Combustion synthesis of advanced materials. [using in-situ infiltration technique

NASA Technical Reports Server (NTRS)

Moore, J. J.; Feng, H. J.; Perkins, N.; Readey, D. W.

1992-01-01

The combustion synthesis of ceramic-metal composites using an in-situ liquid infiltration technique is described. The effect of varying the reactants and their stoichiometry to provide a range of reactant and product species i.e. solids, liquids and gases, with varying physical properties e.g. thermal conductivity, on the microstructure and morphology of synthesized products is also described. Alternatively, conducting the combustion synthesis reaction in a reactive gas environment is also discussed, in which advantages can be gained from the synergistic effects of combustion synthesis and vapor phase transport. In each case, the effect of the presence or absence of gravity (density) driven fluid flow and vapor transport is discussed as is the potential for producing new and perhaps unique materials by conducting these SHS reactions under microgravity conditions.

Automatic programming for critical applications

NASA Technical Reports Server (NTRS)

Loganantharaj, Raj L.

1988-01-01

The important phases of a software life cycle include verification and maintenance. Usually, the execution performance is an expected requirement in a software development process. Unfortunately, the verification and the maintenance of programs are the time consuming and the frustrating aspects of software engineering. The verification cannot be waived for the programs used for critical applications such as, military, space, and nuclear plants. As a consequence, synthesis of programs from specifications, an alternative way of developing correct programs, is becoming popular. The definition, or what is understood by automatic programming, has been changed with our expectations. At present, the goal of automatic programming is the automation of programming process. Specifically, it means the application of artificial intelligence to software engineering in order to define techniques and create environments that help in the creation of high level programs. The automatic programming process may be divided into two phases: the problem acquisition phase and the program synthesis phase. In the problem acquisition phase, an informal specification of the problem is transformed into an unambiguous specification while in the program synthesis phase such a specification is further transformed into a concrete, executable program.

Highly Non-Linear Optical (NLO) organic crystals

NASA Technical Reports Server (NTRS)

Harris, J. Milton

1987-01-01

This research project involves the synthesis and characterization of organic materials having powerful nonlinear optical (NLO) properties and the growth of highly ordered crystals and monomolecular films of these materials. Research in four areas is discussed: theoretical design of new materials, characterization of NLO materials, synthesis of new materials and development of coupling procedures for forming layered films, and improvement of the techniques for vapor phase and solution phase growth of high quality organic crystals. Knowledge gained from these experiments will form the basis for experiments in the growth of these crystals.

Custom-designed nanomaterial libraries for testing metal oxide toxicity

PubMed Central

Pokhrel, Suman; Nel, André E.; Mädler, Lutz

2014-01-01

Conspectus Advances in aerosol technology over the past 10 years have provided methods that enable the generation and design of ultrafine nanoscale materials for different applications. The particles are produced combusting a precursor solution and its chemical reaction in the in the gas phase. Flame spray pyrolysis (FSP) is a highly versatile technique for single step and scalable synthesis of nanoscale materials. New innovations in particle synthesis using FSP technology and its precursor chemistry have enabled flexible dry synthesis of loosely-agglomerated highly crystalline ultrafine powders (porosity ≥ 90%) of binary, ternary and mixed binary or ternary oxides. The flame spray pyrolysis lies at the intersection of combustion science, aerosols technology and materials chemistry. The interdisciplinary research is not only inevitable but is becoming increasingly crucial in the design of nanoparticles (NPs) made in the gas phase. The increasing demand especially in the bio-applications for particles with specific material composition, high purity and crystallinity can be often fulfilled with the fast, single step FSP technique. PMID:23194152

Tolerance analysis program

NASA Technical Reports Server (NTRS)

Watson, H. K.

1971-01-01

Digital computer program determines tolerance values of end to end signal chain or flow path, given preselected probability value. Technique is useful in the synthesis and analysis phases of subsystem design processes.

Synthesis and characterization of polycrystalline CdSiP2

NASA Astrophysics Data System (ADS)

Bereznaya, S. A.; Korotchenko, Z. V.; Sarkisov, S. Yu; Korolkov, I. V.; Kuchumov, B. M.; Saprykin, A. I.; Atuchin, V. V.

2018-05-01

A modified method is proposed for the CdSiP2 compound synthesis from elemental starting components. The developed technique allows completing the synthesis process within 30 h. The phase and chemical composition of the synthesized material were confirmed by the x-ray diffraction analysis and scanning electron microscopy with energy-dispersive spectroscopy. The transparent crystal block sized 3 × 3 × 2 mm3 was cut from the polycrystalline ingot and characterized by optical methods.

Purification of biomaterials by phase partitioning

NASA Technical Reports Server (NTRS)

Harris, J. M.

1984-01-01

A technique which is particularly suited to microgravity environments and which is potentially more powerful than electrophoresis is phase partitioning. Phase partitioning is purification by partitioning between the two immiscible aqueous layers formed by solution of the polymers poly(ethylene glycol) and dextran in water. This technique proved to be very useful for separations in one-g but is limited for cells because the cells are more dense than the phase solutions thus tend to sediment to the bottom of the container before reaching equilibrium with the preferred phase. There are three phases to work in this area: synthesis of new polymers for affinity phase partitioning; development of automated apparatus for ground-based separations; and design of apparatus for performing simple phase partitioning space experiments, including examination of mechanisms for separating phases in the absence of gravity.

Combinatorial synthesis of phosphors using arc-imaging furnace

NASA Astrophysics Data System (ADS)

Ishigaki, Tadashi; Toda, Kenji; Yoshimura, Masahiro; Uematsu, Kazuyoshi; Sato, Mineo

2011-10-01

We have applied a novel 'melt synthesis technique' rather than a conventional solid-state reaction to rapidly synthesize phosphor materials. During a synthesis, the mixture of oxides or their precursors is melted by light pulses (10-60 s) in an arc-imaging furnace on a water-cooled copper hearth to form a globule of 1-5 mm diameter, which is then rapidly cooled by turning off the light. Using this method, we synthesized several phosphor compounds including Y3Al5O12:Ce(YAG) and SrAl2O4:Eu,Dy. Complex phosphor oxides are difficult to produce by conventional solid-state reaction techniques because of the slow reaction rates among solid oxides; as a result, the oxides form homogeneous compounds or solid solutions. On the other hand, melt reactions are very fast (10-60 s) and result in homogeneous compounds owing to rapid diffusion and mixing in the liquid phase. Therefore, melt synthesis techniques are suitable for preparing multi component homogeneous compounds and solid solutions.

Synthesis of an un-supported, high-flow ZSM-22 zeolite membrane

DOEpatents

Thoma, Steven G [Albuquerque, NM; Nenoff, Tina M [Albuquerque, NM

2006-10-10

Novel methods for synthesizing wholly un-supported, high-flow catalytic membranes consisting of 100% crystalline ZSM-22 crystals with no binder phase, having sufficient porosity to allow high Weight Hourly Space Velocities of feedstock to pass through without generating back pressure. The ZSM-22 membranes perform favorably to existing bulk ZSM-22 catalysts (e.g., via 1-butene conversion and selectivity). The method of membrane synthesis, based on Vapor Phase Transport, allows free-standing, binder-less membranes to be fabricated in varied geometries and sizes so that membranes can be tailor-made for particular geometries applications. The ZSM-22 precursor gel may be consolidated into a semi-cohesive body prior to vapor phase crystallization, for example, by uniaxial pressing. These crystalline membranes may be modified by ion exchange, pore ion exchange, framework exchange, synthesis modification techniques to incorporate other elements into the framework, such as K, H, Mg, Zn, V, Ga, and Pt.

Synthesis of nanostructured iron oxides and new magnetic ceramics using sol-gel and SPS techniques

NASA Astrophysics Data System (ADS)

Papynov, E. K.; Shichalin, O. O.; Belov, A. A.; Portnyagin, A. S.; Mayorov, V. Yu.; Gridasova, E. A.; Golub, A. V.; Nepomnyashii, A. S.; Tananaev, I. G.; Avramenko, V. A.

2017-02-01

The original way of synthesis of nanostructured iron oxides and based on them magnetic ceramics via sequential combination of sol-gel and SPS technologies has been suggested. High quality of nanostructured iron oxides is defined by porous structure (Sspec up to 47,3 n2/g) and by phase composition of mixed and individual crystal phases (γ-Fe2O3/Fe3O4 i α-Fe2O3), depending on synthesis conditions. High-temperature SPS consolidation of nanostructured hematite powder, resulting in magnetic ceramics of high mechanical strength (fracture strength 249 MPa) has been investigated. Peculiarities of change of phase composition and composite's microstructure in the range of SPS temperatures from 700 to 900 °C have been revealed. Magnetic properties have been studied and regularities of change of magnetization (Ms) and coercive force (Hc) values of the ceramics with respect to SPS sintering temperature have been described.

Microwave-assisted synthesis of medicinally relevant indoles.

PubMed

Patil, S A; Patil, R; Miller, D D

2011-01-01

Indoles represent an important structural class in medicinal chemistry with broad spectrum of biological activities. The synthesis of indoles, therefore, has attracted enormous attention from synthetic chemists. Microwave methods for the preparation of indole analogs have been developed to speed up the synthesis, therefore, microwave assisted organic synthesis (MAOS) in controlled conditions is an invaluable technique for medicinal chemistry. In this review, indole forming classical reactions such as Fischer, Madelung, Bischler-Mohlau, Batcho-Leimgruber, Hemetsberger-Knittel, Graebe-Ullmann, Diels-Alder and Wittig type reactions using microwave radiation has been summarized. In addition, metal mediated cyclizations along with solid phase synthesis of indoles have been discussed. © 2011 Bentham Science Publishers Ltd.

Student-Driven Design of Peptide Mimetics: Microwave-Assisted Synthesis of Peptoid Oligomers

ERIC Educational Resources Information Center

Pohl, Nicola L. B.; Kirshenbaum, Kent; Yoo, Barney; Schulz, Nathan; Zea, Corbin J.; Streff, Jennifer M.; Schwarz, Kimberly L.

2011-01-01

An experiment for the undergraduate organic laboratory is described in which peptide mimetic oligomers called "peptoids" are built stepwise on a solid-phase resin. Students employ two modern strategies to facilitate rapid multistep syntheses: solid-phase techniques to obviate the need for intermediate purifications and microwave irradiation to…

One Step Combustion Synthesis Of YAG:Ce Phosphor For Solid State Lighting

NASA Astrophysics Data System (ADS)

Yadav, Pooja; Gupta, K. Vijay Kumar; Muley, Aarti; Joshi, C. P.; Moharil, S. V.

2011-10-01

YAG:Ce is an important phosphor having applications in various fields ranging from solid state lighting to scintillation detectors. YAG phosphors doped with activators are mainly synthesized by solid state reaction techniques that require high sintering temperatures (above 1500°C) to eliminate YAM and YAP phases. Though several soft chemical routes have been explored for synthesis of YAG, most of these methods are complex and phase pure materials are not obtained in one step, but prolonged annealing at temperatures around 1000 C or above becomes necessary. One step combustion synthesis of YAG:Ce3+ and related phosphors carried out at 500 C furnace temperature is reported here. Activation with Ce3+ could be achieved during the synthesis without taking recourse to any post-combustion thermal treatment. LEDs prepared from the combustion synthesized YAG:Ce3+, exhibited properties comparable to those produced from the commercial phosphor.

SPS-RS technique for solid-phase “in situ” synthesis of biocompatible ZrO2 porous ceramics

NASA Astrophysics Data System (ADS)

Shichalin, O. O.; Medkov, M. A.; Grishchenko, D. N.; Mayorov, V. Yu; Fedorets, A. N.; Belov, A. A.; Golub, A. V.; Gridasova, E. A.; Papynov, E. K.

2018-02-01

The prospective method of spark plasma sintering-reaction synthesis (SPS-RS) for fabrication of ceramics based on ZrO2 and biocompatible with living tissue is presented. Nanostructured ceramics has high mechanical strength (more than 400 MPa) and controlled porosity depending on specified sintering conditions. Biocompatible phases Ca10(PO4)6(OH)2 are formed “in situ” during SPS sintering of ZrO2 powder due to chemical interaction of phosphate precursors preliminary introduced into the mixture. The effective method to improve (to develop) porous structure of bioceramics obtained by SPS or SPS-RS techniques using poreforming agent (carbon black) is proposed. Suggested original SPS-RS “in situ” technique provides fabrication of new ZrO2 ceramics containing biocompatible phosphate components and possessing unique structural and mechanical characteristics. Such ceramics is indispensable for bone-ceramic implants that are able to activate processes of osteogenesis during bone tissue recovery.

Silicon nanowire synthesis by a vapor-liquid-solid approach.

PubMed

Mao, Aaron; Ng, H T; Nguyen, Pho; McNeil, Melanie; Meyyappan, M

2005-05-01

Synthesis of silicon nanowires is studied by using a vapor-liquid-solid growth technique. Silicon tetrachloride reduction with hydrogen in the gas phase is used with gold serving as catalyst to facilitate growth. Only a narrow set of conditions of SiCl4 concentration and temperature yield straight nanowires. High concentrations and temperatures generally result in particulates, catalyst coverage and deactivation, and coatinglike materials.

Silicon nanowire synthesis by a vapor-liquid-solid approach

NASA Technical Reports Server (NTRS)

Mao, Aaron; Ng, H. T.; Nguyen, Pho; McNeil, Melanie; Meyyappan, M.

2005-01-01

Synthesis of silicon nanowires is studied by using a vapor-liquid-solid growth technique. Silicon tetrachloride reduction with hydrogen in the gas phase is used with gold serving as catalyst to facilitate growth. Only a narrow set of conditions of SiCl4 concentration and temperature yield straight nanowires. High concentrations and temperatures generally result in particulates, catalyst coverage and deactivation, and coatinglike materials.

Preparation and characterization of maghemite nanoparticles from mild steel for magnetically guided drug therapy.

PubMed

Kumar, Nitesh; Kulkarni, Kaustubh; Behera, Laxmidhar; Verma, Vivek

2017-08-01

Maghemite (γ-Fe 2 O 3 ) nanoparticles for therapeutic applications are prepared from mild steel but the existing synthesis technique is very cumbersome. The entire process takes around 100 days with multiple steps which lack proper understanding. In the current work, maghemite nanoparticles of cuboidal and spheroidal morphologies were prepared from mild steel chips by a novel cost effective oil reduction technique for magnetically guided intravascular drug delivery. The technique developed in this work yields isometric sized γ-Fe 2 O 3 nanoparticles in 6 h with higher saturation magnetization as compared to the existing similar solid state synthesis route. Mass and heat flow kinetics during the heating and quenching steps were studied with the help of Finite element simulations. Qualitative and quantitative analysis of the γ-Fe 2 O 3 phase is performed with the help of x-ray diffraction, transmission electron microscope and x-ray photoelectron spectroscopy. Mechanism for the α-Fe 2 O 3 (haematite) to γ-Fe 2 O 3 (maghemite) phase evolution during the synthesis process is also investigated. Maghemite (γ-Fe 2 O 3 ) nanoparticles were prepared bya novel cost effective oil reduction technique as mentioned below in the figure. The raw materials included mild steel chips which is one of the most abundant engineering materials. These particles can be used as ideal nanocarriers for targeted drug delivery through the vascular network.

Structure tracking aided design and synthesis of Li 3V 2(PO 4) 3 nanocrystals as high-power cathodes for lithium ion batteries

DOE PAGES

Wang, Liping; Bai, Jianming; Gao, Peng; ...

2015-07-30

In this study, preparing new electrode materials with synthetic control of phases and electrochemical properties is desirable for battery applications but hardly achievable without knowing how the synthesis reaction proceeds. Herein, we report on structure tracking-aided design and synthesis of single-crystalline Li 3V 2(PO 4) 3 (LVP) nanoparticles with extremely high rate capability. A comprehensive investigation was made to the local structural orderings of the involved phases and their evolution toward forming LVP phase using in situ/ex situ synchrotron X-ray and electron-beam diffraction, spectroscopy, and imaging techniques. The results shed light on the thermodynamics and kinetics of synthesis reactions andmore » enabled the design of a cost-efficient synthesis protocol to make nanocrystalline LVP, wherein solvothermal treatment is a crucial step leading to an amorphous intermediate with local structural ordering resembling that of LVP, which, upon calcination at moderate temperatures, rapidly transforms into the desired LVP phase. The obtained LVP particles are about 50 nm, coated with a thin layer of amorphous carbon and featured with excellent cycling stability and rate capability – 95% capacity retention after 200 cycles and 66% theoretical capacity even at a current rate of 10 C. The structure tracking based method we developed in this work offers a new way of designing battery electrodes with synthetic control of material phases and properties.« less

Persistent dopants and phase segregation in organolead mixed-halide perovskites

DOE PAGES

Rosales, Bryan A.; Men, Long; Cady, Sarah D.; ...

2016-07-25

Organolead mixed-halide perovskites such as CH 3NH 3PbX 3–aX' a (X, X' = I, Br, Cl) are interesting semiconductors because of their low cost, high photovoltaic power conversion efficiencies, enhanced moisture stability, and band gap tunability. Using a combination of optical absorption spectroscopy, powder X-ray diffraction (XRD), and, for the first time, 207Pb solid state nuclear magnetic resonance (ssNMR), we probe the extent of alloying and phase segregation in these materials. Because 207Pb ssNMR chemical shifts are highly sensitive to local coordination and electronic structure, and vary linearly with halogen electronegativity and band gap, this technique can provide the truemore » chemical speciation and composition of organolead mixed-halide perovskites. We specifically investigate samples made by three different preparative methods: solution phase synthesis, thermal annealing, and solid phase synthesis. 207Pb ssNMR reveals that nonstoichiometric dopants and semicrystalline phases are prevalent in samples made by solution phase synthesis. We show that these nanodomains are persistent after thermal annealing up to 200 °C. Further, a novel solid phase synthesis that starts from the parent, single-halide perovskites can suppress phase segregation but not the formation of dopants. Our observations are consistent with the presence of miscibility gaps and spontaneous spinodal decomposition of the mixed-halide perovskites at room temperature. This underscores how strongly different synthetic procedures impact the nanostructuring and composition of organolead halide perovskites. In conclusion, better optoelectronic properties and improved device stability and performance may be achieved through careful manipulation of the different phases and nanodomains present in these materials.« less

Persistent dopants and phase segregation in organolead mixed-halide perovskites

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

Rosales, Bryan A.; Men, Long; Cady, Sarah D.

Organolead mixed-halide perovskites such as CH 3NH 3PbX 3–aX' a (X, X' = I, Br, Cl) are interesting semiconductors because of their low cost, high photovoltaic power conversion efficiencies, enhanced moisture stability, and band gap tunability. Using a combination of optical absorption spectroscopy, powder X-ray diffraction (XRD), and, for the first time, 207Pb solid state nuclear magnetic resonance (ssNMR), we probe the extent of alloying and phase segregation in these materials. Because 207Pb ssNMR chemical shifts are highly sensitive to local coordination and electronic structure, and vary linearly with halogen electronegativity and band gap, this technique can provide the truemore » chemical speciation and composition of organolead mixed-halide perovskites. We specifically investigate samples made by three different preparative methods: solution phase synthesis, thermal annealing, and solid phase synthesis. 207Pb ssNMR reveals that nonstoichiometric dopants and semicrystalline phases are prevalent in samples made by solution phase synthesis. We show that these nanodomains are persistent after thermal annealing up to 200 °C. Further, a novel solid phase synthesis that starts from the parent, single-halide perovskites can suppress phase segregation but not the formation of dopants. Our observations are consistent with the presence of miscibility gaps and spontaneous spinodal decomposition of the mixed-halide perovskites at room temperature. This underscores how strongly different synthetic procedures impact the nanostructuring and composition of organolead halide perovskites. In conclusion, better optoelectronic properties and improved device stability and performance may be achieved through careful manipulation of the different phases and nanodomains present in these materials.« less

Modeling of reverberant room responses for two-dimensional spatial sound field analysis and synthesis.

PubMed

Bai, Mingsian R; Li, Yi; Chiang, Yi-Hao

2017-10-01

A unified framework is proposed for analysis and synthesis of two-dimensional spatial sound field in reverberant environments. In the sound field analysis (SFA) phase, an unbaffled 24-element circular microphone array is utilized to encode the sound field based on the plane-wave decomposition. Depending on the sparsity of the sound sources, the SFA stage can be implemented in two manners. For sparse-source scenarios, a one-stage algorithm based on compressive sensing algorithm is utilized. Alternatively, a two-stage algorithm can be used, where the minimum power distortionless response beamformer is used to localize the sources and Tikhonov regularization algorithm is used to extract the source amplitudes. In the sound field synthesis (SFS), a 32-element rectangular loudspeaker array is employed to decode the target sound field using pressure matching technique. To establish the room response model, as required in the pressure matching step of the SFS phase, an SFA technique for nonsparse-source scenarios is utilized. Choice of regularization parameters is vital to the reproduced sound field. In the SFS phase, three SFS approaches are compared in terms of localization performance and voice reproduction quality. Experimental results obtained in a reverberant room are presented and reveal that an accurate room response model is vital to immersive rendering of the reproduced sound field.

Synthesis of oligonucleotides on a soluble support

PubMed Central

2017-01-01

Oligonucleotides are usually prepared in lab scale on a solid support with the aid of a fully automated synthesizer. Scaling up of the equipment has allowed industrial synthesis up to kilogram scale. In spite of this, solution-phase synthesis has received continuous interest, on one hand as a technique that could enable synthesis of even larger amounts and, on the other hand, as a gram scale laboratory synthesis without any special equipment. The synthesis on a soluble support has been regarded as an approach that could combine the advantageous features of both the solution and solid-phase syntheses. The critical step of this approach is the separation of the support-anchored oligonucleotide chain from the monomeric building block and other small molecular reagents and byproducts after each coupling, oxidation and deprotection step. The techniques applied so far include precipitation, extraction, chromatography and nanofiltration. As regards coupling, all conventional chemistries, viz. phosphoramidite, H-phosphonate and phosphotriester strategies, have been attempted. While P(III)-based phosphoramidite and H-phosphonate chemistries are almost exclusively used on a solid support, the “outdated” P(V)-based phosphotriester chemistry still offers one major advantage for the synthesis on a soluble support; the omission of the oxidation step simplifies the coupling cycle. Several of protocols developed for the soluble-supported synthesis allow the preparation of both DNA and RNA oligomers of limited length in gram scale without any special equipment, being evidently of interest for research groups that need oligonucleotides in large amounts for research purposes. However, none of them has really tested at such a scale that the feasibility of their industrial use could be critically judged. PMID:28781703

Fast conventional Fmoc solid-phase peptide synthesis with HCTU.

PubMed

Hood, Christina A; Fuentes, German; Patel, Hirendra; Page, Karen; Menakuru, Mahendra; Park, Jae H

2008-01-01

1H-Benzotriazolium 1-[bis(dimethyl-amino)methylene]-5-chloro-hexafluorophosphate (1-),3-oxide (HCTU) is a nontoxic, nonirritating and noncorrosive coupling reagent. Seven biologically active peptides (GHRP-6, (65-74)ACP, oxytocin, G-LHRH, C-peptide, hAmylin(1-37), and beta-amyloid(1-42)) were synthesized with reaction times reduced to deprotection times of 3 min or less and coupling times of 5 min or less using HCTU as the coupling reagent. Expensive coupling reagents or special techniques were not used. Total peptide synthesis times were dramatically reduced by as much as 42.5 h (1.8 days) without reducing the crude peptide purities. It was shown that HCTU can be used as an affordable, efficient coupling reagent for fast Fmoc solid-phase peptide synthesis.

Photon induced facile synthesis and growth of CuInS2 absorber thin film for photovoltaic applications

NASA Astrophysics Data System (ADS)

Singh, Manjeet; Jiu, Jinting; Suganuma, Katsuaki

2016-04-01

In this paper, we demonstrate the use of high intensity pulsed light technique for the synthesis of phase pure CuInS2 (CIS) thin film at room temperature. The intense pulse of light is used to induce sintering of binary sulfides CuS and In2S3 to produce CIS phase without any direct thermal treatment. Light energy equivalent to the 706 mJ/cm2 is found to be the best energy to convert the CIS precursor film deposited at room temperature into CIS pure phase and well crystalline film. The CIS absorber film thus prepared is useful in making printed solar cell at room temperature on substrate with large area.

Insights into Metal Oxide and Zero-Valent Metal Nanocrystal Formation on Multiwalled Carbon Nanotube Surfaces during Sol-Gel Process.

PubMed

Das, Dipesh; Sabaraya, Indu V; Sabo-Attwood, Tara; Saleh, Navid B

2018-06-05

Carbon nanotubes are hybridized with metal crystals to impart multifunctionality into the nanohybrids (NHs). Simple but effective synthesis techniques are desired to form both zero-valent and oxides of different metal species on carbon nanotube surfaces. Sol-gel technique brings in significant advantages and is a viable technique for such synthesis. This study probes the efficacy of sol-gel process and aims to identify underlying mechanisms of crystal formation. Standard electron potential (SEP) is used as a guiding parameter to choose the metal species; i.e., highly negative SEP (e.g., Zn) with oxide crystal tendency, highly positive SEP (e.g., Ag) with zero-valent crystal-tendency, and intermediate range SEP (e.g., Cu) to probe the oxidation tendency in crystal formation are chosen. Transmission electron microscopy and X-ray diffraction are used to evaluate the synthesized NHs. Results indicate that SEP can be a reliable guide for the resulting crystalline phase of a certain metal species, particularly when the magnitude of this parameter is relatively high. However, for intermediate range SEP-metals, mix phase crystals can be expected. For example, Cu will form Cu₂O and zero-valent Cu crystals, unless the synthesis is performed in a reducing environment.

The Development of High Transition Temperature Superconducting Ceramic Thick Films and Wire Composites

DTIC Science & Technology

1991-12-02

number of protein or sugar agents were experimented with including Agar, pectin, carboxymethylcellulose, gelatin, alginic acid, xanthan gum , guar gum ...I) Introduction and Description of Scientific Goals 1 II) Material and Powder Synthesis 1 A) Freeze Dried Fabrication of Powders 1 B) Utilization of...composites. II). Material and Powder Synthesis The availability of a reliable technique for producing large quantities of phase pure, submicron powders

Carbon-based nanomaterial synthesis using nanosecond electrical discharges in immiscible layered liquids: n-heptane and water

NASA Astrophysics Data System (ADS)

Hamdan, Ahmad; Cha, Min Suk

2018-06-01

Plasmas in- or in-contact with liquids have been extensively investigated due to their high potential for a wide range of applications including, but not limited to, water treatment, material synthesis and functionalization, bio-medical applications, and liquid fuel reformation. Recently, we successfully developed a discharge using two immiscible liquids, having very different electrical permittivities, which could significantly intensify the electric field intensity. Here, we establish nanosecond discharges at the interface n-heptane-water (with respective relative dielectric permittivities of 2 and 80) to enable the synthesis of carbon-based nanomaterials. A characterization of the as-synthesized material and the annealed (500 °C) material, using various techniques (Fourier-transform, infra-red, scanning and transmission electron microscopes, etc), shows that the as-synthesized material is a mixture of two carbon-based phases: a crystalline phase (graphite like) embedded into a phase of hydrogenated amorphous carbon. The existence of two-phases may be explained by the non-homogeneity of the discharge that induces various chemical reactions in the plasma channel.

Synthesis and characterization of vanadiumoxidecatalysts supported on copper orthophosphates

NASA Astrophysics Data System (ADS)

Ouchabi, M.; Baalala, M.; Elaissi, A.; Loulidi, I.; Bensitel, M.

2017-03-01

Synthesis of a pure copper orthophosphate (CuP) prepared by Coprecipitation, and CuP modified by impregnation of vanadium (2-12 wt % of V2O5) have been carried out. The solids obtained were investigated as synthesized or after calcination by various physico-chemical techniques such as X-Ray Diffraction (XRD), Infrared Spectroscopy (IR), Thermogravimetric analysis (TGA), and differential thermal analysis (DTA). The results revealed that the solids V/CuP consisted of copper orthophosphate Cu3(PO4)2 as major phases, together with V2O5 as minor phase. The diffraction lines of V2O5 increase by increasing the vanadium content.

Method and apparatus for spur-reduced digital sinusoid synthesis

NASA Technical Reports Server (NTRS)

Zimmerman, George A. (Inventor); Flanagan, Michael J. (Inventor)

1995-01-01

A technique for reducing the spurious signal content in digital sinusoid synthesis is presented. Spur reduction is accomplished through dithering both amplitude and phase values prior to word-length reduction. The analytical approach developed for analog quantization is used to produce new bounds on spur performance in these dithered systems. Amplitude dithering allows output word-length reduction without introducing additional spurs. Effects of periodic dither similar to that produced by a pseudo-noise (PN) generator are analyzed. This phase dithering method provides a spur reduction of 6(M + 1) dB per phase bit when the dither consists of M uniform variates. While the spur reduction is at the expense of an increase in system noise, the noise power can be made white, making the power spectral density small. This technique permits the use of a smaller number of phase bits addressing sinusoid look-up tables, resulting in an exponential decrease in system complexity. Amplitude dithering allows the use of less complicated multipliers and narrower data paths in purely digital applications, as well as the use of coarse-resolution, highly-linear digital-to-analog converters (DAC's) to obtain spur performance limited by the DAC linearity rather than its resolution.

Solid phase monofunctionalization of gold nanoparticles using ionic exchange resin as polymer support.

PubMed

Zou, Jianhua; Dai, Qiu; Wang, Jinhai; Liu, Xiong; Huo, Qun

2007-07-01

A solid phase modification method using anionic exchange resin as polymer support was developed for the synthesis of monofunctional gold nanoparticles. Based on a "catch and release" mechanism to control the number of functional groups attached to the nanoparticle surface, bifunctional thiol ligands with a carboxylic acid end group were first immobilized at a controlled density on anionic exchange resin through electrostatic interactions. Gold nanoparticles were then immobilized to the anionic exchange resin by a one-to-one place exchange reaction between resin-bound thiol ligands and butanethiol-protected gold nanoparticles in solution. After cleaving off from the resin under mild conditions, gold nanoparticles with a single carboxyl group attached to the surface were obtained as the major product. Experimental conditions such as the solvents used for ligand loading and solid phase place exchange reaction, and the loading density of the ligands, were found to play a critical role towards the successful synthesis of monofunctional nanoparticles. Overall, the noncovalent bond-based ligand immobilization technique reported here greatly simplified the process of solid phase monofunctionalization of nanoparticles compared to a previously reported covalent bond-based ligand immobilization technique.

NBIT Program Phase I (2007-2010). Part 1, Chapters 1 Through 4

DTIC Science & Technology

2009-08-27

2 schematically shows the sample prepared before hydrothermal synthesis . The thin layer of Zn was convered to ZnO nanowires during hydrothermal ... Nanoparticle -Based Magnetically Amplified Surface Plasmon Resonance (Mag-SPR) Techniques; Jinwoo Cheon (Yonsei University, Korea) and A. Paul...Ion; Chapter 3 ? Ultra-Sensitive Biological Detection via Nanoparticle -Based Magnetically Amplified Surface Plasmon Resonance (Mag-SPR) Techniques

Hydrophobic benzyl amines as supports for liquid-phase C-terminal amidated peptide synthesis: application to the preparation of ABT-510.

PubMed

Matsumoto, Emiko; Fujita, Yuko; Okada, Yohei; Kauppinen, Esko I; Kamiya, Hidehiro; Chiba, Kazuhiro

2015-09-01

C-terminal amidation is one of the most common modification of peptides and frequently found in bioactive peptides. However, the C-terminal modification must be creative, because current chemical synthetic techniques of peptides are dominated by the use of C-terminal protecting supports. Therefore, it must be carried out after the removal of such supports, complicating reaction work-up and product isolation. In this context, hydrophobic benzyl amines were successfully added to the growing toolbox of soluble tag-assisted liquid-phase peptide synthesis as supports, leading to the total synthesis of ABT-510 (2). Although an ethyl amide-forming type was used in the present work, different types of hydrophobic benzyl amines could also be simply designed and prepared through versatile reductive aminations in one step. The standard acidic treatment used in the final deprotection step for peptide synthesis gave the desired C-terminal secondary amidated peptide with no epimerization. Copyright © 2015 European Peptide Society and John Wiley & Sons, Ltd.

Corona-assisted flame synthesis of ultrafine titania particles

NASA Astrophysics Data System (ADS)

Vemury, Srinivas; Pratsinis, Sotiris E.

1995-06-01

Synthesis of ultrafine titania particles is investigated in a diffusion flame aerosol reactor in the presence of a gaseous electric discharge (corona) created by two needle electrodes. The corona wind flattens the flame and reduces the particle residence time at high temperatures, resulting in smaller primary particle sizes and lower level of crystallinity. Increasing the applied potential from 5 to 8 kV reduces the particle size from 50 to 25 nm and the rutile content from 20 to 8 wt %. Coronas provide a clean and simple technique that facilitates gas phase synthesis of nanosized materials with controlled size and crystallinity.

The use of solid supports to generate nucleic acid carriers.

PubMed

Unciti-Broceta, Asier; Díaz-Mochón, Juan José; Sánchez-Martín, Rosario M; Bradley, Mark

2012-07-17

Nucleic acids are the foundation stone of all cellular processes. Consequently, the use of DNA or RNA to treat genetic and acquired disorders (so called gene therapy) offers enormous potential benefits. The restitution of defective genes or the suppression of malignant genes could target a range of diseases, including cancers, inherited diseases (cystic fibrosis, muscular dystrophy, etc.), and viral infections. However, this strategy has a major barrier: the size and charge of nucleic acids largely restricts their transit into eukaryotic cells. Potential strategies to solve this problem include the use of a variety of natural and synthetic nucleic acid carriers. Driven by the aim and ambition of translating this promising therapeutic approach into the clinic, researchers have been actively developing advanced delivery systems for nucleic acids for more than 20 years. A decade ago we began our investigations of solid-phase techniques to construct families of novel nucleic acid carriers for transfection. We envisaged that the solid-phase synthesis of polycationic dendrimers and derivatized polyamimes would offer distinct advantages over solution phase techniques. Notably in solid phase synthesis we could take advantage of mass action and streamlined purification procedures, while simplifying the handling of compounds with high polarities and plurality of functional groups. Parallel synthesis methods would also allow rapid access to libraries of compounds with improved purities and yields over comparable solution methodologies and facilitate the development of structure activity relationships. We also twisted the concept of the solid-phase support on its head: we devised miniaturized solid supports that provided an innovative cell delivery vehicle in their own right, carrying covalently conjugated cargos (biomolecules) into cells. In this Account, we summarize the main outcomes of this series of chemically related projects.

Blind separation of overlapping partials in harmonic musical notes using amplitude and phase reconstruction

NASA Astrophysics Data System (ADS)

de León, Jesús Ponce; Beltrán, José Ramón

2012-12-01

In this study, a new method of blind audio source separation (BASS) of monaural musical harmonic notes is presented. The input (mixed notes) signal is processed using a flexible analysis and synthesis algorithm (complex wavelet additive synthesis, CWAS), which is based on the complex continuous wavelet transform. When the harmonics from two or more sources overlap in a certain frequency band (or group of bands), a new technique based on amplitude similarity criteria is used to obtain an approximation to the original partial information. The aim is to show that the CWAS algorithm can be a powerful tool in BASS. Compared with other existing techniques, the main advantages of the proposed algorithm are its accuracy in the instantaneous phase estimation, its synthesis capability and that the only input information needed is the mixed signal itself. A set of synthetically mixed monaural isolated notes have been analyzed using this method, in eight different experiments: the same instrument playing two notes within the same octave and two harmonically related notes (5th and 12th intervals), two different musical instruments playing 5th and 12th intervals, two different instruments playing non-harmonic notes, major and minor chords played by the same musical instrument, three different instruments playing non-harmonically related notes and finally the mixture of a inharmonic instrument (piano) and one harmonic instrument. The results obtained show the strength of the technique.

Nanofibers and their applications in tissue engineering

PubMed Central

Vasita, Rajesh; Katti, Dhirendra S

2006-01-01

Developing scaffolds that mimic the architecture of tissue at the nanoscale is one of the major challenges in the field of tissue engineering. The development of nanofibers has greatly enhanced the scope for fabricating scaffolds that can potentially meet this challenge. Currently, there are three techniques available for the synthesis of nanofibers: electrospinning, self-assembly, and phase separation. Of these techniques, electrospinning is the most widely studied technique and has also demonstrated the most promising results in terms of tissue engineering applications. The availability of a wide range of natural and synthetic biomaterials has broadened the scope for development of nanofibrous scaffolds, especially using the electrospinning technique. The three dimensional synthetic biodegradable scaffolds designed using nanofibers serve as an excellent framework for cell adhesion, proliferation, and differentiation. Therefore, nanofibers, irrespective of their method of synthesis, have been used as scaffolds for musculoskeletal tissue engineering (including bone, cartilage, ligament, and skeletal muscle), skin tissue engineering, vascular tissue engineering, neural tissue engineering, and as carriers for the controlled delivery of drugs, proteins, and DNA. This review summarizes the currently available techniques for nanofiber synthesis and discusses the use of nanofibers in tissue engineering and drug delivery applications. PMID:17722259

Nonequilibrium synthesis of NbAl3 and Nb-Al-V alloys by laser cladding. I - Microstructure evolution

NASA Technical Reports Server (NTRS)

Sircar, S.; Chattopadhyay, K.; Mazumder, J.

1992-01-01

The evolution of the microstructure in NbAl3 synthesized by a laser cladding technique (a rapid solidification process, with cooling rates up to 10 exp 6 C/sec) is investigated, and the phases are identified using convergent beam electron diffraction. Two new metastable phases were identified and characterized in detail. The effect of adding V on the final microstructure was also investigated, and the various phase chemistries and the partitioning of different elements into different phases were studied.

Combinatorial synthesis of phosphors using arc-imaging furnace

PubMed Central

Ishigaki, Tadashi; Toda, Kenji; Yoshimura, Masahiro; Uematsu, Kazuyoshi; Sato, Mineo

2011-01-01

We have applied a novel ‘melt synthesis technique’ rather than a conventional solid-state reaction to rapidly synthesize phosphor materials. During a synthesis, the mixture of oxides or their precursors is melted by light pulses (10–60 s) in an arc-imaging furnace on a water-cooled copper hearth to form a globule of 1–5 mm diameter, which is then rapidly cooled by turning off the light. Using this method, we synthesized several phosphor compounds including Y3Al5O12:Ce(YAG) and SrAl2O4:Eu,Dy. Complex phosphor oxides are difficult to produce by conventional solid-state reaction techniques because of the slow reaction rates among solid oxides; as a result, the oxides form homogeneous compounds or solid solutions. On the other hand, melt reactions are very fast (10–60 s) and result in homogeneous compounds owing to rapid diffusion and mixing in the liquid phase. Therefore, melt synthesis techniques are suitable for preparing multi component homogeneous compounds and solid solutions. PMID:27877432

Evaluation of substitution monopole models for tire noise sound synthesis

NASA Astrophysics Data System (ADS)

Berckmans, D.; Kindt, P.; Sas, P.; Desmet, W.

2010-01-01

Due to the considerable efforts in engine noise reduction, tire noise has become one of the major sources of passenger car noise nowadays and the demand for accurate prediction models is high. A rolling tire is therefore experimentally characterized by means of the substitution monopole technique, suiting a general sound synthesis approach with a focus on perceived sound quality. The running tire is substituted by a monopole distribution covering the static tire. All monopoles have mutual phase relationships and a well-defined volume velocity distribution which is derived by means of the airborne source quantification technique; i.e. by combining static transfer function measurements with operating indicator pressure measurements close to the rolling tire. Models with varying numbers/locations of monopoles are discussed and the application of different regularization techniques is evaluated.

Synthesis and measurement of ultrafast waveforms from five discrete optical harmonics.

PubMed

Chan, Han-Sung; Hsieh, Zhi-Ming; Liang, Wei-Hong; Kung, A H; Lee, Chao-Kuei; Lai, Chien-Jen; Pan, Ru-Pin; Peng, Lung-Han

2011-03-04

Achieving the control of light fields in a manner similar in sophistication to the control of electromagnetic fields in the microwave and radiofrequency regimes has been a major challenge in optical physics research. We manipulated the phase and amplitude of five discrete harmonics spanning the blue to mid-infrared frequencies to produce instantaneous optical fields in the shape of square, sawtooth, and subcycle sine and cosine pulses at a repetition rate of 125 terahertz. Furthermore, we developed an all-optical shaper-assisted linear cross-correlation technique to retrieve these fields and thereby verified their shapes and confirmed the critical role of carrier-envelope phase in Fourier synthesis of optical waveforms.

Musical sound analysis/synthesis using vector-quantized time-varying spectra

NASA Astrophysics Data System (ADS)

Ehmann, Andreas F.; Beauchamp, James W.

2002-11-01

A fundamental goal of computer music sound synthesis is accurate, yet efficient resynthesis of musical sounds, with the possibility of extending the synthesis into new territories using control of perceptually intuitive parameters. A data clustering technique known as vector quantization (VQ) is used to extract a globally optimum set of representative spectra from phase vocoder analyses of instrument tones. This set of spectra, called a Codebook, is used for sinusoidal additive synthesis or, more efficiently, for wavetable synthesis. Instantaneous spectra are synthesized by first determining the Codebook indices corresponding to the best least-squares matches to the original time-varying spectrum. Spectral index versus time functions are then smoothed, and interpolation is employed to provide smooth transitions between Codebook spectra. Furthermore, spectral frames are pre-flattened and their slope, or tilt, extracted before clustering is applied. This allows spectral tilt, closely related to the perceptual parameter ''brightness,'' to be independently controlled during synthesis. The result is a highly compressed format consisting of the Codebook spectra and time-varying tilt, amplitude, and Codebook index parameters. This technique has been applied to a variety of harmonic musical instrument sounds with the resulting resynthesized tones providing good matches to the originals.

The modeling and synthesis of nanodiamonds by laser ablation of graphite and diamond-like carbon in liquid-confined ambient

NASA Astrophysics Data System (ADS)

Basso, L.; Gorrini, F.; Bazzanella, N.; Cazzanelli, M.; Dorigoni, C.; Bifone, A.; Miotello, A.

2018-01-01

Nanodiamonds have attracted considerable interest for their potential applications in quantum computation, sensing, and bioimaging. However, synthesis of nanodiamonds typically requires high pressures and temperatures, and is still a challenge. Here, we demonstrate production of nanodiamonds by pulsed laser ablation of graphite and diamond-like carbon in water. Importantly, this technique enables production of nanocrystalline diamonds at room temperature and standard pressure conditions. Moreover, we propose a method for the purification of nanodiamonds from graphitic and amorphous carbon phases that do not require strong acids and harsh chemical conditions. Finally, we present a thermodynamic model that describes the formation of nanodiamonds during pulsed laser ablation. We show that synthesis of the crystalline phase is driven by a graphite-liquid-diamond transition process that occurs at the extreme thermodynamic conditions reached inside the ablation plume.

Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03217a Click here for additional data file.

PubMed Central

Crawford, Deborah; Casaban, José; Haydon, Robert; Giri, Nicola; McNally, Tony

2015-01-01

Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)2(PPh3)2 as well as the commercially important metal organic frameworks (MOFs) Cu3(BTC)2 (HKUST-1), Zn(2-methylimidazolate)2 (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h–1 rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3–4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h–1. The space time yields (STYs) for these methods of up to 144 × 103 kg per m3 per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally. PMID:29308131

Fast synthesis and consolidation of porous FeAl by pressureless Spark Plasma Sintering

NASA Astrophysics Data System (ADS)

Dudina, D. V.; Brester, A. E.; Anisimov, A. G.; Bokhonov, B. B.; Legan, M. A.; Novoselov, A. N.; Skovorodin, I. N.; Uvarov, N. F.

2017-07-01

We report one-step fast synthesis and consolidation of iron aluminide FeAl of high open porosity by pressureless reactive Spark Plasma Sintering (SPS). The starting material of the Fe-40at.%Al composition was a mixture of an iron powder with an average particle diameter of 4 μm and an aluminum powder with an average particle diameter of 6 μm. The rationale behind the choice of the SPS as a processing technique and fine and comparable sizes of the two reactants for the synthesis of high-open porosity FeAl was realization of fast full chemical conversion of Fe and Al into single-phase FeAl reducing the time available for the compact shrinkage. According to the XRD phase analysis, single-phase FeAl compacts formed after SPS at 800 and 900°C. These compacts had open porosities of 41 and 46%, respectively. The transverse rupture strength of the compacts sintered at 700-900°C was found to change little with the sintering temperature in the selected range.

A library synthesis of 4-hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester derivatives as anti-tumor agents.

PubMed

Hayakawa, Ichiro; Shioya, Rieko; Agatsuma, Toshinori; Furukawa, Hidehiko; Naruto, Shunji; Sugano, Yuichi

2004-09-06

As a result of a hit-to-lead program using a technique of solution-phase parallel synthesis, a highly potent (2,4-dimethoxyphenyl)-[6-(3-fluorophenyl)-4-hydroxy-3-methylbenzofuran-2-yl]methanone (15b) was synthesized as an optimized derivative of 4-hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester (1), which was discovered as a screening hit from small-molecule libraries and exhibited selective cytotoxicity against a tumorigenic cell line.

Changing vacancy balance in ZnO by tuning synthesis between zinc/oxygen lean conditions

NASA Astrophysics Data System (ADS)

Venkatachalapathy, Vishnukanthan; Galeckas, Augustinas; Zubiaga, Asier; Tuomisto, Filip; Kuznetsov, Andrej Yu.

2010-08-01

The nature of intrinsic defects in ZnO films grown by metal organic vapor phase epitaxy was studied by positron annihilation and photoluminescence spectroscopy techniques. The supply of Zn and O during the film synthesis was varied by applying different growth temperatures (325-485 °C), affecting decomposition of the metal organic precursors. The microscopic identification of vacancy complexes was derived from a systematic variation in the defect balance in accordance with Zn/O supply trends.

Product-oriented Software Certification Process for Software Synthesis

NASA Technical Reports Server (NTRS)

Nelson, Stacy; Fischer, Bernd; Denney, Ewen; Schumann, Johann; Richardson, Julian; Oh, Phil

2004-01-01

The purpose of this document is to propose a product-oriented software certification process to facilitate use of software synthesis and formal methods. Why is such a process needed? Currently, software is tested until deemed bug-free rather than proving that certain software properties exist. This approach has worked well in most cases, but unfortunately, deaths still occur due to software failure. Using formal methods (techniques from logic and discrete mathematics like set theory, automata theory and formal logic as opposed to continuous mathematics like calculus) and software synthesis, it is possible to reduce this risk by proving certain software properties. Additionally, software synthesis makes it possible to automate some phases of the traditional software development life cycle resulting in a more streamlined and accurate development process.

Synthesis of Ge-nanoparticles in organic solution

NASA Astrophysics Data System (ADS)

Pugsley, Andrew James

Much interest is focused on the synthesis of semiconductor particles from organic solution, in order to provide luminescent tracers for biological assays. However, group IV semiconductors have been largely neglected be cause of the lack of suitable nanoparticle formation reactions by solution-phase chemistries. A potentially useful new route to solution-based synthesis of nanocrystalline-Si,Ge involves the reaction between Zintl phases (NaSi, Mg 2Ge) that formally contain anionic semiconducting group species (Si-, Ge4-) and liquid phase SiCU, GeCU, etc. Luminescent nanoparticles formed by these reactions in organic solvents (e.g. diglyme) have been decribed in work from the Kauzlarich group at UC Davis (California, USA). The aim of this project has been to characterise the structural chemistry and luminescent properties of the products of the reaction, as well as following the course of the reaction in situ via synchrotron measurements. The product of the reaction has been characterised by TEM and x-ray absorption spectroscopy as well as other techniques. In order to analyse the x-ray absorption spectroscopy data, a number of model compounds have been studied, including the precursor material which was previously uncharacterised by this technique. An in situ reaction cell has been designed and built and used at a number of synchrotron beamlines to follow the course of the reaction. It has been found that the presence of even low concentrations of water can greatly affect the formation reaction, this is described herein.

Creating wavelet-based models for real-time synthesis of perceptually convincing environmental sounds

NASA Astrophysics Data System (ADS)

Miner, Nadine Elizabeth

1998-09-01

This dissertation presents a new wavelet-based method for synthesizing perceptually convincing, dynamic sounds using parameterized sound models. The sound synthesis method is applicable to a variety of applications including Virtual Reality (VR), multi-media, entertainment, and the World Wide Web (WWW). A unique contribution of this research is the modeling of the stochastic, or non-pitched, sound components. This stochastic-based modeling approach leads to perceptually compelling sound synthesis. Two preliminary studies conducted provide data on multi-sensory interaction and audio-visual synchronization timing. These results contributed to the design of the new sound synthesis method. The method uses a four-phase development process, including analysis, parameterization, synthesis and validation, to create the wavelet-based sound models. A patent is pending for this dynamic sound synthesis method, which provides perceptually-realistic, real-time sound generation. This dissertation also presents a battery of perceptual experiments developed to verify the sound synthesis results. These experiments are applicable for validation of any sound synthesis technique.

Synthesis and characterization of nanostructured titanium carbide for fuel cell applications

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

Singh, Paviter; Singh, Harwinder; Singh, Bikramjeet

2016-04-13

Titanium carbide (TiC) nanoparticles have been successfully synthesized by carbo-thermic reaction of titanium and acetone at 800 °C. This method is relatively low temperature synthesis route. It can be used for large scale production of TiC. The synthesized nanoparticles have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and differential thermal analyzer (DTA) techniques. XRD analysis confirmed the formation of single phase TiC. XRD analysis confirmed that the particles are spherical in shape with an average particle size of 13 nm. DTA analysis shows that the phase is stable upto 900 °C and the material can be used formore » high temperature applications.« less

Static inverter with synchronous output waveform synthesized by time-optimal-response feedback

NASA Technical Reports Server (NTRS)

Kernick, A.; Stechschulte, D. L.; Shireman, D. W.

1976-01-01

Time-optimal-response 'bang-bang' or 'bang-hang' technique, using four feedback control loops, synthesizes static-inverter sinusoidal output waveform by self-oscillatory but yet synchronous pulse-frequency-modulation (SPFM). A single modular power stage per phase of ac output entails the minimum of circuit complexity while providing by feedback synthesis individual phase voltage regulation, phase position control and inherent compensation simultaneously for line and load disturbances. Clipped sinewave performance is described under off-limit load or input voltage conditions. Also, approaches to high power levels, 3-phase arraying and parallel modular connection are given.

A comparative study of the properties of five-layered Aurivillius oxides A2Bi4Ti5O18 (A = Ba, Pb, and Sr) synthesized by different wet chemical routes

NASA Astrophysics Data System (ADS)

Dubey, Shivangi; Subohi, Oroosa; Kurchania, Rajnish

2018-07-01

This paper reports the detailed study of the effect of different wet chemical synthesis routes (solution combustion, co-precipitation, and sol-gel route) on the microstructure, phase formation, dielectric, electrical, and ferroelectric properties of five-layered Aurivillius oxides: A2Bi4Ti5O18 (A = Ba, Pb, and Sr). Different synthesis parameters like the precursors used, synthesis temperature, and reaction time affects the morphology of the ceramics. Microstructure in turn influences the dielectric and ferroelectric properties. It was observed that the sol-gel-synthesized ceramics possess higher dielectric constant and remanent polarization, low dielectric loss due to lower conductivity in these samples as a result of higher density in these compounds as compared to those synthesized by other wet chemical synthesis routes such as solution combustion route and co-precipitation technique. The XRD data are used for phase analysis and surface morphology is studied using SEM images. Dielectric and electrical properties are investigated as a function of frequency and temperature.

The 3-5 semiconductor solid solution single crystal growth. [low gravity float zone growth experiments using gallium indium antimonides and cadmium tellurides

NASA Technical Reports Server (NTRS)

Gertner, E. R.

1980-01-01

Techniques used for liquid and vapor phase epitaxy of gallium indium arsenide are described and the difficulties encountered are examined. Results show that the growth of bulk III-V solid solution single crystals in a low gravity environment will not have a major technological impact. The float zone technique in a low gravity environment is demonstrated using cadmium telluride. It is shown that this approach can result in the synthesis of a class of semiconductors that can not be grown in normal gravity because of growth problems rooted in the nature of their phase diagrams.

Comparison of characteristics of hydroxyapatite powders synthesized from cuttlefish bone via precipitation and ball milling techniques

NASA Astrophysics Data System (ADS)

Faksawat, K.; Kaewwiset, W.; Limsuwan, P.; Naemchanthara, K.

2017-09-01

The aim of this work was to compare characteristics of hydroxyapatite synthesized by precipitation and ball milling techniques. The cuttlefish bone powder was a precursor in calcium source and the di ammonium hydrogen orthophosphate powders was a precursor in phosphate source. The hydroxyapatite was synthesized by the both techniques such as precipitation and ball milling techniques. The phase formation, chemical structure and morphology of the both hydroxyapatite powders have been examined by X-ray diffractometer (XRD), Fourier transform infrared spectroscope (FTIR) and field emission scanning electron microscope (FESEM), respectively. The results show that the hydroxyapatite synthesized by precipitation technique formed hydroxyapatite phase slower than the hydroxyapatite synthesized by ball milling technique. The FTIR results show the chemical structures of sample in both techniques are similar. The morphology of the hydroxyapatite from the both techniques were sphere like shapes and particle size was about in nano scale. The average particle size of the hydroxyapatite by ball milling technique was less than those synthesized by precipitation technique. This experiment indicated that the ball milling technique take time less than the precipitation technique in hydroxyapatite synthesis.

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.

Synthesis and Characterization of Quenched and Crystalline Phases: Q-Carbon, Q-BN, Diamond and Phase-Pure c-BN

NASA Astrophysics Data System (ADS)

Bhaumik, Anagh; Narayan, Jagdish

2018-04-01

We report the synthesis and characterization of quenched (Q-carbon and Q-BN) and crystalline (diamond and c-BN) phases using a non-equilibrium technique. These phases are formed as a result of the melting and subsequent quenching of amorphous carbon and nanocrystalline h-BN in a super undercooled state by using high-power nanosecond laser pulses. Pulsed laser annealing also leads to the formation of nanoneedles, microneedles and single-crystal thin films of diamond and c-BN. This formation is dependent on the nucleation and growth times, which are controlled by laser energy density and thermal conductivities of substrate and as-deposited thin film. The diamond nuclei present in the Q-carbon structure ( 80% sp 3) can also be grown to larger sizes using the equilibrium hot filament chemical vapor deposition process. The texture of diamond and c-BN crystals is <111> under epitaxial growth and <110> under rapid unseeded crystallization. Our nanosecond laser processing opens up a roadmap to the fabrication of novel phases on heat-sensitive substrates.

Combined Theoretical and in Situ Scattering Strategies for Optimized Discovery and Recovery of High-Pressure Phases: A Case Study of the GaN–Nb 2 O 5 System

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

Woerner, William R.; Qian, Guang-Rui; Oganov, Artem R.

2016-04-04

The application of pressure in solid-state synthesis provides a route for the creation of new and exciting materials. However, the onerous nature of high-pressure techniques limits their utility in materials discovery. The systematic search for novel oxynitrides—semiconductors for photocatalytic overall water splitting—is a representative case where quench high-pressure synthesis is useful and necessary in order to obtain target compounds. We utilize state of the art crystal structure prediction theory (USPEX) and in situ synchrotron-based X-ray scattering to speed up the discovery and optimization of novel compounds using high-pressure synthesis. Using this approach, two novel oxynitride phases were discovered in themore » GaN–Nb2O5 system. The (Nb2O5)0.84:(NbO2)0.32:(GaN)0.82 rutile structured phase was formed at 1 GPa and 900 °C and gradually transformed to a α-PbO2-related structure above 2.8 GPa and 1000 °C. The low-pressure rutile type phase was found to have a direct optical band gap of 0.84 eV and an indirect gap of 0.51 eV.« less

Combined Theoretical and in Situ Scattering Strategies for Optimized Discovery and Recovery of High-Pressure Phases: A Case Study of the GaN–Nb 2O 5 System

DOE PAGES

Woerner, William R.; Qian, Guang-Rui; Oganov, Artem R.; ...

2016-03-22

The application of pressure in solid-state synthesis provides a route for the creation of new and exciting materials. However, the onerous nature of high-pressure techniques limits their utility in materials discovery. The systematic search for novel oxynitrides—semiconductors for photocatalytic overall water splitting—is a representative case where quench high-pressure synthesis is useful and necessary in order to obtain target compounds. In this paper, we utilize state of the art crystal structure prediction theory (USPEX) and in situ synchrotron-based X-ray scattering to speed up the discovery and optimization of novel compounds using high-pressure synthesis. Using this approach, two novel oxynitride phases weremore » discovered in the GaN–Nb 2O 5 system. The (Nb 2O 5) 0.84:(NbO 2) 0.32:(GaN) 0.82 rutile structured phase was formed at 1 GPa and 900°C and gradually transformed to a α-PbO 2-related structure above 2.8 GPa and 1000°C. The low-pressure rutile type phase was found to have a direct optical band gap of 0.84 eV and an indirect gap of 0.51 eV.« less

Thyrotropin-Releasing Hormone Loaded and Chitosan Engineered Polymeric Nanoparticles: Towards Effective Delivery of Neuropeptides.

PubMed

Kaur, Sarabjit; Bhararia, Avani; Sharma, Krishna; Mittal, Sherry; Jain, Rahul; Wangoo, Nishima; Sharma, Rohit K

2016-05-01

Thyrotropin-Releasing Hormone (TRH), a tripeptide amide with molecular formula L-pGlu-L-His-L- Pro-NH2, is used in the treatment of brain/spinal injury and certain central nervous system (CNS) disorders, including schizophrenia, Alzheimer's disease, epilepsy, depression, shock and ischemia due to its profound effects on the CNS. However, TRH's therapeutic activity is severely hampered because of instability and hydrophilicity owing to its peptidic nature which results into ineffective penetration into the blood brain barrier. In the present study, we report the synthesis and stability studies of novel chitosan engineered TRH encapsulated poly(lactide-co-glycolide) (PLGA) based nanoformulation. The aim of such an encapsulation is to allow effective delivery of TRH in biological systems as the peptidase degrade naked TRH. The synthesis of TRH was carried out manually in solution phase followed by its encapsulation using PLGA to form polymeric nanoparticles (NPs) via nanoprecipitation technique. Different parameters such as type of organic phase, concentration of stabilizer, ratio of organic phase and aqueous phase, rate of addition of organic phase were optimized, tested and evaluated for particle size, encapsulation efficiency, and stability of NPs. The TRH-PLGA NPs were then surface modified with chitosan to achieve positive surface charge rendering them potential membrane penetrating agents. PLGA, PLGA-TRH, Chitosan-PLGA and Chitosan-PLGA-TRH NPs were characterized and analyzed using Dynamic Light Scattering (DLS), Transmissiom Electron Microscopy (TEM) and Infra-red spectroscopic techniques.

Precursor routes to quaternary intermetallics: Synthesis, crystal structure, and physical properties of clathrate-II Cs8Na16Al24Si112

NASA Astrophysics Data System (ADS)

Wei, Kaya; Dong, Yongkwan; Nolas, George S.

2016-05-01

A new quaternary clathrate-II composition, Cs8Na16Al24Si112, was synthesized by kinetically controlled thermal decomposition (KCTD) employing both NaSi and NaAlSi as the precursors and CsCl as a reactive flux. The crystal structure and composition of Cs8Na16Al24Si112 were investigated using both Rietveld refinement and elemental analysis, and the temperature dependent transport properties were investigated. Our results indicate that KCTD with multiple precursors is an effective method for the synthesis of multinary inorganic phases that are not easily accessible by traditional solid-state synthesis or crystal growth techniques.

Synthesis and Primary Characterization of Self-Assembled Peptide-Based Hydrogels

PubMed Central

Nagarkar, Radhika P.; Schneider, Joel P.

2009-01-01

Summary Hydrogels based on peptide self-assembly form an important class of biomaterials that find application in tissue engineering and drug delivery. It is essential to prepare peptides with high purity to achieve batch-to-batch consistency affording hydrogels with reproducible properties. Automated solid-phase peptide synthesis coupled with optimized Fmoc (9-fluorenylmethoxycarbonyl) chemistry to obtain peptides in high yield and purity is discussed. Details of isolating a desired peptide from crude synthetic mixtures and assessment of the peptide’s final purity by high-performance liquid chromatography and mass spectrometry are provided. Beyond the practical importance of synthesis and primary characterization, techniques used to investigate the properties of hydrogels are briefly discussed. PMID:19031061

Optical properties of spin-on deposited low temperature titanium oxide thin films

NASA Astrophysics Data System (ADS)

Rantala, J. T.; Kärkkäinen, A. H. O.

2003-06-01

This letter presents a method to fabricate high quality, high refractive index titanium oxide thin films by applying liquid phase spin-on deposition combined with low temperature annealing. The synthesis of the liquid form titanium oxide material is carried out using a sol-gel synthesis technique. The material can be annealed at low temperature (150 C°) to achieve relatively high refractive index of 1.94 at 632.8 nm wavelength, whereas annealing at 350 C° results in index of 2.03 at 632.8 nm. Film depositions are demonstrated on silicon substrates with 0.5% uniformity in thickness. Refractive indices and extinction coefficients are characterized over a broad wavelength range to demonstrate the optical performance of this novel aqueous phase spin-on deposited hybrid titanium oxide material.

Application of morphological synthesis for understanding electrode microstructure evolution as a function of applied charge/discharge cycles

DOE PAGES

Glazoff, Michael V.; Dufek, Eric J.; Shalashnikov, Egor V.

2016-09-15

Morphological analysis and synthesis operations were employed for analysis of electrode microstructure transformations and evolution accompanying the application of charge/discharge cycles to electrochemical storage systems (batteries). Using state-of-the-art morphological algorithms, it was possible to predict microstructure evolution in porous Si electrodes for Li-ion batteries with sufficient accuracy. Algorithms for image analyses (segmentation, feature extraction, and 3D-reconstructions using 2D-images) were also developed. Altogether, these techniques could be considered supplementary to phase-field mesoscopic approach to microstructure evolution that is based upon clear and definitive changes in the appearance of microstructure. However, unlike in phase-field, the governing equations for morphological approach are geometry-,more » not physics-based. Similar non-physics based approach to understanding different phenomena was attempted with the introduction of cellular automata. It is anticipated that morphological synthesis and analysis will represent a useful supplementary tool to phase-field and will render assistance to unraveling the underlying microstructure-property relationships. The paper contains data on electrochemical characterization of different electrode materials that was conducted in parallel to morphological study.« less

Continuous microwave flow synthesis of mesoporous hydroxyapatite.

PubMed

Akram, Muhammad; Alshemary, Ammar Z; Goh, Yi-Fan; Wan Ibrahim, Wan Aini; Lintang, Hendrik O; Hussain, Rafaqat

2015-11-01

We have successfully used continuous microwave flow synthesis (CMFS) technique for the template free synthesis of mesoporous hydroxyapatite. The continuous microwave flow reactor consisted of a modified 2.45GHz household microwave, peristaltic pumps and a Teflon coil. This cost effective and efficient system was exploited to produce semi-crystalline phase pure nano-sized hydroxyapatite. Effect of microwave power, retention time and the concentration of reactants on the phase purity, degree of crystallinity and surface area of the final product was studied in detail. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used to study the phase purity and composition of the product, while transmission electron microscopy (TEM) was used to study the effect of process parameters on the morphology of hydroxyapatite. The TEM analysis confirmed the formation of spherical particles at low microwave power; however the morphology of the particles changed to mesoporous needle and rod-like structure upon exposing the reaction mixture to higher microwave power and longer retention time inside the microwave. The in-vitro ion dissolution behavior of the as synthesized hydroxyapatite was studied by determining the amount of Ca(2+) ion released in SBF solution. Copyright © 2015 Elsevier B.V. All rights reserved.

Selective synthesis and characterization of single-crystal silver molybdate/tungstate nanowires by a hydrothermal process.

PubMed

Cui, Xianjin; Yu, Shu-Hong; Li, Lingling; Biao, Liu; Li, Huabin; Mo, Maosong; Liu, Xian-Ming

2004-01-05

Selective synthesis of uniform single crystalline silver molybdate/tungstate nanorods/nanowires in large scale can be easily realized by a facile hydrothermal recrystallization technique. The synthesis is strongly dependent on the pH conditions, temperature, and reaction time. The phase transformation was examined in details. Pure Ag(2)MoO(4) and Ag(6)Mo(10)O(33) can be easily obtained under neutral condition and pH 2, respectively, whereas other mixed phases of Mo(17)O(47), Ag(2)Mo(2)O(7,) Ag(6)Mo(10)O(33) were observed under different pH conditions. Ag(6)Mo(10)O(33) nanowires with uniform diameter 50-60 nm and length up to several hundred micrometers were synthesized in large scale for the first time at 140 degrees C. The melting point of Ag(6)Mo(10)O(33) nanowires were found to be about 238 degrees C. Similarly, Ag(2)WO(4), and Ag(2)W(2)O(7) nanorods/nanowires can be selectively synthesized by controlling pH value. The results demonstrated that this route could be a potential mild way to selectively synthesize various molybdate nanowires with various phases in large scale.

Solid-state reaction synthesis for mixed-phase Eu3+-doped bismuth molybdate and its luminescence properties

NASA Astrophysics Data System (ADS)

Liang, Danyang; Ding, Yu; Wang, Nan; Cai, Xiaomeng; Li, Jia; Han, Linyu; Wang, Shiqi; Han, Yuanyuan; Jia, Guang; Wang, Liyong

2017-09-01

A method for mixed-phase bismuth molybdate doped with Eu3+ ions was developed by solid-state reaction assisting with polyvinyl alcohol (PVA). The results of powder X-ray diffraction showed a mixed-phase structure and the microscopical characterization technology revealed the formation process with the addition of PVA. As a structure inducer, the PVA molecules played a vital role in the formation of phase structure. The as-obtained Eu3+-doped bismuth molybdates were also characterized by using different spectroscopic techniques including FTIR and photoluminescence (PL). The results show that doping concentration, PVA addition and calcination temperature affect photoluminescence properties remarkably.

Microwave-assisted solid-phase peptide synthesis of the 60-110 domain of human pleiotrophin on 2-chlorotrityl resin.

PubMed

Friligou, Irene; Papadimitriou, Evangelia; Gatos, Dimitrios; Matsoukas, John; Tselios, Theodore

2011-05-01

A fast and efficient microwave-assisted solid phase peptide synthesis (MW-SPPS) of a 51mer peptide, the main heparin-binding site (60-110) of human pleiotrophin (hPTN), using 2-chlorotrityl chloride resin (CLTR-Cl) following the 9-fluorenylmethyloxycarbonyl/tert-butyl (Fmoc/tBu) methodology and with the standard N,N'-diisopropylcarbodiimide/1-hydroxybenzotriazole (DIC/HOBt) coupling reagents, is described. An MW-SPPS protocol was for the first time successfully applied to the acid labile CLTR-Cl for the faster synthesis of long peptides (51mer peptide) and with an enhanced purity in comparison to conventional SPPS protocols. The synthesis of such long peptides is not trivial and it is generally achieved by recombinant techniques. The desired linear peptide was obtained in only 30 h of total processing time and in 51% crude yield, in which 60% was the purified product obtained with 99.4% purity. The synthesized peptide was purified by reversed phase high performance liquid chromatography (RP-HPLC) and identified by electrospray ionization mass spectrometry (ESI-MS). Then, the regioselective formation of the two disulfide bridges of hPTN 60-110 was successfully achieved by a two-step procedure, involving an oxidative folding step in dimethylsulfoxide (DMSO) to form the Cys(77)-Cys(109) bond, followed by iodine oxidation to form the Cys(67)-Cys(99) bond.

An alternative gas sensor material: Synthesis and electrical characterization of SmCoO{sub 3}

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

Michel, Carlos Rafael; Delgado, Emilio; Santillan, Gloria

2007-01-18

Single-phase perovskite SmCoO{sub 3} was prepared by a wet-chemical synthesis technique using metal-nitrates and citric acid; after its characterization by thermal analyses and X-ray diffraction, sintering at 900 deg. C in air, gave single phase and well crystallized powders. The powders were mixed with an organic solvent to prepare a slurry, which was deposited on alumina substrates as thick films, using the screen-printing technique. Electrical and gas sensing properties of sintered SmCoO{sub 3} films were investigated in air, O{sub 2} and CO{sub 2}, the results show that sensitivity reached a maximum value at 420 deg. C, for both gases. Dynamicmore » tests revealed a better behavior of SmCoO{sub 3} in CO{sub 2} than O{sub 2}, due to a fast response and a larger electrical resistance change to this gas. X-ray diffraction made on powders after electrical characterization in gases, showed that perovskite-type structure was preserved.« less

Synthesis of dynamic phase profile by the correlation technique for spatial control of optical beams in multiplexing and switching

NASA Astrophysics Data System (ADS)

Bugaychuk, Svitlana A.; Gnatovskyy, Vladimir O.; Sidorenko, Andrey V.; Pryadko, Igor I.; Negriyko, Anatoliy M.

2015-11-01

New approach for the correlation technique, which is based on multiple periodic structures to create a controllable angular spectrum, is proposed and investigated both theoretically and experimentally. The transformation of an initial laser beam occurs due to the actions of consecutive phase periodic structures, which may differ by their parameters. Then, after the Fourier transformation of a complex diffraction field, the output diffraction orders will be changed both by their intensities and by their spatial position. The controllable change of output angular spectrum is carried out by a simple control of the parameters of the periodic structures. We investigate several simple examples of such management.

Flight control synthesis for flexible aircraft using Eigenspace assignment

NASA Technical Reports Server (NTRS)

Davidson, J. B.; Schmidt, D. K.

1986-01-01

The use of eigenspace assignment techniques to synthesize flight control systems for flexible aircraft is explored. Eigenspace assignment techniques are used to achieve a specified desired eigenspace, chosen to yield desirable system impulse residue magnitudes for selected system responses. Two of these are investigated. The first directly determines constant measurement feedback gains that will yield a close-loop system eigenspace close to a desired eigenspace. The second technique selects quadratic weighting matrices in a linear quadratic control synthesis that will asymptotically yield the close-loop achievable eigenspace. Finally, the possibility of using either of these techniques with state estimation is explored. Application of the methods to synthesize integrated flight-control and structural-mode-control laws for a large flexible aircraft is demonstrated and results discussed. Eigenspace selection criteria based on design goals are discussed, and for the study case it would appear that a desirable eigenspace can be obtained. In addition, the importance of state-space selection is noted along with problems with reduced-order measurement feedback. Since the full-state control laws may be implemented with dynamic compensation (state estimation), the use of reduced-order measurement feedback is less desirable. This is especially true since no change in the transient response from the pilot's input results if state estimation is used appropriately. The potential is also noted for high actuator bandwidth requirements if the linear quadratic synthesis approach is utilized. Even with the actuator pole location selected, a problem with unmodeled modes is noted due to high bandwidth. Some suggestions for future research include investigating how to choose an eigenspace that will achieve certain desired dynamics and stability robustness, determining how the choice of measurements effects synthesis results, and exploring how the phase relationships between desired eigenvector elements effects the synthesis results.

Easy parallel screening of reagent stability, quality control, and metrology in solid phase peptide synthesis (SPPS) and peptide couplings for microarrays

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

Achyuthan, Komandoor E.; Wheeler, David R.

Evaluating the stability of coupling reagents, quality control (QC), and surface functionalization metrology are all critical to the production of high quality peptide microarrays. We describe a broadly applicable screening technique for evaluating the fidelity of solid phase peptide synthesis (SPPS), the stability of activation/coupling reagents, and a microarray surface metrology tool. This technique was used to assess the stability of the activation reagent 1-{[1-(Cyano-2-ethoxy-2-oxo-ethylidenaminooxy)dimethylamino-morpholinomethylene]}methaneaminiumHexafluorophosphate (COMU) (Sigma-Aldrich, St. Louis, MO, USA) by SPPS of Leu-Enkephalin (YGGFL) or the coupling of commercially synthesized YGGFL peptides to (3-aminopropyl)triethyoxysilane-modified glass surfaces. Coupling efficiency was quantitated by fluorescence signaling based on immunoreactivity of themore » YGGFL motif. It was concluded that COMU solutions should be prepared fresh and used within 5 h when stored at ~23 °C and not beyond 24 h if stored refrigerated, both in closed containers. Caveats to gauging COMU stability by absorption spectroscopy are discussed. Commercial YGGFL peptides needed independent QC, due to immunoreactivity variations for the same sequence synthesized by different vendors. This technique is useful in evaluating the stability of other activation/coupling reagents besides COMU and as a metrology tool for SPPS and peptide microarrays.« less

Easy parallel screening of reagent stability, quality control, and metrology in solid phase peptide synthesis (SPPS) and peptide couplings for microarrays

DOE PAGES

Achyuthan, Komandoor E.; Wheeler, David R.

2015-08-27

Evaluating the stability of coupling reagents, quality control (QC), and surface functionalization metrology are all critical to the production of high quality peptide microarrays. We describe a broadly applicable screening technique for evaluating the fidelity of solid phase peptide synthesis (SPPS), the stability of activation/coupling reagents, and a microarray surface metrology tool. This technique was used to assess the stability of the activation reagent 1-{[1-(Cyano-2-ethoxy-2-oxo-ethylidenaminooxy)dimethylamino-morpholinomethylene]}methaneaminiumHexafluorophosphate (COMU) (Sigma-Aldrich, St. Louis, MO, USA) by SPPS of Leu-Enkephalin (YGGFL) or the coupling of commercially synthesized YGGFL peptides to (3-aminopropyl)triethyoxysilane-modified glass surfaces. Coupling efficiency was quantitated by fluorescence signaling based on immunoreactivity of themore » YGGFL motif. It was concluded that COMU solutions should be prepared fresh and used within 5 h when stored at ~23 °C and not beyond 24 h if stored refrigerated, both in closed containers. Caveats to gauging COMU stability by absorption spectroscopy are discussed. Commercial YGGFL peptides needed independent QC, due to immunoreactivity variations for the same sequence synthesized by different vendors. This technique is useful in evaluating the stability of other activation/coupling reagents besides COMU and as a metrology tool for SPPS and peptide microarrays.« less

Effect of synthesis method on structure, band gap and surface morphology of delafossite oxides, CuAlO2 and CuFeO2

NASA Astrophysics Data System (ADS)

Shah, Aadil Abass; Azam, Ameer

2018-04-01

In this research work we have reported the synthesis of two different delafossites, CuAlO2 and CuFeO2 by two different synthesis methods viz hydrothermal method and the combustion method. The effect of synthesis on structure, band gap and morphology of the synthesized delafossites was carried out using various techniques. The phase and structure of the synthesized delafossites were studied and confirmed using X-ray diffraction and the crystallite size was calculated. FTIR measurements showed the presence of different stretching modes and functional groups in the synthesized oxides. The surface morphology was studied using the scanning electron microscopy. The band gap of the synthesized delafossite oxides was found to be in the range of 2.8 and 3.3 eV.

High pressure synthesis of a hexagonal close-packed phase of the high-entropy alloy CrMnFeCoNi

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Park, Sulgiye; Rittman, Dylan R.; Zinkle, Steven J.; Bei, Hongbin; Lang, Maik; Ewing, Rodney C.; Mao, Wendy L.

2017-05-01

High-entropy alloys, near-equiatomic solid solutions of five or more elements, represent a new strategy for the design of materials with properties superior to those of conventional alloys. However, their phase space remains constrained, with transition metal high-entropy alloys exhibiting only face- or body-centered cubic structures. Here, we report the high-pressure synthesis of a hexagonal close-packed phase of the prototypical high-entropy alloy CrMnFeCoNi. This martensitic transformation begins at 14 GPa and is attributed to suppression of the local magnetic moments, destabilizing the initial fcc structure. Similar to fcc-to-hcp transformations in Al and the noble gases, the transformation is sluggish, occurring over a range of >40 GPa. However, the behaviour of CrMnFeCoNi is unique in that the hcp phase is retained following decompression to ambient pressure, yielding metastable fcc-hcp mixtures. This demonstrates a means of tuning the structures and properties of high-entropy alloys in a manner not achievable by conventional processing techniques.

Synthesis of compounds related to the anti-migraine drug eletriptan hydrobromide.

PubMed

Madasu, Suri Babu; Vekariya, Nagaji Ambabhai; Kiran, M N V D Hari; Gupta, Badarinadh; Islam, Aminul; Douglas, Paul S; Babu, Korupolu Raghu

2012-01-01

Eletriptan hydrobromide (1) is a selective serotonin (5-HT(1)) agonist, used for the acute treatment of the headache phase of migraine attacks. During the manufacture of eletriptan hydrobromide the formation of various impurities were observed and identified by LC-MS. To control the formation of these impurities during the preparation of active pharmaceutical ingredients, the structure of the impurities must be known. Major impurities of the eletriptan hydrobromide synthesis were prepared and characterized by using various spectroscopic techniques, i.e., mass spectroscopy, FTIR , (1)H NMR, (13)C NMR/DEPT, and further confirmed by co-injection in HPLC. The present study will be of great help in the synthesis of highly pure eletriptan hydrobromide related compounds.

Synthesis of compounds related to the anti-migraine drug eletriptan hydrobromide

PubMed Central

Madasu, Suri Babu; Kiran, M N V D Hari; Gupta, Badarinadh; Islam, Aminul; Douglas, Paul S; Babu, Korupolu Raghu

2012-01-01

Summary Eletriptan hydrobromide (1) is a selective serotonin (5-HT1) agonist, used for the acute treatment of the headache phase of migraine attacks. During the manufacture of eletriptan hydrobromide the formation of various impurities were observed and identified by LC–MS. To control the formation of these impurities during the preparation of active pharmaceutical ingredients, the structure of the impurities must be known. Major impurities of the eletriptan hydrobromide synthesis were prepared and characterized by using various spectroscopic techniques, i.e., mass spectroscopy, FTIR , 1H NMR, 13C NMR/DEPT, and further confirmed by co-injection in HPLC. The present study will be of great help in the synthesis of highly pure eletriptan hydrobromide related compounds. PMID:23019477

Ultrasound with low intensity assisted the synthesis of nanocrystalline TiO2 without calcination.

PubMed

Ghows, Narjes; Entezari, Mohamad H

2010-06-01

A novel method has been developed for the preparation of nano-sized TiO(2) with anatase phase. Nanoparticles with diameter about 6 nm were prepared at a relatively low temperature (75 degrees C) and short time. The synthesis was carried out by the hydrolysis of titanium tetra-isopropoxide (TTIP) in the presence of water, ethanol, and dispersant under ultrasonic irradiation (500 kHz) at low intensity. The results show that variables such as water/ethanol ratio, irradiation time, and temperature have a great influence on the particle size and crystalline phases of TiO(2) nanoparticles. Characterization of the product was carried out by different techniques such as powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and UV-vis spectroscopy. (c) 2010 Elsevier B.V. All rights reserved.

Atomic engineering of mixed ferrite and core-shell nanoparticles.

PubMed

Morrison, Shannon A; Cahill, Christopher L; Carpenter, Everett E; Calvin, Scott; Harris, Vincent G

2005-09-01

Nanoparticulate ferrites such as manganese zinc ferrite and nickel zinc ferrite hold great promise for advanced applications in power electronics. The use of these materials in current applications requires fine control over the nanoparticle size as well as size distribution to maximize their packing density. While there are several techniques for the synthesis of ferrite nanoparticles, reverse micelle techniques provide the greatest flexibility and control over size, crystallinity, and magnetic properties. Recipes for the synthesis of manganese zinc ferrite, nickel zinc ferrite, and an enhanced ferrite are presented along with analysis of the crystalline and magnetic properties. Comparisons are made on the quality of nanoparticles produced using different surfactant systems. The importance of various reaction conditions is explored with a discussion on the corresponding effects on the magnetic properties, particle morphology, stoichiometry, crystallinity, and phase purity.

Synthesis of highly aligned carbon nanotubes by one-step liquid-phase process: Effects of carbon sources on morphology of carbon nanotubes

NASA Astrophysics Data System (ADS)

Yamagiwa, Kiyofumi; Kuwano, Jun

2017-06-01

This paper describes a unique and innovative synthesis technique for carbon nanotubes (CNTs) by a one-step liquid-phase process under ambient pressure. Vertically aligned multi-walled CNT arrays with a maximum height of 100 µm are prepared on stainless steel substrates, which are submerged and electrically heated in straight-chain primary alcohols with n C = 1-4 (n C: number of C atoms in the molecule) containing an appropriate amount of cobalt-based organometallic complex as a catalyst precursor. Structural isomers of butanol were also used for the synthesis to examine the effects of structural factors on the morphology of the deposited products. Notably, 2-methyl-2-propanol, which is a tertiary alcohol, produced only a small amount of low-crystallinity carbonaceous deposits, whereas vertically aligned CNTs were grown from the other isomers of butanol. These results suggest that the presence or absence of β-hydrogen in the molecular structure is a key factor for understanding the dissociation behavior of the carbon source molecules on the catalyst.

High-fraction brookite films from amorphous precursors.

PubMed

Haggerty, James E S; Schelhas, Laura T; Kitchaev, Daniil A; Mangum, John S; Garten, Lauren M; Sun, Wenhao; Stone, Kevin H; Perkins, John D; Toney, Michael F; Ceder, Gerbrand; Ginley, David S; Gorman, Brian P; Tate, Janet

2017-11-09

Structure-specific synthesis processes are of key importance to the growth of polymorphic functional compounds such as TiO 2 , where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO 2 , a promising photocatalyst, has been difficult in both powder and thin-film forms due to the disparity of reported synthesis techniques, their highly specific nature, and lack of mechanistic understanding. In this work, we report the growth of high-fraction (~95%) brookite thin films prepared by annealing amorphous titania precursor films deposited by pulsed laser deposition. We characterize the crystallization process, eliminating the previously suggested roles of substrate templating and Na helper ions in driving brookite formation. Instead, we link phase selection directly to film thickness, offering a novel, generalizable route to brookite growth that does not rely on the presence of extraneous elements or particular lattice-matched substrates. In addition to providing a new synthesis route to brookite thin films, our results take a step towards resolving the problem of phase selection in TiO 2 growth, contributing to the further development of this promising functional material.

Synthesis and characterization of barium silicide (BaSi2) nanowire arrays for potential solar applications.

PubMed

Pokhrel, Ankit; Samad, Leith; Meng, Fei; Jin, Song

2015-11-07

In order to utilize nanostructured materials for potential solar and other energy-harvesting applications, scalable synthetic techniques for these materials must be developed. Herein we use a vapor phase conversion approach to synthesize nanowire (NW) arrays of semiconducting barium silicide (BaSi2) in high yield for the first time for potential solar applications. Dense arrays of silicon NWs obtained by metal-assisted chemical etching were converted to single-crystalline BaSi2 NW arrays by reacting with Ba vapor at about 930 °C. Structural characterization by X-ray diffraction and high-resolution transmission electron microscopy confirm that the converted NWs are single-crystalline BaSi2. The optimal conversion reaction conditions allow the phase-pure synthesis of BaSi2 NWs that maintain the original NW morphology, and tuning the reaction parameters led to a controllable synthesis of BaSi2 films on silicon substrates. The optical bandgap and electrochemical measurements of these BaSi2 NWs reveal a bandgap and carrier concentrations comparable to previously reported values for BaSi2 thin films.

Influence of hydrothermal synthesis parameters on the properties of hydroxyapatite nanoparticles.

PubMed

Kuśnieruk, Sylwia; Wojnarowicz, Jacek; Chodara, Agnieszka; Chudoba, Tadeusz; Gierlotka, Stanislaw; Lojkowski, Witold

2016-01-01

Hydroxyapatite (HAp) nanoparticles of tunable diameter were obtained by the precipitation method at room temperature and by microwave hydrothermal synthesis (MHS). The following parameters of the obtained nanostructured HAp were determined: pycnometric density, specific surface area, phase purity, lattice parameters, particle size, particle size distribution, water content, and structure. HAp nanoparticle morphology and structure were determined using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). X-ray diffraction measurements confirmed crystalline HAp was synthesized, which was pure in terms of phase. It was shown that by changing the synthesis parameters, the diameter of HAp nanoparticles could be controlled. The average diameter of the HAp nanoparticles was determined by Scherrer's equation via the Nanopowder XRD Processor Demo web application, which interprets the results of specific surface area and TEM measurements using the dark-field technique. The obtained nanoparticles with average particle diameter ranging from 8-39 nm were characterized by having homogeneous morphology with a needle shape and a narrow particle size distribution. Strong similarities were found when comparing the properties of some types of nanostructured hydroxyapatite with natural occurring apatite found in animal bones and teeth.

Minimum entropy deconvolution optimized sinusoidal synthesis and its application to vibration based fault detection

NASA Astrophysics Data System (ADS)

Li, Gang; Zhao, Qing

2017-03-01

In this paper, a minimum entropy deconvolution based sinusoidal synthesis (MEDSS) filter is proposed to improve the fault detection performance of the regular sinusoidal synthesis (SS) method. The SS filter is an efficient linear predictor that exploits the frequency properties during model construction. The phase information of the harmonic components is not used in the regular SS filter. However, the phase relationships are important in differentiating noise from characteristic impulsive fault signatures. Therefore, in this work, the minimum entropy deconvolution (MED) technique is used to optimize the SS filter during the model construction process. A time-weighted-error Kalman filter is used to estimate the MEDSS model parameters adaptively. Three simulation examples and a practical application case study are provided to illustrate the effectiveness of the proposed method. The regular SS method and the autoregressive MED (ARMED) method are also implemented for comparison. The MEDSS model has demonstrated superior performance compared to the regular SS method and it also shows comparable or better performance with much less computational intensity than the ARMED method.

Dispersive Solid Phase Extraction for the Analysis of Veterinary Drugs Applied to Food Samples: A Review

PubMed Central

Islas, Gabriela; Hernandez, Prisciliano

2017-01-01

To achieve analytical success, it is necessary to develop thorough clean-up procedures to extract analytes from the matrix. Dispersive solid phase extraction (DSPE) has been used as a pretreatment technique for the analysis of several compounds. This technique is based on the dispersion of a solid sorbent in liquid samples in the extraction isolation and clean-up of different analytes from complex matrices. DSPE has found a wide range of applications in several fields, and it is considered to be a selective, robust, and versatile technique. The applications of dispersive techniques in the analysis of veterinary drugs in different matrices involve magnetic sorbents, molecularly imprinted polymers, carbon-based nanomaterials, and the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method. Techniques based on DSPE permit minimization of additional steps such as precipitation, centrifugation, and filtration, which decreases the manipulation of the sample. In this review, we describe the main procedures used for synthesis, characterization, and application of this pretreatment technique and how it has been applied to food analysis. PMID:29181027

Synthesis of zinc sulfide nanoparticles and their incorporation into poly(hydroxybutyrate) matrix in the formation of a novel nanocomposite

NASA Astrophysics Data System (ADS)

Riaz, Shahina; Raza, Zulfiqar Ali; Majeed, Muhammad Irfan; Jan, Tariq

2018-05-01

In the present study, zinc sulfide (ZnS) nanoparticles (NPs) were successfully synthesized through a modified chemical precipitation protocol and then mediated into poly(hydroxybutyrate) (PHB) matrix to get ZnS/PHB nanocomposite. Mean diameter and zeta potential of ZnS NPs, as determined using dynamic light scattering technique (DLS), were observed to be 53 nm and ‑89 mV, respectively. The structural investigations performed using x-ray diffraction (XRD) technique depicted the phase purity of ZnS NPs exhibiting cubic crystal structure. Fourier transform infrared (FTIR) spectroscopic analysis was conducted to identify the presence or absence of bonding vibrational modes on the surface of synthesized single phase ZnS NPs. The FTIR analysis confirmed the metal to sulphur bond formation by showing the characteristic band at 1123 cm‑1. The UV–vis absorption spectra of ZnS NPs confirmed the synthesis of particles in nanoscale regime showing a λ max of 302 nm. These NPs were then successfully incorporated into PHB matrix to synthesize ZnS/PHB nanocomposite. The synthesis of nanocomposite was confirmed by EDX analysis. The chemical bonding and structural properties of ZnS/PHB nanocomposite were determined by FTIR and XRD analysis, respectively. The FTIR analysis confirmed the synthesis of ZnS/PHB nanocomposite. Moreover, XRD analysis showed that structure of nanocomposite was completely controlled by ZnS NPs as pure PHB exhibited orthorhombic crystal structure while the nanocomposite demonstrated cubic crystal structure of ZnS. Thermal properties of nanocomposite were studied through thermogravimetric analysis revealing that the incorporation of ZnS NPs into PHB matrix lead to enhance heat resistance properties of PHB.

Solution phase synthesis of aluminum-doped silicon nanoparticles via room-temperature, solvent based chemical reduction of silicon tetrachloride

NASA Astrophysics Data System (ADS)

Mowbray, Andrew James

We present a method of wet chemical synthesis of aluminum-doped silicon nanoparticles (Al-doped Si NPs), encompassing the solution-phase co-reduction of silicon tetrachloride (SiCl4) and aluminum chloride (AlCl 3) by sodium naphthalide (Na[NAP]) in 1,2-dimethoxyethane (DME). The development of this method was inspired by the work of Baldwin et al. at the University of California, Davis, and was adapted for our research through some noteworthy procedural modifications. Centrifugation and solvent-based extraction techniques were used throughout various stages of the synthesis procedure to achieve efficient and well-controlled separation of the Si NP product from the reaction media. In addition, the development of a non-aqueous, formamide-based wash solution facilitated simultaneous removal of the NaCl byproduct and Si NP surface passivation via attachment of 1-octanol to the particle surface. As synthesized, the Si NPs were typically 3-15 nm in diameter, and were mainly amorphous, as opposed to crystalline, as concluded from SAED and XRD diffraction pattern analysis. Aluminum doping at various concentrations was accomplished via the inclusion of aluminum chloride (AlCl3); which was in small quantities dissolved into the synthesis solution to be reduced alongside the SiCl4 precursor. The introduction of Al into the chemically-reduced Si NP precipitate was not found to adversely affect the formation of the Si NPs, but was found to influence aspects such as particle stability and dispersibility throughout various stages of the procedure. Analytical techniques including transmission electron microscopy (TEM), FTIR spectroscopy, and ICP-optical emission spectroscopy were used to comprehensively characterize the product NPs. These methods confirm both the presence of Al and surface-bound 1-octanol in the newly formed Si NPs.

Process for production of solution-derived (Pb,La)(Nb,Sn,Zr,Ti)O{sub 3} thin films and powders

DOEpatents

Boyle, T.J.

1999-01-12

A simple and rapid process for synthesizing (Pb,La)(Nb,Sn,Zr,Ti)O{sub 3} precursor solutions and subsequent ferroelectric thin films and powders of the perovskite phase of these materials has been developed. This process offers advantages over standard methods, including: rapid solution synthesis (<10 minutes), use of commercially available materials, film production under ambient conditions, ease of lanthanum dissolution at high concentrations, and no heating requirements during solution synthesis. For lanthanum-doped ferroelectric materials, the lanthanum source can be added with total synthesis time less than 10 minutes. Films and powders are crystallized at approximately 650 C and exhibit ferroelectric properties comparable to films and powders produced by other techniques which require higher crystallization temperatures. 2 figs.

Electrochemical Synthesis of Magnesium Hexaboride by Molten Salt Technique

PubMed Central

Angappan, S.; Kalaiselvi, N.; Sudha, R.; Visuvasam, A.

2014-01-01

The present work reports electrochemical synthesis of MgB6 from molten salts using the precursor consists of LiF–B2O3–MgCl2. An attempt has been made to synthesize metastable phase MgB6 crystal by electrolysis method. DTA/TGA studies were made to determine the eutectic point of the melt and it was found to be around 900°C. The electrolysis was performed at 900°C under argon atmosphere, at current density of 1.5 A/cm2. The electrodeposited crystals were examined using XRD, SEM, and XPS. From the above studies, the electrochemical synthesis method for hypothetical MgB6 from chloro-oxy-fluoride molten salt system is provided. Mechanism for the formation of magnesium hexaboride is discussed. PMID:27350961

Electrochemical Synthesis of Magnesium Hexaboride by Molten Salt Technique.

PubMed

Angappan, S; Kalaiselvi, N; Sudha, R; Visuvasam, A

2014-01-01

The present work reports electrochemical synthesis of MgB6 from molten salts using the precursor consists of LiF-B2O3-MgCl2. An attempt has been made to synthesize metastable phase MgB6 crystal by electrolysis method. DTA/TGA studies were made to determine the eutectic point of the melt and it was found to be around 900°C. The electrolysis was performed at 900°C under argon atmosphere, at current density of 1.5 A/cm(2). The electrodeposited crystals were examined using XRD, SEM, and XPS. From the above studies, the electrochemical synthesis method for hypothetical MgB6 from chloro-oxy-fluoride molten salt system is provided. Mechanism for the formation of magnesium hexaboride is discussed.

Process for production of solution-derived (Pb,La)(Nb,Sn,Zr,Ti)O.sub.3 thin films and powders

DOEpatents

Boyle, Timothy J.

1999-01-01

A simple and rapid process for synthesizing (Pb,La)(Nb,Sn,Zr,Ti)O.sub.3 precursor solutions and subsequent ferroelectric thin films and powders of the perovskite phase of these materials has been developed. This process offers advantages over standard methods, including: rapid solution synthesis (<10 minutes), use of commercially available materials, film production under ambient conditions, ease of lanthanum dissolution at high concentrations, and no heating requirements during solution synthesis. For lanthanum-doped ferroelectric materials, the lanthanum source can be added with total synthesis time less than 10 minutes. Films and powders are crystallized at approximately 650.degree. C. and exhibit ferroelectric properties comparable to films and powders produced by other techniques which require higher crystallization temperatures.

Synthesis and Physical Properties of Poly(Perfluoroalkylether)Urethanes

DTIC Science & Technology

1989-05-30

Differential scanning calorimetry and dynamic mechanical analysis showed that the incorporation of PFEG into the soft segment phase slightly enhanced...for all the polymers, using electron spectroscopy for chemical analysis (ESCA). The dynamic contact angle results indicate that the polymer surfaces...these polymers were evaluated by a variety of techniques. Differential scanning calorimetry and dynamic mechanical analysis showed that the

Input and Output Mechanisms and Devices. Phase I: Adding Voice Output to a Speaker-Independent Recognition System.

ERIC Educational Resources Information Center

Scott Instruments Corp., Denton, TX.

This project was designed to develop techniques for adding low-cost speech synthesis to educational software. Four tasks were identified for the study: (1) select a microcomputer with a built-in analog-to-digital converter that is currently being used in educational environments; (2) determine the feasibility of implementing expansion and playback…

Synthesis and characterization of nanometric zinc oxide for a stationary phase in liquid chromatography

NASA Astrophysics Data System (ADS)

Gordillo-Delgado, F.; Soto-Barrera, C. C.; Plazas-Saldaña, J.

2017-01-01

The increasing demand for equipment to remove organic compounds in industry and research activity has led to evaluate nanometric zinc oxide (ZnO). In this work, we present the ZnO nanoparticles synthesis for reusing of discarded columns, as a low-cost alternative. The compound was obtained by sol-gel technique using zinc chloride and sodium hydroxide as precursors and a drying temperature of 169°C. An X-ray diffractometer was used to estimate the average particle size at 20.3±0.2nm the adsorption capacity was 0.0144L/g and the chemical resistance was tested with HCl and NaOH. The ZnO nanopowder was packed with 100psi pressure in an empty C-18 column cavity. The column packing resolution was evaluated using a high performance liquid chromatographer (HPLC-Thermo Scientific Dionex UltiMate 3000); using a caffeine standard, the following parameters were established: solvent flow: 1.2mL/min, average column temperature: 40°C, running time: 10 minutes, mobile phase acetonitrile-water composition (9:1). These results validate the potential of ZnO nanopowder as a column packing material in HPLC technique.

Electrosynthesis of cerium hexaboride by the molten salt technique

NASA Astrophysics Data System (ADS)

Amalajyothi, K.; Berchmans, L. John; Angappan, S.; Visuvasam, A.

2008-07-01

Molten salts are well thought-out as the incredibly promising medium for chemical and electrochemical synthesis of compounds. Hence a stab has been made on the electrochemical synthesis of CeB 6 using molten salt technique. The electrolyte consisted of lithium fluoride (LiF), boron trioxide (B 2O 3) and cerium chloride (CeCl 3). Electrochemical experiments were carried out in an inconal reactor in an argon atmosphere. Electrolysis was executed in a high-density graphite crucible, which doles out as the electrolyte clutching vessel as well as the anode. The cathode was made up of a molybdenum rod. The electrolysis was carried out at 900 °C at different current densities intended for the synthesis of CeB 6 crystals. After the electrolysis, the cathode product was removed and cleaned using dilute HCl solution. The crystals were scrutinized by X-ray diffraction (XRD) to make out the phase and the purity. It has been observed that CeB 6 crystals are synthesized at all current densities and the product has traces of impurities.

Crystal structure, magnetic properties and advances in hexaferrites: A brief review

NASA Astrophysics Data System (ADS)

Jotania, Rajshree

2014-10-01

Hexaferrites are hard magnetic materials and specifically ferri-magnetic oxides with hexagonal magnetoplumbite type crystallographic structure. Hexagonal ferrites are used as permanent magnets, high-density perpendicular and magneto-optical recording media, and microwave devices like resonance isolators, filters, circulators, phase shifters because of their high magnetic permeability, high electrical resistivity and moderable permittivity. In addition to these; hexagonal ferrites have excellent chemical stability, mechanical hardness and low eddy current loss at high frequencies. The preparation of hexaferrites is a complicated process. Various experimental techniques like standard ceramic techniques, solvent free synthesis route, co precipitation, salt-melt, ion exchange, sol-gel, citrate synthesis, hydrothermal synthesis, spray drying, water-in-oil microemulsion, reverse micelle etc are used to prepare hexaferrite materials. Structural, dielectric and magnetic properties, crystallite size of hexaferrites depend upon nature of substituted ions, method of preparation, sintering temperature and time. The recent interest is nanotechnology, the development of hexaferrite fibres and composites with carbon nano tubes (CNT). Magnetic properties of some doped and un-doped hexaferrites are discussed here. Recent advances in hexaferrites also highlighted in present paper.

Robust image registration for multiple exposure high dynamic range image synthesis

NASA Astrophysics Data System (ADS)

Yao, Susu

2011-03-01

Image registration is an important preprocessing technique in high dynamic range (HDR) image synthesis. This paper proposed a robust image registration method for aligning a group of low dynamic range images (LDR) that are captured with different exposure times. Illumination change and photometric distortion between two images would result in inaccurate registration. We propose to transform intensity image data into phase congruency to eliminate the effect of the changes in image brightness and use phase cross correlation in the Fourier transform domain to perform image registration. Considering the presence of non-overlapped regions due to photometric distortion, evolutionary programming is applied to search for the accurate translation parameters so that the accuracy of registration is able to be achieved at a hundredth of a pixel level. The proposed algorithm works well for under and over-exposed image registration. It has been applied to align LDR images for synthesizing high quality HDR images..

Synthesis and Characterization of TiNi1+xSn Thermoelectric Alloys

NASA Astrophysics Data System (ADS)

Young, Jacob Steele

Thermoelectric materials, a unique semiconductor-like class of materials, can convert waste heat into electricity and vice versa. An investigation into the synthesis and characterization of half-Heusler TiNi1+xSn alloys was conducted. An arc-melting and annealing procedure was conducted to achieve the desired phase equilibrium. Additional Ni was added as an interstitial dopant to form a small amount of full-Heusler TiNi2Sn phase, which has been seen to improve upon thermoelectric properties in the literature. Annealing time (0 to 21 days), annealing temperature (700 to 900 °C), and nickel content (x = 0, 0.15) were investigated as key synthesis parameters. Results illustrate that before annealing, many binary and ternary phases are present. The final phase distribution after annealing, a two-phase mixture containing TiNiSn and TiNi2Sn, was analyzed using XRD, SEM, EBSD, and EDS techniques. The electrical conductivity (1515 to 1618 S cm -1 from 30 to 340 °C), Seebeck coefficient (-25 to -53 microV K-1 from 30 to 414 °C), thermal conductivity (6.68 to 6.90 W m-1 K-1 from 318 to 414 °C), and thermoelectric figure of merit, ZT, (0.009 to 0.046 from 30 to 430 °C) of single phase TiNiSn using the arc-melting and annealing synthesis method was measured and compared to other methods found in literature. The lattice constants of TiNiSn and TiNi2Sn as a function of annealing time, annealing temperature, and composition were calculated based on XRD and deviated slightly from the ICDD standards due to Ni-defect behavior (TiNiSn: +0.04 to 0.47% deviation, TiNi2Sn: -0.09 to -0.40%). The activation energy for conduction (bandgap) of TiNiSn was derived from the measured electrical conductivity and was approximately 0 eV, implying a metallic conduction behavior. Optimum annealing conditions were determined in order to achieve phase equilibrium with minimum time (14 to 21 days) and temperature required (700 °C).

The Effect of Gravity on the Combustion Synthesis of Porous Ceramics and Metal Matrix Composites

NASA Technical Reports Server (NTRS)

Moore, J. J.; Woodger, T. C.; Wolanski, T.; Yi, H. C.; Guigne, J. Y.

1997-01-01

Combustion synthesis (self propagating, high temperature synthesis-SHS) is a novel technique that is capable of producing many advanced materials. The ignition temperature (Tig) of such combustion synthesis reactions is often coincident with that of the lowest melting point reactant. The resultant liquid metal wets and spreads around the other solid reactant particles of higher melting points, thereby improving the reactant contact and kinetics, followed by formation of the required compounds. This ignition initiates a combustion propagating wave whose narrow reaction front rapidly travels through the reactants. Since this process is highly exothermic, the heat released by combustion often melts the reactant particles ahead of the combustion front and ignites the adjacent reactant layer, resulting in a self-sustaining reaction. Whenever a fluid phase (liquid or gas) is generated by the reaction system, gravity-driven phenomena can occur. Such phenomena include convective flows of fluid by conventional or unstable convection and settling of the higher density phases. A combustion process is often associated with various kinds of fluid flow. For instance, if the SHS reaction is carried out under inert or reactive gas atmospheres, or a volatile, e.g., B2O3, is deliberately introduced as a reactant, convective flows of the gas will occur due to a temperature gradient existing in the atmosphere when a combustion wave is initiated. The increased gas flow will produce a porous (or expanded) SHS product. Owing to the highly exothermic nature of many SHS reactions, liquid phase(s) can also form before, at, or after the combustion front. The huge temperature gradient at the combustion front can induce convective flows (conventional or unstable) of the liquid phase. Each of these types of convective fluid flow can change the combustion behavior of the synthesizing reaction, and, therefore, the resultant product microstructure. In addition, when two or more phases of different density are produced at or ahead of the propagating combustion front settling of the higher density phase will occur resulting in a non-uniform product microstructure and properties.

Image Reconstruction for Interferometric Imaging of Geosynchronous Satellites

NASA Astrophysics Data System (ADS)

DeSantis, Zachary J.

Imaging distant objects at a high resolution has always presented a challenge due to the diffraction limit. Larger apertures improve the resolution, but at some point the cost of engineering, building, and correcting phase aberrations of large apertures become prohibitive. Interferometric imaging uses the Van Cittert-Zernike theorem to form an image from measurements of spatial coherence. This effectively allows the synthesis of a large aperture from two or more smaller telescopes to improve the resolution. We apply this method to imaging geosynchronous satellites with a ground-based system. Imaging a dim object from the ground presents unique challenges. The atmosphere creates errors in the phase measurements. The measurements are taken simultaneously across a large bandwidth of light. The atmospheric piston error, therefore, manifests as a linear phase error across the spectral measurements. Because the objects are faint, many of the measurements are expected to have a poor signal-to-noise ratio (SNR). This eliminates possibility of use of commonly used techniques like closure phase, which is a standard technique in astronomical interferometric imaging for making partial phase measurements in the presence of atmospheric error. The bulk of our work has been focused on forming an image, using sub-Nyquist sampled data, in the presence of these linear phase errors without relying on closure phase techniques. We present an image reconstruction algorithm that successfully forms an image in the presence of these linear phase errors. We demonstrate our algorithm’s success in both simulation and in laboratory experiments.

A Tikhonov Regularization Scheme for Focus Rotations with Focused Ultrasound Phased Arrays

PubMed Central

Hughes, Alec; Hynynen, Kullervo

2016-01-01

Phased arrays have a wide range of applications in focused ultrasound therapy. By using an array of individually-driven transducer elements, it is possible to steer a focus through space electronically and compensate for acoustically heterogeneous media with phase delays. In this paper, the concept of focusing an ultrasound phased array is expanded to include a method to control the orientation of the focus using a Tikhonov regularization scheme. It is then shown that the Tikhonov regularization parameter used to solve the ill-posed focus rotation problem plays an important role in the balance between quality focusing and array efficiency. Finally, the technique is applied to the synthesis of multiple foci, showing that this method allows for multiple independent spatial rotations. PMID:27913323

A Tikhonov Regularization Scheme for Focus Rotations With Focused Ultrasound-Phased Arrays.

PubMed

Hughes, Alec; Hynynen, Kullervo

2016-12-01

Phased arrays have a wide range of applications in focused ultrasound therapy. By using an array of individually driven transducer elements, it is possible to steer a focus through space electronically and compensate for acoustically heterogeneous media with phase delays. In this paper, the concept of focusing an ultrasound-phased array is expanded to include a method to control the orientation of the focus using a Tikhonov regularization scheme. It is then shown that the Tikhonov regularization parameter used to solve the ill-posed focus rotation problem plays an important role in the balance between quality focusing and array efficiency. Finally, the technique is applied to the synthesis of multiple foci, showing that this method allows for multiple independent spatial rotations.

Fluorous tagging strategy for solution-phase synthesis of small molecules, peptides and oligosaccharides

PubMed Central

Zhang, Wei

2005-01-01

The purification of reaction mixtures is a slow process in organic synthesis, especially during the production of large numbers of analogs and compound libraries. Phase-tag methods such as solid-phase synthesis and fluorous synthesis, provide efficient ways of addressing the separation issue. Fluorous synthesis employs functionalized perfluoroalkyl groups attached to substrates or reagents. The separation of the resulting fluorous molecules can be achieved using strong and selective fluorous liquid-liquid extraction, fluorous silica gel-based solid-phase extraction or high-performance liquid chromatography. Fluorous technology is a novel solution-phase method, which has the advantages of fast reaction times in homogeneous environments, being readily adaptable to literature conditions, having easy intermediate analysis, and having flexibility in reaction scale and scope. In principle, any synthetic methods that use a solid-support could be conducted in solution-phase by replacing the polymer linker with a corresponding fluorous tag. This review summarizes the progress of fluorous tags in solution-phase synthesis of small molecules, peptides and oligosaccharides. PMID:15595439

Simple glucose reduction route for one-step synthesis of copper nanofluids

NASA Astrophysics Data System (ADS)

Shenoy, U. Sandhya; Shetty, A. Nityananda

2014-01-01

One-step method has been employed in the synthesis of copper nanofluids. Copper nitrate is reduced by glucose in the presence of sodium lauryl sulfate. The synthesized particles are characterized by X-ray diffraction technique for the phase structure; electron diffraction X-ray analysis for chemical composition; transmission electron microscopy and field emission scanning electron microscopy for the morphology; Fourier-transform infrared spectroscopy and ultraviolet-visible spectroscopy for the analysis of ingredients of the solution. Thermal conductivity, sedimentation and rheological measurements have also been carried out. It is found that the reaction parameters have considerable effect on the size of the particle formed and rate of the reaction. The techniques confirm that the synthesized particles are copper. The reported method showed promising increase in the thermal conductivity of the base fluid and is found to be reliable, simple and cost-effective method for preparing heat transfer fluids with higher stability.

Time-controlled synthesis mechanism analysis of kesterite-phased Cu2ZnSnS4 nanorods via colloidal route

NASA Astrophysics Data System (ADS)

Jain, Shefali; Singh, Dinesh; Vijayan, N.; Sharma, Shailesh Narain

2018-05-01

In this work, stable Cu2ZnSnS4 (CZTS) nanocrystals (NCs) in pure kesterite phase were synthesized by a facile one-pot rapid injection technique (colloidal route). Time-dependent reaction mechanism for the synthesis of CZTS nanoparticles is explained. When TOP-S (Tri-octyl phosphine-sulphur) was injected in the CuZnSn-complex with TOPO (Tri-octyl phosphine oxide) as capping ligand, orthorhombic phase Cu2-X S nanoparticles of spherical shape were found at nucleation sites. With an advancement in the reaction time, Sn got infused in Cu2-X S to form Cu2SnS3 and its shape got deformed. Further increase in reaction time infuses Zn to form Cu2ZnSnS4 with the gradual vanishing of Cu2-X S and Cu2SnS3 phases and finally, the rod-shaped CZTS Np's were obtained. This factor of reaction time, which influence the morphology and size were studied in detail. The structural and optical properties of the pure kesterite phase CZTS nanorods were also analysed. The band gap of the rod-like CZTS is determined to be around 1.43 eV, which is an optimum value for solar photoelectric conversion.

Factors controlling crystallization of miserite glass-ceramic.

PubMed

Muhammed, Fenik K; Moorehead, Robert; van Noort, Richard; Pollington, Sarah

2015-12-01

The purpose of this study was to investigate a range of variables affecting the synthesis of a miserite glass-ceramic (GC). Miserite glass was synthesized by the melt quench technique. The crystallization kinetics of the glass were determined using Differential Thermal Analysis (DTA). The glasses were ground with dry ball-milling and then sieved to different particle sizes prior to sintering. These particle sizes were submitted to heat treatment regimes in a high temperature furnace to form the GC. The crystal phases of the GC were analyzed by X-ray diffraction (XRD). Scanning electron microscopy (SEM) was used to examine the microstructure of the cerammed glass. XRD analysis confirmed that the predominant crystalline phase of the GC was miserite along with a minor crystalline phase of cristobalite only when the particle size is <20 μm and the heat treatment at 1000°C was carried out for 4h and slowly cooled at the furnace rate. For larger particle sizes and faster cooling rates, a pseudowollastonite crystalline phase was produced. Short sintering times produced either a pseudowollastonite or xonotolite crystalline phase. The current study has shown that particle size and heat treatment schedules are major factors in controlling the synthesis of miserite GC. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Search for new phases in the Praseodymium-Silicon system

NASA Astrophysics Data System (ADS)

de La Venta, Jose; Basaran, Ali C.; Grant, Ted; Gallardo-Amores, J.; Ramirez, J. G.; Suchomel, M. R.; Alario-Franco, M. A.; Fisk, Zachary; Schuller, Ivan K.

2013-03-01

We searched for new superconducting and magnetic phases in the Pr-Si system using high-pressure high-temperature and conventional arc melting syntheses. High pressure synthesis is a unique technique which allows incorporation of elements into compounds which otherwise cannot be synthesized at ambient pressure Both high and low Si concentration areas of the phase diagram were explored. To investigate the high Si concentration compounds, PrSi2 with an excess of Si was subjected to HP-HT synthesis. To explore the high Pr concentration binary compound Pr5Si3, we have synthesized undoped Pr5Si3 as well as different samples doped with C or B. High resolution X-ray powder diffraction, Magnetic Field Modulated Microwave Spectroscopy and magnetic characterization found that the addition of C gave rise to multiple previously-unknown ferromagnetic phases. Furthermore, X-ray refinement of the undoped samples confirmed the existence of the so far unconfirmed Pr3Si2 phase. Work supported by AFOSR MURI #F49550-09-1-0577 dedicated to Search for New Superconductors for Energy and Power A. Use of the Advanced Photon Source at ANL was supported by the U. S. DoE, Office of Basic Energy Sciences, Contract No. DE-AC02-06CH11357.

Gas Phase Nanoparticle Synthesis

NASA Astrophysics Data System (ADS)

Granqvist, Claes; Kish, Laszlo; Marlow, William

This book deals with gas-phase nanoparticle synthesis and is intended for researchers and research students in nanomaterials science and engineering, condensed matter physics and chemistry, and aerosol science. Gas-phase nanoparticle synthesis is instrumental to nanotechnology - a field in current focus that raises hopes for environmentally benign, resource-lean manufacturing. Nanoparticles can be produced by many physical, chemical, and even biological routes. Gas-phase synthesis is particularly interesting since one can achieve accurate manufacturing control and hence industrial viability.

Facile preparation of an alternating copolymer-based high molecular shape-selective organic phase for reversed-phase liquid chromatography.

PubMed

Mallik, Abul K; Noguchi, Hiroki; Rahman, Mohammed Mizanur; Takafuji, Makoto; Ihara, Hirotaka

2018-06-22

The synthesis of a new alternating copolymer-grafted silica phase is described for the separation of shape-constrained isomers of polycyclic aromatic hydrocarbons (PAHs) and tocopherols in reversed-phase high-performance liquid chromatography (RP-HPLC). Telomerization of the monomers (octadecyl acrylate and N-methylmaleimide) was carried out with a silane coupling agent; 3-mercaptopropyltrimethoxysilane (MPS), and the telomer (T) was grafted onto porous silica surface to prepare the alternating copolymer-grafted silica phase (Sil-alt-T). The new hybrid material was characterized by elemental analyses, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and solid-state 13 C and 29 Si cross-polarization magic-angle spinning (CP/MAS) NMR spectroscopy. The results of 13 C CP/MAS NMR demonstrated that the alkyl chains of the grafted polymers in Sil-alt-T remained disordered, amorphous, and mobile represented by gauche conformational form. Separation abilities and molecular-shape selectivities of the prepared organic phase were evaluated by the separation of PAHs isomers and Standard Reference Material 869b, Column Selectivity Test Mixture for Liquid Chromatography, respectively and compared with commercially available octadecylsilylated silica (ODS) and C 30 columns as well as previously reported alternating copolymer-based column. The effectiveness of this phase is also demonstrated by the separation of tocopherol isomers. Oriented functional groups along the polymer main chains and cavity formations are investigated to be the driving force for better separation with multiple-interactions with the solutes. One of the advantages of the Sil-alt-T phase to that of the previously reported phase is the synthesis of the telomer first and then immobilized onto silica surface. In this case, the telomer was characterized easily with simple spectroscopic techniques and the molecular mass and polydispersity index of the telomer were determined by size exclusion chromatography (SEC) before grafting onto silica surface. Moreover, both of the monomers were commercially available. Therefore, the technique of preparation was very facile and better separation was achieved with the Sil-alt-T phase compared to the ODS, C 30 and other previously reported alternating copolymer-based columns. Copyright © 2018 Elsevier B.V. All rights reserved.

Investigation of phase transition properties of ZrO2 thin films

NASA Astrophysics Data System (ADS)

Kumar, Davinder; Singh, Avtar; Kaur, Manpreet; Rana, Vikrant Singh; Kaur, Raminder

2018-05-01

This paper presents the synthesis of transparent thin films of zirconium oxide (ZrO2) deposited on glass substrates by sol-gel dip coating technique. Synthesized films were characterized for different annealing time and withdrawal speed. Change in crystallographic properties of thin films was investigated by using X-ray diffraction. Surface morphology of transparent thin films was estimated by using scanning electron microscope.

Optical aperture synthesis: limitations and interest for the earth observation

NASA Astrophysics Data System (ADS)

Brouard, Laurent; Safa, Frederic; Crombez, Vincent; Laubier, David

2017-11-01

For very large telescope diameters, typically above 4 meters, monolithic telescopes can hardly be envisaged for space applications. Optical aperture synthesis can be envisaged in the future for improving the image resolution from high altitude orbits by co-phasing several individual telescopes of smaller size and reconstituting an aperture of large surface. The telescopes can be deployed on a single spacecraft or distributed on several spacecrafts in free flying formation. Several future projects are based on optical aperture synthesis for science or earth observation. This paper specifically discusses the limitations and interest of aperture synthesis technique for Earth observation from high altitude orbits, in particular geostationary orbit. Classical Fizeau and Michelson configurations are recalled, and system design aspects are investigated: synthesis of the Modulation Transfer Function (MTF), integration time and imaging procedure are first discussed then co-phasing strategies and instrument metrology are developed. The discussion is supported by specific designs made at EADS Astrium. As example, a telescope design is presented with a surface of only 6.6 m2 for the primary mirror for an external diameter of 10.6 m allowing a theoretical resolution of 1.2 m from geostationary orbit with a surface lower than 10% of the overall surface. The impact is that the integration time is increasing leading to stringent satellite attitude requirements. Image simulation results are presented. The practical implementation of the concept is evaluated in terms of system impacts in particular spacecraft attitude control, spacecraft operations and imaging capability limitations.

Optimization and scale up of microfluidic nanolipomer production method for preclinical and potential clinical trials.

PubMed

Gdowski, Andrew; Johnson, Kaitlyn; Shah, Sunil; Gryczynski, Ignacy; Vishwanatha, Jamboor; Ranjan, Amalendu

2018-02-12

The process of optimization and fabrication of nanoparticle synthesis for preclinical studies can be challenging and time consuming. Traditional small scale laboratory synthesis techniques suffer from batch to batch variability. Additionally, the parameters used in the original formulation must be re-optimized due to differences in fabrication techniques for clinical production. Several low flow microfluidic synthesis processes have been reported in recent years for developing nanoparticles that are a hybrid between polymeric nanoparticles and liposomes. However, use of high flow microfluidic synthetic techniques has not been described for this type of nanoparticle system, which we will term as nanolipomer. In this manuscript, we describe the successful optimization and functional assessment of nanolipomers fabricated using a microfluidic synthesis method under high flow parameters. The optimal total flow rate for synthesis of these nanolipomers was found to be 12 ml/min and flow rate ratio 1:1 (organic phase: aqueous phase). The PLGA polymer concentration of 10 mg/ml and a DSPE-PEG lipid concentration of 10% w/v provided optimal size, PDI and stability. Drug loading and encapsulation of a representative hydrophobic small molecule drug, curcumin, was optimized and found that high encapsulation efficiency of 58.8% and drug loading of 4.4% was achieved at 7.5% w/w initial concentration of curcumin/PLGA polymer. The final size and polydispersity index of the optimized nanolipomer was 102.11 nm and 0.126, respectively. Functional assessment of uptake of the nanolipomers in C4-2B prostate cancer cells showed uptake at 1 h and increased uptake at 24 h. The nanolipomer was more effective in the cell viability assay compared to free drug. Finally, assessment of in vivo retention in mice of these nanolipomers revealed retention for up to 2 h and were completely cleared at 24 h. In this study, we have demonstrated that a nanolipomer formulation can be successfully synthesized and easily scaled up through a high flow microfluidic system with optimal characteristics. The process of developing nanolipomers using this methodology is significant as the same optimized parameters used for small batches could be translated into manufacturing large scale batches for clinical trials through parallel flow systems.

One pot synthesis of exchange coupled Nd2Fe14B/alpha-Fe by pechini type sol-gel method.

PubMed

Hussain, Abid; Jadhav, Abhijit P; Baek, Yeon Kyung; Choi, Hul Jin; Lee, Jaeho; Kang, Young Soo

2013-11-01

In this work, a combination of nanoparticles of Nd2Fe14B hard magnetic phase and alpha-Fe soft magnetic phase were synthesized by one pot chemical synthesis technique using sol-gel method. A gel of Nd-Fe-B was prepared using NdCl3 x 6H2O, FeCl3 x 6H2O, H3BO3, citric acid, and ethylene glycol by pechini type sol-gel method. The gel was subsequently calcined and annealed to obtain the mixed oxide powders. The produced metal oxide particles were identified with XRD, SEM, TEM to obtain the crystal structure, shape and domain structure of them. The nanoparticles of mixed phase of Nd2Fe14B/alpha-Fe were obtained from these oxides by a process of reduction-diffusion in vacuum by employing CaH2 as reducing agent. During this process it was optimized by controlling temperature, reaction time and concentration of the reducing agent (CaH2). The phase formation of Nd2Fe14B was resulted by the direct diffusion of NdH2, Fe and B. The magnetic property of produced hard and soft phases was successfully identified with vibrating sample magnetometer (VSM). The mixed domains of the hard and soft phases were identified with selected area electron diffraction method (SAED) patterns.

Facile synthesis of flexible macroporous polypropylene sponges for separation of oil and water

PubMed Central

Wang, Guowei; Uyama, Hiroshi

2016-01-01

Oil spill disasters always occur accidentally, accompanied by the release of plenty of crude oil that could spread quickly over a wide area, creating enormous damage to the fragile marine ecological system. Therefore, the facile large-scale synthesis of hydrophobic three-dimensional (3-D) porous sorbents from low cost raw materials is in urgent demand. In this study, we report the facile template-free synthesis of polypropylene (PP) sponge by using a thermally-induced phase separation (TIPS) technique. The obtained sponge showed macroporous structure, excellent mechanical property, high hydrophobicity, and superoleophilicity. Oil could be separated from an oil/water mixture by simple immersing the sponge into the mixture and subsequent squeezing the sponge. All of these features make this sponge the most promising oil sorbent that will replace commercial non-woven PP fabrics. PMID:26880297

Synthesis of D-[U-{sup 13}C]Glucal, D-[U-{sup 13}C] Galactal, and L-[U-{sup 13}C]Fucose for NMR structure studies of oligosaccharides

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

Wu, R.; Unkefer, C.J.; Silks, L.A. III

1996-12-31

The role of carbohydrates is well recognized in a variety of important biological phenomena such as cell surface recognition. Recent advances in carbohydrate chemistry, including the development of solid phase synthesis methods, have helped to provide significant quantities of material by offering general protocols for synthesis of well-defined, pure material. However, the study of the solution structure of oligosaccharides by nuclear magnetic resonance techniques have been hampered by the lack of enriched {sup 13}C material. In an effort to help alleviate this situation, we have been interested in the construction of the title compounds from a single economical carbon source,more » D-[U-{sup 13}C]glucose. Details of the syntheses will be provided.« less

In-situ x-ray studies of compositional control during synthesis of LaGaO 3 by radio frequency-magnetron sputtering

DOE PAGES

Highland, Matthew J.; Fong, Dillon D.; Ju, Guangxu; ...

2015-08-28

In-situ synchrotron x-ray scattering has been used to monitor and control the synthesis of LaGaO 3 epitaxial thin films by 90° off-axis RF-magnetron sputtering. We compared films deposited from a single LaGaO 3 source with those prepared by alternating deposition from separate La 2O 3 and Ga 2O 3 sources. The conditions for growth of stoichiometric films were determined by real-time monitoring of secondary phase formation as well as from features in the diffuse scatter from island formation during synthesis. Our results provide atomic-scale insight into the mechanisms taking place during reactive epitaxial growth and demonstrate how in-situ techniques canmore » be utilized to achieve stoichiometric control in ultrathin films.« less

High-pressure phase transitions of nitinol NiTi to a semiconductor with an unusual topological structure

NASA Astrophysics Data System (ADS)

Liu, Guangtao; Liu, Hanyu; Feng, Xiaolei; Redfern, Simon A. T.

2018-04-01

Systematic ab initio structure simulations have been used to explore the high-pressure behavior of nitinol (NiTi) at zero temperature. Our crystal structure prediction and first-principles calculations reveal that the known B 19 phase is dynamically unstable, and an orthorhombic structure (Pbcm) and a face-centered-cubic B 32 structure (F d 3 ¯m ) become stable above ˜4 and 29 GPa, respectively. The predicted, highest-pressure, B 32 phase is composed of two interpenetrating diamond structures, with a structural topology that is quite distinct from that of the other phases of NiTi. Interestingly, the B 32 phase shows an unusual semiconducting characteristic as a result of its unique band structure and the nature of 3 d orbitals localization, whose expected synthesis pressure is accessible to current experimental techniques.

High-fraction brookite films from amorphous precursors

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

Haggerty, James E. S.; Schelhas, Laura T.; Kitchaev, Daniil A.

2017-11-09

Structure-specific synthesis processes are of key importance to the growth of polymorphic functional compounds such as TiO 2, where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO 2, a promising photocatalyst, has been difficult in both powder and thin-film forms due to the disparity of reported synthesis techniques, their highly specific nature, and lack of mechanistic understanding. In this work, we report the growth of high-fraction (~95%) brookite thin films prepared by annealing amorphous titania precursor films deposited by pulsed laser deposition. We characterize the crystallization process, eliminating themore » previously suggested roles of substrate templating and Na helper ions in driving brookite formation. Instead, we link phase selection directly to film thickness, offering a novel, generalizable route to brookite growth that does not rely on the presence of extraneous elements or particular lattice-matched substrates. In addition to providing a new synthesis route to brookite thin films, our results take a step towards resolving the problem of phase selection in TiO 2 growth, contributing to the further development of this promising functional material.« less

Ultrafast Synthesis and Related Phase Evolution of Mg2Si and Mg2Sn Compounds

NASA Astrophysics Data System (ADS)

Zhang, Qiang; Lu, Qiangbing; Yan, Yonggao; Su, Xianli; Tang, Xinfeng

2017-05-01

Both Mg2Si and Mg2Sn compounds were synthesized by an ultra-fast self-propagating high-temperature synthesis (SHS) method. The data regarding SHS were obtained via theoretical calculation combined with experiments, showing that the adiabatic temperature T ad and ignition temperature T ig of Mg2Si are a little higher than those of Mg2Sn. The mechanism of phase evolution and the concomitant microstructure evolution during the synthesis process of Mg2Si and Mg2Sn compounds were investigated by adopting SHS technique coupled with a sudden quenching treatment. Differential scanning calorimetry (DSC), field emission scanning electron microscopy (FESEM), and x-ray powder diffraction (XRD) results indicate that Mg2Si compound can be directly synthesized through the reaction of Mg and Si elements at around 850 K. Correspondingly, the formation of Mg2Sn needs to undergo melting of Sn and the subsequent feeble reaction between Mg and Sn elements before the large scale transformation at 730 K. As the groundwork, this research embodies great significance for future study on the ultrafast SHS process of the ternary Mg2Si1- x Sn x solid solutions.

THE MECHANISM OF 5-AMINOURACIL-INDUCED SYNCHRONY OF CELL DIVISION IN VI CIA FABA ROOT MERISTEMS

PubMed Central

Prensky, Wolf; Smith, Harold H.

1965-01-01

Cessation of mitosis was brought about in Vicia faba roots incubated for 24 hours in the thymine analogue, 5-aminouracil. Recovery of mitotic activity began 8 hours after removal from 5-aminouracil and reached a peak at 15 hours. If colchicine was added 4 hours before the peak of mitoses, up to 80 per cent of all cells accumulated in mitotic division stages. By use of single and double labeling techniques, it was shown that synchrony of cell divisions resulted from depression in the rate of DNA synthesis by 5-aminouracil, which brought about an accumulation of cells in the S phase of the cell cycle. Treatment with 5-aminouracil may have also caused a delay in the rate of exit of cells from the G2 period. It appeared to have no effect on the duration of the G1 period. When roots were removed from 5-aminouracil, DNA synthesis resumed in all cells in the S phase. Although thymidine antagonized the effects of 5-aminouracil, an exogenous supply of it was not necessary for the resumption of DNA synthesis, as shown by incorporation studies with tritiated deoxycytidine. PMID:19866644

Solid-state reactions during mechanical alloying of ternary Fe-Al-X (X=Ni, Mn, Cu, Ti, Cr, B, Si) systems: A review

NASA Astrophysics Data System (ADS)

Hadef, Fatma

2016-12-01

The last decade has witnessed an intensive research in the field of nanocrystalline materials due to their enhanced properties. A lot of processing techniques were developed in order to synthesis these novel materials, among them mechanical alloying or high-energy ball milling. In fact, mechanical alloying is one of the most common operations in the processing of solids. It can be used to quickly and easily synthesize a variety of technologically useful materials which are very difficult to manufacture by other techniques. One advantage of MA over many other techniques is that is a solid state technique and consequently problems associated with melting and solidification are bypassed. Special attention is being paid to the synthesis of alloys through reactions mainly occurring in solid state in many metallic ternary Fe-Al-X systems, in order to improve mainly Fe-Al structural and mechanical properties. The results show that nanocrystallization is the common result occurring in all systems during MA process. The aim of this work is to illustrate the uniqueness of MA process to induce phase transformation in metallic Fe-Al-X (X=Ni, Mn, Cu, Ti, Cr, B, Si) systems.

Direct on-chip DNA synthesis using electrochemically modified gold electrodes as solid support

NASA Astrophysics Data System (ADS)

Levrie, Karen; Jans, Karolien; Schepers, Guy; Vos, Rita; Van Dorpe, Pol; Lagae, Liesbet; Van Hoof, Chris; Van Aerschot, Arthur; Stakenborg, Tim

2018-04-01

DNA microarrays have propelled important advancements in the field of genomic research by enabling the monitoring of thousands of genes in parallel. The throughput can be increased even further by scaling down the microarray feature size. In this respect, microelectronics-based DNA arrays are promising as they can leverage semiconductor processing techniques with lithographic resolutions. We propose a method that enables the use of metal electrodes for de novo DNA synthesis without the need for an insulating support. By electrochemically functionalizing gold electrodes, these electrodes can act as solid support for phosphoramidite-based synthesis. The proposed method relies on the electrochemical reduction of diazonium salts, enabling site-specific incorporation of hydroxyl groups onto the metal electrodes. An automated DNA synthesizer was used to couple phosphoramidite moieties directly onto the OH-modified electrodes to obtain the desired oligonucleotide sequence. Characterization was done via cyclic voltammetry and fluorescence microscopy. Our results present a valuable proof-of-concept for the integration of solid-phase DNA synthesis with microelectronics.

Synthesis and morphological examination of high-purity Ca(OH)2 nanoparticles suitable to consolidate porous surfaces

NASA Astrophysics Data System (ADS)

Madrid, Juan Antonio; Lanzón, Marcos

2017-12-01

Adequate synthetic methods to obtain pure Ca(OH)2 nanoparticles are scarcely documented in the literature. This paper presents a complete methodology to obtain highly-pure Ca(OH)2 nanoparticles that are appropriate for strengthening heritage materials. The precipitation synthesis was operated in controlled atmosphere to avoid carbonation by atmospheric CO2. A complete purification method was developed to eliminate the sodium chloride generated in the reaction. Several analytical techniques, such as electrical conductivity, pH, ion chromatography, X-ray diffraction (XRD) and thermogravimetric analysis coupled to mass spectrometry (TGA-MS) were used to analyse both the aqueous medium and solid phase. The amount of material obtained in the synthesis (yield) was quantified throughout the purification procedure. The influence of temperature on the nanoparticles' size and stability was studied by transmission electron microscopy (HRTEM) and sedimentation tests (light scattering). It was found that the synthesis yielded high-purity nanoparticles, whose morphological features were greatly affected by the reaction temperature.

Synthesis and characterization of a model dual-phase system using the spark plasma sintering technique

NASA Astrophysics Data System (ADS)

Teimouri, M.; Godfrey, A.

2017-07-01

Samples of a model dual-phase system, consisting of copper and AISI-420 martensitic steel have been synthesized using spark plasma sintering, with the objective of developing a microstructural analogue for dual-phase steels, in which the volume fraction and size of each phase can be controlled independently. Microstructural investigation of the samples, including fractography of samples deformed in tension until failure, show that densification is strongly temperature dependent. Samples sintered at temperatures of 900 °C or above at a pressure of 60 MPa show a density of more than 98%. The best mechanical properties, in terms of ultimate tensile strength and ductility is found in samples sintered at a temperature of 1000 °C, where a density of nearly 99% is achieved.

New polymers for low-gravity purification of cells by phase partitioning

NASA Technical Reports Server (NTRS)

Harris, J. M.

1983-01-01

A potentially powerful technique for separating different biological cell types is based on the partitioning of these cells between the immiscible aqueous phases formed by solution of certain polymers in water. This process is gravity-limited because cells sediment rather than associate with the phase most favored on the basis of cell-phase interactions. In the present contract we have been involved in the synthesis of new polymers both to aid in understanding the partitioning process and to improve the quality of separations. The prime driving force behind the design of these polymers is to produce materials which will aid in space experiments to separate important cell types and to study the partitioning process in the absence of gravity (i.e., in an equilibrium state).

Cell Partition in Two Polymer Aqueous Phases

NASA Technical Reports Server (NTRS)

Harris, J. M.

1985-01-01

Partition of biological cells in two phase aqueous polymer systems is recognized as a powerful separation technique which is limited by gravity. The synthesis of new, selective polymer ligand conjugates to be used in affinity partition separations is of interest. The two most commonly used polymers in two phase partitioning are dextran and polyethylene glycol. A thorough review of the chemistry of these polymers was begun, particularly in the area of protein attachment. Preliminary studies indicate the importance in affinity partitioning of minimizing gravity induced randomizing forces in the phase separation process. The PEG-protein conjugates that were prepared appear to be ideally suited for achieving high quality purifications in a microgravity environment. An interesting spin-off of this synthetic work was the observation of catalytic activity for certain of our polymer derivatives.

Primary Phase Field of the Pb-Doped 2223 High-Tc Superconductor in the (Bi, Pb)-Sr-Ca-Cu-O System

PubMed Central

Wong-Ng, W.; Cook, L. P.; Kearsley, A.; Greenwood, W.

1999-01-01

Both liquidus and subsolidus phase equilibrium data are of central importance for applications of high temperature superconductors in the (Bi, Pb)-Sr-Ca-Cu-O system, including material synthesis, melt processing and single crystal growth. The subsolidus equilibria of the 110 K high-Tc Pb-doped 2223 ([Bi, Pb], Sr, Ca, Cu) phase and the location of the primary phase field (crystallization field) have been determined in this study. For the quantitative determination of liquidus data, a wicking technique was developed to capture the melt for quantitative microchemical analysis. A total of 29 five-phase volumes that include the 2223 phase as a component was obtained. The initial melt compositions of these volumes range from a mole fraction of 7.3 % to 28.0 % for Bi, 11.3 % to 27.8 % for Sr, 1.2 % to 19.4 % for Pb, 9.8 % to 30.8 % for Ca, and 17.1 % to 47.0 % for Cu. Based on these data, the crystallization field for the 2223 phase was constructed using the convex hull technique. A section of this “volume” was obtained by holding two components of the composition at the median value, allowing projection on the other three axes to show the extent of the field.

Synthesizing Aluminum alloys by double mechanical alloying

NASA Astrophysics Data System (ADS)

Froyen, L.; Delaey, L.; Niu, X. P.; Le Brun, P.; Peytour, C.

1995-03-01

A new synthesis technique, namely double mechanical alloying (dMA), has been developed to fabricate aluminum alloys containing the finely distributed intermetallic compounds and inert dispersoids Al4C3 and Al2O3 The technique consists mainly of three steps: a primary milling stage of elemental powders (MAI) followed by a heat treatment to promote the formation of intermetallic phases, a secondary milling stage (MA2) to refine the microstructure, and consolidation of the produced powders. The results of mechanical and tribological properties of the resulting materials indicate that the dMA is a promising technique for the fabrication of aluminum alloys for applications requiring wear resistance and high-temperature performance.

Evaluation of Airborne l- Band Multi-Baseline Pol-Insar for dem Extraction Beneath Forest Canopy

NASA Astrophysics Data System (ADS)

Li, W. M.; Chen, E. X.; Li, Z. Y.; Jiang, C.; Jia, Y.

2018-04-01

DEM beneath forest canopy is difficult to extract with optical stereo pairs, InSAR and Pol-InSAR techniques. Tomographic SAR (TomoSAR) based on different penetration and view angles could reflect vertical structure and ground structure. This paper aims at evaluating the possibility of TomoSAR for underlying DEM extraction. Airborne L-band repeat-pass Pol-InSAR collected in BioSAR 2008 campaign was applied to reconstruct the 3D structure of forest. And sum of kronecker product and algebraic synthesis algorithm were used to extract ground structure, and phase linking algorithm was applied to estimate ground phase. Then Goldstein cut-branch approach was used to unwrap the phases and then estimated underlying DEM. The average difference between the extracted underlying DEM and Lidar DEM is about 3.39 m in our test site. And the result indicates that it is possible for underlying DEM estimation with airborne L-band repeat-pass TomoSAR technique.

Phase analysis of ZrO2-SiO2 systems synthesized through Ball milling mechanical activations

NASA Astrophysics Data System (ADS)

Nurlaila, Rizka; Musyarofah, Muwwaqor, Nibras Fuadi; Triwikantoro, Kuswoyo, Anton; Pratapa, Suminar

2017-01-01

Zircon powders have been produced from raw materials of amorphous zirconia and amorphous silica powders obtained from natural zircon sand of Kalimantan Tengah, Indonesia. Synthesis process was started with the extraction of zircon powder to produce sodium silicate solution and pure zircon powder. The amorphous zirconia and silica powders were prepared by alkali fusion and co-precipitation techniques. The powders were mixed using a planetary ball mill, followed by a calcination of various holding time of 3, 10, and 15 h. Phase characterization was done using X-Ray Diffraction (XRD) technique and analysis of the diffraction data was carried out using Rietica and MAUD software. The identified phases after the calcination were zircon, tetragonal zirconia, and cristobalite. The highest zircon content was obtained in the sample calcinated for15 hours - reaching 99.66 %wt. Crystallite size analysis revealed that the samples calcinated for 3, 10, and 15 h exhibited zircon crystal size of 176 (1) nm, 191 (1) nm and 233 (1) nm respectively.

Hydrothermal Synthesis of Nanoclusters of ZnS Comprised on Nanowires

PubMed Central

Ibupoto, Zafar Hussain; Khun, Kimleang; Liu, Xianjie; Willander, Magnus

2013-01-01

Cetyltrimethyl ammonium bromide cationic (CTAB) surfactant was used as template for the synthesis of nanoclusters of ZnS composed of nanowires, by hydrothermal method. The structural and morphological studies were performed by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) techniques. The synthesized ZnS nanoclusters are composed of nanowires and high yield on the substrate was observed. The ZnS nanocrystalline consists of hexagonal phase and polycrystalline in nature. The chemical composition of ZnS nanoclusters composed of nanowires was studied by X-ray photo electron microscopy (XPS). This investigation has shown that the ZnS nanoclusters are composed of Zn and S atoms. PMID:28348350

Hydrothermal Synthesis of Nanoclusters of ZnS Comprised on Nanowires.

PubMed

Ibupoto, Zafar Hussain; Khun, Kimleang; Liu, Xianjie; Willander, Magnus

2013-09-09

Cetyltrimethyl ammonium bromide cationic (CTAB) surfactant was used as template for the synthesis of nanoclusters of ZnS composed of nanowires, by hydrothermal method. The structural and morphological studies were performed by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) techniques. The synthesized ZnS nanoclusters are composed of nanowires and high yield on the substrate was observed. The ZnS nanocrystalline consists of hexagonal phase and polycrystalline in nature. The chemical composition of ZnS nanoclusters composed of nanowires was studied by X-ray photo electron microscopy (XPS). This investigation has shown that the ZnS nanoclusters are composed of Zn and S atoms.

One step synthesis of porous graphene by laser ablation: A new and facile approach

NASA Astrophysics Data System (ADS)

Kazemizadeh, Fatemeh; Malekfar, Rasoul

2018-02-01

Porous graphene (PG) was obtained using one step laser process. Synthesis was carried out by laser ablation of nickel-graphite target under ultra-high flow of argon gas. The field emission scanning electron microscopy (FE-SEM) results showed the formation of a porous structure and the transmission electron microscopy (TEM) revealed that the porosity of PGs increase under intense laser irradiation. Structural characterization study using Raman spectroscopy, X-ray powder diffraction (XRD) and selected area electron diffraction (SAED) technique showed that the obtained PGs display high crystalline structure in the form of few layer rhombohedral graphitic arrangement that can be interpreted as the phase prior to the formation of other carbon nanostructures.

Mono-Amine Functionalized Phthalocyanines: Mwave-Assisted Solid-Phase Synthesis and Bioconjugation Strategies

PubMed Central

Erdem, S. Sibel; Nesterova, Irina V.; Soper, Steven A.; Hammer, Robert P.

2009-01-01

Phthalocyanines (Pcs) are excellent candidates for use as fluors for near-infrared (near-IR) fluorescent tagging of biomolecules for a wide variety of bioanalytical applications. Mono-functionalized Pcs, having two different types of peripheral substitutents; one for covalent conjugation of the Pc to biomolecules and others to improve the solubility of the macrocycle, ideally suit for the desired applications. To date, difficulties faced during the purification of the mono-functionalized Pcs limited their usage in various types of applications. Herein are reported a new synthetic method for rapid synthesis of the target Pcs and bioconjugation techniques for labeling of the oligonucleotides with the near-IR flours. A novel synthetic route was developed utilizing a hydrophilic, polyethylene glycol-based (PEG) support with an acid labile Rink Amide linker. The Pcs were functionalized with an amine group for covalent conjugation purposes and were decorated with short PEG chains, serving as solubilizing groups. Mwave-assisted solid-phase synthetic method was successfully applied to obtain pure asymmetrically-substituted mono-amine functionalized Pcs in a short period of time. Three different bioconjugation techniques, reductive amination, amidation and Huisgen cycloaddition, were employed for covalent conjugation of Pcs to oligonucleotides. The described μwave-assisted bioconjugation methods give an opportunity to synthesize and isolate the Pc-oligonucleotide conjugate in a few hours. PMID:19911767

Size-controlled synthesis of nanocrystalline CdSe thin films by inert gas condensation

NASA Astrophysics Data System (ADS)

Sharma, Jeewan; Singh, Randhir; Kumar, Akshay; Singh, Tejbir; Agrawal, Paras; Thakur, Anup

2018-02-01

Size, shape and structure are considered to have significant influence on various properties of semiconducting nanomaterials. Different properties of these materials can be tailored by controlling the size. Size-controlled CdSe crystallites ranging from ˜ 04 to 95 nm were deposited by inert gas-condensation technique (IGC). In IGC method, by controlling the inert gas pressure in the condensation chamber and the substrate temperature or both, it was possible to produce nanoparticles with desired size. Structure and crystallite size of CdSe thin films were determined from Hall-Williamson method using X-ray diffraction data. The composition of CdSe samples was estimated by X-ray microanalysis. It was confirmed that CdSe thin film with different nanometer range crystallite sizes were synthesized with this technique, depending upon the synthesis conditions. The phase of deposited CdSe thin films also depend upon deposition conditions and cubic to hexagonal phase transition was observed with increase in substrate temperature. The effect of crystallite size on optical and electrical properties of these films was also studied. The crystallite size affects the optical band gap, electrical conductivity and mobility activation of nanocrystalline CdSe thin films. Mobility activation study suggested that there is a quasi-continuous linear distribution of three different trap levels below the conduction band.

A laser-deposition approach to compositional-spread discovery of materials on conventional sample sizes

NASA Astrophysics Data System (ADS)

Christen, Hans M.; Ohkubo, Isao; Rouleau, Christopher M.; Jellison, Gerald E., Jr.; Puretzky, Alex A.; Geohegan, David B.; Lowndes, Douglas H.

2005-01-01

Parallel (multi-sample) approaches, such as discrete combinatorial synthesis or continuous compositional-spread (CCS), can significantly increase the rate of materials discovery and process optimization. Here we review our generalized CCS method, based on pulsed-laser deposition, in which the synchronization between laser firing and substrate translation (behind a fixed slit aperture) yields the desired variations of composition and thickness. In situ alloying makes this approach applicable to the non-equilibrium synthesis of metastable phases. Deposition on a heater plate with a controlled spatial temperature variation can additionally be used for growth-temperature-dependence studies. Composition and temperature variations are controlled on length scales large enough to yield sample sizes sufficient for conventional characterization techniques (such as temperature-dependent measurements of resistivity or magnetic properties). This technique has been applied to various experimental studies, and we present here the results for the growth of electro-optic materials (SrxBa1-xNb2O6) and magnetic perovskites (Sr1-xCaxRuO3), and discuss the application to the understanding and optimization of catalysts used in the synthesis of dense forests of carbon nanotubes.

Selective filling for patterning in microfluidic channels and integration of chromatography in "lab-on-a-chip" devices using sol-gel technology

NASA Astrophysics Data System (ADS)

Jindal, Rohit

The last decade has seen tremendous advancement in the development of miniaturized chemical analysis system also known as "lab-on-a-chip". It is believed that the true potential of these devices will be achieved by integrating various functions such as separation, reaction, sensing, mixing, pumping, injection and detection onto a single chip. The ability to pattern different functionalities is indispensable for the development of highly integrated devices. In this work, a simple method based on the concept of selective filling is described for patterning in the microfluidic channels. It is based on the difference in the free energy of filling between an open and a covered part of the channel. This method was used for the integration of chromatography in the microfluidic devices. A chromatographic column was realized by utilizing sol-gel as an immobilization matrix for entrapping reversed phase chromatographic particles. Localization of the stationary phase was achieved using the selective filling technique. Channels were fabricated in quartz using photolithography and wet etching. Electroosmotic flow was used for manipulating fluid movement in the channels. Cross channel design was used for making a pulse injection of the solutes in the separation channel. An optical fiber setup was developed for carrying out on-chip UV absorbance detection. Stationary phase was created under different sol-gel synthesis conditions. It was established that the sol-gel synthesis carried out under acidic conditions provides the optimum synthesis conditions for creating separation column. Chromatographic performance of the stationary phase material was demonstrated by separating peptides present in a mixture. The sol-gel immobilization method was extended for the integration of micropump in the chip. The micropump enables pumping of the fluid in field free channels. Preliminary results, demonstrating the potential of carbon nanotubes as a support material in the microfluidic channels, were obtained using CVD (chemical vapor deposition) grown tubes in the channel. Results obtained in this work demonstrate the potential of selective filling technique along with sol-gel technology as a useful tool for the fabrication of multifunctional "lab-on-a-chip" devices.

Discovery-Synthesis, Design, and Prediction of Chalcogenide Phases

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

Kanatzidis, Mercouri G.

The discovery of new materials and their efficient syntheses is a fundamental goal of chemistry. A related objective is to identify foundational and rational approaches to enhance the art of synthesis by combining the exquisite predictability of organic synthesis with the high yields of solid-state chemistry. In contrast to so-called solid-state methods, inorganic syntheses in liquid fluxes permit bond formation, framework assembly, and crystallization at lower temperatures because of facile diffusion and chemical reactions with and within the flux itself. The fluxes are bona fide solvents similar to conventional organic or aqueous solvents. Such reactions can produce a wide rangemore » of materials, often metastable, from oxides to intermetallics, but typically the formation mechanisms are poorly understood. This article discusses how one can design, perform, observe, understand, and engineer the formation of compounds from inorganic melts. The focus is also design concepts such as "dimensional reduction", "phase homologies", and "panoramic synthesis", and their broad applicability. When well-defined building blocks are present and stable in the reaction, prospects for increased structural diversity and product control increase substantially. Common structural motifs within these materials systems may be related to structural precursors in the melt that may be controlled by tuning reaction conditions and composition. Stabilization of a particular building block is often accomplished with tuning of the flux composition, which controls the Lewis basicity and redox potential. In such tunable and dynamic fluxes, the synthesis can be directed toward new materials. Using complementary techniques of in situ X-ray diffraction, we can create time-dependent maps of reaction space and probe the mobile species present in melts. Lastly, certain thoughts toward the ultimate goal of targeted materials synthesis by controlling inorganic melt chemistry are discussed.« less

Discovery-Synthesis, Design, and Prediction of Chalcogenide Phases

DOE PAGES

Kanatzidis, Mercouri G.

2017-03-09

The discovery of new materials and their efficient syntheses is a fundamental goal of chemistry. A related objective is to identify foundational and rational approaches to enhance the art of synthesis by combining the exquisite predictability of organic synthesis with the high yields of solid-state chemistry. In contrast to so-called solid-state methods, inorganic syntheses in liquid fluxes permit bond formation, framework assembly, and crystallization at lower temperatures because of facile diffusion and chemical reactions with and within the flux itself. The fluxes are bona fide solvents similar to conventional organic or aqueous solvents. Such reactions can produce a wide rangemore » of materials, often metastable, from oxides to intermetallics, but typically the formation mechanisms are poorly understood. This article discusses how one can design, perform, observe, understand, and engineer the formation of compounds from inorganic melts. The focus is also design concepts such as "dimensional reduction", "phase homologies", and "panoramic synthesis", and their broad applicability. When well-defined building blocks are present and stable in the reaction, prospects for increased structural diversity and product control increase substantially. Common structural motifs within these materials systems may be related to structural precursors in the melt that may be controlled by tuning reaction conditions and composition. Stabilization of a particular building block is often accomplished with tuning of the flux composition, which controls the Lewis basicity and redox potential. In such tunable and dynamic fluxes, the synthesis can be directed toward new materials. Using complementary techniques of in situ X-ray diffraction, we can create time-dependent maps of reaction space and probe the mobile species present in melts. Lastly, certain thoughts toward the ultimate goal of targeted materials synthesis by controlling inorganic melt chemistry are discussed.« less

Synthesis, crystal growth and characterization of a phase matchable nonlinear optical single crystal: p-chloro dibenzylideneacetone

NASA Astrophysics Data System (ADS)

Ravindra, H. J.; John Kiran, A.; Nooji, Satheesha Rai; Dharmaprakash, S. M.; Chandrasekharan, K.; Kalluraya, Balakrishna; Rotermund, Fabian

2008-05-01

Good quality single crystals of p-chloro dibenzylideneacetone (CDBA) of size 13 mm×8 mm×2 mm were grown by slow evaporation solution growth technique. The grown crystals were confirmed by elemental analysis, Fourier transform infrared (FTIR) analysis and single crystal X-ray diffraction techniques. From the thermo gravimetric/differential thermal (TG/DT) analysis, the CDBA was found to be thermally stable up to 250 °C. The mechanical stability of the crystal is comparable with that of the other reported chalcones. The lower optical cut-off wavelength for this crystal was observed at 440 nm. The laser damage threshold of the crystal was 0.6 GW/cm 2 at 532 nm. The second harmonic generation conversion efficiency of the powder sample of CDBA was found to be 4.5 times greater than that of urea. We also demonstrate the existence of the phase matching property in this crystal using Kurtz powder technique.

Sustainable steric stabilization of colloidal titania nanoparticles

NASA Astrophysics Data System (ADS)

Elbasuney, Sherif

2017-07-01

A route to produce a stable colloidal suspension is essential if mono-dispersed particles are to be successfully synthesized, isolated, and used in subsequent nanocomposite manufacture. Dispersing nanoparticles in fluids was found to be an important approach for avoiding poor dispersion characteristics. However, there is still a great tendency for colloidal nanoparticles to flocculate over time. Steric stabilization can prevent coagulation by introducing a thick adsorbed organic layer which constitutes a significant steric barrier that can prevent the particle surfaces from coming into direct contact. One of the main features of hydrothermal synthesis technique is that it offers novel approaches for sustainable nanoparticle surface modification. This manuscript reports on the sustainable steric stabilization of titanium dioxide nanoparticles. Nanoparticle surface modification was performed via two main approaches including post-synthesis and in situ surface modification. The tuneable hydrothermal conditions (i.e. temperature, pressure, flow rates, and surfactant addition) were optimized to enable controlled steric stabilization in a continuous fashion. Effective post synthesis surface modification with organic ligand (dodecenyl succinic anhydride (DDSA)) was achieved; the optimum surface coating temperature was reported to be 180-240 °C to ensure DDSA ring opening and binding to titania nanoparticles. Organic-modified titania demonstrated complete change in surface properties from hydrophilic to hydrophobic and exhibited phase transfer from the aqueous phase to the organic phase. Exclusive surface modification in the reactor was found to be an effective approach; it demonstrated surfactant loading level 2.2 times that of post synthesis surface modification. Titania was also stabilized in aqueous media using poly acrylic acid (PAA) as polar polymeric dispersant. PAA-titania nanoparticles demonstrated a durable amorphous polymeric layer of 2 nm thickness. This manuscript revealed the state of the art for the real development of stable colloidal mono-dispersed particles with controlled surface properties.

Nanostructures by ion beams

NASA Astrophysics Data System (ADS)

Schmidt, B.

Ion beam techniques, including conventional broad beam ion implantation, ion beam synthesis and ion irradiation of thin layers, as well as local ion implantation with fine-focused ion beams have been applied in different fields of micro- and nanotechnology. The ion beam synthesis of nanoparticles in high-dose ion-implanted solids is explained as phase separation of nanostructures from a super-saturated solid state through precipitation and Ostwald ripening during subsequent thermal treatment of the ion-implanted samples. A special topic will be addressed to self-organization processes of nanoparticles during ion irradiation of flat and curved solid-state interfaces. As an example of silicon nanocrystal application, the fabrication of silicon nanocrystal non-volatile memories will be described. Finally, the fabrication possibilities of nanostructures, such as nanowires and chains of nanoparticles (e.g. CoSi2), by ion beam synthesis using a focused Co+ ion beam will be demonstrated and possible applications will be mentioned.

Synthesis of Mikto-Arm Star Peptide Conjugates.

PubMed

Koo, Jin Mo; Su, Hao; Lin, Yi-An; Cui, Honggang

2018-01-01

Mikto-arm star peptide conjugates are an emerging class of self-assembling peptide-based structural units that contain three or more auxiliary segments of different chemical compositions and/or functionalities. This group of molecules exhibit interesting self-assembly behavior in solution due to their chemically asymmetric topology. Here we describe the detailed procedure for synthesis of an ABC Mikto-arm star peptide conjugate in which two immiscible entities (a saturated hydrocarbon and a hydrophobic and lipophobic fluorocarbon) are conjugated onto a short β-sheet forming peptide sequence, GNNQQNY, derived from the Sup35 prion, through a lysine junction. Automated and manual Fmoc-solid phase synthesis techniques are used to synthesize the Mikto-arm star peptide conjugates, followed by HPLC purification. We envision that this set of protocols can afford a versatile platform to synthesize a new class of peptidic building units for diverse applications.

Synthesis of porous Cu from Al-Cu-Co decagonal quasicrystalline alloys

NASA Astrophysics Data System (ADS)

Kalai Vani, V.; Kwon, O. J.; Hong, S. M.; Fleury, E.

2011-07-01

The formation of a porous Cu structure from cast Al-Cu-Co decagonal quasicrystalline alloys has been studied using a selective corrosion technique. Two alkaline solutions were selected based on the electrochemical properties of the constituent elements. Selective corrosion of Al and Co was achieved by chemical immersion of the cast Al-Cu-Co alloy in both 5 M NaOH and 0.5 M Na2CO3 solutions; values for BET surface-to-weight ratio of up to 30 m2/g could be reached. Microstructural analyses indicated that the architecture of the resulting porous structures was composed of a needle-type phase, remaining from the decagonal phase, in addition to Cu and Cu-Co phases.

Optimization of infrared two-color multicycle field synthesis for intense-isolated-attosecond-pulse generation

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

Lan Pengfei; Takahashi, Eiji J.; Midorikawa, Katsumi

2010-11-15

We present the optimization of the two-color synthesis method for generating an intense isolated attosecond pulse (IAP) in the multicycle regime. By mixing an infrared assistant pulse with a Ti:sapphire main pulse, we show that an IAP can be produced using a multicycle two-color pulse with a duration longer than 30 fs. We also discuss the influence of the carrier-envelope phase (CEP) and the relative intensity on the generation of IAPs. By optimizing the wavelength of the assistant field, IAP generation becomes insensitive to the CEP slip. Therefore, the optimized two-color method enables us to relax the requirements of pulsemore » duration and easily produce the IAP with a conventional multicycle laser pulse. In addition, it enables us to markedly suppress the ionization of the harmonic medium. This is a major advantage for efficiently generating intense IAPs from a neutral medium by applying the appropriate phase-matching and energy-scaling techniques.« less

Synthesis, surface chemistry and pseudocapacitance mechanisms of VN nanocrystals derived by a simple two-step halide approach

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

Choi, Daiwon; Jampani, Prashanth H.; Jayakody, J. R. P.

Chloroamide precursors generated via a simple two-step ammonolysis reaction of transition metal chloride in the liquid phase at room temperature were heat treated in ammonia at moderate temperature to yield nano-sized VN crystallites. Grain growth inhibited by lowering the synthesis temperature (≈400°C) yielded agglomerated powders of spherical crystallites of cubic phase of VN with particle sizes as small as 6nm in diameter. X-ray diffraction, FTIR, mass spectroscopy (MS), and nuclear magnetic resonance (NMR) spectroscopy assessed the ammonolysis and nitridation reaction of the VCl 4-NH 3 system. X-ray Rietveld refinement, the BET technique and high-resolution transmission microscopy (HRTEM), energy dispersive x-raymore » (EDX) and thermogravimetric analysis (TGA) helped assess the crystallographic and microstructural nature of the VN nanocrystals. The surface chemistry and redox reaction leading to the gravimetric pseudo-capacitance value of (≈855 F/g) measured for the VN nanocrystals was determined and validated using FTIR, XPS and cyclic voltammetry analyses.« less

Synthesis, characterization and theoretical study in gaseous and solid phases of the imine 4-Acetyl-N-(4-methoxybenzylidene)aniline

NASA Astrophysics Data System (ADS)

Batista, J. F. N.; Cruz, J. W.; Doriguetto, A. C.; Torres, C.; de Almeida, E. T.; Camps, I.

2017-11-01

In the present paper we describe the synthesis and characterization of the Schiff's base or imine 4-Acetyl-N-(4-methoxybenzylidene)aniline (1), which provided experimental support for the theoretical calculations. The imine was characterized by infrared spectroscopy and single crystal XRD techniques. The computational studies were performed using the density functional theory (DFT) for the gaseous and solid phases. As similar compounds already shown biological activity, the pharmacokinetic properties of (1) were evaluated. Our results shown that (1), in its gaseous form, it is electronically stable and has pharmacological drug like properties. Due to its structural similarity with commercial drugs, it is a promise candidate to act as a nonsteroidal anti-inflammatory and to treat dementia, sleep disorders, alcohol dependence, and psychosis. From the solid state calculations we obtain that (1) is a low gap semiconductor and can act as an absorber for electromagnetic radiations with energy greater that ∼ 0.9eV .

Cell cycle progression is regulated by intertwined redox oscillators.

PubMed

da Veiga Moreira, Jorgelindo; Peres, Sabine; Steyaert, Jean-Marc; Bigan, Erwan; Paulevé, Loïc; Nogueira, Marcel Levy; Schwartz, Laurent

2015-05-29

The different phases of the eukaryotic cell cycle are exceptionally well-preserved phenomena. DNA decompaction, RNA and protein synthesis (in late G1 phase) followed by DNA replication (in S phase) and lipid synthesis (in G2 phase) occur after resting cells (in G0) are committed to proliferate. The G1 phase of the cell cycle is characterized by an increase in the glycolytic metabolism, sustained by high NAD+/NADH ratio. A transient cytosolic acidification occurs, probably due to lactic acid synthesis or ATP hydrolysis, followed by cytosolic alkalinization. A hyperpolarized transmembrane potential is also observed, as result of sodium/potassium pump (NaK-ATPase) activity. During progression of the cell cycle, the Pentose Phosphate Pathway (PPP) is activated by increased NADP+/NADPH ratio, converting glucose 6-phosphate to nucleotide precursors. Then, nucleic acid synthesis and DNA replication occur in S phase. Along with S phase, unpublished results show a cytosolic acidification, probably the result of glutaminolysis occurring during this phase. In G2 phase there is a decrease in NADPH concentration (used for membrane lipid synthesis) and a cytoplasmic alkalinization occurs. Mitochondria hyperfusion matches the cytosolic acidification at late G1/S transition and then triggers ATP synthesis by oxidative phosphorylation. We hypothesize here that the cytosolic pH may coordinate mitochondrial activity and thus the different redox cycles, which in turn control the cell metabolism.

Aerosol Route Synthesis and Applications of Doped Nanostructured Materials

NASA Astrophysics Data System (ADS)

Sahu, Manoranjan

Nanotechnology presents an attractive opportunity to address various challenges in air and water purification, energy, and other environment issues. Thus, the development of new nanoscale materials in low-cost scalable synthesis processes is important. Furthermore, the ability to independently manipulate the material properties as well as characterize the material at different steps along the synthesis route will aide in product optimization. In addition, to ensure safe and sustainable development of nanotechnology applications, potential impacts need to be evaluated. In this study, nanomaterial synthesis in a single-step gas phase reactor to continuously produce doped metal oxides was demonstrated. Copper-doped TiO2 nanomaterial properties (composition, size, and crystal phase) were independently controlled based on nanoparticle formation and growth mechanisms dictated by process control parameters. Copper dopant found to significantly affect TiO2 properties such as particle size, crystal phase, stability in the suspension, and absorption spectrum (shift from UV to visible light absorption). The in-situ charge distribution characterization of the synthesized nanomaterials was carried out by integrating a tandem differential mobility analyzer (TDMA) set up with the flame reactor synthesis system. Both singly- and doubly- charged nanoparticles were measured, with the charged fractions dependent on particle mobility and dopant concentration. A theoretical calculation was conducted to evaluate the relative importance of the two charging mechanisms, diffusion and thermo-ionization, in the flame. Nanoparticle exposure characterization was conducted during synthesis as a function of operating condition, product recovery and handling technique, and during maintenance of the reactors. Strategies were then indentified to minimize the exposure risk. The nanoparticle exposure potential varied depending on the operating conditions such as precursor feed rate, working conditions of the fume hood, ventilation system, and distance from the reactors. Nanoparticle exposure varied during product recovery and handling depending on the quantity of nanomaterial handled. Most nanomaterial applications require nanomaterials to be in solution. Thus, the role of nanomaterial physio-chemical properties (size, crystal phase, dopant types and concentrations) on dispersion properties was investigated based on hydrodynamic size and surface charge. Dopant type and concentration were found to significantly affect iso-electric point (IEP)-shifting the IEP to a high or lower pH value compared to pristine TiO2 based on the oxidation state of the dopant. The microbial inactivation effectiveness of as-synthesized nanomaterials was investigated under different light irradiation conditions. Microbial inactivation was found to strongly depend on the light irradiation condition as well as on material properties such chemical composition, crystal phase, and particle size. The potential interaction mechanisms of copper-doped TiO2 nanomaterial with microbes were also explored. The studies conducted as part of this dissertation addressed issues in nanomaterial synthesis, characterization and their potential environmental applications.

Symmetry transition via tetravalent impurity and investigations on magnetic properties of Li0.5Fe2.5O4

NASA Astrophysics Data System (ADS)

Kounsalye, Jitendra S.; Kharat, Prashant B.; Chavan, Apparao R.; Humbe, Ashok V.; Borade, R. M.; Jadhav, K. M.

2018-04-01

The present study, deals with the phase symmetry transformation of lithium ferrite after introducing tetravalent (Ti4+) impurity. The sol-gel auto combustion technique was adopted for the synthesis of nanoparticle samples with generic chemical formula Li0.5Fe2.5O4 and Li0.55Ti0.10Fe2.35O4. The synthesized nanoparticles were characterized by X-ray diffraction (XRD) technique for structural analysis. The XRD patterns show the single phase cubic structure without any impurity phase but the P4332 to Fd-3m transformation was observed after introducing Ti4+ impurity. The Nano size of the synthesized particles was confirmed by crystallite size ( 20nm) calculated using Debye-Scherrer's formula. The Fourier transform infrared spectroscopy (FTIR) studies shows shifting of band frequencies which reflect the structural changes after tetravalent substitutional impurities. The magnetic properties were studied through pulse field hysteresis loop (M-H loop) technique at room temperature, the M-H loops showdecrease in magnetic properties afternonmagnetic Ti4+ ion substitution. This is attributed to transition of inverse spinel structure of lithium ferrite to random spinel structure.

High-Throughput Synthesis and Characterization of Eu Doped Ba xSr2- xSiO4 Thin Film Phosphors.

PubMed

Frost, Sara; Guérin, Samuel; Hayden, Brian E; Soulié, Jean-Philippe; Vian, Chris

2018-06-20

High-throughput techniques have been employed for the synthesis and characterization of thin film phosphors of Eu-doped Ba x Sr 2- x SiO 4 . Direct synthesis from evaporation of the constituent elements under a flux of atomic oxygen on a sapphire substrate at 850 °C was used to directly produce thin film libraries (415 nm thickness) of the crystalline orthosilicate phase with the desired compositional variation (0.24 > x > 1.86). The orthosilicate phase could be synthesized as a pure, or predominantly pure, phase. Annealing the as synthesized library in a reducing atmosphere resulted in the reduction of the Eu while retaining the orthosilicate phase, and resulted in a materials thin film library where fluorescence excited by blue light (450 nm) was observable by the naked eye. Parallel screening of the fluorescence from the combinatorial libraries of Eu doped Ba x Sr 2- x SiO 4 has been implemented by imaging the fluorescent radiation over the library using a monochrome digital camera using a series of color filters. Informatics tools have been developed to allow the 1931 CIE color coordinates and the relative quantum efficiencies of the materials library to be rapidly assessed and mapped against composition, crystal structure and phase purity. The range of compositions gave values of CIE x between 0.17 and 0.52 and CIE y between 0.48 and 0.69 with relative efficiencies in the range 2.0 × 10 -4 -7.6 × 10 -4 . Good agreement was obtained between the thin film phosphors and the fluorescence characteristics of a number of corresponding bulk phosphor powders. The thermal quenching of fluorescence in the thin film libraries was also measured in the temperature range 25-130 °C: The phase purity of the thin film was found to significantly influence both the relative quantum efficiency and the thermal quenching of the fluorescence.

The Effect of Heat Treatment on the Crystallography and Mineral Magnetism of Pyrrhotite

NASA Astrophysics Data System (ADS)

Hobart, K.; Feinberg, J. M.; Jones, D. S.

2017-12-01

Pyrrhotite (Fe1-xS, 0 ≤ x ≤ 0.125) is the second most common sulfide mineral after pyrite in the Earth's crust, and its properties are of interest to a wide variety of scientific disciplines, including electrical engineering, physical chemistry, planetary geology and meteoritics, and economic geology. The physical properties of pyrrhotite are highly dependent on slight variations in composition and the ordering of iron vacancies, resulting in a number of possible phases between the endmember compositions of FeS and Fe7S8­­. A common complication in studies on pyrrhotite is that different phases are frequently intergrown, making it difficult to isolate a natural single phase. This has led many researchers to rely on synthesis techniques, which produce a specific structure by using precise iron/sulfur ratios, heating protocols, and controlled cooling. One of the most common synthesis treatments used to create 4C pyrrhotite is an extended heating and annealing process, which is believed to allow the reordering of vacancies to a more thermodynamically stable, ordered state with elevated saturation magnetization. The process was first studied in detail by Schwarz and Vaughan (1972) who produced synthetic pyrrhotite at varying Fe/S ratios with annealing at either 700, 300, or 144°C. The most common method for producing 4C pyrrhotite is heating at 500°C for 24 hours under a vacuum followed by annealing at 250°C for 50 hours. While this technique has been broadly applied in diverse disciplines, there is debate about whether it produces ferrimagnetic, monoclinic 4C pyrrhotite or a different metastable disordered phase. We examined this process using a combination of rock magnetic, X-ray diffraction, and electron imaging techniques to study the effect of heating and annealing on a natural sample of pyrrhotite. Due to the lack of a Besnus transition in the annealed material, our data suggest that the increased magnetization we found following annealing, rather than being an increase in 4C ferrimagnetic pyrrhotite, was the preservation of a ferrimagnetic metastable phase which represents an intermediate to the original intergrown phases. Further work will examine the differences between heat treatments on synthetic and natural pyrrhotites.

Research Support for the Laboratory for Lightwave Technology

DTIC Science & Technology

1992-12-31

34 .. . ."/ 12a. DISTRIBUTION AVAILABILITY STATEMENT 12b. DISTRIBUTION CODE UNLIMITED 13. ABSTRACT (Mawimum 200words) 4 SEE ATTACHED ABSTRACT DT I 14. SUBJECT...8217TERMS 15. NUMBER OF PAGES 16. PRICE CODE 17. SECURITY CLASSIFICATION 18. SECURITY CLASSIFICATION 19. SECURITY CLASSIFICATION 20. LIMITATION OF ABSTRACT...temperature ceramic nano- phase single crystal oxides that may be produced at a high rate . The synthesis of both glasses and ceramics using novel techniques

Responsive copolymers for enhanced petroleum recovery

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

McCormick, Charles; Hester, Roger

The objectives of this work were to: synthesize responsive, amphiphilic systems; characterize molecular structure and solution behavior; measure rheological properties of the aqueous fluids including behavior in fixed geometry flow profiles and beds; and to tailor final polymer compositions for in situ rheology control under simulated reservoir conditions. This report focuses on the first phase of the research emphasizing synthesis and the development of photophysical techniques and rheological means of following segmental organization at the structural level.

Nanocrystalline sp{sup 2} and sp{sup 3} carbons: CVD synthesis and applications

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

Terranova, M. L.; Rossi, M.; Tamburri, E., E-mail: emanuela.tamburri@uniroma2.it

The design and production of innovative materials based on nanocrystalline sp{sup 2}- and sp{sup 3}-coordinated carbons is presently a focus of the scientific community. We present a review of the nanostructures obtained in our labs using a series of synthetic routes, which make use of chemical vapor deposition (CVD) techniques for the selective production of non-planar graphitic nanostructures, nanocrystalline diamonds, and hybrid two-phase nanostructures.

EM Propagation & Atmospheric Effects Assessment

DTIC Science & Technology

2008-09-30

The split-step Fourier parabolic equation ( SSPE ) algorithm provides the complex amplitude and phase (group delay) of the continuous wave (CW) signal...the APM is based on the SSPE , we are implementing the more efficient Fourier synthesis technique to determine the transfer function. To this end a...needed in order to sample H(f) via the SSPE , and indeed with the proper parameters chosen, the two pulses can be resolved in the time window shown in

Synthesis of Perfluorinated Ethers by Solution Phase Direct Fluorination: An Adaptation of the La-Mar Technique

DTIC Science & Technology

1990-08-22

Six of the 3 perfluorinated ethers prepared have been previously synthesized by other methods: perfluoro -5,5-bis(ethoxy- f methyl) -3,7-dioxanonane...from partially fluorinated starting material [34]. Third, as with perfluoroalkanes and simple perfluoroethers , Clark’s experimental results indicated 3...a highly branched perfluoroether ) by direct fluorination 3 in solution. Second, since some of these perfluorinated compounds had been previously

1. Innovative Relaxor-Based PiezoCrystals: Phase Diagrams, Crystal Growth, Domain Structures and Electric Properties. 2. Piezo- and Ferroelectric Materials Based on Morphotropic Phase Boundary Synthesis, Characterization and Structure - Property Relations

DTIC Science & Technology

2006-03-31

crystals by the flux method and modified Bridgman technique, the growth results were hardly reproducible, and the quality of the crystals was still a serious... growth . 2.2.1.2.2) Solution Bridgman Growth A modified Bridgman method using excess of PbO as solvent was developed for the growth of PZNT91/9 crystals ...of growth , the grown crystal can be rotated via the A120 3 rod which was driven by a motor at a speed of 0 to 30 rmp. Figure 15(b) gives the

Investigating Processes of Materials Formation via Liquid Phase and Cryogenic TEM

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

De Yoreo, James J.; Sommerdijk, Nico

2016-06-14

The formation of materials in solutions is a widespread phenomenon in synthetic, biological and geochemical systems, occurring through dynamic processes of nucleation, self-assembly, crystal growth, and coarsening. The recent advent of liquid phase TEM and advances in cryogenic TEM are transforming our understanding of these phenomena by providing new insights into the underlying physical and chemical mechanisms. The techniques have been applied to metallic and semiconductor nanoparticles, geochemical and biological minerals, electrochemical systems, macromolecular complexes, and selfassembling systems, both organic and inorganic. New instrumentation and methodologies currently on the horizon promise new opportunities for advancing the science of materials synthesis.

Antibacterial studies of novel Cu2WS4 ternary chalcogenide synthesized by hydrothermal process

NASA Astrophysics Data System (ADS)

Kannan, Selvaraj; Vinitha, Perumal; Mohanraj, Kannusamy; Sivakumar, Ganesan

2018-02-01

This is the first report for the synthesis of L-cysteine mediated Cu2WS4 nanoparticles for different temperatures by an inexpensive and less pollutive hydrothermal method. The as-synthesized particles were characterized by XRD, FTIR, FESEM, UV-vis diffuse reflectance and PL spectra technique respectively. The phase purity and structural confirmation were studied by X-ray powder diffraction technique. It is observed that the synthesis temperature affecting the crystalline size. The optical analysis of the Cu2WS4 nanoparticles showed direct band gap in the range of 2.1-2.3 eV. The intensity of the PL emission spectra decreases with increase of reaction temperature. The antibacterial performance of Cu2WS4 nanoparticles were investigated by agar well diffusion method and the results confirm that the antibacterial activity of Cu2WS4 against Gram-positive (B. subtilis, M. luteus) and Gram-negative (E. coli, P. aeruginosa and K. pneumoniae) bacteria.

Isomorphic introduction of d(0) transition metals to mesoporous silica

NASA Astrophysics Data System (ADS)

Morey, Mark Sanson

1998-12-01

Early transition metals (Ti, V, Zr, Mo, W) have been incorporated in the mesoporous silicate system by hydrothermal and post-synthesis treatments. The materials were studied by diffraction, adsorption and spectroscopic techniques and were found to have catalytic, halogenation activity toward organic substrates at neutral pH. Intense interest has been shown in the new class of silica-based, mesoporous materials due to their high potential for catalytic applications. Their synthesis occurs via a cooperative self-assembly of surfactant/silicate pairs to form numerous, extended network structures upon silicate condensation based on liquid crystal phases of surfactant/water systems. Surfactant micelle removal by calcination generates a well defined pore system with a narrow pore size distribution. Of these phases, the cubic MCM-48 form possesses a high surface area (1200-1500msp2/g), a 3-D array of pores, and a large pore diameter (20-100A) so that selectivity for large (>10A kinetic diameter) molecules is possible. For this work, the MCM-48 phase was chosen since its branched, bi-continuous pore array would be less likely to clog during use than a one dimensional array. Two techniques for transition metal incorporation are compared consisting of hydrothermal and post-synthesis treatment. A brief description of an attempt to synthesize mesoporous molybdena will be included. The first approach consists of combining various metal and Si precursors in the starting gel, while exploring a broad region of the multi-component phase diagram. The second pathway involves grafting metal species on a pure silica, MCM-48 support by anchoring them to surface silanols using reactive metal alkoxides. Bulk structural characterization by X-ray powder diffraction and nitrogen adsorption shows that the pore structure is maintained after incorporation of metal species by both methods. Spectroscopic methods (FTIR/RAMAN and UV/VIS) are used to gain insight into the local metal/silica environments. The post-synthesis and grafted materials have been shown to exhibit activity in the bromination of large, organic molecules such as phenol red at neutral pH and is a first for a non-biological system. In nature, vanadium bromoperoxidase accomplishes this task, effectively producing brominated, marine natural products with interesting pharmacological properties. The five metals were meticulously chosen based on their well known oxidative properties and ease of incorporation into the silica matrix. A discussion of the relative rates of halogenation will be based on the metal's ability to coordinate and activate peroxide ligands.

Cavitational synthesis of nanostructured inorganic materials for enhanced heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Krausz, Ivo Michael

The synthesis of nanostructured inorganic materials by hydrodynamic cavitation processing was investigated. The goal of this work was to develop a general synthesis technique for nanostructured materials with a control over crystallite size in the 1--20 nm range. Materials with crystallite sizes in this range have shown enhanced catalytic activity compared to materials with larger crystallite sizes. Several supported and unsupported inorganic materials were studied to understand the effects of cavitation on crystallite size. Cavitation processing of calcium fluoride resulted in more spherical particles, attached to one another by melted necks. This work produced the first evidence of shock wave heating of nanostructured materials by hydrodynamic cavitation processing. Hydrodynamic cavitation synthesis of various catalytic support materials indicated that their phase composition and purity could be controlled by adjustment of the processing parameters. Zirconia/alumina supports synthesized using hydro-dynamic cavitation and calcined to 1368 K retained a high purity cubic zirconia phase, whereas classically prepared samples showed a phase transformation to monoclinic zirconia. Similarly, the synthesis of alumina resulted in materials with varying Bohmite and Bayerite contents as a function of the process parameters. High temperature calcination resulted in stable alumina supports with varying amounts of delta-, and theta-alumina. Synthesis studies of palladium and silver showed modest variations in crystallite size as a function of cavitation process parameters. Calcination resulted in larger grain materials, indicating a disappearance of intergrain boundaries. Based on these results, a new synthesis method was studied involving controlled agglomeration of small silver crystallites by hydrodynamic cavitation processing, followed by deposition on alumina. The optimal pH, concentration, and processing time for controlling the silver crystallite size in the cavitation equipment were determined using a statistical design of experiments approach. Three series of alumina supported silver catalysts were prepared, with silver weight loadings of 1%, 2%, and 5%. Variation of cavitation processing time between 1--64 min allowed the systematic control of silver crystallite size in the range of 3--19 nm. The preferred oxidation of CO in hydrogen (PROX) was chosen as a catalytic test reaction, because of its increasing importance for fuel cell applications. It was found that the catalytic activity was significantly increased for silver crystallite sizes below 5 nm. This work is the first experimental evidence of independent crystallite size control by hydrodynamic cavitation for alumina supported silver catalysts. The synthesis method involving controlled agglomeration and calcination is a general synthesis procedure that can be used to synthesize a wide range of novel catalysts and advanced materials.

Effect of substrate temperature in the synthesis of BN nanostructures

NASA Astrophysics Data System (ADS)

Sajjad, M.; Zhang, H. X.; Peng, X. Y.; Feng, P. X.

2011-06-01

Boron nitride (BN) nanostructures were grown on molybdenum discs at different substrate temperatures using the short-pulse laser plasma deposition technique. Large numbers of randomly oriented nanorods of fiber-like structures were obtained. The variation in the length and diameter of the nanorods as a function of the substrate temperature was systematically studied. The surface morphologies of the samples were studied using scanning electron microscopy. Energy dispersive x-ray spectroscopy confirmed that both the elements boron and nitrogen are dominant in the nanostructure. The x-ray diffraction (XRD) technique was used to analyse BN phases. The XRD peak that appeared at 26° showed the presence of hexagonal BN phase, whereas the peak at 44° was related to cubic BN content in the samples. Raman spectroscopic analysis showed vibrational modes of sp2- and sp3-type bonding in the sample. The Raman spectra agreed well with XRD results.

Synthesis of t-Butyl (2R)-Hydroxyisovalerate, A Precursor of Aureobasidin B

NASA Astrophysics Data System (ADS)

Maharani, R.; Puspitasari, D.; Taufiqqurahman; Huspa, D. H. P.; Hidayat, A. T.; Sumiarsa, D.; Hidayat, I. W.

2017-02-01

Aureobasidins are a family of cyclodepsipeptides have antifungal properties. They were isolated from the black yeast Aureobasidium pullulans R106 and over 30 derivatives have been successfully characterized. There are few publications reporting the total synthesis of aureobasidins. The limited reports of the synthesis of the aureobasidin derivatives are due to the difficult access to the preparations of precursors. The aim of this research is to synthesise a precursor of aureobasidin B, t-butyl (2R)-hydroxyisovalerate (t-Bu-Hiv), that is prepared for the total synthesis of aureobasidin B. The synthesis of AbB is planned to be undertaken by using a solid phase method, so the ester formation between t-Bu-Hiv and the Fmoc-β-hydroxymethylvaline will be carried out in solution phase to form depsidipeptide. The t-butyl group was used as protecting agent that is due to the straightforward elimination of the protecting group from the Fmoc-depsidipeptide. The t-Bu-Hiv acid was prepared from D-valine through diazotisation to form (2R)-acetyloxyisovaleric acid in 62.7% yield. Product of the first step was then protected by t-butyl group by using Boc-anhydride in t-butanol to give t-butil (2R)-acetyloxyisovalerate in 44% yield. In the last step, the acetyloxy group was eliminated by using potassium carbonate in methanol/water to give the desired product, t-Bu-Hiv in 33.5% yield. The t-Bu-Hiv is ready to be combined with Fmoc-β-hydroxymethylvaline to result in depsidipeptide that will be attached to the resin in the total synthesis of AbB. Each stage of this synthesis was controlled by thin layer chromatography and all products were purified by open column chromatography. All the synthesized products were characterized by various spectroscopic techniques, including infrared spectrophotometer, mass spectroscopy (ESI-MS), 1H-NMR and 13C-NMR.

Ambient synthesis, characterization, and electrochemical activity of LiFePO₄ nanomaterials derived from iron phosphate intermediates

DOE PAGES

Patete, Jonathan M.; Wong, Stanislaus S.; Scofield, Megan E.; ...

2015-05-30

LiFePO₄ materials have become increasingly popular as a cathode material due to the many benefits they possess including thermal stability, durability, low cost, and long life span. Nevertheless, to broaden the general appeal of this material for practical electrochemical applications, it would be useful to develop a relatively mild, reasonably simple synthesis method of this cathode material. Herein, we describe a generalizable, 2-step methodology of sustainably synthesizing LiFePO₄ by incorporating a template-based, ambient, surfactantless, seedless, U-tube protocol in order to generate size and morphologically tailored, crystalline, phase-pure nanowires. The purity, composition, crystallinity, and intrinsic quality of these wires were systematicallymore » assessed using transmission electron microscopy TEM, HRTEM, SEM, XRD, SAED, EDAX and high-resolution synchrotron XRD. From these techniques, we were able to determine that there is an absence of defects present in our wires, supporting the viability of our synthetic approach. Electrochemical analysis was also employed to assess their electrochemical activity. Although our nanowires do not contain any noticeable impurities, we attribute their less than optimal electrochemical rigor to differences in the chemical bonding between our LiFePO₄ nanowires and their bulk-like counterparts. Specifically, we demonstrate for the first time experimentally that the Fe-O3 chemical bond plays an important role in determining the overall conductivity of the material, an assertion which is further supported by recent first principles calculations. Nonetheless, our ambient, solution-based synthesis technique is capable of generating highly crystalline and phase-pure energy-storage-relevant nanowires that can be tailored so as to fabricate different sized materials of reproducible, reliable morphology.« less

A simple method for the small scale synthesis and solid-phase extraction purification of steroid sulfates.

PubMed

Waller, Christopher C; McLeod, Malcolm D

2014-12-01

Steroid sulfates are a major class of steroid metabolite that are of growing importance in fields such as anti-doping analysis, the detection of residues in agricultural produce or medicine. Despite this, many steroid sulfate reference materials may have limited or no availability hampering the development of analytical methods. We report simple protocols for the rapid synthesis and purification of steroid sulfates that are suitable for adoption by analytical laboratories. Central to this approach is the use of solid-phase extraction (SPE) for purification, a technique routinely used for sample preparation in analytical laboratories around the world. The sulfate conjugates of sixteen steroid compounds encompassing a wide range of steroid substitution patterns and configurations are prepared, including the previously unreported sulfate conjugates of the designer steroids furazadrol (17β-hydroxyandrostan[2,3-d]isoxazole), isofurazadrol (17β-hydroxyandrostan[3,2-c]isoxazole) and trenazone (17β-hydroxyestra-4,9-dien-3-one). Structural characterization data, together with NMR and mass spectra are reported for all steroid sulfates, often for the first time. The scope of this approach for small scale synthesis is highlighted by the sulfation of 1μg of testosterone (17β-hydroxyandrost-4-en-3-one) as monitored by liquid chromatography-mass spectrometry (LCMS). Copyright © 2014 Elsevier Inc. All rights reserved.

Rapid hydrothermal flow synthesis and characterisation of carbonate- and silicate-substituted calcium phosphates

PubMed Central

Knowles, Jonathan C; Rehman, Ihtesham; Darr, Jawwad A

2013-01-01

A range of crystalline and nano-sized carbonate- and silicate-substituted hydroxyapatite has been successfully produced by using continuous hydrothermal flow synthesis technology. Ion-substituted calcium phosphates are better candidates for bone replacement applications (due to improved bioactivity) as compared to phase-pure hydroxyapatite. Urea was used as a carbonate source for synthesising phase pure carbonated hydroxyapatite (CO3-HA) with ≈5 wt% substituted carbonate content (sample 7.5CO3-HA) and it was found that a further increase in urea concentration in solution resulted in biphasic mixtures of carbonate-substituted hydroxyapatite and calcium carbonate. Transmission electron microscopy images revealed that the particle size of hydroxyapatite decreased with increasing urea concentration. Energy-dispersive X-ray spectroscopy result revealed a calcium deficient apatite with Ca:P molar ratio of 1.45 (±0.04) in sample 7.5CO3-HA. For silicate-substituted hydroxyapatite (SiO4-HA) silicon acetate was used as a silicate ion source. It was observed that a substitution threshold of ∼1.1 wt% exists for synthesis of SiO4-HA in the continuous hydrothermal flow synthesis system, which could be due to the decreasing yields with progressive increase in silicon acetate concentration. All the as-precipitated powders (without any additional heat treatments) were analysed using techniques including Transmission electron microscopy, X-ray powder diffraction, Differential scanning calorimetry, Thermogravimetric analysis, Raman spectroscopy and Fourier transform infrared spectroscopy. PMID:22983020

Synthesis of nanocrystalline ZnO thin films by electron beam evaporation

NASA Astrophysics Data System (ADS)

Kondkar, V.; Rukade, D.; Bhattacharyya, V.

2018-05-01

Nanocrystalline ZnO thin films have potential for applications in variety of optoelectronic devices. In the present study, nanocrystalline thin films of ZnO are grown on fused silica substrate using electron beam (e-beam) evaporation technique. Phase identification is carried out using Glancing angle X-ray diffraction (GAXRD) and Raman spectroscopy. Ultraviolet-Visible (UV-Vis) spectroscopic analysis is carried out to calculate energy band gap of the ZnO film. Surface morphology of the film is investigated using atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). Highly quality nanocrystalline thin films of hexagonal wurtzite ZnO are synthesized using e-beam evaporation technique.

Carbon nanotubes: physics and applications

NASA Astrophysics Data System (ADS)

Bellucci, S.

2005-01-01

We overview definitions, properties and applications of Carbon nanotubes (CNTs). We describe the CNTs lifecycle: starting with phases and requirements, going through the different synthesis methods, describing then the various purification techniques. The fundamentals of functionalization and the use of defects in CNTs are reviewed, in connection also to ion irradiation techniques. Metal oxides and other semiconducting 1D nanostructures are then considered, before entering the description of the main features of the present status of INFN-LNF research in nanoscience, focusing on CNTs, as well as on aluminium nitride NTs (AlN NTs). We conclude our review by illustrating device application criteria for many applications in different areas of the field of nanotechnology.

Effects of Residual Solvent Molecules Facilitating the Infiltration Synthesis of ZnO in a Nonreactive Polymer

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

Ye, Xinyi; Kestell, John; Kisslinger, Kim

Infiltration synthesis, the atomic-layer-deposition-based organic–inorganic material hybridization technique that enables unique hybrid composites with improved material properties and inorganic nanostructures replicated from polymer templates, is shown to be driven by the binding reaction between reactive chemical groups of polymers and perfusing vapor-phase material precursors. Here in this paper, we discover that residual solvent molecules from polymer processing can react with infiltrating material precursors to enable the infiltration synthesis of metal oxides in a nonreactive polymer. The systematic study, which combines in situ quartz crystal microgravimetry, polarization-modulated infrared reflection–absorption spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy, shows that the ZnOmore » infiltration synthesis in nominally nonreactive SU-8 polymer is mediated by residual processing solvent cyclopentanone, a cyclic ketone whose Lewis-basic terminal carbonyl group can react with the infiltrating Lewis-acidic Zn precursor diethylzinc (DEZ). In addition, we find favorable roles of residual epoxy rings in the SU-8 film in further assisting the infiltration synthesis of ZnO. Lastly, the discovered rationale not only improves the understanding of infiltration synthesis mechanism, but also potentially expands its application to more diverse polymer systems for the generation of unique functional organic–inorganic hybrids and inorganic nanostructures.« less

Effects of Residual Solvent Molecules Facilitating the Infiltration Synthesis of ZnO in a Nonreactive Polymer

DOE PAGES

Ye, Xinyi; Kestell, John; Kisslinger, Kim; ...

2017-05-04

Infiltration synthesis, the atomic-layer-deposition-based organic–inorganic material hybridization technique that enables unique hybrid composites with improved material properties and inorganic nanostructures replicated from polymer templates, is shown to be driven by the binding reaction between reactive chemical groups of polymers and perfusing vapor-phase material precursors. Here in this paper, we discover that residual solvent molecules from polymer processing can react with infiltrating material precursors to enable the infiltration synthesis of metal oxides in a nonreactive polymer. The systematic study, which combines in situ quartz crystal microgravimetry, polarization-modulated infrared reflection–absorption spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy, shows that the ZnOmore » infiltration synthesis in nominally nonreactive SU-8 polymer is mediated by residual processing solvent cyclopentanone, a cyclic ketone whose Lewis-basic terminal carbonyl group can react with the infiltrating Lewis-acidic Zn precursor diethylzinc (DEZ). In addition, we find favorable roles of residual epoxy rings in the SU-8 film in further assisting the infiltration synthesis of ZnO. Lastly, the discovered rationale not only improves the understanding of infiltration synthesis mechanism, but also potentially expands its application to more diverse polymer systems for the generation of unique functional organic–inorganic hybrids and inorganic nanostructures.« less

Bulk nucleation and growth of inorganic nanowires and nanotubes

NASA Astrophysics Data System (ADS)

Sharma, Shashank

The nanometer scale materials such as nanowires and nanotubes will be of particular interest as building blocks for designing novel sensors, catalysts, electronic, optical, and optoelectronic devices. However, in order to realize these applications, bulk amounts of nanowires and nanotubes need to be synthesized with precise control over the nanostructure characteristics. In addition, the structure-property relationships for one-dimensional structures are expected to be different than their bulk when their diameters are less than a characteristic Bohr exciton radius. This fundamental curiosity also necessitates bulk synthesis of nanostructures. The current bulk nanowire synthesis methods utilize either nanometer scale porous molds or nanometer scale transition metal clusters to template one-dimensional growth. All these techniques have inherent limitations in terms of control over the nanowire diameter distribution, composition, the growth direction, and the ability to generate abrupt interfaces within individual nanowires. In this dissertation, a new concept for bulk nucleation and growth of one-dimensional nanostructures is proposed and demonstrated for a variety of inorganic material systems. In this technique, multiple nanowires nucleate and grow from pools of low-melting metal melts when exposed to an activated gas phase containing the necessary precursors. This concept, hereby termed Low Melting Metals and Activated Gas phase (LMAG) mediated method, is specifically demonstrated for the synthesis of, (a) silicon nanowires grown using molten gallium and silane precursors; (b) silicon compound nanowires using solution of molten gallium and appropriate gas phase precursors, and (c) metal-oxide nanostructures grown using direct reaction of the respective metal melts and oxygen precursors. Nanowires resulted from the same molten gallium pool at high densities (>1011/cm2) and with narrow diameter distribution. The silicon nanowires synthesized using the LMAG technique were single crystalline, defect free, and contained a non uniform, extremely thin oxide sheath (<1.5 nm). The nanowire diameter could be varied from 3 to 100 nm, with lengths up to hundreds of microns. Unique tubular and paintbrush-like morphologies were obtained in gallium oxide (Ga2O3) nanostructures. Small gallium droplets (<100 nm size) allowed Ga2O3 nanowire growth parallel to the substrate, followed by 2-dimensional nanoweb formation. These experiments using small gallium droplets resulted in the growth of crystalline Ga2O3 nanotubes with outer diameters as small as 5 nm and inner diameters as small as 2.5 nm.

Yeast cell surface display for lipase whole cell catalyst and its applications

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

Liu, Yun; Zhang, Rui; Lian, Zhongshuai

The cell surface display technique allows for the expression of target proteins or peptides on the microbial cell surface by fusing an appropriate protein as an anchoring motif. Yeast display systems, such as Pichia pastoris, Yarowia lipolytica and Saccharomyces cerevisiae, are ideal, alternative and extensive display systems with the advantage of simple genetic manipulation and post-translational modification of expressed heterologous proteins. Engineered yeasts show high performance characteristics and variant utilizations. Herein, we comprehensively summarize the variant factors affecting lipase whole cell catalyst activity and display efficiency, including the structure and size of target proteins, screening anchor proteins, type and chainmore » length of linkers, and the appropriate matching rules among the above-mentioned display units. Furthermore, we also address novel approaches to enhance stability and activity of recombinant lipases, such as VHb gene co-expression, multi-enzyme co-display technique, and the micro-environmental interference and self-assembly techniques. Finally, we represent the variety of applications of whole cell surface displayed lipases on yeast cells in non-aqueous phases, including synthesis of esters, PUFA enrichment, resolution of chiral drugs, organic synthesis and biofuels. We demonstrate that the lipase surface display technique is a powerful tool for functionalizing yeasts to serve as whole cell catalysts, and increasing interest is providing an impetus for broad application of this technique.« less

Temporal and pharmacological division of fibroblast cyclooxygenase expression into transcriptional and translational phases

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

Raz, A.; Wyche, A.; Needleman, P.

1989-03-01

The authors have recently shown that the synthesis of cyclooxygenase in human dermal fibroblasts is markedly stimulated by the cytokine interleukin 1 (IL-1). They now show that the temporal sequence of the induced synthesis of PG synthase can be separated into an early transcriptional (i.e., actinomycin D inhibitable) phase and a subsequent translational (cycloheximide but not actinomycin D inhibitable) phase and that IL-1 exerts its effect during the transcriptional phase. Phorbol 12-myristate 13-acetate also stimulates synthesis of PG synthase and, together with IL-1, produces a synergistic stimulatory effect. Inhibitors of protein kinase C activation abolished the stimulatory effect of IL-1,more » suggesting that protein kinase C activation is a critical event in the signal-transduction sequence of the IL-1-induced increase of PG synthase synthesis. The antiinflammatory glucocorticosteroids dexamethasone and triamcinolone, but not progesterone or testosterone, were potent inhibitors of PG synthase synthesis when added during the translational phase of the synthesis sequence. The glucocorticosteroid effect was blocked by RNA and protein synthesis inhibitors. This report suggests that glucocorticosteroids exert their effect via a newly synthesized protein, causing a profound translational control of PG synthase synthesis. This novel mechanism of suppression of arachidonate metabolism is distinct from any influence of steroids on phospholipase A{sub 2} activity.« less

Single crystal, liquid crystal, and hybrid organic semiconductors

NASA Astrophysics Data System (ADS)

Twieg, Robert J.; Getmanenko, Y.; Lu, Z.; Semyonov, A. N.; Huang, S.; He, P.; Seed, A.; Kiryanov, A.; Ellman, B.; Nene, S.

2003-07-01

The synthesis and characterization of organic semiconductors is being pursued in three primary structure formats: single crystal, liquid crystal and organic-inorganic hybrid. The strategy here is to share common structures, synthesis methods and fabrication techniques across these formats and to utilize common characterization tools such as the time of flight technique. The single crystal efforts concentrate on aromatic and heteroaromatic compounds including simple benzene derivatives and derivatives of the acenes. The structure-property relationships due to incorporation of small substituents and heteroatoms are being examined. Crystals are grown by solution, melt or vapor transport techniques. The liquid crystal studies exploit their self-organizing properties and relative ease of sample preparation. Though calamitic systems tha deliver the largest mobilities are higher order smectics, even some unusual twist grain boundary phases are being studied. We are attempting to synthesize discotic acene derivatives with appropriate substitution patterns to render them mesogenic. The last format being examined is the hybrid organic-inorganic class. Here, layered materials of alternating organic and inorganic composition are designed and synthesized. Typical materials are conjugated aromatic compounds, usually functinalized with an amine or a pyridine and reacted with appropriate reactive metal derivatives to incorporate them into metal oxide or sulfide layers.

Carbothermal shock synthesis of high-entropy-alloy nanoparticles

NASA Astrophysics Data System (ADS)

Yao, Yonggang; Huang, Zhennan; Xie, Pengfei; Lacey, Steven D.; Jacob, Rohit Jiji; Xie, Hua; Chen, Fengjuan; Nie, Anmin; Pu, Tiancheng; Rehwoldt, Miles; Yu, Daiwei; Zachariah, Michael R.; Wang, Chao; Shahbazian-Yassar, Reza; Li, Ju; Hu, Liangbing

2018-03-01

The controllable incorporation of multiple immiscible elements into a single nanoparticle merits untold scientific and technological potential, yet remains a challenge using conventional synthetic techniques. We present a general route for alloying up to eight dissimilar elements into single-phase solid-solution nanoparticles, referred to as high-entropy-alloy nanoparticles (HEA-NPs), by thermally shocking precursor metal salt mixtures loaded onto carbon supports [temperature ~2000 kelvin (K), 55-millisecond duration, rate of ~105 K per second]. We synthesized a wide range of multicomponent nanoparticles with a desired chemistry (composition), size, and phase (solid solution, phase-separated) by controlling the carbothermal shock (CTS) parameters (substrate, temperature, shock duration, and heating/cooling rate). To prove utility, we synthesized quinary HEA-NPs as ammonia oxidation catalysts with ~100% conversion and >99% nitrogen oxide selectivity over prolonged operations.

Anion Exchange in II-VI Semiconducting Nanostructures via Atomic Templating.

PubMed

Agarwal, Rahul; Krook, Nadia M; Ren, Ming-Liang; Tan, Liang Z; Liu, Wenjing; Rappe, Andrew M; Agarwal, Ritesh

2018-03-14

Controlled chemical transformation of nanostructures is a promising technique to obtain precisely designed novel materials, which are difficult to synthesize otherwise. We report high-temperature vapor-phase anion-exchange reactions to chemically transform II-VI semiconductor nanostructures (100-300 nm length scale) while retaining the single crystallinity, crystal structure, morphology, and even defect distribution of the parent material via atomic templating. The concept of atomic templating is employed to obtain kinetically controlled, thermodynamically metastable structural phases such as zincblende CdSe and CdS from zincblende CdTe upon complete chemical replacement of Te with Se or S. The underlying transformation mechanisms are explained through first-principles density functional theory calculations. Atomic templating is a unique path to independently tune materials' phase and composition at the nanoscale, allowing the synthesis of novel materials.

Shaping Crystal-Crystal Phase Transitions

NASA Astrophysics Data System (ADS)

Du, Xiyu; van Anders, Greg; Dshemuchadse, Julia; Glotzer, Sharon

Previous computational and experimental studies have shown self-assembled structure depends strongly on building block shape. New synthesis techniques have led to building blocks with reconfigurable shape and it has been demonstrated that building block reconfiguration can induce bulk structural reconfiguration. However, we do not understand systematically how this transition happens as a function of building block shape. Using a recently developed ``digital alchemy'' framework, we study the thermodynamics of shape-driven crystal-crystal transitions. We find examples of shape-driven bulk reconfiguration that are accompanied by first-order phase transitions, and bulk reconfiguration that occurs without any thermodynamic phase transition. Our results suggest that for well-chosen shapes and structures, there exist facile means of bulk reconfiguration, and that shape-driven bulk reconfiguration provides a viable mechanism for developing functional materials.

In Situ X-Ray Studies of Crystallization Kinetics and Ordering in Functional Organic and Hybrid Materials

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

Yang, Bin; Keum, Jong K.; Geohegan, David B.

In-Situ and time-resolved X-ray scattering and diffraction is dedicated to yielding the change of structural information as the materials are processed or grown in a controlled environment. In this chapter, we introduce the use of in situ and time-resolved X-ray techniques to understand molecular packing, crystal orientation, and phase transformation during the synthesis and processing of functional organic semiconductors, organic nanowires, and hybrid perovskite materials.

Experiences of self-practice/self-reflection in cognitive behavioural therapy: a meta-synthesis of qualitative studies.

PubMed

Gale, Corinne; Schröder, Thomas

2014-12-01

Self-practice/self-reflection is a valuable training strategy which involves therapists applying therapeutic techniques to themselves, and reflecting on the process. To undertake a meta-synthesis of qualitative studies exploring therapists' experiences of self-practice/self-reflection in cognitive behavioural therapy (CBT). This would integrate, and interpret, the current literature in order to develop a new understanding, and contribute to the development of CBT training programmes. The meta-synthesis encompassed three distinct phases: undertaking a comprehensive and systematic literature search; critically appraising the papers; and synthesising the data using the meta-ethnographic method. The literature search identified 378 papers, ten met the criteria for inclusion. After critical appraisal, all were included in the synthesis. The synthesis identified 14 constructs, which fell into three broad categories: 'experience of self-practice/self-reflection'; 'outcomes of self-practice/self-reflection'; and 'implications for training'. This synthesis found that self-practice allows therapists to put themselves into their clients' shoes, experiencing the benefits that therapy can bring but also the problems that clients can run in to. This experience increases therapists' empathy for their clients, allowing them to draw on their own experiences in therapy. As a result, therapists tend to feel both more confident in themselves and more competent as a therapist. The self-practice/self-reflection process was facilitated by reflective writing and working with others, particularly peers. Self-practice/self-reflection is a valuable training strategy in CBT, which has a range of beneficial outcomes. It can also be used as a means of continuing personal and professional development. Self-practice of CBT techniques, and reflecting on the process, can be a useful training strategy and helpful for ongoing development Therapists could consider developing a 'self-case' study, rather than using the exercises as one-off techniques, recording reflections in writing, and sharing reflections with peers. Self-practice/self-reflection can be particularly helpful for increasing empathy for clients, highlighting the difficulties they may encounter. © 2014 The British Psychological Society.

Formation and Evolution of X-ray Binaries

NASA Astrophysics Data System (ADS)

Fragkos, Anastasios

X-ray binaries - mass-transferring binary stellar systems with compact object accretors - are unique astrophysical laboratories. They carry information about many complex physical processes such as star formation, compact object formation, and evolution of interacting binaries. My thesis work involves the study of the formation and evolution of Galactic and extra-galacticX-ray binaries using both detailed and realistic simulation tools, and population synthesis techniques. I applied an innovative analysis method that allows the reconstruction of the full evolutionary history of known black hole X-ray binaries back to the time of compact object formation. This analysis takes into account all the available observationally determined properties of a system, and models in detail four of its evolutionary evolutionary phases: mass transfer through the ongoing X-ray phase, tidal evolution before the onset of Roche-lobe overflow, motion through the Galactic potential after the formation of the black hole, and binary orbital dynamics at the time of core collapse. Motivated by deep extra-galactic Chandra survey observations, I worked on population synthesis models of low-mass X-ray binaries in the two elliptical galaxies NGC3379 and NGC4278. These simulations were targeted at understanding the origin of the shape and normalization of the observed X-ray luminosity functions. In a follow up study, I proposed a physically motivated prescription for the modeling of transient neutron star low-mass X-ray binary properties, such as duty cycle, outburst duration and recurrence time. This prescription enabled the direct comparison of transient low-mass X-ray binary population synthesis models to the Chandra X-ray survey of the two ellipticals NGC3379 and NGC4278. Finally, I worked on population synthesismodels of black holeX-ray binaries in the MilkyWay. This work was motivated by recent developments in observational techniques for the measurement of black hole spin magnitudes in black hole X-ray binaries. The accuracy of these techniques depend on misalignment of the black hole spin with respect to the orbital angular momentum. In black hole X-ray binaries, this misalignment can occur during the supernova explosion that forms the compact object. In this study, I presented population synthesis models of Galactic black hole X-ray binaries, and examined the distribution of misalignment angles, and its dependence on the model parameters.

Racemic synthesis and solid phase peptide synthesis application of the chimeric valine/leucine derivative 2-amino-3,3,4-trimethyl-pentanoic acid.

PubMed

Pelà, M; Del Zoppo, L; Allegri, L; Marzola, E; Ruzza, C; Calo, G; Perissutti, E; Frecentese, F; Salvadori, S; Guerrini, R

2014-07-01

The synthesis of non natural amino acid 2-amino-3,3,4-trimethyl-pentanoic acid (Ipv) ready for solid phase peptide synthesis has been developed. Copper (I) chloride Michael addition, followed by a Curtius rearrangement are the key steps for the lpv synthesis. The racemic valine/leucine chimeric amino acid was then successfully inserted in position 5 of neuropeptide S (NPS) and the diastereomeric mixture separated by reverse phase HPLC. The two diastereomeric NPS derivatives were tested for intracellular calcium mobilization using HEK293 cells stably expressing the mouse NPS receptor where they behaved as partial agonist and pure antagonist.

Hollow latex particles: synthesis and applications.

PubMed

McDonald, Charles J; Devon, Michael J

2002-12-02

One of the major developments in emulsion polymerization over the last two decades has been the ability to make hollow latex particles. This has contributed many fundamental insights into the synthesis and the development of structure in particles. Hollow latex particles also enhance the performance of industrial coatings and potentially are useful in other technologies such as microencapsulation and controlled release. Ever since the publication of the initial process patents describing these particles, there has been a global R&D effort to extend the synthetic techniques and applications. One prominent synthetic approach to hollow particles is based on osmotic swelling. This dominates the literature, and usually starts with the synthesis of a structured latex particle containing an ionizable core that is subsequently expanded with the addition of base. Fundamental to this approach are a sophisticated control of transport phenomena, chemical reactivity within the particle, and the thermoplastic properties of the polymer shell. Hydrocarbon encapsulation technology has also been employed to make hollow latex particles. One approach involves a dispersed ternary system that balances transport, conversion kinetics, and phase separation variables to achieve the hollow morphology. Other techniques, including the use of blowing agents, are also present in the literature. The broad range of approaches that affords particles with a hollow structure demonstrates the unique flexibility of the emulsion polymerization process.

Technical Report: Understanding Functional Lyotropic Liquid Crystal Network Phase Self-Assembly and the Properties of Nanoconfined Water

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

Mahanthappa, Mahesh K; Yethiraj, Arun

Through the synergistic interplay of molecular dynamics (MD) simulations, chemical synthesis, and materials characterization by X-ray and neutron scattering techniques, this project investigated the phase behaviors of new classes of aqueous lyotropic liquid crystals (LLCs) and the properties of water nanoconfined within their pores. A portion of our studies focused on the synthesis of new classes of alkylsulfonic acid and alkylphosphonate amphiphiles, which were shown to undergo water-induced self-assembly to form a wide variety of nanostructured morphologies with unusually high degrees of long-range translational order observed by small- angle X-ray scattering (SAXS). Sample LLC morphologies that were observed include themore » lamellar (L!), tricontinuous double gyroid (G), hexagonally-packed cylinders (H), and low symmetry discontinuous micellar (I) Frank-Kasper phases. Since the G and H phases are the most promising for the development of selective ion transporting membranes for energy applications, we sought the characterize the structure and dynamics of water confined within the sub-3 nm pores of these LLCs using wide-angle neutron diffraction (WAND) and quasielastic neutron scattering (QENS) experiments performed at the Spallation Neutron Source at Oak Ridge National Laboratory. Using molecular dynamics (MD) simulations, we validated models for analyzing this QENS data to obtain water self-diffusion coefficients in LLC G and H phases of carboxylate and sulfonate surfactant LLCs as a function of the identities of their charge compensating counterions.« less

Comparison of the solid-phase fragment condensation and phase-change approaches in the synthesis of salmon I calcitonin.

PubMed

Gatos, D; Tzavara, C

2001-02-01

Salmon I calcitonin was synthesized using both phase-change and conventional solid-phase fragment condensation (SPFC) approaches, utilizing the Rink amide linker (Fmoc-amido-2,4-dimethoxybenzyl-4-phenoxyacetic acid) combined with 2-chlorotrityl resin and the Fmoc/tBu(Trt)-based protection scheme. Phase-change synthesis, performed by the selective detachment of the fully protected C-terminal 22-mer peptide-linker from the resin and subsequent condensation in solution with the N-terminal 1-10 fragment, gave a product of slightly less purity (85 vs. 92%) than the corresponding synthesis on the solid-phase. In both cases salmon I calcitonin was easily obtained in high purity.

Methanol synthesis on ZnO(0001{sup ¯}). IV. Reaction mechanisms and electronic structure

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

Frenzel, Johannes, E-mail: johannes.frenzel@theochem.rub.de; Marx, Dominik

2014-09-28

Methanol synthesis from CO and H{sub 2} over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partiallymore » hydroxylated and defective ZnO(0001{sup ¯}) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving “near-surface” molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H{sub 2} stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are discussed based on extensive electronic structure analysis.« less

Flow chemistry: intelligent processing of gas-liquid transformations using a tube-in-tube reactor.

PubMed

Brzozowski, Martin; O'Brien, Matthew; Ley, Steven V; Polyzos, Anastasios

2015-02-17

CONSPECTUS: The previous decade has witnessed the expeditious uptake of flow chemistry techniques in modern synthesis laboratories, and flow-based chemistry is poised to significantly impact our approach to chemical preparation. The advantages of moving from classical batch synthesis to flow mode, in order to address the limitations of traditional approaches, particularly within the context of organic synthesis are now well established. Flow chemistry methodology has led to measurable improvements in safety and reduced energy consumption and has enabled the expansion of available reaction conditions. Contributions from our own laboratories have focused on the establishment of flow chemistry methods to address challenges associated with the assembly of complex targets through the development of multistep methods employing supported reagents and in-line monitoring of reaction intermediates to ensure the delivery of high quality target compounds. Recently, flow chemistry approaches have addressed the challenges associated with reactions utilizing reactive gases in classical batch synthesis. The small volumes of microreactors ameliorate the hazards of high-pressure gas reactions and enable improved mixing with the liquid phase. Established strategies for gas-liquid reactions in flow have relied on plug-flow (or segmented flow) regimes in which the gas plugs are introduced to a liquid stream and dissolution of gas relies on interfacial contact of the gas bubble with the liquid phase. This approach confers limited control over gas concentration within the liquid phase and is unsuitable for multistep methods requiring heterogeneous catalysis or solid supported reagents. We have identified the use of a gas-permeable fluoropolymer, Teflon AF-2400, as a simple method of achieving efficient gas-liquid contact to afford homogeneous solutions of reactive gases in flow. The membrane permits the transport of a wide range of gases with significant control of the stoichiometry of reactive gas in a given reaction mixture. We have developed a tube-in-tube reactor device consisting of a pair of concentric capillaries in which pressurized gas permeates through an inner Teflon AF-2400 tube and reacts with dissolved substrate within a liquid phase that flows within a second gas impermeable tube. This Account examines our efforts toward the development of a simple, unified methodology for the processing of gaseous reagents in flow by way of development of a tube-in-tube reactor device and applications to key C-C, C-N, and C-O bond forming and hydrogenation reactions. We further describe the application to multistep reactions using solid-supported reagents and extend the technology to processes utilizing multiple gas reagents. A key feature of our work is the development of computer-aided imaging techniques to allow automated in-line monitoring of gas concentration and stoichiometry in real time. We anticipate that this Account will illustrate the convenience and benefits of membrane tube-in-tube reactor technology to improve and concomitantly broaden the scope of gas/liquid/solid reactions in organic synthesis.

Synthesis and characterization of a new microporous cesium silicotitanate (SNL-B) molecular sieve

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

NYMAN,MAY D.; GU,B.X.; WANG,L.M.

2000-03-20

Ongoing hydrothermal Cs-Ti-Si-O-H{sub 2}O phase investigations has produced several new ternary phases including a novel microporous Cs-silicotitanate molecular sieve, SNL-B with the approximate formula of Cs{sub 3}TiSi{sub 3}O{sub 9.5}{center_dot}3H{sub 2}O. SNL-B is only the second molecular sieve Cs-silicotitanate phase reported to have been synthesized by hydrothermal methods. Crystallites are very small (0.1 x 2 microns) with a blade-like morphology. SNL-B is confirmed to be a 3-dimensional molecular sieve by a variety of characterization techniques (N{sub 2} adsorption, ion exchange, water adsorption/desorption, solid state CP-MAS NMR). SNL-B is able to desorb and adsorb water from its pores while retaining its crystalmore » structure and exchanges Cs cations readily. Additional techniques were used to describe fundamental properties (powder X-ray diffraction, FTIR, {sup 29}Si and {sup 133}/Cs MAS NMR, DTA, SEM/EDS, ion selectivity, and radiation stability). The phase relationships of metastable SNL-B to other hydrothermally synthesized Cs-Ti-Si-O-H{sub 2}O phases are discussed, particularly its relationship to a Cs-silicotitanate analogue of pharmacosiderite, and a novel condensed phase, a polymorph of Cs{sub 2}TiSi{sub 6}O{sub 15}(SNL-A).« less

Age-Related Enhancement of a Protein Synthesis-Dependent Late Phase of LTP Induced by Low Frequency Paired-Pulse Stimulation in Hippocampus

ERIC Educational Resources Information Center

Huang, Yan-You; Kandel, Eric R.

2006-01-01

Protein synthesis-dependent late phase of LTP (L-LTP) is typically induced by repeated high-frequency stimulation (HFS). This form of L-LTP is reduced in the aged animal and is positively correlated with age-related memory loss. Here we report a novel form of protein synthesis-dependent late phase of LTP in the CA1 region of hippocampus induced by…

Late Protein Synthesis-Dependent Phases in CTA Long-Term Memory: BDNF Requirement

PubMed Central

Martínez-Moreno, Araceli; Rodríguez-Durán, Luis F.; Escobar, Martha L.

2011-01-01

It has been proposed that long-term memory (LTM) persistence requires a late protein synthesis-dependent phase, even many hours after memory acquisition. Brain-derived neurotrophic factor (BDNF) is an essential protein synthesis product that has emerged as one of the most potent molecular mediators for long-term synaptic plasticity. Studies in the rat hippocampus have been shown that BDNF is capable to rescue the late-phase of long-term potentiation as well as the hippocampus-related LTM when protein synthesis was inhibited. Our previous studies on the insular cortex (IC), a region of the temporal cortex implicated in the acquisition and storage of conditioned taste aversion (CTA), have demonstrated that intracortical delivery of BDNF reverses the deficit in CTA memory caused by the inhibition of IC protein synthesis due to anisomycin administration during early acquisition. In this work, we first analyze whether CTA memory storage is protein synthesis-dependent in different time windows. We observed that CTA memory become sensible to protein synthesis inhibition 5 and 7 h after acquisition. Then, we explore the effect of BDNF delivery (2 μg/2 μl per side) in the IC during those late protein synthesis-dependent phases. Our results show that BDNF reverses the CTA memory deficit produced by protein synthesis inhibition in both phases. These findings support the notion that recurrent rounds of consolidation-like events take place in the neocortex for maintenance of CTA memory trace and that BDNF is an essential component of these processes. PMID:21960964

Structural phase analysis and photoluminescence properties of Mg-doped TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Ali, T.; Ashraf, M. Anas; Ali, S. Asad; Ahmed, Ateeq; Tripathi, P.

2018-05-01

In this paper, we report the synthesis, characterization and photoluminescence properties of Mg-doped TiO2 nanoparticles (NPs). The samples were synthesized by sol-gel method and characterized using the standard analytical techniques such as X-ray diffraction (XRD), Transmission electron microscope (TEM), Energy dispersive X-ray spectroscopy (EDX), UV-visible and photoluminescence spectroscopy. The powder XRD spectra revealed that the synthesized samples are pure and crystalline in nature and showing tetragonal anatase phase of TiO2 NPs. UV-visible spectrum illustrates that an absorption edge shifts toward the visible region. This study may provide a new insight for making the nanomaterials which can be used in photocatalytic applications.

Microfluidic Reactors for the Controlled Synthesis of Nanoparticles

NASA Astrophysics Data System (ADS)

Erdem, Emine Yegan

Nanoparticles have attracted a lot of attention in the past few decades due to their unique, size-dependent properties. In order to use these nanoparticles in devices or sensors effectively, it is important to maintain uniform properties throughout the system; therefore nanoparticles need to have uniform sizes -- or monodisperse. In order to achieve monodispersity, an extreme control over the reaction conditions is required during their synthesis. These reaction conditions such as temperature, concentration of reagents, residence times, etc. affect the structure of nanoparticles dramatically; therefore when the conditions vary locally in the reaction vessel, different sized nanoparticles form, causing polydispersity. In widely-used batch wise synthesis techniques, large sized reaction vessels are used to mix and heat reagents. In these types of systems, it is very hard to avoid thermal gradients and to achieve rapid mixing times as well as to control residence times. Also it is not possible to make rapid changes in the reaction parameters during the synthesis. The other drawback of conventional methods is that it is not possible to separate the nucleation of nanoparticles from their growth; this leads to combined nucleation and growth and subsequently results in polydisperse size distributions. Microfluidics is an alternative method by which the limitations of conventional techniques can be addressed. Due to the small size, it is possible to control temperature and concentration of reagents precisely as well as to make rapid changes in mixing ratios of reagents or temperature of the reaction zones. There have been several microfluidic reactors -- (microreactors) in literature that were designed to improve the size distribution of nanoparticles. In this work, two novel microfluidic systems were developed for achieving controlled synthesis of nanoparticles. The first microreactor was made out of a chemically robust polymer, polyurethane, and it was used for low temperature nanoparticle synthesis. This microreactor was fabricated by using a CO 2-laser printer, which is an inexpensive method for fabricating microfluidic devices and it is a relatively fast way compared to other fabrication techniques. Iron oxide nanoparticle synthesis was demonstrated using this reactor and size distributions with a standard deviation of 10% was obtained. The second microreactor presented in this work was designed to produce monodisperse nanoparticles by utilizing thermally isolated heated and cooled regions for separating nucleation and growth processes. This microreactor was made out of silicon and it was used to demonstrate the synthesis of TiO 2 nanoparticles. Size distributions with less than 10% standard deviation were achieved. This microreactor also provides a platform for studying the effects of temperature and residence times which is very important to understand the reaction kinetics of nanoparticle synthesis. In this work, two microfluidic techniques for retrieving nanoparticles from the microreactors were also discussed. The first method was based on trapping the aqueous droplet phase inside the microchannel and the second method was utilizing a micropost array to direct droplets from the oil solution to the pure water. As a final step, a printing technique was used to print nanoparticles synthesized inside the microreactors for future applications. This ability is important for achieving smart surfaces that can utilize the properties of nanoparticles for sensing applications in the future.

Assembly of Oriented Virus Arrays by Chemo-Selective Ligation Methods and Nanolithography Techniques

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

Camarero, J A; Cheung, C L; Lin, T

2002-12-02

The present work describes our ongoing efforts towards the creation of nano-scaled ordered arrays of protein/virus covalently attached to site-specific chemical linkers patterned by different nanolithograpy techniques. We will present a new and efficient solid-phase approach for the synthesis of chemically modified long alkyl-thiols. These compounds can be used to introduce chemoselective reacting groups onto gold and silicon-based surfaces. Furthermore, these modified thiols have been used to create nanometric patterns by using different nanolithography techniques. We will show that these patterns can react chemoselectively with proteins and/or virus which have been chemically or recombinantly modified to contain complementary chemical groupsmore » at specific positions thus resulting in the oriented attachment of the protein or virus to the surface.« less

The Use of Aryl Hydrazide Linkers for the Solid Phase Synthesis of Chemically Modified Peptides

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

Woo, Y; Mitchell, A R; Camarero, J A

2006-11-03

Since Merrifield introduced the concept of solid phase synthesis in 1963 for the rapid preparation of peptides, a large variety of different supports and resin-linkers have been developed that improve the efficiency of peptide assembly and expand the myriad of synthetically feasible peptides. The aryl hydrazide is one of the most useful resin-linkers for the synthesis of chemically modified peptides. This linker is completely stable during Boc- and Fmoc-based solid phase synthesis and yet it can be cleaved under very mild oxidative conditions. The present article reviews the use of this valuable linker for the rapid and efficient synthesis ofmore » C-terminal modified peptides, head-to-tail cyclic peptides and lipidated peptides.« less

Rare earth indates (RE: La-Yb): influence of the synthesis route and heat treatment on the crystal structure.

PubMed

Shukla, Rakesh; Grover, Vinita; Srinivasu, Kancharlapalli; Paul, Barnita; Roy, Anushree; Gupta, Ruma; Tyagi, Avesh Kumar

2018-05-15

Rare earth indates are an interesting class of compounds with rich crystallography. The present study explores the crystallographic phases observed in REInO3 (RE: La-Yb) systems and their dependence on synthesis routes and annealing temperature. All REInO3 compositions were synthesized by a solid state route as well as gel-combustion synthesis (GC) followed by annealing at different temperatures. The systems were well characterized by powder XRD studies and were analysed by Rietveld refinement for the structural parameters. The cell parameters were observed to decrease in accordance with the trend in ionic radii on proceeding from lighter to heavier rare earth ions. Interestingly, the synthesis route and the annealing temperature had a profound bearing on the phase relationships observed in the REInO3 series. The solid state synthesized samples depicted an orthorhombic phase (Pbnm) field for LaInO3 to SmInO3, followed by a hexagonal-type phase (P63cm) for GdInO3 to DyInO3. However, the phase field distribution was greatly influenced upon employing gel-combustion (GC) wherein both single-phasic hexagonal and orthorhombic phase fields were found to shrink. Annealing the GC-synthesized compositions to still higher temperatures (1250 °C) further evolved the phase boundaries. An important outcome of the study is observance of polymorphism in SmInO3 which crystallized in the hexagonal phase when synthesized by GC and orthorhombic phase by solid state synthesis. This reveals the all-important role played by synthesis conditions. The existence and energetics of the two polymorphs have been elucidated and discussed with the aid of theoretical studies.

Magnetic nanoparticles-nylon 6 composite for the dispersive micro solid phase extraction of selected polycyclic aromatic hydrocarbons from water samples.

PubMed

Reyes-Gallardo, Emilia M; Lucena, R; Cárdenas, S; Valcárcel, M

2014-06-06

In this article, the easy synthesis of magnetic nanoparticles-nylon 6 composite is presented, characterized and applied in the microextraction field. The one-step synthesis of the composite is performed by a solvent changeover playing with the different solubility of the polymeric network in formic acid and water. The new material has been characterized by different techniques including infrared spectroscopy, transmission and scanning microscopy. The extraction performance of the composite under a dispersive micro solid phase extraction format has been evaluated by determining four polycyclic aromatic hydrocarbons (benzo[b]fluoranthene, fluoranthene, indeno[1,2,3-cd]pyrene and phenanthrene) in water using ultra performance liquid chromatography (UPLC) combined with photo diode array detection. The developed methodology allows the determination of the analytes with limits of detection in the range from 0.05 μg/L (benzo[b]fluoranthene) to 0.58 μg/L (phenanthrene). The repeatability of the method was better than 6.9% at the limit of quantification level. The relative recoveries varied in the interval 80-111%. Copyright © 2014 Elsevier B.V. All rights reserved.

Binary Alkali-Metal Silicon Clathrates by Spark Plasma Sintering: Preparation and Characterization

PubMed Central

Veremchuk, Igor; Beekman, Matt; Antonyshyn, Iryna; Schnelle, Walter; Baitinger, Michael; Nolas, George S.; Grin, Yuri

2016-01-01

The binary intermetallic clathrates K8-xSi46 (x = 0.4; 1.2), Rb6.2Si46, Rb11.5Si136 and Cs7.8Si136 were prepared from M4Si4 (M = K, Rb, Cs) precursors by spark-plasma route (SPS) and structurally characterized by Rietveld refinement of PXRD data. The clathrate-II phase Rb11.5Si136 was synthesized for the first time. Partial crystallographic site occupancy of the alkali metals, particularly for the smaller Si20 dodecahedra, was found in all compounds. SPS preparation of Na24Si136 with different SPS current polarities and tooling were performed in order to investigate the role of the electric field on clathrate formation. The electrical and thermal transport properties of K7.6Si46 and K6.8Si46 in the temperature range 4–700 K were investigated. Our findings demonstrate that SPS is a novel tool for the synthesis of intermetallic clathrate phases that are not easily accessible by conventional synthesis techniques. PMID:28773710

Liquid-phase synthesis of vertically aligned carbon nanotubes and related nanomaterials on preheated alloy substrates

NASA Astrophysics Data System (ADS)

Yamagiwa, Kiyofumi

2018-02-01

Carbon nanotubes (CNTs) and related nanocarbons were selectively synthesized on commercially available alloy substrates by a simple liquid-phase technique. Fe- and Ni-rich stainless-steel (JIS SUS316L and Inconel®600, respectively) and Ni-Cu alloy (Monel®400) substrates were used for the synthesis, and each substrate was preheated in air to promote the self-formation of catalyst nanolayers on the surface. The substrates were resistance heated in ethanol without any addition of catalysts to grow CNTs. The yield of the CNTs effectively increased when the preheating process was employed. Highly aligned CNT arrays grew on the SUS316L substrate, while non-aligned CNTs and distinctive twisted fibers were observed on the other substrates. An Fe oxide layer was selectively formed on the preheated SUS316L substrate promoting the growth of the CNT arrays. Characterizations including cyclic voltammetry for the arrays revealed that the CNTs possess a comparatively defect-rich surface, which is a desirable characteristic for its application such as electrode materials for capacitors.

One pot synthesis of pure micro/nano photoactive α-PbO crystals

NASA Astrophysics Data System (ADS)

Bhagat, Dharini; Waldiya, Manmohansingh; Vanpariya, Anjali; Mukhopadhyay, Indrajit

2018-05-01

The present study reports a simple, fast and cost effective precipitation technique for synthesis of pure α-PbO powder. Lead monoxide powder with tetragonal structure was synthesized chemically at an elevated temperature using lead acetate and sodium hydroxide solution bath. XRD powder diffraction was used to find the structural properties as well as phase transition from alpha to beta. Study revealed that synthesized PbO powder was crystalline with tetragonal symmetry, having an average crystallite size of 70 nm and lattice constants; a=3.97Å, b=3.97Å, and c=5.02Å. Phase transition from tetragonal to orthorhombic structure was studied by comparing the XRD data of the annealed samples in the temperature range from 200 °C to 600 °C. UV-Visible spectroscopy was used to find out the optical properties of prepared PbO powder. Diffuse reflectance and absorbance spectra confirmed the formation of α-PbO with obtained direct band gap of 1.9 eV. Synthesized lead monoxide (α-PbO) powder has promising application in energy conversion as well as energy storage applications.

Sol-gel synthesis of fine Gd{sub 2}CuO{sub 4} particles: Influence of synthesis variables

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

Mahia, J.; Vazquez-Vazquez, C.; Basadre-Pampin, M.I.

1996-02-01

Fine particles of Gd{sub 2}CuO{sub 4} were prepared by a sol-gel reaction of an aqueous solution of metal nitrates in the presence of urea, which leads to high-homogeneity polycrystalline powders of Gd{sub 2}CuO{sub 4}. The authors have studied the synthesis conditions, demonstrating the existence of a relationship between the calcination temperature and the heating time needed to attain the pure phase. Gd{sub 2}CuO{sub 4} was obtained at temperatures of the order of 650 C, lower than temperatures employed in the conventional ceramic technique. The influence of the [urea]/[salts] ratio and an excess of Cu(II) in the starting solution was alsomore » studied and discussed. X-ray powder diffraction inductively coupled plasma atomic emission spectroscopy (ICPAES), photon correlation spectroscopy (PCS), and transmission electron microscopy (TEM) were used to characterize the Gd{sub 2}CuO{sub 4} samples obtained.« less

One-pot synthesis of LaFeO3-NiFe2O4 nanocomposite ceramic by egg-white method and its magnetic and dielectric properties

NASA Astrophysics Data System (ADS)

Muthu, K. Sudalai; Lakshminarasimhan, N.; Perumal, P.

2017-10-01

A facile, one-pot synthesis of nanocomposite of LaFeO3-NiFe2O4 was demonstrated by using egg-white method. The same method was adopted to synthesize the individual component oxide nanoparticles of LaFeO3 (LFO) and NiFe2O4 (NFO). The phase formation of individual components and the nanocomposite was confirmed using powder X-Ray diffraction (XRD) technique. The measured room temperature magnetic properties of LFO, NFO and LFO-NFO nanoparticles revealed an enhancement in the properties of the nanocomposite. The dielectric behaviours of LFO, NFO and LFO-NFO pellets sintered at different temperatures such as 800, 900 and 1000 °C were investigated and correlated with the microstructures.

Enhanced low-temperature lithium storage performance of multilayer graphene made through an improved ionic liquid-assisted synthesis

NASA Astrophysics Data System (ADS)

Raccichini, Rinaldo; Varzi, Alberto; Chakravadhanula, Venkata Sai Kiran; Kübel, Christian; Balducci, Andrea; Passerini, Stefano

2015-05-01

The electrochemical properties of graphene are strongly depending on its synthesis. Between the different methods proposed so far, liquid phase exfoliation turns out to be a promising method for the production of graphene. Unfortunately, the low yield of this technique, in term of solid material obtained, still limit its use to small scale applications. In this article we propose a low cost and environmentally friendly method for producing multilayer crystalline graphene with high yield. Such innovative approach, involving an improved ionic liquid assisted, microwave exfoliation of expanded graphite, allows the production of graphene with advanced lithium ion storage performance, for the first time, at low temperatures (<0 °C), as low as -30 °C, with respect to commercially available graphite.

Telluride Misfit Layer Compounds: [(PbTe) 1.17 ] m (TiTe 2 ) n

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

Moore, Daniel B.; Beekman, Matt; Disch, Sabrina

Telluride misfit layer compounds are reported for the first time. These compounds were synthesized using a novel approach of structurally designing a precursor that would form the desired product upon low-temperature annealing, which allows the synthesis of kinetically stable products that do not appear on the equilibrium phase diagram. Four new compounds of the [(PbTe)1.17]m(TiTe2)n family are reported, and their structures were examined by a variety of X-ray diffraction techniques.

Foldable polymers as probes

DOEpatents

Li, Alexander D. Q. [Pullman, WA; Wang, Wei [Pullman, WA

2007-07-03

Disclosed herein are novel probes, which can be used to detect and identify target molecules of interest in a sample. The disclosed probes can be used to monitor conformational changes induced by molecular recognition events in addition to providing signaling the presence and/or identity of a target molecule. Methods, including solid phase synthesis techniques, for making probe molecules that exhibit changes in their optical properties upon target molecule binding are described in the disclosure. Also disclosed herein are novel chromophore moieties, which have tailored fluorescent emission spectra.

Foldable polymers as probes

DOEpatents

Li, Alexander D. Q. [Pullman, WA; Wang, Wei [Pullman, WA

2009-07-07

Disclosed herein are novel probes, which can be used to detect and identify target molecules of interest in a sample. The disclosed probes can be used to monitor conformational changes induced by molecular recognition events in addition to providing signaling the presence and/or identity of a target molecule. Methods, including solid phase synthesis techniques, for making probe molecules that exhibit changes in their optical properties upon target molecule binding are described in the disclosure. Also disclosed herein are novel chromophore moieties, which have tailored fluorescent emission spectra.

Telluride Misfit Layer Compounds: [(PbTe) 1.17 ] m (TiTe 2 ) n

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

Moore, Daniel B.; Beekman, Matt; Disch, Sabrina

2014-04-09

Telluride misfit layer compounds are reported for the first time. These compounds were synthesized using a novel approach of structurally designing a precursor that would form the desired product upon low-temperature annealing, which allows the synthesis of kinetically stable products that do not appear on the equilibrium phase diagram. Four new compounds of the [(PbTe)1.17]m(TiTe2)n family are reported, and their structures were examined by a variety of X-ray diffraction techniques.

SOLID-LIQUID PHASE TRANSFER CATALYZED SYNTHESIS OF CINNAMYL ACETATE-KINETICS AND ANALYSIS OF FACTORS AFFECTING THE REACTION IN A BATCH REACTOR

EPA Science Inventory

The use of solid-liquid phase transfer catalysis has an advantage of carrying out reaction between two immiscible substrates, one in solid phase and the other in liquid phase, with high selectivity and at relatively low temperatures. In this study we investigated the synthesis ci...

Characterizing the Three-Dimensional Structure of Block Copolymers via Sequential Infiltration Synthesis and Scanning Transmission Electron Tomography

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

Segal-Peretz, Tamar; Winterstein, Jonathan; Doxastakis, Manolis

Understanding and controlling the three-dimensional structure of block copolymer (BCP) thin films is critical for utilizing these materials for sub-20 nm nanopatterning in semiconductor devices, as well as in membranes and solar cell applications. Combining an atomic layer deposition (ALD) based technique for enhancing the contrast of BCPs in transmission electron microscopy (TEM) together with scanning TEM (STEM) tomography reveals and characterizes the three-dimensional structures of poly(styrene-block-methyl methacrylate) (PS-b-PMMA) thin films with great clarity. Sequential infiltration synthesis (SIS), a block-selective technique for growing inorganic materials in BCPs films in ALD, and an emerging tool for enhancing the etch contrast ofmore » BCPs, was harnessed to significantly enhance the high-angle scattering from the polar domains of BCP films in the TEM. The power of combining SIS and STEM tomography for three dimensional (3D) characterization of BCPs films was demonstrated with the following cases: self-assembled cylindrical, lamellar, and spherical PS-PMMA thin films. In all cases, STEM tomography has revealed 3D structures that were hidden underneath the surface, including: 1) the 3D structure of defects in cylindrical and lamellar phases, 2) non-perpendicular 3D surface of grain boundaries in the cylindrical phase, and 3) the 3D arrangement of spheres in body centered cubic (BCC) and hexagonal closed pack (HCP) morphologies in the spherical phase. The 3D data of the spherical morphologies was compared to coarse-grained simulations and assisted in validating the simulations’ parameters. STEM tomography of SIS-treated BCP films enables the characterization of the exact structure used for pattern transfer, and can lead to better understating of the physics which is utilized in BCP lithography.« less

Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers

DOEpatents

Alivisatos, A. Paul; Colvin, Vicki L.

1998-01-01

Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed.

Bioinspired synthesis of magnetic nanoparticles

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

David, Anand

2009-01-01

The synthesis of magnetic nanoparticles has long been an area of active research. Magnetic nanoparticles can be used in a wide variety of applications such as magnetic inks, magnetic memory devices, drug delivery, magnetic resonance imaging (MRI) contrast agents, and pathogen detection in foods. In applications such as MRI, particle uniformity is particularly crucial, as is the magnetic response of the particles. Uniform magnetic particles with good magnetic properties are therefore required. One particularly effective technique for synthesizing nanoparticles involves biomineralization, which is a naturally occurring process that can produce highly complex nanostructures. Also, the technique involves mild conditions (ambientmore » temperature and close to neutral pH) that make this approach suitable for a wide variety of materials. The term 'bioinspired' is important because biomineralization research is inspired by the naturally occurring process, which occurs in certain microorganisms called 'magnetotactic bacteria'. Magnetotactic bacteria use biomineralization proteins to produce magnetite crystals having very good uniformity in size and morphology. The bacteria use these magnetic particles to navigate according to external magnetic fields. Because these bacteria synthesize high quality crystals, research has focused on imitating aspects of this biomineralization in vitro. In particular, a biomineralization iron-binding protein found in a certain species of magnetotactic bacteria, magnetospirillum magneticum, AMB-1, has been extracted and used for in vitro magnetite synthesis; Pluronic F127 gel was used to increase the viscosity of the reaction medium to better mimic the conditions in the bacteria. It was shown that the biomineralization protein mms6 was able to facilitate uniform magnetite synthesis. In addition, a similar biomineralization process using mms6 and a shorter version of this protein, C25, has been used to synthesize cobalt ferrite particles. The overall goal of this project is to understand the mechanism of magnetite particle synthesis in the presence of the biomineralization proteins, mms6 and C25. Previous work has hypothesized that the mms6 protein helps to template magnetite and cobalt ferrite particle synthesis and that the C25 protein templates cobalt ferrite formation. However, the effect of parameters such as the protein concentration on the particle formation is still unknown. It is expected that the protein concentration significantly affects the nucleation and growth of magnetite. Since the protein provides iron-binding sites, it is expected that magnetite crystals would nucleate at those sites. In addition, in the previous work, the reaction medium after completion of the reaction was in the solution phase, and magnetic particles had a tendency to fall to the bottom of the medium and aggregate. The research presented in this thesis involves solid Pluronic gel phase reactions, which can be studied readily using small-angle x-ray scattering, which is not possible for the solution phase experiments. In addition, the concentration effect of both of the proteins on magnetite crystal formation was studied.« less

Non-nucleoside building blocks for copper-assisted and copper-free click chemistry for the efficient synthesis of RNA conjugates.

PubMed

Jayaprakash, K N; Peng, Chang Geng; Butler, David; Varghese, Jos P; Maier, Martin A; Rajeev, Kallanthottathil G; Manoharan, Muthiah

2010-12-03

Novel non-nucleoside alkyne monomers compatible with oligonucleotide synthesis were designed, synthesized, and efficiently incorporated into RNA and RNA analogues during solid-phase synthesis. These modifications allowed site-specific conjugation of ligands to the RNA oligonucleotides through copper-assisted (CuAAC) and copper-free strain-promoted azide-alkyne cycloaddition (SPAAC) reactions. The SPAAC click reactions of cyclooctyne-oligonucleotides with various classes of azido-functionalized ligands in solution phase and on solid phase were efficient and quantitative and occurred under mild reaction conditions. The SPAAC reaction provides a method for the synthesis of oligonucleotide-ligand conjugates uncontaminated with copper ions.

Use of the 2-chlorotrityl chloride resin for microwave-assisted solid phase peptide synthesis.

PubMed

Ieronymaki, Matthaia; Androutsou, Maria Eleni; Pantelia, Anna; Friligou, Irene; Crisp, Molly; High, Kirsty; Penkman, Kirsty; Gatos, Dimitrios; Tselios, Theodore

2015-09-01

A fast and efficient microwave (MW)-assisted solid-phase peptide synthesis protocol using the 2-chlorotrityl chloride resin and the Fmoc/tBu methodology, has been developed. The established protocol combines the advantages of MW irradiation and the acid labile 2-chlorotrityl chloride resin. The effect of temperature during the MW irradiation, the degree of resin substitution during the coupling of the first amino acids and the rate of racemization for each amino acid were evaluated. The suggested solid phase methodology is applicable for orthogonal peptide synthesis and for the synthesis of cyclic peptides. © 2015 Wiley Periodicals, Inc.

Nucleation of metastable aragonite CaCO3 in seawater.

PubMed

Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; Persson, Kristin A; Ceder, Gerbrand

2015-03-17

Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem"--the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite--which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg:Ca [corrected] ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.

Nucleation of metastable aragonite CaCO 3 in seawater

DOE PAGES

Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; ...

2015-03-04

Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters ofmore » surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing “calcite–aragonite problem”––the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite––which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg–Ca ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. The ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.« less

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

Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei

Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters ofmore » surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing “calcite–aragonite problem”––the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite––which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg–Ca ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. The ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.« less

Size-dependent surface phase change of lithium iron phosphate during carbon coating

NASA Astrophysics Data System (ADS)

Wang, Jiajun; Yang, Jinli; Tang, Yongji; Liu, Jian; Zhang, Yong; Liang, Guoxian; Gauthier, Michel; Karen Chen-Wiegart, Yu-Chen; Norouzi Banis, Mohammad; Li, Xifei; Li, Ruying; Wang, Jun; Sham, T. K.; Sun, Xueliang

2014-03-01

Carbon coating is a simple, effective and common technique for improving the conductivity of active materials in lithium ion batteries. However, carbon coating provides a strong reducing atmosphere and many factors remain unclear concerning the interface nature and underlying interaction mechanism that occurs between carbon and the active materials. Here, we present a size-dependent surface phase change occurring in lithium iron phosphate during the carbon coating process. Intriguingly, nanoscale particles exhibit an extremely high stability during the carbon coating process, whereas microscale particles display a direct visualization of surface phase changes occurring at the interface at elevated temperatures. Our findings provide a comprehensive understanding of the effect of particle size during carbon coating and the interface interaction that occurs on carbon-coated battery material—allowing for further improvement in materials synthesis and manufacturing processes for advanced battery materials.

PAH1-encoded Phosphatidate Phosphatase Plays a Role in the Growth Phase- and Inositol-mediated Regulation of Lipid Synthesis in Saccharomyces cerevisiae*

PubMed Central

Pascual, Florencia; Soto-Cardalda, Aníbal; Carman, George M.

2013-01-01

In the yeast Saccharomyces cerevisiae, the synthesis of phospholipids in the exponential phase of growth occurs at the expense of the storage lipid triacylglycerol. As exponential phase cells progress into the stationary phase, the synthesis of triacylglycerol occurs at the expense of phospholipids. Early work indicates a role of the phosphatidate phosphatase (PAP) in this metabolism; the enzyme produces the diacylglycerol needed for the synthesis of triacylglycerol and simultaneously controls the level of phosphatidate for the synthesis of phospholipids. Four genes (APP1, DPP1, LPP1, and PAH1) encode PAP activity in yeast, and it has been unclear which gene is responsible for the synthesis of triacylglycerol throughout growth. An analysis of lipid synthesis and composition, as well as PAP activity in various PAP mutant strains, showed the essential role of PAH1 in triacylglycerol synthesis throughout growth. Pah1p is a phosphorylated enzyme whose in vivo function is dependent on its dephosphorylation by the Nem1p-Spo7p protein phosphatase complex. nem1Δ mutant cells exhibited defects in triacylglycerol synthesis and lipid metabolism that mirrored those imparted by the pah1Δ mutation, substantiating the importance of Pah1p dephosphorylation throughout growth. An analysis of cells bearing PPAH1-lacZ and PPAH1-DPP1 reporter genes showed that PAH1 expression was induced throughout growth and that the induction in the stationary phase was stimulated by inositol supplementation. A mutant analysis indicated that the Ino2p/Ino4p/Opi1p regulatory circuit and transcription factors Gis1p and Rph1p mediated this regulation. PMID:24196957

DETECTING LOW-LEVEL SYNTHESIS IMPURITIES IN MODIFIED PHOSPHOROTHIOATE OLIGONUCLEOTIDES USING LIQUID CHROMATOGRAPHY – HIGH RESOLUTION MASS SPECTROMETRY

PubMed Central

Nikcevic, Irena; Wyrzykiewicz, Tadeusz K.; Limbach, Patrick A.

2010-01-01

Summary An LC-MS method based on the use of high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS) for profiling oligonucleotides synthesis impurities is described. Oligonucleotide phosphorothioatediesters (phosphorothioate oligonucleotides), in which one of the non-bridging oxygen atoms at each phosphorus center is replaced by a sulfur atom, are now one of the most popular oligonucleotide modifications due to their ease of chemical synthesis and advantageous pharmacokinetic properties. Despite significant progress in the solid-phase oligomerization chemistry used in the manufacturing of these oligonucleotides, multiple classes of low-level impurities always accompany synthetic oligonucleotides. Liquid chromatography-mass spectrometry has emerged as a powerful technique for the identification of these synthesis impurities. However, impurity profiling, where the entire complement of low-level synthetic impurities is identified in a single analysis, is more challenging. Here we present an LC-MS method based the use of high resolution-mass spectrometry, specifically Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS or FTMS). The optimal LC-FTMS conditions, including the stationary phase and mobile phases for the separation and identification of phosphorothioate oligonucleotides, were found. The characteristics of FTMS enable charge state determination from single m/z values of low-level impurities. Charge state information then enables more accurate modeling of the detected isotopic distribution for identification of the chemical composition of the detected impurity. Using this approach, a number of phosphorothioate impurities can be detected by LC-FTMS including failure sequences carrying 3′-terminal phosphate monoester and 3′-terminal phosphorothioate monoester, incomplete backbone sulfurization and desulfurization products, high molecular weight impurities, and chloral, isobutyryl, and N3 (2-cyanoethyl) adducts of the full length product. When compared with low resolution LC-MS, ~60% more impurities can be identified when charge state and isotopic distribution information is available and used for impurity profiling. PMID:21811394

Protocol for the Solid-phase Synthesis of Oligomers of RNA Containing a 2'-O-thiophenylmethyl Modification and Characterization via Circular Dichroism.

PubMed

Francis, Andrew J; Resendiz, Marino J E

2017-07-28

Solid-phase synthesis has been used to obtain canonical and modified polymers of nucleic acids, specifically of DNA or RNA, which has made it a popular methodology for applications in various fields and for different research purposes. The procedure described herein focuses on the synthesis, purification, and characterization of dodecamers of RNA 5'-[CUA CGG AAU CAU]-3' containing zero, one, or two modifications located at the C2'-O-position. The probes are based on 2-thiophenylmethyl groups, incorporated into RNA nucleotides via standard organic synthesis and introduced into the corresponding oligonucleotides via their respective phosphoramidites. This report makes use of phosphoramidite chemistry via the four canonical nucleobases (Uridine (U), Cytosine (C), Guanosine (G), Adenosine (A)), as well as 2-thiophenylmethyl functionalized nucleotides modified at the 2'-O-position; however, the methodology is amenable for a large variety of modifications that have been developed over the years. The oligonucleotides were synthesized on a controlled-pore glass (CPG) support followed by cleavage from the resin and deprotection under standard conditions, i.e., a mixture of ammonia and methylamine (AMA) followed by hydrogen fluoride/triethylamine/N-methylpyrrolidinone. The corresponding oligonucleotides were purified via polyacrylamide electrophoresis (20% denaturing) followed by elution, desalting, and isolation via reversed-phase chromatography (Sep-pak, C18-column). Quantification and structural parameters were assessed via ultraviolet-visible (UV-vis) and circular dichroism (CD) photometric analysis, respectively. This report aims to serve as a resource and guide for beginner and expert researchers interested in embarking in this field. It is expected to serve as a work-in-progress as new technologies and methodologies are developed. The description of the methodologies and techniques within this document correspond to a DNA/RNA synthesizer (refurbished and purchased in 2013) that uses phosphoramidite chemistry.

Simple sol-gel synthesis and characterization of new CoTiO3/CoFe2O4 nanocomposite by using liquid glucose, maltose and starch as fuel, capping and reducing agents.

PubMed

Ansari, Fatemeh; Sobhani, Azam; Salavati-Niasari, Masoud

2018-03-15

The sol-gel auto-combustion technique is an effective method for the synthesis of the composites. In this research for the first time, CoTiO 3 /CoFe 2 O 4 nanocomposites are successfully synthesized via a new sol-gel auto-combustion technique. The glucose, maltose and starch are used as fuel, capping and reducing agents, also the optimal reducing agent is chosen. The effects of quantity of reducing agent, molar ratio of Ti:Co, calcination temperature and time on the morphology, particle size, magnetic property, purity and phase of the nanocomposites are investigated. XRD patterns show formation of CoTiO 3 /CoFe 2 O 4 spherical nanoparticles with nearly evenly distribution, when the molar ratio of Co/Ti is 1:1. EDS analysis confirm results of XRD. The magnetic behavior of the nanocomposites is studied by VSM. The nanocomposites exhibit a high coercivity at room temperature. Copyright © 2017 Elsevier Inc. All rights reserved.

Combinatorial synthesis and hydrogenation of Mg/Al libraries prepared by electron beam physical vapor deposition.

PubMed

Garcia, Gemma; Doménech-Ferrer, Roger; Pi, Francesc; Santiso, Josep; Rodríguez-Viejo, Javier

2007-01-01

We have grown thin film libraries of the Mg-Al system using a high-throughput synthesis methodology that combines the sequential deposition of pure elements (Mg and Al) by an electron-beam (e-beam) evaporation technique and the use of a special set of moving shadow masks. This novel mask has been designed to simultaneously prepare four identical arrays of different compositions that will permit the characterization of the same library after several treatments. Wavelength dispersive spectroscopy (WDS) and micro-X-ray diffraction have been used as high-throughput screening techniques for the determination of the composition and structure of every member of the library in the as-deposited state and after hydrogenation at 1 atm of H2 during 24 h at three different temperatures: 60, 80, and 110 degrees C. We have analyzed the influence of the Mg-Al ratio on the hydrogenation of magnesium, as well as on the appearance of complex hydride phases. We have also found that aluminum can act as a catalyzer for the hydrogenation reaction of magnesium.

Electrical properties of polycrystalline methane hydrate

USGS Publications Warehouse

Du Frane, W. L.; Stern, L.A.; Weitemeyer, K.A.; Constable, S.; Pinkston, J.C.; Roberts, J.J.

2011-01-01

Electromagnetic (EM) remote-sensing techniques are demonstrated to be sensitive to gas hydrate concentration and distribution and complement other resource assessment techniques, particularly seismic methods. To fully utilize EM results requires knowledge of the electrical properties of individual phases and mixing relations, yet little is known about the electrical properties of gas hydrates. We developed a pressure cell to synthesize gas hydrate while simultaneously measuring in situ frequency-dependent electrical conductivity (σ). Synthesis of methane (CH4) hydrate was verified by thermal monitoring and by post run cryogenic scanning electron microscope imaging. Impedance spectra (20 Hz to 2 MHz) were collected before and after synthesis of polycrystalline CH4 hydrate from polycrystalline ice and used to calculate σ. We determined the σ of CH4 hydrate to be 5 × 10−5 S/m at 0°C with activation energy (Ea) of 30.6 kJ/mol (−15 to 15°C). After dissociation back into ice, σ measurements of samples increased by a factor of ~4 and Ea increased by ~50%, similar to the starting ice samples.

Ferrous sulfate based low temperature synthesis and magnetic properties of nickel ferrite nanostructures

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

Tejabhiram, Y., E-mail: tejabhiram@gmail.com; Pradeep, R.; Helen, A.T.

2014-12-15

Highlights: • Novel low temperature synthesis of nickel ferrite nanoparticles. • Comparison with two conventional synthesis techniques including hydrothermal method. • XRD results confirm the formation of crystalline nickel ferrites at 110 °C. • Superparamagnetic particles with applications in drug delivery and hyperthermia. • Magnetic properties superior to conventional methods found in new process. - Abstract: We report a simple, low temperature and surfactant free co-precipitation method for the preparation of nickel ferrite nanostructures using ferrous sulfate as the iron precursor. The products obtained from this method were compared for their physical properties with nickel ferrites produced through conventional co-precipitationmore » and hydrothermal methods which used ferric nitrate as the iron precursor. X-ray diffraction analysis confirmed the synthesis of single phase inverse spinel nanocrystalline nickel ferrites at temperature as low as 110 °C in the low temperature method. Electron microscopy analysis on the samples revealed the formation of nearly spherical nanostructures in the size range of 20–30 nm which are comparable to other conventional methods. Vibrating sample magnetometer measurements showed the formation of superparamagnetic particles with high magnetic saturation 41.3 emu/g which corresponds well with conventional synthesis methods. The spontaneous synthesis of the nickel ferrite nanoparticles by the low temperature synthesis method was attributed to the presence of 0.808 kJ mol{sup −1} of excess Gibbs free energy due to ferrous sulfate precursor.« less

The Scaled-Up Synthesis of Nanostructured Ultra-High-Temperature Ceramics and Resistance Sintering of Tantalum Carbide Nanopowders and Composites

NASA Astrophysics Data System (ADS)

Kelly, James P.

Ultra-high temperature ceramics (UHTCs) are a unique class of materials with the potential to withstand harsh environments due to covalent bonding, which gives these materials high melting temperatures, although decomposition temperatures should also be considered. For example, the melting temperature of TaC is near 4000 K, but may vaporize at lower temperatures. The high melting temperatures also make them difficult to process without high pressures and temperatures and to achieve dense ceramics with a nanostructure. Such materials however are appealing for aerospace technologies. The ability to generate high density compacts and maintain a nanostructure could allow for unprecedented control and improvement to the mechanical properties. The goal of this work is to develop processes for the synthesis and consolidation of nanostructured UHTCs. A self-propagating solvothermal synthesis technique for making UHTC nanopowders is presented. The technique is fast, scalable, and requires minimal external energy input. Synthesis of transition metal boride, carbide, and nitride powders is demonstrated. TaC is synthesized using a range of synthesis conditions and characterized to determine the fundamental mechanisms controlling the nanopowder characteristics. Discussion on purification of the powders is also presented. The sintering of TaC nanopowders produced by the solvothermal synthesis method is performed by resistance sintering. The effects of temperature, heating rate, and dwell time on densification and grain growth is presented. Adequate powder processing, carbon content, volatilization, and additives are found to be critical factors affecting the densification, microstructure, and grain growth. The optimal range of carbon addition for minimizing oxygen content is determined. WC and ZrC are evaluated as additives for reducing grain growth of TaC. Secondary phases and/or solid solutions are capable of suppressing grain growth. A unified approach to solid solution chemistries to control the densification, microstructure, and properties of UHTCs in general is presented. This work has important consequences on advancing the properties of UHTCs.

Synthesis of 1 nm Pd Nanoparticles in a Microfluidic Reactor: Insights from in Situ X ray Absorption Fine Structure Spectroscopy and Small-Angle X ray Scattering

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

Karim, Ayman M.; Al Hasan, Naila M.; Ivanov, Sergei A.

2015-06-11

In this paper we show that the temporal separation of nucleation and growth is not a necessary condition for the colloidal synthesis of monodisperse nanoparticles. The synthesis mechanism of Pd nanoparticles was determined by in situ XAFS and SAXS in a microfluidic reactor capable of millisecond up to an hour time resolution. The SAXS results showed two autocatalytic growth phases, a fast growth phase followed by a very slow growth phase. The steady increase in the number of particles throughout the two growth phases indicates the synthesis is limited by slow continuous nucleation. The transition from fast to slow growthmore » was caused by rapid increase in bonding with the capping agent as shown by XAFS. Based on this fundamental understanding of the synthesis mechanism, we show that 1 nm monodisperse Pd nanoparticles can be synthesized at low temperature using a strong binding capping agent such as trioctylphosphine (TOP).« less

Deductive Glue Code Synthesis for Embedded Software Systems Based on Code Patterns

NASA Technical Reports Server (NTRS)

Liu, Jian; Fu, Jicheng; Zhang, Yansheng; Bastani, Farokh; Yen, I-Ling; Tai, Ann; Chau, Savio N.

2006-01-01

Automated code synthesis is a constructive process that can be used to generate programs from specifications. It can, thus, greatly reduce the software development cost and time. The use of formal code synthesis approach for software generation further increases the dependability of the system. Though code synthesis has many potential benefits, the synthesis techniques are still limited. Meanwhile, components are widely used in embedded system development. Applying code synthesis to component based software development (CBSD) process can greatly enhance the capability of code synthesis while reducing the component composition efforts. In this paper, we discuss the issues and techniques for applying deductive code synthesis techniques to CBSD. For deductive synthesis in CBSD, a rule base is the key for inferring appropriate component composition. We use the code patterns to guide the development of rules. Code patterns have been proposed to capture the typical usages of the components. Several general composition operations have been identified to facilitate systematic composition. We present the technique for rule development and automated generation of new patterns from existing code patterns. A case study of using this method in building a real-time control system is also presented.

Time Dependent Structural Evolution of Porous Organic Cage CC3

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

Lucero, Jolie; Elsaidi, Sameh; Anderson, Ryther

Porous organic cage compounds are emerged with remarkable structural diversity and functionality that have applications in gas separation, catalysis and energy storage. Fundamental understanding of nucleation and growth of such materials have significant implications for understanding molecularly directed self-assembly phenomena. Herein we followed the structural evolution of a prototypical type of porous organic cage, CC3 as a function of synthesis time. Three distinctive crystal formation stages were identified: at short synthesis times, a rapid crystal growth stage in which amorphous agglomerates transformed into larger irregular particles was observed. At intermediate synthesis times, a decrease in crystal size over time wasmore » observed presumably due to crystal fragmentation, redissolution and/or homogeneous nucleation led. Finally, at longer synthesis times, a regrowth process was observed in which particles coalesced through Ostwald ripening leading to a continuous increase in crystal size. Molecular simulation studies, based on the construction of in silico CC3 models and simulation of XRD patterns and nitrogen isotherms, confirm the samples at different synthesis times to be a mixture of CC3α and CC3 amorphous phases. The CC3α phase is found to contract at different synthesis times, and the amorphous phase is found to essentially disappear at the longest synthesis time. Nitrogen and carbon dioxide adsorption properties of these CC3 phases were evaluated, and were highly dependent on synthesis time.« less

Propagation phasor approach for holographic image reconstruction

PubMed Central

Luo, Wei; Zhang, Yibo; Göröcs, Zoltán; Feizi, Alborz; Ozcan, Aydogan

2016-01-01

To achieve high-resolution and wide field-of-view, digital holographic imaging techniques need to tackle two major challenges: phase recovery and spatial undersampling. Previously, these challenges were separately addressed using phase retrieval and pixel super-resolution algorithms, which utilize the diversity of different imaging parameters. Although existing holographic imaging methods can achieve large space-bandwidth-products by performing pixel super-resolution and phase retrieval sequentially, they require large amounts of data, which might be a limitation in high-speed or cost-effective imaging applications. Here we report a propagation phasor approach, which for the first time combines phase retrieval and pixel super-resolution into a unified mathematical framework and enables the synthesis of new holographic image reconstruction methods with significantly improved data efficiency. In this approach, twin image and spatial aliasing signals, along with other digital artifacts, are interpreted as noise terms that are modulated by phasors that analytically depend on the lateral displacement between hologram and sensor planes, sample-to-sensor distance, wavelength, and the illumination angle. Compared to previous holographic reconstruction techniques, this new framework results in five- to seven-fold reduced number of raw measurements, while still achieving a competitive resolution and space-bandwidth-product. We also demonstrated the success of this approach by imaging biological specimens including Papanicolaou and blood smears. PMID:26964671

Panoscopic approach for high-performance Te-doped skutterudite

DOE PAGES

Liang, Tao; Su, Xianli; Yan, Yonggao; ...

2017-02-24

One-step plasma-activated sintering (OS-PAS) fabrication of single-phase high-performance CoSb 3-based skutterudite thermoelectric material with a hierarchical structure on a time scale of a few minutes is first reported here. The formation mechanism of the CoSb 3 phase and the effects of the current and pressure fields on the phase transformation and microstructure evolution are studied in the one-step PAS process. The application of the panoscopic approach to this system and its effect on the transport properties are investigated. The results show that the hierarchical structure forms during the formation of the skutterudite phase under the effects of both current andmore » sintering pressure. The samples fabricated by the OS-PAS technique have defined hierarchical structures, which scatter phonons more intensely over a broader range of frequencies and significantly reduce the lattice thermal conductivity. High-performance bulk Te-doped skutterudite with the maximum ZT of 1.1 at 820 K for the composition CoSb 2.875Te 0.125 was obtained. Such high ZT values rival those obtained from single filled skutterudites. As a result, this newly developed OS-PAS technique enhances the thermoelectric performance, dramatically shortens the synthesis period and provides a facile method for obtaining hierarchical thermoelectric materials on a large scale.« less

A novel route for the synthesis of nanotubes and fullerene-like nanostructures of molybdenum disulfide

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

Panigrahi, Pravas Kumar, E-mail: pravas.iit@gmail.com; Pathak, Amita, E-mail: ami@chem.iitkgp.ernet.in

Graphical abstract: Nanotubes and fullerene-like nanostructures of MoS{sub 2} were synthesized via a microwave-assisted route in solution phase. Highlights: Black-Right-Pointing-Pointer Microwave-assisted route for synthesis of nanotube and fullerene-like nanostructures of MoS{sub 2}. Black-Right-Pointing-Pointer Morphological analysis of the synthesized products. Black-Right-Pointing-Pointer Solvent plays important role in the modification of morphology of MoS{sub 2}. -- Abstract: The paper described the synthesis of nanotubes and fullerene-like nanostructures of MoS{sub 2} through a technically simple, rapid, and energy-efficient microwave-assisted synthesis technique, which involved the use of elemental sulfur dissolved in a mixture of monoethanolamine and hydrazine hydrate as the sulfide source. The microwave inducedmore » reaction between the molybdate with sulfide ions, in the presence of hydrazine hydrate in the reaction medium, resulted in the formation of gray colored powders of amorphous MoS{sub 2}. The as-obtained powders were calcined at 600 Degree-Sign C for 2 h and characterized by different techniques. HRTEM analysis of the calcined samples indicated the formation of fullerene-like MoS{sub 2} structures when the starting solution mixture was irradiated with microwave for a period of 200 s, while on 600 s of irradiation of the same revealed the formation of folded sheets like MoS{sub 2} nanotubes. BET surface areas of the calcined samples have been measured and a plausible reaction mechanism for the formation of nanotubes and fullerene-like nanostructures of MoS{sub 2} has been proposed.« less

Cooperative control theory and integrated flight and propulsion control

NASA Technical Reports Server (NTRS)

Schmidt, David K.; Schierman, John D.

1995-01-01

The major contribution of this research was the exposition of the fact that airframe and engine interactions could be present, and their effects could include loss of stability and performance of the control systems. Also, the significance of two directional, as opposed to one-directional, coupling was identified and explained. A multivariable stability and performance analysis methodology was developed, and applied to several candidate aircraft configurations. In these example evaluations, the significance of these interactions was underscored. Also exposed was the fact that with interactions present along with some integrated control approaches, the engine command/limiting logic (which represents an important nonlinear component of the engine control system) can impact closed-loop airframe/engine system stability. Finally, a brief investigation of control-law synthesis techniques appropriate for the class of systems was pursued, and it was determined that multivariable techniques, including model-following formulations of LQG and/or H infinity methods, showed promise. However, for practical reasons, decentralized control architectures are preferred, which is an architecture incompatible with these synthesis methods. The major contributions of the second phase of the grant was the development of conditions under which no decentralized controller could achieve closed loop system requirements on stability and/or performance. Sought were conditions that depended only on properties of the plant and the requirement, and independent of any particular control law or synthesis approach. Therefore, they could be applied a priori, before synthesis of a candidate control law. Under this grant, such conditions were found regarding stability, and encouraging initial results were obtained regarding performance.

Synthesis of α-MoO3 nano-flakes by dry oxidation of RF sputtered Mo thin films and their application in gas sensing

NASA Astrophysics Data System (ADS)

Dwivedi, Priyanka; Dhanekar, Saakshi; Das, Samaresh

2016-11-01

Synthesis of orthorhombic (α) MoO3 nano-flakes by dry oxidation of RF sputtered Mo thin film is presented. The influence of Mo thickness variation, oxidation temperature and time on the crystallographic structure, surface morphology and roughness of MoO3 thin films was studied using SEM, AFM, XRD and Raman spectroscopy. A structural study shows that MoO3 is polycrystalline in nature with an α phase. It was noticed that oxidation temperature plays an important role in the formation of nano-flakes. The synthesis technique proposed is simple and suitable for large scale productions. The synthesis parameters were optimized for the fabrication of sensors. Chrome gold-based IDE (interdigitated electrodes) structures were patterned for the electrical detection of organic vapors. Sensors were exposed to wide range 5-100 ppm of organic vapors like ethanol, acetone, IPA (isopropanol alcohol) and water vapors. α-MoO3 nano-flakes have demonstrated selective sensing to acetone in the range of 10-100 ppm at 150 °C. The morphology of such nanostructures has potential in applications such as sensor devices due to their high surface area and thermal stability.

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

Camarero, J A; Hackel, B J; de Yoreo, J J

C-terminal peptide thioesters are key intermediates for the synthesis/semisynthesis of proteins and for the production of cyclic peptides by native chemical ligation. They can be synthetically prepared by solid-phase peptide synthesis (SPPS) methods or biosynthetically by protein splicing techniques. Until recently, the chemical synthesis of C-terminal a-thioester peptides by SPPS was largely restricted to the Boc/Benzyl methodology because of the poor stability of the thioester bond to the basic conditions employed for the deprotection of the N{sup {alpha}}-Fmoc group. In the present work, we describe a new method for the SPPS of C-terminal thioesters by Fmoc/t-Bu chemistry. This method ismore » based on the use of an aryl hydrazide linker, which is totally stable to the Fmoc-SPPS conditions. Once the peptide synthesis has been completed, activation of the linker can be achieved by mild oxidation. This step transforms the hydrazide group into a highly reactive diazene intermediate which can react with different H-AA-SEt to yield the corresponding {alpha}-thioester peptide in good yields. This method has been successfully used for the generation of different thioester peptides, circular peptides and a fully functional SH3 protein domain.« less

Self-assembly of large-scale crack-free gold nanoparticle films using a ‘drain-to-deposit’ strategy

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

Yang, Guang; Hallinan, Daniel T.

2016-04-26

Gold nanoparticles are widely studied due to the ease of controlled synthesis, facile surface modification, and interesting physical properties. However, a technique for depositing large-area, crack-free monolayers on solid substrates is lacking. Herein is presented a method for accomplishing this. Spherical gold nanoparticles were synthesized as an aqueous dispersion. Assembly into monolayers and ligand exchange occurred simultaneously at an organic/aqueous interface. Then the monolayer film was deposited onto arbitrary solid substrates by slowly pumping out the lower, aqueous phase. This allowed the monolayer film (and liquid–liquid interface) to descend without significant disturbance, eventually reaching substrates contained in the aqueous phase.more » The resulting macroscopic quality of the films was found to be superior to films transferred by Langmuir techniques. The surface plasmon resonance and Raman enhancement of the films were evaluated and found to be uniform across the surface of each film.« 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.

Effect of the synthesis conditions on the electrochemical properties of LiFePO{sub 4} obtained from NH{sub 4}FePO{sub 4}

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

Prosini, Pier Paolo, E-mail: pierpaolo.prosini@enea.it; Gislon, Paola; Cento, Cinzia

Graphical abstract: - Highlights: • Four different samples of FAP were synthesized by precipitation techniques. • The samples were used as precursors to synthesize electrochemical active LiFePO{sub 4}. • Their morphology, composition, structure and electrochemical performance were studied. • The LiFePO{sub 4} electrochemical performance resulted affected by the preparation method - Abstract: In this paper the morphological, structural and electrochemical properties of crystalline lithium iron phosphate (LiFePO{sub 4}) obtained from ferrous ammonium phosphate (FAP) have been studied. The FAP was obtained following four different processes, namely: (1) homogeneous phase precipitation, (2) heterogeneous phase precipitation from stoichiometric sodium phosphate, (3) heterogeneousmore » phase precipitation from stoichiometric ammonium phosphate, and (4) heterogeneous phase precipitation from over stoichiometric ammonium phosphate. Lithium iron phosphate was prepared by solid state reaction of FAP with lithium hydroxide. In order to evaluate the effect of reaction time and synthesis temperature the LiFePO{sub 4} was prepared varying the heating temperatures (550, 600 and 700 °C) and the reaction times (1 or 2 h). The morphology of the materials was evaluated by scanning electron microscopy while the chemical composition was determined by electron energy loss spectroscopy. X-ray diffraction was used to evaluate phase composition, crystal structure and crystallite size. The so obtained LiFePO{sub 4}'s were fully electrochemical characterized and a correlation was found between the crystal size and the electrochemical performance.« less

Increasing reconstruction quality of diffractive optical elements displayed with LC SLM

NASA Astrophysics Data System (ADS)

Cheremkhin, Pavel A.; Evtikhiev, Nikolay N.; Krasnov, Vitaly V.; Rodin, Vladislav G.; Starikov, Sergey N.

2015-03-01

Phase liquid crystal (LC) spatial light modulators (SLM) are actively used in various applications. However, majority of scientific applications require stable phase modulation which might be hard to achieve with commercially available SLM due to its consumer origin. The use of digital voltage addressing scheme leads to phase temporal fluctuations, which results in lower diffraction efficiency and reconstruction quality of displayed diffractive optical elements (DOE). Due to high periodicity of fluctuations it should be possible to use knowledge of these fluctuations during DOE synthesis to minimize negative effect. We synthesized DOE using accurately measured phase fluctuations of phase LC SLM "HoloEye PLUTO VIS" to minimize its negative impact on displayed DOE reconstruction. Synthesis was conducted with versatile direct search with random trajectory (DSRT) method in the following way. Before DOE synthesis begun, two-dimensional dependency of SLM phase shift on addressed signal level and time from frame start was obtained. Then synthesis begins. First, initial phase distribution is created. Second, random trajectory of consecutive processing of all DOE elements is generated. Then iterative process begins. Each DOE element sequentially has its value changed to one that provides better value of objective criterion, e.g. lower deviation of reconstructed image from original one. If current element value provides best objective criterion value then it left unchanged. After all elements are processed, iteration repeats until stagnation is reached. It is demonstrated that application of SLM phase fluctuations knowledge in DOE synthesis with DSRT method leads to noticeable increase of DOE reconstruction quality.

An enhancement of photoluminescence property of Ag doped La2O3 thin films at room temperature

NASA Astrophysics Data System (ADS)

Jbeli, R.; Boukhachem, A.; Ben Jemaa, I.; Mahdhi, N.; Saadallah, F.; Elhouichet, H.; Alleg, S.; Amlouk, M.; Ezzaouïa, H.

2017-09-01

Metal transition doped oxide thin films or nanocomposites have recently emerged at the forefront of potentials research. With the focus mainly on efficiency, the aspect of stability against optical irradiation of such materials has so far not been thoroughly addressed. This work covers the synthesis of silver doped lanthanum oxide thin films (La2O3:Ag) which have been prepared by the spray pyrolysis technique on glass substrates at 460 °C. Then, Ag thin films were grown on lanthanum oxide thin films by thermal evaporation. The present work aims to reach the synthesis of La2O3:Ag thin films using both the spray pyrolysis and thermal evaporation techniques. First, X-ray diffraction analysis shows that undoped and Ag doped films crystallize in a mixture of hexagonal and cubic phase with crystallites oriented along (001) direction. Raman spectroscopy shows the bands positions corresponding to hexagonal and cubic phases. On the other hand, an attempt regarding their optical properties has been carried out by means of photoluminescence measurements. Second, from electrical conductivity measurements, the activation energy decreases from 1.42 to 1.09 eV with the increase of annealing time and the charge carriers are following the CBH model as dominant charge transport mechanism. Finally, the annealing time influences the surface wettability property and transforms La2O3 character from hydrophobic (θ > 90°) to hydrophilic (θ < 90°).

An enhancement of photoluminescence property of Ag doped La2O3 thin films at room temperature.

PubMed

Jbeli, R; Boukhachem, A; Ben Jemaa, I; Mahdhi, N; Saadallah, F; Elhouichet, H; Alleg, S; Amlouk, M; Ezzaouïa, H

2017-09-05

Metal transition doped oxide thin films or nanocomposites have recently emerged at the forefront of potentials research. With the focus mainly on efficiency, the aspect of stability against optical irradiation of such materials has so far not been thoroughly addressed. This work covers the synthesis of silver doped lanthanum oxide thin films (La 2 O 3 :Ag) which have been prepared by the spray pyrolysis technique on glass substrates at 460°C. Then, Ag thin films were grown on lanthanum oxide thin films by thermal evaporation. The present work aims to reach the synthesis of La 2 O 3 :Ag thin films using both the spray pyrolysis and thermal evaporation techniques. First, X-ray diffraction analysis shows that undoped and Ag doped films crystallize in a mixture of hexagonal and cubic phase with crystallites oriented along (001) direction. Raman spectroscopy shows the bands positions corresponding to hexagonal and cubic phases. On the other hand, an attempt regarding their optical properties has been carried out by means of photoluminescence measurements. Second, from electrical conductivity measurements, the activation energy decreases from 1.42 to 1.09eV with the increase of annealing time and the charge carriers are following the CBH model as dominant charge transport mechanism. Finally, the annealing time influences the surface wettability property and transforms La 2 O 3 character from hydrophobic (θ>90°) to hydrophilic (θ<90°). Copyright © 2017 Elsevier B.V. All rights reserved.

Nd: YAG laser irradiation effects on structural and magnetic properties of Ni1+xZrxFe2-2xO4 nanoparticles

NASA Astrophysics Data System (ADS)

Saraf, Tukaram S.; Kounsalye, Jitendra S.; Birajdar, Shankar D.; Shamkuwar, N. R.

2018-05-01

The effect of 112 mJ Nd: YAG laser irradiation on structural, morphological, infrared and magnetic properties of Ni1+xZrxFe2-2xO4 spinel ferrite nanoparticles has been systematically investigated in the present work. The sol-gel auto combustion synthesis method was successfully executed for the synthesis of the present system. All the samples were characterized by X-ray diffraction technique (XRD), scanning electron microscopy (SEM) and infrared spectroscopy (IR) technique. The magnetic properties of the present samples were measured by pulse field hysteresis loop technique. All the properties were measured for laser irradiated samples as well, to understand the effect of irradiation on the properties. The single-phase cubic spinel structure was confirmed by X-ray diffraction patterns of all samples and the disordered structure was observed for irradiated samples. The two principle absorption bands in IR spectra also confirm the formation of the spinel structure. Spherical and agglomerated morphology was observed for Zr4+ substituted nickel ferrite, whereas scratched morphology was observed for the irradiated samples. The grain size confirms the nanocrystalline nature, the crystallite size also evident the same. The magnetic parameters decreased after Zr4+ ion doping and strongly influenced by the irradiation.

Direct synthesis of BiCuChO-type oxychalcogenides by mechanical alloying

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

Pele, Vincent; Barreteau, Celine; CNRS, Orsay F-91405

2013-07-15

We report on the direct synthesis of BiCuChO based materials by mechanical alloying (Ch=Se, Te). We show that contrary to the synthesis paths used in the previous reports dealing with this family of materials, which use costly annealings in closed silica tubes under controlled atmosphere, this new synthesis route enables the synthesis of pure phase materials at room temperature under air, with reasonable milling time. This synthesis procedure is easily scalable for large scale applications. - Highlights: • Phase pure BiCuSeO doped and undoped prepared by mechanical alloying. • Synthesis performed under air at room temperature. • Electrical properties similarmore » to that of samples synthesized by a classical path.« less

In Situ Environmental TEM in Imaging Gas and Liquid Phase Chemical Reactions for Materials Research.

PubMed

Wu, Jianbo; Shan, Hao; Chen, Wenlong; Gu, Xin; Tao, Peng; Song, Chengyi; Shang, Wen; Deng, Tao

2016-11-01

Gas and liquid phase chemical reactions cover a broad range of research areas in materials science and engineering, including the synthesis of nanomaterials and application of nanomaterials, for example, in the areas of sensing, energy storage and conversion, catalysis, and bio-related applications. Environmental transmission electron microscopy (ETEM) provides a unique opportunity for monitoring gas and liquid phase reactions because it enables the observation of those reactions at the ultra-high spatial resolution, which is not achievable through other techniques. Here, the fundamental science and technology developments of gas and liquid phase TEM that facilitate the mechanistic study of the gas and liquid phase chemical reactions are discussed. Combined with other characterization tools integrated in TEM, unprecedented material behaviors and reaction mechanisms are observed through the use of the in situ gas and liquid phase TEM. These observations and also the recent applications in this emerging area are described. The current challenges in the imaging process are also discussed, including the imaging speed, imaging resolution, and data management. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of a metal oxide with a room-temperature photoreversible phase transition.

PubMed

Ohkoshi, Shin-Ichi; Tsunobuchi, Yoshihide; Matsuda, Tomoyuki; Hashimoto, Kazuhito; Namai, Asuka; Hakoe, Fumiyoshi; Tokoro, Hiroko

2010-07-01

Photoinduced phase-transition materials, such as chalcogenides, spin-crossover complexes, photochromic organic compounds and charge-transfer materials, are of interest because of their application to optical data storage. Here we report a photoreversible metal-semiconductor phase transition at room temperature with a unique phase of Ti(3)O(5), lambda-Ti(3)O(5). lambda-Ti(3)O(5) nanocrystals are made by the combination of reverse-micelle and sol-gel techniques. Thermodynamic analysis suggests that the photoinduced phase transition originates from a particular state of lambda-Ti(3)O(5) trapped at a thermodynamic local energy minimum. Light irradiation causes reversible switching between this trapped state (lambda-Ti(3)O(5)) and the other energy-minimum state (beta-Ti(3)O(5)), both of which are persistent phases. This is the first demonstration of a photorewritable phenomenon at room temperature in a metal oxide. lambda-Ti(3)O(5) satisfies the operation conditions required for a practical optical storage system (operational temperature, writing data by short wavelength light and the appropriate threshold laser power).

A Comparison of Wavetable and FM Data Reduction Methods for Resynthesis of Musical Sounds

NASA Astrophysics Data System (ADS)

Horner, Andrew

An ideal music-synthesis technique provides both high-level spectral control and efficient computation. Simple playback of recorded samples lacks spectral control, while additive sine-wave synthesis is inefficient. Wavetable and frequencymodulation synthesis, however, are two popular synthesis techniques that are very efficient and use only a few control parameters.

Synthesis and nonstoichiometry of the zirconium trihalides

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

Daake, R.L.; Corbett, J.D.

1978-05-01

The synthesis of ZrX/sub 3/ (X = Cl, Br, I) by reaction of the corresponding tetrahalides with ZrCl, ZrBr, or ZrI/sub 1.8/ in sealed tantalum tubing gives high-purity, single-phase products, thereby avoiding problems of the relatively low reactivity of and contamination by zirconium powder reductant used previously. Phase limits for the three trihalides established by isopiestic equilibration with the adjoining phases are 2.94 (2) less than or equal to Cl:Zr less than or equal to 3.03 (2) (440/sup 0/C), 2.87 (2) less than or equal to Br:Zr less than or equal to 3.23 (2) (435/sup 0/C), and 2.83 (5) (775/supmore » 0/C) less than or equal to I:Zr less than or equal to 3.43 (5) (475/sup 0/C). The hexagonal lattice constants for the bromide phase (Guinier techniques) decrease linearly with increasing bromide content across the entire range without the development of any additional lines. The variation of the c dimension for ZrI/sub 3/ (and HfI/sub 3/) on oxidation is in the opposite direction, and in this case extra lines from a presumed superlattice structure developed toward the upper limit. The structural implications of these results are considered. The reported structure for ..cap alpha..-ZrCl/sub 3/, an unusual BiI/sub 3/-type variant, was based on a misassigned ZrCl powder pattern and therefore appears to be in error. 25 references.« less

Synthesis, structural properties and thermal stability of Mn-doped hydroxyapatite

NASA Astrophysics Data System (ADS)

Paluszkiewicz, Czesława; Ślósarczyk, Anna; Pijocha, Dawid; Sitarz, Maciej; Bućko, Mirosław; Zima, Aneta; Chróścicka, Anna; Lewandowska-Szumieł, Małgorzata

2010-07-01

Hydroxyapatite (HA) - Ca 10(PO 4) 6(OH) 2 is a basic inorganic model component of hard biological tissues, such as bones and teeth. The significant property of HA is its ability to exchange Ca 2+ ions, which influences crystallinity, physico-chemical and biological properties of modified hydroxyapatite materials. In this work, FTIR, Raman spectroscopy, XRD, SEM and EDS techniques were used to determine thermal stability, chemical and phase composition of Mn containing hydroxyapatite (MnHA). Described methods confirmed thermal decomposition and phase transformation of MnHA to αTCP, βTCP and formation of Mn 3O 4 depending on sintering temperature and manganese content. In vitro biological evaluation of Mn-modified HA ceramics was also performed using human osteoblast cells.

R. Bruce Merrifield and Solid-Phase Peptide Synthesis: A Historical Assessment

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

Mitchell, A R

2007-12-04

Bruce Merrifield, trained as a biochemist, had to address three major challenges related to the development and acceptance of solid-phase peptide synthesis (SPPS). The challenges were (1) to reduce the concept of peptide synthesis on a insoluble support to practice, (2) overcome the resistance of synthetic chemists to this novel approach, and (3) establish that a biochemist had the scientific credentials to effect the proposed revolutionary change in chemical synthesis. How these challenges were met is discussed in this article.

The Seminal Literature of Nanotechnology Research

DTIC Science & Technology

2005-01-01

membrane-based synthetic approach to nanomaterials (Martin, 1994) was followed by synthesis of thiol derivatized gold nanoparticles in a two phase liquid... nanoparticles into macroscopic materials (Mirkin et al, 1996). A study on general synthesis of compound semiconductor nanowires provided a rational...Bethell D, Schiffrin DJ, Whyman R. (1994). Synthesis of thiol-derivatized gold nanoparticles in a 2-phase liquid-liquid system. Journal of the

The formation of α-phase SnS nanostructure from a hybrid, multi-layered S/Sn/S/Sn/S thin films: Phase stability, surface morphology and optical studies

NASA Astrophysics Data System (ADS)

Baby, Benjamin Hudson; Bharathi Mohan, D.

2017-11-01

Single phase of SnS thin film was fabricated from S/Sn/S/Sn/S multilayer prepared by using atmospheric pressure and vacuum thermal evaporation methods Glancing angle high vacuum thermal evaporation technique was employed to grow Sn nanorods which facilitated the sulphur diffusion in a faster manner to prepare SnS nanoparticles. The sulphur deposition temperature, sulphur deposition time and tin deposition time were successfully tailored in the synthesis process and stabilized α-phase SnS by probing through confocal micro-Raman spectrometer. X-ray diffraction confirms the formation of SnS crystal structure at sulphur deposition temperature 200 °C. The mechanism of formation of highly porous SnS phase with flower like morphology is explained from the morphological analysis of post deposition annealed film. The complete absence of any oxidation state as evident from Raman as well as EDAX analysis confirms that the proposed sulphurization method could be a suitable, simple and cheap technique for the successful sulphurization of metal films. Band gap calculation from Tauc plot showed a direct band gap value of 1.5 eV for films with single phase of SnS which can be used as a p-type absorber layer in thin film solar cells. Emission studies showed the energy transitions attributed to band edge transition and due to the presence of intrinsic defects.

Synthesis of TiO2 Nanoparticles from Ilmenite Through the Mechanism of Vapor-Phase Reaction Process by Thermal Plasma Technology

NASA Astrophysics Data System (ADS)

Samal, Sneha

2017-11-01

Synthesis of nanoparticles of TiO2 was carried out by non-transferred arc thermal plasma reactor using ilmenite as the precursor material. The powder ilmenite was vaporized at high temperature in plasma flame and converted to a gaseous state of ions in the metastable phase. On cooling, chamber condensation process takes place on recombination of ions for the formation of nanoparticles. The top-to-bottom approach induces the disintegration of complex ilmenite phases into simpler compounds of iron oxide and titanium dioxide phases. The vapor-phase reaction mechanism was carried out in thermal plasma zone for the synthesis of nanoparticles from ilmenite compound in a plasma reactor. The easy separation of iron particles from TiO2 was taken place in the plasma chamber with deposition of light TiO2 particles at the top of the cooling chamber and iron particles at the bottom. The dissociation and combination process of mechanism and synthesis are studied briefly in this article. The product TiO2 nanoparticle shows the purity with a major phase of rutile content. TiO2 nanoparticles produced in vapor-phase reaction process shows more photo-induced capacity.

Synthesis and electronic properties of nanophase semiconductor materials

NASA Astrophysics Data System (ADS)

Sailor, Michael J.

1993-05-01

The objective of the research effort is to understand and learn to control the morphologic and electronic properties of electrodeposited nanophase semiconductors. The initial work has focused on electrodeposition of nanophase CdSe, using a sequential monolayer deposition technique that we are developing. We are currently extending the synthesis phase of this project into silicon, silicon carbide, and phosphor materials. This work also encompasses studying semiconductor electrodeposition into materials with restricted dimensions, such as microporous alumina and porous silicon membranes. By growing films with very small grain sizes, we hope to produce and study materials that display unusual electronic or luminescent effects. We are primarily interested in the electronic properties of the II-VI and group IV materials, for potential applications in nanoscale electronics and optical detector technologies. The phosphors are being studied for their potential as efficient high-resolution display materials.

Molecular Modeling in Drug Design for the Development of Organophosphorus Antidotes/Prophylactics.

DTIC Science & Technology

1986-06-01

multidimensional statistical QSAR analysis techniques to suggest new structures for synthesis and evaluation. C. Application of quantum chemical techniques to...compounds for synthesis and testing for antidotal potency. E. Use of computer-assisted methods to determine the steric constraints at the active site...modeling techniques to model the enzyme acetylcholinester-se. H. Suggestion of some novel compounds for synthesis and testing for reactivating

Two-dimensional tantalum disulfide: controlling structure and properties via synthesis

NASA Astrophysics Data System (ADS)

Zhao, Rui; Grisafe, Benjamin; Krishna Ghosh, Ram; Holoviak, Stephen; Wang, Baoming; Wang, Ke; Briggs, Natalie; Haque, Aman; Datta, Suman; Robinson, Joshua

2018-04-01

Tantalum disulfide (TaS2) is a transition metal dichalcogenide (TMD) that exhibits phase transition induced electronic property modulation at low temperature. However, the appropriate phase must be grown to enable the semiconductor/metal transition that is of interest for next generation electronic applications. In this work, we demonstrate direct and controllable synthesis of ultra-thin 1T-TaS2 and 2H-TaS2 on a variety of substrates (sapphire, SiO2/Si, and graphene) via powder vapor deposition. The synthesis process leads to single crystal domains ranging from 20 to 200 nm thick and 1-10 µm on a side. The TaS2 phase (1T or 2H) is controlled by synthesis temperature, which subsequently is shown to control the electronic properties. Furthermore, this work constitutes the first demonstration of a metal-insulator phase transition in directly synthesized 1T-TaS2 films and domains by electronic means.

Grained composite materials prepared by combustion synthesis under mechanical pressure

DOEpatents

Dunmead, Stephen D.; Holt, Joseph B.; Kingman, Donald D.; Munir, Zuhair A.

1990-01-01

Dense, finely grained composite materials comprising one or more ceramic phase or phase and one or more metallic and/or intermetallic phase or phases are produced by combustion synthesis. Spherical ceramic grains are homogeneously dispersed within the matrix. Methods are provided, which include the step of applying mechanical pressure during or immediately after ignition, by which the microstructures in the resulting composites can be controllably selected.

Preparation of Conjugates of Cytotoxic Lupane Triterpenes with Biotin.

PubMed

Soural, Miroslav; Hodon, Jiri; Dickinson, Niall J; Sidova, Veronika; Gurska, Sona; Dzubak, Petr; Hajduch, Marian; Sarek, Jan; Urban, Milan

2015-12-16

To better understand the mechanism of action of antitumor triterpenes, we are developing methods to identify their molecular targets. A promising method is based on combination of quantitative proteomics with SILAC and uses active compounds anchored to magnetic beads via biotin-streptavidin interaction. We developed a simple and fast solid-phase synthetic technique to connect terpenes to biotin through a linker. Betulinic acid was biotinylated from three different conjugation sites for use as a standard validation tool since many molecular targets of this triterpene are already known. Then, a set of four other cytotoxic triterpenoids was biotinylated. Biotinylated terpenes were similarly cytotoxic to their nonbiotinylated parents, which suggests that the target identification should not be influenced by linker or biotin. The developed solid-phase synthetic approach is the first attempt to use solid-phase synthesis to connect active triterpenes to biotin and is applicable as a general procedure for routine conjugation of triterpenes with other molecules of choice.

Synthesis of zirconium dioxide by ultrasound assisted precipitation: effect of calcination temperature.

PubMed

Prasad, Krishnamurthy; Pinjari, D V; Pandit, A B; Mhaske, S T

2011-09-01

Nanostructured zirconium dioxide was synthesized from zirconyl nitrate using both conventional and ultrasound assisted precipitation in alkaline medium. The synthesized samples were calcinated at temperatures ranging from 400°C to 900°C in steps of 100°C. The ZrO(2) specimens were characterized using X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The thermal characteristics of the samples were studied via Differential Scanning Calorimetry-Thermo-Gravimetry Analysis (DSC-TGA). The influence of the calcination temperature on the phase transformation process from monoclinic to tetragonal to cubic zirconia and its consequent effect on the crystallite size and % crystallinity of the synthesized ZrO(2) was studied and interpreted. It was observed that the ultrasound assisted technique helped to hasten to the phase transformation and also at some point resulted in phase stabilization of the synthesized zirconia. Copyright © 2011 Elsevier B.V. All rights reserved.

Large scale synthesis of nanostructured zirconia-based compounds from freeze-dried precursors

NASA Astrophysics Data System (ADS)

Gómez, A.; Villanueva, R.; Vie, D.; Murcia-Mascaros, S.; Martínez, E.; Beltrán, A.; Sapiña, F.; Vicent, M.; Sánchez, E.

2013-01-01

Nanocrystalline zirconia powders have been obtained at the multigram scale by thermal decomposition of precursors resulting from the freeze-drying of aqueous acetic solutions. This technique has equally made possible to synthesize a variety of nanostructured yttria or scandia doped zirconia compositions. SEM images, as well as the analysis of the XRD patterns, show the nanoparticulated character of those solids obtained at low temperature, with typical particle size in the 10-15 nm range when prepared at 673 K. The presence of the monoclinic, the tetragonal or both phases depends on the temperature of the thermal treatment, the doping concentration and the nature of the dopant. In addition, Rietveld refinement of the XRD profiles of selected samples allows detecting the coexistence of the tetragonal and the cubic phases for high doping concentration and high thermal treatment temperatures. Raman experiments suggest the presence of both phases also at relatively low treatment temperatures.

Magnetic properties of Li0.5Fe2.5O4 nanoparticles synthesized by solution combustion method

NASA Astrophysics Data System (ADS)

Naderi, P.; Masoudpanah, S. M.; Alamolhoda, S.

2017-11-01

In this research, lithium ferrite (Li0.5Fe2.5O4) powders were prepared by solution combustion synthesis using glycine and citric acid fuels at various fuel to oxidant molar ratios ( ϕ = 0.5, 1 and 1.5). Phase evolution, microstructure and magnetic properties were characterized by thermal analysis, infrared spectroscopy, X-ray diffraction, electron microscopy and vibration sample magnetometry techniques. Single-phase lithium ferrite was formed using glycine fuel at all fuel to oxidant ratios, while some impurity α-Fe2O3 phase was appeared using citric acid fuel at ϕ ≥ 1. The phase and crystallite size mainly depended on the combustion rate through fuel type. Bulky microstructure observed for citric acid fuel was attributed to its slow combustion, while the fast exhausting of gaseous products led to spongy microstructure for glycine fuel. The highest saturation magnetization of 59.3 emu/g and coercivity of 157 Oe were achieved for the as-combusted powders using glycine fuel.

Mesomorphic behaviors of a series of heterocyclic thiophene-imine-ester-based liquid crystals

NASA Astrophysics Data System (ADS)

Foo, K.-L.; Ha, S.-T.; Yeap, G. Y.; Lee, S. L.

2018-05-01

The synthesis and characterization of a series of heterocyclic liquid crystal, 4-{[(thiophen-2-yl)methylidene]amino}phenyl 4-alkoxybenzoates possessing even number of carbon atoms at the alkoxy chain (CnH2n+1O-, n = 6, 8, 10, 12, 14, 16, 18) are reported. The molecular structures of title compounds were elucidated using Fourier-transform infrared spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopic techniques along with mass spectrometric analysis. The phase behavior of these compounds was characterized and studied by differential scanning calorimetry and polarizing optical microscopy. All members exhibited enantiotropic nematic phase except for the highest member (n = 18) which is a non-mesogen. Influence of alkoxy chain length on the transition temperatures of crystal-to-nematic (melting point) and nematic-to-isotropic (clearing point) was studied. Nematic phase range was found to increase from n = 6 to n = 10, then it started to descend from n = 12 to n = 16 and finally the nematic phase disappeared when n changed to 18.

Investigation on phase transitions of 1-decylammonium hydrochloride as the potential thermal energy storage material

NASA Astrophysics Data System (ADS)

Dan, Wen-Yan; Di, You-Ying; He, Dong-Hua; Liu, Yu-Pu

2011-02-01

1-Decylammonium hydrochloride was synthesized by the method of liquid phase synthesis. Chemical analysis, elemental analysis, and X-ray single crystal diffraction techniques were applied to characterize its composition and structure. Low-temperature heat capacities of the compounds were measured with a precision automated adiabatic calorimeter over the temperature range from 78 to 380 K. Three solid-solid phase transitions have been observed at the peak temperatures of 307.52 ± 0.13, 325.02 ± 0.19, and 327.26 ± 0.07 K. The molar enthalpies and entropies of three phase transitions were determined based on the analysis of heat capacity curves. Experimental molar heat capacities were fitted to two polynomial equations of the heat capacities as a function of temperature by least square method. Smoothed heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15 K were calculated and tabulated at intervals of 5 K based on the fitted polynomials.

Aqueous-organic phase-transfer of highly stable gold, silver, and platinum nanoparticles and new route for fabrication of gold nanofilms at the oil/water interface and on solid supports.

PubMed

Feng, Xingli; Ma, Houyi; Huang, Shaoxin; Pan, Wei; Zhang, Xiaokai; Tian, Fang; Gao, Caixia; Cheng, Yingwen; Luo, Jingli

2006-06-29

A simple but effective aqueous-organic phase-transfer method for gold, silver, and platinum nanoparticles was developed on the basis of the decrease of the PVP's solubility in water with the temperature increase. The present method is superior in the transfer efficiency of highly stable nanoparticles to the common phase-transfer methods. The gold, silver, and platinum nanoparticles transferred to the 1-butanol phase dispersed well, especially silver and platinum particles almost kept the previous particle size. Electrochemical synthesis of gold nanoparticles in an oil-water system was achieved by controlling the reaction temperature at 80 degrees C, which provides great conveniences for collecting metal particles at the oil/water interface and especially for fabricating dense metal nanoparticle films. A technique to fabricate gold nanofilms on solid supports was also established. The shapes and sizes of gold nanoparticles as the building blocks may be controllable through changing reaction conditions.

Low-temperature solvothermal approach to the synthesis of La4Ni3O8 by topotactic oxygen deintercalation.

PubMed

Blakely, Colin K; Bruno, Shaun R; Poltavets, Viktor V

2011-07-18

A chimie douce solvothermal reduction method is proposed for topotactic oxygen deintercalation of complex metal oxides. Four different reduction techniques were employed to qualitatively identify the relative reduction activity of each including reduction with H(2) and NaH, solution-based reduction using metal hydrides at ambient pressure, and reduction under solvothermal conditions. The reduction of the Ruddlesden-Popper nickelate La(4)Ni(3)O(10) was used as a test case to prove the validity of the method. The completely reduced phase La(4)Ni(3)O(8) was produced via the solvothermal technique at 150 °C--a lower temperature than by other more conventional solid state oxygen deintercalation methods.

Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers

DOEpatents

Alivisatos, A.P.; Colvin, V.L.

1998-05-12

Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed. 10 figs.

Passivity-based Robust Control of Aerospace Systems

NASA Technical Reports Server (NTRS)

Kelkar, Atul G.; Joshi, Suresh M. (Technical Monitor)

2000-01-01

This report provides a brief summary of the research work performed over the duration of the cooperative research agreement between NASA Langley Research Center and Kansas State University. The cooperative agreement which was originally for the duration the three years was extended by another year through no-cost extension in order to accomplish the goals of the project. The main objective of the research was to develop passivity-based robust control methodology for passive and non-passive aerospace systems. The focus of the first-year's research was limited to the investigation of passivity-based methods for the robust control of Linear Time-Invariant (LTI) single-input single-output (SISO), open-loop stable, minimum-phase non-passive systems. The second year's focus was mainly on extending the passivity-based methodology to a larger class of non-passive LTI systems which includes unstable and nonminimum phase SISO systems. For LTI non-passive systems, five different passification. methods were developed. The primary effort during the years three and four was on the development of passification methodology for MIMO systems, development of methods for checking robustness of passification, and developing synthesis techniques for passifying compensators. For passive LTI systems optimal synthesis procedure was also developed for the design of constant-gain positive real controllers. For nonlinear passive systems, numerical optimization-based technique was developed for the synthesis of constant as well as time-varying gain positive-real controllers. The passivity-based control design methodology developed during the duration of this project was demonstrated by its application to various benchmark examples. These example systems included longitudinal model of an F-18 High Alpha Research Vehicle (HARV) for pitch axis control, NASA's supersonic transport wind tunnel model, ACC benchmark model, 1-D acoustic duct model, piezo-actuated flexible link model, and NASA's Benchmark Active Controls Technology (BACT) Wing model. Some of the stability results for linear passive systems were also extended to nonlinear passive systems. Several publications and conference presentations resulted from this research.

Synthesis of solid solutions of perovskites

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

Dambekalne, M.Y.; Antonova, M.K.; Perro, I.T.

The authors carry out thermographic studies, using a derivatograph, in order to understand the nature of the processes taking place during the synthesis of solid solutions of perovskites. Based on the detailed studies on the phase transformations occurring in the charges of the PSN-PMN solid solutions and on the selection of the optimum conditions for carrying out their synthesis, the authors obtained a powder containing a minimum quantity of the undesirable pyrochlore phase and by sintering it using the hot pressing method, they produced single phase ceramic specimens containing the perovskite phase alone with a density close to the theoreticalmore » value and showing zero apparent porosity and water absorption.« less

One-pot solvothermal synthesis of dual-phase titanate/titania Nanoparticles and their adsorption and photocatalytic Performances

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

Cheng, Yu Hua; Gong, Dangguo; Tang, Yuxin

2014-06-01

Dual phase titanate/titania nanoparticles undergo phase transformation gradually with the increase of solvothermal synthesis temperature from 100 °C to 200 °C, and eventually are fully transformed into anatase TiO{sub 2}. The crystal structure change results in the changes of optical absorption, sensitizer/dopant formation and surface area of the materials which finally affect the overall dye removal ability. Reactions under dark and light have been conducted to distinguish the contributions of surface adsorption from photocatalytic degradation. The sample synthesized at 160 °C (S160) shows the best performances for both adsorption under dark and photocatalytic degradation of methylene blue (MB) under visiblemore » light irradiation. The adsorption mechanism for S160 is determined as monolayer adsorption based on the adsorption isotherm test under dark condition, and an impressive adsorption capacity of 162.19 mg/g is achieved. For the photocatalytic application, this sample at 0.1 g/L loading is also able to degrade 20 ppm MB within 6 hours under the visible light (>420 nm) condition. - Graphical abstract: The effect of solvothermal synthesis temperature on the formation and dye removal performance of dual phase titanate/titania nanoparticles was unveiled and optimized. - Highlights: • Low temperature one-pot solvothermal synthesis of dual-phase photocatalysts. • Correlation of the synthesis temperature is made with the phase composition. • Adsorption isotherm, kinetics, photocatalytic degradation were studied. • Synthesis at 160 °C yields the best material for adsorption of MB in dark. • The same sample also shows the best visible light degradation of MB.« less

Preparation, Processing, and Characterization of Oriented Polycrystalline Zeolite and Aluminophosphate Membranes

NASA Astrophysics Data System (ADS)

Stoeger, Jared Andrew

Since the advent of zeolite membranes, speculation on their industrial applicability has been closely monitored, although widespread commercialization has been hampered by limitations in fabrication and post-synthesis processing. Economical, energy-efficient technology breakthroughs require an evaluation of a range of material candidates which show robustness and reliability. Straightforward manufacturing techniques should be devised to generate thousands of square meters of membrane area; however, this demands control of structural characteristics on the scale of nanometers. As described in this dissertation, the path forward will be forged by exploiting the intrinsic crystalline properties of zeolites or aluminophosphates for the next advancement in membrane technology. A facile method is described for the preparation of silicalite-1 (MFI zeolite type) membranes using the secondary growth technique on symmetric porous stainless steel tubes. Activation through rapid thermal processing (RTP), a lamp-based heat-treatment process used as a critical fabrication step in silicon integrated circuit manufacturing, is proven to reduce the density of non-zeolitic transport pathways which are detrimental to high-resolution molecular sieving. RTP-treated membranes are shown to have enhanced performance in the binary separation of vapor-phase isomers (p-/o-xylene), gas-phase isomers (n-/i-butane), and alcohol/water when compared to membranes activated at a much slower heating rate but otherwise similarly-prepared. The performance is discussed in the context of the market potential for industrially-attractive separations: the recovery of p-xylene from an isomeric mixture or alcohol biofuels from aqueous post-fermentation streams. Hydrothermal growth techniques for the preparation and characterization of continuous aluminophosphate (AFI zeolite type) membranes with a preferential crystallographic alignment on porous alpha-Al2O3 disc supports are demonstrated. A mechanism is proposed for flake-like crystal formation in the early stages of in-plane crystalline intergrowth between oriented columnar crystals by electric heating. It is shown that elevated temperatures induce a phase transformation to a densified aluminophosphate phase despite framework metal substitution or alternative heat-treatment conditions. Additionally, stability and membrane characteristics following in situ microwave growth using a TiO2-coated support are examined. Indications of improved quality validate the candidacy of the microwave-grown membranes with regard to the potential for carbon nanotube synthesis in the aligned one-dimensional channels for high flux, high separation factor membrane fabrication.

New coumarin carboxylates having trifluoromethyl, diethylamino and morpholino terminal groups: Synthesis and mesomorphic characterisations

NASA Astrophysics Data System (ADS)

Srinivasa, Hosapalya Thimmaiah; Harishkumar, Hosanagara Narayana; Palakshamurthy, Bandrehalli Siddagangappa

2017-03-01

New set of trifluromethyl, diethylamino and morpholino derived coumarin compounds were prepared by reacting various coumarin 3-carboxylic acids with various phenyl esters with peripheral alkyl, ester and polar cyano moieties in the presence of EDC.HCl/DMAP as esterification agent. The chemical structures of new coumarin derivatives were confirmed by standard spectroscopic techniques and mesomorphic behaviours were established by polarised optical microscopy (POM) and differential scanning calorimetry (DSC). Trifluoromethane and morpholino derivatives show SmA/Nematic phase, while diethylamino derivatives did not show liquid crystalline property.

Investigation of Optical and Electrical Properties of Wide Band Gap Materials

DTIC Science & Technology

1976-06-01

porous and heterogeneous. 22 IF 3. CRYSTAL GROWTH OF HgS A. Background fI’ Mercury sulfide is a wide bandgap semiconductor which is of considerable...I24 I 23 Mercury sulfide exists in two modifications, cinnabar (a-HgS) and metacinnabar (0-HgS). The a phase crystallizes in an unusual, dihedrally...5.817 ) at 26 °C, with Eg = -0.15 eV. An early technique, reported by Hamilton 31, on the synthesis of single crystals of the sulphides of Zn, Cd

Effects of randomized supplementation of methionine or alanine on cysteine and glutathione production during the early phase of treatment of children with edematous malnutrition123

PubMed Central

Green, Curtis O; Hsu, Jean W; Taylor-Bryan, Carolyn; Reid, Marvin; Forrester, Terrence; Jahoor, Farook

2014-01-01

Background: We have shown that a low glutathione concentration and synthesis rate in erythrocytes are associated with a shortage of protein-derived cysteine in children with edematous severe acute malnutrition (SAM). Objective: We tested the hypothesis that methionine supplementation may increase protein-derived cysteine and upregulate cysteine synthesis, thereby improving glutathione synthesis during the early treatment of edematous SAM. Design: The cysteine flux, its de novo synthesis and release from protein breakdown, and erythrocyte glutathione synthesis rate were measured in 12 children with edematous SAM in the fed state by using stable isotope tracers at 3 clinical phases as follows: 3 ± 1 d (±SE) [clinical phase 1 (CP1)], 8 ± 1 d [clinical phase 2 (CP2)], and 14 ± 2 d (clinical phase 3) after admission. Subjects were randomly assigned to receive equimolar supplements (0.5 mmol ⋅ kg−1 ⋅ d−1) of methionine or alanine (control) immediately after CP1. Results: In the methionine compared with the alanine group, cysteine flux derived from protein breakdown was faster at CP2 than CP1 (P < 0.05), and the change in plasma cysteine concentration from CP1 to CP2 was greater (P < 0.05). However, there was no evidence of a difference in cysteine de novo synthesis and its total flux or erythrocyte glutathione synthesis rate and concentration between groups. Conclusions: Methionine supplementation increased cysteine flux from body protein but had no significant effect on glutathione synthesis rates. Although cysteine is made from methionine, increased dietary cysteine may be necessary to partially fulfill its demand in edematous SAM because glutathione synthesis rates and concentrations were less than previous values shown at full recovery. This study was registered at clinicaltrials.gov as NCT00473031. PMID:24598154

Physiological-phased kinetic characteristics of microalgae Chlorella vulgaris growth and lipid synthesis considering synergistic effects of light, carbon and nutrients.

PubMed

Liao, Qiang; Chang, Hai-Xing; Fu, Qian; Huang, Yun; Xia, Ao; Zhu, Xun; Zhong, Nianbing

2018-02-01

To comprehensively understand kinetic characteristics of microalgae growth and lipid synthesis in different phases, a phase-feeding strategy was proposed to simultaneously regulate light, carbon and nutrients in adaption, growth and stationary phases of microalgae cultivation. Physiological-phased kinetic characteristics of microalgae Chlorella vulgaris growth and lipid synthesis under synergistic effects of light, carbon and nutrients were investigated, and supply-demand relationships of electrons and energy between light and dark reactions of photosynthesis process were discussed. Finally, the optimized cultivation strategy for microalgae in various phases were obtained, under which the lipid productivity was significantly improved from 130.11 mg/L/d to 163.42 mg/L/d. The study provided some important guidance for the large-scale production of biofuels from microalgae. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hydrothermal Synthesis of Dicalcium Silicate Based Cement

NASA Astrophysics Data System (ADS)

Dutta, N.; Chatterjee, A.

2017-06-01

It is imperative to develop low energy alternative binders considering the large amounts of energy consumed as well as carbon dioxide emissions involved in the manufacturing of ordinary Portland cement. This study is on the synthesis of a dicalcium silicate based binder using a low temperature hydrothermal route.The process consists of synthesizing an intermediate product consisting of a calcium silicate hydrate phase with a Ca:Si ratio of 2:1 and further thermal treatment to produce the β-Ca2SiO4 (C2S) phase.Effect of various synthesis parameters like water to solid ratio, dwell time and temperature on the formation of the desired calcium silicate hydrate phase is reported along with effect of heating conditions for formation of the β-C2S phase. Around 77.45% of β-C2S phase was synthesized by thermal treatment of the intermediate phase at 820°C.

Investigation of the automated solid-phase synthesis of a 38mer peptide with difficult sequence pattern under different synthesis strategies.

PubMed

Winkler, Dirk F H; Tian, Kerry

2015-04-01

Difficult peptides are a constant challenge in solid-phase peptide synthesis. In particular, hydroxyl amino acids such as serine can cause severe breakdowns in coupling yields even several amino acids after the insertion of the critical amino acid. This paper investigates several methods of improving synthesis yields of difficult peptides including the use of different resins, activators and the incorporation of a structure-breaking pseudoproline dipeptide building block both alone and in combination with each other.

NWR (National Weather Service) voice synthesis project, phase 1

NASA Astrophysics Data System (ADS)

Sampson, G. W.

1986-01-01

The purpose of the NOAA Weather Radio (NWR) Voice Synthesis Project is to provide a demonstration of the current voice synthesis technology. Phase 1 of this project is presented, providing a complete automation of an hourly surface aviation observation for broadcast over NWR. In examining the products currently available on the market, the decision was made that synthetic voice technology does not have the high quality speech required for broadcast over the NWR. Therefore the system presented uses the phrase concatenation type of technology for a very high quality, versatile, voice synthesis system.

Gas-phase synthesis of singly and multiply charged polyoxovanadate anions employing electrospray ionization and collision induced dissociation.

PubMed

Al Hasan, Naila M; Johnson, Grant E; Laskin, Julia

2013-09-01

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including VxOy(n-) and VxOyCl(n-) ions (x = 1-14, y = 2-36, n = 1-3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V14O36Cl(L)5 (L = Et4N(+), tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged VxOyCl(n-) and VxOyCl(L)((n-1)-) clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller VxOyCl((1-2)-) and VxOy ((1-2)-) anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged VxOyCl and VxOy species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of VxOyCl and VxOy anions through low-energy CID. Furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.

Gas-Phase Synthesis of Singly and Multiply Charged Polyoxovanadate Anions Employing Electrospray Ionization and Collision Induced Dissociation

NASA Astrophysics Data System (ADS)

Al Hasan, Naila M.; Johnson, Grant E.; Laskin, Julia

2013-09-01

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including VxOy n- and VxOyCln- ions (x = 1-14, y = 2-36, n = 1-3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V14O36Cl(L)5 (L = Et4N+, tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged VxOyCln- and VxOyCl(L)(n-1)- clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller VxOyCl(1-2)- and VxOy (1-2)- anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged VxOyCl and VxOy species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of VxOyCl and VxOy anions through low-energy CID. Furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.

Development of nanostructured EuAl2O4 phosphors with strong long-UV excitation.

PubMed

Hirata, Gustavo A; Bosze, Eric J; McKittrick, Joanna

2008-12-01

Fueled by the need to develop novel materials for applications in solid state white-emitting lamps we have improved a new low-cost, clean and efficient technique to produce high luminescence phosphors with strong excitation in the long-UV range (350-400 nm) which makes them useful for applications in GaN-based solid state lamps. In this work, pressurized combustion synthesis has been successfully used to develop EuAl2O4 (europium aluminate), a new green photoluminescent material with monoclinic structure. The combustion synthesis reaction conditions can be adjusted to produce either the AlEuO3 orthorhombic phase at low pressures (0.1 MPa), or the new monoclinic EuAl2O4 phase, which is apparently more thermodynamically favorable at higher combustion reaction pressures (1.4 MPa). The luminescent material is a high surface area powder (approximately 50 m2/g) composed mainly of nanostructured needles and plates with 5-10 nm in diameter and 100-150 nm in length. A broad emission peak centered at 530 nm with a decay time of 1.5 approximately 2 ms is obtained at the maximum excitation wavelength lambda(exc) = 370 nm.

Direct synthesis of antimicrobial coatings based on tailored bi-elemental nanoparticles

NASA Astrophysics Data System (ADS)

Benetti, Giulio; Cavaliere, Emanuele; Canteri, Adalberto; Landini, Giulia; Rossolini, Gian Maria; Pallecchi, Lucia; Chiodi, Mirco; Van Bael, Margriet J.; Winckelmans, Naomi; Bals, Sara; Gavioli, Luca

2017-03-01

Ultrathin coatings based on bi-elemental nanoparticles (NPs) are very promising to limit the surface-related spread of bacterial pathogens, particularly in nosocomial environments. However, tailoring the synthesis, composition, adhesion to substrate, and antimicrobial spectrum of the coating is an open challenge. Herein, we report on a radically new nanostructured coating, obtained by a one-step gas-phase deposition technique, and composed of bi-elemental Janus type Ag/Ti NPs. The NPs are characterized by a cluster-in-cluster mixing phase with metallic Ag nano-crystals embedded in amorphous TiO2 and present a promising antimicrobial activity including also multidrug resistant strains. We demonstrate the flexibility of the method to tune the embedded Ag nano-crystals dimension, the total relative composition of the coating, and the substrate type, opening the possibility of tailoring the dimension, composition, antimicrobial spectrum, and other physical/chemical properties of such multi-elemental systems. This work is expected to significantly spread the range of applications of NPs coatings, not only as an effective tool in the prevention of healthcare-associated infections but also in other technologically relevant fields like sensors or nano-/micro joining.

Brownmillerite CaCoO2.5: Synthesis, Re-entrant Structural Transitions and Magnetic properties

NASA Astrophysics Data System (ADS)

Zhang, Junjie; Zheng, Hong; Malliakas, Christos; Allred, Jared; Ren, Yang; Li, Qing'an; Han, Tianheng; Mitchell, John

2015-03-01

Cobalt oxides attract both fundamental and technological attention due to their physical properties including thermoelectricity, giant magnetoresistance, superconductivity and multiferroicity. Here we report the first synthesis of CaCoO2.5 single crystals using a high pressure optical-image floating zone technique. We find that it is an ordered oxygen-deficient perovskite of the brownmillerite type, and it undergoes an unprecedented re-entrant structural phase transitions (Pcmb --> P2/c11 --> P121/m1 --> Pcmb) with decreasing temperature. We describe its temperature-dependent structural, thermal, and magnetic properties, including AFM ordering near 240 K, with a weakly spin canted ferromagnet ground state below 140 K. The magnetic response of CaCoO2.5 depends markedly on the cooling rate and field history. Magnetization data also imply the potential of a distinct, field-induced phase arising uniquely from the P121/m1 structure, revealed as kinetically trapped by a rapid-cooling protocol. Work in the Materials Science Division at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Division of Materials Science and Engineering.

The green hydrothermal synthesis of nanostructured Cu2ZnSnSe4 as solar cell material and study of their structural, optical and morphological properties

NASA Astrophysics Data System (ADS)

Vanalakar, S. A.; Agawane, G. L.; Kamble, A. S.; Patil, P. S.; Kim, J. H.

2017-12-01

Cu2ZnSnSe4 (CZTSe) has attracted intensive attention as an absorber material for the thin-film solar cells due to its high absorption coefficient, direct band gap, low toxicity, and abundance of its constituent elements. In this study nanostructured CZTSe nanoparticles are prepared via green hydrothermal synthesis without using toxic solvents, organic amines, catalysts or noxious chemicals. The structural, optical, and morphological properties of CZTSe nanostructured powder were studied using X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), UV-vis absorption spectroscopy, and transmission electron microscope (TEM) techniques. Raman peaks at 170, 195, and 232 cm-1 confirm the formation of pure phase CZTSe nanostructured particles. In addition, the EDS and XPS results confirm the appropriate chemical purity of the annealed CZTSe nanoparticles. Meanwhile, the TEM analysis showed the presence of phase pure oval like CZTSe particle with size of about 80-140 nm. The UV-Vis-NIR absorption spectra analysis showed that the optical band gap of CZTSe nanostructured particles is about 1.14 eV. This band gap energy is close to the optimum value of a photovoltaic solar cell absorber material.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

Synthesis of polyetherimide / halloysite nanotubes (PEI/HNTs) based nanocomposite membrane towards hydrogen storage

NASA Astrophysics Data System (ADS)

Muthu, R. Naresh; Rajashabala, S.; Kannan, R.

2018-04-01

Even though hydrogen is considered as green and clean energy sources of future, the blooming of hydrogen economy mainly relies on the development of safe and efficient hydrogen storage medium. The present work is aimed at the synthesis and characterization of polyetherimide/acid treated halloysite nanotubes (PEI/A-HNTs) nanocomposite membranes for solid state hydrogen storage medium, where phase inversion technique was adopted for the synthesis of nanocomposite membrane. The synthesized PEI/A-HNTs nanocomposite membranes were characterized by XRD, FTIR, SEM, EDX, CHNS elemental analysis and TGA. Hydrogenation studies were performed using a Sievert's-like hydrogenation setup. The important conclusions arrived from the present work are the PEI/A-HNTs nanocomposite membranes have better performance with a maximum hydrogen storage capacity of 3.6 wt% at 100 °C than pristine PEI. The adsorbed hydrogen possesses the average binding energy of 0.31 eV which lies in the recommended range of US- DOE 2020 targets. Hence it is expected that the PEI/A-HNTs nanocomposite membranes may have bright extent in the scenario of hydrogen fuel cell applications.

Transportation Life Cycle Assessment (LCA) Synthesis, Phase II

DOT National Transportation Integrated Search

2018-04-24

The Transportation Life Cycle Assessment (LCA) Synthesis includes an LCA Learning Module Series, case studies, and analytics on the use of the modules. The module series is a set of narrated slideshows on topics related to environmental LCA. Phase I ...

Solid-Phase and Microwave-Assisted Syntheses of 2,5-Diketopiperazines: Small Molecules with Great Potential

PubMed Central

O'Neill, J.C.; Blackwell, H. E.

2008-01-01

Diketopiperazines (DKPs) are a well-known class of heterocycles that have recently emerged as a promising biologically active scaffold. Solid-phase organic synthesis has become an important tool in the combinatorial exploration of these privileged structures, expediting the synthesis and, therefore, the discovery of active compounds. To date, certain DKPs have shown potent activities against a range of diseases and biological phenomena, including bacterial infections, various cancers, asthma, infertility, premature labor, and HIV. Recent applications of solid-phase DKP synthesis, with a particular focus on cyclative cleavage and microwave-assisted reactions, are highlighted herein. PMID:18288948

The Proteome and Lipidome of Thermococcus kodakarensis across the Stationary Phase

PubMed Central

Yoshinaga, Marcos Y.; Garcia Prado, Franka; Hinrichs, Kai-Uwe; Thomm, Michael

2016-01-01

The majority of cells in nature probably exist in a stationary-phase-like state, due to nutrient limitation in most environments. Studies on bacteria and yeast reveal morphological and physiological changes throughout the stationary phase, which lead to an increased ability to survive prolonged nutrient limitation. However, there is little information on archaeal stationary phase responses. We investigated protein- and lipid-level changes in Thermococcus kodakarensis with extended time in the stationary phase. Adaptations to time in stationary phase included increased proportion of membrane lipids with a tetraether backbone, synthesis of proteins that ensure translational fidelity, specific regulation of ABC transporters (upregulation of some, downregulation of others), and upregulation of proteins involved in coenzyme production. Given that the biological mechanism of tetraether synthesis is unknown, we also considered whether any of the protein-level changes in T. kodakarensis might shed light on the production of tetraether lipids across the same period. A putative carbon-nitrogen hydrolase, a TldE (a protease in Escherichia coli) homologue, and a membrane bound hydrogenase complex subunit were candidates for possible involvement in tetraether-related reactions, while upregulation of adenosylcobalamin synthesis proteins might lend support to a possible radical mechanism as a trigger for tetraether synthesis. PMID:27274708

The Proteome and Lipidome of Thermococcus kodakarensis across the Stationary Phase.

PubMed

Gagen, Emma J; Yoshinaga, Marcos Y; Garcia Prado, Franka; Hinrichs, Kai-Uwe; Thomm, Michael

2016-01-01

The majority of cells in nature probably exist in a stationary-phase-like state, due to nutrient limitation in most environments. Studies on bacteria and yeast reveal morphological and physiological changes throughout the stationary phase, which lead to an increased ability to survive prolonged nutrient limitation. However, there is little information on archaeal stationary phase responses. We investigated protein- and lipid-level changes in Thermococcus kodakarensis with extended time in the stationary phase. Adaptations to time in stationary phase included increased proportion of membrane lipids with a tetraether backbone, synthesis of proteins that ensure translational fidelity, specific regulation of ABC transporters (upregulation of some, downregulation of others), and upregulation of proteins involved in coenzyme production. Given that the biological mechanism of tetraether synthesis is unknown, we also considered whether any of the protein-level changes in T. kodakarensis might shed light on the production of tetraether lipids across the same period. A putative carbon-nitrogen hydrolase, a TldE (a protease in Escherichia coli) homologue, and a membrane bound hydrogenase complex subunit were candidates for possible involvement in tetraether-related reactions, while upregulation of adenosylcobalamin synthesis proteins might lend support to a possible radical mechanism as a trigger for tetraether synthesis.

Microwave-assisted one-pot synthesis of ring-fused aminals under catalyst- and solvent-free conditions

EPA Science Inventory

Heterocyclic compounds hold a special place in drug discovery and variety of techniques such as combinatorial synthesis, parallel synthesis, and automated library production to increase the output of these entities has been developed. Although most of these techniques are rapid a...

Mechanism of Formation of Li 7 P 3 S 11 Solid Electrolytes through Liquid Phase Synthesis

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

Wang, Yuxing; Lu, Dongping; Bowden, Mark

Crystalline Li7P3S11 is a promising solid electrolyte for all solid state lithium/lithium ion batteries. A controllable liquid phase synthesis of Li7P3S11 is more desirable compared to conventional mechanochemical synthesis, but recent attempts suffer from reduced ionic conductivities. Here we elucidate the formation mechanism of crystalline Li7P3S11 synthesized in the liquid phase (acetonitrile, or ACN). We conclude that the crystalline Li7P3S11 forms through a two-step reaction: 1) formation of solid Li3PS4∙ACN and amorphous Li2S∙P2S5 phases in the liquid phase; 2) solid-state conversion of the two phases. The implication of this two-step reaction mechanism to the morphology control and the transport propertiesmore » of liquid phase synthesized Li7P3S11 is identified and discussed.« less

Synthesis of Chemiluminescent Esters: A Combinatorial Synthesis Experiment for Organic Chemistry Students

ERIC Educational Resources Information Center

Duarte, Robert; Nielson, Janne T.; Dragojlovic, Veljko

2004-01-01

A group of techniques aimed at synthesizing a large number of structurally diverse compounds is called combinatorial synthesis. Synthesis of chemiluminescence esters using parallel combinatorial synthesis and mix-and-split combinatorial synthesis is experimented.

Method and apparatus for millimeter-wave detection of thermal waves for materials evaluation

DOEpatents

Gopalsami, Nachappa; Raptis, Apostolos C.

1991-01-01

A method and apparatus for generating thermal waves in a sample and for measuring thermal inhomogeneities at subsurface levels using millimeter-wave radiometry. An intensity modulated heating source is oriented toward a narrow spot on the surface of a material sample and thermal radiation in a narrow volume of material around the spot is monitored using a millimeter-wave radiometer; the radiometer scans the sample point-by-point and a computer stores and displays in-phase and quadrature phase components of thermal radiations for each point on the scan. Alternatively, an intensity modulated heating source is oriented toward a relatively large surface area in a material sample and variations in thermal radiation within the full field of an antenna array are obtained using an aperture synthesis radiometer technique.

Spectroscopic characterizations of a mixed surfactant mesophase and its application in materials synthesis

NASA Astrophysics Data System (ADS)

Liu, Limin

A viscous lyotropic crystalline mesophase containing bis (2-ethylhexyl) sodium sulfosuccinate (AOT), alpha-phosphatidylcholine (lecithin), with comparable volume fractions of isooctane and water was characterized by Fourier-transform 31P and 1H nuclear magnetic resonance (NMR) spectroscopy. Shear alignment on the reverse hexagonal mesophase was reflected through both 31P NMR and 1H NMR spectra. A complicated 31P spectrum was observed as a result of superposition of chemical shifts according to the distribution of crystalline domains prior to shear. The initially disordered samples with polydomain structures became macroscopically aligned after Couette shear and the alignment retained for a long period of time. 31P NMR chemical shift anisotropy characteristics were used to elucidate orientation of the hexagonal phase. Interestingly, 1H NMR of the water, methyl and methylene groups exhibited spectral changes upon shear alignment closely corresponding with that of 31P NMR spectra. A reverse hexagonal to lamellar phase transition was manifested as an expanding of the expressed 31P NMR chemical shift anisotropy and an apparent reversal of the powder pattern with increasing water content and/or temperature. Correspondingly, 1H NMR spectra also experienced a spectral pattern transition as the water content or temperature was increased. These observations complement the findings of mesophase alignment obtained using small angle neutron scattering (SANS) and imply that 31P and 1H NMR spectroscopy can be used as probes to define microstructure and monitor orientation changes in this binary surfactant system. This is especially beneficial if these mesophases are used as templates for materials synthesis. The mesophase retains its alignment for extended periods allowing materials synthesis to be decoupled from the application of shear. Highly aligned string-like silica nanostructures were obtained through templated synthesis in the columnar hexagonal structure of the viscous lyotropic crystalline mesophase. A two-step procedure was used to first shear-align the surfactant mesophase, and then conduct synthesis under quiescent conditions in the mesophase. Polystyrene was post-grafted to the silica surface without disturbing its nanostring morphology. The coupling of materials synthesis in surfactant mesophases with processing techniques (e.g. extrusion) may result in functional materials, such as new catalyst support and membrane nanoarchitectures.

Synthesis and characterization of nickel oxide particulate annealed at different temperatures

NASA Astrophysics Data System (ADS)

Sharma, Khem Raj; Thakur, Shilpa; Negi, N. S.

2018-04-01

Nickel oxide has been synthesized by solution combustion technique. The nickel oxide ceramic was annealed at 600°C and 1000°C for 2 hours. Structural, electrical, dielectric and magnetic properties were analyzed which are strongly dependent upon the synthesis method. Structural properties were examined by X-ray diffractometer (XRD), which confirmed the purity and cubic phase of nickel oxide. XRD data reveals the increase in crystallite size and decrease in full width half maximum (FWHM) as the annealing temperature increases. Electrical conductivity is found to increase from 10-6 to 10-5 (Ω-1cm-1) after annealing. Dielectric constant is observed to increase from 26 to 175 when the annealing temperature is increased from 600°C to 1000°C. Low value of coercive field is found which shows weak ferromagnetic behavior of NiO. It is observed that all the properties of NiO particulate improve with increasing annealing temperature.

Synthesis and characterization of novel low density polyethylene-multiwall carbon nanotube porous composites

NASA Astrophysics Data System (ADS)

Rizvi, Reza; Kim, Jae-Kyung; Naguib, Hani

2009-10-01

This study details the synthesis and characterization of novel porous composites of low density polyethylene (PE) and multiwalled carbon nanotubes (MWNT). PE-MWNT composites were prepared by melt blending the components in a twin screw compounder and porous structures were produced by a batch technique using CO2 as the solvent. The composites were characterized for dispersion using scanning electron microscopy and transmission electron microscopy; the results indicate a finely dispersed MWNT phase in PE. Thermal, rheological, electrical and mechanical properties of the composites were characterized and results indicate an electrical and rheological percolation threshold concentration of between 1 and 2 wt% MWNT in PE. Substantial improvements in the mechanical and electrical properties of PE were observed with the addition of 5 wt% MWNT. The porous PE-MWNT composites fabricated in this study were found to be conductive and have potential applications as anti-static materials for electrostatic discharge prevention.

Epitaxial growth of hybrid nanostructures

NASA Astrophysics Data System (ADS)

Tan, Chaoliang; Chen, Junze; Wu, Xue-Jun; Zhang, Hua

2018-02-01

Hybrid nanostructures are a class of materials that are typically composed of two or more different components, in which each component has at least one dimension on the nanoscale. The rational design and controlled synthesis of hybrid nanostructures are of great importance in enabling the fine tuning of their properties and functions. Epitaxial growth is a promising approach to the controlled synthesis of hybrid nanostructures with desired structures, crystal phases, exposed facets and/or interfaces. This Review provides a critical summary of the state of the art in the field of epitaxial growth of hybrid nanostructures. We discuss the historical development, architectures and compositions, epitaxy methods, characterization techniques and advantages of epitaxial hybrid nanostructures. Finally, we provide insight into future research directions in this area, which include the epitaxial growth of hybrid nanostructures from a wider range of materials, the study of the underlying mechanism and determining the role of epitaxial growth in influencing the properties and application performance of hybrid nanostructures.

Drug Design Relating Amebicides to Inhibition of Protein Synthesis.

DTIC Science & Technology

1977-09-01

A study of the effect of emetine on protein synthesis in E. histolytica was made on log phase amebas as compared to stationary phase amebas ...Sensitivity to emetine was maintained independently of the rate of protein synthesis. Furthermore, both stages of amebas had the same capacity to bind emetine...elongation site. Finally, evidence was obtained that the capacity to bind emetine provides a basis for conferring drug resistance in amebas . A direct

Solution-phase parallel synthesis of aryloxyimino amides via a novel multicomponent reaction among aromatic (Z)-chlorooximes, isocyanides, and electron-deficient phenols.

PubMed

Mercalli, Valentina; Giustiniano, Mariateresa; Del Grosso, Erika; Varese, Monica; Cassese, Hilde; Massarotti, Alberto; Novellino, Ettore; Tron, Gian Cesare

2014-11-10

A library of 41 aryloxyimino amides was prepared via solution phase parallel synthesis by extending the multicomponent reaction of (Z)-chlorooximes and isocyanides to the use of electron-deficient phenols. The resulting aryloxyiminoamide derivatives can be used as intermediates for the synthesis of benzo[d]isoxazole-3-carboxamides, dramatically reducing the number of synthetic steps required by other methods reported in literature.

N-Sulfanylethylaminooxybutyramide (SEAoxy): A Crypto-Thioester Compatible with Fmoc Solid-Phase Peptide Synthesis.

PubMed

Tsuda, Shugo; Mochizuki, Masayoshi; Sakamoto, Ken; Denda, Masaya; Nishio, Hideki; Otaka, Akira; Yoshiya, Taku

2016-11-18

An N-sulfanylethylaminooxybutyramide (SEAoxy) has been developed as a novel thioester equivalent for native chemical ligation. SEAoxy peptide was straightforwardly synthesized by conventional Fmoc solid-phase peptide synthesis without a problem. Moreover, SEAoxy peptide could be directly applied to native chemical ligation owing to the intramolecular N-to-S acyl shift that releases the peptide-thioester in situ. This methodology was successfully applied to the synthesis of two bioactive peptides.

Chemical methods for peptide and protein production.

PubMed

Chandrudu, Saranya; Simerska, Pavla; Toth, Istvan

2013-04-12

Since the invention of solid phase synthetic methods by Merrifield in 1963, the number of research groups focusing on peptide synthesis has grown exponentially. However, the original step-by-step synthesis had limitations: the purity of the final product decreased with the number of coupling steps. After the development of Boc and Fmoc protecting groups, novel amino acid protecting groups and new techniques were introduced to provide high quality and quantity peptide products. Fragment condensation was a popular method for peptide production in the 1980s, but unfortunately the rate of racemization and reaction difficulties proved less than ideal. Kent and co-workers revolutionized peptide coupling by introducing the chemoselective reaction of unprotected peptides, called native chemical ligation. Subsequently, research has focused on the development of novel ligating techniques including the famous click reaction, ligation of peptide hydrazides, and the recently reported α-ketoacid-hydroxylamine ligations with 5-oxaproline. Several companies have been formed all over the world to prepare high quality Good Manufacturing Practice peptide products on a multi-kilogram scale. This review describes the advances in peptide chemistry including the variety of synthetic peptide methods currently available and the broad application of peptides in medicinal chemistry.

Synthesis of iron oxides nanoparticles with very high saturation magnetization form TEA-Fe(III) complex via electrochemical deposition for supercapacitor applications

NASA Astrophysics Data System (ADS)

Elrouby, Mahmoud; Abdel-Mawgoud, A. M.; El-Rahman, Rehab Abd

2017-11-01

This work is devoted to the synthesis of magnetic iron oxides nanoparticles with very high saturation magnetization to be qualified for supercapacitor applications using, a simple electrodeposition technique. It is found that the electrochemical reduction process depends on concentration, temperature, deposition potential and the scan rate of potential. The nature of electrodeposition process has been characterized via voltammetric and chronoamperometric techniques. The morphology of the electrodeposits has been investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure and phase content of these investigated electrodeposits have been examined and calculated. The obtained iron oxides show a high saturation magnetization (Ms) of about 229 emu g-1. The data exhibited a relation between Ms of electrodeposited iron oxide and specific capacitance. This relation exhibits that the highest Ms value of electrodeposited iron oxides gives also highest specific capacitance of about 725 Fg-1. Moreover, the electrodeposited iron oxides exhibit a very good stability. The new characteristics of the electro synthesized iron oxides at our optimized conditions, strongly qualify them as a valuable material for high-performance supercapacitor applications.

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

Ethylene Control of Anthocyanin Synthesis in Sorghum

PubMed Central

Craker, L. E.; Standley, L. A.; Starbuck, M. J.

1971-01-01

Light-induced anthocyanin synthesis in Sorghum vulgare L. seedlings was both promoted and inhibited by ethylene treatment. The rate of anthocyanin formation in sorghum tissue was dependent upon the time of ethylene treatment in relation to light exposure and the stage of the anthocyanin synthesis process. Those plants receiving ethylene treatment during the early lag phase of anthocyanin synthesis had higher anthocyanin content at 24 hours than control plants receiving no ethylene treatment. Plants receiving ethylene treatment after the lag phase had lower anthocyanin content at 24 hours than control plants receiving no ethylene treatment. PMID:16657796

Synthesis of flower-like molybdenum sulfide/graphene hybrid as an efficient oxygen reduction electrocatalyst for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Arunchander, A.; Peera, S. Gouse; Sahu, A. K.

2017-06-01

Nanostructured transition metal chalcogenides (TMCs) have significant interest towards electrochemical devices such as fuel cells, metal-ion batteries, due to their unique physical and electrochemical properties. Herein, we report a facile hydrothermal synthesis of flower-like nanostructured molybdenum sulphide and its incorporation on to graphene as a potential oxygen reduction reaction catalyst in alkaline medium. The phase purity and morphological evolution of MoS2 is systematically studied through X-ray diffraction and scanning electron microscopic techniques. The electronic states of metal and non-metallic species are deeply studied by X-ray photoelectron spectroscopy. The effect of annealing temperatures and TMC concentrations are also investigated by electrochemical techniques such as cyclic and linear sweep voltammograms. The optimised electrocatalyst (MoS2/G-500) delivers significant ORR activity with onset and half-wave potentials of 0.91 and 0.80 V (vs. RHE), respectively. Superior durability compared to state-of-art Pt/C catalyst is ascertained by repeating potential cycles for about 5000 times and also by chronoamperometric technique. Finally, the hybrid catalyst is evaluated in AEMFC as cathode catalyst which delivers peak power density of about 29 mW cm-2 under ambient temperature and pressure. The present findings emphasis that MoS2/G catalyst is promising as cost-effective and alternative to noble metal-based catalysts for fuel cell applications.

Plasma-assisted synthesis of MoS2

NASA Astrophysics Data System (ADS)

Campbell, Philip M.; Perini, Christopher J.; Chiu, Johannes; Gupta, Atul; Ray, Hunter S.; Chen, Hang; Wenzel, Kevin; Snyder, Eric; Wagner, Brent K.; Ready, Jud; Vogel, Eric M.

2018-03-01

There has been significant interest in transition metal dichalcogenides (TMDs), including MoS2, in recent years due to their potential application in novel electronic and optical devices. While synthesis methods have been developed for large-area films of MoS2, many of these techniques require synthesis temperatures of 800 °C or higher. As a result of the thermal budget, direct synthesis requiring high temperatures is incompatible with many integrated circuit processes as well as flexible substrates. This work explores several methods of plasma-assisted synthesis of MoS2 as a way to lower the synthesis temperature. The first approach used is conversion of a naturally oxidized molybdenum thin film to MoS2 using H2S plasma. Conversion is demonstrated at temperatures as low as 400 °C, and the conversion is enabled by hydrogen radicals which reduce the oxidized molybdenum films. The second method is a vapor phase reaction incorporating thermally evaporated MoO3 exposed to a direct H2S plasma, similar to chemical vapor deposition (CVD) synthesis of MoS2. Synthesis at 400 °C results in formation of super-stoichiometric MoS2 in a beam-interrupted growth process. A final growth method relies on a cyclical process in which a small amount of Mo is sputtered onto the substrate and is subsequently sulfurized in a H2S plasma. Similar results could be realized using an atomic layer deposition (ALD) process to deposit the Mo film. Compared to high temperature synthesis methods, the lower temperature samples are lower quality, potentially due to poor crystallinity or higher defect density in the films. Temperature-dependent conductivity measurements are consistent with hopping conduction in the plasma-assisted synthetic MoS2, suggesting a high degree of disorder in the low-temperature films. Optimization of the plasma-assisted synthesis process for slower growth rate and better stoichiometry is expected to lead to high quality films at low growth temperature.

Synthesis of peptides containing overlapping lanthionine bridges on the solid phase: an analogue of rings D and E of the lantibiotic nisin.

PubMed

Mothia, Begum; Appleyard, Antony N; Wadman, Sjoerd; Tabor, Alethea B

2011-08-19

A methodology for the solid-phase synthesis of the overlapping lanthionine bridges found in many lantibiotics has been developed. A novel Teoc/TMSE-protected lanthionine derivative has been synthesized, and this lanthionine, and an Aloc/allyl-protected lanthionine derivative, have been incorporated into a linear peptide using solid-phase peptide synthesis. Selective deprotection of the silyl protecting groups, followed by sequential cyclization, deprotection of the allyl protecting groups, and further cyclization, enabled the regioselective formation of an analogue of rings D and E of nisin. © 2011 American Chemical Society

Synthesis and binding studies of Alzheimer ligands on solid support.

PubMed

Rzepecki, Petra; Geib, Nina; Peifer, Manuel; Biesemeier, Frank; Schrader, Thomas

2007-05-11

Aminopyrazole derivatives constitute the first class of nonpeptidic rationally designed beta-sheet ligands. Here we describe a double solid-phase protocol for both synthesis and affinity testing. The presented solid-phase synthesis of four types of hybrid compounds relies on the Fmoc strategy and circumvents subsequent HPLC purification by precipitating the final product from organic solution in pure form. Hexa- and octapeptide pendants with internal di- and tetrapeptide bridges are now amenable in high yields to combinatorial synthesis of compound libraries for high-throughput screening purposes. Solid-phase peptide synthesis (SPPS) on an acid-resistant PAM allows us, after PMB deprotection, to subject the free aminopyrazole binding sites in an immobilized state to on-bead assays with fluorescence-labeled peptides. From the fluorescence emission intensity decrease, individual binding constants can be calculated via reference curves by simple application of the law of mass action. Gratifyingly, host/guest complexation can be monitored quantitatively even for those ligands, which are almost insoluble in water.

Heterogeneous Two-Phase Pillars in Epitaxial NiFe 2 O 4 -LaFeO 3 Nanocomposites

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

Comes, Ryan B.; Perea, Daniel E.; Spurgeon, Steven R.

2017-07-10

Self-assembled epitaxial oxide nanocomposites have been explored for a wide range of applications, including multiferroic and magnetoelectric properties, plasmonics, and catalysis. These so-called “vertically aligned nanocomposites” form spontaneously during the deposition process when segregation into two phases is energetically favorable as compared to a solid solution. However, there has been surprisingly little work understanding the driving forces that govern the synthesis of these materials, which can include point defect energetics, surface diffusion, and interfacial energies. To explore these factors, La-Ni-Fe-O films have been synthesized by molecular beam epitaxy and it is shown that these phase segregate into spinel-perovskite nanocomposites. Usingmore » complementary scanning transmission electron microscopy and atom-probe tomography, the elemental composition of each phase is examined and found that Ni ions are exclusively found in the spinel phase. From correlative analysis, a model for the relative favorability of the Ni2+ and Ni3+ valences under the growth conditions is developed. It is shown that multidimensional characterization techniques provide previously unobserved insight into the growth process and complex driving forces for phase segregation.« less

Synthesis of monoclinic potassium niobate nanowires that are stable at room temperature.

PubMed

Kim, Seungwook; Lee, Ju-Hyuck; Lee, Jaeyeon; Kim, Sang-Woo; Kim, Myung Hwa; Park, Sungnam; Chung, Haegeun; Kim, Yong-Il; Kim, Woong

2013-01-09

We report the synthesis of KNbO(3) nanowires (NWs) with a monoclinic phase, a phase not observed in bulk KNbO(3) materials. The monoclinic NWs can be synthesized via a hydrothermal method using metallic Nb as a precursor. The NWs are metastable, and thermal treatment at ∼450 °C changed the monoclinic phase into the orthorhombic phase, which is the most stable phase of KNbO(3) at room temperature. Furthermore, we fabricated energy-harvesting nanogenerators by vertically aligning the NWs on SrTiO(3) substrates. The monoclinic NWs showed significantly better energy conversion characteristics than orthorhombic NWs. Moreover, the frequency-doubling efficiency of the monoclinic NWs was ∼3 times higher than that of orthorhombic NWs. This work may contribute to the synthesis of materials with new crystalline structures and hence improve the properties of the materials for various applications.

K[AsW{sub 2}O{sub 9}], the first member of the arsenate–tungsten bronze family: Synthesis, structure, spectroscopic and non-linear optical properties

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

Alekseev, Evgeny V., E-mail: e.alekseev@fz-juelich.de; Institut für Kristallographie, RWTH Aachen, Jägerstraße 17–19 D-52066 Aachen; Felbinger, Olivier

K[AsW{sub 2}O{sub 9}], prepared by high-temperature solid-state reaction, is the first member of the arsenate–tungsten bronze family. The structure of K[AsW{sub 2}O{sub 9}] is based on a 3-dimensional (3D) oxotungstate–arsenate framework with the non-centrosymmetric P2{sub 1}2{sub 1}2{sub 1} space group, a=4.9747(3) Å, b=9.1780(8) Å, c=16.681(2) Å. The material was characterized using X-ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), Raman and infrared (IR) spectroscopic techniques. The results of DSC demonstrate that this phase is stable up to 1076 K. Second harmonic generation (SHG) measurements performed on a powder sample demonstrate noticeable (0.1 of LiIO{sub 3}) non-linear optical (NLO)more » activity. - Graphical abstract: K[AsW{sub 2}O{sub 9}], the first member of arsenate–tungsten bronze family exhibit new three dimensional structure type, significant thermal stability and NLO properties. Highlights: • K[AsW{sub 2}O{sub 9}], the first member of the arsenate–tungsten bronze family was synthesized with solid state reaction technique. • Structure of this phase was investigated with X-ray diffraction, IR and Raman spectroscopy and electron microscopy. • Thermal stability of the phase was determinate with DSC techniques. • NLO properties were investigated.« less

Diffraction Techniques in Structural Biology

PubMed Central

Egli, Martin

2016-01-01

A detailed understanding of chemical and biological function and the mechanisms underlying the molecular activities ultimately requires atomic-resolution structural data. Diffraction-based techniques such as single-crystal X-ray crystallography, electron microscopy, and neutron diffraction are well established and they have paved the road to the stunning successes of modern-day structural biology. The major advances achieved in the last 20 years in all aspects of structural research, including sample preparation, crystallization, the construction of synchrotron and spallation sources, phasing approaches, and high-speed computing and visualization, now provide specialists and nonspecialists alike with a steady flow of molecular images of unprecedented detail. The present unit combines a general overview of diffraction methods with a detailed description of the process of a single-crystal X-ray structure determination experiment, from chemical synthesis or expression to phasing and refinement, analysis, and quality control. For novices it may serve as a stepping-stone to more in-depth treatises of the individual topics. Readers relying on structural information for interpreting functional data may find it a useful consumer guide. PMID:27248784

Diffraction Techniques in Structural Biology

PubMed Central

Egli, Martin

2010-01-01

A detailed understanding of chemical and biological function and the mechanisms underlying the activities ultimately requires atomic-resolution structural data. Diffraction-based techniques such as single-crystal X-ray crystallography, electron microscopy and neutron diffraction are well established and have paved the road to the stunning successes of modern-day structural biology. The major advances achieved in the last 20 years in all aspects of structural research, including sample preparation, crystallization, the construction of synchrotron and spallation sources, phasing approaches and high-speed computing and visualization, now provide specialists and non-specialists alike with a steady flow of molecular images of unprecedented detail. The present chapter combines a general overview of diffraction methods with a step-by-step description of the process of a single-crystal X-ray structure determination experiment, from chemical synthesis or expression to phasing and refinement, analysis and quality control. For novices it may serve as a stepping-stone to more in-depth treatises of the individual topics. Readers relying on structural information for interpreting functional data may find it a useful consumer guide. PMID:20517991

Diffraction Techniques in Structural Biology.

PubMed

Egli, Martin

2016-06-01

A detailed understanding of chemical and biological function and the mechanisms underlying the molecular activities ultimately requires atomic-resolution structural data. Diffraction-based techniques such as single-crystal X-ray crystallography, electron microscopy, and neutron diffraction are well established and they have paved the road to the stunning successes of modern-day structural biology. The major advances achieved in the last twenty years in all aspects of structural research, including sample preparation, crystallization, the construction of synchrotron and spallation sources, phasing approaches, and high-speed computing and visualization, now provide specialists and nonspecialists alike with a steady flow of molecular images of unprecedented detail. The present unit combines a general overview of diffraction methods with a detailed description of the process of a single-crystal X-ray structure determination experiment, from chemical synthesis or expression to phasing and refinement, analysis, and quality control. For novices it may serve as a stepping-stone to more in-depth treatises of the individual topics. Readers relying on structural information for interpreting functional data may find it a useful consumer guide. © 2016 by John Wiley & Sons, Inc. Copyright © 2016 John Wiley & Sons, Inc.

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

Moorhouse, Saul J.; Wu, Yue; O’Hare, Dermot, E-mail: dermot.ohare@chem.ox.ac.uk

A newly developed in situ monochromatic high-energy X-ray diffraction setup was used to investigate the synthesis of MOFs using cation-impregnated polymer resin beads as a ion source. The Co–NDC–DMF (NDC=2,6-naphthalenedicarboxylate; DMF=dimethylformamide) system was investigated, a system which is known to produce at least three distinct frameworks. It was found that the resin-assisted synthesis results in the preferential formation of a topology previously impossible to synthesise in bulk, while the comparable nitrate-salt synthesis appeared to form an alternative phases. It was also found that the resin-assisted synthesis is highly diffusion-controlled. - Graphical abstract: In situ monochromatic high-energy X-ray diffraction study ofmore » a MOF synthesis. - Highlights: • Resin-assisted solvothermal MOF synthesis was studied using in situ diffraction. • Full kinetics of reaction can be obtained from in situ data. • Kinetics show that this resin-assisted synthesis is diffusion controlled. • Resin-assisted synthesis enables the production of an alternative bulk phase.« less

Synthesis of phase-pure and monodisperse iron oxide nanoparticles by thermal decomposition

NASA Astrophysics Data System (ADS)

Hufschmid, Ryan; Arami, Hamed; Ferguson, R. Matthew; Gonzales, Marcela; Teeman, Eric; Brush, Lucien N.; Browning, Nigel D.; Krishnan, Kannan M.

2015-06-01

Superparamagnetic iron oxide nanoparticles (SPIONs) are used for a wide range of biomedical applications requiring precise control over their physical and magnetic properties, which are dependent on their size and crystallographic phase. Here we present a comprehensive template for the design and synthesis of iron oxide nanoparticles with control over size, size distribution, phase, and resulting magnetic properties. We investigate critical parameters for synthesis of monodisperse SPIONs by organic thermal decomposition. Three different, commonly used, iron containing precursors (iron oleate, iron pentacarbonyl, and iron oxyhydroxide) are evaluated under a variety of synthetic conditions. We compare the suitability of these three kinetically controlled synthesis protocols, which have in common the use of iron oleate as a starting precursor or reaction intermediate, for producing nanoparticles with specific size and magnetic properties. Monodisperse particles were produced over a tunable range of sizes from approximately 2-30 nm. Reaction parameters such as precursor concentration, addition of surfactant, temperature, ramp rate, and time were adjusted to kinetically control size and size-distribution, phase, and magnetic properties. In particular, large quantities of excess surfactant (up to 25 : 1 molar ratio) alter reaction kinetics and result in larger particles with uniform size; however, there is often a trade-off between large particles and a narrow size distribution. Iron oxide phase, in addition to nanoparticle size and shape, is critical for establishing magnetic properties such as differential susceptibility (dm/dH) and anisotropy. As an example, we show the importance of obtaining the required size and iron oxide phase for application to Magnetic Particle Imaging (MPI), and describe how phase purity can be controlled. These results provide much of the information necessary to determine which iron oxide synthesis protocol is best suited to a particular application.

Printing Peptide arrays with a complementary metal oxide semiconductor chip.

PubMed

Loeffler, Felix F; Cheng, Yun-Chien; Muenster, Bastian; Striffler, Jakob; Liu, Fanny C; Ralf Bischoff, F; Doersam, Edgar; Breitling, Frank; Nesterov-Mueller, Alexander

2013-01-01

: In this chapter, we discuss the state-of-the-art peptide array technologies, comparing the spot technique, lithographical methods, and microelectronic chip-based approaches. Based on this analysis, we describe a novel peptide array synthesis method with a microelectronic chip printer. By means of a complementary metal oxide semiconductor chip, charged bioparticles can be patterned on its surface. The bioparticles serve as vehicles to transfer molecule monomers to specific synthesis spots. Our chip offers 16,384 pixel electrodes on its surface with a spot-to-spot pitch of 100 μm. By switching the voltage of each pixel between 0 and 100 V separately, it is possible to generate arbitrary particle patterns for combinatorial molecule synthesis. Afterwards, the patterned chip surface serves as a printing head to transfer the particle pattern from its surface to a synthesis substrate. We conducted a series of proof-of-principle experiments to synthesize high-density peptide arrays. Our solid phase synthesis approach is based on the 9-fluorenylmethoxycarbonyl protection group strategy. After melting the particles, embedded monomers diffuse to the surface and participate in the coupling reaction to the surface. The method demonstrated herein can be easily extended to the synthesis of more complicated artificial molecules by using bioparticles with artificial molecular building blocks. The possibility of synthesizing artificial peptides was also shown in an experiment in which we patterned biotin particles in a high-density array format. These results open the road to the development of peptide-based functional modules for diverse applications in biotechnology.

Controlling Particle Morphologies at Fluid Interfaces: Macro- and Micro- approaches

NASA Astrophysics Data System (ADS)

Beesabathuni, Shilpa Naidu

The controlled generation of varying shaped particles is important for many applications: consumer goods, biomedical diagnostics, food processing, adsorbents and pharmaceuticals which can benefit from the availability of geometrically complex and chemically inhomogeneous particles. This thesis presents two approaches to spherical and non-spherical particle synthesis using macro and microfluidics. In the first approach, a droplet microfluidic technique is explored to fabricate spherical conducting polymer, polyaniline, particles with precise control over morphology and functionality. Microfluidics has recently emerged as an important alternate to the synthesis of complex particles. The conducting polymer, polyaniline, is widely used and known for its stability, high conductivity, and favorable redox properties. In this approach, monodisperse micron-sized polyaniline spherical particles were synthesized using two-phase droplet microfluidics from Aniline and Ammonium persulfate oxidative polymerization in an oil-based continuous phase. The morphology of the polymerized particles is porous in nature which can be used for encapsulation as well as controlled release applications. Encapsulation of an enzyme, glucose oxidase, was also performed using the technique to synthesize microspheres for glucose sensing. The polymer microspheres were characterized using SEM, UV-Vis and EDX to understand the relationship between their microstructure and stability. In the second approach, molten drop impact in a cooling aqueous medium to generate non-spherical particles was explored. Viscoelastic wax based materials are widely used in many applications and their performance and application depends on the particle morphology and size. The deformation of millimeter size molten wax drops as they impacted an immiscible liquid interface was investigated. Spherical molten wax drops impinged on a cooling water bath, then deformed and as a result of solidification were arrested into various shapes such as ellipsoids, mushrooms, spherulites and discs. The final morphology of the wax particles is governed by the interfacial, inertial, viscous and thermal effects, which can be studied over a range of Weber, Capillary, Reynolds and Stefan numbers. A simplified Stefan problem for a spherical drop was solved. The time required to initiate a phase transition at the interface of the molten wax and water after impact was estimated and correlated with the drop deformation history and final wax particle shape to develop a capability to predict the shape. While the microfluidic synthesis approach offers precise control over morphology and functionality, large particle throughput is a limitation. The drop impact in a liquid medium emulsion approach is limited to crosslinking or heat sensitive materials but can be extended to large scale production for industrial applications. Both approaches are simple, robust and cost effective making them viable and attractive solutions for complex particle synthesis. The choice of the approach is dependent on considerations such as particle material, size, shape, throughput and end application.

Double labeling of human leukemic cells using /sup 3/H-cytarabine and monoclonal antibody against bromodeoxyuridine

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

Raza, A.; Preisler, H.D.

A new technique using immunofluorescence and autoradiography is described, in which the DNA of cells in S phase are labeled with two different probes. This method makes it possible to study the relationship between DNA synthesis and the uptake and/or incorporation of chemotherapeutic agents into normal or neoplastic cells. An example is provided in which the incorporation of /sup 3/H-cytarabine into DNA is demonstrated to occur only in cells which were synthesizing DNA during exposure to /sup 3/H-cytarabine. Other radioactively labeled probes can be used as well.

Study on different characteristics of doped tri calcium phosphate at different sintering temperatures

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

Samanta, Sujan Krishna, E-mail: itssujan@rediffmail.com; Chanda, Abhijit, E-mail: abhijitchanda.biomed@gmail.com

2016-04-13

Pure β-tricalcium phosphate (β-TCP), Zn-doped (3wt %) β-TCP and Mg- doped (3wt %) β-TCP samples were prepared by using a wet chemical precipitation synthesis technique, followed by calcination at 800 °C in air. The developed materials were subjected to sintering at different temperatures. Density and porosity were compared. The X-ray diffractometry (XRD) and Fourier-transformed infrared (FTIR) spectrometer were used to examine the changes in crystalline phases and presence of functional groups of TCP ceramics. The scanning electron microscopy (SEM) was used to study the pore formation, pore size, grain size.

Vapor-crystal phase transition in synthesis of paracetamol films by vacuum evaporation and condensation

NASA Astrophysics Data System (ADS)

Belyaev, A. P.; Rubets, V. P.; Antipov, V. V.; Bordei, N. S.; Zarembo, V. I.

2014-03-01

We report on the structural and technological investigations of the vapor-crystal phase transition during synthesis of paracetamol films of the monoclinic system by vacuum evaporation and condensation in the temperature range 220-320 K. The complex nature of the transformation accompanied by the formation of a gel-like phase is revealed. The results are interpreted using a model according to which the vapor-crystal phase transition is not a simple first-order phase transition, but is a nonlinear superposition of two phase transitions: a first-order transition with a change in density and a second-order phase transition with a change in ordering. Micrographs of the surface of the films are obtained at different phases of formation.

An Intelligent Harmonic Synthesis Technique for Air-Gap Eccentricity Fault Diagnosis in Induction Motors

NASA Astrophysics Data System (ADS)

Li, De Z.; Wang, Wilson; Ismail, Fathy

2017-11-01

Induction motors (IMs) are commonly used in various industrial applications. To improve energy consumption efficiency, a reliable IM health condition monitoring system is very useful to detect IM fault at its earliest stage to prevent operation degradation, and malfunction of IMs. An intelligent harmonic synthesis technique is proposed in this work to conduct incipient air-gap eccentricity fault detection in IMs. The fault harmonic series are synthesized to enhance fault features. Fault related local spectra are processed to derive fault indicators for IM air-gap eccentricity diagnosis. The effectiveness of the proposed harmonic synthesis technique is examined experimentally by IMs with static air-gap eccentricity and dynamic air-gap eccentricity states under different load conditions. Test results show that the developed harmonic synthesis technique can extract fault features effectively for initial IM air-gap eccentricity fault detection.

Synthesis and Properties of Nanoparticle Forms Saponite Clay, Cancrinite Zeolite and Phase Mixtures Thereof.

PubMed

Shao, Hua; Pinnavaia, Thomas J

2010-09-01

The low-temperature synthesis (90°C) of nanoparticle forms of a pure phase smectic clay (saponite) and zeolite (cancrinite) is reported, along with phase mixtures thereof. A synthesis gel corresponding to the Si:Al:Mg unit cell composition of saponite (3.6:0.40:3.0) and a NaOH/Si ratio of 1.39 affords the pure phase clay with disordered nanolayer stacking. Progressive increases in the NaOH/Si ratio up to a value of 8.33 results in the co-crystallization of first garronite and then cancrinite zeolites with nanolath morphology. The resulting phase mixtures exhibit a compound particulate structure of intertwined saponite nanolayers and cancrinite nanolaths that cannot be formed through physical mixing of the pure phase end members. Under magnesium-free conditions, pure phase cancrinite nanocrystals are formed. The Si/Al ratio of the reaction mixture affects the particle morphology as well as the chemical composition of the cancrinite zeolite. Ordinarily, cancrinite crystallizes with a Si/Al ratio of 1.0, but a silicon-rich form of the zeolite (Si/Al=1.25) is crystallized at low temperature from a silica rich synthesis gel, as evidenced by (29)Si NMR spectroscopy and XEDS-TEM. Owing to the exceptionally high external surface areas of the pure phase clay (875 m(2)/g) and zeolite end members (8.9 - 40 m(2)/g), as well as their unique mixed phase composites (124 - 329 m(2)/g), these synthetic derivatives are promising model nanoparticles for studies of the bioavailability of poly-aromatic hydrocarbons immobilized in silicate bearing sediments and soils.

Crystallization of rhenium salts in a simulated low-activity waste borosilicate glass

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

Riley, Brian J.; McCloy, John S.; Goel, Ashutosh

2013-04-01

This study presents a new method for looking at the solubility of volatile species in simulated low-activity waste glass. The present study looking at rhenium salts is also applicable to real applications involving radioactive technetium salts. In this synthesis method, oxide glass powder is mixed with the volatiles species, vacuum-sealed in a fused quartz ampoule, and then heat-treated under vacuum in a furnace. This technique restricts the volatile species to the headspace above the melt but still within the sealed ampoule, thus maximizing the volatile concentration in contact with the glass. Various techniques were used to measure the solubility ofmore » rhenium in glass and include energy dispersive spectroscopy, wavelength dispersive spectroscopy, laser ablation inductively-coupled plasma mass spectroscopy, and inductively-coupled plasma optical emission spectroscopy. The Re-solubility in this glass was determined to be ~3004 parts per million Re atoms. Above this concentration, the salts separated out of the melt as inclusions and as a low viscosity molten salt phase on top of the melt observed during and after cooling. This salt phase was analyzed with X-ray diffraction, scanning electron microscopy as well as some of the other aforementioned techniques and identified to be composed of alkali perrhenate and alkali sulfate.« less

Synthesis of visible light driven cobalt tailored Ag{sub 2}O/TiON nanophotocatalyst by reverse micelle processing for degradation of Eriochrome Black T

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

Hussain, Syed Tajammul, E-mail: dr_tajammul@yahoo.ca; Rashid; Department of Chemistry, Quaid-i-Azam University, Islamabad

2013-02-15

Graphical abstract: Cobalt tailored Ag{sub 2}O/TiON nanophotocatalyst is synthesized using reverse micelle technique and it showed extraordinary photocatalytic activity. Display Omitted Highlights: ► TiON/Ag{sub 2}O/Co nanophotocatalyst is synthesized using microemulsion technique. ► Low temperature anatase phase and outstanding photocatlytic activity is observed. ► Effect of temperature and inert atmosphere on materials phase is investigated. ► Homogeneous dopants distribution and oxygen vacancies are examined. ► Enhancement in surface area, quantum efficiency and optical properties is observed. -- Abstract: An ultra efficient cobalt tailored silver and nitrogen co-doped titania (TiON/Ag{sub 2}O/Co) visible nanophotocatalyst is successfully synthesized using modified reverse micelle processing. Composition,more » phase, distribution of dopants, functional group analysis, optical properties and morphology of synthesized materials are investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM) based techniques and others. Charge states of titanium (Ti) and silver are explored through core-loss electron energy loss spectroscopy (EELS) analysis and X ray photoelectron spectroscopy (XPS). Our characterization results showed that the synthesized nanophotocatalyst consisted of anatase phased qausispherical nanoparticles that exhibited homogeneous distribution of dopants, large surface area, high quantum efficiency and enhanced optical properties. At lower content of doped Co ions, the TiON/Ag{sub 2}O responded with extraordinary photocatalytic properties. The cobalt tailored nanophotocatalyst showed remarkable activity against Eriochrome Black T (EBT). Moreover, comparative degradation behavior of EBT with TiON, Ag{sub 2}O/TiON and Co/Ag{sub 2}O/TiON is also investigated.« less

Preparation & characterization of high purity Cu2 ZnSn(SxSe1-x)4 nanoparticles

NASA Astrophysics Data System (ADS)

Negash, Bethlehem G.

Research in thin film solar cells applies novel techniques to synthesize cost effective and highly efficient absorber materials in order to generate electricity directly from solar energy. Of these materials, copper zinc tin sulfoselenide (Cu2ZnSn(SxSe1-x) 4) nanoparticles have shown great promise in solar cell applications due to optimal material properties as well as low cost & relative abundance of materials.1,2 Sulfoselenide nanoparticles have also a broader impact in other industries including electronics3, LED 4, and biomedical research5. Of the many routes of manufacturing these class of semiconductors, colloidal synthesis of Cu 2ZnSn(SxSe1-x)4 offers a scalable, low cost and high-throughput route for manufacturing high efficiency thin-film solar cells. Hydrazine processed Cu2ZnSn(SxSe1-x )4 devices have reached a record power conversion efficiency (PCE) of 12.6%, much higher than the 9.6% reported for physical vapor deposition (PVD) systems.6,7. Despite high efficiencies, wet synthesis of nanoparticles, however, is made more complicated in multi-element, quaternary and quinary systems such as copper zinc tin sulfoselenide (CZTSSe) and copper indium gallium diselenide (CIGSe). One major disadvantage in these systems is growth of the desired quaternary or quinary phase in competition with unwanted binary and ternary phases with low energy of formation.8,9 Moreover, various reaction parameters such as reaction time, temperature, and choice of ligand also affect, chemical as well as physical properties of resulting nanoparticles. Understanding of the formation mechanisms of the particles is necessary in order to address some of these challenges in wet synthesis of CZTSSe nanoparticles. In this study, we investigate synthesis conditions & reaction parameters which yield high purity Cu2ZnSn(SxSe1-x) 4 nanoparticles as well as attempt to understand the growth mechanism of these nanoparticles. This was achieved by manipulating anion precursor preparation routes as well order in which precursors are introduced into a reaction system. We report a new solution based sulfoselenide preparation route which has been used to synthesize high purity Cu2ZnSn(S xSe1-x)4 nanoparticles. Uniform phase Cu 2ZnSn(SxSe1-x)4 nanoparticles were successfully synthesized over a wide range of varying chalcogen ratios. It was found that anion precursor solution plays a key role in determining the morphology & phase purity of the final nanoparticles, as observed from X-ray Diffraction (XRD) and Raman spectroscopy. A uniform sulfoselenide solution is needed to produce high purity Cu2ZnSn(SxSe1-x )4 nanoparticles with narrow phase distribution. Moreover, the relative reactivity of each anion must be balanced in order to yield uniform phase nanoparticles. The findings of this study as well as the reported mixed chalcogen precursor preparation route can be applied in various industries, including photovoltaics to produce uniform phase, solution processed sulfoselenide nanoparticles.

Pyrrole-Imidazole Polyamides: Manual Solid-Phase Synthesis.

PubMed

Pauff, Steven M; Fallows, Andrew J; Mackay, Simon P; Su, Wu; Cullis, Paul M; Burley, Glenn A

2015-12-01

Pyrrole-imidazole polyamides (PAs) are a family of DNA-binding peptides that bind in the minor groove of double-stranded DNA (dsDNA) in a sequence-selective, programmable fashion. This protocol describes a detailed manual procedure for the solid-phase synthesis of this family of compounds. The protocol entails solution-phase synthesis of the Boc-protected pyrrole (Py) and imidazole (Im) carboxylic acid building blocks. This unit also describes the importance of choosing the appropriate condensing agent to form the amide linkages between each building block. Finally, a monomeric coupling protocol and a fragment-based approach are described that delivers PAs in 13% to 30% yield in 8 days. Copyright © 2015 John Wiley & Sons, Inc.

Convergent solid-phase and solution approaches in the synthesis of the cysteine-rich Mdm2 RING finger domain.

PubMed

Vasileiou, Zoe; Barlos, Kostas; Gatos, Dimitrios

2009-12-01

The RING finger domain of the Mdm2, located at the C-terminus of the protein, is necessary for regulation of p53, a tumor suppressor protein. The 48-residues long Mdm2 peptide is an important target for studying its interaction with small anticancer drug candidates. For the chemical synthesis of the Mdm2 RING finger domain, the fragment condensation on solid-phase and the fragment condensation in solution were studied. The latter method was performed using either protected or free peptides at the C-terminus as the amino component. Best results were achieved using solution condensation where the N-component was applied with the C-terminal carboxyl group left unprotected. The developed method is well suited for large-scale synthesis of Mdm2 RING finger domain, combining the advantages of both solid-phase and solution synthesis. (c) 2009 European Peptide Society and John Wiley & Sons, Ltd.

High-throughput continuous hydrothermal synthesis of nanomaterials (part II): unveiling the as-prepared CexZryYzO2-δ phase diagram.

PubMed

Quesada-Cabrera, Raul; Weng, Xiaole; Hyett, Geoff; Clark, Robin J H; Wang, Xue Z; Darr, Jawwad A

2013-09-09

High-throughput continuous hydrothermal flow synthesis was used to manufacture 66 unique nanostructured oxide samples in the Ce-Zr-Y-O system. This synthesis approach resulted in a significant increase in throughput compared to that of conventional batch or continuous hydrothermal synthesis methods. The as-prepared library samples were placed into a wellplate for both automated high-throughput powder X-ray diffraction and Raman spectroscopy data collection, which allowed comprehensive structural characterization and phase mapping. The data suggested that a continuous cubic-like phase field connects all three Ce-Zr-O, Ce-Y-O, and Y-Zr-O binary systems together with a smooth and steady transition between the structures of neighboring compositions. The continuous hydrothermal process led to as-prepared crystallite sizes in the range of 2-7 nm (as determined by using the Scherrer equation).

Synthesis and characterization of wide range mesogenic esters based on asymmetrical 2,5-disubstituted 1,3,4-thiadiazole

NASA Astrophysics Data System (ADS)

Tomi, Ivan H. R.; Jaffer, Hamed J.; Aldhaif, Yasmeen A.

2018-04-01

A homologous series of new 13 esters, 4-(5-(p-tolyl)-1,3,4-thiadiazol-2-yl)-phenyl-4-alkoxybenzoate, (IVn), based on 1,3,4-thiadiazole core has been synthesized. The structures of these esters were confirmed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and mass techniques. Their mesophases behavior was investigated with hot-stage polarizing optical microscope and differential scanning calorimetry. The thermal stability for most of these derivatives was measured by thermal gravimetric analysis. All the target esters showed enantiotropic mesomorphic behaviors with nematic and nematic/smectic C phases. The phase transition temperatures and liquid crystalline properties were affected by the nature of heterocyclic ring and the length of the alkoxy chain. Only the nematic phase was observed in the first 10 derivatives, (n = 1-10), while the last 3, (n = 12, 16 and 18) showed nematic and smectic C phases. These compounds demonstrated high liquid crystalline ranges, both in heating and cooling cycles. The mesomorphic results obtained were compared with the reported analogs of similar constituents.

Universal photonic quantum gates assisted by ancilla diamond nitrogen-vacancy centers coupled to resonators

NASA Astrophysics Data System (ADS)

Wei, Hai-Rui; Long, Gui Lu

2015-03-01

We propose two compact, economic, and scalable schemes for implementing optical controlled-phase-flip and controlled-controlled-phase-flip gates by using the input-output process of a single-sided cavity strongly coupled to a single nitrogen-vacancy-center defect in diamond. Additional photonic qubits, necessary for procedures based on the parity-check measurement or controlled-path and merging gates, are not employed in our schemes. In the controlled-path gate, the paths of the target photon are conditionally controlled by the control photon, and these two paths can be merged back into one by using a merging gate. Only one half-wave plate is employed in our scheme for the controlled-phase-flip gate. Compared with the conventional synthesis procedures for constructing a controlled-controlled-phase-flip gate, the cost of which is two controlled-path gates and two merging gates, or six controlled-not gates, our scheme is more compact and simpler. Our schemes could be performed with a high fidelity and high efficiency with current achievable experimental techniques.

Phase Concentration Determination of Fe 16N 2 Using State of the Art Neutron Scattering Techniques

DOE PAGES

Bennett, S. P.; Feygenson, M.; Jiang, Y.; ...

2016-03-25

Limitation on the availability of rare earth elements have made it imperative that new high energy product rare earth free permanent magnet materials are developed for the next generation of energy systems. One promising low cost permanent magnet candidate for a high energy magnet is -Fe 16N 2, whose giant magnetic moment has been predicted to be well above any other from conventional first principles calculations. Despite its great promise, the phase is metastable; making synthesis of the pure phase difficult, resulting in less than ideal magnetic characteristics. This instability gives way to a slew of possible secondary phases (i.e.more » -Fe, Fe 2O 3, Fe 8N, Fe 4N ) whose concentrations are difficult to detect by conventional x-ray diffraction. Moreover, we show how high resolution neutron diffraction and polarized neutron reflectometry can be used to extract the phase concentration ratio of the giant magnetic phase from ultra-small powder sample sizes (~0.1g) and thin films. These studies have led to the discovery of promising fabrication methods for both homogeneous thin films, and nanopowders containing the highest reported to date (>95%) phase concentrations of room temperature stable -Fe 16N 2.« less

Associative Memory Synthesis, Performance, Storage Capacity And Updating: New Heteroassociative Memory Results

NASA Astrophysics Data System (ADS)

Casasent, David; Telfer, Brian

1988-02-01

The storage capacity, noise performance, and synthesis of associative memories for image analysis are considered. Associative memory synthesis is shown to be very similar to that of linear discriminant functions used in pattern recognition. These lead to new associative memories and new associative memory synthesis and recollection vector encodings. Heteroassociative memories are emphasized in this paper, rather than autoassociative memories, since heteroassociative memories provide scene analysis decisions, rather than merely enhanced output images. The analysis of heteroassociative memories has been given little attention. Heteroassociative memory performance and storage capacity are shown to be quite different from those of autoassociative memories, with much more dependence on the recollection vectors used and less dependence on M/N. This allows several different and preferable synthesis techniques to be considered for associative memories. These new associative memory synthesis techniques and new techniques to update associative memories are included. We also introduce a new SNR performance measure that is preferable to conventional noise standard deviation ratios.

Growth and characterization of Pt-Si droplets for silicon nanowires synthesis

NASA Astrophysics Data System (ADS)

Khumalo, Z. M.; Topić, M.; Mtshali, C. B.; Blumenthal, M.

2018-02-01

The formation of platinum silicide phases as a function of the annealing temperature was investigated using in-situ real-time Rutherford backscattering spectrometry. The in-situ real-time RBS revealed the reaction of platinum and silicon to start at about 220 °C to form platinum silicide phases, Pt2Si and PtSi in sequence. Scanning electron microscope revealed the morphological change in the platinum layer (formation of droplets) at 800 °C. The particle induced X-ray emission analysis showed the variation of platinum intensity, in the droplets areas, between 1600 and 2000 counts. The surrounding areas are left almost uncovered due to platinum film dewetting. In-plane as well as out-of-plane silicon nanowires were observed to form at 800 °C and 1000 °C using pulsed laser ablation and thermal annealing techniques, respectively.

Technology development for iron Fischer-Tropsch catalysts

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

O`Brien, R.J.; Raje, A.; Keogh, R.A.

1995-12-31

The objective of this research project is to develop the technology for the production of physically robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry phase synthesis reactor development. The catalysts that are developed shall be suitable for testing in the Advanced Fuels Development Facility at LaPorte, Texas, to produce either low-or high-alpha product distributions. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the {open_quotes}standard-catalyst{close_quotes} developed by German workers for slurry phase synthesis. In parallel, work will be conducted to design a high-alphamore » iron catalyst this is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.« less

Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst

DOE PAGES

Lu, Yongwu; Yu, Fei; Hu, Jin; ...

2012-04-12

Zn-Mn promoted Cu-Fe based catalyst was synthesized by the co-precipitation method. Mixed alcohols synthesis from syngas was studied in a half-inch tubular reactor system after the catalyst was reduced. Zn-Mn promoted Cu-Fe based catalyst was characterized by SEM-EDS, TEM, XRD, and XPS. The liquid phase products (alcohol phase and hydrocarbon phase) were analyzed by GC-MS and the gas phase products were analyzed by GC. The results showed that Zn-Mn promoted Cu-Fe based catalyst had high catalytic activity and high alcohol selectivity. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbons were also very high. Cumore » (111) was the active site for mixed alcohols synthesis, Fe 2C (101) was the active site for olefin and paraffin synthesis. The reaction mechanism of mixed alcohols synthesis from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Here, Zn-Mn promoted Cu-Fe based catalyst can be regarded as a potential candidate for catalytic conversion of biomass-derived syngas to mixed alcohols.« less

Protein synthesis and the recovery of both survival and cytoplasmic "petite" mutation in ultraviolet-treated yeast cells. II. Mitochondrial protein synthesis.

PubMed

Heude, M; Chanet, R

1975-04-01

The contribution of mitochondrial proteins in the repair of UV-induced lethal and cytoplasmic genetic damages was studied in dark liquid held exponential and stationary phase yeast cells. This was performed by using the specific inhibitors, erythromycin (ER) anc chloramphenicol (CAP). It was shown that mitochondrial proteins are involved in the recovery of stationary phase cells. Mitochondrial proteins are partly implicated in the mechanisms leading to the restoration of the (see article) genotype in UV-irradiated dark liquid held exponential phase cells. Here again, in stationary phase cells, mitochondrial enzymes do not seem to participate in the negative liquid holding (NLH) process for the (see article) induction, as shown by inhibiting mitochondrial protein synthesis or both mitochondrial and nuclear protein synthesis. When cells are grown in glycerol, the response after dark liquid holding of UV-treated cells in the different growth stages are similar to that found for glucose-grown cells. In other words, the fate of cytoplasmic genetic damage, in particular, is not correlated with the repressed or derepressed state of the mitochondria.

A COMPARISON OF EXPERIMENTS AND THREE-DIMENSIONAL ANALYSIS TECHNIQUES. PART II. UNPOISONED UNIFORM SLAB CORE WITH A PARTIALLY INSERTED HAFNIUM ROD AND A PARTIALLY INSERTED WATER GAP

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

Roseberry, R.J.

The experimental measurements and nuclear analysis of a uniformly loaded, unpoisoned slab core with a partially inserted hafnium rod and/or a partially inserted water gap are described. Comparisons of experimental data with calculated results of the UFO core and flux synthesis techniques are given. It is concluded that one of the flux synthesis techniques and the UFO code are able to predict flux distributions to within approximately -5% of experiment for most cases, with a maximum error of approximately -10% for a channel at the core- reflector boundary. The second synthesis technique failed to give comparable agreement with experiment evenmore » when various refinements were used, e.g. increasing the number of mesh points, performing the flux synthesis technique of iteration, and spectrum-weighting the appropriate calculated fluxes through the use of the SWAKRAUM code. These results are comparable to those reported in Part I of this study. (auth)« less

Solution-based colloidal synthesis of hybrid P3HT: Ternary CuInSe2 nanocomposites using a novel combination of capping agents for low-cost photovoltaics

NASA Astrophysics Data System (ADS)

Sharma, Shailesh Narain; Chawla, Parul; Akanksha; Srivastava, A. K.

2016-06-01

In this work, ternary CuInSe2 (CISe) chalcopyrite nanocrystallites efficiently passivated by a novel combination of capping agents viz: aniline and 1-octadecene during chemical route synthesis were dispersed in conducting polymer matrix poly(3-hexylthiophene) (P3HT). By varying the composition and concentration of the ligands, the properties of the resulting CISe nanocrystallites and its corresponding polymer nanocomposites thus could be tailored. The structural, morphological and optical studies accomplished by various complimentary techniques viz. Transmission Electron Microscopy (TEM), Contact angle, Photoluminescence (PL) and Raman have enabled us to compare the different hybrid organic (polymer)-inorganic nanocomposites. On the basis of aniline-octadecene equilibrium phase diagram, the polydispersity of the CISe nanocrystals could be tuned by using controlled variations in the reaction conditions of nucleation and growth such as composition of the solvent and temperature. To the best of author's knowledge, the beneficial effects of both the capping agents; aniline and octadecene contributing well in tandem in the development of large-sized (100-125 nm) high quality, sterically- and photo-oxidative stable polycrystalline CISe and its corresponding polymer (P3HT):CISe composites with enhanced charge transfer efficiency has been reported for the first time. The low-cost synthesis and ease of preparation renders this method of great potential for its possible application in low-cost hybrid organic-inorganic photovoltaics. The figure shows the Temperature vs Mole fraction graph of two different phases (aniline and 1-octadecene) in equilibrium.

5' modification of duplex DNA with a ruthenium electron donor-acceptor pair using solid-phase DNA synthesis

NASA Technical Reports Server (NTRS)

Frank, Natia L.; Meade, Thomas J.

2003-01-01

Incorporation of metalated nucleosides into DNA through covalent modification is crucial to measurement of thermal electron-transfer rates and the dependence of these rates with structure, distance, and position. Here, we report the first synthesis of an electron donor-acceptor pair of 5' metallonucleosides and their subsequent incorporation into oligonucleotides using solid-phase DNA synthesis techniques. Large-scale syntheses of metal-containing oligonucleotides are achieved using 5' modified phosporamidites containing [Ru(acac)(2)(IMPy)](2+) (acac is acetylacetonato; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (3) and [Ru(bpy)(2)(IMPy)](2+) (bpy is 2,2'-bipyridine; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (4). Duplexes formed with the metal-containing oligonucleotides exhibit thermal stability comparable to the corresponding unmetalated duplexes (T(m) of modified duplex = 49 degrees C vs T(m) of unmodified duplex = 47 degrees C). Electrochemical (3, E(1/2) = -0.04 V vs NHE; 4, E(1/2) = 1.12 V vs NHE), absorption (3, lambda(max) = 568, 369 nm; 4, lambda(max) = 480 nm), and emission (4, lambda(max) = 720 nm, tau = 55 ns, Phi = 1.2 x 10(-)(4)) data for the ruthenium-modified nucleosides and oligonucleotides indicate that incorporation into an oligonucleotide does not perturb the electronic properties of the ruthenium complex or the DNA significantly. In addition, the absence of any change in the emission properties upon metalated duplex formation suggests that the [Ru(bpy)(2)(IMPy)](2+)[Ru(acac)(2)(IMPy)](2+) pair will provide a valuable probe for DNA-mediated electron-transfer studies.

Synthesis of zirconia monoliths for chromatographic separations.

PubMed

Randon, Jérôme; Huguet, Samuel; Piram, Anne; Puy, Guillaume; Demesmay, Claire; Rocca, Jean-Louis

2006-03-17

The aim of this work is to join the advantages of two different kinds of stationary phases: monolithic columns and zirconia-based supports. On the one hand, silica monolithic columns allow a higher efficiency with a lower back-pressure than traditional packed columns. On the other hand, chromatographic stationary phases based on zirconia have a higher thermal and chemical stability and specific surface properties. Combining these advantages, a zirconia monolith with a macroporous framework could be a real improvement in separation sciences. Two main strategies can be used in order to obtain a zirconia surface on a monolithic skeleton: coating or direct synthesis. The coverage by a zirconia layer of the surface of a silica-based monolith can be performed using the chemical properties of the silanol surface groups. We realized this coverage using zirconium alkoxide and we further grafted n-dodecyl groups using phosphate derivatives. Any loss of efficiency was observed and fast separations have been achieved. The main advance reported in this paper is related to the preparation of zirconia monoliths by a sol-gel process starting from zirconium alkoxide. The synthesis parameters (hydrolysis ratio, porogen type, precursor concentration, drying step, etc.) were defined in order to produce a macroporous zirconia monoliths usable in separation techniques. We produced various homogeneous structures: zirconia rod 2 cm long with a diameter of 2.3 mm, and zirconia monolith inside fused silica capillaries with a 75 microm I.D. These monoliths have a skeleton size of 2 microm and have an average through pore size of 6 microm. Several separations have been reported.

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

Hong, Seung Sae; Yu, Jung Ho; Lu, Di

Long-range order and phase transitions in two-dimensional (2D) systems—such as magnetism, superconductivity, and crystallinity—have been important research topics for decades. The issue of 2D crystalline order has reemerged recently, with the development of exfoliated atomic crystals. Understanding the dimensional limit of crystalline phases, with different types of bonding and synthetic techniques, is at the foundation of low-dimensional materials design. We study ultrathin membranes of SrTiO 3, an archetypal perovskite oxide with isotropic (3D) bonding. Atomically controlled membranes are released after synthesis by dissolving an underlying epitaxial layer. Although all unreleased films are initially single-crystalline, the SrTiO 3 membrane lattice collapsesmore » below a critical thickness (5 unit cells). This crossover from algebraic to exponential decay of the crystalline coherence length is analogous to the 2D topological Berezinskii-Kosterlitz-Thouless (BKT) transition. Finally, the transition is likely driven by chemical bond breaking at the 2D layer-3D bulk interface, defining an effective dimensional phase boundary for coherent crystalline lattices.« less

Synthesis of YAG nanopowder by the co-precipitation method: Influence of pH and study of the reaction mechanisms

NASA Astrophysics Data System (ADS)

Marlot, Caroline; Barraud, Elodie; Le Gallet, Sophie; Eichhorn, Marc; Bernard, Frédéric

2012-07-01

YAG nanopowders with an average grain size of 30 nm have been successfully synthesized by the co-precipitation method using nitrates with precipitant of ammonium hydrogen carbonate. The influence of precipitation conditions such as pH, aging time and calcination temperature on the formation of secondary phases has been studied. The accurate control of pH value at every stage of precipitation process is crucial to avoid the presence of YAM (Yttrium Aluminium Monoclinic, Y4Al2O9) and yttrium oxide (Y2O3) after calcination. The reaction mechanisms have been investigated using different techniques such as infrared spectroscopy, x-ray diffraction and thermal analyses. The YAG phase is formed around 1050 °C passing through an intermediate phase called YAP (Yttrium Aluminium Perovskite, YAlO3). Local chemical heterogeneities are responsible for the deviation of the Y:Al ratio and the formation of YAP during heat treatment.

Spark plasma sintering synthesis of Ni1-xZnxFe2O4 ferrites: Mössbauer and catalytic study

NASA Astrophysics Data System (ADS)

Velinov, Nikolay; Manova, Elina; Tsoncheva, Tanya; Estournès, Claude; Paneva, Daniela; Tenchev, Krassimir; Petkova, Vilma; Koleva, Kremena; Kunev, Boris; Mitov, Ivan

2012-08-01

Nickel-zinc ferrite nanoparticles, Ni1-xZnxFe2O4 (x = 0, 0.2, 0.5, 0.8, 1.0) were prepared by combination of chemical precipitation and spark plasma sintering (SPS) techniques and conventional thermal treatment of the obtained precursors. The phase composition and structural properties of the obtained materials were investigated by X-ray diffraction and Mössbauer spectroscopy and their catalytic activity in methanol decomposition was tested. A strong effect of reaction medium leading to the transformation of ferrites to a complex mixture of different iron containing phases was detected. A tendency of formation of Fe-carbide was found for the samples synthesized by SPS, while predominantly iron-nickel alloys ware registered in TS obtained samples. The catalytic activity and selectivity in methanol decomposition to CO and methane depended on the current phase composition of the obtained ferrites, which was formed by the influence of the reaction medium.

Study on crystallization kinetics and phase evolution in Li2O-Al2O3-GeO2-P2O5 glass-ceramics system

NASA Astrophysics Data System (ADS)

Das, Anurup; Dixit, Anupam; Goswami, Madhumita; Mythili, R.; Hajra, R. N.

2018-04-01

To address the safety issues related to liquid electrolyte and improve the battery performance, Solid State Electrolytes (SSEs) are now in frontier area of research interest. We report here synthesis of Li-SSE based on Li2O-Al2O3-GeO2-P2O5 (LAGP) system with NASICON structure. Glass sample with nominal composition Li1.5Al0.5Ge1.5P2.5Si0.5O12 was prepared by melt-quenching technique. Non-isothermal crystallization kinetics was studied using DSC and activation energy of crystallisation was calculated to be ˜ 246 kJ/mol using Kissinger's equation. XRD of heat treated samples show the formation of required LiGe2(PO4)3 phase along with other minor phases. Compositional analysis using SEM-EDX confirms enrichment of Ge and Si along the grain boundaries.

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

Tracy, Cameron L.; Park, Sulgiye; Rittman, Dylan R.

High-entropy alloys, near-equiatomic solid solutions of five or more elements, represent a new strategy for the design of materials with properties superior to those of conventional alloys. However, their phase space remains constrained, with transition metal high-entropy alloys exhibiting only face- or body-centered cubic structures. Here, we report the high-pressure synthesis of a hexagonal close-packed phase of the prototypical high-entropy alloy CrMnFeCoNi. This martensitic transformation begins at 14 GPa and is attributed to suppression of the local magnetic moments, destabilizing the initial fcc structure. Similar to fcc-to-hcp transformations in Al and the noble gases, the transformation is sluggish, occurring overmore » a range of >40 GPa. However, the behaviour of CrMnFeCoNi is unique in that the hcp phase is retained following decompression to ambient pressure, yielding metastable fcc-hcp mixtures. This demonstrates a means of tuning the structures and properties of high-entropy alloys in a manner not achievable by conventional processing techniques.« less

Protein synthesis and the recovery of both survival and cytoplasmic "petite" mutation in ultraviolet-treated yeast cells. I. Nuclear-directed protein synthesis.

PubMed

Heude, M; Chanet, R; Moustacchi, E

1975-04-01

The contribution of nuclear-directed protein synthesis in the repair of lethal and mitochondrial genetic damage after UV-irradiation of exponential and stationary phage haploid yeast cells was examined. This was carried out using cycloheximide (CH), a specific inhibitor of nuclear protein synthesis. It appears that nuclear protein synthesis is required for the increase in survival seen after the liquid holding of cells at both stages, as well as for the "petite" recovery seen after the liquid holding of exponential phase cells. The characteristic negative liquid holding effect observed for the UV induction of "petites" in stationary phase cells (increase of the frequency of "petites" during storage) remained following all the treatments which inhibited nuclear protein synthesis. However, the application of photoreactivating light following dark holding with cycloheximide indicates that some steps of the repair of both nuclear and mitochondrial damage are performed in the absence of a synthesis of proteins.

Fischer Indole Synthesis in the Gas Phase, the Solution Phase, and at the Electrospray Droplet Interface.

PubMed

Bain, Ryan M; Ayrton, Stephen T; Cooks, R Graham

2017-07-01

Previous reports have shown that reactions occurring in the microdroplets formed during electrospray ionization can, under the right conditions, exhibit significantly greater rates than the corresponding bulk solution-phase reactions. The observed acceleration under electrospray ionization could result from a solution-phase, a gas-phase, or an interfacial reaction. This study shows that a gas-phase ion/molecule (or ion/ion) reaction is not responsible for the observed rate enhancement in the particular case of the Fischer indole synthesis. The results show that the accelerated reaction proceeds in the microdroplets, and evidence is provided that an interfacial process is involved. Graphical Abstract .

Hydrothermal route to VO2 (B) nanorods: controlled synthesis and characterization

NASA Astrophysics Data System (ADS)

Song, Shaokun; Huang, Qiwei; Zhu, Wanting

2017-10-01

One-dimensional vanadium dioxides have attracted intensive attention owing to their distinctive structure and novel applications in catalysis, high energy lithium-ion batteries, chemical sensors/actuators and electrochemical devices etc. In this paper, large-scale VO2 (B) nanorods have been successfully synthesized via a versatile and environment friendly hydrothermal strategy using V2O5 as vanadium source and carbohydrates/alcohols as reductant. The obtained samples are characterized by XRD, FT-IR, TEM, and XPS techniques to investigate the effects of chemical parameters such as reductants, temperature, and time of synthesis on the structure and morphology of products. Results show that pure B phase VO2 with homogeneous nanorod-like morphology can be prepared easily at 180 °C for 3 days with glycerol as reluctant. Typically, the nanorod-like products are 0.5-1 μm long and 50 nm width. Furthermore, it is also confirmed that the products are consisted of VO2, corresponding to the B phase. More importantly, this novel approach is efficient, free of any harmful solvents and surfactants. Therefore, this efficient, green, and cost-saving route will have great potential in the large-scale fabrication of 1D VO2 (B) nanorods from the economic and environmental point of view.

Methodical thermolysis of [Ba2Ti2(thd)4(OnPr)8(nPrOH)2] under autogenous pressure followed by combustion for the synthesis of dielectric tetragonal BaTiO3 nanopowder.

PubMed

Pol, Vilas G; Thiyagarajan, P; Moreno, Jose M Calderon; Popa, Monica; Kessler, Vadim G; Gohil, Suresh; Seisenbaeva, Gulaim A

2009-07-06

The tetragonal BaTiO(3) nanopowder is synthesized in a solvent-less, efficient process by the thermolysis of a single [Ba(2)Ti(2)(thd)(4)(OnPr)(8)(nPrOH)(2)] precursor in a closed reactor at 700 degrees C under autogenous pressure, followed by combustion. This paper compiles the synthesis of the [Ba(2)Ti(2)(thd)(4)(OnPr)(8)(nPrOH)(2)] precursor, its analysis by mass spectrometry, and implementation for the fabrication of dielectric tetragonal BaTiO(3) nanopowder by controlled efficient thermal decomposition. The as-prepared, intermediate, and final forms of the obtained nanomaterials are systematically analysed by XRD, Raman, and EDS measurements to gain structural and compositional information. Employing HR-SEM, TEM, and HR-TEM techniques, the morphological changes during the structural evolution of all the phases are pursued. The mechanistic elucidation for the fabrication of BaTiO(3) nanopowder is developed on the basis of TGA and DTA data obtained for the initial [Ba(2)Ti(2)(thd)(4)(OnPr)(8)(nPrOH)(2)] reactant as well as the as-prepared BaCO(3) with amorphous Ti phase.

A dimethyl ketal-protected benzoin-based linker suitable for photolytic release of unprotected peptides.

PubMed

Chumachenko, Nataliya; Novikov, Yehor; Shoemaker, Richard K; Copley, Shelley D

2011-11-18

Photolabile 3',5'-dimethoxybenzoin-based linkers are advantageous for a variety of solid-phase synthetic procedures and manipulations of biomolecules because UV irradiation in aqueous media provides fast and essentially quantitative release of tethered molecules, while generating unreactive side products. Practical applications of previously reported linkers are compromised to some extent by the 1,3-dithiane protection of the benzoin carbonyl group and the lengthy synthesis. We have extended the group of photocleavable 3',5'-dimethoxybenzoin-based linkers by designing and synthesizing a linker in which the carbonyl group is protected as a dimethyl ketal. This protection is compatible with commonly used esterification and amide bond formation techniques, including the Fmoc/tBu strategy for solid phase peptide synthesis, is stable under mild acidic conditions, and can be quantitatively removed in <5 min by 3% TFA in dichloromethane. Irradiation of beads carrying peptides attached to the linker at 350 nm in aqueous or partially aqueous media affords >90% release after 30 min. The linker was synthesized from commercially available starting materials in five steps with an overall yield of 40% and without any column chromatography purification. Additionally, we developed a route to a dithiane-protected linker that requires only two steps and proceeds in 65% yield, a significant improvement over previous synthetic routes.

Calcium titanium silicate based glass-ceramic for nuclear waste immobilisation

NASA Astrophysics Data System (ADS)

Sharma, K.; Srivastav, A. P.; Goswami, M.; Krishnan, Madangopal

2018-04-01

Titanate based ceramics (synroc) have been studied for immobilisation of nuclear wastes due to their high radiation and thermal stability. The aim of this study is to synthesis glass-ceramic with stable phases from alumino silicate glass composition and study the loading behavior of actinides in glass-ceramics. The effects of CaO and TiO2 addition on phase evolution and structural properties of alumino silicate based glasses with nominal composition x(10CaO-9TiO2)-y(10Na2O-5 Al2O3-56SiO2-10B2O3); where z = x/y = 1.4-1.8 are reported. The glasses are prepared by melt-quench technique and characterized for thermal and structural properties using DTA and Raman Spectroscopy. Glass transition and peak crystallization temperatures decrease with increase of CaO and TiO2 content, which implies the weakening of glass network and increased tendency of glasses towards crystallization. Sphene (CaTiSiO5) and perovskite (CaTiO3) crystalline phases are confirmed from XRD which are well known stable phase for conditioning of actinides. The microsturcture and elemental analysis indicate the presence of actinide in stable crystalline phases.

Effects of (monomer - crosslinker – initiator) composition during non imprinted polymers synthesis for catechin retention

NASA Astrophysics Data System (ADS)

Triadhi, U.; Zulfikar, M. A.; Setiyanto, H.; Amran, M. B.

2018-05-01

MISPE (molecularly imprinted Solid Phase Extraction) is a separation technique using a solid adsorbent as a principle of MI (molecularly imprinted). Methacrylic acid (MAA) was used as a monomer, ethylene glycol dimethacrylate (EGDMA) as a crosslinker, benzoyl peroxide (BPO) as an initiator and acetonitrile (ACN) as a porogen. Catechin will be used as the template. Thermal and microwave methods were employed in the synthesis method. When analyzed using FTIR spectra, it was found that there were no significant differences between NIP (non-imprinted polymer) resulting from thermal method and that resulting from microwave method. Preparation of polymers by microwave method required 4 mins at 60-65 °C, significantly less than thermal method, that took 60 minutes at the same temperature. The variations of mole ratios of the monomer, the crosslinker, and the initiator were also performed. Based on the FTIR spectra, intensity of some peaks were changed due to the decreases of concentration. The optimum composition for NIP synthesis was MAA: EGDMA: BPO ratio of 5:30:0.5 (in mmole). The TGA curve showed that the NIP sythesized using microwave method experienced mass loss of around 98.50% at 604.8 °C.

Flash microwave synthesis and sintering of nanosized La{sub 0.75}Sr{sub 0.25}Cr{sub 0.93}Ru{sub 0.07}o{sub 3-{delta}} for fuel cell application

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

Combemale, L., E-mail: lionel.combemale@u-bourgogne.f; Caboche, G.; Stuerga, D.

2009-10-15

Perovskite-oxide nanocrystals of La{sub 0.75}Sr{sub 0.25}Cr{sub 0.93}Ru{sub 0.07}O{sub 3-{delta}} with a mean size around 10 nm were prepared by microwave flash synthesis. This reaction was performed in alcoholic solution using metallic salts, sodium ethoxide and microwave autoclave. The obtained powder was characterised after purification by energy dispersive X-ray analysis (EDX), X-ray powder diffraction (XRD), BET adsorption technique, photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM). The results show that integrated perovskite-type phase and uniform particle size were obtained in the microwave treated samples. At last the synthesised powder was directly used in a sintering process. A porous solid, inmore » accordance with the expected applications, was then obtained at low sintering temperature (1000 deg. C) without use of pore forming agent. - Graphical abstract: TEM photograph of La{sub 0.75}Sr{sub 0.25}Cr{sub 0.93}Ru{sub 0.07}O{sub 3-{delta}} obtained by microwave flash synthesis. This picture confirms the nanometric size of the ceramic particles.« less

Biogenic synthesis of silver nanoparticles by leaf extract of Cassia angustifolia

NASA Astrophysics Data System (ADS)

Amaladhas, T. Peter; Sivagami, S.; Akkini Devi, T.; Ananthi, N.; Priya Velammal, S.

2012-12-01

In this study Cassia angustifolia (senna) is used for the environmentally friendly synthesis of silver nanoparticles. Stable silver nanoparticles having symmetric surface plasmon resonance (SPR) band centred at 420 nm were obtained within 10 min at room temperature by treating aqueous solutions of silver nitrate with C. angustifolia leaf extract. The water soluble components from the leaves, probably the sennosides, served as both reducing and capping agents in the synthesis of silver nanoparticles. The nanoparticles were characterized using UV-Vis, Fourier transform infrared (FTIR) spectroscopic techniques and transmission electron microscopy (TEM). The nanoparticles were poly-dispersed, spherical in shape with particle size in the range 9-31 nm, the average size was found to be 21.6 nm at pH 11. The zeta potential was -36.4 mV and the particles were stable for 6 months. The crystalline phase of the nanoparticles was confirmed from the selected area diffraction pattern (SAED). The rate of formation and size of silver nanoparticles were pH dependent. Functional groups responsible for capping of silver nanoparticles were identified from the FTIR spectrum. The synthesized silver nanoparticles exhibited good antibacterial potential against Escherichia coli and Staphylococcus aureus.

The self-assembly of redox active peptides: Synthesis and electrochemical capacitive behavior.

PubMed

Piccoli, Julia P; Santos, Adriano; Santos-Filho, Norival A; Lorenzón, Esteban N; Cilli, Eduardo M; Bueno, Paulo R

2016-05-01

The present work reports on the synthesis of a redox-tagged peptide with self-assembling capability aiming applications in electrochemically active capacitive surfaces (associated with the presence of the redox centers) generally useful in electroanalytical applications. Peptide containing ferrocene (fc) molecular (redox) group (Ac-Cys-Ile-Ile-Lys(fc)-Ile-Ile-COOH) was thus synthesized by solid phase peptide synthesis (SPPS). To obtain the electrochemically active capacitive interface, the side chain of the cysteine was covalently bound to the gold electrode (sulfur group) and the side chain of Lys was used to attach the ferrocene in the peptide chain. After obtaining the purified redox-tagged peptide, the self-assembly and redox capability was characterized by cyclic voltammetry (CV) and electrochemical impedance-based capacitance spectroscopy techniques. The obtained results confirmed that the redox-tagged peptide was successfully attached by forming an electroactive self-assembled monolayer onto gold electrode. The design of redox active self-assembly ferrocene-tagged peptide is predictably useful in the development of biosensor devices precisely to detect, in a label-free platform, those biomarkers of clinical relevance. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 357-367, 2016. © 2016 Wiley Periodicals, Inc.

Laser ablation synthesis of arsenic-phosphide Asm Pn clusters from As-P mixtures. Laser desorption ionisation with quadrupole ion trap time-of-flight mass spectrometry: The mass spectrometer as a synthesizer.

PubMed

Kubáček, Pavel; Prokeš, Lubomír; Pamreddy, Annapurna; Peña-Méndez, Eladia María; Conde, José Elias; Alberti, Milan; Havel, Josef

2018-05-30

Only a few arsenic phosphides are known. A high potential for the generation of new compounds is offered by Laser Ablation Synthesis (LAS) and when Laser Desorption Ionization (LDI) is coupled with simultaneous Time-Of-Flight Mass Spectrometry (TOFMS), immediate identification of the clusters can be achieved. LAS was used for the generation of arsenic phosphides via laser ablation of phosphorus-arsenic mixtures while quadrupole ion trap time-of-flight mass spectrometry (QIT-TOFMS) was used to acquire the mass spectra. Many new As m P n ± clusters (479 binary and 369 mono-elemental) not yet described in the literature were generated in the gas phase and their stoichiometry determined. The likely structures for some of the observed clusters arbitrary selected (20) were computed by density functional theory (DFT) optimization. LAS is an advantageous approach for the generation of new As m P n clusters, while mass spectrometry was found to be an efficient technique for the determination of cluster stoichiometry. The results achieved might inspire the synthesis of new materials. Copyright © 2018 John Wiley & Sons, Ltd.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation

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

Chopade, Sujay A.; Anderson, Evan L.; Schmidt, Peter W.

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethylmore » sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.« less

Chronological protein synthesis in regenerating rat liver.

PubMed

He, Jinjun; Hao, Shuai; Zhang, Hao; Guo, Fuzheng; Huang, Lingyun; Xiao, Xueyuan; He, Dacheng

2015-07-01

Liver regeneration has been studied for decades; however, its regulation remains unclear. In this study, we report a dynamic tracing of protein synthesis in rat regenerating liver with a new proteomic technique, (35) S in vivo labeling analysis for dynamic proteomics (SiLAD). Conventional proteomic techniques typically measure protein alteration in accumulated amounts. The SiLAD technique specifically detects protein synthesis velocity instead of accumulated amounts of protein through (35) S pulse labeling of newly synthesized proteins, providing a direct way for analyzing protein synthesis variations. Consequently, protein synthesis within short as 30 min was visualized and protein regulations in the first 8 h of regenerating liver were dynamically traced. Further, the 3.5-5 h post partial hepatectomy (PHx) was shown to be an important regulatory turning point by acute regulation of many proteins in the initiation of liver regeneration. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dehydration and dehydroxylation of C-S-H phases synthesized on silicon wafers

NASA Astrophysics Data System (ADS)

Giraudo, Nicolas; Bergdolt, Samuel; Laye, Fabrice; Krolla, Peter; Lahann, Joerg; Thissen, Peter

2018-03-01

In this work, the synthesis of specific ultrathin Calcium-Silicate-Hydrate (C-S-H) phases on silicon wafers and their transformation into C-S phases is achieved. Specific mineral phases are identified, and the synthesis is successful controlled. Samples are investigated by means of Fourier Transform Infrared (FTIR) spectroscopy and X-ray Diffraction (XRD) and the results are analyzed based on first-principles calculations. When C-S-H phases are transformed into C-S phases, only a few reflexes are detected on XRD, and the coherent scattering domains decrease with the increment of the temperature and time of exposure. This behavior is explained by the Ca/Si changes, which are identified by changes in the FTIR spectra. A thermodynamic analysis is performed with the help of first-principles calculations to underline the influence of the calcium-to-silicon (Ca/Si) ratio in the process of dehydroxylation. To increase the Ca/Si ratio water is partially substituted by methanol at the synthesis. This is observed in the FTIR spectra and is confirmed by lower temperatures of dehydroxylation. The catalytic nature of calcium towards the dehydroxylation is confirmed. The core of this work lies in the preparation of a model, which perfection makes possible to model reactivity, stability and mechanical properties using first-principles calculations, and is the starting point for the synthesis of many others.

DNA-Encoded Solid-Phase Synthesis: Encoding Language Design and Complex Oligomer Library Synthesis.

PubMed

MacConnell, Andrew B; McEnaney, Patrick J; Cavett, Valerie J; Paegel, Brian M

2015-09-14

The promise of exploiting combinatorial synthesis for small molecule discovery remains unfulfilled due primarily to the "structure elucidation problem": the back-end mass spectrometric analysis that significantly restricts one-bead-one-compound (OBOC) library complexity. The very molecular features that confer binding potency and specificity, such as stereochemistry, regiochemistry, and scaffold rigidity, are conspicuously absent from most libraries because isomerism introduces mass redundancy and diverse scaffolds yield uninterpretable MS fragmentation. Here we present DNA-encoded solid-phase synthesis (DESPS), comprising parallel compound synthesis in organic solvent and aqueous enzymatic ligation of unprotected encoding dsDNA oligonucleotides. Computational encoding language design yielded 148 thermodynamically optimized sequences with Hamming string distance ≥ 3 and total read length <100 bases for facile sequencing. Ligation is efficient (70% yield), specific, and directional over 6 encoding positions. A series of isomers served as a testbed for DESPS's utility in split-and-pool diversification. Single-bead quantitative PCR detected 9 × 10(4) molecules/bead and sequencing allowed for elucidation of each compound's synthetic history. We applied DESPS to the combinatorial synthesis of a 75,645-member OBOC library containing scaffold, stereochemical and regiochemical diversity using mixed-scale resin (160-μm quality control beads and 10-μm screening beads). Tandem DNA sequencing/MALDI-TOF MS analysis of 19 quality control beads showed excellent agreement (<1 ppt) between DNA sequence-predicted mass and the observed mass. DESPS synergistically unites the advantages of solid-phase synthesis and DNA encoding, enabling single-bead structural elucidation of complex compounds and synthesis using reactions normally considered incompatible with unprotected DNA. The widespread availability of inexpensive oligonucleotide synthesis, enzymes, DNA sequencing, and PCR make implementation of DESPS straightforward, and may prompt the chemistry community to revisit the synthesis of more complex and diverse libraries.

Ferroelectric Liquid Crystals: Synthesis and Thermal Behavior of Optically Active, Three-Ring Schiff Bases and Salicylaldimines.

PubMed

Veerabhadraswamy, Bhyranalyar N; Rao, Doddamane S Shankar; Yelamaggad, Channabasaveshwar V

2018-04-16

The chiral ferroelectric smectic C (SmC*) phase, characterized by a helical superstructure, has been well exploited in developing high-resolution microdisplays that have been effectively employed in the fabrication of a wide varieties of portable devices. Although, an overwhelming number of optically active (chiral) liquid crystals (LCs) exhibiting a SmC* phase have been designed and synthesized, the search for new systems continues so as to realize mesogens capable of meeting technical necessities and specifications for their end-use. In continuation of our research work in this direction, herein we report the design, synthesis, and thermal behavior of twenty new optically active, three-ring calamitic LCs belonging to four series. The first two series comprise five pairs of enantiomeric Schiff bases whereas the other two series are composed of five pairs of enantiomeric salicylaldimines. In each pair of optical isomers, the configuration of a chiral center in one stereoisomer is opposite to that of the analogous center in the other isomer as they are derived from (3 S)-3,7-dimethyloctyloxy and (3 R)-3,7-dimethyloctyloxy tails. To probe the structure-property correlations in each series, the length of the n-alkoxy tail situated at the other end of the mesogens has been varied from n-octyloxy to n-dodecyloxy. The measurement of optical activity of these chiral mesogens was carried out by recording their specific rotations. As expected, enantiomers rotate plane polarized light in the opposite direction but by the same magnitude. The thermal behavior of the compounds was established by using a combination of optical polarizing microscopy, differential scanning calorimetry, and powder X-ray diffraction. These complementary techniques demonstrate the existence of the expected, thermodynamically stable, chiral smectic C (SmC*) LC phase besides blue phase I/II (BPI or BPII) and chiral nematic (N*) phase. However, as noted in our previous analogous study, the vast majority of the Schiff bases show an additional metastable, unfamiliar smectic (SmX) phase just below the SmC* phase. Notably, the SmC* phase persists over the temperature range ≈80-115 °C. Two mesogens chosen each from Schiff bases and salicylaldimines were investigated for their electrical switching behavior. The study reveals the ferroelectric switching characteristics of the SmC* phase featuring the spontaneous polarization (P S ) in the range 69-96 nC cm -2 . The helical twist sense of the SmC* phase as well as the N* phase formed by a pair of enantiomeric Schiff bases and salicylaldimines has been established with the help of circular dichroism (CD) spectroscopic technique. As expected, the SmC* and the N* phase of a pair of enantiomers showed mirror image CD signals. Most importantly, the reversal of helical handedness from left to right and vice versa has been evidenced during the N* to SmC* phase transition, implying that the screw sense of the helical array of the N* phase and the SmC* phase of an enantiomer is opposite. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of excessive acute-phase response on liver regeneration after partial hepatectomy in rats.

PubMed

Kusashio, Kimihiko; Shimizu, Hiroaki; Kimura, Fumio; Yoshidome, Hiroyuki; Ohtsuka, Masayuki; Kato, Atsushi; Yoshitomi, Hideyuki; Furukawa, Katsunori; Fukada, Tadaomi; Miyazaki, Masaru

2009-01-01

Acute-phase response (APR) is known to have a protective role against infection and tissue injury including partial hepatectomy (HTX). In this study, the effect of excessive APR on liver regeneration was investigated using a rat hepatectomized model. Experimental APR was induced by subcutaneous injection of turpentine oil, immediately, 24 h and 48 h after 50% HTX. Serum IL-6 and hepatic alpha2-macroglobulin mRNA was evaluated in rats receiving turpentine or saline as control after HTX. DNA synthesis and PCNA labeling index in the remnant liver was also investigated. Furthermore, in vitro total hepatic protein synthesis (TPS) and secretory protein synthesis (SPS) in the remnant liver were measured. Liver regeneration was significantly inhibited after HTX in the turpentine group, compared to the control. DNA synthesis and PCNA labeling index was also significantly decreased on days 1 and 2. A remarkable increase in the serum IL-6 and hepatic alpha2-macroglobulin mRNA was found in the turpentine group. Furthermore, SPS was significantly upregulated in the turpentine group, although TPS was almost similar between the groups. Induction of excessive APR after HTX inhibits liver regeneration. Acute phase protein synthesis is remarkably upregulated within the capacity of hepatic protein synthesis, most probably by a reduction in replicative protein synthesis, suggesting that APR may be more appropriate biological response for ensuring immediate survival.

Improvement in synthesis of (K 0.5Na 0.5)NbO 3 powders by Ge 4+ acceptor doping

DOE PAGES

Zhao, Yajing; Chen, Yan; Chen, Kepi

2016-11-17

In this study, the effects of doping with GeO 2 on the synthesis temperature, phase structure and morphology of (K 0.5Na 0.5)NbO 3 (KNN) ceramic powders were studied using XRD and SEM. The results show that KNN powders with good crystallinity and compositional homogeneity can be obtained after calcination at up to 900°C for 2 h. Introducing 0.5 mol.% GeO 2 into the starting mixture improved the synthesis of the KNN powders and allowed the calcination temperature to be decreased to 800°C, which can be ascribed to the formation of the liquid phase during the synthesis.

Self-assembly concepts in the formation of nanostructured particles using a liquid-phase synthesis method

NASA Astrophysics Data System (ADS)

Nandiyanto, Asep Bayu Dani

2016-02-01

When synthesizing particles using a liquid-phase synthesis method, reactant components show interaction with the reaction system itself. However, current reports described successful synthesis of material with only partial information on the component-component interaction and possible self-assembly mechanism occurring during the material synthesis process. Here, self-assembly concepts in the formation of nanostructured particles are presented. Influences of self-assembly parameters (i.e., surface charge, size, and concentration of components involving the reaction) on self-organized material fabrication are described. Because understanding the interaction of the component provides significant information in regard to practical uses, this report can be relevant to further material development and fabrication.

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

Underwood, R.P.

As part of the DOE-sponsored contract Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal-Derived Syngas'' experimental evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives. Building on a technology base acquired during the development of the Liquid Phase Methanol (LPMEOH) process, this work focused on the development of slurry reactor based processes. The experimental investigations, which involved bench-scale reactor studies, focused primarily on three areas: (1) One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbonmore » mixtures using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same slurry reactor. (2) Slurry-phase conversion of syngas to mixed alcohols using various catalysts. (3) One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols synthesis catalyst and dehydration catalyst in the same slurry reactor. The experimental results indicate that, of the three types of processes investigated, slurry phase conversion of syngas to mixed alcohols shows the most promise for further process development. Evaluations of various mixed alcohols catalysts show that a cesium-promoted Cu/ZnO/Al[sub 2]O[sub 3] methanol synthesis catalyst, developed in Air Products' laboratories, has the highest performance in terms of rate and selectivity for C[sub 2+]-alcohols. In fact, once-through conversion at industrially practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for branched alcohols, potential precursors to iso-olefins for use in etherification.« less

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

Underwood, R.P.

As part of the DOE-sponsored contract ``Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal-Derived Syngas`` experimental evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives. Building on a technology base acquired during the development of the Liquid Phase Methanol (LPMEOH) process, this work focused on the development of slurry reactor based processes. The experimental investigations, which involved bench-scale reactor studies, focused primarily on three areas: (1) One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbonmore » mixtures using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same slurry reactor. (2) Slurry-phase conversion of syngas to mixed alcohols using various catalysts. (3) One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols synthesis catalyst and dehydration catalyst in the same slurry reactor. The experimental results indicate that, of the three types of processes investigated, slurry phase conversion of syngas to mixed alcohols shows the most promise for further process development. Evaluations of various mixed alcohols catalysts show that a cesium-promoted Cu/ZnO/Al{sub 2}O{sub 3} methanol synthesis catalyst, developed in Air Products` laboratories, has the highest performance in terms of rate and selectivity for C{sub 2+}-alcohols. In fact, once-through conversion at industrially practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for branched alcohols, potential precursors to iso-olefins for use in etherification.« less

Calculation and application of activity discriminants in lead optimization.

PubMed

Luo, Xincai; Krumrine, Jennifer R; Shenvi, Ashok B; Pierson, M Edward; Bernstein, Peter R

2010-11-01

We present a technique for computing activity discriminants of in vitro (pharmacological, DMPK, and safety) assays and the application to the prediction of in vitro activities of proposed synthetic targets during the lead optimization phase of drug discovery projects. This technique emulates how medicinal chemists perform SAR analysis and activity prediction. The activity discriminants that are functions of 6 commonly used medicinal chemistry descriptors can be interpreted easily by medicinal chemists. Further, visualization with Spotfire allows medicinal chemists to analyze how the query molecule is related to compounds tested previously, and to evaluate easily the relevance of the activity discriminants to the activities of the query molecule. Validation with all compounds synthesized and tested in AstraZeneca Wilmington since 2006 demonstrates that this approach is useful for prioritizing new synthetic targets for synthesis. Copyright © 2010 Elsevier Inc. All rights reserved.

Spray pyrolytic deposition of α-MoO3 film and its use in dye-sensitized solar cell

NASA Astrophysics Data System (ADS)

Tamboli, Parvin S.; Jagtap, Chaitali V.; Kadam, Vishal S.; Ingle, Ravi V.; Vhatkar, Rajiv S.; Mahajan, Smita S.; Pathan, Habib M.

2018-04-01

Thermal decomposition of ammonium para molybdate tetrahydrate precursor has been studied to determine degradation temperatures in air atmosphere. Current work explores the synthesis of α-MoO3 films by an economical spray pyrolysis technique using ammonium para molybdate tetrahydrate precursor in the presence of compressed air. A variety of characterization techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-visible spectroscopy, Fourier transform infrared, and Raman spectroscopy were carried out, and the studies have confirmed that orthorhombic phase formation of MoO3 takes place with spongy mesh-type structure. The study of electro-catalytic activity of α-MoO3 in titania-based dye-sensitized solar cell is also carried out by cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel curves to evaluate its performance as a counter electrode.

Concise solid-phase synthesis of inverse poly(amidoamine) dendrons using AB2 building blocks.

PubMed

Huang, Adela Ya-Ting; Tsai, Ching-Hua; Chen, Hsing-Yin; Chen, Hui-Ting; Lu, Chi-Yu; Lin, Yu-Ting; Kao, Chai-Lin

2013-06-28

A concise solid-phase synthesis of inverse poly(amidoamine) dendrons was developed. Upon introduction of AB2-type monomers, each dendron generation was constructed via one reaction. G2 to G5 dendrons were constructed in a peptide synthesizer in 93%, 89%, 82%, and 78% yields, respectively, within 5 days.

Synthesis and characterization of copper zinc oxide nanoparticles obtained via metathesis process

NASA Astrophysics Data System (ADS)

Phoohinkong, Weerachon; Foophow, Tita; Pecharapa, Wisanu

2017-09-01

Copper-doped zinc oxide nanoparticles were successfully synthesized by grinding copper acetate and zinc acetate powder with different starting molar ratios in combined with sodium hydroxide. The effect of initial copper and zinc molar ratios on the product samples was investigated and discussed. Relevant ligand coordination type of reactant acetate salt precursors and product samples were investigated by Fourier transform infrared spectroscopy (FTIR). The particle shapes and surface morphologies were characterized by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Phase structures of prepared samples were studied by x-ray powder diffraction (XRD) and x-ray absorption near-edge spectroscopy (XANES) was applied to investigate the local structure of Cu and Zn environment atoms. The results demonstrate that the, particle size of as-synthesized products affected by copper concentration in the precursor trend to gradually decreases from nanorod shape with diameter around 50-100 nm to irregular particle structure around 5 nm associated with an increase in the concentration of copper in precursor. Moreover, it is noticed that shape and morphology of the products are strongly dependent on Cu:Zn ratios during the synthesis. Nanocrystallines Cu-doped ZnO by the substitution in Zn site with a high crystallization degree of hexagonal wurtzite structure were obtained. This synthesis technique is suggested as a potential effective technique for preparing copper zinc oxide nanoparticles with various atomic ratio in wide range of applications. Contribution at the 4th Southeast Asia Conference on Thermoelectrics 2016 (SACT 2016), 15-18 December 2016, Da Nang City, Vietnam.

Gas-Phase Synthesis of Singly and Multiply Charged Polyoxovanadate Anions Employing Electrospray Ionization and Collision Induced Dissociation

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

Al Hasan, Naila M.; Johnson, Grant E.; Laskin, Julia

2013-07-02

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including V xO y n– and V xO yCl n– ions (x = 1–14, y = 2–36, n = 1–3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V 14O 36Cl(L) 5 (L = Et 4N +, tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged V xO yCl n– and V xOmore » yCl(L) (n–1)– clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller V xO yCl (1–2)– and V xO y (1–2)– anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged V xO yCl and V xO y species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of V xO yCl and V xO y anions through low-energy CID. Finally and furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.« less

9-Fluorenylmethyloxycarbonyl/ tbutyl-based convergent protein synthesis.

PubMed

Barlos, K; Gatos, D

1999-01-01

Besides linear solid phase peptide synthesis, segment condensation in solution and chemical ligation, convergent peptide synthesis (CPS) was developed in order to enable the efficient preparation of complex peptides and small proteins. According to this synthetic strategy, solid phase synthesized and suitably protected peptide fragments corresponding to the entire peptide/protein-sequence are condensed on a solid support or in solution, to the target protein. This review summarizes CPS performed utilizing the mild 9-fluorenylmethyloxycarbonyl/tbutyloxycarbonyl-based protecting scheme for the amino acids. Copyright 1999 John Wiley & Sons, Inc.

Precursor routes to quaternary intermetallics: Synthesis, crystal structure, and physical properties of clathrate-II Cs{sub 8}Na{sub 16}Al{sub 24}Si{sub 112}

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

Wei, Kaya; Dong, Yongkwan; Nolas, George S., E-mail: gnolas@usf.edu

A new quaternary clathrate–II composition, Cs{sub 8}Na{sub 16}Al{sub 24}Si{sub 112}, was synthesized by kinetically controlled thermal decomposition (KCTD) employing both NaSi and NaAlSi as the precursors and CsCl as a reactive flux. The crystal structure and composition of Cs{sub 8}Na{sub 16}Al{sub 24}Si{sub 112} were investigated using both Rietveld refinement and elemental analysis, and the temperature dependent transport properties were investigated. Our results indicate that KCTD with multiple precursors is an effective method for the synthesis of multinary inorganic phases that are not easily accessible by traditional solid-state synthesis or crystal growth techniques. - Graphical abstract: Quaternary Cs{sub 8}Na{sub 16}Al{sub 24}S{submore » 112} clathrate–II was synthesized for the first time by kinetically controlled thermal decomposition (KCTD) employing a NaSi+NaAlSi precursor mixture with CsCl as the reactive flux, and the structural and transport properties were investigated. Our approach demonstrates a new synthetic pathway for the synthesis of multinary inorganic compounds. This work reports the exploration of a new clathrate composition as this class of materials continues to be of interest for thermoelectrics and other energy-related applications.« less

Lithium Assisted “Dissolution–Alloying” Synthesis of Nanoalloys from Individual Bulk Metals

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

Barkholtz, Heather M.; Gallagher, James R.; Li, Tao

2016-04-12

We report new fundamental chemistry involved in the synthesis of bimetallic nanoalloys via dissolving the pure bulk transition metals in molten lithium. It is revealed at the atomic level that when two pure bulk transition metals such as Pd and Pt are placed in molten lithium (similar to 200 degrees C), they undergo a dissolution process in which the metal-metal bonds in pure bulk transition metals are completely ruptured, which results in the existence of individual Pd and Pt atoms surrounded by lithium atoms, as is evident by synchrotron X-ray adsorption techniques. Then, upon the conversion of metal lithium tomore » LiOH in humid air, the Pd and Pt atoms undergo an alloying process to aggregate into nanoalloys. This method was further expanded to include PdZn, which is notoriously difficult to prepare via traditional nanoalloy synthesis methods due to the easily oxidizable Zn component. The constantly reducing environment of metallic Li allowed for preparation of PdZn nanoalloys with minimal Zn oxidation via dissolution-alloying of individual bulk transition metals in molten lithium. Additionally, this lithium assisted "dissolution-alloying" method bypasses many complications intrinsic to conventional ion reduction-based nanoalloy synthesis including the necessity of ligated metal ions, the use of proper reducing agents and dispersing surfactants, and the presence of segregated phases due to different reduction potentials of the constituent metal ions.« less

Lithium assisted “dissolution–alloying” synthesis of nanoalloys from individual bulk metals

DOE PAGES

Barkholtz, Heather M.; Gallagher, James R.; Li, Tao; ...

2016-03-27

Here, we report new fundamental chemistry involved in the synthesis of bimetallic nanoalloys via dissolving the pure bulk transition metals in molten lithium. It is revealed at the atomic level that when two pure bulk transition metals such as Pd and Pt are placed in molten lithium (~200°C), they undergo a dissolution process in which the metal-metal bonds in pure bulk transition metals are completely ruptured, resulting in the existence of individual Pd and Pt atoms surrounded by lithium atoms, as is evident by synchrotron Xray adsorption techniques. Then, upon the conversion of metal lithium to LiOH in humid air,more » the Pd and Pt atoms undergo an alloying process, to aggregate into nanoalloys. This method was further expanded to include PdZn, which is notoriously difficult to prepare via traditional nanoalloy synthesis methods due to the easily oxidizable Zn component. The constantly reducing environment of metallic Li allowed for preparation of PdZn nanoalloys with minimal Zn oxidation via dissolution-alloying of individual bulk transition metals in molten lithium. Additionally, this lithium assisted “dissolutionalloying” method bypasses many complications intrinsic to conventional ion reductionbased nanoalloy synthesis including the necessity of ligated metal ions, the use of proper reducing agents and dispersing surfactants, and the presence of segregated phases due to different reduction potentials of the constituent metal ions.« less

Titanium(IV) isopropoxide mediated solution phase reductive amination on an automated platform: application in the generation of urea and amide libraries.

PubMed

Bhattacharyya, S; Fan, L; Vo, L; Labadie, J

2000-04-01

Amine libraries and their derivatives are important targets for high throughput synthesis because of their versatility as medicinal agents and agrochemicals. As a part of our efforts towards automated chemical library synthesis, a titanium(IV) isopropoxide mediated solution phase reductive amination protocol was successfully translated to automation on the Trident(TM) library synthesizer of Argonaut Technologies. An array of 24 secondary amines was prepared in high yield and purity from 4 primary amines and 6 carbonyl compounds. These secondary amines were further utilized in a split synthesis to generate libraries of ureas, amides and sulfonamides in solution phase on the Trident(TM). The automated runs included 192 reactions to synthesize 96 ureas in duplicate and 96 reactions to synthesize 48 amides and 48 sulfonamides. A number of polymer-assisted solution phase protocols were employed for parallel work-up and purification of the products in each step.

A comparison of the suppression of human transferrin synthesis by lead and lipopolysaccharide.

PubMed

Barnum-Huckins, K M; Martinez, A O; Rivera, E V; Adrian, E K; Herbert, D C; Weaker, F J; Walter, C A; Adrian, G S

1997-03-14

Transferrin, as the major iron-transport protein in serum and other body fluids, has a central role in managing iron the body receives. Liver is a major site of transferrin synthesis, and in this study we present evidence that liver synthesis of human transferrin is suppressed by both the toxic metal lead and bacterial lipopolysaccharide, an inducer of the hepatic acute phase response. The responses of intact endogenous transferrin in the human hepatoma cell line HepG2 and chimeric human transferrin-chloramphenicol acetyltransferase genes in transgenic mice were examined. In HepG2 cells, 35S-transferrin protein synthesis and mRNA levels were suppressed by 100 microM and 10 microM lead acetate as early as 24 h after the initial treatment. Yet, synthesis of two proteins known to respond in the hepatic acute phase reaction, complement C3 and albumin, was not altered by the lead treatment. In transgenic mouse liver, lead suppressed expression of chimeric human transferrin genes at both the protein and mRNA levels, but LPS only suppressed at the protein level. The study indicates that lead suppresses human transferrin synthesis by a mechanism that differs from the hepatic acute phase response and that lead may also affect iron metabolism in humans by interfering with transferrin levels.

Synthesis and characterization of supported polysugar-stabilized palladium nanoparticle catalysts for enhanced hydrodechlorination of trichloroethylene

NASA Astrophysics Data System (ADS)

Bacik, Deborah B.; Zhang, Man; Zhao, Dongye; Roberts, Christopher B.; Seehra, Mohinar S.; Singh, Vivek; Shah, Naresh

2012-07-01

Palladium (Pd) nanoparticle catalysts were successfully synthesized within an aqueous phase using sodium carboxymethyl cellulose (CMC) as a capping ligand which offers a green alternative to conventional nanoparticle synthesis techniques. The CMC-stabilized Pd nanoparticles were subsequently dispersed within support materials using the incipient wetness impregnation technique for utilization in heterogeneous catalyst systems. The unsupported and supported (both calcined and uncalcined) Pd nanoparticle catalysts were characterized using transmission electron microscopy, energy dispersive x-ray spectrometry, x-ray diffraction, and Brunauer-Emmett-Teller surface area measurement and their catalytic activity toward the hydrodechlorination of trichloroethylene (TCE) in aqueous media was examined using homogeneous and heterogeneous catalyst systems, respectively. The unsupported Pd nanoparticles showed considerable activity toward the degradation of TCE, as demonstrated by the reaction kinetics. Although the supported Pd nanoparticle catalysts had a lower catalytic activity than the unsupported particles that were homogeneously dispersed in the aqueous solutions, the supported catalysts retained sufficient activity toward the degradation of TCE. In addition, the use of the hydrophilic Al2O3 support material induced a mass transfer resistance to TCE that affected the initial hydrodechlorination rate. This paper demonstrates that supported Pd catalysts can be applied to the heterogeneous catalytic hydrodechlorination of TCE.

Synthesis and characterization of nanostructured CaSiO3 biomaterial

NASA Astrophysics Data System (ADS)

Jagadale, Pramod N.; Kulal, Shivaji R.; Joshi, Meghanath G.; Jagtap, Pramod P.; Khetre, Sanjay M.; Bamane, Sambhaji R.

2013-04-01

Here we report a successful preparation of nanostructured calcium silicate by wet chemical approach. The synthesized sample was characterized by various physico-chemical methods. Thermal stability was investigated using thermo-gravimetric and differential thermal analysis (TG-DTA). Structural characterization of the sample was carried out by the X-ray diffraction technique (XRD) which confirmed its single phase hexagonal structure. Transmission electron microscopy (TEM) was used to study the nanostructure of the ceramics while homogeneous grain distribution was revealed by scanning electron microscopy studies (SEM). The elemental analysis data obtained from energy dispersive X-ray spectroscopy (EDAX) were in close agreement with the starting composition used for the synthesis. Superhydrophilic nature of CaSiO3 was investigated at room temperature by sessile drop technique. Effect of porous nanosized CaSiO3 on early adhesion and proliferation of human bone marrow mesenchymal stem cells (BMMSCs) and cord blood mesenchymal stem (CBMSCs) cells was measured in vitro. MTT cytotoxicity test and cell adhesion test showed that the material had good biocompatibility and promoted cell viability and cell proliferation. It has been stated that the cell viability and proliferation are significantly affected by time and concentration of CaSiO3. These findings indicate that the CaSiO3 ceramics has good biocompatibility and that it is promising as a biomaterial.

Synthesis and study on the luminescence properties of cadmium borate phosphors

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

Annalakshmi, O.; Jose, M.T., E-mail: mtjosein@yahoo.co.in; Venkatraman, B.

2014-02-01

Highlights: • Cadmium borate synthesized by solid state sintering technique. • Neutron sensitivity of the material ten times that of TLD-600. • Gamma sensitivity is found to be twice that of TLD-100. • Gamma response is linear from 0.1 to 10{sup 3} mGy. - Abstract: Cadmium borate compound prepared through wet chemical reaction from the starting chemicals followed by high temperature solid state synthesis below the melting point to get the final TL phosphor powder. Phase purity and bond details of cadmium borate crystals are characterized using X-ray diffraction technique and infrared spectroscopy. Feasibility of these materials for radiation dosimetrymore » applications was studied after gamma and neutron irradiation. Gamma irradiation of undoped phosphors show a single peak around 185 °C whereas doping with gadolinium and silver, new more intense peak observed at 290 °C. Irradiation to thermal neutrons revealed single peak around 170 °C for all the phosphors. TL emission spectra and photoluminescence (PL) studies were also carried out on the phosphors. These borate materials are found to be highly sensitive to neutrons and hence can be used for neutron detection. Neutron sensitivity of the material is about ten times that of TLD-600.« less

Synthesis and characterization of LTA nanozeolite using barley husk silica: Mercury removal from standard and real solutions

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

Azizi, Seyed Naser, E-mail: azizi@umz.ac.ir; Dehnavi, Ahmad Roozbehani, E-mail: Roozbehanisulfur@yahoo.com; Joorabdoozha, Amir

2013-05-15

Highlights: ► Silica extraction from barley husk with high purity for the synthesis of A nanozeolite. ► Free template A nanozeolite synthesized via new source of silica at low temperature. ► Optimization of SiO{sub 2}/Al{sub 2}O{sub 3}, Na{sub 2}O/SiO{sub 2} ratios, temperature and time of the synthesis. ► Utilizing of synthesized A nanozeolite for mercury removal from aqueous solutions. ► Mercury removal at optimized pH, contact time and adsorbent dose from real solution. - Abstract: In this study, synthesized Lined Type A (LTA) nanozeolite from barley husk silica (BHS) was used for mercury removal from standard and real aqueous solutions.more » The BHS in amorphous phase with 80% purity was extracted from barley husk ash (BHA), and used effectively as a new source of silica for the synthesis of NaA nanozeolite. The NaA nanocrystal in pure phase has been synthesized at low temperature, without adding any organic additives. The effects of heating time, reaction temperature, SiO{sub 2}/Al{sub 2}O{sub 3}, and Na{sub 2}O/SiO{sub 2} mole ratios on the crystallization of NaA nanozeolite were studied. The adsorption capacity of mercury (II) was studied as a function of pH, contact time, and amount of adsorbent. The crystallization of NaA nanozeolite from BHS was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), Brunauer–Emmett–Teller (BET), and FTIR techniques. Moreover, concentration of Hg{sup 2+} ions in the aqueous solutions was analyzed by hydride generation atomic absorption spectroscopy method (HG-AAS). The standard and real samples analysis showed that NaA nanozeolite is capable of Hg{sup 2+} ions removal from the aqueous solutions. Efficiency of mercury (II) adsorption from real solutions onto the nano-sized NaA zeolite was 98%.« less

Matrix Synthesis and Characterization

NASA Technical Reports Server (NTRS)

1984-01-01

The role of NASA in the area of composite material synthesis; evaluation techniques; prediction analysis techniques; solvent-resistant tough composite matrix; resistance to paint strippers; acceptable processing temperature and pressure for thermoplastics; and the role of computer modeling and fiber interface improvement were discussed.

Hydrothermal synthesis of stable metallic 1T phase WS2 nanosheets for thermoelectric application

NASA Astrophysics Data System (ADS)

Piao, Mingxing; Chu, Jin; Wang, Xiao; Chi, Yao; Zhang, Heng; Li, Chaolong; Shi, Haofei; Joo, Min-Kyu

2018-01-01

Two-dimensional materials have gained great attention as a promising thermoelectric (TE) material due to their unique density of state with confined electrons and holes. Here, we synthesized 1T phase tungsten disulfide (WS2) nanosheets with high TE performance via the hydrothermal method. Flexible WS2 nanosheets restacked thin films were fabricated by employing the vacuum filtration technique. The measured electrical conductivity was 45 S cm-1 with a Seebeck coefficient of +30 μV K-1 at room temperature, indicating a p-type characteristic. Furthermore, the TE performance could be further improved by thermal annealing treatment. It was found the electrical conductivity could be enhanced 2.7 times without sacrificing the Seebeck coefficient, resulting in the power factor of 9.40 μW m-1 K-2. Moreover, such 1T phase WS2 nanosheets possess high phase stability since the TE properties maintained constant at least half one year in the air atmosphere. Notably, other kinds of 1T phase transitional metal dichalcogenides (TMDCs) with excellent TE performance also could be imitated by using the procedure in this work. Finally, we believe a variety of materials based on 1T phase TMDCs nanosheets have great potential as candidate for future TE applications.

Cell cycle arrest by prostaglandin A1 at the G1/S phase interface with up-regulation of oncogenes in S-49 cyc- cells

NASA Technical Reports Server (NTRS)

Hughes-Fulford, M.

1994-01-01

Our previous studies have implied that prostaglandins inhibit cell growth independent of cAMP. Recent reports, however, have suggested that prostaglandin arrest of the cell cycle may be mediated through protein kinase A. In this report, in order to eliminate the role of c-AMP in prostaglandin mediated cell cycle arrest, we use the -49 lymphoma variant (cyc-) cells that lack adenylate cyclase activity. We demonstrate that dimethyl prostaglandin A1 (dmPGA1) inhibits DNA synthesis and cell growth in cyc- cells. DNA synthesis is inhibited 42% by dmPGA1 (50 microM) despite the fact that this cell line lacks cellular components needed for cAMP generation. The ability to decrease DNA synthesis depends upon the specific prostaglandin structure with the most effective form possessing the alpha, beta unsaturated ketone ring. Dimethyl PGA1 is most effective in inhibiting DNA synthesis in cyc- cells, with prostaglandins PGE1 and PGB1 being less potent inhibitors of DNA synthesis. DmPGE2 caused a significant stimulation of DNA synthesis. S-49 cyc- variant cells exposed to (30-50 microns) dmPGA1, arrested in the G1 phase of the cell cycle within 24 h. This growth arrest was reversed when the prostaglandin was removed from the cultured cells; growth resumed within hours showing that this treatment is not toxic. The S-49 cyc- cells were chosen not only for their lack of adenylate cyclase activity, but also because their cell cycle has been extensively studied and time requirements for G1, S, G2, and M phases are known. Within hours after prostaglandin removal the cells resume active DNA synthesis, and cell number doubles within 15 h suggesting rapid entry into S-phase DNA synthesis from the G1 cell cycle block.(ABSTRACT TRUNCATED AT 250 WORDS).

Advanced techniques for characterization of ion beam modified materials

DOE PAGES

Zhang, Yanwen; Debelle, Aurélien; Boulle, Alexandre; ...

2014-10-30

Understanding the mechanisms of damage formation in materials irradiated with energetic ions is essential for the field of ion-beam materials modification and engineering. Utilizing incident ions, electrons, photons, and positrons, various analysis techniques, including Rutherford backscattering spectrometry (RBS), electron RBS, Raman spectroscopy, high-resolution X-ray diffraction, small-angle X-ray scattering, and positron annihilation spectroscopy, are routinely used or gaining increasing attention in characterizing ion beam modified materials. The distinctive information, recent developments, and some perspectives in these techniques are reviewed in this paper. Applications of these techniques are discussed to demonstrate their unique ability for studying ion-solid interactions and the corresponding radiationmore » effects in modified depths ranging from a few nm to a few tens of μm, and to provide information on electronic and atomic structure of the materials, defect configuration and concentration, as well as phase stability, amorphization and recrystallization processes. Finally, such knowledge contributes to our fundamental understanding over a wide range of extreme conditions essential for enhancing material performance and also for design and synthesis of new materials to address a broad variety of future energy applications.« less

Synthesis of 3'-, or 5'-, or internal methacrylamido-modified oligonucleotides

DOEpatents

Golova, Julia B.; Chernov, Boris K.

2010-04-27

New modifiers were synthesized for incorporation of a methacrylic function in 3'-, 5'- and internal positions of oligonucleotides during solid phase synthesis. A modifier was used for synthesis of 5'-methacrylated oligonucleotides for preparation of microarrays by a co-polymerization method.

Penicillinase Studies on L-Phase Variants, G-Phase Variants, and Reverted Strains of Staphylococcus aureus

PubMed Central

Simon, Harold J.; Yin, Elaine Jong

1970-01-01

L-phase variants and small colony (G-phase) variants derived from penicillinase-producing Staphylococcus aureus strains were tested for penicillinase (beta lactamase) production. A refined variation of the modified Gots test for penicillinase was used to demonstrate penicillinase synthesis. Penicillinase synthesis was reduced in L-phase variants and G-phase variants when compared to parental strains. After reversion of variants to vegetative stages had been induced, revertants were tested for production of penicillinase, coagulase, and alpha hemolysin, mannitol fermentation, and pigment production, and comparisons were made between parent and reverted vegetative forms. All revertants of G-phase variants retained penicillinase activity. Most revertants of L-phase variants showed reduction or loss of penicillinase activity. Retention of coagulase activity, alpha hemolysin production, mannitol fermentation, pigmentation, and phage type varied among revertants. Images PMID:16557890

Precursor Ion–Ion Aggregation in the Brust–Schiffrin Synthesis of Alkanethiol Nanoparticles

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

Graham, Trent R.; Renslow, Ryan; Govind, Niranjan

Tetraoctylammonium bromide is used in the Brust-Schiffrin nanoparticle synthesis to phase-transfer chloroaurate ions from the aqueous phase to the organic phase. While it is established that the quaternary ammonium complex self-associates in the organic phase, the actual self-assembled structure is debated. We have confirmed the presence of ion-ion aggregates through quantitative 1H Nuclear Magnetic Resonance spectroscopy (NMR), pulsed field gradient, diffusion-ordered NMR (DOSY-NMR) and density functional theory (DFT) based NMR shift calculations. Tetraoctylammonium complexes (TOA-X, where X = Br, Cl, AuCl4-xBrx, AuBr4/Br and AuCl4-xBrx/Br) were investigated to measure the extraction of water into the organic phase. 1H NMR and DFTmore » based NMR shielding calculations indicated that deshielding of water is due to hydration of the anion and not the formation of the aqueous core of a reverse micelle. DOSYNMR results were consistent with the formation of small aggregates at typical Brust-Schiffrin synthesis concentrations. The extent of aggregation correlated with the size and electronegativity of the anion and was analyzed with a modified, isodesmic, indefinite aggregation model. The substitution of bromoauric acid for chlororoauric acid at conditions emulating the Brust-Schiffrin synthesis increased the aggregation of the quaternary ammonium complex. The increase in aggregation corresponded with an increase in the size of the produced nanoparticles from 4.3 to 4.6 nm. Understanding the selfassembly and supramolecular structure of precursors in the Brust-Schiffrin synthesis will enable further refinement of models that predict the growth of noble metal nanoparticles.« less

Titanium dioxide nanoparticles: Impact of increasing ionic strength during synthesis, reflux, and hydrothermal aging

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

Isley, Sara L.; Jordan, David S.; Penn, R. Lee

2009-01-08

This work investigates the role of ionic strength during synthesis, reflux, and hydrothermal aging of sol-gel synthesized titanium dioxide. Research presented here uses X-ray diffraction data and Rietveld refinements to quantify anatase, brookite, and rutile phases as functions of synthetic and aging variables. In addition, the Scherrer equation is used to obtain average crystallite sizes for each phase quantified. Results presented in this work demonstrate that the most control over the sol-gel products can be obtained by modifying the pH during hydrolysis. In addition, while varying the ionic strength during reflux and hydrothermal aging can result in enhanced control overmore » the crystalline phase and crystallite size, the most control can be achieved by varying the ionic strength during synthesis. Finally, sol-gel synthesis at low pH (-0.6) and high-chloride concentration (3 M NaCl) produced a heterogeneous sample composed of nanocrystalline anatase (3.8 nm) and rutile (2.9 nm)« less

Application of 2-chlorotrityl resin in solid phase synthesis of (Leu15)-gastrin I and unsulfated cholecystokinin octapeptide. Selective O-deprotection of tyrosine.

PubMed

Barlos, K; Gatos, D; Kapolos, S; Poulos, C; Schäfer, W; Yao, W Q

1991-12-01

The carboxyl terminal dipeptide amide, Fmoc-Asp-Phe-NH2, of gastrin and cholecystokinin (CCK) has been attached in high yield through its free side chain carboxyl group to the acid labile 2-chlorotrityl resin. The obtained peptide resin ester has been applied in the solid phase synthesis of partially protected (Leu15)-gastrin I utilising Fmoc-amino acids. Quantitative cleavage of this peptide from resin, with the t-butyl type side chain protection intact is achieved using mixtures of acetic acid/trifluoroethanol/dichloromethane. Under the same conditions complete detritylation of the tyrosine phenoxy function occurs simultaneously. Thus, the solid-phase synthesis of peptides selectively deprotected at the side chain of tyrosine is rendered possible by the use of 2-chlorotrityl resin and Fmoc-Tyr(Trt)-OH. The efficiency of this approach has been proved by the subsequent high-yield synthesis of three model peptides and the CCK-octapeptide.

Automatic reactor for solid-phase synthesis of molecularly imprinted polymeric nanoparticles (MIP NPs) in water.

PubMed

Poma, Alessandro; Guerreiro, Antonio; Caygill, Sarah; Moczko, Ewa; Piletsky, Sergey

We report the development of an automated chemical reactor for solid-phase synthesis of MIP NPs in water. Operational parameters are under computer control, requiring minimal operator intervention. In this study, "ready for use" MIP NPs with sub-nanomolar affinity are prepared against pepsin A, trypsin and α-amylase in only 4 hours.

Automatic reactor for solid-phase synthesis of molecularly imprinted polymeric nanoparticles (MIP NPs) in water

PubMed Central

Poma, Alessandro; Guerreiro, Antonio; Caygill, Sarah; Moczko, Ewa; Piletsky, Sergey

2015-01-01

We report the development of an automated chemical reactor for solid-phase synthesis of MIP NPs in water. Operational parameters are under computer control, requiring minimal operator intervention. In this study, “ready for use” MIP NPs with sub-nanomolar affinity are prepared against pepsin A, trypsin and α-amylase in only 4 hours. PMID:26722622

Multilayer graphene on insulator formed by Co-induced layer exchange

NASA Astrophysics Data System (ADS)

Murata, Hiromasa; Toko, Kaoru; Suemasu, Takashi

2017-05-01

The direct synthesis of multilayer graphene (MLG) on arbitrary substrates is essential for incorporating carbon wirings and heat spreaders into electronic devices. Here, we applied the metal-induced layer exchange (MILE) technique, developed for group-IV semiconductors, to a sputtered amorphous carbon (a-C) thin film using Co as a catalyst. MLG was formed on a SiO2 substrate at 800 °C for 10 min; however, it disappeared during wet etching for removing Co. This behavior was attributed to the small contact area between MLG and SiO2 caused by the deformation of the Co layer during annealing. By preparing the Co layer at 200 °C, its thermal stability was improved, resulting in the synthesis of MLG on the substrate through MILE. Raman measurements indicated good crystal quality of the MLG compared with that obtained by conventional metal-induced solid-phase crystallization. MILE was thus proven to be useful not only for group-IV semiconductors but also for carbon materials on insulators.

Synthesis and characterization of in situ TiC-TiB2 composite coatings by reactive plasma spraying on a magnesium alloy

NASA Astrophysics Data System (ADS)

Zou, Binglin; Tao, Shunyan; Huang, Wenzhi; Khan, Zuhair S.; Fan, Xizhi; Gu, Lijian; Wang, Ying; Xu, Jiaying; Cai, Xiaolong; Ma, Hongmei; Cao, Xueqiang

2013-01-01

TiC-TiB2 composite coatings were successfully synthesized using the technique of reactive plasma spraying (RPS) on a magnesium alloy. Phase composition, microstructure and wear resistance of the coatings were characterized by using X-ray diffraction, scanning electron microscopy and pin-on-disk wear test, respectively. The results showed that the resultant product in the RPS coatings was composed of TiC and TiB2. Depending on the ignition of self-propagating high-temperature synthesis reaction in the agglomerate particles, the RPS coatings displayed porous and dense microstructures. The porosity of the RPS coatings, to some extent, decreased when the feed powders were plasma sprayed with Ni powders. The RPS coatings provided good wear resistance for the substrate under various loads. For high loads (e.g., ≥15 N), the wear resistance could be significantly improved by the proper addition of Ni into the RPS coatings.

A COMPARISON OF EXPERIMENTS AND THREE-DIMENSIONAL ANALYSIS TECHNIQUES. PART I. UNPOISONED UNIFORM SLAB CORE WITH A PARTIALLY INSERTED HAFNIUM ROD

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

Renzi, N.E.; Roseberry, R.J.

>The experimental measurements and nuclear analysis of a uniformly loaded, unpoisoned slab core with a partially insented hafnium rod are described. Comparisons of experimental data with calculated results of the UFO code and flux synthesis techniques are given. It was concluded that one of the flux synthesis techniques and the UFO code are able to predict flux distributions to within approximately 5% of experiment for most cases. An error of approximately 10% was found in the synthesis technique for a channel near the partially inserted rod. The various calculations were able to predict neutron pulsed shutdowns to only approximately 30%.more » (auth)« less

Ant colony optimisation-direct cover: a hybrid ant colony direct cover technique for multi-level synthesis of multiple-valued logic functions

NASA Astrophysics Data System (ADS)

Abd-El-Barr, Mostafa

2010-12-01

The use of non-binary (multiple-valued) logic in the synthesis of digital systems can lead to savings in chip area. Advances in very large scale integration (VLSI) technology have enabled the successful implementation of multiple-valued logic (MVL) circuits. A number of heuristic algorithms for the synthesis of (near) minimal sum-of products (two-level) realisation of MVL functions have been reported in the literature. The direct cover (DC) technique is one such algorithm. The ant colony optimisation (ACO) algorithm is a meta-heuristic that uses constructive greediness to explore a large solution space in finding (near) optimal solutions. The ACO algorithm mimics the ant's behaviour in the real world in using the shortest path to reach food sources. We have previously introduced an ACO-based heuristic for the synthesis of two-level MVL functions. In this article, we introduce the ACO-DC hybrid technique for the synthesis of multi-level MVL functions. The basic idea is to use an ant to decompose a given MVL function into a number of levels and then synthesise each sub-function using a DC-based technique. The results obtained using the proposed approach are compared to those obtained using existing techniques reported in the literature. A benchmark set consisting of 50,000 randomly generated 2-variable 4-valued functions is used in the comparison. The results obtained using the proposed ACO-DC technique are shown to produce efficient realisation in terms of the average number of gates (as a measure of chip area) needed for the synthesis of a given MVL function.

Thin Film Synthesis of New Complex Titanates.

NASA Astrophysics Data System (ADS)

Salvador, Paul

2008-03-01

Thin film deposition methods allow for one to synthesize rationally specific compositions in targeted crystal structures. Because most of the thermodynamic and kinetic variables that control the range of materials that can be synthesized are unknown for specific compounds/processes, epitaxial stabilization and design of artificially layered crystals are driven through empirical investigations. Using examples taken primarily from the family of complex titanates, which exhibit a range of interesting physicochemical behaviors, the thermodynamic and kinetic factors that control materials design using thin film deposition are discussed. The phase competition between the pyrochlore and the (110) layered perovskite structure in the RE2Ti2O7 family (RE = rare-earth, Bi) will be explored, using pulsed laser deposition as a synthesis method. For RE = Gd, Sm, Nd, and La, the phase stability over a wide range of conditions is dictated entirely by substrate choice, indicating that the free energies of the phases are similar enough such that by controlling nucleation one controls the phase formation. In a related fashion, the growth of AETi2O5 films (AE = Ba or Sr) will be discussed with respect to the formation of single-phase films or films that phase separate into AETiO3 and TiO2. The entire Ba1-xSrxTi2O5 series was grown and will be discussed with respect to growth technique (using MBE and PLD) and/or substrate choice. In this case, rock-salt substrates, which are not expected to interact strongly with any phase in the system, allow for the formation of single-phase films. Finally, several examples will be discussed with respect to the (SrO)m(TiO2)n system, which includes the perovskite SrTiO3 and the Ruddlesden-Popper phase Sr2TiO4, grown using layer-by-layer molecular beam epitaxy. The solid phase epitaxial formation of the perovskite SrTiO3 from superlattices of rock-salt SrO and anatase TiO2 is discussed from both a kinetic and thermodynamic perspective by exploring the growth of a range of m and n values. Using similar arguments for stability, new layered intergrowths in the SrmTiO2+m family are presented and their structures are discussed.

Nanocrystalline hydroxyapatite ceramics prepared by hydrolysis in polyol medium

NASA Astrophysics Data System (ADS)

Mechay, Abderrahmen; Feki, Hafed E. L.; Schoenstein, Fréderic; Jouini, Noureddine

2012-07-01

This Letter describes a new approach for the synthesis of hydroxyapatite nanoparticles, which involves precipitation and hydrolysis reactions conducted in polyol medium. In fact, ammonium-hydrogen phosphate and calcium nitrate were dissolved in polyol, and then heated at the boiling point of the polyol (ethane1, 2diol or propane1, 2diol). Besides, the phase and composition of the polycrystalline were studied by TGA/DTA, FT-IR, TEM and XRD techniques. The nanoparticles thus obtained present interesting morphological characters varying from needle to very thin platelet. Moreover, the hydroxyapatite prepared in ployol shows higher cristallinity in comparison with that obtained by other 'chimie douce' methods.

Design of stapled DNA-minor-groove-binding molecules with a mutable atom simulated annealing method

NASA Astrophysics Data System (ADS)

Walker, Wynn L.; Kopka, Mary L.; Dickerson, Richard E.; Goodsell, David S.

1997-11-01

We report the design of optimal linker geometries for the synthesis of stapledDNA-minor-groove-binding molecules. Netropsin, distamycin, and lexitropsinsbind side-by-side to mixed-sequence DNA and offer an opportunity for thedesign of sequence-reading molecules. Stapled molecules, with two moleculescovalently linked side-by-side, provide entropic gains and restrain theposition of one molecule relative to its neighbor. Using a free-atom simulatedannealing technique combined with a discrete mutable atom definition, optimallengths and atomic composition for covalent linkages are determined, and anovel hydrogen bond `zipper' is proposed to phase two molecules accuratelyside-by-side.

Synthesis and properties of nanocrystalline copper indium oxide thin films deposited by Rf magnetron sputtering.

PubMed

Singh, Mandeep; Singh, V N; Mehta, B R

2008-08-01

Nanocrystalline copper indium oxide (CuInO2) thin films with particle size ranging from 25 nm to 71 nm have been synthesized from a composite target using reactive Rf magnetron sputtering technique. X-ray photoelectron spectroscopy (XPS) combined with glancing angle X-ray diffraction (GAXRD) analysis confirmed the presence of delafossite CuInO2 phase in these films. The optical absorption studies show the presence of two direct band gaps at 3.3 and 4.3 eV, respectively. The resistance versus temperature measurements show thermally activated hopping with activation energy of 0.84 eV to be the conduction mechanism.

SOLID-STATE SYNTHESIS AND SOME PROPERTIES OF MAGNESIUM-DOPED COPPER ALUMINUM OXIDES

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

Liu, Chang; Ren, Fei; Wang, Hsin

2010-01-01

Copper aluminum oxide (CuAlO2) with delafossite structure is a promising candidate for high temperature thermoelectric applications because of its modest band gap, high stability and low cost. We investigate magnesium doping on the aluminum site as a means of producing higher electrical conductivity and optimized Seebeck coefficient. Powder samples were synthesized using solid-state reaction and bulk samples were prepared using both cold-pressing and hot-pressing techniques. Composition analysis, microstructural examination and transport property measurements were performed, and the results suggest that while hot-pressing can achieve high density samples, secondary phases tend to form and lower the performance of the materials.

Serial multiplier arrays for parallel computation

NASA Technical Reports Server (NTRS)

Winters, Kel

1990-01-01

Arrays of systolic serial-parallel multiplier elements are proposed as an alternative to conventional SIMD mesh serial adder arrays for applications that are multiplication intensive and require few stored operands. The design and operation of a number of multiplier and array configurations featuring locality of connection, modularity, and regularity of structure are discussed. A design methodology combining top-down and bottom-up techniques is described to facilitate development of custom high-performance CMOS multiplier element arrays as well as rapid synthesis of simulation models and semicustom prototype CMOS components. Finally, a differential version of NORA dynamic circuits requiring a single-phase uncomplemented clock signal introduced for this application.

Synthesis and characterization of Zn-Mg ferrite

NASA Astrophysics Data System (ADS)

Singh, Shailndra; Barbar, S. K.; Ram, Sahi

2018-05-01

The Zn-Mg ferrite sample of general formula Zn0.5Mg0.5Fe2O4 have been prepared by standard solid state reaction technique using high purity oxides. X-ray diffraction analysis shows the formation of a zinc-magnesium ferrite cubic phase at room temperature with space group Fd3m. FTIR spectra show two significant absorption bands first at 665.15 cm-1 corresponding to tetrahedral (A) and second band at 434 cm-1 corresponding to octahedral (B) sites of the spinel. Morphology of the sample determined by the SEM measurement and EDS analysis has confirmed the composition of atoms in the sample.

Detection of Changes in the Medicago sativa Retinoblastoma-Related Protein (MsRBR1) Phosphorylation During Cell Cycle Progression in Synchronized Cell Suspension Culture.

PubMed

Ayaydin, Ferhan; Kotogány, Edit; Ábrahám, Edit; Horváth, Gábor V

2017-01-01

Deepening our knowledge on the regulation of the plant cell division cycle depends on techniques that allow for the enrichment of cell populations in defined cell cycle phases. Synchronization of cell division can be achieved using different plant tissues; however, well-established cell suspension cultures provide large amount of biological sample for further analyses. Here, we describe the methodology of the establishment, propagation, and analysis of a Medicago sativa suspension culture that can be used for efficient synchronization of the cell division. A novel 5-ethynyl-2'-deoxyuridine (EdU)-based method is used for the estimation of cell fraction that enters DNA synthesis phase of the cell cycle and we also demonstrate the changes in the phosphorylation level of Medicago sativa retinoblastoma-related protein (MsRBR1) during cell cycle progression.

The sensitivity of gas-phase models of dense interstellar clouds to changes in dissociative recombination branching ratios

NASA Technical Reports Server (NTRS)

Millar, T. J.; Defrees, D. J.; Mclean, A. D.; Herbst, E.

1988-01-01

The approach of Bates to the determination of neutral product branching ratios in ion-electron dissociative recombination reactions has been utilized in conjunction with quantum chemical techniques to redetermine branching ratios for a wide variety of important reactions of this class in dense interstellar clouds. The branching ratios have then been used in a pseudo time-dependent model calculation of the gas phase chemistry of a dark cloud resembling TMC-1 and the results compared with an analogous model containing previously used branching ratios. In general, the changes in branching ratios lead to stronger effects on calculated molecular abundances at steady state than at earlier times and often lead to reductions in the calculated abundances of complex molecules. However, at the so-called 'early time' when complex molecule synthesis is most efficient, the abundances of complex molecules are hardly affected by the newly used branching ratios.

Application of gas diffusion electrodes in bioelectrochemical syntheses and energy conversion.

PubMed

Horst, Angelika E W; Mangold, Klaus-Michael; Holtmann, Dirk

2016-02-01

Combining the advantages of biological components (e.g., reaction specificity, self-replication) and electrochemical techniques in bioelectrochemical systems offers the opportunity to develop novel efficient and sustainable processes for the production of a number of valuable products. The choice of electrode material has a great impact on the performance of bioelectrochemical systems. In addition to the redox process at the electrodes, interactions of biocatalysts with electrodes (e.g., enzyme denaturation or biofouling) need to be considered. In recent years, gas diffusion electrodes (GDEs) have proved to be very attractive electrodes for bioelectrochemical purposes. GDEs are porous electrodes, that posses a large three-phase boundary surface. At this interface, a solid catalyst supports the electrochemical reaction between gaseous and liquid phase. This mini-review discusses the application of GDEs in microbial and enzymatic fuel cells, for microbial electrolysis, in biosensors and for electroenzymatic synthesis reactions. © 2015 Wiley Periodicals, Inc.

Synthesis of mesoporous poly(melamine-formaldehyde) particles by inverse emulsion polymerization.

PubMed

Schwarz, Dana; Weber, Jens

2017-07-15

Mesoporous poly(melamine-formaldehyde) (MF) particles with surface areas of up to 200m 2 g -1 were synthesized by an inverse emulsion polymerization using dodecane and Span80® as continuous phase. The finer details of the shape control (using emulsion techniques) and the porosity control (using silica nanoparticles as hard-template) are discussed. The impact of phase-separation processes on the observable porosity of the 20-200µm sized spherical particles is analysed by gas sorption methods and electron microscopy. The high density of amine and triazine functional groups in the porous MF particles make the material a promising adsorber for heavy metal ions and methylene blue. In a preliminary column experiment, the synthesized material exhibited a total capacity of 2.54mmol/g (≙ 812.4mg/g) for the adsorption of methylene blue. Copyright © 2017 Elsevier Inc. All rights reserved.

DGK1-encoded Diacylglycerol Kinase Activity Is Required for Phospholipid Synthesis during Growth Resumption from Stationary Phase in Saccharomyces cerevisiae*

PubMed Central

Fakas, Stylianos; Konstantinou, Chrysanthos; Carman, George M.

2011-01-01

In the yeast Saccharomyces cerevisiae, triacylglycerol mobilization for phospholipid synthesis occurs during growth resumption from stationary phase, and this metabolism is essential in the absence of de novo fatty acid synthesis. In this work, we provide evidence that DGK1-encoded diacylglycerol kinase activity is required to convert triacylglycerol-derived diacylglycerol to phosphatidate for phospholipid synthesis. Cells lacking diacylglycerol kinase activity (e.g. dgk1Δ mutation) failed to resume growth in the presence of the fatty acid synthesis inhibitor cerulenin. Lipid analysis data showed that dgk1Δ mutant cells did not mobilize triacylglycerol for membrane phospholipid synthesis and accumulated diacylglycerol. The dgk1Δ phenotypes were partially complemented by preventing the formation of diacylglycerol by the PAH1-encoded phosphatidate phosphatase and by channeling diacylglycerol to phosphatidylcholine via the Kennedy pathway. These observations, coupled to an inhibitory effect of dioctanoyl-diacylglycerol on the growth of wild type cells, indicated that diacylglycerol kinase also functions to alleviate diacylglycerol toxicity. PMID:21071438

Variable dimensionality in the uranium fluoride/2-methyl-piperazine system: Synthesis and structures of UFO-5, -6, and -7; Zero-, one-, and two-dimensional materials with unprecedented topologies

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

Francis, R.J.; Halasyamani, P.S.; Bee, J.S.

Recently, low temperature (T < 300 C) hydrothermal reactions of inorganic precursors in the presence of organic cations have proven highly productive for the synthesis of novel solid-state materials. Interest in these materials is driven by the astonishingly diverse range of structures produced, as well as by their many potential materials chemistry applications. This report describes the high yield, phase pure hydrothermal syntheses of three new uranium fluoride phases with unprecedented structure types. Through the systematic control of the synthesis conditions the authors have successfully controlled the architecture and dimensionality of the phase formed and selectively synthesized novel zero-, one-,more » and two-dimensional materials.« less

Synthesis and modification of nano-sized TiO{sub 2} for photo-degradation process under visible light irradiation; a Placket–Burman experimental design

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

Izadyar, Soheila; Fatemi, Shohreh, E-mail: shfatemi@ut.ac.ir; Mousavand, Tahereh

2013-09-01

Graphical abstract: - Highlights: • Nanosized TiO{sub 2} doped with nitrogen and iron was produced by sol-gel method. • Linear models were derived to relate the phase and particle size to synthesis factors. • High photocatalytic activity was observed for acetaldehyde degradation. - Abstract: In this research, nitrogen and iron (III) co-doped nano TiO{sub 2} (N-Fe-TiO{sub 2}) was prepared by sol-gel method using ammonium chloride and iron chloride solutions as nitrogen and iron sources, respectively. The effect of synthesis parameters (weight ratios of N/TiO{sub 2} and Fe/TiO{sub 2}, synthesis temperature, calcination time and temperature) was simultaneously investigated on the qualitymore » of the N-Fe-TiO{sub 2} product by a two-level Placket–Burman experimental design. The synthesized powders were characterized by XRD, XPS and UV–Vis spectroscopy techniques. The mean crystal size and anatase content were determined and evaluated as the linear functions of so-called synthesis parameters by the statistical analysis and regression. The 2%N-1%Fe-TiO{sub 2} product by 11 nm mean crystal size and 78% anatase content, synthesized at 35 °C and calcined at 500 °C during 2 h, exhibited the most significant activity during the photo-degradation of acetaldehyde under visible light irradiation and its efficiency was obtained about four times more than photocatalytic activity of Degussa TiO{sub 2}-P25.« less

Plasma Processing of Lunar Regolith Simulant for Diverse Applications

NASA Technical Reports Server (NTRS)

Schofield, Elizabeth C.; Sen, Subhayu; O'Dell, J. Scott

2008-01-01

Versatile manufacturing technologies for extracting resources from the moon are needed to support future space missions. Of particular interest is the production of gases and metals from lunar resources for life support, propulsion, and in-space fabrication. Deposits made from lunar regolith could yield highly emissive coatings and near-net shaped parts for replacement or repair of critical components. Equally important is development of high fidelity lunar simulants for ground based validation of potential lunar surface operations. Described herein is an innovative plasma processing technique for insitu production of gases, metals, coatings, and deposits from lunar regolith, and synthesis of high fidelity lunar simulant from NASA issued lunar simulant JSC-1. Initial plasma reduction trials of JSC-1 lunar simulant have indicated production of metallic iron and magnesium. Evolution of carbon monoxide has been detected subsequent to reduction of the simulant using the plasma process. Plasma processing of the simulant has also resulted in glassy phases resembling the volcanic glass and agglutinates found in lunar regolith. Complete and partial glassy phase deposits have been obtained by varying the plasma process variables. Experimental techniques, product characterization, and process gas analysis will be discussed.

Microstructures and Hardness of the High Chromium Oxide Dispersion Strengthened Alloy Fe-25Cr-Y2O3Sintered by the Arc Plasma Sintering (APS)

NASA Astrophysics Data System (ADS)

Bandriyana; Dimyati, Arbi; Sujatno, Agus; Salam, Rohmad; Sumaryo; Untoro, Pudji; Suharno, Bambang

2018-03-01

High chromium ODS alloy has been developed for application as structural material in high temperature nuclear reactor. In the present study, Fe-25Cr-Y2O3 with dispersed 0.5 wt.% Ytria (Y2O3) were synthesized and characterized by means of various techniques as a function of milling time 1, 2 and 3 hours. The alloy synthesis was carried out by the Mechanical Alloying (MA) process and subsequent sintering by means the new plasma technique using the APS apparatus. Scaning Electron Microscopy (SEM) and X-ray diffraction (XRD) were conducted for morphology and phase analysis. Evaluation of the mechanical properties was studied based on the Vickers hardness measurement. SEM examination revealed that the sample after sintering by APS method at different milling duration exhibited some particle aglomeration and homogenized oxide dispersion that obviously strengthened the alloy. The XRD test, however, proved the formation of the main phase Fe-Cr. The alloy showed exceptionally high hardness of 193 VHR which is mainly due to the grain refining that increase by the increasing of the milling time.

Automating Traceability for Generated Software Artifacts

NASA Technical Reports Server (NTRS)

Richardson, Julian; Green, Jeffrey

2004-01-01

Program synthesis automatically derives programs from specifications of their behavior. One advantage of program synthesis, as opposed to manual coding, is that there is a direct link between the specification and the derived program. This link is, however, not very fine-grained: it can be best characterized as Program is-derived- from Specification. When the generated program needs to be understood or modified, more $ne-grained linking is useful. In this paper, we present a novel technique for automatically deriving traceability relations between parts of a specification and parts of the synthesized program. The technique is very lightweight and works -- with varying degrees of success - for any process in which one artifact is automatically derived from another. We illustrate the generality of the technique by applying it to two kinds of automatic generation: synthesis of Kalman Filter programs from speci3cations using the Aut- oFilter program synthesis system, and generation of assembly language programs from C source code using the GCC C compilel: We evaluate the effectiveness of the technique in the latter application.

Anh To | NREL

Science.gov Websites

pyrolysis vapors Catalytic depolymerization of biomass Process scale-up for catalyst synthesis and testing continuous flow reactors (gas & liquid phases) Catalyst synthesis: zeolites, supported metals, and

The synthesis of glutamic acid in the absence of enzymes: Implications for biogenesis

NASA Technical Reports Server (NTRS)

Morowitz, Harold; Peterson, Eta; Chang, Sherwood

1995-01-01

This paper reports on the non-enzymatic aqueous phase synthesis of amino acids from keto acids, ammonia and reducing agents. The facile synthesis of key metabolic intermediates, particularly in the glycolytic pathway, the citric acid cycle, and the first step of amino acid synthesis, lead to new ways of looking at the problem of biogenesis.

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

Zhao, Yajing; Chen, Yan; Chen, Kepi

In this study, the effects of doping with GeO 2 on the synthesis temperature, phase structure and morphology of (K 0.5Na 0.5)NbO 3 (KNN) ceramic powders were studied using XRD and SEM. The results show that KNN powders with good crystallinity and compositional homogeneity can be obtained after calcination at up to 900°C for 2 h. Introducing 0.5 mol.% GeO 2 into the starting mixture improved the synthesis of the KNN powders and allowed the calcination temperature to be decreased to 800°C, which can be ascribed to the formation of the liquid phase during the synthesis.

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

Biasotto, G.; Simoes, A.Z., E-mail: alezipo@yahoo.com; Foschini, C.R.

Highlights: Black-Right-Pointing-Pointer BiFeO{sub 3} (BFO) nanoparticles were grown by hydrothermal microwave method (HTMW). Black-Right-Pointing-Pointer The soaking time is effective in improving phase formation. Black-Right-Pointing-Pointer Rietveld refinement reveals an orthorhombic structure. Black-Right-Pointing-Pointer The observed magnetism of the BFO crystallites is a consequence of particle size. Black-Right-Pointing-Pointer The HTMW is a genuine technique for low temperatures and short times of synthesis. -- Abstract: Hydrothermal microwave method (HTMW) was used to synthesize crystalline bismuth ferrite (BiFeO{sub 3}) nanoparticles (BFO) in the temperature of 180 Degree-Sign C with times ranging from 5 min to 1 h. BFO nanoparticles were characterized by means of X-raymore » analyses, FT-IR, Raman spectroscopy, TG-DTA and FE-SEM. X-ray diffraction results indicated that longer soaking time was benefit to refraining the formation of any impurity phases and growing BFO crystallites into almost single-phase perovskites. Typical FT-IR spectra for BFO nanoparticles presented well defined bands, indicating a substantial short-range order in the system. TG-DTA analyses confirmed the presence of lattice OH{sup -} groups, commonly found in materials obtained by HTMW process. Compared with the conventional solid-state reaction process, submicron BFO crystallites with better homogeneity could be produced at the temperature as low as 180 Degree-Sign C. These results show that the HTMW synthesis route is rapid, cost effective, and could be used as an alternative to obtain BFO nanoparticles in the temperature of 180 Degree-Sign C for 1 h.« less

Synthesis and high (pressure, temperature) stability of ZnTiO3 polymorphs studied by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Bernert, T.; Ruiz-Fuertes, J.; Bayarjargal, L.; Winkler, B.

2015-05-01

The phase-purity of ilmenite-type ZnTiO3 prepared by the ceramic method was investigated in dependence of the conditions during ball milling. The previously proposed addition of 2 ml ethanol to the starting materials led to a significant contamination of the product phase after a subsequent sintering process at 1073 K. However, by omitting ethanol this synthesis route led to a phase-pure sample of ZnTiO3 as confirmed by X-ray powder diffraction and Raman spectroscopy. High-temperature high-pressure experiments gave an ilmenite-type to perovskite-type phase boundary with a slope of dT/dP∼-135 K GPa-1 crossing ambient temperature conditions at ∼ 24 GPa in good agreement with previous calculations. Room-temperature high-pressure Raman spectroscopy experiments have shown the stability of the ilmenite-type phase up to a pressure of at least 38.5 GPa, the highest pressure applied in this study, indicating the presence of a kinetic barrier in this phase transition. The synthesis of ferroelectric LiNbO3-type ZnTiO3 was confirmed by second harmonic generation.

The effect of B{sub 2}O{sub 3} flux on growth NLBCO superconductor by solid state reaction and wet-mixing methods

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

Suharta, W. G., E-mail: wgsuharta@gmail.com; Wendri, N.; Ratini, N.

The synthesis of B{sub 2}O{sub 3} flux substituted NLBCO superconductor NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂} has been done using solid state reaction and wet-mixing methods in order to obtain homogeneous crystals and single phase. From DTA/TGA characteritations showed the synthesis process by wet-mixing requires a lower temperature than the solid state reaction in growing the superconductor NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂}. Therefore, in this research NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂} sample calcinated at 650°C for wet-mixing method and 820°C for solid state reaction methods. The all samples was sintered at 950°C for ten hours. Crystallinity of the sample was confirmedmore » using X-ray techniques and generally obtained sharp peaks that indicates the sample already well crystallized. Search match analyses for diffraction data gave weight fractions of impurity phase of the solid state reaction method higher than wet-mixing method. In this research showed decreasing the price of the lattice parameter about 1% with the addition of B{sub 2}O{sub 3} flux for the both synthesis process and 2% of wet mixing process for all samples. Characterization using scanning electron microscopy (SEM) showed the distribution of crystal zise for wet-mixing method more homogeneous than solid state reaction method, with he grain size of samples is around 150–250 nm. The results of vibrating sample magnetometer (VSM) showed the paramagnetic properties for all samples.« less

Stochastic Endogenous Replication Stress Causes ATR-Triggered Fluctuations in CDK2 Activity that Dynamically Adjust Global DNA Synthesis Rates.

PubMed

Daigh, Leighton H; Liu, Chad; Chung, Mingyu; Cimprich, Karlene A; Meyer, Tobias

2018-06-04

Faithful DNA replication is challenged by stalling of replication forks during S phase. Replication stress is further increased in cancer cells or in response to genotoxic insults. Using live single-cell image analysis, we found that CDK2 activity fluctuates throughout an unperturbed S phase. We show that CDK2 fluctuations result from transient ATR signals triggered by stochastic replication stress events. In turn, fluctuating endogenous CDK2 activity causes corresponding decreases and increases in DNA synthesis rates, linking changes in stochastic replication stress to fluctuating global DNA replication rates throughout S phase. Moreover, cells that re-enter the cell cycle after mitogen stimulation have increased CDK2 fluctuations and prolonged S phase resulting from increased replication stress-induced CDK2 suppression. Thus, our study reveals a dynamic control principle for DNA replication whereby CDK2 activity is suppressed and fluctuates throughout S phase to continually adjust global DNA synthesis rates in response to recurring stochastic replication stress events. Copyright © 2018. Published by Elsevier Inc.

Synthesis of high-oxidation Y-Ba-Cu-O phases in superoxygenated thin films

NASA Astrophysics Data System (ADS)

Zhang, H.; Gauquelin, N.; McMahon, C.; Hawthorn, D. G.; Botton, G. A.; Wei, J. Y. T.

2018-03-01

It is known that solid-state reaction in high-pressure oxygen can stabilize high-oxidation phases of Y-Ba-Cu-O superconductors in powder form. We extend this superoxygenation concept of synthesis to thin films which, due to their large surface-to-volume ratio, are more reactive thermodynamically. Epitaxial thin films of YBa2Cu3O7 -δ grown by pulsed laser deposition are annealed at up to 700 atm O2 and 900 ∘C , in conjunction with Cu enrichment by solid-state diffusion. The films show the clear formation of Y2Ba4Cu7O15 -δ and Y2Ba4Cu8O16 as well as regions of YBa2Cu5O9 -δ and YBa2Cu6O10 -δ phases, according to scanning transmission electron microscopy, x-ray diffraction, and x-ray absorption spectroscopy. Similarly annealed YBa2Cu3O7 -δ powders show no phase conversion. Our results demonstrate a route of synthesis towards discovering more complex phases of cuprates and other superconducting oxides.

Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) process. Technical progress report number 9, July 1--September 30, 1996

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

NONE

The Liquid Phase Methanol (LPMEOH{trademark}) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the US Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). The LPMEOH{trademark} Process Demonstration Unit is being built at a site located at the Eastman Chemical Company (Eastman) complex in Kingsport. The project involves the construction of an 80,000 gallons per day (260 tons per day (TPD)) methanol unit utilizing coal-derived synthesis gas from Eastman`s integrated coal gasification facility. The new equipment consists of synthesis gas feed preparation and compression facilities, the liquid phase reactor and auxiliaries,more » product distillation facilities, and utilities. This liquid phase process suspends fine catalyst particles in an inert liquid, forming a slurry. The slurry dissipates the heat of the chemical reaction away from the catalyst surface, protecting the catalyst and allowing the methanol synthesis reaction to proceed at higher rates. At the Eastman complex, the technology is being integrated with existing coal-gasifiers.« less

Formation of sodium bismuth titanate-barium titanate during solid-state synthesis

DOE PAGES

Hou, Dong; Aksel, Elena; Fancher, Chris M.; ...

2017-01-12

Phase formation of sodium bismuth titanate (Na 0.5Bi 0.5TiO 3 or NBT) and its solid solution with barium titanate (BaTiO 3 or BT) during the calcination process is studied using in situ high-temperature diffraction. The reactant powders were mixed and heated to 1000°C, while X-ray diffraction patterns were recorded continuously. Phase evolutions from starting materials to final perovskite products are observed, and different transient phases are identified. The formation mechanism of NBT and NBT–xBT perovskite structures is discussed, and a reaction sequence is suggested based on the observations. The in situ study leads to a new processing approach, which ismore » the use of nano-TiO 2, and gives insights to the particle size effect for solid-state synthesis products. Lastly, it was found that the use of nano-TiO 2 as reactant powder accelerates the synthesis process, decreases the formation of transient phases, and helps to obtain phase-pure products using a lower thermal budget.« less

Machine-learned and codified synthesis parameters of oxide materials

NASA Astrophysics Data System (ADS)

Kim, Edward; Huang, Kevin; Tomala, Alex; Matthews, Sara; Strubell, Emma; Saunders, Adam; McCallum, Andrew; Olivetti, Elsa

2017-09-01

Predictive materials design has rapidly accelerated in recent years with the advent of large-scale resources, such as materials structure and property databases generated by ab initio computations. In the absence of analogous ab initio frameworks for materials synthesis, high-throughput and machine learning techniques have recently been harnessed to generate synthesis strategies for select materials of interest. Still, a community-accessible, autonomously-compiled synthesis planning resource which spans across materials systems has not yet been developed. In this work, we present a collection of aggregated synthesis parameters computed using the text contained within over 640,000 journal articles using state-of-the-art natural language processing and machine learning techniques. We provide a dataset of synthesis parameters, compiled autonomously across 30 different oxide systems, in a format optimized for planning novel syntheses of materials.

Green Chemistry Techniques for Gold Nanoparticles Synthesis

NASA Astrophysics Data System (ADS)

Cannavino, Sarah A.; King, Christy A.; Ferrara, Davon W.

Gold nanoparticles (AuNPs) are often utilized in many technological and research applications ranging from the detection of tumors, molecular and biological sensors, and as nanoantennas to probe physical processes. As these applications move from the research laboratory to industrial settings, there is a need to develop efficient and sustainable synthesis techniques. Recent research has shown that several food products and beverages containing polyphenols, a common antioxidant, can be used as reducing agents in the synthesis of AuNPs in solution. In this study, we explore a variety of products to determine which allow for the most reproducible solution of nanoparticles based on the size and shapes of particles present. We analyzed the AuNPs solutions using extinction spectroscopy and atomic force microscopy. We also develop a laboratory activity to introduce introductory chemistry and physics students to AuNP synthesis techniques and analysis.

Study of various synthesis techniques of nanomaterials

NASA Astrophysics Data System (ADS)

Patil, Madhuri; Sharma, Deepika; Dive, Avinash; Mahajan, Sandeep; Sharma, Ramphal

2018-05-01

Development of synthesis techniques of realizing nano-materials over a range of sizes, shapes, and chemical compositions is an important aspect of nanotechnology. The remarkable size dependent physical & chemical properties of particles have fascinated and inspired research activity in this direction. This paper describes some aspects on synthesis and characterization of particles of metals, metal alloys, and oxides, either in the form of thin films or bulk shapes. A brief discussion on processing of thin-films is also described.

Solid phase synthesis of phosphorothioate oligonucleotides utilizing diethyldithiocarbonate disulfide (DDD) as an efficient sulfur transfer reagent.

PubMed

Cheruvallath, Zacharia S; Kumar, R Krishna; Rentel, Claus; Cole, Douglas L; Ravikumar, Vasulinga T

2003-04-01

Diethyldithiodicarbonate (DDD), a cheap and easily prepared compound, is found to be a rapid and efficient sulfurizing reagent in solid phase synthesis of phosphorothioate oligodeoxyribonucleotides via the phosphoramidite approach. Product yield and quality based on IP-LC-MS compares well with high quality oligonucleotides synthesized using phenylacetyl disulfide (PADS) which is being used for manufacture of our antisense drugs.

Polymer-Supported Reagents and [to the first power]H-[to the nineteenth power]F NMR Couplings: The Synthesis of 2-Fluoroacetophenone

ERIC Educational Resources Information Center

Pohl, Nicola; Schwarz, Kimberly

2008-01-01

We describe an experiment for the undergraduate organic laboratory curriculum in which 2-bromoacetophenone is converted to 2-fluoroacetophenone using a solid-phase nucleophilic fluorine source. The experiment introduces students to the utility of solid-phase reagents in organic synthesis, to NMR-active nuclei other than [to the first power]H…

Synthesis of 4-(5-iodo-3-methylpyrazolyl) phenylsulfonamide and its elaboration to a COX II inhibitor library by solution-phase suzuki coupling using Pd/C as a solid-supported catalyst.

PubMed

Organ, Michael G; Mayer, Stanislas

2003-01-01

An effective synthesis of 4-(5-iodo-3-methylpyrazolyl) phenylsulfonamide has been developed. This aromatic iodide template served as an efficient oxidative addition partner for the preparation of a solution-phase library of Celecoxib analogues via Suzuki coupling using Pd/C, a readily filterable catalyst.

Facile room-temperature solution-phase synthesis of a spherical covalent organic framework for high-resolution chromatographic separation.

PubMed

Yang, Cheng-Xiong; Liu, Chang; Cao, Yi-Meng; Yan, Xiu-Ping

2015-08-07

A simple and facile room-temperature solution-phase synthesis was developed to fabricate a spherical covalent organic framework with large surface area, good solvent stability and high thermostability for high-resolution chromatographic separation of diverse important industrial analytes including alkanes, cyclohexane and benzene, α-pinene and β-pinene, and alcohols with high column efficiency and good precision.

Elucidation of the surface characteristics and electrochemistry of high-performance LiNiO 2

DOE PAGES

Xu, Jing; Lin, Feng; Nordlund, Dennis; ...

2016-02-25

Phase pure LiNiO 2 was prepared using a solid-state method and the optimal synthesis conditions led to a remarkably high capacity of 200 mA h g $-$1 with excellent retention. The combination of bulk and surface characterization elucidated an essential role of the excess Li in phase formation during synthesis and the subsequent electrochemical performance.

Inflammation-induced synthesis of proteoheparan sulfate: a novel acute-phase reactant in rat hepatocytes

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

Djovkar, A.; Gressner, A.M.

1987-03-01

The synthesis of proteoheparan sulfate in hepatocytes is positively regulated under acute-phase conditions produced either by turpentine or deep back incision. In both cases the incorporation of (/sup 35/S)sulfate and (/sup 14/C)glucosamine is doubled during a 4-h incubation period if compared with control rat hepatocytes. Neither the fractional secretion rate of heparan sulfate into the medium (less than 0.1 of cell-associated glycosaminoglycans) nor the composition of newly formed proteoglycans in hepatocytes are affected during acute phase reaction.

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.

Nanoribbons: From fundamentals to state-of-the-art applications

NASA Astrophysics Data System (ADS)

Yagmurcukardes, M.; Peeters, F. M.; Senger, R. T.; Sahin, H.

2016-12-01

Atomically thin nanoribbons (NRs) have been at the forefront of materials science and nanoelectronics in recent years. State-of-the-art research on nanoscale materials has revealed that electronic, magnetic, phononic, and optical properties may differ dramatically when their one-dimensional forms are synthesized. The present article aims to review the recent advances in synthesis techniques and theoretical studies on NRs. The structure of the review is organized as follows: After a brief introduction to low dimensional materials, we review different experimental techniques for the synthesis of graphene nanoribbons (GNRs) with their advantages and disadvantages. In addition, theoretical investigations on width and edge-shape-dependent electronic and magnetic properties, functionalization effects, and quantum transport properties of GNRs are reviewed. We then devote time to the NRs of the transition metal dichalcogenides (TMDs) family. First, various synthesis techniques, E-field-tunable electronic and magnetic properties, and edge-dependent thermoelectric performance of NRs of MoS2 and WS2 are discussed. Then, strongly anisotropic properties, growth-dependent morphology, and the weakly width-dependent bandgap of ReS2 NRs are summarized. Next we discuss TMDs having a T-phase morphology such as TiSe2 and stable single layer NRs of mono-chalcogenides. Strong edge-type dependence on characteristics of GaS NRs, width-dependent Seebeck coefficient of SnSe NRs, and experimental analysis on the stability of ZnSe NRs are reviewed. We then focus on the most recently emerging NRs belonging to the class of transition metal trichalcogenides which provide ultra-high electron mobility and highly anisotropic quasi-1D properties. In addition, width-, edge-shape-, and functionalization-dependent electronic and mechanical properties of blackphosphorus, a monoatomic anisotropic material, and studies on NRs of group IV elements (silicene, germanene, and stanene) are reviewed. Observation of substrate-independent quantum well states, edge and width dependent properties, the topological phase of silicene NRs are reviewed. In addition, H2 concentration-dependent transport properties and anisotropic dielectric function of GeNRs and electric field and strain sensitive I-V characteristics of SnNRs are reviewed. We review both experimental and theoretical studies on the NRs of group III-V compounds. While defect and N-termination dependent conductance are highlighted for boron nitride NRs, aluminum nitride NRs are of importance due to their dangling bond, electric field, and strain dependent electronic and magnetic properties. Finally, superlattice structure of NRs of GaN/AlN, Si/Ge, G/BN, and MoS2/WS2 is reviewed.

A review on development of solid phase microextraction fibers by sol-gel methods and their applications.

PubMed

Kumar, Ashwini; Gaurav; Malik, Ashok Kumar; Tewary, Dhananjay Kumar; Singh, Baldev

2008-03-03

Solid phase microextraction (SPME) is an innovative, solvent free technology that is fast, economical and versatile. SPME is a fiber coated with a liquid (polymer), a solid (sorbent) or a combination of both. The fiber coating takes up the compounds from the sample by absorption in the case of liquid coatings or adsorption in the case of solid coatings. The SPME fiber is then transferred with the help of a syringe like device into the analytical instrument for desorption and analysis of the target analytes. The sol-gel process provides a versatile method to prepare size, shape and charge selective materials of high purity and homogeneity by means of preparation techniques different from the traditional ones, for the chemical analysis. This review is on the current state of the art and future trends in the developments of solid phase microextraction (SPME) fibers using sol-gel method. To achieve more selective determination of different compound classes, the variety of different coating material for SPME fibers has increased. Further developments in SPME as a highly efficient extraction technique, will greatly depend on new breakthroughs in the area of new coating material developments for the SPME fibers. In sol-gel approach, appropriate sol-gel precursors and other building blocks can be selected to create a stationary phase with desired structural and surface properties. This approach is efficient in integrating the advantageous properties of organic and inorganic material systems and thereby increasing and improving the extraction selectivity of the produced amalgam organic-inorganic stationary phases. This review is mainly focused on recent advanced developments in the design, synthesis, characterisation, properties and application of sol-gel in preparation of coatings for the SPME fibers.

Immobilization methods for the rapid total chemical synthesis of proteins on microtiter plates.

PubMed

Zitterbart, Robert; Krumrey, Michael; Seitz, Oliver

2017-07-01

The chemical synthesis of proteins typically involves the solid-phase peptide synthesis of unprotected peptide fragments that are stitched together in solution by native chemical ligation (NCL). The process is slow, and throughput is limited because of the need for repeated high performance liquid chromatography purification steps after both solid-phase peptide synthesis and NCL. With an aim to provide faster access to functional proteins and to accelerate the functional analysis of synthetic proteins by parallelization, we developed a method for the high performance liquid chromatography-free synthesis of proteins on the surface of microtiter plates. The method relies on solid-phase synthesis of unprotected peptide fragments, immobilization of the C-terminal fragment and on-surface NCL with an unprotected peptide thioester in crude form. Herein, we describe the development of a suitable immobilization chemistry. We compared (i) formation of nickel(II)-oligohistidine complexes, (ii) Cu-based [2 + 3] alkine-azide cycloaddition and (iii) hydrazone ligation. The comparative study identified the hydrazone ligation as most suitable. The sequence of immobilization via hydrazone ligation, on-surface NCL and radical desulfurization furnished the targeted SH3 domains in near quantitative yield. The synthetic proteins were functional as demonstrated by an on-surface fluorescence-based saturation binding analysis. Copyright © 2017 European Peptide Society and John Wiley & Sons, Ltd. Copyright © 2017 European Peptide Society and John Wiley & Sons, Ltd.

Synthesis of a single phase of high-entropy Laves intermetallics in the Ti-Zr-V-Cr-Ni equiatomic alloy

NASA Astrophysics Data System (ADS)

Yadav, T. P.; Mukhopadhyay, Semanti; Mishra, S. S.; Mukhopadhyay, N. K.; Srivastava, O. N.

2017-12-01

The high-entropy Ti-Zr-V-Cr-Ni (20 at% each) alloy consisting of all five hydride-forming elements was successfully synthesised by the conventional melting and casting as well as by the melt-spinning technique. The as-cast alloy consists entirely of the micron size hexagonal Laves Phase of C14 type; whereas, the melt-spun ribbon exhibits the evolution of nanocrystalline Laves phase. There was no evidence of any amorphous or any other metastable phases in the present processing condition. This is the first report of synthesising a single phase of high-entropy complex intermetallic compound in the equiatomic quinary alloy system. The detailed characterisation by X-ray diffraction, scanning and transmission electron microscopy and energy-dispersive X-ray spectroscopy confirmed the existence of a single-phase multi-component hexagonal C14-type Laves phase in all the as-cast, melt-spun and annealed alloys. The lattice parameter a = 5.08 Å and c = 8.41 Å was determined from the annealed material (annealing at 1173 K). The thermodynamic calculations following the Miedema's approach support the stability of the high-entropy multi-component Laves phase compared to that of the solid solution or glassy phases. The high hardness value (8.92 GPa at 25 g load) has been observed in nanocrystalline high-entropy alloy ribbon without any cracking. It implies that high-yield strength ( 3.00 GPa) and the reasonable fracture toughness can be achieved in this high-entropy material.

Purification of a benzodiazepine from bovine brain and detection of benzodiazepine-like immunoreactivity in human brain.

PubMed Central

Sangameswaran, L; Fales, H M; Friedrich, P; De Blas, A L

1986-01-01

An endogenous brain substance that binds to the central-type benzodiazepine receptors with agonist properties is present in both rat and bovine brains. This substance has been purified to homogeneity from bovine brain by immunoaffinity chromatography on immobilized monoclonal anti-benzodiazepine antibody followed by gel filtration on Sephadex G-25 and two reversed-phase HPLC steps. The purified substance was characterized as the benzodiazepine N-desmethyldiazepam (nordiazepam). The techniques used for the identification were mass spectrometry, HPLC, spectrophotometry, benzodiazepine receptor binding, and immunological techniques. Benzodiazepine-like immunoreactivity was also found in all the human brains tested, including six brains that had been stored in paraffin since 1940, fifteen years before the first synthesis of benzodiazepines. These results show that benzodiazepine-like molecules of natural origin--and possibly benzodiazepines themselves--are present in human and other mammalian brains. Images PMID:3024172

Enhancement in surface area and magnetization of CoFe2O4 nanoparticles for targeted drug delivery application

NASA Astrophysics Data System (ADS)

Kale, Swati B.; Somvanshi, Sandeep B.; Sarnaik, M. N.; More, S. D.; Shukla, S. J.; Jadhav, K. M.

2018-05-01

This paper reports facile synthesis, characterizations by X-ray diffraction and scanning electron microscopy and magnetic behaviour of cobalt ferrite nanoparticles. Cobalt ferrite nanoparticles were prepared by sol-gel auto combustion technique using glycine as a fuel. Phase purity and nanocrystalline nature of the prepared sample was confirmed through X-ray diffraction technique. No extra peak other than cubic spinel structure was observed in the XRD pattern. The crystallite size calculated by using Scherrer's formula is of the order of 21.6 nm indicating the nanocrystalline nature of the prepared cobalt ferrite sample. The surface morphological studies were carried out using scanning electron microscope (SEM). SEM image shows homogeneous, agglomerated particles with sponge-like form. The saturation magnetization, coercivity and remenance magnetization obtained by hysteresis curve clearly gives the evidence of excellent and enhanced magnetic behaviour.

Synthesis and characterization of porous CaCO3 micro/nano-particles

NASA Astrophysics Data System (ADS)

Achour, A.; Arman, A.; Islam, M.; Zavarian, A. A.; Basim Al-Zubaidi, A.; Szade, J.

2017-06-01

Porous CaCO3 particles, both micro and nano sized, were synthesized in a mixture of Ca(OH)2, hyaluronic acid (HA), glycine, NaOH and NaCl solution with supercritical carbon dioxide. The particles were characterized using X-Ray Diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscope, Raman spectroscope (RS), X-ray photoelectron spectroscope (XPS) and scanning electron microscope techniques. All these techniques showed that the particles crystallize into only one CaCO3 structure, namely the vaterite phase. In addition, FTIR, RS and XPS indicated the presence of residual reactive species i.e. glycine, NaCl, and HA. The XRD results confirmed the presence of NaCl and γ-glycine, which is a crystalline material. Moreover, the HA seems to be mostly embedded in the bulk of the micro-particles. Such materials are promising for biomedical applications such as drug delivery.

A Laboratory Preparation of Aspartame Analogs Using Simultaneous Multiple Parallel Synthesis Methodology

ERIC Educational Resources Information Center

Qvit, Nir; Barda, Yaniv; Gilon, Chaim; Shalev, Deborah E.

2007-01-01

This laboratory experiment provides a unique opportunity for students to synthesize three analogues of aspartame, a commonly used artificial sweetener. The students are introduced to the powerful and useful method of parallel synthesis while synthesizing three dipeptides in parallel using solid-phase peptide synthesis (SPPS) and simultaneous…

Microstructure and phase analysis of Zirconia-ODS (Oxide Dispersion Strengthen) alloy sintered by APS with milling time variation

NASA Astrophysics Data System (ADS)

Sugeng, Bambang; Bandriyana, B.; Sugeng, Bambang; Salam, Rohmad; Sumariyo; Sujatno, Agus; Dimyati, Arbi

2018-03-01

Investigation on the relationship between the process conditions of milling time and the microstructure on the synthesis of the zirconia-ODS steel alloy has been performed. The elemental composition of the alloy was determined on 20 wt% Cr and zirconia dispersoid of 0.50 wt%. The synthesis was carried out by powder metallurgy method with milling time of 3, 5 and 7 hours, static compression of 20 Ton and sintering process for 4 minutes using the APS (Arc Plasma Sintering) equipment. SEM-EDX and XRD test was carried out to characterize the phase and morphology of the alloy and the effect to the mechanical properties was evaluated by the Vickers Hardness testing. The synthesis produced sample of ODS steel with good dense and very little porous with the Fe-Cr phase that clearly observed in the XRD peak pattern. In addition milling time increased the homogeneously of Fe-Cr phase formulation, enhanced the grain refinement of the structure and increase the hardness of the alloy.

Healthy Cities Phase V evaluation: further synthesizing realism.

PubMed

de Leeuw, Evelyne; Green, Geoff; Tsouros, Agis; Dyakova, Mariana; Farrington, Jill; Faskunger, Johan; Grant, Marcus; Ison, Erica; Jackisch, Josephine; Lafond, Leah Janss; Lease, Helen; Mackiewicz, Karolina; Östergren, Per-Olof; Palmer, Nicola; Ritsatakis, Anna; Simos, Jean; Spanswick, Lucy; Webster, Premila; Zamaro, Gianna; Crown, June; Kickbusch, Ilona; Rasmussen, Niels; Scally, Gabriel; Biddle, Marian; Earl, Suzanne; Petersen, Connie; Devlin, Joan

2015-06-01

In this article we reflect on the quality of a realist synthesis paradigm applied to the evaluation of Phase V of the WHO European Healthy Cities Network. The programmatic application of this approach has led to very high response rates and a wealth of important data. All articles in this Supplement report that cities in the network move from small-scale, time-limited projects predominantly focused on health lifestyles to the significant inclusion of policies and programmes on systems and values for good health governance. The evaluation team felt that, due to time and resource limitations, it was unable to fully exploit the potential of realist synthesis. In particular, the synthetic integration of different strategic foci of Phase V designation areas did not come to full fruition. We recommend better and more sustained integration of realist synthesis in the practice of Healthy Cities in future Phases. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Optimization of hydrothermal synthesis of pure phase zeolite Na-P1 from South African coal fly ashes.

PubMed

Musyoka, Nicholas M; Petrik, Leslie F; Gitari, Wilson M; Balfour, Gillian; Hums, Eric

2012-01-01

This study was aimed at optimizing the synthesis conditions for pure phase zeolite Na-P1 from three coal fly ashes obtained from power stations in the Mpumalanga province of South Africa. Synthesis variables evaluated were: hydrothermal treatment time (12-48 hours), temperature (100-160°C) and varying molar quantities of water during the hydrothermal treatment step (H(2)O:SiO(2) molar ratio ranged between 0-0.49). The optimum synthesis conditions for preparing pure phase zeolite Na-P1 were achieved when the molar regime was 1 SiO(2): 0.36 Al(2)O(3): 0.59 NaOH: 0.49 H(2)O and ageing was done at 47°C for 48 hours. The optimum hydrothermal treatment time and temperature was 48 hours and 140°C, respectively. Fly ashes sourced from two coal-fired power plants (A, B) were found to produce nearly same high purity zeolite Na-P1 under identical conditions whereas the third fly ash (C) lead to a low quality zeolite Na-P1 under these conditions. The cation exchange capacity for the high pure phase was found to be 4.11 meq/g. These results highlight the fact that adjustment of reactant composition and presynthesis or synthesis parameters, improved quality of zeolite Na-P1 can be achieved and hence an improved potential for application of zeolites prepared from coal fly ash.

Older adults' perspectives on the process of becoming users of assistive technology: a qualitative systematic review and meta-synthesis.

PubMed

Larsen, Stina Meyer; Mortensen, Rikke Falgreen; Kristensen, Hanne Kaae; Hounsgaard, Lise

2018-04-22

To identify, synthesize, and evaluate existing literature concerning the process of becoming a user of assistive technology (AT). A systematic review and meta-synthesis were carried out. Five bibliographic databases (MEDLINE via PubMed, CINAHL, Web of Science, PsycINFO and SocINDEX) were systematically searched up to 13 th of March 2017, using two sets of search terms: (i) elderly and synonyms and (ii) assistive technology and similar words, and combined with a qualitative research filter. Articles were screened, read and critically assessed. The meta-synthesis was guided by Ricoeur's theory of interpretation. Seventeen out of 4645 articles were included. Five phases emerged relating to the process of becoming a user of AT: phase A: Evaluating need, phase B: Acknowledging need, phase C: Incorporating the AT into daily life, phase D: Using the AT, and phase E: Future use. Three transitions, describing factors essential to moving from one phase to the next, were identified; from phase A-B: Valued activities are threatened, from phase B-C: Obtaining the AT and from phase C-D: Trust in the AT. No transition was identified from phase D-E. The meta-synthesis led to a deeper understanding of the process of older adults becoming users of AT, by exploring findings across the included articles. The identified phases and transitions in the systematic review serve as an analytical framework for understanding the process from the older adult's perspective. This review advocates for using a client-centred approach throughout the entire delivery process. Implications for rehabilitation The process of the older adult becoming a user of AT involves an individualized time factor, and this supports the practice of individualized follow-up. The process of becoming a user of AT is closely related to self-image; healthcare professionals should support not only the use of AT but also the older adult's emotional adjustment to a new self-image. The process is highly influenced by the older adult's social context; healthcare professionals should consider involving the client's social network in the AT delivery process.

Solution based synthesis of mixed-phase materials in the Li2TiO3-Li4SiO4 system

NASA Astrophysics Data System (ADS)

Hanaor, Dorian A. H.; Kolb, Matthias H. H.; Gan, Yixiang; Kamlah, Marc; Knitter, Regina

2015-01-01

As candidate tritium breeder materials for use in the ITER helium cooled pebble bed, ceramic multiphasic compounds lying in the region of the quasi-binary lithium metatitanate-lithium orthosilicate system may exhibit mechanical and physical advantages relative to single phase materials. Here we present an organometallic solution-based synthesis procedure for the low-temperature fabrication of compounds in the Li2TiO3-Li4SiO4 region and investigate phase stability and transformations through temperature varied X-ray diffraction and scanning calorimetry. Results demonstrate that the metatitanate and metasilicate phases Li2TiO3 and Li2SiO3 readily crystallise in nanocrystalline form at temperatures below 180 °C. Lithium deficiency in the region of 5% results from Li sublimation from Li4SiO4 and/or from excess Li incorporation in the metatitanate phase and brings about a stoichiometry shift, with product compounds exhibiting mixed lithium orthosilicate/metasilicate content towards the Si rich region and predominantly Li2TiO3 content towards the Ti rich region. Above 1150 °C the transformation of monoclinic to cubic γ-Li2TiO3 disordered solid-solution occurs while the melting of silicate phases indicates a likely monotectic type system with a solidus line in the region 1050-1100 °C. Synthesis procedures involving a lithium chloride precursor are not likely to be a viable option for breeder pebble synthesis as this route was found to yield materials with a more significant Li-deficiency exhibiting the crystallisation of the Li2TiSiO5 phase at intermediate compositions.

Ultrafast synthesis of LTA nanozeolite using a two-phase segmented fluidic microreactor.

PubMed

Zhou, Jianhai; Jiang, Hao; Xu, Jian; Hu, Jun; Liu, Honglai; Hu, Ying

2013-08-01

Fast synthesis of nanosized zeolite is desirable for many industrial applications. An ultrafast synthesis of LTA nanozeolite by the organic-additive-free method in a two-phase segmented fluidic microreactor has been realized. The results reveal that the obtained LTA nanozeolites through microreactor are much smaller and higher crystallinity than those under similar conditions through conventional macroscale batch reactor. By investing various test conditions, such as the crystallization temperature, the flow rate, the microchannel length, and the aging time of gel solution, this two-phase segmented fluidic microreactor system enables us to develop an ultrafast method for nanozeolite production. Particularly, when using a microreactor with the microchannel length of 20 m, it only takes 10 min for the crystallization and no aging process to successfully produce the crystalline LTA nanozeolites at 95 degrees C.

Process optimization using combinatorial design principles: parallel synthesis and design of experiment methods.

PubMed

Gooding, Owen W

2004-06-01

The use of parallel synthesis techniques with statistical design of experiment (DoE) methods is a powerful combination for the optimization of chemical processes. Advances in parallel synthesis equipment and easy to use software for statistical DoE have fueled a growing acceptance of these techniques in the pharmaceutical industry. As drug candidate structures become more complex at the same time that development timelines are compressed, these enabling technologies promise to become more important in the future.

Structural and physical property study of sol-gel synthesized CoFe2-xHoxO4 nano ferrites

NASA Astrophysics Data System (ADS)

Patankar, K. K.; Ghone, D. M.; Mathe, V. L.; Kaushik, S. D.

2018-05-01

CoFe2-xHoxO4 (x = 0.00, 0.05, 0.10, 0.15, 0.20) ferrites were prepared by the suitably modified Sol-Gel technique. X-ray diffraction (XRD) analysis revealed that the substituted samples show phase pure formation till 10% substitution, which is far higher phase pure than the earlier reports. Upon further substitution an inevitable secondary phase of HoFeO3 along with the spinel phase despite regulating synthesis parameters in the sol-gel reaction route. These results are further corroborated more convincingly by room temperature neutron diffraction. Morphological features of the ferrites were studied by Scanning Electron Microscopy (SEM). The magnetic parameters viz. the saturation magnetization (Ms), coercivity (Hc) and remanence (Mr) were determined from room temperature isothermal magnetization. These parameters were found to decrease with increase in Ho substitution. The decrease in magnetization is analyzed in the light of exchange interactions between rare earth and transition metal ions. Magnetostriction measurements revealed interesting results and the presence of a secondary phase was found to be responsible for decreased measu-red magnetostriction values. The solubility limit of Ho in CoFe2O4 lattice is also reflected from the X-ray and neutron diffraction analysis and magnetostriction studies.

Anisotropic imprint of amorphization and phase separation in manganite thin films via laser interference irradiation.

PubMed

Ding, Junfeng; Lin, Zhipeng; Wu, Jianchun; Dong, Zhili; Wu, Tom

2015-02-04

Materials with mesoscopic structural and electronic phase separation, either inherent from synthesis or created via external means, are known to exhibit functionalities absent in the homogeneous counterparts. One of the most notable examples is the colossal magnetoresistance discovered in mixed-valence manganites, where the coexistence of nano- to micrometer-sized phase-separated domains dictates the magnetotransport. However, it remains challenging to pattern and process such materials into predesigned structures and devices. In this work, a direct laser interference irradiation (LII) method is employed to produce periodic stripes in thin films of a prototypical phase-separated manganite Pr0.65 (Ca0.75 Sr0.25 )0.35 MnO3 (PCSMO). LII induces selective structural amorphization within the crystalline PCSMO matrix, forming arrays with dimensions commensurate with the laser wavelength. Furthermore, because the length scale of LII modification is compatible to that of phase separation in PCSMO, three orders of magnitude of increase in magnetoresistance and significant in-plane transport anisotropy are observed in treated PCSMO thin films. Our results show that LII is a rapid, cost-effective and contamination-free technique to tailor and improve the physical properties of manganite thin films, and it is promising to be generalized to other functional materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selection of Compositions in Ti-Cr-C-Steel, Ti-B, Ti-B-Me Systems and Establishing Synthesis Parameters for Obtaining Product by “SHS-Electrical Rolling”

NASA Astrophysics Data System (ADS)

Aslamazashvili, Zurab; Tavadze, Giorgi; Chikhradze, Mikheil; Namicheishvili, Teimuraz; Melashvili, Zaqaria

2017-12-01

For the production materials by the proposed Self-propagating High-Temperature Synthesis (SHS) - Electric Rolling method, there are no limitations in the length of the material and the width only depends on the length of rolls. The innovation method enables to carry out the process in nonstop regime, which is possible by merging energy consuming SHS method and Electrical Rolling. For realizing the process it is mandatory and sufficient, that initial components, after initiation by thermal pulse, could interaction with the heat emission, which itself ensures the self-propagation of synthesis front in lieu of heat transfer in the whole sample. Just after that process, the rolls instantly start rotation with the set speed to ensure the motion of material. This speed should be equal to the speed of propagation of synthesis front. The synthesized product in hot plastic condition is delivered to the rolls in nonstop regime, simultaneously, providing the current in deformation zone in order to compensate the energy loses. As a result by using the innovation SHS -Electrical Rolling technology we obtain long dimensional metal-ceramic product. In the presented paper optimal compositions of SHS chasms were selected in Ti-Cr-C-Steel, Ti-B and Ti-B-Me systems. For the selection of the compounds the thermodynamic analysis has been carried out which enabled to determine adiabatic temperature of synthesis theoretically and to determine balanced concentrations of synthesized product at synthesis temperature. Thermodynamic analysis also gave possibility to determine optimal compositions of chasms and define the conditions, which are important for correct realization of synthesis process. For obtaining non porous materials and product by SHS-Electrical Rolling, it is necessary to select synthesis and compacting parameters correctly. These parameters are the pressure and the time. In Ti-Cr-C-Steel, Ti-B and Ti-B-Me systems the high quality (nonporous or low porosity <2%) of materials and product is directly depended on the liquid phase content just after the passing of synthesis front in the sample. The more content of liquid phase provides the higher quality of material. The content of liquid phase itself depends on synthesis parameters: speed and temperature of synthesis. The higher the speed and temperature of synthesis we have, higher the content of liquid phase is formed. The speed and the temperature of synthesis depend on the Δρ relative density of sample formed from initial chasm, this mean it depends on the pressure of formation of the sample. The paper describes the results of determination of optimal pressures in Ti-Cr-C-Steel, Ti-B and Ti-B-Me systems. Their values are defined as 50-70 MPa, 180-220 MPa and 45-70 MPa.

Low toxic maghemite nanoparticles for theranostic applications.

PubMed

Kuchma, Elena A; Zolotukhin, Peter V; Belanova, Anna A; Soldatov, Mikhail A; Lastovina, Tatiana A; Kubrin, Stanislav P; Nikolsky, Anatoliy V; Mirmikova, Lidia I; Soldatov, Alexander V

2017-01-01

Iron oxide nanoparticles have numerous and versatile biological properties, ranging from direct and immediate biochemical effects to prolonged influences on tissues. Most applications have strict requirements with respect to the chemical and physical properties of such agents. Therefore, developing rational design methods of synthesis of iron oxide nanoparticles remains of vital importance in nanobiomedicine. Low toxic superparamagnetic iron oxide nanoparticles (SPIONs) for theranostic applications in oncology having spherical shape and maghemite structure were produced using the fast microwave synthesis technique and were fully characterized by several complementary methods (transmission electron microscopy [TEM], X-ray diffraction [XRD], dynamic light scattering [DLS], X-ray photoelectron spectroscopy [XPS], X-ray absorption near edge structure [XANES], Mossbauer spectroscopy, and HeLa cells toxicity testing). TEM showed that the majority of the obtained nanoparticles were almost spherical and did not exceed 20 nm in diameter. The averaged DLS hydrodynamic size was found to be ~33 nm, while that of nanocrystallites estimated by XRD waŝ16 nm. Both XRD and XPS studies evidenced the maghemite (γ-Fe 2 O 3 ) atomic and electronic structure of the synthesized nanoparticles. The XANES data analysis demonstrated the structure of the nanoparticles being similar to that of macroscopic maghemite. The Mossbauer spectroscopy revealed the γ-Fe 2 O 3 phase of the nanoparticles and vibration magnetometry study showed that reactive oxygen species in HeLa cells are generated both in the cytoplasm and the nucleus. Quasispherical Fe 3+ SPIONs having the maghemite structure with the average size of 16 nm obtained by using the fast microwave synthesis technique are expected to be of great value for theranostic applications in oncology and multimodal anticancer therapy.

Mechanochemical synthesis of low-fluorine doped aluminum hydroxide fluorides

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

Scalise, V.; Scholz, G., E-mail: gudrun.scholz@rz.hu-berlin.de; Kemnitz, E., E-mail: erhard.kemnitz@chemie.hu-berlin.de

2016-11-15

Different aluminum hydroxide fluorides with varying Al/F molar ratios from 1:1.5 up to 1:0.05 were successfully synthesized by mechanochemical reactions. The characterization of the products by XRD, {sup 27}Al and {sup 19}F MAS NMR, thermal analysis, nitrogen adsorption and zeta potential techniques allows a detailed understanding of the structure and surface properties of the products. Using γ-Al(OH){sub 3} and β-AlF{sub 3}·3H{sub 2}O as OH- and F-sources, respectively, strongly disordered products were obtained with an Al: F molar ratio higher than 1:0.25. The fluorination degree has affected the amount of 4- and 5-fold coordinated Al sites, not present in the reactants.more » An evolution of the sub-coordinated Al-species has been detected also as a consequence of annealing processes. Obviously, these species affect the phase transition to alumina, by decreasing the transition temperature of the formation of α-Al{sub 2}O{sub 3}. Synthesis conditions (milling time, fluorination degree) play a crucial role for the product composition. - Graphical abstract: The impact of the combined action of the milling and the different fluorine doping on the structure of new aluminum hydroxide fluorides was followed by {sup 27}Al and {sup 19}F NMR and by other complementary techniques. - Highlights: • Low F-doped Al-hydroxide fluorides can be successfully prepared by mechanosynthesis. • Both F-doping and mechanochemical synthesis introduce a high number of defects in the structure. • The fluorination degree affects the amount of 4- and 5-fold coordinated Al sites as well as the transition temperature to corundum.« less

Low toxic maghemite nanoparticles for theranostic applications

PubMed Central

Zolotukhin, Peter V; Belanova, Anna A; Soldatov, Mikhail A; Lastovina, Tatiana A; Kubrin, Stanislav P; Nikolsky, Anatoliy V; Mirmikova, Lidia I

2017-01-01

Background Iron oxide nanoparticles have numerous and versatile biological properties, ranging from direct and immediate biochemical effects to prolonged influences on tissues. Most applications have strict requirements with respect to the chemical and physical properties of such agents. Therefore, developing rational design methods of synthesis of iron oxide nanoparticles remains of vital importance in nanobiomedicine. Methods Low toxic superparamagnetic iron oxide nanoparticles (SPIONs) for theranostic applications in oncology having spherical shape and maghemite structure were produced using the fast microwave synthesis technique and were fully characterized by several complementary methods (transmission electron microscopy [TEM], X-ray diffraction [XRD], dynamic light scattering [DLS], X-ray photoelectron spectroscopy [XPS], X-ray absorption near edge structure [XANES], Mossbauer spectroscopy, and HeLa cells toxicity testing). Results TEM showed that the majority of the obtained nanoparticles were almost spherical and did not exceed 20 nm in diameter. The averaged DLS hydrodynamic size was found to be ~33 nm, while that of nanocrystallites estimated by XRD waŝ16 nm. Both XRD and XPS studies evidenced the maghemite (γ-Fe2O3) atomic and electronic structure of the synthesized nanoparticles. The XANES data analysis demonstrated the structure of the nanoparticles being similar to that of macroscopic maghemite. The Mossbauer spectroscopy revealed the γ-Fe2O3 phase of the nanoparticles and vibration magnetometry study showed that reactive oxygen species in HeLa cells are generated both in the cytoplasm and the nucleus. Conclusion Quasispherical Fe3+ SPIONs having the maghemite structure with the average size of 16 nm obtained by using the fast microwave synthesis technique are expected to be of great value for theranostic applications in oncology and multimodal anticancer therapy. PMID:28919740

Feedback control laws for highly maneuverable aircraft

NASA Technical Reports Server (NTRS)

Garrard, William L.; Balas, Gary J.

1994-01-01

During the first half of the year, the investigators concentrated their efforts on completing the design of control laws for the longitudinal axis of the HARV. During the second half of the year they concentrated on the synthesis of control laws for the lateral-directional axes. The longitudinal control law design efforts can be briefly summarized as follows. Longitudinal control laws were developed for the HARV using mu synthesis design techniques coupled with dynamic inversion. An inner loop dynamic inversion controller was used to simplify the system dynamics by eliminating the aerodynamic nonlinearities and inertial cross coupling. Models of the errors resulting from uncertainties in the principal longitudinal aerodynamic terms were developed and included in the model of the HARV with the inner loop dynamic inversion controller. This resulted in an inner loop transfer function model which was an integrator with the modeling errors characterized as uncertainties in gain and phase. Outer loop controllers were then designed using mu synthesis to provide robustness to these modeling errors and give desired response to pilot inputs. Both pitch rate and angle of attack command following systems were designed. The following tasks have been accomplished for the lateral-directional controllers: inner and outer loop dynamic inversion controllers have been designed; an error model based on a linearized perturbation model of the inner loop system was derived; controllers for the inner loop system have been designed, using classical techniques, that control roll rate and Dutch roll response; the inner loop dynamic inversion and classical controllers have been implemented on the six degree of freedom simulation; and lateral-directional control allocation scheme has been developed based on minimizing required control effort.

Development of a direct-sampling digital correlation radiometer for earth remote sensing applications

NASA Astrophysics Data System (ADS)

Fischman, Mark Andrew

Synthetic thinned array radiometry, or STAR, has emerged as an attractive technique for high spatial resolution satellite imaging at L-band frequencies (1.4 GHz), especially for recovering soil moisture information. However, the implementation of aperture synthesis is limited by the complexity of controlling and synchronizing over 100 microwave heterodyne receivers in the array. In this dissertation, a 1.4 GHz direct-sampling digital radiometer (DSDR) is investigated as an alternative receiver architecture which simplifies the circuitry at each element and leads toward single-chip integration. A discrete-time statistical model of the direct-sampling radiometer is developed for the two constituent parts of aperture synthesis: the total power DSDR and the two-element correlation DSDR. General expressions for noise-equivalent sensitivity (NEDeltaT) and phase stability are derived in terms of quantization resolution, converter bias error, sampling rate, and rms timing jitter. Theoretical results show that a 3-bit L-band DSDR could attain a sensitivity within 4% of the figure for an ideal analog radiometer, and that sampling jitter has a negligible impact on the phase coherence between receivers. To accommodate large baseline STAR, which may suffer from fringe washing effects, a novel band division correlation (BDC) processor is proposed. Numerical simulations of a 27 meter L-band STAR sensor show that BDC improves spatial resolution by 40% at the swath edge. An L-band correlation DSDR prototype was designed and evaluated in a series of lab and field experiments. From noise floor tests, the observed sensitivity of the correlation DSDR fell within +/-0.4 dB of the theoretical NEDeltaT limit. Measurement of partially correlated noise sources demonstrated less than 0.1 dB loss in the cross-correlation output, implying a high level of phase stability in the samplers. However, an excess loss in fringe washing was discovered due to the non-linear nature of A/D conversion; as a remedy, coherence loss may be alleviated by applying the BDC technique. The DSDR hardware has served as a test bed for several important technologies, including wideband flash A/D conversion, field programmable logic, embedded systems, and thermoelectric temperature control.

Synthesis of Micelles Guided Magnetite (Fe3O4) Hollow Spheres and their application for AC Magnetic Field Responsive Drug Release

PubMed Central

Mandal Goswami, Madhuri

2016-01-01

This paper reports on synthesis of hollow spheres of magnetite, guided by micelles and their application in drug release by the stimulus responsive technique. Here oleyelamine micelles are used as the core substance for the formation of magnetite nano hollow spheres (NHS). Diameter and shell thickness of NHS have been changed by changing concentration of the micelles. Mechanism of NHS formation has been established by investigating the aliquot collected at different time during the synthesis of NHS. It has been observed that oleyelamine as micelles play an important role to generate hollow-sphere particles of different diameter and thickness just by varying its amount. Structural analysis was done by XRD measurement and morphological measurements, SEM and TEM were performed to confirm the shape and size of the NHS. FTIR measurement support the formation of magnetite phase too. Frequency dependent AC magnetic measurements and AC magnetic field stimulated drug release event by these particles provide a direction of the promising application of these NHS for better cancer treatment in near future. Being hollow & porous in structure and magnetic in nature, such materials will also be useful in other applications such as in removal of toxic materials, magnetic separation etc. PMID:27796329

Synthesis of Non-uniformly Pr-doped SrTiO3 Ceramics and Their Thermoelectric Properties

PubMed Central

Mehdizadeh Dehkordi, Arash; Bhattacharya, Sriparna; Darroudi, Taghi; Zeng, Xiaoyu; Alshareef, Husam N.; Tritt, Terry M.

2015-01-01

We demonstrate a novel synthesis strategy for the preparation of Pr-doped SrTiO3 ceramics via a combination of solid state reaction and spark plasma sintering techniques. Polycrystalline ceramics possessing a unique morphology can be achieved by optimizing the process parameters, particularly spark plasma sintering heating rate. The phase and morphology of the synthesized ceramics were investigated in detail using X-ray diffraction, scanning electron microcopy and energy-dispersive X-ray spectroscopy. It was observed that the grains of these bulk Pr-doped SrTiO3 ceramics were enhanced with Pr-rich grain boundaries. Electronic and thermal transport properties were also investigated as a function of temperature and doping concentration. Such a microstructure was found to give rise to improved thermoelectric properties. Specifically, it resulted in a significant improvement in carrier mobility and the thermoelectric power factor. Simultaneously, it also led to a marked reduction in the thermal conductivity. As a result, a significant improvement (> 30%) in the thermoelectric figure of merit was achieved for the whole temperature range over all previously reported maximum values for SrTiO3-based ceramics. This synthesis demonstrates the steps for the preparation of bulk polycrystalline ceramics of non-uniformly Pr-doped SrTiO3. PMID:26327483

One-step microwave-assisted synthesis of water-dispersible Fe3O4 magnetic nanoclusters for hyperthermia applications

NASA Astrophysics Data System (ADS)

Sathya, Ayyappan; Kalyani, S.; Ranoo, Surojit; Philip, John

2017-10-01

To realize magnetic hyperthermia as an alternate stand-alone therapeutic procedure for cancer treatment, magnetic nanoparticles with optimal performance, within the biologically safe limits, are to be produced using simple, reproducible and scalable techniques. Herein, we present a simple, one-step approach for synthesis of water-dispersible magnetic nanoclusters (MNCs) of superparamagnetic iron oxide by reducing of Fe2(SO4)3 in sodium acetate (alkali), poly ethylene glycol (capping ligand), and ethylene glycol (solvent and reductant) in a microwave reactor. The average size and saturation magnetization of the MNC's are tuned from 27 to 52 nm and 32 to 58 emu/g by increasing the reaction time from 10 to 600 s. Transmission electron microscopy images reveal that each MNC composed of large number of primary Fe3O4 nanoparticles. The synthesised MNCs show excellent colloidal stability in aqueous phase due to the adsorbed PEG layer. The highest SAR value of 215 ± 10 W/gFe observed in 52 nm size MNC at a frequency of 126 kHz and field of 63 kA/m suggest the potential use of these MNC in hyperthermia applications. This study further opens up the possibilities to develop metal ion-doped MNCs with tunable sizes suitable for various biomedical applications using microwave assisted synthesis.

Synthesis of Non-uniformly Pr-doped SrTiO3 Ceramics and Their Thermoelectric Properties.

PubMed

Mehdizadeh Dehkordi, Arash; Bhattacharya, Sriparna; Darroudi, Taghi; Zeng, Xiaoyu; Alshareef, Husam N; Tritt, Terry M

2015-08-15

We demonstrate a novel synthesis strategy for the preparation of Pr-doped SrTiO3 ceramics via a combination of solid state reaction and spark plasma sintering techniques. Polycrystalline ceramics possessing a unique morphology can be achieved by optimizing the process parameters, particularly spark plasma sintering heating rate. The phase and morphology of the synthesized ceramics were investigated in detail using X-ray diffraction, scanning electron microcopy and energy-dispersive X-ray spectroscopy. It was observed that the grains of these bulk Pr-doped SrTiO3 ceramics were enhanced with Pr-rich grain boundaries. Electronic and thermal transport properties were also investigated as a function of temperature and doping concentration. Such a microstructure was found to give rise to improved thermoelectric properties. Specifically, it resulted in a significant improvement in carrier mobility and the thermoelectric power factor. Simultaneously, it also led to a marked reduction in the thermal conductivity. As a result, a significant improvement (> 30%) in the thermoelectric figure of merit was achieved for the whole temperature range over all previously reported maximum values for SrTiO3-based ceramics. This synthesis demonstrates the steps for the preparation of bulk polycrystalline ceramics of non-uniformly Pr-doped SrTiO3.

Effect of reaction solvent on hydroxyapatite synthesis in sol-gel process

NASA Astrophysics Data System (ADS)

Nazeer, Muhammad Anwaar; Yilgor, Emel; Yagci, Mustafa Baris; Unal, Ugur; Yilgor, Iskender

2017-12-01

Synthesis of hydroxyapatite (HA) through sol-gel process in different solvent systems is reported. Calcium nitrate tetrahydrate (CNTH) and diammonium hydrogen phosphate (DAHP) were used as calcium and phosphorus precursors, respectively. Three different synthesis reactions were carried out by changing the solvent media, while keeping all other process parameters constant. A measure of 0.5 M aqueous DAHP solution was used in all reactions while CNTH was dissolved in distilled water, tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) at a concentration of 0.5 M. Ammonia solution (28-30%) was used to maintain the pH of the reaction mixtures in the 10-12 range. All reactions were carried out at 40 ± 2°C for 4 h. Upon completion of the reactions, products were filtered, washed and calcined at 500°C for 2 h. It was clearly demonstrated through various techniques that the dielectric constant and polarity of the solvent mixture strongly influence the chemical structure and morphological properties of calcium phosphate synthesized. Water-based reaction medium, with highest dielectric constant, mainly produced β-calcium pyrophosphate (β-CPF) with a minor amount of HA. DMF/water system yielded HA as the major phase with a very minor amount of β-CPF. THF/water solvent system with the lowest dielectric constant resulted in the formation of pure HA.

A hybrid analog-digital phase-locked loop for frequency mode non-contact scanning probe microscopy.

PubMed

Mehta, M M; Chandrasekhar, V

2014-01-01

Non-contact scanning probe microscopy (SPM) has developed into a powerful technique to image many different properties of samples. The conventional method involves monitoring the amplitude, phase, or frequency of a cantilever oscillating at or near its resonant frequency as it is scanned across the surface of a sample. For high Q factor cantilevers, monitoring the resonant frequency is the preferred method in order to obtain reasonable scan times. This can be done by using a phase-locked-loop (PLL). PLLs can be obtained as commercial integrated circuits, but these do not have the frequency resolution required for SPM. To increase the resolution, all-digital PLLs requiring sophisticated digital signal processors or field programmable gate arrays have also been implemented. We describe here a hybrid analog/digital PLL where most of the components are implemented using discrete analog integrated circuits, but the frequency resolution is provided by a direct digital synthesis chip controlled by a simple peripheral interface controller (PIC) microcontroller. The PLL has excellent frequency resolution and noise, and can be controlled and read by a computer via a universal serial bus connection.

A hybrid analog-digital phase-locked loop for frequency mode non-contact scanning probe microscopy

NASA Astrophysics Data System (ADS)

Mehta, M. M.; Chandrasekhar, V.

2014-01-01

Non-contact scanning probe microscopy (SPM) has developed into a powerful technique to image many different properties of samples. The conventional method involves monitoring the amplitude, phase, or frequency of a cantilever oscillating at or near its resonant frequency as it is scanned across the surface of a sample. For high Q factor cantilevers, monitoring the resonant frequency is the preferred method in order to obtain reasonable scan times. This can be done by using a phase-locked-loop (PLL). PLLs can be obtained as commercial integrated circuits, but these do not have the frequency resolution required for SPM. To increase the resolution, all-digital PLLs requiring sophisticated digital signal processors or field programmable gate arrays have also been implemented. We describe here a hybrid analog/digital PLL where most of the components are implemented using discrete analog integrated circuits, but the frequency resolution is provided by a direct digital synthesis chip controlled by a simple peripheral interface controller (PIC) microcontroller. The PLL has excellent frequency resolution and noise, and can be controlled and read by a computer via a universal serial bus connection.

Two-dimensional limit of crystalline order in perovskite membrane films

PubMed Central

Hong, Seung Sae; Yu, Jung Ho; Lu, Di; Marshall, Ann F.; Hikita, Yasuyuki; Cui, Yi; Hwang, Harold Y.

2017-01-01

Long-range order and phase transitions in two-dimensional (2D) systems—such as magnetism, superconductivity, and crystallinity—have been important research topics for decades. The issue of 2D crystalline order has reemerged recently, with the development of exfoliated atomic crystals. Understanding the dimensional limit of crystalline phases, with different types of bonding and synthetic techniques, is at the foundation of low-dimensional materials design. We study ultrathin membranes of SrTiO3, an archetypal perovskite oxide with isotropic (3D) bonding. Atomically controlled membranes are released after synthesis by dissolving an underlying epitaxial layer. Although all unreleased films are initially single-crystalline, the SrTiO3 membrane lattice collapses below a critical thickness (5 unit cells). This crossover from algebraic to exponential decay of the crystalline coherence length is analogous to the 2D topological Berezinskii-Kosterlitz-Thouless (BKT) transition. The transition is likely driven by chemical bond breaking at the 2D layer-3D bulk interface, defining an effective dimensional phase boundary for coherent crystalline lattices. PMID:29167822

Effect of microwave-assisted sintering on dielectric properties of CaCu3Ti4O12 ceramic

NASA Astrophysics Data System (ADS)

Rani, Suman; Ahlawat, Neetu; Punia, R.; Kundu, R. S.; Ahlawat, N.

2016-05-01

In this present work, CaCu3Ti4O12 (CCTO) was synthesized by conventional solid-state reaction technique. The synthesis process was carried out in two phases; by conventional process (calcination and sintering at 1080°C for 10 hours) and phase II involves the micro assisted pre sintering of conventionally calcined CCTO for very short soaking time of 30 min at 1080°C in a microwave furnace followed by sintering at 1080°C for 10 hours in conventional furnace. X-ray diffraction (XRD) patterns confirmed the formation of single phase ceramic. Dielectric properties were studied over the frequency range from 50Hz -5MHz at temperatures (273K-343K). It was observed that pre- microwave sintering enhance the dielectric constant values from 10900 to 11893 and respectively reduces the dielectric loss values from 0.49 to 0.34 at room temperature(1 KHz). CCTO ceramics which are found desirable for many technological applications. The effect is more pronounced at low frequencies of applied electric field.

Enhanced power factor of higher manganese silicide via melt spin synthesis method

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

Shi, Xiaoya; Li, Qiang, E-mail: liqiang@bnl.gov; Shi, Xun

We report on the thermoelectric properties of the higher manganese silicide MnSi{sub 1.75} synthesized by means of a one-step non-equilibrium method. The ultrahigh cooling rate generated from the melt-spin technique is found to be effective in reducing second phases, which are inevitable during the traditional solid state diffusion processes. Aside from being detrimental to thermoelectric properties, second phases skew the revealing of the intrinsic properties of this class of materials, for example, the optimal level of carrier concentration. With this melt-spin sample, we are able to formulate a simple model based on a single parabolic band that can well describemore » the carrier concentration dependence of the Seebeck coefficient and power factor of the data reported in the literature. An optimal carrier concentration around 5 × 10{sup 20 }cm{sup −3} at 300 K is predicted according to this model. The phase-pure melt-spin sample shows the largest power factor at high temperature, resulting in the highest zT value among the three samples in this paper.« less

Accurate and agile digital control of optical phase, amplitude and frequency for coherent atomic manipulation of atomic systems.

PubMed

Thom, Joseph; Wilpers, Guido; Riis, Erling; Sinclair, Alastair G

2013-08-12

We demonstrate a system for fast and agile digital control of laser phase, amplitude and frequency for applications in coherent atomic systems. The full versatility of a direct digital synthesis radiofrequency source is faithfully transferred to laser radiation via acousto-optic modulation. Optical beatnotes are used to measure phase steps up to 2π, which are accurately implemented with a resolution of ≤ 10 mrad. By linearizing the optical modulation process, amplitude-shaped pulses of durations ranging from 500 ns to 500 ms, in excellent agreement with the programmed functional form, are demonstrated. Pulse durations are limited only by the 30 ns rise time of the modulation process, and a measured extinction ratio of > 5 × 10(11) is achieved. The system presented here was developed specifically for controlling the quantum state of trapped ions with sequences of multiple laser pulses, including composite and bichromatic pulses. The demonstrated techniques are widely applicable to other atomic systems ranging across quantum information processing, frequency metrology, atom interferometry, and single-photon generation.

Two-dimensional limit of crystalline order in perovskite membrane films

DOE PAGES

Hong, Seung Sae; Yu, Jung Ho; Lu, Di; ...

2017-11-17

Long-range order and phase transitions in two-dimensional (2D) systems—such as magnetism, superconductivity, and crystallinity—have been important research topics for decades. The issue of 2D crystalline order has reemerged recently, with the development of exfoliated atomic crystals. Understanding the dimensional limit of crystalline phases, with different types of bonding and synthetic techniques, is at the foundation of low-dimensional materials design. We study ultrathin membranes of SrTiO 3, an archetypal perovskite oxide with isotropic (3D) bonding. Atomically controlled membranes are released after synthesis by dissolving an underlying epitaxial layer. Although all unreleased films are initially single-crystalline, the SrTiO 3 membrane lattice collapsesmore » below a critical thickness (5 unit cells). This crossover from algebraic to exponential decay of the crystalline coherence length is analogous to the 2D topological Berezinskii-Kosterlitz-Thouless (BKT) transition. Finally, the transition is likely driven by chemical bond breaking at the 2D layer-3D bulk interface, defining an effective dimensional phase boundary for coherent crystalline lattices.« less

Full field gas phase velocity measurements in microgravity

NASA Technical Reports Server (NTRS)

Griffin, Devon W.; Yanis, William

1995-01-01

Measurement of full-field velocities via Particle Imaging Velocimetry (PIV) is common in research efforts involving fluid motion. While such measurements have been successfully performed in the liquid phase in a microgravity environment, gas-phase measurements have been beset by difficulties with seeding and laser strength. A synthesis of techniques developed at NASA LeRC exhibits promise in overcoming these difficulties. Typical implementation of PIV involves forming the light from a pulsed laser into a sheet that is some fraction of a millimeter thick and 50 or more millimeters wide. When a particle enters this sheet during a pulse, light scattered from the particle is recorded by a detector, which may be a film plane or a CCD array. Assuming that the particle remains within the boundaries of the sheet for the second pulse and can be distinguished from neighboring particles, comparison of the two images produces an average velocity vector for the time between the pulses. If the concentration of particles in the sampling volume is sufficiently large but the particles remain discrete, a full field map may be generated.

Synthesis of water soluble glycine capped silver nanoparticles and their surface selective interaction

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

Agasti, Nityananda, E-mail: nnagasti@gmail.com; Singh, Vinay K.; Kaushik, N.K.

Highlights: • Synthesis of water soluble silver nanoparticles at ambient reaction conditions. • Glycine as stabilizing agent for silver nanoparticles. • Surface selective interaction of glycine with silver nanoparticles. • Glycine concentration influences crystalinity and optical property of silver nanoparticles. - Abstract: Synthesis of biocompatible metal nanoparticles has been an area of significant interest because of their wide range of applications. In the present study, we have successfully synthesized water soluble silver nanoparticles assisted by small amino acid glycine. The method is primarily based on reduction of AgNO{sub 3} with NaBH{sub 4} in aqueous solution under atmospheric air in themore » presence of glycine. UV–vis spectroscopy, transmission electron microscopy (TEM), X–ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TG) and differential thermal analysis (DTA) techniques used for characterization of resulting silver nanoparticles demonstrated that, glycine is an effective capping agent to stabilize silver nanoparticles. Surface selective interaction of glycine on (1 1 1) face of silver nanoparticles has been investigated. The optical property and crystalline behavior of silver nanoparticles were found to be sensitive to concentration of glycine. X–ray diffraction studies ascertained the phase specific interaction of glycine on silver nanoparticles. Silver nanoparticles synthesized were of diameter 60 nm. We thus demonstrated an efficient synthetic method for synthesis of water soluble silver nanoparticles capped by amino acid under mild reaction conditions with excellent reproducibility.« less

Synthesis and properties of transition-metal arsenide nanostructures: From superparamagnetism to superconductivity

NASA Astrophysics Data System (ADS)

Desai, Prachi

This dissertation study focuses on developing new protocols for synthesis of nanostructured transition-metal pnictides including superconducting LiFeAs and studying their structure- property relationship. Nanostructured materials are known to differ in properties compared to their bulk counterparts owing to enhanced surface area and increased packing efficiency in devices. Synthetic chemistry skills and nanofabrication techniques like wet chemistry, electrodeposition, solvothermal, hydrothermal and lithography, are extremely useful for creating nanostructures of these functional materials. This is a challenging task simply because maintaining the phase composition same as that of the bulk material along with achieving nanostructures (nanoparticles, nanowires, nanopillars etc.) simultaneously is not easy. Papers I and II showcase novel synthesis methods for E based pnictides [EPn where E = 1st row transition elements and Pn = P, As etc.]. The superparamagnetism of transition-metal pnictides (e.g. FeAs, CoAs) nanomaterials obtained by this method have interesting magnetic features like high blocking temperatures and inter-particle magnetic exchange. Paper III, shows the concept of generalized protocol of EAs synthesis and discusses the principles behind this method. This protocol has been tested for applicability to not only FeAs, but also MnAs, CoAs and CrAs systems. Generalization of this method along with the discovery of superparamagnetic behavior in FeAs is one of the key findings of this research work. Alongside, paper IV shows the formation of Co3O4 nanowires through solid-solid conversion route aided by sacrificial templates.

TiO2 synthesized by microwave assisted solvothermal method: Experimental and theoretical evaluation

NASA Astrophysics Data System (ADS)

Moura, K. F.; Maul, J.; Albuquerque, A. R.; Casali, G. P.; Longo, E.; Keyson, D.; Souza, A. G.; Sambrano, J. R.; Santos, I. M. G.

2014-02-01

In this study, a microwave assisted solvothermal method was used to synthesize TiO2 with anatase structure. The synthesis was done using Ti (IV) isopropoxide and ethanol without templates or alkalinizing agents. Changes in structural features were observed with increasing time of synthesis and evaluated using periodic quantum chemical calculations. The anatase phase was obtained after only 1 min of reaction besides a small amount of brookite phase. Experimental Raman spectra are in accordance with the theoretical one. Micrometric spheres constituted by nanometric particles were obtained for synthesis from 1 to 30 min, while spheres and sticks were observed after 60 min.

Effect of the Polymeric Stabilizer in the Aqueous Phase Fischer-Tropsch Synthesis Catalyzed by Colloidal Cobalt Nanocatalysts

PubMed Central

Delgado, Jorge A.; Claver, Carmen; Castillón, Sergio; Curulla-Ferré, Daniel; Godard, Cyril

2017-01-01

A series of small and well defined cobalt nanoparticles were synthesized by the chemical reduction of cobalt salts in water using NaBH4 as a reducing agent and using various polymeric stabilizers. The obtained nanocatalysts of similar mean diameters (ca. 2.6 nm) were fully characterized and tested in the aqueous phase Fischer-Tropsch Synthesis (AFTS). Interestingly, the nature and structure of the stabilizers used during the synthesis of the CoNPs affected the reduction degree of cobalt and the B-doping of these NPs and consequently, influenced the performance of these nanocatalysts in AFTS. PMID:28336892

Fractional order PIλ controller synthesis for steam turbine speed governing systems.

PubMed

Chen, Kai; Tang, Rongnian; Li, Chuang; Lu, Junguo

2018-06-01

The current state of the art of fractional order stability theory is hardly to build connection between the time domain analysis and frequency domain synthesis. The existing tuning methodologies for fractional order PI λ D μ are not always satisfy the given gain crossover frequency and phase margin simultaneously. To overcome the drawbacks in the existing synthesis of fractional order controller, the synthesis of optimal fractional order PI λ controller for higher-order process is proposed. According to the specified phase margin, the corresponding upper boundary of gain crossover frequency and stability surface in parameter space are obtained. Sweeping the order parameter over λ∈(0,2), the complete set of stabilizing controller which guarantees both pre-specifying phase frequency characteristic can be collected. Whereafter, the optimal fractional order PI λ controller is applied to the speed governing systems of steam turbine generation units. The numerical simulation and hardware-in-the-loop simulation demonstrate the effectiveness and satisfactory closed-loop performance of obtained fractional order PI λ controller. Copyright © 2018 ISA. Published by Elsevier Ltd. All rights reserved.

Role of Plasma Temperature and Residence Time in Stagnation Plasma Synthesis of c-BN Nanopowders

DTIC Science & Technology

2013-01-01

outer diameter of 15mm. A center injection 19 nozzle of 1.4mm diameter is implemented for precursor introduction. Plasma and sheath gas ... Gas Phase Synthesis of Nanoparticles..................................................... 5 2.2 Cubic Boron Nitride Synthesis...11 2.2.4 Effects of gas composition ............................................................................................ 11

TiO{sub 2} synthesized by microwave assisted solvothermal method: Experimental and theoretical evaluation

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

Moura, K.F.; Maul, J.; Albuquerque, A.R.

2014-02-15

In this study, a microwave assisted solvothermal method was used to synthesize TiO{sub 2} with anatase structure. The synthesis was done using Ti (IV) isopropoxide and ethanol without templates or alkalinizing agents. Changes in structural features were observed with increasing time of synthesis and evaluated using periodic quantum chemical calculations. The anatase phase was obtained after only 1 min of reaction besides a small amount of brookite phase. Experimental Raman spectra are in accordance with the theoretical one. Micrometric spheres constituted by nanometric particles were obtained for synthesis from 1 to 30 min, while spheres and sticks were observed aftermore » 60 min. - Graphical abstract: FE-SEM images of anatase obtained with different periods of synthesis associated with the order–disorder degree. Display Omitted - Highlights: • Anatase microspheres were obtained by the microwave assisted hydrothermal method. • Only ethanol and titanium isopropoxide were used as precursors during the synthesis. • Raman spectra and XRD patterns were compared with quantum chemical calculations. • Time of synthesis increased the short-range disorder in one direction and decreased in another.« less

An exploratory study on the driving method of speech synthesis based on the human eye reading imaging data

NASA Astrophysics Data System (ADS)

Gao, Pei-pei; Liu, Feng

2016-10-01

With the development of information technology and artificial intelligence, speech synthesis plays a significant role in the fields of Human-Computer Interaction Techniques. However, the main problem of current speech synthesis techniques is lacking of naturalness and expressiveness so that it is not yet close to the standard of natural language. Another problem is that the human-computer interaction based on the speech synthesis is too monotonous to realize mechanism of user subjective drive. This thesis introduces the historical development of speech synthesis and summarizes the general process of this technique. It is pointed out that prosody generation module is an important part in the process of speech synthesis. On the basis of further research, using eye activity rules when reading to control and drive prosody generation was introduced as a new human-computer interaction method to enrich the synthetic form. In this article, the present situation of speech synthesis technology is reviewed in detail. Based on the premise of eye gaze data extraction, using eye movement signal in real-time driving, a speech synthesis method which can express the real speech rhythm of the speaker is proposed. That is, when reader is watching corpora with its eyes in silent reading, capture the reading information such as the eye gaze duration per prosodic unit, and establish a hierarchical prosodic pattern of duration model to determine the duration parameters of synthesized speech. At last, after the analysis, the feasibility of the above method is verified.

Natural Product Total Synthesis in the Organic Laboratory: Total Synthesis of Caffeic Acid Phenethyl Ester (CAPE), a Potent 5-Lipoxygenase Inhibitor from Honeybee Hives

ERIC Educational Resources Information Center

Touaibia, Mohamed; Guay, Michel

2011-01-01

Natural products play a critical role in modern organic synthesis and learning synthetic techniques is an important component of the organic laboratory experience. In addition to traditional one-step organic synthesis laboratories, a multistep natural product synthesis is an interesting experiment to challenge students. The proposed three-step…

Microwave-assisted solid phase conversion study of Meldrum's acid to ethylenetetracarboxylic dianhydride (C 6O 6)

NASA Astrophysics Data System (ADS)

Taherpour, Avat (Arman)

2010-01-01

Utilization of microwave irradiation provides an effective method for fast synthesizing of some important compounds. Microwave-assisted solid phase is an especial class in chemical synthesis. By the use of MW-irradiation on chemicals, sometimes interesting results can be seen. The synthesis of the interesting molecule ethylenetetracarboxylic dianhydride (C 6O 6) was attempted with a few different methods. In this study, the microwave-assisted solid phase conversion of Meldrum's acid to ethylenetetracarboxylic dianhydride was reported. This conversion was characterized by FT-IR, GC/MS and NMR spectroscopy results.

Carbon and Hydrogen Isotope Measurements of Alcohols and Organic Acids by Online Pyroprobe-GC-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.

2012-01-01

The detection of methane in the atmosphere of Mars, combined with evidence showing widespread water-rock interaction during martian history, suggests that the production of methane on Mars may be the result of mineral surface-catalyzed CO2 and or CO reduction during Fisher-Tropsch Type (FTT) reactions. A better understanding of these reaction pathways and corresponding C and H isotope fractionations is critical to deciphering the synthesis of organic compounds produced under abiotic hydrothermal conditions. Described here is a technique for the extraction and analysis of both C and H isotopes from alcohols (C1-C4) and organic acids (C1-C6). This work is meant to provide a "proof of concept" for making meaningful isotope measurements on complex mixtures of solid-phase hydrocarbons and other intermediary products produced during high-temperature and high-pressure synthesis on mineral-catalyzed surfaces. These analyses are conducted entirely "on-line" utilizing a CDS model 5000 Pyroprobe connected to a Thermo Trace GC Ultra that is interfaced with a Thermo MAT 253 isotope ratio mass spectrometer operating in continuous flow mode. Also, this technique is designed to carry a split of the GC-separated product to a DSQ II quadrupole mass spectrometer as a means of making semi-quantitative compositional measurements. Therefore, both chemical and isotopic measurements can be carried out on the same sample.

Enhanced oxidation stability of quasi core-shell alloyed CdSeS quantum dots prepared through aqueous microwave synthesis technique.

PubMed

Zhan, Hong-Ju; Zhou, Pei-Jiang; Ma, Rong; Liu, Xi-Jing; He, Yu-Ning; Zhou, Chuan-Yun

2014-01-01

Quasi core shell alloyed CdSeS quantum dots (QDs) have been prepared through a facile aqueous-phase route employing microwave irradiation technique. The optical spectroscopy and structure characterization evidenced the quasi core shell alloyed structures of CdSeS QDs. The X-ray diffraction patterns of the obtained CdSeS QDs displayed peak positions very close to those of bulk cubic CdS crystal structures and the result of X-ray photoelectron spectroscopy data re-confirmed the thick CdS shell on the CdSe core. The TEM images and HRTEM images of the CdSeS QDs ascertained the well-defined spherical particles and a relatively narrow size distribution. On the basis, the stability of the obtained QDs in an oxidative environment was also discussed using etching reaction by H2O2. The experiments result showed the as-prepared QDs present high tolerance towards H2O2, obviously superior to the commonly used CdTe QDs and core-shell CdTe/CdS QDs, which was attributed to the unique quasi core-shell CdSeS crystal structure and the small lattice mismatch between CdSe and CdS semiconductor materials. This assay provided insight to obtain high stable crystal structured semiconductor nanocrystals in the design and synthesis process.

A comparative structural study of wet and dried ettringite

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

Renaudin, G.; CNRS, UMR 6002, LMI, F-63177 Aubiere; Filinchuk, Y.

2010-03-15

Two different techniques were used to compare structural characteristics of 'wet' ettringite (stored in the synthesis mother liquid) and 'dried' ettringite (dried to 35% relative humidity over saturated CaCl{sub 2} solution). Lattice parameters and the water content in the channel region of the structure (site occupancy factor of the water molecule not bonded to cations) as well as microstructure parameters (size and strain) were determined from a Rietveld refinement on synchrotron powder diffraction data. Local environment of sulphate anions and of the hydrogen bonding network was characterized by Raman spectroscopy. Both techniques led to the same conclusion: the 'wet' ettringitemore » sample immersed in the mother solution from the synthesis presents similar structural features as ettringite dried to 35% relative humidity. An increase of the a lattice parameter combined with a decrease of the c lattice parameter occurs on drying. The amount of structural water, the point symmetry of sulphate and the hydrogen bond network are unchanged when passing from the wet to the dried ettringite powder. Ettringite does not form a high-hydrate polymorph in equilibrium with alkaline solution, in contrast to the AFm phases that lose water molecules on drying. According to these results we conclude that ettringite precipitated in aqueous solution at the early hydration stages is of the same chemical composition as ettringite present in the hardening concrete.« less