were used to study the chemical composition of hydrophobic coatings and to get insights into the physicochemical processes involved in plasma treatment. SEM analysis reveals that at high monomer concentration, coatings possess a three-dimensional pattern with a characteristic interconnected porous network structure. EDX analysis reveals that plasma polymerization of fluorinated monomers takes place preferentially at the surface of cotton fabric and negligible polymerization takes place inside the cotton fabric. Wetting time measurements confirm the hydrophobicity of cotton coatings obtained although equilibrium moisture content was slightly decreased. Additionally, the abrasion behavior and resistance to washing of plasma-coated cotton has been evaluated.

Surface modification of titanium substrates with silver nanoparticles embedded sulfhydrylated chitosan/gelatin polyelectrolyte multilayer films for antibacterial application.

PubMed

Li, Wen; Xu, Dawei; Hu, Yan; Cai, Kaiyong; Lin, Yingcheng

2014-06-01

To develop Ti implants with potent antibacterial activity, a novel "sandwich-type" structure of sulfhydrylated chitosan (Chi-SH)/gelatin (Gel) polyelectrolyte multilayer films embedding silver (Ag) nanoparticles was coated onto titanium substrate using a spin-assisted layer-by-layer assembly technique. Ag ions would be enriched in the polyelectrolyte multilayer films via the specific interactions between Ag ions and -HS groups in Chi-HS, thus leading to the formation of Ag nanoparticles in situ by photo-catalytic reaction (ultraviolet irradiation). Contact angle measurement and field emission scanning electron microscopy equipped with energy dispersive X-ray spectroscopy were employed to monitor the construction of Ag-containing multilayer on titanium surface, respectively. The functional multilayered films on titanium substrate [Ti/PEI/(Gel/Chi-SH/Ag) n /Gel] could efficiently inhibit the growth and activity of Bacillus subtitles and Escherichia coli onto titanium surface. Moreover, studies in vitro confirmed that Ti substrates coating with functional multilayer films remained the biological functions of osteoblasts, which was reflected by cell morphology, cell viability and ALP activity measurements. This study provides a simple, versatile and generalized methodology to design functional titanium implants with good cyto-compatibility and antibacterial activity for potential clinical applications.

Density driven structural transformations in amorphous semiconductor clathrates

DOE PAGES

Tulk, Christopher A.; dos Santos, Antonio M.; Neuefeind, Joerg C.; ...

2015-01-16

The pressure induced crystalline collapse at 14.7 GPa and polyamorphic structures of the semiconductor clathrate Sr8Ga16Ge30 are reported up to 35 GPa. In-situ total scattering measurements under pressure allow the direct microscopic inspection of the mechanisms associated with pressure induced amorphization in these systems, as well as the structure of the recovered phase. It is observed that, between 14.7 and 35 GPa the second peak in the structure factor function gradually disappears. Analysis of the radial distribution function extracted from those data indicate that this feature is associated with gradual cage collapse and breakdown of the tetrahedral structure with themore » consequent systematic lengthening of the nearest-neighbor framework bonds. This suggests an overall local coordination change to an even higher density amorphous form. Upon recovery from high pressure, the sample remains amorphous, and while there is some indication of the guest-host cage reforming, it doesn't seem that the tetrahedral coordination is recovered. As such, the compresion-decompression process in this systems gives rise to three distict amorphous forms.« less

Surface dynamics of micellar diblock copolymer films

NASA Astrophysics Data System (ADS)

Song, Sanghoon; Cha, Wonsuk; Kim, Hyunjung; Jiang, Zhang; Narayanan, Suresh

2011-03-01

We studied the structure and surface dynamics of poly(styrene)-b-poly(dimethylsiloxane) (PS-b-PDMS) diblock copolymer films with micellar PDMS surrounded by PS shells. By `in-situ' high resolution synchrotron x-ray reflectivity and diffuse scattering, we obtained exact thickness, electron density and surface tension. A segregation layer near the top surface was appeared with increasing temperature Surface dynamics were measured as a function of film thickness and temperature by x-ray photon correlation spectroscopy. The best fit to relaxation time constants as a function of in-plane wavevectors were analyzed with a theory based on capillary waves with hydrodynamics with bilayer model Finally the viscosities for the top segregated layer as well as for the bottom layer are obtained at given temperatures This work was supported by National Research Foundation of Korea (R15-2008-006-01001-0), Seoul Research and Business Development Program (10816), and Sogang University Research Grant (2010).

Layer-by-layer cell membrane assembly

NASA Astrophysics Data System (ADS)

Matosevic, Sandro; Paegel, Brian M.

2013-11-01

Eukaryotic subcellular membrane systems, such as the nuclear envelope or endoplasmic reticulum, present a rich array of architecturally and compositionally complex supramolecular targets that are as yet inaccessible. Here we describe layer-by-layer phospholipid membrane assembly on microfluidic droplets, a route to structures with defined compositional asymmetry and lamellarity. Starting with phospholipid-stabilized water-in-oil droplets trapped in a static droplet array, lipid monolayer deposition proceeds as oil/water-phase boundaries pass over the droplets. Unilamellar vesicles assembled layer-by-layer support functional insertion both of purified and of in situ expressed membrane proteins. Synthesis and chemical probing of asymmetric unilamellar and double-bilayer vesicles demonstrate the programmability of both membrane lamellarity and lipid-leaflet composition during assembly. The immobilized vesicle arrays are a pragmatic experimental platform for biophysical studies of membranes and their associated proteins, particularly complexes that assemble and function in multilamellar contexts in vivo.

Micro-structurally detailed model of a therapeutic hydrogel injectate in a rat biventricular cardiac geometry for computational simulations

PubMed Central

Sirry, Mazin S.; Davies, Neil H.; Kadner, Karen; Dubuis, Laura; Saleh, Muhammad G.; Meintjes, Ernesta M.; Spottiswoode, Bruce S.; Zilla, Peter; Franz, Thomas

2013-01-01

Biomaterial injection based therapies have showed cautious success in restoration of cardiac function and prevention of adverse remodelling into heart failure after myocardial infarction (MI). However, the underlying mechanisms are not well understood. Computational studies utilised simplified representations of the therapeutic myocardial injectates. Wistar rats underwent experimental infarction followed by immediate injection of polyethylene glycol hydrogel in the infarct region. Hearts were explanted, cryo-sectioned and the region with the injectate histologically analysed. Histological micrographs were used to reconstruct the dispersed hydrogel injectate. Cardiac magnetic resonance imaging (CMRI) data from a healthy rat were used to obtain an end-diastolic biventricular geometry which was subsequently adjusted and combined with the injectate model. The computational geometry of the injectate exhibited microscopic structural details found the in situ. The combination of injectate and cardiac geometry provides realistic geometries for multiscale computational studies of intra-myocardial injectate therapies for the rat model that has been widely used for MI research. PMID:23682845

New spiro-oxindole constructed with pyrrolidine/thioxothiazolidin-4-one derivatives: Regioselective synthesis, X-ray crystal structures, Hirshfeld surface analysis, DFT, docking and antimicrobial studies

NASA Astrophysics Data System (ADS)

Barakat, Assem; Soliman, Saied M.; Al-Majid, Abdullah Mohammed; Ali, M.; Islam, Mohammad Shahidul; Elshaier, Yaseen A. M. M.; Ghabbour, Hazem A.

2018-01-01

In this work, polycyclic heterocycles containing spirooxindole, pyrrolidine, and thioxothiazolidin-4-one rings have been synthesized via the regioselective 1,3-dipolar cycloaddition of azomethine ylide, which is generated in situ by the condensation of the dicarbonyl compound isatin and the secondary amino acid (L-proline), with 5-arylidine-2-thioxothiazolidin-4-one as the dipolarophile. The structure of the synthesized compounds 4a and 4b were determined by using X-ray single crystal diffraction, and also, Hirshfeld surface analysis were reported. Their geometric parameters were calculated using density functional theory at the B3LYP/6-311G (d,p) level of theory. Both compounds showed antimicrobial and antifungal activity better than selected standards (ampicillin and gentamicin in case of antibacterial activity and Amphotericin A and fluconazole in case of antifungal activity). Molecular docking study of the synthesized compounds indicated that phenyl group plays an important role in determination of compound interaction inside the receptors.

Revised description of the fine structure of in situ "zooxanthellae" genus Symbiodinium.

PubMed

Wakefield, T S; Farmer, M A; Kempf, S C

2000-08-01

The fine structure of the symbiotic dinoflagellate genus Symbiodinium has been well described. All of the published descriptions are based on tissue that was fixed in standard aldehyde and osmium fixatives and dehydrated in an ethanol series before embedding. When the technique of freeze-substitution was used to fix tissue from Cassiopeia xamachana, Aiptasia pallida, and Phyllactis flosculifera and prepare it for embedding, thecal vesicles were revealed within the in situ symbionts of all three species. Although these structures have been identified in cultured symbionts, they have never been described in the in situ symbionts. A review of the literature has revealed several instances where thecal vesicles were either overlooked or identified incorrectly. Thus the formal description of the genus Symbiodinium, which describes the in situ symbionts, contains information that is based on artifact and should be revised. A revision of the genus is suggested, and the true nature of these structures and their significance in the symbiotic association are discussed.

Determination of the solubility of tin indium oxide using in situ and ex x-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gonzalez, G. B.; Mason, T. O.; Okasinski, J. S.

A novel approach to determine the thermodynamic solubility of tin in indium oxide via the exsolution from tin overdoped nano-ITO powders is presented. High-energy, in situ and ex situ synchrotron X-ray diffraction was utilized to study the solubility limit at temperatures ranging from 900 C to 1375 C. The tin exsolution from overdoped nanopowders and the formation of In{sub 4}Sn{sub 3}O{sub 12} were observed in situ during the first 4-48 h of high-temperature treatment. Samples annealed between 900 C and 1175 C were also studied ex situ with heat treatments for up to 2060 h. Structural results obtained from Rietveldmore » analysis include compositional phase analysis, atomic positions, and lattice parameters. The tin solubility in In{sub 2}O{sub 3} was determined using the phase analysis compositions from X-ray diffraction and the elemental compositions obtained from X-ray fluorescence. Experimental complications that can lead to incorrect tin solubility values in the literature are discussed.« less

Synthesis of branched metal nanostructures with controlled architecture and composition

NASA Astrophysics Data System (ADS)

Ortiz, Nancy

On account of their small size, metal nanoparticles are proven to be outstanding catalysts for numerous chemical transformations and represent promising platforms for applications in the fields of electronics, chemical sensing, medicine, and beyond. Many properties of metal nanoparticles are size-dependent and can be further manipulated through their shape and architecture (e.g., spherical vs. branched). Achieving morphology control of nanoparticles through solution-based techniques has proven challenging due to limited knowledge of morphology development in nanosyntheses. To overcome these complications, a systematic examination of the local ligand environment of metal precursors on nanostructure formation was undertaken to evaluate its contribution to nanoparticle nucleation rate and subsequent growth processes. Specifically, this thesis will provide evidence from ex situ studies---Transmission Electron Microscopy (TEM) and UV-visible spectroscopy (UV-Vis)---that support the hypothesis that strongly coordinated ligands delay burst-like nucleation to generate spherical metal nanoparticles and ligands with intermediate binding affinity regulate the gradual reduction of metal precursors to promote aggregated assembly of nanodendrites. These ex situ studies were coupled with a new in situ perspective, providing detailed understanding of metal precursor transformation, its direct relation to nanoparticle morphology development, and the ligand influence towards the formation of structurally complex metal nanostructures, using in situ synchrotron X-ray Diffraction (XRD) and Ultra Small-Angle X-ray Scattering (USAXS). The principles extracted from the study of monometallic nanostructure formation were also found to be generally applicable to the synthesis of bimetallic nanostructures, e.g., Pd-Pt architectures, with either core-shell or alloyed structures that were readily achieved by ligand selection. These outcomes provide a direct connection between fundamental principles of coordination chemistry and nanoparticle formation, with a stronger foundation for the predictive synthesis of future nanomaterials with controllable structural features.

In situ electron microscopy four-point electromechanical characterization of freestanding metallic and semiconducting nanowires.

PubMed

Bernal, Rodrigo A; Filleter, Tobin; Connell, Justin G; Sohn, Kwonnam; Huang, Jiaxing; Lauhon, Lincoln J; Espinosa, Horacio D

2014-02-26

Electromechanical coupling is a topic of current interest in nanostructures, such as metallic and semiconducting nanowires, for a variety of electronic and energy applications. As a result, the determination of structure-property relations that dictate the electromechanical coupling requires the development of experimental tools to perform accurate metrology. Here, a novel micro-electro-mechanical system (MEMS) that allows integrated four-point, uniaxial, electromechanical measurements of freestanding nanostructures in-situ electron microscopy, is reported. Coupled mechanical and electrical measurements are carried out for penta-twinned silver nanowires, their resistance is identified as a function of strain, and it is shown that resistance variations are the result of nanowire dimensional changes. Furthermore, in situ SEM piezoresistive measurements on n-type, [111]-oriented silicon nanowires up to unprecedented levels of ∼7% strain are demonstrated. The piezoresistance coefficients are found to be similar to bulk values. For both metallic and semiconducting nanowires, variations of the contact resistance as strain is applied are observed. These variations must be considered in the interpretation of future two-point electromechanical measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chalk-calcite-microfluidic experiments: construction and flooding of microsystems with reactive fluids

NASA Astrophysics Data System (ADS)

Neuville, Amélie; Thuy Luu, Thi; Dysthe, Dag Kristian; Vinningland, Jan Ludvig; Hiorth, Aksel

2015-04-01

Direct in situ observation of the pore structure changes that occur when chalk is flooded with brines could resolve many of the open questions that remain about the interactions between mineralogical alterations and oil-liberating mechanisms. Experiments on core scale and field tests that have been carried out the last decade have clearly shown that water chemistry affects the final oil recovery. However, there is generally no consensus in the scientific community of why additional oil is released. In this work, our aim is to focus on in-situ observations of single phase flow and interactions at the pore scale. To do so, we create several types of custom-made microsystems with chalk and calcite crystals. We then do experiments with reacting fluids in these microsystems. During these experiments, we realize in-situ observations (geometrical characteristics, reaction rate) using microsopy techniques (white light vertical/phase shift interferometric microscopy, and classical microscopy), and show how they vary as function as the water chemistry. In simple systems made of calcite, we obtain reactive rates that are coherent with the litterature and with numerical simulations based on Lattice-Boltzmann methods.

Tube Formation in Nanoscale Materials

PubMed Central

2008-01-01

The formation of tubular nanostructures normally requires layered, anisotropic, or pseudo-layered crystal structures, while inorganic compounds typically do not possess such structures, inorganic nanotubes thus have been a hot topic in the past decade. In this article, we review recent research activities on nanotubes fabrication and focus on three novel synthetic strategies for generating nanotubes from inorganic materials that do not have a layered structure. Specifically, thermal oxidation method based on gas–solid reaction to porous CuO nanotubes has been successfully established, semiconductor ZnS and Nb2O5nanotubes have been prepared by employing sacrificial template strategy based on liquid–solid reaction, and an in situ template method has been developed for the preparation of ZnO taper tubes through a chemical etching reaction. We have described the nanotube formation processes and illustrated the detailed key factors during their growth. The proposed mechanisms are presented for nanotube fabrication and the important pioneering studies are discussed on the rational design and fabrication of functional materials with tubular structures. It is the intention of this contribution to provide a brief account of these research activities. PMID:20592945

Intracellular production of hydrogels and synthetic RNA granules by multivalent enhancers

PubMed Central

Nakamura, Hideki; Lee, Albert A.; Afshar, Ali Sobhi; Watanabe, Shigeki; Rho, Elmer; Razavi, Shiva; Suarez, Allison; Lin, Yu-Chun; Tanigawa, Makoto; Huang, Brian; DeRose, Robert; Bobb, Diana; Hong, William; Gabelli, Sandra B.; Goutsias, John; Inoue, Takanari

2018-01-01

Non-membrane bound, hydrogel-like entities, such as RNA granules, nucleate essential cellular functions through their unique physico-chemical properties. However, these intracellular hydrogels have not been as extensively studied as their extracellular counterparts, primarily due to technical challenges in probing these materials in situ. Here, by taking advantage of a chemically inducible dimerization paradigm, we developed iPOLYMER, a strategy for rapid induction of protein-based hydrogels inside living cells. A series of biochemical and biophysical characterizations, in conjunction with computational modeling, revealed that the polymer network formed in the cytosol resembles a physiological hydrogel-like entity that behaves as a size-dependent molecular sieve. We studied several properties of the gel and functionalized it with RNA binding motifs that sequester polyadenine-containing nucleotides to synthetically mimic RNA granules. Therefore, we here demonstrate that iPOLYMER presents a unique and powerful approach to synthetically reconstitute hydrogel-like structures including RNA granules in intact cells. PMID:29115293

Advanced sample environments for in situ neutron diffraction studies of nuclear materials

NASA Astrophysics Data System (ADS)

Reiche, Helmut Matthias

Generation IV nuclear reactor concepts, such as the supercritical-water-cooled nuclear reactor (SCWR), are actively researched internationally. Operating conditions above the critical point of water (374°C, 22.1 MPa) and fuel core temperature that potentially exceed 1850°C put a high demand on the surrounding materials. For their safe application, it is essential to characterize and understand the material properties on an atomic scale such as crystal structure and grain orientation (texture) changes as a function of temperature and stress. This permits the refinement of models predicting the macroscopic behavior of the material. Neutron diffraction is a powerful tool in characterizing such crystallographic properties due to their deep penetration depth into condensed matter. This leads to the ability to study bulk material properties, as opposed to surface effects, and allows for complex sample environments to study e.g. the individual contributions of thermo-mechanical processing steps during manufacturing, operating or accident scenarios. I present three sample environments for in situ neutron diffraction studies that provide such crystallographic information and have been successfully commissioned and integrated into the user program of the High Pressure -- Preferred Orientation (HIPPO) diffractometer at the Los Alamos Neutron Science Center (LANSCE) user facility. I adapted a sample changer for reliable and fast automated texture measurements of multiple specimens. I built a creep furnace combining a 2700 N load frame with a resistive vanadium furnace, capable of temperatures up to 1000°C, and manipulated by a pair of synchronized rotation stages. This combination allows following deformation and temperature dependent texture and strain evolutions in situ. Utilizing the presented sample changer and creep furnace we studied pressure tubes made of Zr-2.5wt%Nb currently employed in CANDURTM nuclear reactors and proposed for future SCWRs, acting as the primary containment vessel of high temperature heavy water (D2O) inside the reactor core. The measured sample texture shows that upon traversing the phase transition, which proceeded according to the Burger orientation relationship, variant selection occurred during heating and cooling of the zirconium alloy. Experimental results of lattice strains depending on the crystallographic orientation can be used to calculate strain pole figures which grant insight into the three-dimensional mechanical response of a polycrystalline aggregate and represent an extremely powerful material model validation tool. Lastly, I developed a resistive graphite high-temperature furnace with sample motion for in situ crystal structure and texture measurements of nuclear materials at steady-state temperatures up to at least 2200°C. This permits in situ observation of e.g. phase transitions and coefficients of thermal expansion, as well as phase formation and texture development during solidification. Utilizing this apparatus, I investigated the carbothermic reduction of UO2 nanopowder forming uranium carbide, a promising Generation IV reactor fuel. The onset of the UO2 + 2C → UC + CO2 reaction was observed at 1440°C with the bulk portion being complete at 1500°C. I describe the novel synthesis for this nanoparticle UO2 powder, which closely imitates observed nano grains in partially burnt reactor fuels. Of the three opposing structure models reported for the non-quenchable cubic UC2 phase, stable between 1769°C and 2560°C, the NaCl-type structure according to Bowman is found to be correct. This is deemed major progress as the CaF2-type structure was used for recent thermal modeling of safety critical factors in nuclear reactors. A temperature dependent increase in density due to carbon diffusion has been observed and quantified. I provide first experimental data of an unspecified, reversible order-disorder transition in this delta-phase with its onset at ˜1800°C which is likely due to rotating C2 molecules in the sublattice.

Techno-functional differentiation of two vitamin B12 producing Lactobacillus plantarum strains: an elucidation for diverse future use.

PubMed

Bhushan, Bharat; Tomar, S K; Chauhan, Arun

2017-01-01

An appropriate selection of Lactobacillus strain (probiotic/starter/functional) on the basis of its techno-functional characteristics is required before developing a novel fermented functional food. We compared vitamin B 12 (B 12 , cobalamin) producing Lactobacillus plantarum isolates, BHM10 and BCF20, for functional (vitamin over-production, genomic insight to B 12 structural genes, and probiotic attributes) and technological [milks (skim and soy) fermentation and B 12 bio-fortification] characteristics. Addition of B 12 precursors (5-amonolevulinate and dimethylbenzimidazole) to cobalamin-free fermentation medium increased vitamin production in BHM10, BCF20, and DSM20016 (a positive standard) by 3.4-, 4.4-, and 3.86-folds, respectively. Three important B 12 structural genes were detected in L. plantarum species (strains BHM10 and BCF20) by PCR for the first time. The gene sequences were submitted to NCBI GenBank and found phylogenetically closer to respective sequences in B 12 producing Lactobacillus reuteri strains. During comparative probiotic testing, BCF20 showed significantly higher (p < 0.05 to p < 0.001) gastrointestinal tolerance and cell surface hydrophobicity (p < 0.05) than BHM10. Moreover, only BCF20 was found positive for BSH activity and also exhibited comparatively better antagonistic potential against potent pathogens. Conversely, high acid and bile susceptible strain BHM10 displayed significantly higher soy milk fermentation and resultant B 12 bio-fortification abilities during technological testing. Two B 12 quantification techniques, UFLC and competitive immunoassay, confirmed the in vitro and in situ bio-production of bio-available form of B 12 after BHM10 fermentation. Conclusively, techno-functional differentiation of two B 12 producing strains elucidates their diverse future use; BCF20 either for B 12 over-production (in vitro) or as a probiotic candidate, while BHM10 for cobalamin bio-fortification (in situ) in soy milk.