Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

PubMed Central

Popolan-Vaida, Denisia M.; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah Y.; Wang, Heng; Sioud, Salim; Raji, Misjudeen A.; Kohse-Höinghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R.

2017-01-01

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels. PMID:29183984

A wearable fingernail chemical sensing platform: pH sensing at your fingertips.

PubMed

Kim, Jayoung; Cho, Thomas N; Valdés-Ramírez, Gabriela; Wang, Joseph

2016-04-01

This article demonstrates an example of a wearable chemical sensor based on a fingernail platform. Fingernails represent an attractive wearable platform, merging beauty products with chemical sensing, to enable monitoring of our surrounding environment. The new colorimetric pH fingernail sensor relies on coating artificial nails with a recognition layer consisted of pH indicators entrapped in a polyvinyl chloride (PVC) matrix. Such color changing fingernails offer fast and reversible response to pH changes, repeated use, and intense color change detected easily with naked eye. The PVC matrix prevents leaching out of the indicator molecules from the fingernail sensor toward such repeated use. The limited narrow working pH range of a single pH indicator has been addressed by multiplexing three different pH indicators: bromothymol blue (pH 6.0-7.6), bromocresol green (pH 3.8-5.4), and cresol red (pH 7.2-8.8), as demonstrated for analyses of real-life samples of acidic, neutral, and basic character. The new concept of an optical wearable chemical sensor on fingernail platforms can be expanded towards diverse analytes for various applications in connection to the judicious design of the recognition layer. Copyright © 2016 Elsevier B.V. All rights reserved.

Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling.

PubMed

Hoyermann, Karlheinz; Mauß, Fabian; Olzmann, Matthias; Welz, Oliver; Zeuch, Thomas

2017-07-19

Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity. Their reactivity is central to our understanding of how volatile organic compounds are degraded in the atmosphere and converted into secondary organic aerosol. Moreover, they sensitively determine ignition timing in internal combustion engines. The intention of this perspective article is to provide the reader with information about the general mechanisms of reactions initiated by addition of atomic and molecular oxygen to alkyl radicals and ozone to alkenes. We will focus on critical branching points in the subsequent reaction mechanisms and discuss them from a consistent point of view. As a first example of our integrated approach, we will show how experiment, theory, and kinetic modeling have been successfully combined in the first infrared detection of Criegee intermediates during the gas phase ozonolysis. As a second example, we will examine the ignition timing of n-heptane/air mixtures at low and intermediate temperatures. Here, we present a reduced, fuel size independent kinetic model of the complex chemistry initiated by peroxy radicals that has been successfully applied to simulate standard n-heptane combustion experiments.

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds.

PubMed

Wang, Zhandong; Popolan-Vaida, Denisia M; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah Y; Wang, Heng; Sioud, Salim; Raji, Misjudeen A; Kohse-Höinghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R; Sarathy, S Mani

2017-12-12

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500-600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound's molecular structure ( n -alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels. Copyright © 2017 the Author(s). Published by PNAS.

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

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

Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability ofmore » liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. In conclusion, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.« less

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

DOE PAGES

Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie; ...

2017-11-28

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability ofmore » liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. In conclusion, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.« less

The Microphenotron: a robotic miniaturized plant phenotyping platform with diverse applications in chemical biology.

PubMed

Burrell, Thomas; Fozard, Susan; Holroyd, Geoff H; French, Andrew P; Pound, Michael P; Bigley, Christopher J; James Taylor, C; Forde, Brian G

2017-01-01

Chemical genetics provides a powerful alternative to conventional genetics for understanding gene function. However, its application to plants has been limited by the lack of a technology that allows detailed phenotyping of whole-seedling development in the context of a high-throughput chemical screen. We have therefore sought to develop an automated micro-phenotyping platform that would allow both root and shoot development to be monitored under conditions where the phenotypic effects of large numbers of small molecules can be assessed. The 'Microphenotron' platform uses 96-well microtitre plates to deliver chemical treatments to seedlings of Arabidopsis thaliana L. and is based around four components: (a) the 'Phytostrip', a novel seedling growth device that enables chemical treatments to be combined with the automated capture of images of developing roots and shoots; (b) an illuminated robotic platform that uses a commercially available robotic manipulator to capture images of developing shoots and roots; (c) software to control the sequence of robotic movements and integrate these with the image capture process; (d) purpose-made image analysis software for automated extraction of quantitative phenotypic data. Imaging of each plate (representing 80 separate assays) takes 4 min and can easily be performed daily for time-course studies. As currently configured, the Microphenotron has a capacity of 54 microtitre plates in a growth room footprint of 2.1 m 2 , giving a potential throughput of up to 4320 chemical treatments in a typical 10 days experiment. The Microphenotron has been validated by using it to screen a collection of 800 natural compounds for qualitative effects on root development and to perform a quantitative analysis of the effects of a range of concentrations of nitrate and ammonium on seedling development. The Microphenotron is an automated screening platform that for the first time is able to combine large numbers of individual chemical

Managing the computational chemistry big data problem: the ioChem-BD platform.

PubMed

Álvarez-Moreno, M; de Graaf, C; López, N; Maseras, F; Poblet, J M; Bo, C

2015-01-26

We present the ioChem-BD platform ( www.iochem-bd.org ) as a multiheaded tool aimed to manage large volumes of quantum chemistry results from a diverse group of already common simulation packages. The platform has an extensible structure. The key modules managing the main tasks are to (i) upload of output files from common computational chemistry packages, (ii) extract meaningful data from the results, and (iii) generate output summaries in user-friendly formats. A heavy use of the Chemical Mark-up Language (CML) is made in the intermediate files used by ioChem-BD. From them and using XSL techniques, we manipulate and transform such chemical data sets to fulfill researchers' needs in the form of HTML5 reports, supporting information, and other research media.

Nitrous oxide production from reactive nitrification intermediates: a concerted action of biological and chemical processes

NASA Astrophysics Data System (ADS)

Brüggemann, Nicolas; Heil, Jannis; Liu, Shurong; Wei, Jing; Vereecken, Harry

2017-04-01

This contribution tries to open up a new perspective on biogeochemical N2O production processes, taking the term bio-geo-chemistry literally. What if a major part of N2O is produced from reactive intermediates of microbiological N turnover processes ("bio…") leaking out of the involved microorganisms into the soil ("…geo…") and then reacting chemically ("…chemistry") with the surrounding matrix? There are at least two major reactive N intermediates that might play a significant role in these coupled biological-chemical reactions, i.e. hydroxylamine (NH2OH) and nitrite (NO2-), both of which are produced during nitrification under oxic conditions, while NO2- is also produced during denitrification under anoxic conditions. Furthermore, NH2OH is assumed to be also a potential intermediate of DNRA and/or anammox. First, this contribution will summarize information about several chemical reactions involving NH2OH and NO2- leading to the formation of N2O. These abiotic reactions are: reactions of NO2- with reduced metal cations, nitrosation reactions of NO2- and soil organic matter (SOM), the reaction between NO2- and NH2OH, and the oxidation of NH2OH by oxidized metal ions. While these reactions can occur over a broad range of soil characteristics, they are ignored in most current N trace gas studies in favor of biological processes only. Disentangling microbiological from purely chemical N2O production is further complicated by the fact that the chemically formed N2O is either undiscernible from N2O produced during nitrification, or shows an intermediate 15N site preference between that of N2O from nitrification and denitrification, respectively. Results from experiments with live and sterilized soil samples, with artificial soil mixtures and with phenolic lignin decomposition model compounds will be presented that demonstrate the potential contribution of these abiotic processes to soil N trace gas emissions, given a substantial leakage rate of these reactive

Use of a biosynthetic intermediate to explore the chemical diversity of pseudo-natural fungal polyketides.

PubMed

Asai, Teigo; Tsukada, Kento; Ise, Satomi; Shirata, Naoki; Hashimoto, Makoto; Fujii, Isao; Gomi, Katsuya; Nakagawara, Kosuke; Kodama, Eiichi N; Oshima, Yoshiteru

2015-09-01

The structural complexity and diversity of natural products make them attractive sources for potential drug discovery, with their characteristics being derived from the multi-step combination of enzymatic and non-enzymatic conversions of intermediates in each biosynthetic pathway. Intermediates that exhibit multipotent behaviour have great potential for use as starting points in diversity-oriented synthesis. Inspired by the biosynthetic pathways that form complex metabolites from simple intermediates, we developed a semi-synthetic process that combines heterologous biosynthesis and artificial diversification. The heterologous biosynthesis of fungal polyketide intermediates led to the isolation of novel oligomers and provided evidence for ortho-quinonemethide equivalency in their isochromene form. The intrinsic reactivity of the isochromene polyketide enabled us to access various new chemical entities by modifying and remodelling the polyketide core and through coupling with indole molecules. We thus succeeded in generating exceptionally diverse pseudo-natural polyketides through this process and demonstrated an advanced method of using biosynthetic intermediates.

Use of a biosynthetic intermediate to explore the chemical diversity of pseudo-natural fungal polyketides

NASA Astrophysics Data System (ADS)

Asai, Teigo; Tsukada, Kento; Ise, Satomi; Shirata, Naoki; Hashimoto, Makoto; Fujii, Isao; Gomi, Katsuya; Nakagawara, Kosuke; Kodama, Eiichi N.; Oshima, Yoshiteru

2015-09-01

The structural complexity and diversity of natural products make them attractive sources for potential drug discovery, with their characteristics being derived from the multi-step combination of enzymatic and non-enzymatic conversions of intermediates in each biosynthetic pathway. Intermediates that exhibit multipotent behaviour have great potential for use as starting points in diversity-oriented synthesis. Inspired by the biosynthetic pathways that form complex metabolites from simple intermediates, we developed a semi-synthetic process that combines heterologous biosynthesis and artificial diversification. The heterologous biosynthesis of fungal polyketide intermediates led to the isolation of novel oligomers and provided evidence for ortho-quinonemethide equivalency in their isochromene form. The intrinsic reactivity of the isochromene polyketide enabled us to access various new chemical entities by modifying and remodelling the polyketide core and through coupling with indole molecules. We thus succeeded in generating exceptionally diverse pseudo-natural polyketides through this process and demonstrated an advanced method of using biosynthetic intermediates.

Structurally Integrated Photoluminescent Chemical and Biological Sensors: An Organic Light-Emitting Diode-Based Platform

NASA Astrophysics Data System (ADS)

Shinar, J.; Shinar, R.

The chapter describes the development, advantages, challenges, and potential of an emerging, compact photoluminescence-based sensing platform for chemical and biological analytes, including multiple analytes. In this platform, the excitation source is an array of organic light-emitting device (OLED) pixels that is structurally integrated with the sensing component. Steps towards advanced integration with additionally a thin-film-based photodetector are also described. The performance of the OLED-based sensing platform is examined for gas-phase and dissolved oxygen, glucose, lactate, ethanol, hydrazine, and anthrax lethal factor.

Renewable platform chemicals from directional microwave-assisted liquefaction coupling stepwise extraction of waste biomass.

PubMed

Feng, Junfeng; Hse, Chungyun; Yang, Zhongzhi; Wang, Kui; Jiang, Jianchun; Xu, Junming

2017-11-01

Directional microwave-assisted liquefaction and stepwise extraction are introduced for producing platform chemicals: aromatics and monosaccharides. When sulfuric acid was used as a catalyst, a 45% monosaccharides yield and a 29% aromatics yield were obtained from bamboo with 0.3g catalyst per 18g methanol and 2g bamboo at 160°C with 10min. Approximately 78-86wt% of the six biomass materials were converted into liquid products. After the stepwise extraction and precipitation process, the yields of monosaccharide derivatives and three phenolic compound fractions were 39-45% and 28-32%, respectively. Monosaccharides from holocellulose collected with a high purity of methyl glycosides were higher than 90%. Aromatic derivatives with different weight-molecular distributions were separated into three fractions with more than 80% phenolics. As their similar chemical properties within each fraction, platform chemicals have great commercial potential for producing high-quality chemicals and biofuels using mild upgrading conditions. Copyright © 2017. Published by Elsevier Ltd.

Toward the realization of a compact chemical sensor platform using quantum cascade lasers

NASA Astrophysics Data System (ADS)

Holthoff, Ellen L.; Marcus, Logan S.; Pellegrino, Paul M.

2015-05-01

The Army is investigating several spectroscopic techniques (e.g., infrared spectroscopy) that could allow for an adaptable sensor platform. Traditionally, chemical sensing platforms have been hampered by the opposing concerns of increasing sensor capability while maintaining a minimal package size. Current sensors, although reasonably sized, are geared to more classical chemical threats, and the ability to expand their capabilities to a broader range of emerging threats is uncertain. Recently, photoacoustic spectroscopy, employed in a sensor format, has shown enormous potential to address these ever-changing threats, while maintaining a compact sensor design. In order to realize the advantage of photoacoustic sensor miniaturization, light sources of comparable size are required. Recent research has employed quantum cascade lasers (QCLs) in combination with MEMS-scale photoacoustic cell designs. The continuous tuning capability of QCLs over a broad wavelength range in the mid-infrared spectral region greatly expands the number of compounds that can be identified. Results have demonstrated that utilizing a tunable QCL with a MEMS-scale photoacoustic cell produces favorable detection limits (ppb levels) for chemical targets (e.g., dimethyl methyl phosphonate (DMMP), vinyl acetate, 1,4-dioxane). Although our chemical sensing research has benefitted from the broad tuning capabilities of QCLs, the limitations of these sources must be considered. Current commercially available tunable systems are still expensive and obviously geared more toward laboratory operation, not fielding. Although the laser element itself is quite small, the packaging, power supply, and controller remain logistical burdens. Additionally, operational features such as continuous wave (CW) modulation and laser output powers while maintaining wide tunability are not yet ideal for a variety of sensing applications. In this paper, we will discuss our continuing evaluation of QCL technology as it matures

Glutamate Induced Thermal Equilibrium Intermediate and Counteracting Effect on Chemical Denaturation of Proteins.

PubMed

Anumalla, Bramhini; Prabhu, N Prakash

2018-01-25

When organisms are subjected to stress conditions, one of their adaptive responses is accumulation of small organic molecules called osmolytes. These osmolytes affect the structure and stability of the biological macromolecules including proteins. The present study examines the effect of a negatively charged amino acid osmolyte, glutamate (Glu), on two model proteins, ribonuclease A (RNase A) and α-lactalbumin (α-LA), which have positive and negative surface charges at pH 7, respectively. These proteins follow two-state unfolding transitions during both heat and chemical induced denaturation processes. The addition of Glu stabilizes the proteins against temperature and induces an early equilibrium intermediate during unfolding. The stability is found to be enthalpy-driven, and the free energy of stabilization is more for α-LA compared to RNase A. The decrease in the partial molar volume and compressibility of both of the proteins in the presence of Glu suggests that the proteins attain a more compact state through surface hydration which could provide a more stable conformation. This is also supported by molecule dynamic simulation studies which demonstrate that the water density around the proteins is increased upon the addition of Glu. Further, the intermediates could be completely destabilized by lower concentrations (∼0.5 M) of guanidinium chloride and salt. However, urea subverts the Glu-induced intermediate formed by α-LA, whereas it only slightly destabilizes in the case of RNase A which has a positive surface charge and could possess charge-charge interactions with Glu. This suggests that, apart from hydration, columbic interactions might also contribute to the stability of the intermediate. Gdm-induced denaturation of RNase A and α-LA in the absence and the presence of Glu at different temperatures was carried out. These results also show the Glu-induced stabilization of both of the proteins; however, all of the unfolding transitions followed two

Waveguide infrared spectrometer platform for point and standoff chemical sensing

NASA Astrophysics Data System (ADS)

Chadha, Suneet; Henning, Pat; Landers, Frank; Weling, Ani

2004-03-01

Advanced autonomous detection of chemical warfare agents and toxic industrial chemicals has long been a major military concern. At present, our capability to rapidly assess the immediate environment is severely limited and our domestic infrastructure is burdened by the meticulous procedures required to rule out false threats. While significant advances have recently been accomplished in remote spectral sensing using rugged FTIRs and point detectors, efforts towards low cost chemical discrimination have been lacking. Foster-Miller has developed a unique waveguide spectrometer which is a paradigm shift from the conventional FTIR approach. The spectrometer provides spectral discrimination over the 3-14 μm range and will be the spectrometer platform for both active and passive detection. Foster-Miller has leveraged its innovations in infrared fiber-optic probes and the recent development of a waveguide spectrometer to build a novel infrared sensor platform for both point and stand-off chemical sensing. A monolithic wedge-grating optic provides the spectral dispersion with low cost thermopile point or array detectors picking off the diffracted wavelengths from the optic. The integrated optic provides spectral discrimination between 3-12 μm with resolution at 16 cm-1 or better and overall optical throughput approaching 35%. The device has a fixed cylindrical grating bonded to the edge of a ZnSe conditioning "wedge". The conditioning optic overcomes limitations of concave gratings as it accepts high angle (large FOV) light at the narrow end of the wedge and progressively conditions it to be near normal to the grating. On return, the diffracted wavelengths are concentrated on the discrete or array detector (pixel) elements by the wedge, providing throughput comparable to that of an FTIR. The waveguide spectrometer coupled to ATR probes, flow through liquid cells or multipass gas cells provides significant cost advantage over conventional sampling methodologies. We will

Lab-on-a-Disc Platform for Automated Chemical Cell Lysis.

PubMed

Seo, Moo-Jung; Yoo, Jae-Chern

2018-02-26

Chemical cell lysis is an interesting topic in the research to Lab-on-a-Disc (LOD) platforms on account of its perfect compatibility with the centrifugal spin column format. However, standard procedures followed in chemical cell lysis require sophisticated non-contact temperature control as well as the use of pressure resistant valves. These requirements pose a significant challenge thereby making the automation of chemical cell lysis on an LOD extremely difficult to achieve. In this study, an LOD capable of performing fully automated chemical cell lysis is proposed, where a combination of chemical and thermal methods has been used. It comprises a sample inlet, phase change material sheet (PCMS)-based temperature sensor, heating chamber, and pressure resistant valves. The PCMS melts and solidifies at a certain temperature and thus is capable of indicating whether the heating chamber has reached a specific temperature. Compared to conventional cell lysis systems, the proposed system offers advantages of reduced manual labor and a compact structure that can be readily integrated onto an LOD. Experiments using Salmonella typhimurium strains were conducted to confirm the performance of the proposed cell lysis system. The experimental results demonstrate that the proposed system has great potential in realizing chemical cell lysis on an LOD whilst achieving higher throughput in terms of purity and yield of DNA thereby providing a good alternative to conventional cell lysis systems.

NMR Crystallography of a Carbanionic Intermediate in Tryptophan Synthase: Chemical Structure, Tautomerization, and Reaction Specificity.

PubMed

Caulkins, Bethany G; Young, Robert P; Kudla, Ryan A; Yang, Chen; Bittbauer, Thomas J; Bastin, Baback; Hilario, Eduardo; Fan, Li; Marsella, Michael J; Dunn, Michael F; Mueller, Leonard J

2016-11-23

Carbanionic intermediates play a central role in the catalytic transformations of amino acids performed by pyridoxal-5'-phosphate (PLP)-dependent enzymes. Here, we make use of NMR crystallography-the synergistic combination of solid-state nuclear magnetic resonance, X-ray crystallography, and computational chemistry-to interrogate a carbanionic/quinonoid intermediate analogue in the β-subunit active site of the PLP-requiring enzyme tryptophan synthase. The solid-state NMR chemical shifts of the PLP pyridine ring nitrogen and additional sites, coupled with first-principles computational models, allow a detailed model of protonation states for ionizable groups on the cofactor, substrates, and nearby catalytic residues to be established. Most significantly, we find that a deprotonated pyridine nitrogen on PLP precludes formation of a true quinonoid species and that there is an equilibrium between the phenolic and protonated Schiff base tautomeric forms of this intermediate. Natural bond orbital analysis indicates that the latter builds up negative charge at the substrate C α and positive charge at C4' of the cofactor, consistent with its role as the catalytic tautomer. These findings support the hypothesis that the specificity for β-elimination/replacement versus transamination is dictated in part by the protonation states of ionizable groups on PLP and the reacting substrates and underscore the essential role that NMR crystallography can play in characterizing both chemical structure and dynamics within functioning enzyme active sites.

NMR Crystallography of a Carbanionic Intermediate in Tryptophan Synthase: Chemical Structure, Tautomerization, and Reaction Specificity

PubMed Central

2016-01-01

Carbanionic intermediates play a central role in the catalytic transformations of amino acids performed by pyridoxal-5′-phosphate (PLP)-dependent enzymes. Here, we make use of NMR crystallography—the synergistic combination of solid-state nuclear magnetic resonance, X-ray crystallography, and computational chemistry—to interrogate a carbanionic/quinonoid intermediate analogue in the β-subunit active site of the PLP-requiring enzyme tryptophan synthase. The solid-state NMR chemical shifts of the PLP pyridine ring nitrogen and additional sites, coupled with first-principles computational models, allow a detailed model of protonation states for ionizable groups on the cofactor, substrates, and nearby catalytic residues to be established. Most significantly, we find that a deprotonated pyridine nitrogen on PLP precludes formation of a true quinonoid species and that there is an equilibrium between the phenolic and protonated Schiff base tautomeric forms of this intermediate. Natural bond orbital analysis indicates that the latter builds up negative charge at the substrate Cα and positive charge at C4′ of the cofactor, consistent with its role as the catalytic tautomer. These findings support the hypothesis that the specificity for β-elimination/replacement versus transamination is dictated in part by the protonation states of ionizable groups on PLP and the reacting substrates and underscore the essential role that NMR crystallography can play in characterizing both chemical structure and dynamics within functioning enzyme active sites. PMID:27779384

Cohort profile: the maternal-infant research on environmental chemicals research platform.

PubMed

Arbuckle, Tye E; Fraser, William D; Fisher, Mandy; Davis, Karelyn; Liang, Chun Lei; Lupien, Nicole; Bastien, Stéphanie; Velez, Maria P; von Dadelszen, Peter; Hemmings, Denise G; Wang, Jingwei; Helewa, Michael; Taback, Shayne; Sermer, Mathew; Foster, Warren; Ross, Greg; Fredette, Paul; Smith, Graeme; Walker, Mark; Shear, Roberta; Dodds, Linda; Ettinger, Adrienne S; Weber, Jean-Philippe; D'Amour, Monique; Legrand, Melissa; Kumarathasan, Premkumari; Vincent, Renaud; Luo, Zhong-Cheng; Platt, Robert W; Mitchell, Grant; Hidiroglou, Nick; Cockell, Kevin; Villeneuve, Maya; Rawn, Dorothea F K; Dabeka, Robert; Cao, Xu-Liang; Becalski, Adam; Ratnayake, Nimal; Bondy, Genevieve; Jin, Xiaolei; Wang, Zhongwen; Tittlemier, Sheryl; Julien, Pierre; Avard, Denise; Weiler, Hope; Leblanc, Alain; Muckle, Gina; Boivin, Michel; Dionne, Ginette; Ayotte, Pierre; Lanphear, Bruce; Séguin, Jean R; Saint-Amour, Dave; Dewailly, Eric; Monnier, Patricia; Koren, Gideon; Ouellet, Emmanuel

2013-07-01

The Maternal-Infant Research on Environmental Chemicals (MIREC) Study was established to obtain Canadian biomonitoring data for pregnant women and their infants, and to examine potential adverse health effects of prenatal exposure to priority environmental chemicals on pregnancy and infant health. Women were recruited during the first trimester from 10 sites across Canada and were followed through delivery. Questionnaires were administered during pregnancy and post-delivery to collect information on demographics, occupation, life style, medical history, environmental exposures and diet. Information on the pregnancy and the infant was abstracted from medical charts. Maternal blood, urine, hair and breast milk, as well as cord blood and infant meconium, were collected and analysed for an extensive list of environmental biomarkers and nutrients. Additional biospecimens were stored in the study's Biobank. The MIREC Research Platform encompasses the main cohort study, the Biobank and follow-up studies. Of the 8716 women approached at early prenatal clinics, 5108 were eligible and 2001 agreed to participate (39%). MIREC participants tended to smoke less (5.9% vs. 10.5%), be older (mean 32.2 vs. 29.4 years) and have a higher education (62.3% vs. 35.1% with a university degree) than women giving birth in Canada. The MIREC Study, while smaller in number of participants than several of the international cohort studies, has one of the most comprehensive datasets on prenatal exposure to multiple environmental chemicals. The biomonitoring data and biological specimen bank will make this research platform a significant resource for examining potential adverse health effects of prenatal exposure to environmental chemicals. © 2013 John Wiley & Sons Ltd and Her Majesty the Queen in Right of Canada. Reproduced with the permission of the Minister of Health.

Oxidase catalysis via aerobically generated hypervalent iodine intermediates

NASA Astrophysics Data System (ADS)

Maity, Asim; Hyun, Sung-Min; Powers, David C.

2018-02-01

The development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

Avogadro: an advanced semantic chemical editor, visualization, and analysis platform

PubMed Central

2012-01-01

Background The Avogadro project has developed an advanced molecule editor and visualizer designed for cross-platform use in computational chemistry, molecular modeling, bioinformatics, materials science, and related areas. It offers flexible, high quality rendering, and a powerful plugin architecture. Typical uses include building molecular structures, formatting input files, and analyzing output of a wide variety of computational chemistry packages. By using the CML file format as its native document type, Avogadro seeks to enhance the semantic accessibility of chemical data types. Results The work presented here details the Avogadro library, which is a framework providing a code library and application programming interface (API) with three-dimensional visualization capabilities; and has direct applications to research and education in the fields of chemistry, physics, materials science, and biology. The Avogadro application provides a rich graphical interface using dynamically loaded plugins through the library itself. The application and library can each be extended by implementing a plugin module in C++ or Python to explore different visualization techniques, build/manipulate molecular structures, and interact with other programs. We describe some example extensions, one which uses a genetic algorithm to find stable crystal structures, and one which interfaces with the PackMol program to create packed, solvated structures for molecular dynamics simulations. The 1.0 release series of Avogadro is the main focus of the results discussed here. Conclusions Avogadro offers a semantic chemical builder and platform for visualization and analysis. For users, it offers an easy-to-use builder, integrated support for downloading from common databases such as PubChem and the Protein Data Bank, extracting chemical data from a wide variety of formats, including computational chemistry output, and native, semantic support for the CML file format. For developers, it can be

Avogadro: an advanced semantic chemical editor, visualization, and analysis platform.

PubMed

Hanwell, Marcus D; Curtis, Donald E; Lonie, David C; Vandermeersch, Tim; Zurek, Eva; Hutchison, Geoffrey R

2012-08-13

The Avogadro project has developed an advanced molecule editor and visualizer designed for cross-platform use in computational chemistry, molecular modeling, bioinformatics, materials science, and related areas. It offers flexible, high quality rendering, and a powerful plugin architecture. Typical uses include building molecular structures, formatting input files, and analyzing output of a wide variety of computational chemistry packages. By using the CML file format as its native document type, Avogadro seeks to enhance the semantic accessibility of chemical data types. The work presented here details the Avogadro library, which is a framework providing a code library and application programming interface (API) with three-dimensional visualization capabilities; and has direct applications to research and education in the fields of chemistry, physics, materials science, and biology. The Avogadro application provides a rich graphical interface using dynamically loaded plugins through the library itself. The application and library can each be extended by implementing a plugin module in C++ or Python to explore different visualization techniques, build/manipulate molecular structures, and interact with other programs. We describe some example extensions, one which uses a genetic algorithm to find stable crystal structures, and one which interfaces with the PackMol program to create packed, solvated structures for molecular dynamics simulations. The 1.0 release series of Avogadro is the main focus of the results discussed here. Avogadro offers a semantic chemical builder and platform for visualization and analysis. For users, it offers an easy-to-use builder, integrated support for downloading from common databases such as PubChem and the Protein Data Bank, extracting chemical data from a wide variety of formats, including computational chemistry output, and native, semantic support for the CML file format. For developers, it can be easily extended via a powerful

No Evidence of Chemical Abundance Variations in the Intermediate-age Cluster NGC 1783

NASA Astrophysics Data System (ADS)

Zhang, Hao; de Grijs, Richard; Li, Chengyuan; Wu, Xiaohan

2018-02-01

We have analyzed multi-passband photometric observations, obtained with the Hubble Space Telescope, of the massive (1.8 × 105 M ⊙), intermediate-age (1.8 Gyr-old) Large Magellanic Cloud star cluster NGC 1783. The morphology of the cluster’s red giant branch does not exhibit a clear broadening beyond its intrinsic width; the observed width is consistent with that owing to photometric uncertainties alone and independent of the photometric selection boundaries we applied to obtain our sample of red giant stars. The color dispersion of the cluster’s red giant stars around the best-fitting ridgeline is 0.062 ± 0.009 mag, which is equivalent to the width of 0.080 ± 0.001 mag derived from artificial simple stellar population tests, that is, tests based on single-age, single-metallicity stellar populations. NGC 1783 is comparably as massive as other star clusters that show clear evidence of multiple stellar populations. After incorporating mass-loss recipes from its current age of 1.8 Gyr to an age of 6 Gyr, NGC 1783 is expected to remain as massive as some other clusters that host clear multiple populations at these intermediate ages. If we were to assume that mass is an important driver of multiple population formation, then NGC 1783 should have exhibited clear evidence of chemical abundance variations. However, our results support the absence of any chemical abundance variations in NGC 1783.

A cell-free testing platform to screen chemicals of potential neurotoxic concern across twenty vertebrate species.

PubMed

Arini, Adeline; Mittal, Krittika; Dornbos, Peter; Head, Jessica; Rutkiewicz, Jennifer; Basu, Niladri

2017-11-01

There is global demand for new in vitro testing tools for ecological risk assessment. The objective of the present study was to apply a set of cell-free neurochemical assays to screen many chemicals across many species in a relatively high-throughput manner. The platform assessed 7 receptors and enzymes that mediate neurotransmission of γ-aminobutyric acid, dopamine, glutamate, and acetylcholine. Each assay was optimized to work across 20 vertebrate species (5 fish, 5 birds, 7 mammalian wildlife, 3 biomedical species including humans). We tested the screening assay platform against 80 chemicals (23 pharmaceuticals and personal care products, 20 metal[loid]s, 22 polycyclic aromatic hydrocarbons and halogenated organic compounds, 15 pesticides). In total, 10 800 species-chemical-assay combinations were tested, and significant differences were found in 4041 cases. All 7 assays were significantly affected by at least one chemical in each species tested. Among the 80 chemicals tested, nearly all resulted in a significant impact on at least one species and one assay. The 5 most active chemicals were prochloraz, HgCl 2 , Sn, benzo[a]pyrene, and vinclozolin. Clustering analyses revealed groupings according to chemicals, species, and chemical-assay combinations. The results show that cell-free assays can screen a large number of samples in a short period of time in a cost-effective manner in a range of animals not easily studied using traditional approaches. Strengths and limitations of this approach are discussed, as well as next steps. Environ Toxicol Chem 2017;36:3081-3090. © 2017 SETAC. © 2017 SETAC.

Smart phones: platform enabling modular, chemical, biological, and explosives sensing

NASA Astrophysics Data System (ADS)

Finch, Amethist S.; Coppock, Matthew; Bickford, Justin R.; Conn, Marvin A.; Proctor, Thomas J.; Stratis-Cullum, Dimitra N.

2013-05-01

Reliable, robust, and portable technologies are needed for the rapid identification and detection of chemical, biological, and explosive (CBE) materials. A key to addressing the persistent threat to U.S. troops in the current war on terror is the rapid detection and identification of the precursor materials used in development of improvised explosive devices, homemade explosives, and bio-warfare agents. However, a universal methodology for detection and prevention of CBE materials in the use of these devices has proven difficult. Herein, we discuss our efforts towards the development of a modular, robust, inexpensive, pervasive, archival, and compact platform (android based smart phone) enabling the rapid detection of these materials.

Developing cellulosic waste products as platform chemicals: protecting group chemistry of α-glucoisosaccharinic acid.

PubMed

Almond, Michael; Suleiman, Mustapha G; Hawkins, Matthew; Winder, Daniel; Robshaw, Thomas; Waddoups, Megan; Humphreys, Paul N; Laws, Andrew P

2018-01-02

Alpha and beta-glucoisosaccharinic acids ((2S,4S)-2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid and (2R,4S)-2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid) which are produced when cellulosic materials are treated with aqueous alkali are potentially valuable platform chemicals. Their highly functionalised carbon skeleton, with fixed chirality at C-2 and C-4, makes them ideal starting materials for use in synthesis. In order to assess the potential of these saccharinic acids as platform chemicals we have explored the protecting group chemistry of the lactone form of alpha-glucoisosaccharinic acid (α-GISAL). We report here the use of single and multiple step reaction pathways leading to the regioselective protection of the three different hydroxyl groups of α-GISAL. We report strategies for protecting the three different hydroxyl groups individually or in pairs. We also report the synthesis of a range of tri-O-protected α-GISAL derivatives where a number of the products contain orthogonal protecting groups. Copyright © 2017 Elsevier Ltd. All rights reserved.

Metabolic engineering of Escherichia coli: a sustainable industrial platform for bio-based chemical production.

PubMed

Chen, Xianzhong; Zhou, Li; Tian, Kangming; Kumar, Ashwani; Singh, Suren; Prior, Bernard A; Wang, Zhengxiang

2013-12-01

In order to decrease carbon emissions and negative environmental impacts of various pollutants, more bulk and/or fine chemicals are produced by bioprocesses, replacing the traditional energy and fossil based intensive route. The Gram-negative rod-shaped bacterium, Escherichia coli has been studied extensively on a fundamental and applied level and has become a predominant host microorganism for industrial applications. Furthermore, metabolic engineering of E. coli for the enhanced biochemical production has been significantly promoted by the integrated use of recent developments in systems biology, synthetic biology and evolutionary engineering. In this review, we focus on recent efforts devoted to the use of genetically engineered E. coli as a sustainable platform for the production of industrially important biochemicals such as biofuels, organic acids, amino acids, sugar alcohols and biopolymers. In addition, representative secondary metabolites produced by E. coli will be systematically discussed and the successful strategies for strain improvements will be highlighted. Moreover, this review presents guidelines for future developments in the bio-based chemical production using E. coli as an industrial platform. Copyright © 2013 Elsevier Inc. All rights reserved.

Renewable platform chemicals from directional microwave-assisted liquefaction coupling stepwise extraction of waste biomass

Treesearch

Junfeng Feng; Chungyun Hse; Zhongzhi Yang; Kui Wang; Jianchun Jiang; Junming Xu

2017-01-01

Directional microwave-assisted liquefaction and stepwise extraction are introduced for producing platform chemicals: aromatics and monosaccharides. When sulfuric acid was used as a catalyst, a 45% monosaccharides yield and a 29% aromatics yield were obtained from bamboo with 0.3 g catalyst per 18 g methanol and 2 g bamboo at 160 °C with 10 min. Approximately 78–86 wt%...

Online chemical modeling environment (OCHEM): web platform for data storage, model development and publishing of chemical information

NASA Astrophysics Data System (ADS)

Sushko, Iurii; Novotarskyi, Sergii; Körner, Robert; Pandey, Anil Kumar; Rupp, Matthias; Teetz, Wolfram; Brandmaier, Stefan; Abdelaziz, Ahmed; Prokopenko, Volodymyr V.; Tanchuk, Vsevolod Y.; Todeschini, Roberto; Varnek, Alexandre; Marcou, Gilles; Ertl, Peter; Potemkin, Vladimir; Grishina, Maria; Gasteiger, Johann; Schwab, Christof; Baskin, Igor I.; Palyulin, Vladimir A.; Radchenko, Eugene V.; Welsh, William J.; Kholodovych, Vladyslav; Chekmarev, Dmitriy; Cherkasov, Artem; Aires-de-Sousa, Joao; Zhang, Qing-You; Bender, Andreas; Nigsch, Florian; Patiny, Luc; Williams, Antony; Tkachenko, Valery; Tetko, Igor V.

2011-06-01

The Online Chemical Modeling Environment is a web-based platform that aims to automate and simplify the typical steps required for QSAR modeling. The platform consists of two major subsystems: the database of experimental measurements and the modeling framework. A user-contributed database contains a set of tools for easy input, search and modification of thousands of records. The OCHEM database is based on the wiki principle and focuses primarily on the quality and verifiability of the data. The database is tightly integrated with the modeling framework, which supports all the steps required to create a predictive model: data search, calculation and selection of a vast variety of molecular descriptors, application of machine learning methods, validation, analysis of the model and assessment of the applicability domain. As compared to other similar systems, OCHEM is not intended to re-implement the existing tools or models but rather to invite the original authors to contribute their results, make them publicly available, share them with other users and to become members of the growing research community. Our intention is to make OCHEM a widely used platform to perform the QSPR/QSAR studies online and share it with other users on the Web. The ultimate goal of OCHEM is collecting all possible chemoinformatics tools within one simple, reliable and user-friendly resource. The OCHEM is free for web users and it is available online at http://www.ochem.eu.

Effect of Intermediate Flush Using Different Devices to Prevent Chemical Smear Layer Formation.

PubMed

Silva, Camilla Corrêa; Ferreira, Vivian Maria Durange; De-Deus, Gustavo; Herrera, Daniel Rodrigo; Prado, Maíra do; Silva, Emmanuel João Nogueira Leal da

2017-01-01

This study compared the effect of intermediate flush with distilled water delivered by conventional irrigation, EndoVac microcannula or Self-Adjusting File (SAF) system in the prevention of chemical smear layer (CSL) formation. Thirty human premolars were used. Canals were prepared with Reciproc system and 5.25% NaOCl. After chemomechanical preparation, samples were divided in 3 groups (n=10) according to the intermediate irrigation protocol with distilled water using: conventional irrigation, EndoVac microcannula or SAF. A final flush with 2% chlorhexidine solution was used and scanning electron microscopy was performed to assess protocol effectiveness. Two calibrated evaluators attributed scores according the presence or absence of CSL on the surface of the root canal walls at the coronal, middle and apical thirds, as follows: (1) no CSL; (2) small amounts of CSL; (3) moderate CSL; and (4) heavy CSL. Differences between protocols were analyzed with Kruskal-Wallis and Mann-Whitney U tests. Friedman and Wilcoxon signed rank tests were used for comparison between each root canal third. SAF resulted in less formation of CSL when compared with the conventional irrigation and EndoVac microcannula (p<0.05). When root canal thirds were analyzed, conventional irrigation and EndoVac groups showed less CSL formation at coronal and middle thirds in comparison to the apical third (p<0.05). In SAF group, there was no difference among the thirds (p>0.05). It may be concluded that an intermediate flush of distilled water, delivered by the SAF system resulted in a better reduction of CSL formation during chemomechanical preparation.

Chemical Sensor Platform for Non-Invasive Monitoring of Activity and Dehydration

PubMed Central

Solovei, Dmitry; Žák, Jaromír; Majzlíková, Petra; Sedláček, Jiří; Hubálek, Jaromír

2015-01-01

A non-invasive solution for monitoring of the activity and dehydration of organisms is proposed in the work. For this purpose, a wireless standalone chemical sensor platform using two separate measurement techniques has been developed. The first approach for activity monitoring is based on humidity measurement. Our solution uses new humidity sensor based on a nanostructured TiO2 surface for sweat rate monitoring. The second technique is based on monitoring of potassium concentration in urine. High level of potassium concentration denotes clear occurrence of dehydration. Furthermore, a Wireless Body Area Network (WBAN) was developed for this sensor platform to manage data transfer among devices and the internet. The WBAN coordinator controls the sensor devices and collects and stores the measured data. The collected data is particular to individuals and can be shared with physicians, emergency systems or athletes' coaches. Long-time monitoring of activity and potassium concentration in urine can help maintain the appropriate water intake of elderly people or athletes and to send warning signals in the case of near dehydration. The created sensor system was calibrated and tested in laboratory and real conditions as well. The measurement results are discussed. PMID:25594591

All-soft, battery-free, and wireless chemical sensing platform based on liquid metal for liquid- and gas-phase VOC detection.

PubMed

Kim, Min-Gu; Alrowais, Hommood; Kim, Choongsoon; Yeon, Pyungwoo; Ghovanloo, Maysam; Brand, Oliver

2017-06-27

Lightweight, flexible, stretchable, and wireless sensing platforms have gained significant attention for personal healthcare and environmental monitoring applications. This paper introduces an all-soft (flexible and stretchable), battery-free, and wireless chemical microsystem using gallium-based liquid metal (eutectic gallium-indium alloy, EGaIn) and poly(dimethylsiloxane) (PDMS), fabricated using an advanced liquid metal thin-line patterning technique based on soft lithography. Considering its flexible, stretchable, and lightweight characteristics, the proposed sensing platform is well suited for wearable sensing applications either on the skin or on clothing. Using the microfluidic sensing platform, detection of liquid-phase and gas-phase volatile organic compounds (VOC) is demonstrated using the same design, which gives an opportunity to have the sensor operate under different working conditions and environments. In the case of liquid-phase chemical sensing, the wireless sensing performance and microfluidic capacitance tunability for different dielectric liquids are evaluated using analytical, numerical, and experimental approaches. In the case of gas-phase chemical sensing, PDMS is used both as a substrate and a sensing material. The gas sensing performance is evaluated and compared to a silicon-based, solid-state gas sensor with a PDMS sensing film.

Biological upgrading of volatile fatty acids, key intermediates for the valorization of biowaste through dark anaerobic fermentation.

PubMed

Singhania, Reeta Rani; Patel, Anil Kumar; Christophe, Gwendoline; Fontanille, Pierre; Larroche, Christian

2013-10-01

VFAs can be obtained from lignocellulosic agro-industrial wastes, sludge, and various biodegradable organic wastes as key intermediates through dark fermentation processes and synthesized through chemical route also. They are building blocks of several organic compounds viz. alcohol, aldehyde, ketones, esters and olefins. These can serve as alternate carbon source for microbial biolipid, biohydrogen, microbial fuel cells productions, methanisation, and for denitrification. Organic wastes are the substrate for VFA platform that is of zero or even negative cost, giving VFA as intermediate product but their separation from the fermentation broth is still a challenge; however, several separation technologies have been developed, membrane separation being the most suitable one. These aspects will be reviewed and results obtained during anaerobic treatment of slaughterhouse wastes with further utilisation of volatile fatty acids for yeast cultivation have been discussed. Copyright © 2012 Elsevier Ltd. All rights reserved.

Catalytic Conversion of Carbohydrates to Initial Platform Chemicals: Chemistry and Sustainability.

PubMed

Mika, László T; Cséfalvay, Edit; Németh, Áron

2018-01-24

The replacement of fossil resources that currently provide more than 90% of our energy needs and feedstocks of the chemical industry in combination with reduced emission of carbon dioxide is one of the most pressing challenges of mankind. Biomass as a globally available resource has been proposed as an alternative feedstock for production of basic building blocks, which could partially or even fully replace the currently utilized fossil-based ones in well-established chemical processes. The destruction of lignocellulosic feed followed by oxygen removal from its cellulose and hemicellulose content by catalytic processes results in the formation of initial platform chemicals (IPCs). However, their sustainable production strongly depends on the availability of resources, their efficient or even industrially viable conversion processes, and replenishment time of feedstocks. Herein, we overview recent advances and developments in catalytic transformations of the carbohydrate content of lignocellulosic biomass to IPCs (i.e., ethanol, 3-hydroxypropionic acid, isoprene, succinic and levulinic acids, furfural, and 5-hydroxymethylfurfural). The mechanistic aspects, development of new catalysts, different efficiency indicators (yield and selectivity), and conversion conditions of their production are presented and compared. The potential biochemical production routes utilizing recently engineered microorganisms are reviewed, as well. The sustainability metrics that could be applied to the chemical industry (individual set of sustainability indicators, composite indices methods, material and energy flow analysis-based metrics, and ethanol equivalents) are also overviewed as well as an outlook is provided to highlight challenges and opportunities associated with this huge research area.

Micro-chemical synthesis of molecular probes on an electronic microfluidic device

PubMed Central

Keng, Pei Yuin; Chen, Supin; Ding, Huijiang; Sadeghi, Saman; Shah, Gaurav J.; Dooraghi, Alex; Phelps, Michael E.; Satyamurthy, Nagichettiar; Chatziioannou, Arion F.; Kim, Chang-Jin “CJ”; van Dam, R. Michael

2012-01-01

We have developed an all-electronic digital microfluidic device for microscale chemical synthesis in organic solvents, operated by electrowetting-on-dielectric (EWOD). As an example of the principles, we demonstrate the multistep synthesis of [18F]FDG, the most common radiotracer for positron emission tomography (PET), with high and reliable radio-fluorination efficiency of [18F]FTAG (88 ± 7%, n = 11) and quantitative hydrolysis to [18F]FDG (> 95%, n = 11). We furthermore show that batches of purified [18F]FDG can successfully be used for PET imaging in mice and that they pass typical quality control requirements for human use (including radiochemical purity, residual solvents, Kryptofix, chemical purity, and pH). We report statistical repeatability of the radiosynthesis rather than best-case results, demonstrating the robustness of the EWOD microfluidic platform. Exhibiting high compatibility with organic solvents and the ability to carry out sophisticated actuation and sensing of reaction droplets, EWOD is a unique platform for performing diverse microscale chemical syntheses in small volumes, including multistep processes with intermediate solvent-exchange steps. PMID:22210110

Developing the Biomolecular Screening Facility at the EPFL into the Chemical Biology Screening Platform for Switzerland.

PubMed

Turcatti, Gerardo

2014-05-01

The Biomolecular Screening Facility (BSF) is a multidisciplinary laboratory created in 2006 at the Ecole Polytechnique Federale de Lausanne (EPFL) to perform medium and high throughput screening in life sciences-related projects. The BSF was conceived and developed to meet the needs of a wide range of researchers, without privileging a particular biological discipline or therapeutic area. The facility has the necessary infrastructure, multidisciplinary expertise and flexibility to perform large screening programs using small interfering RNAs (siRNAs) and chemical collections in the areas of chemical biology, systems biology and drug discovery. In the framework of the National Centres of Competence in Research (NCCR) Chemical Biology, the BSF is hosting 'ACCESS', the Academic Chemical Screening Platform of Switzerland that provides the scientific community with chemical diversity, screening facilities and know-how in chemical genetics. In addition, the BSF started its own applied research axes that are driven by innovation in thematic areas related to preclinical drug discovery and discovery of bioactive probes.

Hydrogenolysis goes bio: from carbohydrates and sugar alcohols to platform chemicals.

PubMed

Ruppert, Agnieszka M; Weinberg, Kamil; Palkovits, Regina

2012-03-12

In view of the diminishing oil resources and the ongoing climate change, the use of efficient and environmentally benign technologies for the utilization of renewable resources has become indispensible. Therein, hydrogenolysis reactions offer a promising possibility for future biorefinery concepts. These reactions result in the cleavage of C-C and C-O bonds by hydrogen and allow direct access to valuable platform chemicals already integrated in today's value chains. Thus, hydrogenolysis bears the potential to bridge currently available technologies and future biomass-based refinery concepts. This Review highlights past and present developments in this field, with special emphasis on the direct utilization of cellulosic feedstocks. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mathematical Calculations Of Heat Transfer For The CNC Deposition Platform Based On Chemical Thermal Method

NASA Astrophysics Data System (ADS)

Essa, Mohammed Sh.; Chiad, Bahaa T.; Hussein, Khalil A.

2018-05-01

Chemical thermal deposition techniques are highly depending on deposition platform temperature as well as surface substrate temperatures, so in this research thermal distribution and heat transfer was calculated to optimize the deposition platform temperature distribution, determine the power required for the heating element, to improve thermal homogeneity. Furthermore, calculate the dissipated thermal power from the deposition platform. Moreover, the thermal imager (thermal camera) was used to estimate the thermal destitution in addition to, the temperature allocation over 400cm2 heated plate area. In order to reach a plate temperature at 500 oC, a plate supported with an electrical heater of power (2000 W). Stainless steel plate of 12mm thickness was used as a heated plate and deposition platform and subjected to lab tests using element analyzer X-ray fluorescence system (XRF) to check its elemental composition and found the grade of stainless steel and found to be 316 L. The total heat losses calculated at this temperature was 612 W. Homemade heating element was used to heat the plate and can reach 450 oC with less than 15 min as recorded from the system.as well as the temperatures recorded and monitored using Arduino/UNO microcontroller with cold-junction-compensated K-thermocouple-to-digital converter type MAX6675.

Bright Side of Lignin Depolymerization: Toward New Platform Chemicals

PubMed Central

2018-01-01

Lignin, a major component of lignocellulose, is the largest source of aromatic building blocks on the planet and harbors great potential to serve as starting material for the production of biobased products. Despite the initial challenges associated with the robust and irregular structure of lignin, the valorization of this intriguing aromatic biopolymer has come a long way: recently, many creative strategies emerged that deliver defined products via catalytic or biocatalytic depolymerization in good yields. The purpose of this review is to provide insight into these novel approaches and the potential application of such emerging new structures for the synthesis of biobased polymers or pharmacologically active molecules. Existing strategies for functionalization or defunctionalization of lignin-based compounds are also summarized. Following the whole value chain from raw lignocellulose through depolymerization to application whenever possible, specific lignin-based compounds emerge that could be in the future considered as potential lignin-derived platform chemicals. PMID:29337543

A Ubiquitous Optical Microsystem Platform with Application to Optical Metrology and Chemical Sensing

NASA Astrophysics Data System (ADS)

Gerling, John David

This dissertation is concerned with the development of a novel, versatile optical sensor platform for optical metrology and chemical sensing. We demonstrate the feasibility of embedding optical components between bonded silicon wafers with receptor cavities and optical windows to create a self-contained sensor microsystem that can be used for in-situ measurement of hostile environments. Arrays of these sensors internal to a silicon wafer can enable optical sensing for in-situ, real-time mapping and process development for the semiconductor industry in the form of an instrumented substrate. Single-die versions of these optical sensor platforms can also enable point-of-care diagnostics, high throughput disease screening, bio-warfare agent detection, and environmental monitoring. Our first discussion will focus on a single-wavelength interferometry-based prototype sensor. Several applications are demonstrated using this single wavelength prototype: refractive index monitoring, SiO2 plasma etching, chemical mechanical polishing, photoresist cure and dissolution, copper etch end-point detection, and also nanopore wetting phenomena. Subsequent sections of this dissertation will describe efforts to improve the optical sensor platform to achieve multi-wavelength sensing function. We explore the use of an off-the-shelf commercial RGB sensor for colorimetric monitoring of copper and aluminum thin-film etchings. We then expand upon our prior work and concepts to realize a fully integrated, chip-sized microspectrometer with a photon engine based on a diffraction grating. The design, fabrication, and demonstration of a working prototype with dimensions < 1 mm thick using standard planar microfabrication techniques is described. Proof-of-concept demonstrations indicate the working principle of dispersion, although with a low spectral resolution of 120 nm. With working knowledge of the issues of the first prototype, we present an improved 5-channel microspectrometer with a

ClusterCAD: a computational platform for type I modular polyketide synthase design

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

Eng, Clara H.; Backman, Tyler W H; Bailey, Constance B.

Here, we present ClusterCAD, a web-based toolkit designed to leverage the collinear structure and deterministic logic of type I modular polyketide synthases (PKSs) for synthetic biology applications. The unique organization of these megasynthases, combined with the diversity of their catalytic domain building blocks, has fueled an interest in harnessing the biosynthetic potential of PKSs for the microbial production of both novel natural product analogs and industrially relevant small molecules. However, a limited theoretical understanding of the determinants of PKS fold and function poses a substantial barrier to the design of active variants, and identifying strategies to reliably construct functional PKSmore » chimeras remains an active area of research. In this work, we formalize a paradigm for the design of PKS chimeras and introduce ClusterCAD as a computational platform to streamline and simplify the process of designing experiments to test strategies for engineering PKS variants. ClusterCAD provides chemical structures with stereochemistry for the intermediates generated by each PKS module, as well as sequence- and structure-based search tools that allow users to identify modules based either on amino acid sequence or on the chemical structure of the cognate polyketide intermediate. ClusterCAD can be accessed at https://clustercad.jbei.org and at http://clustercad.igb.uci.edu.« less

ClusterCAD: a computational platform for type I modular polyketide synthase design

DOE PAGES

Eng, Clara H.; Backman, Tyler W H; Bailey, Constance B.; ...

2017-10-11

Here, we present ClusterCAD, a web-based toolkit designed to leverage the collinear structure and deterministic logic of type I modular polyketide synthases (PKSs) for synthetic biology applications. The unique organization of these megasynthases, combined with the diversity of their catalytic domain building blocks, has fueled an interest in harnessing the biosynthetic potential of PKSs for the microbial production of both novel natural product analogs and industrially relevant small molecules. However, a limited theoretical understanding of the determinants of PKS fold and function poses a substantial barrier to the design of active variants, and identifying strategies to reliably construct functional PKSmore » chimeras remains an active area of research. In this work, we formalize a paradigm for the design of PKS chimeras and introduce ClusterCAD as a computational platform to streamline and simplify the process of designing experiments to test strategies for engineering PKS variants. ClusterCAD provides chemical structures with stereochemistry for the intermediates generated by each PKS module, as well as sequence- and structure-based search tools that allow users to identify modules based either on amino acid sequence or on the chemical structure of the cognate polyketide intermediate. ClusterCAD can be accessed at https://clustercad.jbei.org and at http://clustercad.igb.uci.edu.« less

Engineering the biological conversion of methanol to specialty chemicals in Escherichia coli

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

Whitaker, W. Brian; Jones, J. Andrew; Bennett, R. Kyle

Methanol is an attractive substrate for biological production of chemicals and fuels. Engineering methylotrophic Escherichia coli as a platform organism for converting methanol to metabolites is desirable. Prior efforts to engineer methylotrophic E. coli were limited by methanol dehydrogenases (Mdhs) with unfavorable enzyme kinetics. We engineered E. coli to utilize methanol using a superior NAD-dependent Mdh from Bacillus stearothermophilus and ribulose monophosphate (RuMP) pathway enzymes from B. methanolicus. Using 13C-labeling, we demonstrate this E. coli strain converts methanol into biomass components. For example, the key TCA cycle intermediates, succinate and malate, exhibit labeling up to 39%, while the lower glycolyticmore » intermediate, 3-phosphoglycerate, up to 53%. Multiple carbons are labeled for each compound, demonstrating a cycling RuMP pathway for methanol assimilation to support growth. In conclusion, by incorporating the pathway to synthesize the flavanone naringenin, we demonstrate the first example of in vivo conversion of methanol into a specialty chemical in E. coli.« less

Engineering the biological conversion of methanol to specialty chemicals in Escherichia coli

DOE PAGES

Whitaker, W. Brian; Jones, J. Andrew; Bennett, R. Kyle; ...

2016-11-01

Methanol is an attractive substrate for biological production of chemicals and fuels. Engineering methylotrophic Escherichia coli as a platform organism for converting methanol to metabolites is desirable. Prior efforts to engineer methylotrophic E. coli were limited by methanol dehydrogenases (Mdhs) with unfavorable enzyme kinetics. We engineered E. coli to utilize methanol using a superior NAD-dependent Mdh from Bacillus stearothermophilus and ribulose monophosphate (RuMP) pathway enzymes from B. methanolicus. Using 13C-labeling, we demonstrate this E. coli strain converts methanol into biomass components. For example, the key TCA cycle intermediates, succinate and malate, exhibit labeling up to 39%, while the lower glycolyticmore » intermediate, 3-phosphoglycerate, up to 53%. Multiple carbons are labeled for each compound, demonstrating a cycling RuMP pathway for methanol assimilation to support growth. In conclusion, by incorporating the pathway to synthesize the flavanone naringenin, we demonstrate the first example of in vivo conversion of methanol into a specialty chemical in E. coli.« less

The chemical, microbial, sensory and technological effects of intermediate salt levels as a sodium reduction strategy in fresh pork sausages.

PubMed

Cluff, MacDonald; Steyn, Hannes; Charimba, George; Bothma, Carina; Hugo, Celia J; Hugo, Arno

2016-09-01

The reduction of sodium in processed meat products is synonymous with the use of salt replacers. Rarely has there been an assessment of the use of intermediate salt levels as a sodium reduction strategy in itself. In this study, 1 and 1.5% salt levels were compared with 0 and 2% controls in fresh pork sausages for effects on chemical, microbial, sensory and technological stability. Although significant (P < 0.001 to P < 0.01) differences were found between the 0 and 2% controls, no significant differences could be detected between the 2, 1.5 and 1% added NaCl treatments for the following: total bacteria counts on days 3, 6 and 9; TBARS of pork sausages stored at 4 °C on days 6 and 9 and stored at -18 °C on days 90 and 180; taste, texture and overall liking during sensory evaluation; and % cooking loss, % total loss and % refrigeration loss. Consumers were able to differentiate between the 2 and 1% added NaCl treatments in terms of saltiness. This study indicated that salt reduction to intermediate levels can be considered a sodium reduction strategy in itself but that further research with regards to product safety is needed. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

Tox21 Enricher: Web-based Chemical/Biological Functional Annotation Analysis Tool Based on Tox21 Toxicity Screening Platform.

PubMed

Hur, Junguk; Danes, Larson; Hsieh, Jui-Hua; McGregor, Brett; Krout, Dakota; Auerbach, Scott

2018-05-01

The US Toxicology Testing in the 21st Century (Tox21) program was established to develop more efficient and human-relevant toxicity assessment methods. The Tox21 program screens >10,000 chemicals using quantitative high-throughput screening (qHTS) of assays that measure effects on toxicity pathways. To date, more than 70 assays have yielded >12 million concentration-response curves. The patterns of activity across assays can be used to define similarity between chemicals. Assuming chemicals with similar activity profiles have similar toxicological properties, we may infer toxicological properties based on its neighbourhood. One approach to inference is chemical/biological annotation enrichment analysis. Here, we present Tox21 Enricher, a web-based chemical annotation enrichment tool for the Tox21 toxicity screening platform. Tox21 Enricher identifies over-represented chemical/biological annotations among lists of chemicals (neighbourhoods), facilitating the identification of the toxicological properties and mechanisms in the chemical set. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR 721.983 - Sulfonyl azide intermediate (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

...). 721.983 Section 721.983 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.983 Sulfonyl azide intermediate (generic). (a) Chemical substance and significant new uses...

SBRC-Nottingham: sustainable routes to platform chemicals from C1 waste gases

PubMed Central

Burbidge, Alan; Minton, Nigel P.

2016-01-01

Synthetic Biology Research Centre (SBRC)-Nottingham (www.sbrc-nottingham.ac.uk) was one of the first three U.K. university-based SBRCs to be funded by the Biotechnology and Biological Sciences Research Council (BBSRC) and Engineering and Physical Sciences Research Council (EPSRC) as part of the recommendations made in the U.K.'s Synthetic Biology Roadmap. It was established in 2014 and builds on the pioneering work of the Clostridia Research Group (CRG) who have previously developed a range of gene tools for the modification of clostridial genomes. The SBRC is primarily focussed on the conversion of single carbon waste gases into platform chemicals with a particular emphasis on the use of the aerobic chassis Cupriavidus necator. PMID:27284026

Using e-Learning Platforms for Mastery Learning in Developmental Mathematics Courses

ERIC Educational Resources Information Center

Boggs, Stacey; Shore, Mark; Shore, JoAnna

2004-01-01

Many colleges and universities have adopted e-learning platforms to utilize computers as an instructional tool in developmental (i.e., beginning and intermediate algebra) mathematics courses. An e-learning platform is a computer program used to enhance course instruction via computers and the Internet. Allegany College of Maryland is currently…

Trace gas measurements from tethered balloon platforms

NASA Technical Reports Server (NTRS)

Bandy, Alan R.; Bandy, Terese L.; Youngbluth, Otto; Owens, Thomas L.

1987-01-01

Instrumentation and chemical sampling and analysis procedures are described for making measurements of atmospheric carbon disulfide in the concentration range 1-1000 pptv from tethered balloon platforms. Results of a study on the CS2 composition of air downward of a saltwater marsh are reported. A method for obtaining the necessary data for solving the budget equations for surface fluxes, chemical formation rates and chemical destruction rates using data acquired from tethered balloon platforms is presented.

Investigation of Chemical Exchange at Intermediate Exchange Rates using a Combination of Chemical Exchange Saturation Transfer (CEST) and Spin-Locking methods (CESTrho)

PubMed Central

Kogan, Feliks; Singh, Anup; Cai, Keija; Haris, Mohammad; Hariharan, Hari; Reddy, Ravinder

2011-01-01

Proton exchange imaging is important as it allows for visualization and quantification of the distribution of specific metabolites with conventional MRI. Current exchange mediated MRI methods suffer from poor contrast as well as confounding factors that influence exchange rates. In this study we developed a new method to measure proton exchange which combines chemical exchange saturation transfer (CEST) and T1ρ magnetization preparation methods (CESTrho). We demonstrated that this new CESTrho sequence can detect proton exchange in the slow to intermediate exchange regimes. It has a linear dependence on proton concentration which allows it to be used to quantitatively measure changes in metabolite concentration. Additionally, the magnetization scheme of this new method can be customized to make it insensitive to changes in exchange rate while retaining its dependency on solute concentration. Finally, we showed the feasibility of using CESTrho in vivo. This sequence is able to detect proton exchange at intermediate exchange rates and is unaffected by the confounding factors that influence proton exchange rates thus making it ideal for the measurement of metabolites with exchangeable protons in this exchange regime. PMID:22009759

Investigation of chemical exchange at intermediate exchange rates using a combination of chemical exchange saturation transfer (CEST) and spin-locking methods (CESTrho).

PubMed

Kogan, Feliks; Singh, Anup; Cai, Keija; Haris, Mohammad; Hariharan, Hari; Reddy, Ravinder

2012-07-01

Proton exchange imaging is important as it allows for visualization and quantification of the distribution of specific metabolites with conventional MRI. Current exchange mediated MRI methods suffer from poor contrast as well as confounding factors that influence exchange rates. In this study we developed a new method to measure proton exchange which combines chemical exchange saturation transfer and T(1)(ρ) magnetization preparation methods (CESTrho). We demonstrated that this new CESTrho sequence can detect proton exchange in the slow to intermediate exchange regimes. It has a linear dependence on proton concentration which allows it to be used to quantitatively measure changes in metabolite concentration. Additionally, the magnetization scheme of this new method can be customized to make it insensitive to changes in exchange rate while retaining its dependency on solute concentration. Finally, we showed the feasibility of using CESTrho in vivo. This sequence is able to detect proton exchange at intermediate exchange rates and is unaffected by the confounding factors that influence proton exchange rates thus making it ideal for the measurement of metabolites with exchangeable protons in this exchange regime. Copyright © 2011 Wiley Periodicals, Inc.

Chemical screening platforms for autophagy drug discovery to identify therapeutic candidates for Huntington's disease and other neurodegenerative disorders.

PubMed

Sarkar, Sovan

2013-01-01

Autophagy is a cellular degradation process involved in the clearance of aggregate-prone proteins associated with neurodegenerative diseases. While the mTOR pathway has been known to be the major regulator of autophagy, recent advancements into the regulation of autophagy have identified mTOR-independent autophagy pathways that are amenable to chemical perturbations. Several chemical and genetic screens have been undertaken to identify small molecule and genetic regulators of autophagy, respectively. The small molecule autophagy enhancers offer great potential as therapeutic candidates not only for neurodegenerative diseases, but also for diverse human diseases where autophagy acts as a protective pathway. This review highlights the various chemical screening platforms for autophagy drug discovery pertinent for the treatment of neurodegenerative diseases.

Biological-inorganic hybrid systems as a generalized platform for chemical production.

PubMed

Nangle, Shannon N; Sakimoto, Kelsey K; Silver, Pamela A; Nocera, Daniel G

2017-12-01

An expanding renewable energy market to supplant petrochemicals has motivated synthesis technologies that use renewable feedstocks, such as CO 2 . Hybrid biological-inorganic systems provide a sustainable, efficient, versatile, and inexpensive chemical synthesis platform. These systems comprise biocompatible electrodes that transduce electrical energy either directly or indirectly into bioavailable energy, such as H 2 and NAD(P)H. In combination, specific bacteria use these energetic reducing equivalents to fix CO 2 into multi-carbon organic compounds. As hybrid biological-inorganic technologies have developed, the focus has shifted from phenomenological and proof-of-concept discovery towards enhanced energy efficiency, production rate, product scope, and industrial robustness. In this review, we highlight the progress and the state-of-the-art of this field and describe the advantages and challenges involved in designing bio- and chemo- compatible systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Topographical and Chemical Imaging of a Phase Separated Polymer Using a Combined Atomic Force Microscopy/Infrared Spectroscopy/Mass Spectrometry Platform

DOE PAGES

Tai, Tamin; Karácsony, Orsolya; Bocharova, Vera; ...

2016-02-18

This article describes how the use of a hybrid atomic force microscopy/infrared spectroscopy/mass spectrometry imaging platform was demonstrated for the acquisition and correlation of nanoscale sample surface topography and chemical images based on infrared spectroscopy and mass spectrometry.

SBRC-Nottingham: sustainable routes to platform chemicals from C1 waste gases.

PubMed

Burbidge, Alan; Minton, Nigel P

2016-06-15

Synthetic Biology Research Centre (SBRC)-Nottingham (www.sbrc-nottingham.ac.uk) was one of the first three U.K. university-based SBRCs to be funded by the Biotechnology and Biological Sciences Research Council (BBSRC) and Engineering and Physical Sciences Research Council (EPSRC) as part of the recommendations made in the U.K.'s Synthetic Biology Roadmap. It was established in 2014 and builds on the pioneering work of the Clostridia Research Group (CRG) who have previously developed a range of gene tools for the modification of clostridial genomes. The SBRC is primarily focussed on the conversion of single carbon waste gases into platform chemicals with a particular emphasis on the use of the aerobic chassis Cupriavidus necator. © 2016 The Author(s).

Engineering the biological conversion of methanol to specialty chemicals in Escherichia coli.

PubMed

Whitaker, W Brian; Jones, J Andrew; Bennett, R Kyle; Gonzalez, Jacqueline E; Vernacchio, Victoria R; Collins, Shannon M; Palmer, Michael A; Schmidt, Samuel; Antoniewicz, Maciek R; Koffas, Mattheos A; Papoutsakis, Eleftherios T

2017-01-01

Methanol is an attractive substrate for biological production of chemicals and fuels. Engineering methylotrophic Escherichia coli as a platform organism for converting methanol to metabolites is desirable. Prior efforts to engineer methylotrophic E. coli were limited by methanol dehydrogenases (Mdhs) with unfavorable enzyme kinetics. We engineered E. coli to utilize methanol using a superior NAD-dependent Mdh from Bacillus stearothermophilus and ribulose monophosphate (RuMP) pathway enzymes from B. methanolicus. Using 13 C-labeling, we demonstrate this E. coli strain converts methanol into biomass components. For example, the key TCA cycle intermediates, succinate and malate, exhibit labeling up to 39%, while the lower glycolytic intermediate, 3-phosphoglycerate, up to 53%. Multiple carbons are labeled for each compound, demonstrating a cycling RuMP pathway for methanol assimilation to support growth. By incorporating the pathway to synthesize the flavanone naringenin, we demonstrate the first example of in vivo conversion of methanol into a specialty chemical in E. coli. Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Carboxylate platform: the MixAlco process part 1: comparison of three biomass conversion platforms.

PubMed

Holtzapple, Mark T; Granda, Cesar B

2009-05-01

To convert biomass to liquid fuels, three platforms are compared: thermochemical, sugar, and carboxylate. To create a common basis, each platform is fed "ideal biomass," which contains polysaccharides (68.3%) and lignin (31.7%). This ratio is typical of hardwood biomass and was selected so that when gasified and converted to hydrogen, the lignin has sufficient energy to produce ethanol from the carboxylic acids produced by the carboxylate platform. Using balanced chemical reactions, the theoretical yield and energy efficiency were determined for each platform. For all platforms, the ethanol yield can be increased by 71% to 107% by supplying external hydrogen produced from other sources (e.g., solar, wind, nuclear, fossil fuels). The alcohols can be converted to alkanes with a modest loss of energy efficiency (3 to 5 percentage points). Of the three platforms considered, the carboxylate platform has demonstrated the highest product yields.

Synthesis of Renewable Lubricant Alkanes from Biomass-Derived Platform Chemicals.

PubMed

Gu, Mengyuan; Xia, Qineng; Liu, Xiaohui; Guo, Yong; Wang, Yanqin

2017-10-23

The catalytic synthesis of liquid alkanes from renewable biomass has received tremendous attention in recent years. However, bio-based platform chemicals have not to date been exploited for the synthesis of highly branched lubricant alkanes, which are currently produced by hydrocracking and hydroisomerization of long-chain n-paraffins. A selective catalytic synthetic route has been developed for the production of highly branched C 23 alkanes as lubricant base oil components from biomass-derived furfural and acetone through a sequential four-step process, including aldol condensation of furfural with acetone to produce a C 13 double adduct, selective hydrogenation of the adduct to a C 13 ketone, followed by a second condensation of the C 13 ketone with furfural to generate a C 23 aldol adduct, and finally hydrodeoxygenation to give highly branched C 23 alkanes in 50.6 % overall yield from furfural. This work opens a general strategy for the synthesis of high-quality lubricant alkanes from renewable biomass. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microfluidic platform for optimization of crystallization conditions

NASA Astrophysics Data System (ADS)

Zhang, Shuheng; Gerard, Charline J. J.; Ikni, Aziza; Ferry, Gilles; Vuillard, Laurent M.; Boutin, Jean A.; Ferte, Nathalie; Grossier, Romain; Candoni, Nadine; Veesler, Stéphane

2017-08-01

We describe a universal, high-throughput droplet-based microfluidic platform for crystallization. It is suitable for a multitude of applications, due to its flexibility, ease of use, compatibility with all solvents and low cost. The platform offers four modular functions: droplet formation, on-line characterization, incubation and observation. We use it to generate droplet arrays with a concentration gradient in continuous long tubing, without using surfactant. We control droplet properties (size, frequency and spacing) in long tubing by using hydrodynamic empirical relations. We measure droplet chemical composition using both an off-line and a real-time on-line method. Applying this platform to a complicated chemical environment, membrane proteins, we successfully handle crystallization, suggesting that the platform is likely to perform well in other circumstances. We validate the platform for fine-gradient screening and optimization of crystallization conditions. Additional on-line detection methods may well be integrated into this platform in the future, for instance, an on-line diffraction technique. We believe this method could find applications in fields such as fluid interaction engineering, live cell study and enzyme kinetics.

Systems metabolic engineering of Corynebacterium glutamicum for the production of the carbon-5 platform chemicals 5-aminovalerate and glutarate.

PubMed

Rohles, Christina Maria; Gießelmann, Gideon; Kohlstedt, Michael; Wittmann, Christoph; Becker, Judith

2016-09-13

The steadily growing world population and our ever luxurious life style, along with the simultaneously decreasing fossil resources has confronted modern society with the issue and need of finding renewable routes to accommodate for our demands. Shifting the production pipeline from raw oil to biomass requires efficient processes for numerous platform chemicals being produced with high yield, high titer and high productivity. In the present work, we established a de novo bio-based production process for the two carbon-5 platform chemicals 5-aminovalerate and glutarate on basis of the lysine-hyperproducing strain Corynebacterium glutamicum LYS-12. Upon heterologous implementation of the Pseudomonas putida genes davA, encoding 5-aminovaleramidase and davB, encoding lysine monooxygenase, 5-aminovalerate production was established. Related to the presence of endogenous genes coding for 5-aminovalerate transaminase (gabT) and glutarate semialdehyde dehydrogenase, 5-aminovalerate was partially converted to glutarate. Moreover, residual L-lysine was secreted as by-product. The issue of by-product formation was then addressed by deletion of the lysE gene, encoding the L-lysine exporter. Additionally, a putative gabT gene was deleted to enhance 5-aminovalerate production. To fully exploit the performance of the optimized strain, fed-batch fermentation was carried out producing 28 g L(-1) 5-aminovalerate with a maximal space-time yield of 0.9 g L(-1) h(-1). The present study describes the construction of a recombinant microbial cell factory for the production of carbon-5 platform chemicals. Beyond a basic proof-of-concept, we were able to specifically increase the production flux of 5-aminovalerate thereby generating a strain with excellent production performance. Additional improvement can be expected by removal of remaining by-product formation and bottlenecks, associated to the terminal pathway, to generate a strain being applicable as centerpiece for a bio

A post-Amadori inhibitor pyridoxamine also inhibits chemical modification of proteins by scavenging carbonyl intermediates of carbohydrate and lipid degradation.

PubMed

Voziyan, Paul A; Metz, Thomas O; Baynes, John W; Hudson, Billy G

2002-02-01

Reactive carbonyl compounds are formed during autoxidation of carbohydrates and peroxidation of lipids. These compounds are intermediates in the formation of advanced glycation end products (AGE) and advanced lipoxidation end products (ALE) in tissue proteins during aging and in chronic disease. We studied the reaction of carbonyl compounds glyoxal (GO) and glycolaldehyde (GLA) with pyridoxamine (PM), a potent post-Amadori inhibitor of AGE formation in vitro and of development of renal and retinal pathology in diabetic animals. PM reacted rapidly with GO and GLA in neutral, aqueous buffer, forming a Schiff base intermediate that cyclized to a hemiaminal adduct by intramolecular reaction with the phenolic hydroxyl group of PM. This bicyclic intermediate dimerized to form a five-ring compound with a central piperazine ring, which was characterized by electrospray ionization-liquid chromatography/mass spectrometry, NMR, and x-ray crystallography. PM also inhibited the modification of lysine residues and loss of enzymatic activity of RNase in the presence of GO and GLA and inhibited formation of the AGE/ALE N(epsilon)-(carboxymethyl)lysine during reaction of GO and GLA with bovine serum albumin. Our data suggest that the AGE/ALE inhibitory activity and the therapeutic effects of PM observed in diabetic animal models depend, at least in part, on its ability to trap reactive carbonyl intermediates in AGE/ALE formation, thereby inhibiting the chemical modification of tissue proteins.

Fabrication of heterogeneous nanomaterial array by programmable heating and chemical supply within microfluidic platform towards multiplexed gas sensing application

PubMed Central

Yang, Daejong; Kang, Kyungnam; Kim, Donghwan; Li, Zhiyong; Park, Inkyu

2015-01-01

A facile top-down/bottom-up hybrid nanofabrication process based on programmable temperature control and parallel chemical supply within microfluidic platform has been developed for the all liquid-phase synthesis of heterogeneous nanomaterial arrays. The synthesized materials and locations can be controlled by local heating with integrated microheaters and guided liquid chemical flow within microfluidic platform. As proofs-of-concept, we have demonstrated the synthesis of two types of nanomaterial arrays: (i) parallel array of TiO2 nanotubes, CuO nanospikes and ZnO nanowires, and (ii) parallel array of ZnO nanowire/CuO nanospike hybrid nanostructures, CuO nanospikes and ZnO nanowires. The laminar flow with negligible ionic diffusion between different precursor solutions as well as localized heating was verified by numerical calculation and experimental result of nanomaterial array synthesis. The devices made of heterogeneous nanomaterial array were utilized as a multiplexed sensor for toxic gases such as NO2 and CO. This method would be very useful for the facile fabrication of functional nanodevices based on highly integrated arrays of heterogeneous nanomaterials. PMID:25634814

Coupling chemical and biological catalysis: a flexible paradigm for producing biobased chemicals.

PubMed

Schwartz, Thomas J; Shanks, Brent H; Dumesic, James A

2016-04-01

Advances in metabolic engineering have allowed for the development of new biological catalysts capable of selectively de-functionalizing biomass to yield platform molecules that can be upgraded to biobased chemicals using high efficiency continuous processing allowed by heterogeneous chemical catalysis. Coupling these disciplines overcomes the difficulties of selectively activating COH bonds by heterogeneous chemical catalysis and producing petroleum analogues by biological catalysis. We show that carboxylic acids, pyrones, and alcohols are highly flexible platforms that can be used to produce biobased chemicals by this approach. More generally, we suggest that molecules with three distinct functionalities may represent a practical upper limit on the extent of functionality present in the platform molecules that serve as the bridge between biological and chemical catalysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

A novel rotating experimental platform in a superconducting magnet.

PubMed

Chen, Da; Cao, Hui-Ling; Ye, Ya-Jing; Dong, Chen; Liu, Yong-Ming; Shang, Peng; Yin, Da-Chuan

2016-08-01

This paper introduces a novel platform designed to be used in a strong static magnetic field (in a superconducting magnet). The platform is a sample holder that rotates in the strong magnetic field. Any samples placed in the platform will rotate due to the rotation of the sample holder. With this platform, a number of experiments such as material processing, culture of biological systems, chemical reactions, or other processes can be carried out. In this report, we present some preliminary experiments (protein crystallization, cell culture, and seed germination) conducted using this platform. The experimental results showed that the platform can affect the processes, indicating that it provides a novel environment that has not been investigated before and that the effects of such an environment on many different physical, chemical, or biological processes can be potentially useful for applications in many fields.

IsoMS: automated processing of LC-MS data generated by a chemical isotope labeling metabolomics platform.

PubMed

Zhou, Ruokun; Tseng, Chiao-Li; Huan, Tao; Li, Liang

2014-05-20

A chemical isotope labeling or isotope coded derivatization (ICD) metabolomics platform uses a chemical derivatization method to introduce a mass tag to all of the metabolites having a common functional group (e.g., amine), followed by LC-MS analysis of the labeled metabolites. To apply this platform to metabolomics studies involving quantitative analysis of different groups of samples, automated data processing is required. Herein, we report a data processing method based on the use of a mass spectral feature unique to the chemical labeling approach, i.e., any differential-isotope-labeled metabolites are detected as peak pairs with a fixed mass difference in a mass spectrum. A software tool, IsoMS, has been developed to process the raw data generated from one or multiple LC-MS runs by peak picking, peak pairing, peak-pair filtering, and peak-pair intensity ratio calculation. The same peak pairs detected from multiple samples are then aligned to produce a CSV file that contains the metabolite information and peak ratios relative to a control (e.g., a pooled sample). This file can be readily exported for further data and statistical analysis, which is illustrated in an example of comparing the metabolomes of human urine samples collected before and after drinking coffee. To demonstrate that this method is reliable for data processing, five (13)C2-/(12)C2-dansyl labeled metabolite standards were analyzed by LC-MS. IsoMS was able to detect these metabolites correctly. In addition, in the analysis of a (13)C2-/(12)C2-dansyl labeled human urine, IsoMS detected 2044 peak pairs, and manual inspection of these peak pairs found 90 false peak pairs, representing a false positive rate of 4.4%. IsoMS for Windows running R is freely available for noncommercial use from www.mycompoundid.org/IsoMS.

Photocrystallographic observation of halide-bridged intermediates in halogen photoeliminations.

PubMed

Powers, David C; Anderson, Bryce L; Hwang, Seung Jun; Powers, Tamara M; Pérez, Lisa M; Hall, Michael B; Zheng, Shao-Liang; Chen, Yu-Sheng; Nocera, Daniel G

2014-10-29

Polynuclear transition metal complexes, which frequently constitute the active sites of both biological and chemical catalysts, provide access to unique chemical transformations that are derived from metal-metal cooperation. Reductive elimination via ligand-bridged binuclear intermediates from bimetallic cores is one mechanism by which metals may cooperate during catalysis. We have established families of Rh2 complexes that participate in HX-splitting photocatalysis in which metal-metal cooperation is credited with the ability to achieve multielectron photochemical reactions in preference to single-electron transformations. Nanosecond-resolved transient absorption spectroscopy, steady-state photocrystallography, and computational modeling have allowed direct observation and characterization of Cl-bridged intermediates (intramolecular analogues of classical ligand-bridged intermediates in binuclear eliminations) in halogen elimination reactions. On the basis of these observations, a new class of Rh2 complexes, supported by CO ligands, has been prepared, allowing for the isolation and independent characterization of the proposed halide-bridged intermediates. Direct observation of halide-bridged structures establishes binuclear reductive elimination as a viable mechanism for photogenerating energetic bonds.

Silicon micro sensors as integrated readout platform for colorimetric and fluorescence based opto-chemical transducers

NASA Astrophysics Data System (ADS)

Will, Matthias; Martan, Tomas; Brodersen, Olaf

2011-09-01

Opto-chemical transducer almost offers unlimited possibilities for detection of physical quantities. New technologies and research show a steady increasing of publications in the area of sensoric principles. For transfer to real world applications the optical response has to be converted into an electrical signal. An exceptional opto chemical transducer loses the attraction if complex and expensive instruments for analysis are requires. Therefore, the readout system must be very compact and producible for low cost. In this presentation, the technology platform as a solution for these problems will be presented. We combine micro structuring of silicon, photodiode fabrication, chip in chip mounting and novel assembly technologies for creation of a flexible sensor platform. This flexible combination of technologies allows fabricating a family of planar optical remission sensors. With variation of design and modifications, we are able to detect colorimetric, fluorescent properties of an sensitive layer attached on the sensor surface. In our sensor with typical size of 6mm x 6mm x 1mm different emitting sources based on LED's or laser diodes, multiple detection cannels for the remitted light and also measurement of temperature are included. Based on these sensors we proof the concept by demonstrating sensors for oxygen, carbon dioxide and ammonia based on colorimetric and fluorescent changes in the transducer layer. In both configurations, LED's irradiated the sensitive polymer layer through a transparent substrate. The absorption or fluorescence properties of dyed polymer are changed by the chemical reaction and light response is detected by PIN diodes. The signal shift is analyzed by using a computer controlled evaluation board of own construction. Accuracy and reliability of the remission sensor system were verified and the whole sensor system was experimentally tested in the range of concentrations from 50 ppm up to 100 000 ppm for CO2 and O2 Furthermore, we develop

A targeted gene expression platform allows for rapid analysis of chemical-induced antioxidant mRNA expression in zebrafish larvae.

PubMed

Mills, Margaret G; Gallagher, Evan P

2017-01-01

Chemical-induced oxidative stress and the biochemical pathways that protect against oxidative damage are of particular interest in the field of toxicology. To rapidly identify oxidative stress-responsive gene expression changes in zebrafish, we developed a targeted panel of antioxidant genes using the Affymetrix QuantiGene Plex (QGP) platform. The genes contained in our panel include eight putative Nrf2 (Nfe2l2a)-dependent antioxidant genes (hmox1a, gstp1, gclc, nqo1, prdx1, gpx1a, sod1, sod2), a stress response gene (hsp70), an inducible DNA damage repair gene (gadd45bb), and three reference genes (actb1, gapdh, hprt1). We tested this platform on larval zebrafish exposed to tert-butyl hydroperoxide (tBHP) and cadmium (Cd), two model oxidative stressors with different modes of action, and compared our results with those obtained using the more common quantitative PCR (qPCR) method. Both methods showed that exposure to tBHP and Cd induced expression of prdx1, gstp1, and hmox1a (2- to 12-fold increase via QGP), indicative of an activated Nrf2 response in larval zebrafish. Both compounds also elicited a general stress response as reflected by elevation of hsp70 and gadd45bb, with Cd being the more potent inducer. Transient changes were observed in sod2 and gpx1a expression, whereas nqo1, an Nrf2-responsive gene in mammalian cells, was minimally affected by either tBHP or Cd chemical exposures. Developmental expression analysis of the target genes by QGP revealed marked upregulation of sod2 between 0-96hpf, and to a lesser extent, of sod1 and gstp1. Once optimized, QGP analysis of these experiments was accomplished more rapidly, using far less tissue, and at lower total costs than qPCR analysis. In summary, the QGP platform as applied to higher-throughput zebrafish studies provides a reasonable cost-effective alternative to qPCR or more comprehensive transcriptomics approaches to rapidly assess the potential for chemicals to elicit oxidative stress as a mechanism of

Intermediate selectivity in the oxidation of phenols using plasmonic Au/ZnO photocatalysts

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

Lin, Feng; Cojocaru, Bogdan E.; Williams, Luke S.

Tunable reaction selectivity on a single catalyst is a continual goal in chemical syntheses. Herein, we report an unexpected light-directed intermediate selectivity using well-known plasmonic photocatalysts. We observed distinct intermediate selectivity behaviors between using UV and visible light irradiations. Chemical computations and quenching experiments suggest that the radicals generated by the plasmonic excitation govern the light-directed selectivity. As a result, the broader impact of this work ranges from selective yield of desirable intermediates for subsequent syntheses without tedious separation procedures, to arousing interest in examining new opportunities for plasmonic photocatalysts.

Intermediate selectivity in the oxidation of phenols using plasmonic Au/ZnO photocatalysts

DOE PAGES

Lin, Feng; Cojocaru, Bogdan E.; Williams, Luke S.; ...

2017-06-20

Tunable reaction selectivity on a single catalyst is a continual goal in chemical syntheses. Herein, we report an unexpected light-directed intermediate selectivity using well-known plasmonic photocatalysts. We observed distinct intermediate selectivity behaviors between using UV and visible light irradiations. Chemical computations and quenching experiments suggest that the radicals generated by the plasmonic excitation govern the light-directed selectivity. As a result, the broader impact of this work ranges from selective yield of desirable intermediates for subsequent syntheses without tedious separation procedures, to arousing interest in examining new opportunities for plasmonic photocatalysts.

Neuroimaging Data Sharing on the Neuroinformatics Database Platform

PubMed Central

Book, Gregory A; Stevens, Michael; Assaf, Michal; Glahn, David; Pearlson, Godfrey D

2015-01-01

We describe the Neuroinformatics Database (NiDB), an open-source database platform for archiving, analysis, and sharing of neuroimaging data. Data from the multi-site projects Autism Brain Imaging Data Exchange (ABIDE), Bipolar-Schizophrenia Network on Intermediate Phenotypes parts one and two (B-SNIP1, B-SNIP2), and Monetary Incentive Delay task (MID) are available for download from the public instance of NiDB, with more projects sharing data as it becomes available. As demonstrated by making several large datasets available, NiDB is an extensible platform appropriately suited to archive and distribute shared neuroimaging data. PMID:25888923

Influence of a NiO intermediate layer on the properties of ZnO grown on Si by chemical bath deposition

NASA Astrophysics Data System (ADS)

Djiokap, S. R. Tankio; Urgessa, Z. N.; Mbulanga, C. M.; Boumenou, C. Kameni; Venter, A.; Botha, J. R.

2018-04-01

In this paper, the growth of ZnO nanorods on bare and NiO-coated p-Si substrates is reported. A two-step chemical bath deposition process has been used to grow the nanorods. X-ray diffraction and scanning probe microscopy confirmed that the NiO films were polycrystalline, and that the average grain size correlated with the NiO layer thickness. The ZnO nanorod morphology, orientation and optical properties seemed to be unaffected by the intermediate NiO layer thickness. Current-voltage measurements confirmed the rectifying behavior of all the ZnO/NiO/Si heterostructures. The inclusion of a NiO layer between the substrate and the ZnO nanorods are shown to cause a reduction in both the forward and reverse bias currents. This is in qualitative agreement with the band diagram of these heterostructures, which suggests that the intermediate NiO layer should act as an electron blocking layer.

Semiempirical Quantum Chemical Calculations Accelerated on a Hybrid Multicore CPU-GPU Computing Platform.

PubMed

Wu, Xin; Koslowski, Axel; Thiel, Walter

2012-07-10

In this work, we demonstrate that semiempirical quantum chemical calculations can be accelerated significantly by leveraging the graphics processing unit (GPU) as a coprocessor on a hybrid multicore CPU-GPU computing platform. Semiempirical calculations using the MNDO, AM1, PM3, OM1, OM2, and OM3 model Hamiltonians were systematically profiled for three types of test systems (fullerenes, water clusters, and solvated crambin) to identify the most time-consuming sections of the code. The corresponding routines were ported to the GPU and optimized employing both existing library functions and a GPU kernel that carries out a sequence of noniterative Jacobi transformations during pseudodiagonalization. The overall computation times for single-point energy calculations and geometry optimizations of large molecules were reduced by one order of magnitude for all methods, as compared to runs on a single CPU core.

Reactive chromophores for sensitive and selective detection of chemical warfare agents and toxic industrial chemicals

NASA Astrophysics Data System (ADS)

Frye-Mason, Greg; Leuschen, Martin; Wald, Lara; Paul, Kateri; Hancock, Lawrence F.

2005-05-01

A reactive chromophore developed at MIT exhibits sensitive and selective detection of surrogates for G-class nerve agents. This reporter acts by reacting with the agent to form an intermediate that goes through an internal cyclization reaction. The reaction locks the molecule into a form that provides a strong fluorescent signal. Using a fluorescent sensor platform, Nomadics has demonstrated rapid and sensitive detection of reactive simulants such as diethyl chloro-phosphate (simulant for sarin, soman, and related agents) and diethyl cyanophosphate (simulant for tabun). Since the unreacted chromophore does not fluoresce at the excitation wavelength used for the cyclized reporter, the onset of fluo-rescence can be easily detected. This fluorescence-based detection method provides very high sensitivity and could enable rapid detection at permissible exposure levels. Tests with potential interferents show that the reporter is very selective, with responses from only a few highly toxic, electrophilic chemicals such as phosgene, thionyl chloride, and strong acids such as HF, HCl, and nitric acid. Dimethyl methyl phosphonate (DMMP), a common and inactive simu-lant for other CW detectors, is not reactive enough to generate a signal. The unique selectivity to chemical reactivity means that a highly toxic and hazardous chemical is present when the reporter responds and illustrates that this sensor can provide very low false alarm rates. Current efforts focus on demonstrating the sensitivity and range of agents and toxic industrial chemicals detected with this reporter as well as developing additional fluorescent reporters for a range of chemical reactivity classes. The goal is to produce a hand-held sensor that can sensitively detect a broad range of chemical warfare agent and toxic industrial chemical threats.

Quantum Monte Carlo for large chemical systems: implementing efficient strategies for petascale platforms and beyond.

PubMed

Scemama, Anthony; Caffarel, Michel; Oseret, Emmanuel; Jalby, William

2013-04-30

Various strategies to implement efficiently quantum Monte Carlo (QMC) simulations for large chemical systems are presented. These include: (i) the introduction of an efficient algorithm to calculate the computationally expensive Slater matrices. This novel scheme is based on the use of the highly localized character of atomic Gaussian basis functions (not the molecular orbitals as usually done), (ii) the possibility of keeping the memory footprint minimal, (iii) the important enhancement of single-core performance when efficient optimization tools are used, and (iv) the definition of a universal, dynamic, fault-tolerant, and load-balanced framework adapted to all kinds of computational platforms (massively parallel machines, clusters, or distributed grids). These strategies have been implemented in the QMC=Chem code developed at Toulouse and illustrated with numerical applications on small peptides of increasing sizes (158, 434, 1056, and 1731 electrons). Using 10-80 k computing cores of the Curie machine (GENCI-TGCC-CEA, France), QMC=Chem has been shown to be capable of running at the petascale level, thus demonstrating that for this machine a large part of the peak performance can be achieved. Implementation of large-scale QMC simulations for future exascale platforms with a comparable level of efficiency is expected to be feasible. Copyright © 2013 Wiley Periodicals, Inc.

Synthesis of iron oxide nanorods via chemical scavenging and phase transformations of intermediates at ambient conditions

NASA Astrophysics Data System (ADS)

Deshmukh, Ruchi; Mehra, Anurag; Thaokar, Rochish

2017-01-01

Chemically induced shape transformations of isotropic seeds, comprised of iron oxyhydroxides and iron oxide borate into nanorods, is reported. Transient growth studies show that the nanorods are formed via phase transformation and aggregation of various metastable species. Addition of tetra- methyl-ammonium hydroxide (TMAH) to the in situ synthesized seeds ensures a typical reaction pathway that favors formation of magnetite (Fe 3 O 4) via the steps of chemical etching, phase transformation of intermediates, and crystal consolidation. Whereas, with addition of sodium hydroxide (NaOH), either magnetite (Fe 3 O 4) or a mixture of ( γ-Fe 2 O 3 + α-FeOOH) is obtained. The shape with both the additives is always that of nanorods. When the seeds treated with TMAH were aged in an ultrasonication bath, rods with almost twice the length and diameter (length = 2800 nm, diameter = 345 nm) are obtained as compared to the sample aged without ultrasonication (length = 1535 nm, diameter = 172 nm). The morphology of nanostructures depending upon other experimental conditions such as, aging the sample at 60 ∘C, seeds synthesized under ultrasonication/ stirring or externally added are also examined and discussed in detail. All the samples show high coercivity and strong ferromagnetic behavior at room temperature and should be promising candidates as ferro-fluids for various applications.

Metal-Organic Framework Thin Film Coated Optical Fiber Sensors: A Novel Waveguide-Based Chemical Sensing Platform.

PubMed

Kim, Ki-Joong; Lu, Ping; Culp, Jeffrey T; Ohodnicki, Paul R

2018-02-23

Integration of optical fiber with sensitive thin films offers great potential for the realization of novel chemical sensing platforms. In this study, we present a simple design strategy and high performance of nanoporous metal-organic framework (MOF) based optical gas sensors, which enables detection of a wide range of concentrations of small molecules based upon extremely small differences in refractive indices as a function of analyte adsorption within the MOF framework. Thin and compact MOF films can be uniformly formed and tightly bound on the surface of etched optical fiber through a simple solution method which is critical for manufacturability of MOF-based sensor devices. The resulting sensors show high sensitivity/selectivity to CO 2 gas relative to other small gases (H 2 , N 2 , O 2 , and CO) with rapid (platform which results in an amplification of inherent optical absorption present within the MOF-based sensing layer with increasing values of effective refractive index associated with adsorption of gases.

Geochemical climate proxies applied to the Neoproterozoic glacial succession on the Yangtze Platform, South China

NASA Astrophysics Data System (ADS)

Dobrzinski, Nicole; Bahlburg, Heinrich; Strauss, Harald; Zhang, Qirui

A Neoproterozoic succession of glaciomarine deposits of probably Sturtian age is preserved on the Yangtze Platform in South China. At that time, the South China block was located in intermediate to low paleolatitudes at ca. 40°. The snowball Earth hypothesis offers one possible explanation for the occurrence of low latitude tillites. The hypothesis is largely based on geological and geochemical observation made in deposits underlying or overlying such tillites on several continents. In contrast our study focuses on evidence offered by the tillites themselves. We use major, trace and rare earth geochemistry to evaluate the environmental conditions prevailing during the glaciation. Of particular interest are the intensity of chemical weathering and the relative degree of oxygenation of Neoproterozoic (Nanhuan-Sinian) marine bottom waters. CIA values were obtained from preglacial sand- and siltstones, the matrix of the glacial deposits, fine-grained clastic sediments of a unit intercalated in the glacial succession, and postglacial siltstones and black shales. The data indicate relatively low degrees of chemical weathering for the glacial deposits. In contrast, pre- and postglacial deposits display comparatively elevated levels. This is also true for the intercalated unit, which we interpret as the product of a warmer and more humid interglacial period. Data for S/TOC, U/Th, Cd, Mo, and the Ceanom of the glaciomarine samples indicate the presence of oxic bottom waters during the glaciation. The snowball Earth hypothesis predicts the shutdown of chemical weathering on the continents and complete anoxia of the global ocean largely covered by sea ice for several million years. The geochemical record of the Neoproterozoic tillites on the Yangtze Platform is difficult to reconcile with the snowball Earth hypothesis.

Single-Cell RNA-Seq Reveals Dynamic Early Embryonic-like Programs during Chemical Reprogramming.

PubMed

Zhao, Ting; Fu, Yao; Zhu, Jialiang; Liu, Yifang; Zhang, Qian; Yi, Zexuan; Chen, Shi; Jiao, Zhonggang; Xu, Xiaochan; Xu, Junquan; Duo, Shuguang; Bai, Yun; Tang, Chao; Li, Cheng; Deng, Hongkui

2018-06-12

Chemical reprogramming provides a powerful platform for exploring the molecular dynamics that lead to pluripotency. Although previous studies have uncovered an intermediate extraembryonic endoderm (XEN)-like state during this process, the molecular underpinnings of pluripotency acquisition remain largely undefined. Here, we profile 36,199 single-cell transcriptomes at multiple time points throughout a highly efficient chemical reprogramming system using RNA-sequencing and reconstruct their progression trajectories. Through identifying sequential molecular events, we reveal that the dynamic early embryonic-like programs are key aspects of successful reprogramming from XEN-like state to pluripotency, including the concomitant transcriptomic signatures of two-cell (2C) embryonic-like and early pluripotency programs and the epigenetic signature of notable genome-wide DNA demethylation. Moreover, via enhancing the 2C-like program by fine-tuning chemical treatment, the reprogramming process is remarkably accelerated. Collectively, our findings offer a high-resolution dissection of cell fate dynamics during chemical reprogramming and shed light on mechanistic insights into the nature of induced pluripotency. Copyright © 2018 Elsevier Inc. All rights reserved.

Progress in standoff surface contaminant detector platform

NASA Astrophysics Data System (ADS)

Dupuis, Julia R.; Giblin, Jay; Dixon, John; Hensley, Joel; Mansur, David; Marinelli, William J.

2017-05-01

Progress towards the development of a longwave infrared quantum cascade laser (QLC) based standoff surface contaminant detection platform is presented. The detection platform utilizes reflectance spectroscopy with application to optically thick and thin materials including solid and liquid phase chemical warfare agents, toxic industrial chemicals and materials, and explosives. The platform employs an ensemble of broadband QCLs with a spectrally selective detector to interrogate target surfaces at 10s of m standoff. A version of the Adaptive Cosine Estimator (ACE) featuring class based screening is used for detection and discrimination in high clutter environments. Detection limits approaching 0.1 μg/cm2 are projected through speckle reduction methods enabling detector noise limited performance. The design, build, and validation of a breadboard version of the QCL-based surface contaminant detector are discussed. Functional test results specific to the QCL illuminator are presented with specific emphasis on speckle reduction.

Studying Reaction Intermediates Formed at Graphenic Surfaces

NASA Astrophysics Data System (ADS)

Sarkar, Depanjan; Sen Gupta, Soujit; Narayanan, Rahul; Pradeep, Thalappil

2014-03-01

We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

Unexpected tautomeric equilibria of the carbanion-enamine intermediate in pyruvate oxidase highlight unrecognized chemical versatility of thiamin

PubMed Central

Meyer, Danilo; Neumann, Piotr; Koers, Eline; Sjuts, Hanno; Lüdtke, Stefan; Sheldrick, George M.; Ficner, Ralf; Tittmann, Kai

2012-01-01

Thiamin diphosphate, the vitamin B1 coenzyme, plays critical roles in fundamental metabolic pathways that require acyl carbanion equivalents. Studies on chemical models and enzymes had suggested that these carbanions are resonance-stabilized as enamines. A crystal structure of this intermediate in pyruvate oxidase at 1.1 Å resolution now challenges this paradigm by revealing that the enamine does not accumulate. Instead, the intermediate samples between the ketone and the carbanion both interlocked in a tautomeric equilibrium. Formation of the keto tautomer is associated with a loss of aromaticity of the cofactor. The alternate confinement of electrons to neighboring atoms rather than π-conjugation seems to be of importance for the enzyme-catalyzed, redox-coupled acyl transfer to phosphate, which requires a dramatic inversion of polarity of the reacting substrate carbon in two subsequent catalytic steps. The ability to oscillate between a nucleophilic (carbanion) and an electrophilic (ketone) substrate center highlights a hitherto unrecognized versatility of the thiamin cofactor. It remains to be studied whether formation of the keto tautomer is a general feature of all thiamin enzymes, as it could provide for stable storage of the carbanion state, or whether this feature represents a specific trait of thiamin oxidases. In addition, the protonation state of the two-electron reduced flavin cofactor can be fully assigned, demonstrating the power of high-resolution cryocrystallography for elucidation of enzymatic mechanisms. PMID:22730460

From D-sorbitol to five-membered bis(cyclo-carbonate) as a platform molecule for the synthesis of different original biobased chemicals and polymers.

PubMed

Furtwengler, Pierre; Avérous, Luc

2018-06-14

Bis(cyclo-carbonate) was successfully synthesized from D-sorbitol (Sorb-BisCC) through an environmentally friendly process with dimethyl carbonate (DMC) as a reactant. In agreement with green chemistry principles, solvent free reactions were catalyzed and took place at low temperature. The reaction yield was increased until 50%, with the use of 1.3.5-triazabicyclo[4.4.0]dec-5-ene as catalyst and a continuous DMC feed to limit the side-reactions or the loss of reactant by azeotropic flux with a reactional subsidiary product. The obtained Sorb-BisCC is a remarkable platform molecule which could compete with others polycyclic platform molecules (isosorbide). Sorb-BisCC can be e.g., used to synthesize different chemicals such as short and long polyols, or novel biobased non-isocyanate polyurethanes (NIPU). Two Sorb-BisCC molecules have been coupled to obtain novel cyclic diols with pendant side chains. Polyether polyols were also obtained by anionic ring opening polymerization. According to the synthesis conditions, these synthetized polyether polyols range from partially to highly cross-linked materials. Finally, NIPU were synthesized with short and biobased fatty diamines. These different modifications and synthesis highlight the versatility of the Sorb-BisCC and demonstrated its high potential as building block. Sorb-BisCC can be considered as a platform molecule to open the way to different original and biobased chemical architectures.

Genomic analysis of thermophilic Bacillus coagulans strains: efficient producers for platform bio-chemicals.

PubMed

Su, Fei; Xu, Ping

2014-01-29

Microbial strains with high substrate efficiency and excellent environmental tolerance are urgently needed for the production of platform bio-chemicals. Bacillus coagulans has these merits; however, little genetic information is available about this species. Here, we determined the genome sequences of five B. coagulans strains, and used a comparative genomic approach to reconstruct the central carbon metabolism of this species to explain their fermentation features. A novel xylose isomerase in the xylose utilization pathway was identified in these strains. Based on a genome-wide positive selection scan, the selection pressure on amino acid metabolism may have played a significant role in the thermal adaptation. We also researched the immune systems of B. coagulans strains, which provide them with acquired resistance to phages and mobile genetic elements. Our genomic analysis provides comprehensive insights into the genetic characteristics of B. coagulans and paves the way for improving and extending the uses of this species.

Genomic analysis of thermophilic Bacillus coagulans strains: efficient producers for platform bio-chemicals

PubMed Central

Su, Fei; Xu, Ping

2014-01-01

Microbial strains with high substrate efficiency and excellent environmental tolerance are urgently needed for the production of platform bio-chemicals. Bacillus coagulans has these merits; however, little genetic information is available about this species. Here, we determined the genome sequences of five B. coagulans strains, and used a comparative genomic approach to reconstruct the central carbon metabolism of this species to explain their fermentation features. A novel xylose isomerase in the xylose utilization pathway was identified in these strains. Based on a genome-wide positive selection scan, the selection pressure on amino acid metabolism may have played a significant role in the thermal adaptation. We also researched the immune systems of B. coagulans strains, which provide them with acquired resistance to phages and mobile genetic elements. Our genomic analysis provides comprehensive insights into the genetic characteristics of B. coagulans and paves the way for improving and extending the uses of this species. PMID:24473268

Space transportation, satellite services, and space platforms

NASA Technical Reports Server (NTRS)

Disher, J. H.

1979-01-01

The paper takes a preview of the progressive development of vehicles for space transportation, satellite services, and orbital platforms. A low-thrust upper stage of either the ion engine or chemical type will be developed to transport large spacecraft and space platforms to and from GEO. The multimission spacecraft, space telescope, and other scientific platforms will require orbital serves going beyond that provided by the Shuttle's remote manipulator system, and plans call for extravehicular activity tools, improved remote manipulators, and a remote manned work station (the cherry picker).

Monash Chemical Yields Project (Monχey) Element production in low- and intermediate-mass stars

NASA Astrophysics Data System (ADS)

Doherty, Carolyn; Lattanzio, John; Angelou, George; Campbell, Simon W.; Church, Ross; Constantino, Thomas; Cristallo, Sergio; Gil-Pons, Pilar; Karakas, Amanda; Lugaro, Maria; Stancliffe, Richard

The Monχey project will provide a large and homogeneous set of stellar yields for the low- and intermediate- mass stars and has applications particularly to galactic chemical evolution modelling. We describe our detailed grid of stellar evolutionary models and corresponding nucleosynthetic yields for stars of initial mass 0.8 M⊙ up to the limit for core collapse supernova (CC-SN) ~ 10 M⊙. Our study covers a broad range of metallicities, ranging from the first, primordial stars (Z = 0) to those of super-solar metallicity (Z = 0.04). The models are evolved from the zero-age main-sequence until the end of the asymptotic giant branch (AGB) and the nucleosynthesis calculations include all elements from H to Bi. A major innovation of our work is the first complete grid of heavy element nucleosynthetic predictions for primordial AGB stars as well as the inclusion of extra-mixing processes (in this case thermohaline) during the red giant branch. We provide a broad overview of our results with implications for galactic chemical evolution as well as highlight interesting results such as heavy element production in dredge-out events of super-AGB stars. We briefly introduce our forthcoming web-based database which provides the evolutionary tracks, structural properties, internal/surface nucleosynthetic compositions and stellar yields. Our web interface includes user- driven plotting capabilities with output available in a range of formats. Our nucleosynthetic results will be available for further use in post processing calculations for dust production yields.

Development and Validation of a Novel Robotic Procedure Specific Simulation Platform: Partial Nephrectomy.

PubMed

Hung, Andrew J; Shah, Swar H; Dalag, Leonard; Shin, Daniel; Gill, Inderbir S

2015-08-01

We developed a novel procedure specific simulation platform for robotic partial nephrectomy. In this study we prospectively evaluate its face, content, construct and concurrent validity. This hybrid platform features augmented reality and virtual reality. Augmented reality involves 3-dimensional robotic partial nephrectomy surgical videos overlaid with virtual instruments to teach surgical anatomy, technical skills and operative steps. Advanced technical skills are assessed with an embedded full virtual reality renorrhaphy task. Participants were classified as novice (no surgical training, 15), intermediate (less than 100 robotic cases, 13) or expert (100 or more robotic cases, 14) and prospectively assessed. Cohort performance was compared with the Kruskal-Wallis test (construct validity). Post-study questionnaire was used to assess the realism of simulation (face validity) and usefulness for training (content validity). Concurrent validity evaluated correlation between virtual reality renorrhaphy task and a live porcine robotic partial nephrectomy performance (Spearman's analysis). Experts rated the augmented reality content as realistic (median 8/10) and helpful for resident/fellow training (8.0-8.2/10). Experts rated the platform highly for teaching anatomy (9/10) and operative steps (8.5/10) but moderately for technical skills (7.5/10). Experts and intermediates outperformed novices (construct validity) in efficiency (p=0.0002) and accuracy (p=0.002). For virtual reality renorrhaphy, experts outperformed intermediates on GEARS metrics (p=0.002). Virtual reality renorrhaphy and in vivo porcine robotic partial nephrectomy performance correlated significantly (r=0.8, p <0.0001) (concurrent validity). This augmented reality simulation platform displayed face, content and construct validity. Performance in the procedure specific virtual reality task correlated highly with a porcine model (concurrent validity). Future efforts will integrate procedure specific

Production of Plant Phthalate and its Hydrogenated Derivative from Bio-Based Platform Chemicals.

PubMed

Lu, Rui; Lu, Fang; Si, Xiaoqin; Jiang, Huifang; Huang, Qianqian; Yu, Weiqiang; Kong, Xiangtao; Xu, Jie

2018-04-06

Direct transformation of bio-based platform chemicals into aromatic dicarboxylic acids and their derivatives, which are widely used for the manufacture of polymers, is of significant importance for the sustainable development of the plastics industry. However, limited successful chemical processes have been reported. This study concerns a sustainable route for the production of phthalate and its hydrogenated derivative from bio-based malic acid and erythritol. The key Diels-Alder reaction is applied to build a substituted cyclohexene structure. The dehydration reaction of malic acid affords fumaric acid with 96.6 % yield, which could be used as the dienophile, and 1,3-butadiene generated in situ through erythritol deoxydehydration serves as the diene. Starting from erythritol and dibutyl fumarate, a 74.3 % yield of dibutyl trans-4-cyclohexene-1,2-dicarboxylate is obtained. The palladium-catalyzed dehydrogenation of the cycloadduct gives a 77.8 % yield of dibutyl phthalate. Dibutyl trans-cyclohexane-1,2-dicarboxylate could be formed in nearly 100 % yield under mild conditions by hydrogenation of the cycloadduct. Furthermore, fumaric acid and fumarate, with trans configurations, were found to be better dienophiles for this Diels-Alder reaction than maleic acid and maleate, with cis configuration, based on the experimental and computational results. This new route will pave the way for the production of environmental friendly plastic materials from plants. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Current technologies, economics, and perspectives for 2,5-dimethylfuran production from biomass-derived intermediates.

PubMed

Saha, Basudeb; Abu-Omar, Mahdi M

2015-04-13

Since the U.S. Department of Energy (DOE) published a perspective article that described the potential of the top ten biomass-derived platform chemicals as petroleum replacements for high-value commodity and specialty chemicals, researchers around the world have been motivated to develop technologies for the conversion of biomass and biomass-derived intermediates into chemicals and fuels. Among several biorefinery processes, the conversion of biomass carbohydrates into 2,5-dimethylfuran (DMF) has received significant attention because of its low oxygen content, high energy content, and high octane value. DMF can further serve as a petroleum-replacement, biorenewable feedstock for the production of p-xylene (pX). In this review, we aim specifically to present a concise and up-to-date analysis of DMF production technologies with a critical discussion on catalytic systems, mechanistic insight, and process economics, which includes sensitivity analysis, so that more effective catalysts can be designed. Special emphasis has been given to bifunctional catalysts that improve DMF yields and selectivity and the synergistic effect of the bifunctional sites. Process economics for the current processes and the scope for further improvement are discussed. It is anticipated that the chemistry detailed in this review will guide researchers to develop more practical catalytic processes to enable the economic production of bio-based DMF. Processes for the upgrade of DMF to pX are also described. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal–Organic Framework Thin Film Coated Optical Fiber Sensors: A Novel Waveguide-Based Chemical Sensing Platform

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

Kim, Ki-Joong; Lu, Ping; Culp, Jeffrey T.

Integration of optical fiber with sensitive thin films offers great potential for the realization of novel chemical sensing platforms. In this study, we present a simple design strategy and high performance of nanoporous metal–organic framework (MOF) based optical gas sensors, which enables detection of a wide range of concentrations of small molecules based upon extremely small differences in refractive indices as a function of analyte adsorption within the MOF framework. Thin and compact MOF films can be uniformly formed and tightly bound on the surface of etched optical fiber through a simple solution method which is critical for manufacturability ofmore » MOF-based sensor devices. The resulting sensors show high sensitivity/selectivity to CO 2 gas relative to other small gases (H 2, N 2, O 2, and CO) with rapid (< tens of seconds) response time and excellent reversibility, which can be well correlated to the physisorption of gases into a nanoporous MOF. We propose a refractive index based sensing mechanism for the MOF-integrated optical fiber platform which results in an amplification of inherent optical absorption present within the MOF-based sensing layer with increasing values of effective refractive index associated with adsorption of gases.« less

Metal–Organic Framework Thin Film Coated Optical Fiber Sensors: A Novel Waveguide-Based Chemical Sensing Platform

DOE PAGES

Kim, Ki-Joong; Lu, Ping; Culp, Jeffrey T.; ...

2018-01-18

Integration of optical fiber with sensitive thin films offers great potential for the realization of novel chemical sensing platforms. In this study, we present a simple design strategy and high performance of nanoporous metal–organic framework (MOF) based optical gas sensors, which enables detection of a wide range of concentrations of small molecules based upon extremely small differences in refractive indices as a function of analyte adsorption within the MOF framework. Thin and compact MOF films can be uniformly formed and tightly bound on the surface of etched optical fiber through a simple solution method which is critical for manufacturability ofmore » MOF-based sensor devices. The resulting sensors show high sensitivity/selectivity to CO 2 gas relative to other small gases (H 2, N 2, O 2, and CO) with rapid (< tens of seconds) response time and excellent reversibility, which can be well correlated to the physisorption of gases into a nanoporous MOF. We propose a refractive index based sensing mechanism for the MOF-integrated optical fiber platform which results in an amplification of inherent optical absorption present within the MOF-based sensing layer with increasing values of effective refractive index associated with adsorption of gases.« less

Integrated microfluidic platforms for investigating neuronal networks

NASA Astrophysics Data System (ADS)

Kim, Hyung Joon

This dissertation describes the development and application of integrated microfluidics-based assay platforms to study neuronal activities in the nervous system in-vitro. The assay platforms were fabricated using soft lithography and micro/nano fabrication including microfluidics, surface patterning, and nanomaterial synthesis. The use of integrated microfluidics-based assay platform allows culturing and manipulating many types of neuronal tissues in precisely controlled microenvironment. Furthermore, they provide organized multi-cellular in-vitro model, long-term monitoring with live cell imaging, and compatibility with molecular biology techniques and electrophysiology experiment. In this dissertation, the integrated microfluidics-based assay platforms are developed for investigation of neuronal activities such as local protein synthesis, impairment of axonal transport by chemical/physical variants, growth cone path finding under chemical/physical cues, and synaptic transmission in neuronal circuit. Chapter 1 describes the motivation, objectives, and scope for developing in-vitro platform to study various neuronal activities. Chapter 2 introduces microfluidic culture platform for biochemical assay with large-scale neuronal tissues that are utilized as model system in neuroscience research. Chapter 3 focuses on the investigation of impaired axonal transport by beta-Amyloid and oxidative stress. The platform allows to control neuronal processes and to quantify mitochondrial movement in various regions of axons away from applied drugs. Chapter 4 demonstrates the development of microfluidics-based growth cone turning assay to elucidate the mechanism underlying axon guidance under soluble factors and shear flow. Using this platform, the behaviors of growth cone of mammalian neurons are verified under the gradient of inhibitory molecules and also shear flow in well-controlled manner. In Chapter 5, I combine in-vitro multicellular model with microfabricated MEA

Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels.

PubMed

De, Sudipta; Saha, Basudeb; Luque, Rafael

2015-02-01

Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Development of a chemically defined platform fed-batch culture media for monoclonal antibody-producing CHO cell lines with optimized choline content.

PubMed

Kuwae, Shinobu; Miyakawa, Ichiko; Doi, Tomohiro

2018-01-11

A chemically defined platform basal medium and feed media were developed using a single Chinese hamster ovary (CHO) cell line that produces a monoclonal antibody (mAb). Cell line A, which showed a peak viable cell density of 5.9 × 10 6  cells/mL and a final mAb titer of 0.5 g/L in batch culture, was selected for the platform media development. Stoichiometrically balanced feed media were developed using glucose as an indicator of cell metabolism to determine the feed rates of all other nutrients. A fed-batch culture of cell line A using the platform fed-batch medium yielded a 6.4 g/L mAb titer, which was 12-fold higher than that of the batch culture. To examine the applicability of the platform basal medium and feed media, three other cell lines (A16, B, and C) that produce mAbs were cultured using the platform fed-batch medium, and they yielded mAb titers of 8.4, 3.3, and 6.2 g/L, respectively. The peak viable cell densities of the three cell lines ranged from 1.3 × 10 7 to 1.8 × 10 7  cells/mL. These results show that the nutritionally balanced fed-batch medium and feeds worked well for other cell lines. During the medium development, we found that choline limitation caused a lower cell viability, a lower mAb titer, a higher mAb aggregate content, and a higher mannose-5 content. The optimal choline chloride to glucose ratio for the CHO cell fed-batch culture was determined. Our platform basal medium and feed media will shorten the medium-development time for mAb-producing cell lines.

Arctic Intermediate Water in the Nordic Seas, 1991-2009

NASA Astrophysics Data System (ADS)

Jeansson, Emil; Olsen, Are; Jutterström, Sara

2017-10-01

The evolution of the different types of Arctic Intermediate Water (AIW) in the Nordic Seas is evaluated and compared utilising hydro-chemical data from 1991 to 2009. It has been suggested that these waters are important components of the Norwegian Sea Arctic Intermediate Water (NSAIW), and of the dense overflows to the North Atlantic. Thus, it is important to understand how their properties and distribution vary with time. The AIWs from the Greenland and Iceland Seas, show different degrees of variability during the studied period; however, only the Greenland Sea Arctic Intermediate Water (GSAIW) shows an increasing temperature and salinity throughout the 2000s, which considerably changed the properties of this water mass. Optimum multiparameter (OMP) analysis was conducted to assess the sources of the NSAIW. The analysis shows that the Iceland Sea Arctic Intermediate Water (ISAIW) and the GSAIW both contribute to NSAIW, at different densities corresponding to their respective density range. This illustrates that they flow largely isopycnally from their source regions to the Norwegian Sea. The main source of the NSAIW, however, is the upper Polar Deep Water, which explains the lower concentrations of oxygen and chlorofluorocarbons, and higher salinity and nutrient concentrations of the NSAIW layer compared with the ISAIW and GSAIW. This shows how vital it is to include chemical tracers in any water mass analysis to correctly assess the sources of the water mass being studied.

Graphene-Plasmonic Hybrid Platform for Label-Free SERS Biomedical Detection

NASA Astrophysics Data System (ADS)

Wang, Pu

Surface Enhanced Raman Scattering (SERS) has attracted explosive interest for the wealth of vibrational information it provides with minimal invasive effects to target analyte. Nanotechnology, especially in the form of noble metal nanoparticles exhibit unique electromagnetic and chemical characteristics that are explored to realize ultra-sensitive SERS detection in chemical and biological analysis. Graphene, atom-thick carbon monolayer, exhibits superior chemical stability and bio-compatibility. A combination of SERS-active metal nanostructures and graphene will create various synergies in SERS. The main objective of this research was to exploit the applications of the graphene-Au tip hybrid platform in SERS. The hybrid platform consists of a periodic Au nano-pyramid substrate to provide reproducible plasmonic enhancement, and the superimposed monolayer graphene sheet, serving as "built-in" Raman marker. Extensive theoretical and experimental studies were conducted to determine the potentials of the hybrid platform as SERS substrate. Results from both Finite-Domain Time-Domain (FDTD) numerical simulation and Raman scattering of graphene suggested that the hybrid platform boosted a high density of hotspots yielding 1000 times SERS enhancement of graphene bands. Ultra-high sensitivity of the hybrid platform was demonstrated by bio-molecules including dye, protein and neurotransmitters. Dopamine and serotonin can be detected and distinguished at 10-9 M concentration in the presence of human body fluid. Single molecule detection was obtained using a bi-analyte technique. Graphene supported a vibration mode dependent SERS chemical enhancement of ˜10 to the analyte. Quantitative evaluation of hotspots was presented using spatially resolved Raman mapping of graphene SERS enhancement. Graphene plays a crucial role in quantifying SERS hotspots and paves the path for defining SERS EF that could be universally applied to various SERS systems. A reproducible and statistically

Catalytic Conversion of Renewable Resources into Bulk and Fine Chemicals.

PubMed

de Vries, Johannes G

2016-12-01

Several strategies can be chosen to convert renewable resources into chemicals. In this account, I exemplify the route that starts with so-called platform chemicals; these are relatively simple chemicals that can be produced in high yield, directly from renewable resources, either via fermentation or via chemical routes. They can be converted into the existing bulk chemicals in a very efficient manner using multistep catalytic conversions. Two examples are given of the conversion of sugars into nylon intermediates. 5-Hydroxymethylfurfural (HMF) can be prepared in good yield from fructose. Two hydrogenation steps convert HMF into 1,6-hexanediol. Oppenauer oxidation converts this product into caprolactone, which in the past, has been converted into caprolactam in a large-scale industrial process by reaction with ammonia. An even more interesting platform chemical is levulinic acid (LA), which can be obtained directly from lignocellulose in good yield by treatment with dilute sulfuric acid at 200°C. Hydrogenation converts LA into gamma-valerolactone, which is ring-opened and esterified in a gas-phase process to a mixture of isomeric methyl pentenoates in excellent selectivity. In a remarkable selective palladium-catalysed isomerising methoxycarbonylation, this mixture is converted in to dimethyl adipate, which is finally hydrolysed to adipic acid. Overall selectivities of both processes are extremely high. The conversion of lignin into chemicals is a much more complicated task in view of the complex nature of lignin. It was discovered that breakage of the most prevalent β-O-4 bond in lignin occurs not only via the well-documented C3 pathway, but also via a C2 pathway, leading to the formation of highly reactive phenylacetaldehydes. These compounds went largely unnoticed as they immediately recondense on lignin. We have now found that it is possible to prevent this by converting these aldehydes in a tandem reaction, as they are formed. For this purpose, we have used

Tectonic Implications of Intermediate-depth Earthquakes Beneath the Northeast Caribbean

NASA Astrophysics Data System (ADS)

Mejia, H.; Pulliam, J.; Huerfano, V.; Polanco Rivera, E.

2016-12-01

The Caribbean-North American plate boundary transitions from normal subduction beneath the Lesser Antilles to oblique subduction at Hispaniola before becoming exclusively transform at Cuba. In the Greater Antilles, large earthquakes occur all along the plate boundary at shallow depths but intermediate-depth earthquakes (50-200 km focal depth) occur almost uniquely beneath eastern Hispaniola. Previous studies have suggested that regional tectonics may be dominated by, for example, opposing subducting slabs, tearing of the subducting North American slab, or "slab push" by the NA slab. In addition, the Bahamas Platform, located north of Hispaniola, is likely causing compressive stresses and clockwise rotation of the island. A careful examination of focal mechanisms of intermediate-depth earthquakes could clarify regional tectonics but seismic stations in the region have historically been sparse, so constraints on earthquake depths and focal mechanisms have been poor. In response, fifteen broadband sensors were deployed in the Dominican Republic in 2014, increasing the number of stations to twenty-two. To determine the roles earthquakes play in regional tectonics, a event catalog was created joining data from our stations and other regional stations for which event depths are greater than 50 km and magnitudes are greater than 3.5. All events have been relocated and focal mechanisms are presented for as many events as possible. Multiple probable fault planes are computed for each event. Compressive (P) and tensional (T) axes, from fault planes, are plotted in 3-dimensions with density distribution contours determined of each axis. Examining relationships between axes distributions and events helps constrain tectonic stresses at intermediate-depths beneath eastern Hispaniola. A majority of events show primary compressive axes oriented in a north-south direction, likely produced by collision with the Bahamas Platform.

Coupled sensor/platform control design for low-level chemical detection with position-adaptive micro-UAVs

NASA Astrophysics Data System (ADS)

Goodwin, Thomas; Carr, Ryan; Mitra, Atindra K.; Selmic, Rastko R.

2009-05-01

We discuss the development of Position-Adaptive Sensors [1] for purposes for detecting embedded chemical substances in challenging environments. This concept is a generalization of patented Position-Adaptive Radar Concepts developed at AFRL for challenging conditions such as urban environments. For purposes of investigating the detection of chemical substances using multiple MAV (Micro-UAV) platforms, we have designed and implemented an experimental testbed with sample structures such as wooden carts that contain controlled leakage points. Under this general concept, some of the members of a MAV swarm can serve as external position-adaptive "transmitters" by blowing air over the cart and some of the members of a MAV swarm can serve as external position-adaptive "receivers" that are equipped with chemical or biological (chem/bio) sensors that function as "electronic noses". The objective can be defined as improving the particle count of chem/bio concentrations that impinge on a MAV-based position-adaptive sensor that surrounds a chemical repository, such as a cart, via the development of intelligent position-adaptive control algorithms. The overall effect is to improve the detection and false-alarm statistics of the overall system. Within the major sections of this paper, we discuss a number of different aspects of developing our initial MAV-Based Sensor Testbed. This testbed includes blowers to simulate position-adaptive excitations and a MAV from Draganfly Innovations Inc. with stable design modifications to accommodate our chem/bio sensor boom design. We include details with respect to several critical phases of the development effort including development of the wireless sensor network and experimental apparatus, development of the stable sensor boom for the MAV, integration of chem/bio sensors and sensor node onto the MAV and boom, development of position-adaptive control algorithms and initial tests at IDCAST (Institute for the Development and

Extremely thermophilic microorganisms as metabolic engineering platforms for production of fuels and industrial chemicals.

PubMed

Zeldes, Benjamin M; Keller, Matthew W; Loder, Andrew J; Straub, Christopher T; Adams, Michael W W; Kelly, Robert M

2015-01-01

Enzymes from extremely thermophilic microorganisms have been of technological interest for some time because of their ability to catalyze reactions of industrial significance at elevated temperatures. Thermophilic enzymes are now routinely produced in recombinant mesophilic hosts for use as discrete biocatalysts. Genome and metagenome sequence data for extreme thermophiles provide useful information for putative biocatalysts for a wide range of biotransformations, albeit involving at most a few enzymatic steps. However, in the past several years, unprecedented progress has been made in establishing molecular genetics tools for extreme thermophiles to the point that the use of these microorganisms as metabolic engineering platforms has become possible. While in its early days, complex metabolic pathways have been altered or engineered into recombinant extreme thermophiles, such that the production of fuels and chemicals at elevated temperatures has become possible. Not only does this expand the thermal range for industrial biotechnology, it also potentially provides biodiverse options for specific biotransformations unique to these microorganisms. The list of extreme thermophiles growing optimally between 70 and 100°C with genetic toolkits currently available includes archaea and bacteria, aerobes and anaerobes, coming from genera such as Caldicellulosiruptor, Sulfolobus, Thermotoga, Thermococcus, and Pyrococcus. These organisms exhibit unusual and potentially useful native metabolic capabilities, including cellulose degradation, metal solubilization, and RuBisCO-free carbon fixation. Those looking to design a thermal bioprocess now have a host of potential candidates to choose from, each with its own advantages and challenges that will influence its appropriateness for specific applications. Here, the issues and opportunities for extremely thermophilic metabolic engineering platforms are considered with an eye toward potential technological advantages for high

Extremely thermophilic microorganisms as metabolic engineering platforms for production of fuels and industrial chemicals

PubMed Central

Zeldes, Benjamin M.; Keller, Matthew W.; Loder, Andrew J.; Straub, Christopher T.; Adams, Michael W. W.; Kelly, Robert M.

2015-01-01

Enzymes from extremely thermophilic microorganisms have been of technological interest for some time because of their ability to catalyze reactions of industrial significance at elevated temperatures. Thermophilic enzymes are now routinely produced in recombinant mesophilic hosts for use as discrete biocatalysts. Genome and metagenome sequence data for extreme thermophiles provide useful information for putative biocatalysts for a wide range of biotransformations, albeit involving at most a few enzymatic steps. However, in the past several years, unprecedented progress has been made in establishing molecular genetics tools for extreme thermophiles to the point that the use of these microorganisms as metabolic engineering platforms has become possible. While in its early days, complex metabolic pathways have been altered or engineered into recombinant extreme thermophiles, such that the production of fuels and chemicals at elevated temperatures has become possible. Not only does this expand the thermal range for industrial biotechnology, it also potentially provides biodiverse options for specific biotransformations unique to these microorganisms. The list of extreme thermophiles growing optimally between 70 and 100°C with genetic toolkits currently available includes archaea and bacteria, aerobes and anaerobes, coming from genera such as Caldicellulosiruptor, Sulfolobus, Thermotoga, Thermococcus, and Pyrococcus. These organisms exhibit unusual and potentially useful native metabolic capabilities, including cellulose degradation, metal solubilization, and RuBisCO-free carbon fixation. Those looking to design a thermal bioprocess now have a host of potential candidates to choose from, each with its own advantages and challenges that will influence its appropriateness for specific applications. Here, the issues and opportunities for extremely thermophilic metabolic engineering platforms are considered with an eye toward potential technological advantages for high

Research on distributed heterogeneous data PCA algorithm based on cloud platform

NASA Astrophysics Data System (ADS)

Zhang, Jin; Huang, Gang

2018-05-01

Principal component analysis (PCA) of heterogeneous data sets can solve the problem that centralized data scalability is limited. In order to reduce the generation of intermediate data and error components of distributed heterogeneous data sets, a principal component analysis algorithm based on heterogeneous data sets under cloud platform is proposed. The algorithm performs eigenvalue processing by using Householder tridiagonalization and QR factorization to calculate the error component of the heterogeneous database associated with the public key to obtain the intermediate data set and the lost information. Experiments on distributed DBM heterogeneous datasets show that the model method has the feasibility and reliability in terms of execution time and accuracy.

Wireless Sensor Network-Based Service Provisioning by a Brokering Platform.

PubMed

Guijarro, Luis; Pla, Vicent; Vidal, Jose R; Naldi, Maurizio; Mahmoodi, Toktam

2017-05-12

This paper proposes a business model for providing services based on the Internet of Things through a platform that intermediates between human users and Wireless Sensor Networks (WSNs). The platform seeks to maximize its profit through posting both the price charged to each user and the price paid to each WSN. A complete analysis of the profit maximization problem is performed in this paper. We show that the service provider maximizes its profit by incentivizing all users and all Wireless Sensor Infrastructure Providers (WSIPs) to join the platform. This is true not only when the number of users is high, but also when it is moderate, provided that the costs that the users bear do not trespass a cost ceiling. This cost ceiling depends on the number of WSIPs, on the value of the intrinsic value of the service and on the externality that the WSIP has on the user utility.

Recent Progress in Optical Biosensors Based on Smartphone Platforms

PubMed Central

Geng, Zhaoxin; Zhang, Xiong; Fan, Zhiyuan; Lv, Xiaoqing; Su, Yue; Chen, Hongda

2017-01-01

With a rapid improvement of smartphone hardware and software, especially complementary metal oxide semiconductor (CMOS) cameras, many optical biosensors based on smartphone platforms have been presented, which have pushed the development of the point-of-care testing (POCT). Imaging-based and spectrometry-based detection techniques have been widely explored via different approaches. Combined with the smartphone, imaging-based and spectrometry-based methods are currently used to investigate a wide range of molecular properties in chemical and biological science for biosensing and diagnostics. Imaging techniques based on smartphone-based microscopes are utilized to capture microscale analysts, while spectrometry-based techniques are used to probe reactions or changes of molecules. Here, we critically review the most recent progress in imaging-based and spectrometry-based smartphone-integrated platforms that have been developed for chemical experiments and biological diagnosis. We focus on the analytical performance and the complexity for implementation of the platforms. PMID:29068375

Recent Progress in Optical Biosensors Based on Smartphone Platforms.

PubMed

Geng, Zhaoxin; Zhang, Xiong; Fan, Zhiyuan; Lv, Xiaoqing; Su, Yue; Chen, Hongda

2017-10-25

With a rapid improvement of smartphone hardware and software, especially complementary metal oxide semiconductor (CMOS) cameras, many optical biosensors based on smartphone platforms have been presented, which have pushed the development of the point-of-care testing (POCT). Imaging-based and spectrometry-based detection techniques have been widely explored via different approaches. Combined with the smartphone, imaging-based and spectrometry-based methods are currently used to investigate a wide range of molecular properties in chemical and biological science for biosensing and diagnostics. Imaging techniques based on smartphone-based microscopes are utilized to capture microscale analysts, while spectrometry-based techniques are used to probe reactions or changes of molecules. Here, we critically review the most recent progress in imaging-based and spectrometry-based smartphone-integrated platforms that have been developed for chemical experiments and biological diagnosis. We focus on the analytical performance and the complexity for implementation of the platforms.

Production of Phloroglucinol, a Platform Chemical, in Arabidopsis using a Bacterial Gene.

PubMed

Abdel-Ghany, Salah E; Day, Irene; Heuberger, Adam L; Broeckling, Corey D; Reddy, Anireddy S N

2016-12-07

Phloroglucinol (1,3,5-trihydroxybenzene; PG) and its derivatives are phenolic compounds that are used for various industrial applications. Current methods to synthesize PG are not sustainable due to the requirement for carbon-based precursors and co-production of toxic byproducts. Here, we describe a more sustainable production of PG using plants expressing a native bacterial or a codon-optimized synthetic PhlD targeted to either the cytosol or chloroplasts. Transgenic lines were analyzed for the production of PG using gas and liquid chromatography coupled to mass spectroscopy. Phloroglucinol was produced in all transgenic lines and the line with the highest PhlD transcript level showed the most accumulation of PG. Over 80% of the produced PG was glycosylated to phlorin. Arabidopsis leaves have the machinery to glycosylate PG to form phlorin, which can be hydrolyzed enzymatically to produce PG. Furthermore, the metabolic profile of plants with PhlD in either the cytosol or chloroplasts was altered. Our results provide evidence that plants can be engineered to produce PG using a bacterial gene. Phytoproduction of PG using a bacterial gene paves the way for further genetic manipulations to enhance the level of PG with implications for the commercial production of this important platform chemical in plants.

Nanopaper as an Optical Sensing Platform.

PubMed

Morales-Narváez, Eden; Golmohammadi, Hamed; Naghdi, Tina; Yousefi, Hossein; Kostiv, Uliana; Horák, Daniel; Pourreza, Nahid; Merkoçi, Arben

2015-07-28

Bacterial cellulose nanopaper (BC) is a multifunctional material known for numerous desirable properties: sustainability, biocompatibility, biodegradability, optical transparency, thermal properties, flexibility, high mechanical strength, hydrophilicity, high porosity, broad chemical-modification capabilities and high surface area. Herein, we report various nanopaper-based optical sensing platforms and describe how they can be tuned, using nanomaterials, to exhibit plasmonic or photoluminescent properties that can be exploited for sensing applications. We also describe several nanopaper configurations, including cuvettes, plates and spots that we printed or punched on BC. The platforms include a colorimetric-based sensor based on nanopaper containing embedded silver and gold nanoparticles; a photoluminescent-based sensor, comprising CdSe@ZnS quantum dots conjugated to nanopaper; and a potential up-conversion sensing platform constructed from nanopaper functionalized with NaYF4:Yb(3+)@Er(3+)&SiO2 nanoparticles. We have explored modulation of the plasmonic or photoluminescent properties of these platforms using various model biologically relevant analytes. Moreover, we prove that BC is and advantageous preconcentration platform that facilitates the analysis of small volumes of optically active materials (∼4 μL). We are confident that these platforms will pave the way to optical (bio)sensors or theranostic devices that are simple, transparent, flexible, disposable, lightweight, miniaturized and perhaps wearable.

Alginate based 3D hydrogels as an in vitro co-culture model platform for the toxicity screening of new chemical entities.

PubMed

Lan, Shih-Feng; Starly, Binil

2011-10-01

Prediction of human response to potential therapeutic drugs is through conventional methods of in vitro cell culture assays and expensive in vivo animal testing. Alternatives to animal testing require sophisticated in vitro model systems that must replicate in vivo like function for reliable testing applications. Advancements in biomaterials have enabled the development of three-dimensional (3D) cell encapsulated hydrogels as in vitro drug screening tissue model systems. In this study, we have developed an in vitro platform to enable high density 3D culture of liver cells combined with a monolayer growth of target breast cancer cell line (MCF-7) in a static environment as a representative example of screening drug compounds for hepatotoxicity and drug efficacy. Alginate hydrogels encapsulated with serial cell densities of HepG2 cells (10(5)-10(8) cells/ml) are supported by a porous poly-carbonate disc platform and co-cultured with MCF-7 cells within standard cell culture plates during a 3 day study period. The clearance rates of drug transformation by HepG2 cells are measured using a coumarin based pro-drug. The platform was used to test for HepG2 cytotoxicity 50% (CT(50)) using commercially available drugs which further correlated well with published in vivo LD(50) values. The developed test platform allowed us to evaluate drug dose concentrations to predict hepatotoxicity and its effect on the target cells. The in vitro 3D co-culture platform provides a scalable and flexible approach to test multiple-cell types in a hybrid setting within standard cell culture plates which may open up novel 3D in vitro culture techniques to screen new chemical entity compounds. Copyright © 2011 Elsevier Inc. All rights reserved.

O-Succinyl-L-homoserine-based C4-chemical production: succinic acid, homoserine lactone, γ-butyrolactone, γ-butyrolactone derivatives, and 1,4-butanediol.

PubMed

Hong, Kuk-Ki; Kim, Jeong Hyun; Yoon, Jong Hyun; Park, Hye-Min; Choi, Su Jin; Song, Gyu Hyeon; Lee, Jea Chun; Yang, Young-Lyeol; Shin, Hyun Kwan; Kim, Ju Nam; Cho, Kyung Ho; Lee, Jung Ho

2014-10-01

There has been a significant global interest to produce bulk chemicals from renewable resources using engineered microorganisms. Large research programs have been launched by academia and industry towards this goal. Particularly, C4 chemicals such as succinic acid (SA) and 1,4-butanediol have been leading the path towards the commercialization of biobased technology with the effort of replacing chemical production. Here we present O-Succinyl-L-homoserine (SH) as a new, potentially important platform biochemical and demonstrate its central role as an intermediate in the production of SA, homoserine lactone (HSL), γ-butyrolactone (GBL) and its derivatives, and 1,4-butanediol (BDO). This technology encompasses (1) the genetic manipulation of Escherichia coli to produce SH with high productivity, (2) hydrolysis into SA and homoserine (HS) or homoserine lactone hydrochloride, and (3) chemical conversion of either HS or homoserine lactone HCL (HSL·HCl) into drop-in chemicals in polymer industry. This production strategy with environmental benefits is discussed in the perspective of targeting of fermented product and a process direction compared to petroleum-based chemical conversion, which may reduce the overall manufacturing cost.

Examining the freezing process of an intermediate bulk containing an industrially relevant protein

PubMed Central

Reinsch, Holger; Spadiut, Oliver; Heidingsfelder, Johannes; Herwig, Christoph

2015-01-01

Numerous biopharmaceuticals are produced in recombinant microorganisms in the controlled environment of a bioreactor, a process known as Upstream Process. To minimize product loss due to physico-chemical and enzymatic degradation, the Upstream Process should be directly followed by product purification, known as Downstream Process. However, the Downstream Process can be technologically complex and time-consuming which is why Upstream and Downstream Process usually have to be decoupled temporally and spatially. Consequently, the product obtained after the Upstream Process, known as intermediate bulk, has to be stored. In those circumstances, a freezing procedure is often performed to prevent product loss. However, the freezing process itself is inseparably linked to physico-chemical changes of the intermediate bulk which may in turn damage the product. The present study analysed the behaviour of a Tris-buffered intermediate bulk containing a biopharmaceutically relevant protein during a bottle freezing process. Major damaging mechanisms, like the spatiotemporal redistribution of ion concentrations and pH, and their influence on product stability were investigated. Summarizing, we show the complex events which happen in an intermediate bulk during freezing and explain the different causes for product loss. PMID:25765305

Wireless Sensor Network-Based Service Provisioning by a Brokering Platform

PubMed Central

Guijarro, Luis; Pla, Vicent; Vidal, Jose R.; Naldi, Maurizio; Mahmoodi, Toktam

2017-01-01

This paper proposes a business model for providing services based on the Internet of Things through a platform that intermediates between human users and Wireless Sensor Networks (WSNs). The platform seeks to maximize its profit through posting both the price charged to each user and the price paid to each WSN. A complete analysis of the profit maximization problem is performed in this paper. We show that the service provider maximizes its profit by incentivizing all users and all Wireless Sensor Infrastructure Providers (WSIPs) to join the platform. This is true not only when the number of users is high, but also when it is moderate, provided that the costs that the users bear do not trespass a cost ceiling. This cost ceiling depends on the number of WSIPs, on the value of the intrinsic value of the service and on the externality that the WSIP has on the user utility. PMID:28498347

Reduction of matrix interferences in furnace atomic absorption with the L'vov Platform

USGS Publications Warehouse

Kaiser, M.L.; Koirtyohann, S.R.; Hinderberger, E.J.; Taylor, Howard E.

1981-01-01

Use of a modified L'vov Platform and ammonium phosphate as a matrix modifier greatly reduced matrix interferences in a commercial Massmann-type atomic absorption furnace. Platforms were readily fabricated from furnace tubes and, once positioned in the furnace, caused no inconvenience in operation. Two volatile elements (Pb, Cd), two of intermediate volatility (Co, Cr) and two which form stable oxides (Al, Sn) were tested in natural water and selected synthetic matrices. In every case for which there was a significant matrix effect during atomization from the tube wall, the platform and platform plus modifier gave improved performance. With lead, for example, an average ratio of 0.48 ?? 0.11 was found when the slope of the standard additions plot for six different natural water samples was compared to the slope of the standard working curve in dilute acid. The average slope ratio between the natural water matrices and the dilute acid matrix was 0.94 ?? 0.03 with the L'vov Platform and 0.96 ?? 0.03 with the platform and matrix modifier. In none of the cases studied did the use of the platform or platform plus modifier cause an interference problem where none existed while atomizing from the tube wall. An additional benefit of the platform was a factor of about two improvement in peak height precision. ?? 1981.

The PubChem chemical structure sketcher

PubMed Central

2009-01-01

PubChem is an important public, Web-based information source for chemical and bioactivity information. In order to provide convenient structure search methods on compounds stored in this database, one mandatory component is a Web-based drawing tool for interactive sketching of chemical query structures. Web-enabled chemical structure sketchers are not new, being in existence for years; however, solutions available rely on complex technology like Java applets or platform-dependent plug-ins. Due to general policy and support incident rate considerations, Java-based or platform-specific sketchers cannot be deployed as a part of public NCBI Web services. Our solution: a chemical structure sketching tool based exclusively on CGI server processing, client-side JavaScript functions, and image sequence streaming. The PubChem structure editor does not require the presence of any specific runtime support libraries or browser configurations on the client. It is completely platform-independent and verified to work on all major Web browsers, including older ones without support for Web2.0 JavaScript objects. PMID:20298522

Impact of sulfur dioxide oxidation by Stabilized Criegee Intermediate on sulfate

EPA Science Inventory

We revise the Carbon Bond chemical mechanism to explicitly represent three Stabilized Criegee Intermediates (SCIs) and their subsequent reactions with sulfur dioxide, water monomer, and water dimer, and incorporate the reactions into the Community Multiscale Air Quality model. Th...

A nanowaveguide platform for collective atom-light interaction

NASA Astrophysics Data System (ADS)

Meng, Y.; Lee, J.; Dagenais, M.; Rolston, S. L.

2015-08-01

We propose a nanowaveguide platform for collective atom-light interaction through evanescent field coupling. We have developed a 1 cm-long silicon nitride nanowaveguide can use evanescent fields to trap and probe an ensemble of 87Rb atoms. The waveguide has a sub-micrometer square mode area and was designed with tapers for high fiber-to-waveguide coupling efficiencies at near-infrared wavelengths (750 nm to 1100 nm). Inverse tapers in the platform adiabatically transfer a weakly guided mode of fiber-coupled light into a strongly guided mode with an evanescent field to trap atoms and then back to a weakly guided mode at the other end of the waveguide. The coupling loss is -1 dB per facet (˜80% coupling efficiency) at 760 nm and 1064 nm, which is estimated by a propagation loss measurement with waveguides of different lengths. The proposed platform has good thermal conductance and can guide high optical powers for trapping atoms in ultra-high vacuum. As an intermediate step, we have observed thermal atom absorption of the evanescent component of a nanowaveguide and have demonstrated the U-wire mirror magneto-optical trap that can transfer atoms to the proximity of the surface.

Intermediate-Band Photometric Luminosity Descrimination for M Stars

NASA Astrophysics Data System (ADS)

Robertson, T. H.; Furiak, N. M.

1995-12-01

Synthetic photometry has been used to design an intermediate-band filter to be used with CCD cameras to facilitate the luminosity classification of M stars. Spectrophotometric data published by Gunn & Stryker (1983) were used to test various bandwidths and centers. Based on these calculations an intermediate-band filter has been purchased. This filter is being used in conjunction with standard BVRI filters to test its effectiveness in luminosity classification of M stars having a wide range of temperatures and different chemical compositions. The results of the theoretical calculations, filter design specifications and preliminary results of the testing program are presented. This research is supported in part by funds provided by Ball State University, The Fund for Astrophysical Research and the Indiana Academy of Science.

A database of archived drilling records of the drill cuttings piles at the North West Hutton oil platform.

PubMed

Marsh, Roy

2003-05-01

Drill cuttings piles are found underneath several hundred oil platforms in the North Sea, and are contaminated with hydrocarbons and chemical products. This study characterised the environmental risk posed by the cuttings pile at the North West Hutton (NWH) oil platform. Data on the drilling fluids and chemical products used over the platform's drilling history were transferred from archived well reports into a custom database, to which were added toxicological and safety data. Although the database contained many gaps, it established that only seven chemical products used at NWH were not in the lowest category of the Offshore Chemicals Notification Scheme, and were used in only small quantities. The study therefore supports the view that the main environmental risk posed by cuttings piles comes from hydrocarbon contamination. The (dated) well records could help future core sampling to be targeted at specific locations in the cuttings piles. Data from many platforms could also be pooled to determine generic 'discharge profiles.' Future study would benefit from the existence, in the public domain, of a standardised, 'legacy' database of chemical products.

Examination of the constructional processes of submarine Cerro Azul and the Galapagos Platform

NASA Astrophysics Data System (ADS)

Lambert, M. K.; Harpp, K. S.; Geist, D. J.; Fornari, D. J.; Kurz, M. D.; Koleszar, A. M.; Rollins, N. A.

2004-05-01

One of the primary goals of the 2001 Drift04 cruise was to examine the constructional processes responsible for the Galapagos platform and to investigate the relationship between the platform and the overlying volcanoes. Cerro Azul volcano is located above the steep escarpment that marks the southwestern limit of the Galapagos platform, at the leading edge of the hotspot. This area is of particular interest in light of a recent seismic tomography experiment by Toomey, Hooft, et al., which suggests that the root of the Galapagos plume is centered between Cerro Azul and adjacent Fernandina Island. During the Drift04 cruise, detailed bathymetric and sidescan sonar studies were carried out across the submarine sector of Cerro Azul and 14 dredges were collected from the same area. Major element analyses of the submarine lavas indicate that the lavas from the platform edge and the subaerial Cerro Azul lavas constitute a suite of petrologically-related lavas. The dredged glasses of the Drift04 cruise have MgO contents of <7.5% and are indistinguishable from published data on Cerro Azul. Whole rock analyses include a highly primitive sample (20 wt% MgO), which probably contains accumulated olivine. All the submarine and subaerial lavas define coherent trends in major element space that are consistent with variable amounts of olivine and olivine+cpx fractionation. Incompatible trace element (ITE) ratios indicate that the mantle source for the submarine platform flows is intermediate in composition between the magmas supplying Fernandina and Cerro Azul. Previous researchers have proposed that two mantle endmembers are interacting across the leading edge of the plume, one focused at Fernandina and the other at Floreana Island. The intermediate ITE ratios of the submarine and subaerial Cerro Azul lavas are consistent both geographically and compositionally with this hypothesis. Naumann and co-workers concluded that the lavas erupted at Cerro Azul were stored in small

NMR analysis of a kinetically trapped intermediate of a disulfide-deficient mutant of the starch-binding domain of glucoamylase.

PubMed

Sugimoto, Hayuki; Noda, Yasuo; Segawa, Shin-ichi

2011-09-16

A thermally unfolded disulfide-deficient mutant of the starch-binding domain of glucoamylase refolds into a kinetically trapped metastable intermediate when subjected to a rapid lowering of temperature. We attempted to characterise this intermediate using multidimensional NMR spectroscopy. The (1)H-(15)N heteronuclear single quantum coherence spectrum after a rapid temperature decrease (the spectrum of the intermediate) showed good chemical shift dispersion but was significantly different from that of the native state, suggesting that the intermediate adopts a nonnative but well-structured conformation. Large chemical shift changes for the backbone amide protons between the native and the intermediate states were observed for residues in the β-sheet consisting of strands 2, 3, 5, 6, and 7 as well as in the C-terminal region. These residues were found to be in close proximity to aromatic residues, suggesting that the chemical shift changes are mainly due to ring current shifts caused by the aromatic residues. The two-dimensional nuclear Overhauser enhancement (NOE) spectroscopy experiments showed that the intermediate contained substantial, native-like NOE connectivities, although there were fewer cross peaks in the spectrum of the intermediate compared with that of the native state. It was also shown that there were native-like interresidue NOEs for residues buried in the protein, whereas many of the NOE cross peaks were lost for the residues involved in a surface-exposed aromatic cluster. These results suggest that, in the intermediate, the aromatic cluster at the surface is structurally less organised, whereas the interior of the protein has relatively rigid, native-like side-chain packing. Copyright © 2011 Elsevier Ltd. All rights reserved.

Recent advances in the metabolic engineering of microorganisms for the production of 3-hydroxypropionic acid as C3 platform chemical.

PubMed

Valdehuesa, Kris Niño G; Liu, Huaiwei; Nisola, Grace M; Chung, Wook-Jin; Lee, Seung Hwan; Park, Si Jae

2013-04-01

Development of sustainable technologies for the production of 3-hydroxypropionic acid (3HP) as a platform chemical has recently been gaining much attention owing to its versatility in applications for the synthesis of other specialty chemicals. Several proposed biological synthesis routes and strategies for producing 3HP from glucose and glycerol are reviewed presently. Ten proposed routes for 3HP production from glucose are described and one of which was recently constructed successfully in Escherichia coli with malonyl-Coenzyme A as a precursor. This resulted in a yield still far from the required level for industrial application. On the other hand, strategies employing engineered E. coli and Klebsiella pneumoniae capable of producing 3HP from glycerol are also evaluated. The titers produced by these recombinant strains reached around 3 %. At its current state, it is evident that a bulk of engineering works is yet to be done to acquire a biosynthesis route for 3HP that is acceptable for industrial-scale production.

Chemically Activated Formation of Organic Acids in Reactions of the Criegee Intermediate with Aldehydes and Ketones

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

Jalan, Amrit; Allen, Joshua W.; Green, William H.

Reactions of the Criegee intermediate (CI, .CH2OO.) are important in atmospheric ozonolysis models. In this work, we compute the rates for reactions between .CH2OO. and HCHO, CH3CHO and CH3COCH3 leading to the formation of secondary ozonides (SOZ) and organic acids. Relative to infinitely separated reactants, the SOZ in all three cases is found to be 48–51 kcal mol-1 lower in energy, formed via 1,3- cycloaddition of .CH2OO. across the CQO bond. The lowest energy pathway found for SOZ decomposition is intramolecular disproportionation of the singlet biradical intermediate formed from cleavage of the O–O bond to form hydroxyalkyl esters. These hydroxyalkylmore » esters undergo concerted decomposition providing a low energy pathway from SOZ to acids. Geometries and frequencies of all stationary points were obtained using the B3LYP/MG3S DFT model chemistry, and energies were refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. RRKM calculations were used to obtain microcanonical rate coefficients (k(E)) and the reservoir state method was used to obtain temperature and pressure dependent rate coefficients (k(T, P)) and product branching ratios. At atmospheric pressure, the yield of collisionally stabilized SOZ was found to increase in the order HCHO o CH3CHO o CH3COCH3 (the highest yield being 10-4 times lower than the initial .CH2OO. concentration). At low pressures, chemically activated formation of organic acids (formic acid in the case of HCHO and CH3COCH3, formic and acetic acid in the case of CH3CHO) was found to be the major product channel in agreement with recent direct measurements. Collisional energy transfer parameters and the barrier heights for SOZ reactions were found to be the most sensitive parameters determining SOZ and organic acid yield.« less

Spatial variation of a short-lived intermediate chemical species in a Couette reactor

NASA Astrophysics Data System (ADS)

Vigil, R. Dennis; Ouyang, Q.; Swinney, Harry L.

1992-04-01

We have conducted experiments and simulations of the spatial variation of a short-lived intermediate species (triiodide) in the autocatalytic oxidation of arsenite by iodate in a reactor that is essentially one dimensional—the Couette reactor. (This reactor consists of two concentric cylinders with the inner one rotating and the outer one at rest; reagents are continuously fed and removed at each end in such a way that there is no net axial flux and there are opposing arsenite and iodate gradients.) The predictions of a one-dimensional reaction-diffusion model, which has no adjustable parameters, are in good qualitative (and, in some cases, quantitative) agreement with experiments. Thus, the Couette reactor, which is used to deliberately create spatial inhomogeneities, can be exploited to enhance the recovery of short-lived intermediate species relative to that which can be obtained with either a batch or continuous-flow stirred-tank reactor.

Spatial and temporal control of microwave triggered chemiluminescence: a protein detection platform.

PubMed

Previte, Michael J R; Aslan, Kadir; Geddes, Chris D

2007-09-15

We have combined the principles of microwave circuitry and antenna design and our recent work in microwave-triggered metal-enhanced chemiluminescence to now "trigger" chemically and enzyme-catalyzed chemiluminescent reactions with spatial and temporal control. With this technology platform, we achieve spatial and temporal control of enzyme and chemically catalyzed chemiluminescence reactions to achieve more than 500-fold increases in "on-demand" photon flux from chemically catalyzed chemiluminescent reactions. We also report a 6-fold increase in photon flux from HRP-catalyzed assays on disposable coverslips functionalized with HRP and placed proximal to the substrates modified with thin-film aluminum triangle disjointed "bow-tie" structures. In addition, we demonstrate the applicability of this technology to develop multiplexed or high-throughput chemiluminescent assays. We also demonstrate the clinical and biological relevance of this technology platform by affixing aluminum structures in proximity to HRP protein immobilized on nitrocellulose to improve the sensitivity for this model Western blot scheme by 50-fold. We believe analytical applications that rely on enzyme-catalyzed chemiluminescence, such as immunoassays, may greatly benefit from this new platform technology.

Brewing as a Comprehensive Learning Platform in Chemical Engineering

ERIC Educational Resources Information Center

Nielsen, Rudi P.; Sørensen, Jens L.; Simonsen, Morten E.; Madsen, Henrik T.; Muff, Jens; Strandgaard, Morten; Søgaard, Erik G.

2016-01-01

Chemical engineering is mostly taught using traditional classroom teaching and laboratory experiments when possible. Being a wide discipline encompassing topics such as analytical chemistry, process design, and microbiology, it may be argued that brewing of beer has many relations to chemical engineering topic-wise. This work illustrates how…

A novel biochemical route for fuels and chemicals production from cellulosic biomass.

PubMed

Fan, Zhiliang; Wu, Weihua; Hildebrand, Amanda; Kasuga, Takao; Zhang, Ruifu; Xiong, Xiaochao

2012-01-01

The conventional biochemical platform featuring enzymatic hydrolysis involves five key steps: pretreatment, cellulase production, enzymatic hydrolysis, fermentation, and product recovery. Sugars are produced as reactive intermediates for subsequent fermentation to fuels and chemicals. Herein, an alternative biochemical route is proposed. Pretreatment, enzymatic hydrolysis and cellulase production is consolidated into one single step, referred to as consolidated aerobic processing, and sugar aldonates are produced as the reactive intermediates for biofuels production by fermentation. In this study, we demonstrate the viability of consolidation of the enzymatic hydrolysis and cellulase production steps in the new route using Neurospora crassa as the model microorganism and the conversion of cellulose to ethanol as the model system. We intended to prove the two hypotheses: 1) cellulose can be directed to produce cellobionate by reducing β-glucosidase production and by enhancing cellobiose dehydrogenase production; and 2) both of the two hydrolysis products of cellobionate--glucose and gluconate--can be used as carbon sources for ethanol and other chemical production. Our results showed that knocking out multiple copies of β-glucosidase genes led to cellobionate production from cellulose, without jeopardizing the cellulose hydrolysis rate. Simulating cellobiose dehydrogenase over-expression by addition of exogenous cellobiose dehydrogenase led to more cellobionate production. Both of the two hydrolysis products of cellobionate: glucose and gluconate can be used by Escherichia coli KO 11 for efficient ethanol production. They were utilized simultaneously in glucose and gluconate co-fermentation. Gluconate was used even faster than glucose. The results support the viability of the two hypotheses that lay the foundation for the proposed new route.

A Novel Biochemical Route for Fuels and Chemicals Production from Cellulosic Biomass

PubMed Central

Fan, Zhiliang; Wu, Weihua; Hildebrand, Amanda; Kasuga, Takao; Zhang, Ruifu; Xiong, Xiaochao

2012-01-01

The conventional biochemical platform featuring enzymatic hydrolysis involves five key steps: pretreatment, cellulase production, enzymatic hydrolysis, fermentation, and product recovery. Sugars are produced as reactive intermediates for subsequent fermentation to fuels and chemicals. Herein, an alternative biochemical route is proposed. Pretreatment, enzymatic hydrolysis and cellulase production is consolidated into one single step, referred to as consolidated aerobic processing, and sugar aldonates are produced as the reactive intermediates for biofuels production by fermentation. In this study, we demonstrate the viability of consolidation of the enzymatic hydrolysis and cellulase production steps in the new route using Neurospora crassa as the model microorganism and the conversion of cellulose to ethanol as the model system. We intended to prove the two hypotheses: 1) cellulose can be directed to produce cellobionate by reducing β-glucosidase production and by enhancing cellobiose dehydrogenase production; and 2) both of the two hydrolysis products of cellobionate—glucose and gluconate—can be used as carbon sources for ethanol and other chemical production. Our results showed that knocking out multiple copies of β-glucosidase genes led to cellobionate production from cellulose, without jeopardizing the cellulose hydrolysis rate. Simulating cellobiose dehydrogenase over-expression by addition of exogenous cellobiose dehydrogenase led to more cellobionate production. Both of the two hydrolysis products of cellobionate: glucose and gluconate can be used by Escherichia coli KO 11 for efficient ethanol production. They were utilized simultaneously in glucose and gluconate co-fermentation. Gluconate was used even faster than glucose. The results support the viability of the two hypotheses that lay the foundation for the proposed new route. PMID:22384058

Joint chemical agent detector (JCAD): the future of chemical agent detection

NASA Astrophysics Data System (ADS)

Laljer, Charles E.

2003-08-01

The Joint Chemical Agent Detector (JCAD) has continued development through 2002. The JCAD has completed Contractor Validation Testing (CVT) that included chemical warfare agent testing, environmental testing, electromagnetic interferent testing, and platform integration validation. The JCAD provides state of the art chemical warfare agent detection capability to military and homeland security operators. Intelligence sources estimate that over twenty countries have active chemical weapons programs. The spread of weapons of mass destruction (and the industrial capability for manufacture of these weapons) to third world nations and terrorist organizations has greatly increased the chemical agent threat to U.S. interests. Coupled with the potential for U.S. involvement in localized conflicts in an operational or support capacity, increases the probability that the military Joint Services may encounter chemical agents anywhere in the world. The JCAD is a small (45 in3), lightweight (2 lb.) chemical agent detector for vehicle interiors, aircraft, individual personnel, shipboard, and fixed site locations. The system provides a common detection component across multi-service platforms. This common detector system will allow the Joint Services to use the same operational and support concept for more efficient utilization of resources. The JCAD detects, identifies, quantifies, and warns of the presence of chemical agents prior to onset of miosis. Upon detection of chemical agents, the detector provides local and remote audible and visual alarms to the operators. Advance warning will provide the vehicle crew and other personnel in the local area with the time necessary to protect themselves from the lethal effects of chemical agents. The JCAD is capable of being upgraded to protect against future chemical agent threats. The JCAD provides the operator with the warning necessary to survive and fight in a chemical warfare agent threat environment.

Chemical compatibility and properties of suspension plasma-sprayed SrTiO3-based anodes for intermediate-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Zhang, Shan-Lin; Li, Cheng-Xin; Li, Chang-Jiu

2014-10-01

La-doped strontium titanate (LST) is a promising, redox-stable perovskite material for direct hydrocarbon oxidation anodes in intermediate-temperature solid oxide fuel cells (IT-SOFCs). In this study, nano-sized LST and Sm-doped ceria (SDC) powders are produced by the sol-gel and glycine-nitrate processes, respectively. The chemical compatibility between LST and electrolyte materials is studied. A LST-SDC composite anode is prepared by suspension plasma spraying (SPS). The effects of annealing conditions on the phase structure, microstructure, and chemical stability of the LST-SDC composite anode are investigated. The results indicate that the suspension plasma-sprayed LST-SDC anode has the same phase structure as the original powders. LST exhibits a good chemical compatibility with SDC and Mg/Sr-doped lanthanum gallate (LSGM). The anode has a porosity of ∼40% with a finely porous structure that provides high gas permeability and a long three-phase boundary for the anode reaction. Single cells assembled with the LST-SDC anode, La0.8Sr0.2Ga0.8Mg0.2O3 electrolyte, and La0.8Sr0.2CoO3-SDC cathode show a good performance at 650-800 °C. The annealing reduces the impedances due to the enhancement in the bonding between the particles in the anode and interface of anode and LSGM electrolyte, thus improving the output performance of the cell.

SPE-IMS-MS: An automated platform for sub-sixty second surveillance of endogenous metabolites and xenobiotics in biofluids

DOE PAGES

Zhang, Xing; Romm, Michelle; Zheng, Xueyun; ...

2016-12-29

Characterization of endogenous metabolites and xenobiotics is essential to deconvoluting the genetic and environmental causes of disease. However, surveillance of chemical exposure and disease-related changes in large cohorts requires an analytical platform that offers rapid measurement, high sensitivity, efficient separation, broad dynamic range, and application to an expansive chemical space. Here in this article, we present a novel platform for small molecule analyses that addresses these requirements by combining solid-phase extraction with ion mobility spectrometry and mass spectrometry (SPE-IMS-MS). This platform is capable of performing both targeted and global measurements of endogenous metabolites and xenobiotics in human biofluids with highmore » reproducibility (CV ≤ 3%), sensitivity (LODs in the pM range in biofluids) and throughput (10-s sample-to-sample duty cycle). We report application of this platform to the analysis of human urine from patients with and without type 1 diabetes, where we observed statistically significant variations in the concentration of disaccharides and previously unreported chemical isomers. Lastly, this SPE-IMS-MS platform overcomes many of the current challenges of large-scale metabolomic and exposomic analyses and offers a viable option for population and patient cohort screening in an effort to gain insights into disease processes and human environmental chemical exposure.« less

SPE-IMS-MS: An automated platform for sub-sixty second surveillance of endogenous metabolites and xenobiotics in biofluids.

PubMed

Zhang, Xing; Romm, Michelle; Zheng, Xueyun; Zink, Erika M; Kim, Young-Mo; Burnum-Johnson, Kristin E; Orton, Daniel J; Apffel, Alex; Ibrahim, Yehia M; Monroe, Matthew E; Moore, Ronald J; Smith, Jordan N; Ma, Jian; Renslow, Ryan S; Thomas, Dennis G; Blackwell, Anne E; Swinford, Glenn; Sausen, John; Kurulugama, Ruwan T; Eno, Nathan; Darland, Ed; Stafford, George; Fjeldsted, John; Metz, Thomas O; Teeguarden, Justin G; Smith, Richard D; Baker, Erin S

2016-12-01

Characterization of endogenous metabolites and xenobiotics is essential to deconvoluting the genetic and environmental causes of disease. However, surveillance of chemical exposure and disease-related changes in large cohorts requires an analytical platform that offers rapid measurement, high sensitivity, efficient separation, broad dynamic range, and application to an expansive chemical space. Here, we present a novel platform for small molecule analyses that addresses these requirements by combining solid-phase extraction with ion mobility spectrometry and mass spectrometry (SPE-IMS-MS). This platform is capable of performing both targeted and global measurements of endogenous metabolites and xenobiotics in human biofluids with high reproducibility (CV 6 3%), sensitivity (LODs in the pM range in biofluids) and throughput (10-s sample-to-sample duty cycle). We report application of this platform to the analysis of human urine from patients with and without type 1 diabetes, where we observed statistically significant variations in the concentration of disaccharides and previously unreported chemical isomers. This SPE-IMS-MS platform overcomes many of the current challenges of large-scale metabolomic and exposomic analyses and offers a viable option for population and patient cohort screening in an effort to gain insights into disease processes and human environmental chemical exposure.

SPE-IMS-MS: An automated platform for sub-sixty second surveillance of endogenous metabolites and xenobiotics in biofluids

PubMed Central

Zhang, Xing; Romm, Michelle; Zheng, Xueyun; Zink, Erika M.; Kim, Young-Mo; Burnum-Johnson, Kristin E.; Orton, Daniel J.; Apffel, Alex; Ibrahim, Yehia M.; Monroe, Matthew E.; Moore, Ronald J.; Smith, Jordan N.; Ma, Jian; Renslow, Ryan S.; Thomas, Dennis G.; Blackwell, Anne E.; Swinford, Glenn; Sausen, John; Kurulugama, Ruwan T.; Eno, Nathan; Darland, Ed; Stafford, George; Fjeldsted, John; Metz, Thomas O.; Teeguarden, Justin G.; Smith, Richard D.; Baker, Erin S.

2017-01-01

Characterization of endogenous metabolites and xenobiotics is essential to deconvoluting the genetic and environmental causes of disease. However, surveillance of chemical exposure and disease-related changes in large cohorts requires an analytical platform that offers rapid measurement, high sensitivity, efficient separation, broad dynamic range, and application to an expansive chemical space. Here, we present a novel platform for small molecule analyses that addresses these requirements by combining solid-phase extraction with ion mobility spectrometry and mass spectrometry (SPE-IMS-MS). This platform is capable of performing both targeted and global measurements of endogenous metabolites and xenobiotics in human biofluids with high reproducibility (CV 6 3%), sensitivity (LODs in the pM range in biofluids) and throughput (10-s sample-to-sample duty cycle). We report application of this platform to the analysis of human urine from patients with and without type 1 diabetes, where we observed statistically significant variations in the concentration of disaccharides and previously unreported chemical isomers. This SPE-IMS-MS platform overcomes many of the current challenges of large-scale metabolomic and exposomic analyses and offers a viable option for population and patient cohort screening in an effort to gain insights into disease processes and human environmental chemical exposure. PMID:29276770

Chemical Indicators.

ERIC Educational Resources Information Center

Prombain, Dorothy R.; And Others

This science sourcebook was written for intermediate grade teachers to provide guidance in teaching a specially developed unit on chemical indicators. Directions and suggestions for guiding student science activities are given. Some of the activities concern soil testing, crystals, and household powders such as sugar and salt. A list of necessary…

15 CFR 742.2 - Proliferation of chemical and biological weapons.

Code of Federal Regulations, 2010 CFR

2010-01-01

... in ECCN 1C350 (precursor and intermediate chemicals used in the production of chemical warfare agents... on the CCL, chemical detection systems controlled by 1A004.c for detecting chemical warfare agents... used in the production of chemical weapons precursors or chemical warfare agents. (vii) Equipment and...

Intermediate treatments

Treesearch

John R. Jones; Wayne D. Shepperd

1985-01-01

Intermediate treatments are those applied after a new stand is successfully established and before the final harvest. These include not only intermediate cuttings - primarily thinning - but also fertilization, irrigation, and protection of the stand from damaging agents.

Lab-on-a-chip platform for high throughput drug discovery with DNA-encoded chemical libraries

NASA Astrophysics Data System (ADS)

Grünzner, S.; Reddavide, F. V.; Steinfelder, C.; Cui, M.; Busek, M.; Klotzbach, U.; Zhang, Y.; Sonntag, F.

2017-02-01

The fast development of DNA-encoded chemical libraries (DECL) in the past 10 years has received great attention from pharmaceutical industries. It applies the selection approach for small molecular drug discovery. Because of the limited choices of DNA-compatible chemical reactions, most DNA-encoded chemical libraries have a narrow structural diversity and low synthetic yield. There is also a poor correlation between the ranking of compounds resulted from analyzing the sequencing data and the affinity measured through biochemical assays. By combining DECL with dynamical chemical library, the resulting DNA-encoded dynamic library (EDCCL) explores the thermodynamic equilibrium of reversible reactions as well as the advantages of DNA encoded compounds for manipulation/detection, thus leads to enhanced signal-to-noise ratio of the selection process and higher library quality. However, the library dynamics are caused by the weak interactions between the DNA strands, which also result in relatively low affinity of the bidentate interaction, as compared to a stable DNA duplex. To take advantage of both stably assembled dual-pharmacophore libraries and EDCCLs, we extended the concept of EDCCLs to heat-induced EDCCLs (hi-EDCCLs), in which the heat-induced recombination process of stable DNA duplexes and affinity capture are carried out separately. To replace the extremely laborious and repetitive manual process, a fully automated device will facilitate the use of DECL in drug discovery. Herein we describe a novel lab-on-a-chip platform for high throughput drug discovery with hi-EDCCL. A microfluidic system with integrated actuation was designed which is able to provide a continuous sample circulation by reducing the volume to a minimum. It consists of a cooled and a heated chamber for constant circulation. The system is capable to generate stable temperatures above 75 °C in the heated chamber to melt the double strands of the DNA and less than 15 °C in the cooled chamber

Development of Photoacoustic Sensing Platforms at the US Army Research Laboratory

DTIC Science & Technology

2016-09-01

RDX and TNT explosives with carbon dioxide laser. J Appl Spectrosc. 2006;73(1):123–129. 45. Petzold A, Niessner R. Photoacoustic soot sensor for in...Development of Photoacoustic Sensing Platforms at the US Army Research Laboratory by Ellen L Holthoff and Paul M Pellegrino Sensors and Electron Devices...NOTES 14. ABSTRACT Traditionally, chemical sensing platforms have been hampered by the opposing concerns of increasing sensor capability while

Study of Chemical Intermediates by Means of ATR-IR Spectroscopy and Hybrid Hard- and Soft-Modelling Multivariate Curve Resolution-Alternating Least Squares

PubMed Central

Ma, Junxiu; Qi, Juan; Gao, Xinyu; Yan, Chunhua; Zhang, Tianlong; Tang, Hongsheng

2017-01-01

3,5-Diamino-1,2,4-triazole (DAT) became a significant energetic materials intermediate, and the study of its reaction mechanism has fundamental significance in chemistry. The aim of this study is to investigate the ability of online attenuated total reflection infrared (ATR-IR) spectroscopy combined with the novel approach of hybrid hard- and soft-modelling multivariate curve resolution-alternating least squares (HS-MCR) analysis to monitor and detect changes in structural properties of compound during 3,5-diamino-1,2,4-triazole (DAT) synthesis processes. The subspace comparison method (SCM) was used to obtain the principal components number, and then the pure IR spectra of each substance were obtained by independent component analysis (ICA) and HS-MCR. The extent of rotation ambiguity was estimated from the band boundaries of feasible solutions calculated using the MCR-BANDS procedure. There were five principal components including two intermediates in the process in the results. The reaction rate constants of DAT formation reaction were also obtained by HS-MCR. HS-MCR was used to analyze spectroscopy data in chemical synthesis process, which not only increase the information domain but also reduce the ambiguities of the obtained results. This study provides the theoretical basis for the optimization of synthesis process and technology of energetic materials and provides a strong technical support of research and development of energy material with extraordinary damage effects. PMID:28386512

"Chemical-Free" Foods: An Investigation of Student's Definitions of a Chemical

NASA Astrophysics Data System (ADS)

Nicoll, Gayle

1997-04-01

There appear to exist at least two definitions of what a chemical is, a popular society definition and a scientific one. This study investigated the pervasiveness of these views among students enrolled in a freshman level college general chemistry course. It was found that only 30 percent of the students in second semester held a scientific definition of a chemical, while another 30 percent held a popular definition. The remaining 40 percent held views intermediate between these. A correlation may exist between the amount of television students watched as they grew up and the type of views they hold about chemicals.

Floor Plans Engine Removal Platform, Hold Down Arm Platform, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

Floor Plans - Engine Removal Platform, Hold Down Arm Platform, Hydraulic Equipment Platforms, Isometric Cutaway of Engine Removal Platform, Isometric Cutaway of Hold Down Arm Platform, Isometric Cutaway of Hydraulic Platforms and Engine Support System Access - Marshall Space Flight Center, Saturn V S-IC Static Test Facility, West Test Area, Huntsville, Madison County, AL

Analytical platform for metabolome analysis of microbial cells using methyl chloroformate derivatization followed by gas chromatography-mass spectrometry.

PubMed

Smart, Kathleen F; Aggio, Raphael B M; Van Houtte, Jeremy R; Villas-Bôas, Silas G

2010-09-01

This protocol describes an analytical platform for the analysis of intra- and extracellular metabolites of microbial cells (yeast, filamentous fungi and bacteria) using gas chromatography-mass spectrometry (GC-MS). The protocol is subdivided into sampling, sample preparation, chemical derivatization of metabolites, GC-MS analysis and data processing and analysis. This protocol uses two robust quenching methods for microbial cultures, the first of which, cold glycerol-saline quenching, causes reduced leakage of intracellular metabolites, thus allowing a more reliable separation of intra- and extracellular metabolites with simultaneous stopping of cell metabolism. The second, fast filtration, is specifically designed for quenching filamentous micro-organisms. These sampling techniques are combined with an easy sample-preparation procedure and a fast chemical derivatization reaction using methyl chloroformate. This reaction takes place at room temperature, in aqueous medium, and is less prone to matrix effect compared with other derivatizations. This protocol takes an average of 10 d to complete and enables the simultaneous analysis of hundreds of metabolites from the central carbon metabolism (amino and nonamino organic acids, phosphorylated organic acids and fatty acid intermediates) using an in-house MS library and a data analysis pipeline consisting of two free software programs (Automated Mass Deconvolution and Identification System (AMDIS) and R).

CONSIDERATION OF REACTION INTERMEDIATES IN STRUCTURE-ACTIVITY RELATIONSHIPS: A KEY TO UNDERSTANDING AND PREDICTION

EPA Science Inventory

Consideration of Reaction Intermediates in Structure- Activity Relationships: A Key to Understanding and Prediction

A structure-activity relationship (SAR) represents an empirical means for generalizing chemical information relative to biological activity, and is frequent...

Characterization of reaction intermediate aggregates in aniline oxidative polymerization at low proton concentration.

PubMed

Ding, Zhongfen; Sanchez, Timothy; Labouriau, Andrea; Iyer, Srinivas; Larson, Toti; Currier, Robert; Zhao, Yusheng; Yang, Dali

2010-08-19

Aggregates of reaction intermediates form during the early stages of aniline oxidative polymerization whenever the initial mole ratio of proton concentration to aniline monomer concentration is low ([H(+)](0)/[An](0) intermediate aggregates show a UV-Vis absorption peak at around 410 nm when dispersed in aqueous solution, whereas the peak is centered on 370 nm when dissolved in an organic solvent such as N-methylpyrrolidone. The electronic band gap decreases when the intermediates aggregate to form a solid, and thus, the absorption peak is red-shifted. Gel permeation chromatography (GPC) shows the aggregates contain a major low molecular weight peak with a long tail. The oligoanilines with low molecular weights consistently show a UV-Vis absorption peak at around 370 nm. Mass spectrometry confirms that the intermediate aggregates contain mainly a component with mass number 363 (M + H(+)), likely a tetramer. UV-Vis, GPC, mass spectrometry, NMR, FTIR, and XRD characterization results are presented and chemical structures for the tetramer are proposed. The major components of the intermediate aggregates are likely highly symmetric phenazine- and dihydrophenazine-containing structures. These particular organic compounds have not been identified before as intermediates. The aggregation and precipitation of the tetramers apparently stabilizes these intermediates. The aggregates are highly crystalline, as evidenced by powder X-ray diffraction. A new reaction mechanism for the formation of these intermediates is proposed.

Sources of Chemical Toxics and Their Precursors in Pharmaceutical Industry

DTIC Science & Technology

2001-09-01

includes a lot of independent units specialized in synthesis of active substances, their processing as pharmaceutical forms, control of intermediate and...materials (ingredients), synthesis intermediates, intermediate forms (solutions, powders), analytical reactives, drugs itself, residues etc. Secondary...specialist scenario The simplest idea is to orient the attack against chemical synthesis facilities friom where a lot of volatile solvents could be spread

An integrated platform for directly widely-targeted quantitative analysis of feces part I: Platform configuration and method validation.

PubMed

Song, Yuelin; Song, Qingqing; Li, Jun; Zheng, Jiao; Li, Chun; Zhang, Yuan; Zhang, Lingling; Jiang, Yong; Tu, Pengfei

2016-07-08

Direct analysis is of great importance to understand the real chemical profile of a given sample, notably biological materials, because either chemical degradation or diverse errors and uncertainties might be resulted from sophisticated protocols. In comparison with biofluids, it is still challenging for direct analysis of solid biological samples using high performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Herein, a new analytical platform was configured by online hyphenating pressurized liquid extraction (PLE), turbulent flow chromatography (TFC), and LC-MS/MS. A facile, but robust PLE module was constructed based on the phenomenon that noticeable back-pressure can be generated during rapid fluid passing through a narrow tube. TFC column that is advantageous at extracting low molecular analytes from rushing fluid was employed to link at the outlet of the PLE module to capture constituents-of-interest. An electronic 6-port/2-position valve was introduced between TFC column and LC-MS/MS to fragment each measurement into extraction and elution phases, whereas LC-MS/MS took the charge of analyte separation and monitoring. As a proof of concept, simultaneous determination of 24 endogenous substances including eighteen steroids, five eicosanoids, and one porphyrin in feces was carried out in this paper. Method validation assays demonstrated the analytical platform to be qualified for directly simultaneous measurement of diverse endogenous analytes in fecal matrices. Application of this integrated platform on homolog-focused profiling of feces is discussed in a companion paper. Copyright © 2016 Elsevier B.V. All rights reserved.

TSCA Chemical Data Reporting Fact Sheet: Reporting Manufactured Chemical Substances from Metal Mining and Related Activities

EPA Pesticide Factsheets

This fact sheet provides guidance on the Chemical Data Reporting (CDR) rule requirements related to the reporting of mined metals, intermediates, and byproducts manufactured during metal mining and related activities.

Freeze-quench (57)Fe-Mössbauer spectroscopy: trapping reactive intermediates.

PubMed

Krebs, Carsten; Bollinger, J Martin

2009-01-01

(57)Fe-Mössbauer spectroscopy is a method that probes transitions between the nuclear ground state (I=1/2) and the first nuclear excited state (I=3/2). This technique provides detailed information about the chemical environment and electronic structure of iron. Therefore, it has played an important role in studies of the numerous iron-containing proteins and enzymes. In conjunction with the freeze-quench method, (57)Fe-Mössbauer spectroscopy allows for monitoring changes of the iron site(s) during a biochemical reaction. This approach is particularly powerful for detection and characterization of reactive intermediates. Comparison of experimentally determined Mössbauer parameters to those predicted by density functional theory for hypothetical model structures can then provide detailed insight into the structures of reactive intermediates. We have recently used this methodology to study the reactions of various mononuclear non-heme-iron enzymes by trapping and characterizing several Fe(IV)-oxo reaction intermediates. In this article, we summarize these findings and demonstrate the potential of the method. © Springer Science+Business Media B.V. 2009

One-Pot Conversion of Carbohydrates into Furan Derivatives via Furfural and 5-Hydroxylmethylfurfural as Intermediates.

PubMed

Liu, Bing; Zhang, Zehui

2016-08-23

Recently, there has been growing interest in the transformation of renewable biomass into value-added fuels and chemicals. The catalytic conversion of naturally abundant carbohydrates can generate two-important furan chemicals: 5-hydroxymethylfurfural (HMF) from C6 carbohydrates and furfural from C5 carbohydrates. Both HMF and furfural have received great interest as precursors in the synthesis of commodity chemicals and liquid fuels. In recent years, a trend has emerged to integrate sequential catalytic processes involving multistep reactions for the direct one-pot transformation of carbohydrates into the aimed fuels and chemicals. One-pot reactions have remarkably unique and environmentally friendly benefits, including the fact that isolation and purification of intermediate compounds can be avoided. Herein, the present article aims to review recent advances in the one-pot conversion of carbohydrates into furan derivatives via furfural and HMF as intermediates. Special attention will be paid to the catalytic systems, mechanistic insight, reaction pathways, and catalyst stability. It is expected that this review will guide researchers to develop effective catalytic systems for the one-pot transformation of carbohydrates into furan derivatives. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR 60.489 - List of chemicals produced by affected facilities.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 7 2014-07-01 2014-07-01 false List of chemicals produced by affected... Equipment Leaks of VOC in the Synthetic Organic Chemicals Manufacturing Industry for which Construction... of chemicals produced by affected facilities. The following chemicals are produced, as intermediates...

Intermediate added salt levels as sodium reduction strategy: Effects on chemical, microbial, textural and sensory quality of polony.

PubMed

Cluff, M; Kobane, I A; Bothma, C; Hugo, C J; Hugo, A

2017-11-01

The purpose of this study was to evaluate the use of intermediate added salt levels (1.33% w/w and 1.84% w/w) as a strategy for reducing the total sodium content of polony, an emulsified, heat-treated meat product, which is reliant on the various functions of salt normally included at a 2.5% (w/w) level. Chemical, microbial, and textural stability over 180days as well as sensory quality were evaluated. At 1.84% (w/w) added salt content, the product was indistinguishable from the positive control except for a slightly wetter cutting surface. A level of 1.33% (w/w) added salt showed similar results, except for a slight variation in initial moisture content and a much wetter cutting surface. The hardest texture was achieved at 1.33% (w/w) added salt up to 90days of shelf-life. Consumers had a slight preference for a lower salt content. From this research it can be recommended that salt reduction as sole approach in sodium reduction should be evaluated for meat products in limiting the possibly costly and negatively perceived use of sodium replacers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemicals from coal - The Eastman experience. [Anhydride

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

Larkins, T.H.

1986-03-01

Tennessee Eastman Company is a major producer of chemicals, fibers and plastics. It is located in Kingsport, Tennessee, headquarters for the Eastman Chemicals Division of Eastman Kodak Company. Eastman Companies employ a total of 12,250 people in Kingsport. Other domestic Eastman Chemicals Division plants are located in Texas, South Carolina, Arkansas and New York. The authors began to witness a flow of products from one of the most highly technical and sophisticated chemical processes in operation in the world. The Eastman ''Chemicals-from-Coal'' facility is not a sunfuel plant. To be sure, we are producing syngas from coal, but the syngasmore » is used to produce acetic anhydride. Acetic anhydride is very important to Eastman. This chemical intermediate eventually finds its way into such diverse products as aspirin, cigarette filters, tool handles, and photographic film. It also is used to make other chemical intermediates such as cellulose esters, anhydrides, triacetin, and acetate ester solvents, all of which have a variety of end uses. The chemicals-from-coal project had its inception in the late 1960's when Eastman stepped up its program of energy conservation and began a search for lower cost chemical feedstocks. Our concern started before the national concern caused by a ten-fold increase in petroleum prices during the past decade.« less

Integrated Proteomic Approaches for Understanding Toxicity of Environmental Chemicals

EPA Science Inventory

To apply quantitative proteomic analysis to the evaluation of toxicity of environmental chemicals, we have developed an integrated proteomic technology platform. This platform has been applied to the analysis of the toxic effects and pathways of many important environmental chemi...

Determination of an ensemble of structures representing the intermediate state of the bacterial immunity protein Im7.

PubMed

Gsponer, Joerg; Hopearuoho, Harri; Whittaker, Sara B-M; Spence, Graham R; Moore, Geoffrey R; Paci, Emanuele; Radford, Sheena E; Vendruscolo, Michele

2006-01-03

We present a detailed structural characterization of the intermediate state populated during the folding and unfolding of the bacterial immunity protein Im7. We achieve this result by incorporating a variety of experimental data available for this species in molecular dynamics simulations. First, we define the structure of the exchange-competent intermediate state of Im7 by using equilibrium hydrogen-exchange protection factors. Second, we use this ensemble to predict Phi-values and compare the results with the experimentally determined Phi-values of the kinetic refolding intermediate. Third, we predict chemical-shift measurements and compare them with the measured chemical shifts of a mutational variant of Im7 for which the kinetic folding intermediate is the most stable state populated at equilibrium. Remarkably, we found that the properties of the latter two species are predicted with high accuracy from the exchange-competent intermediate that we determined, suggesting that these three states are characterized by a similar architecture in which helices I, II, and IV are aligned in a native-like, but reorganized, manner. Furthermore, the structural ensemble that we obtained enabled us to rationalize the results of tryptophan fluorescence experiments in the WT protein and a series of mutational variants. The results show that the integration of diverse sets of experimental data at relatively low structural resolution is a powerful approach that can provide insights into the structural organization of this conformationally heterogeneous three-helix intermediate with unprecedented detail and highlight the importance of both native and non-native interactions in stabilizing its structure.

Neoproterozoic low- paleolatitude glacial successions on the Yangtze platform, South China

NASA Astrophysics Data System (ADS)

Dobrzinski, N.; Bahlburg, H.; Stauss, H.; Zhang, Q. R.

2003-04-01

Successions of glaciomarine sediments were deposited on the Yangtze platform (South China) during Neoproterozoic time (between c. 748 Ma and 599 Ma), although the platform was situated in low to intermediate paleolatitudes. Our study focuses on sedimentological and geochemical analyses and on paleoclimate interpretation of Sinian glacial successions on the Yangtze platform. This glacial succession comprises a lower glacial unit of diamictites (Dongshanfeng Fm.), followed by a unit of siliciclastic fine-grained and partly cross bedded sediments (Datangpo Fm.) and another unit of glacial diamictites (Nantuo Fm.). The upper diamictite unit is often covered by limestones (cap carbonates) and overlain by black shales and dolomites (Doushantuo Fm.). Geochemical proxies, e.g. the chemical index of alteration (CIA) and V/Cr, help to identify the environmental conditions, which are associated with climate changes. Finegrained siliciclastic sediments between two units of diamictite reflect interglacial conditions documented by sedimentological structures and our geochemical data (CIA values around 70). V/Cr ratios (begin{math}< 2) show oxic conditions during the time of deposition. Carbon isotope data of carbonate samples from the interglacial unit, the cap carbonate and the carbonates of the overlying Doushantuo Formation provide a temporal record of changes in the carbon isotopic composition of Neoproterozoic seawater. Interglacial carbonates display begin{math}δ13 C values between -2.6 and +1.1 per mill. begin{math}δ13C values between -4.8 and -1.9 per mill characterize the cap carbonate level. In the Doushantuo Formation, an evolution of the carbon isotopic composition from -3.3 to +6.5 per mill is discernible. The increase in begin{math}δ13C in the Doushantuo Formation could be due to an increase in the fractional burial of organic carbon. Recent geochemical work suggests that both continents and oceans were completely ice covered in Neoproterozoic time (the

Optoelectrofluidic platforms for chemistry and biology.

PubMed

Hwang, Hyundoo; Park, Je-Kyun

2011-01-07

Extraordinary advances in lab on a chip systems have been made on the basis of the development of micro/nanofluidics and its fusion with other technologies based on electrokinetics and optics. Optoelectrofluidic technology, which has been recently introduced as a new manipulation scheme, allows programmable manipulation of particles or fluids in microenvironments based on optically induced electrokinetics. Herein, the behaviour of particles or fluids can be controlled by inducing or perturbing electric fields on demand in an optical manner, which includes photochemical, photoconductive, and photothermal effects. This elegant scheme of the optoelectrofluidic platform has attracted attention in various fields of science and engineering. A lot of research on optoelectrofluidic manipulation technologies has been reported and the field has advanced rapidly, although some technical hurdles still remain. This review describes recent developments and future perspectives of optoelectrofluidic platforms for chemical and biological applications.

Luminescent Lanthanide MOFs: A Unique Platform for Chemical Sensing

PubMed Central

Zhao, Shu-Na; Wang, Guangbo

2018-01-01

In recent years, lanthanide metal–organic frameworks (LnMOFs) have developed to be an interesting subclass of MOFs. The combination of the characteristic luminescent properties of Ln ions with the intriguing topological structures of MOFs opens up promising possibilities for the design of LnMOF-based chemical sensors. In this review, we present the most recent developments of LnMOFs as chemical sensors by briefly introducing the general luminescence features of LnMOFs, followed by a comprehensive investigation of the applications of LnMOF sensors for cations, anions, small molecules, nitroaromatic explosives, gases, vapors, pH, and temperature, as well as biomolecules. PMID:29642458

Optofluidic platforms based on surface-enhanced Raman scattering.

PubMed

Lim, Chaesung; Hong, Jongin; Chung, Bong Geun; deMello, Andrew J; Choo, Jaebum

2010-05-01

We report recent progress in the development of surface-enhanced Raman scattering (SERS)-based optofluidic platforms for the fast and sensitive detection of chemical and biological analytes. In the current context, a SERS-based optofluidic platform is defined as an integrated analytical device composed of a microfluidic element and a sensitive Raman spectrometer. Optofluidic devices for SERS detection normally involve nanocolloid-based microfluidic systems or metal nanostructure-embedded microfluidic systems. In the current review, recent advances in both approaches are surveyed and assessed. Additionally, integrated real-time sensing systems that combine portable Raman spectrometers with microfluidic devices are also reviewed. Such real-time sensing systems have significant utility in environmental monitoring, forensic science and homeland defense applications.

Spectroscopic Characterization of the Water Oxidation Intermediates in the Blue Dimer Ru-Based Catalyst for Artificial Photosynthesis

NASA Astrophysics Data System (ADS)

Moonshiram, Dooshaye; Pushkar, Yulia; Jurss, Jonah; Concepcion, Javier; Meyer, Thomas; Zakharova, Taisiya; Alperovich, Igor

2012-02-01

Utilization of sunlight requires solar capture, light-to-energy conversion and storage. One effective way to store energy is to convert it into chemical energy by fuel-forming reactions, such as water splitting into hydrogen and oxygen. Ruthenium complexes are among few molecular-defined catalysts capable of water splitting. Mechanistic insights about such catalysts can be acquired by spectroscopic analysis of short-lived intermediates of catalytic water oxidation. Use of techniques such as EPR and X-ray absorption spectroscopy (XAS) are used to determine electronic requirements of catalytic water oxidation. About 30 years ago Meyer and coworkers reported first ruthenium-based catalyst for water oxidation, the ``blue dimer''. We performed EPR studies and characterized structures and electronic configurations of intermediates of water oxidation by the ``blue dimer''. Intermediates were prepared chemically by oxidation of Ru-complexes with defined number of Ce (IV) equivalents and freeze-quenched at controlled times. Changes in oxidation state of Ru atom were detected by XANES at Ru K-edges. K-edges are sensitive to changes in Ru oxidation state for Blue Dimer [3,3]^4+, [3,4]^4+, [3,4]'^4+ and [4,5]^3+ allowing a clear assignment of Ru oxidation state in intermediates. EXAFS demonstrated structural changes.

Identification and characterization of the intermediate phase in hybrid organic-inorganic MAPbI3 perovskite.

PubMed

Guo, Xin; McCleese, Christopher; Kolodziej, Charles; Samia, Anna C S; Zhao, Yixin; Burda, Clemens

2016-03-07

Perovskite films were prepared using single step solution deposition at different annealing temperatures and annealing times. The crystal structure, phases and grain size were investigated with XRD, XPS and SEM/EDX. The prepared films show a typical orientation of tetragonal perovskite phase and a gradual transition at room temperature from the yellow intermediate phase to the black perovskite phase. Films with high purity were obtained by sintering at 100 °C. In addition, the chemical composition and crystal structure of intermediate phase were investigated in detail. FTIR, UV-vis and NMR spectra revealed the occurance of DMF complexes. Interestingly, the intermediate phase could be transformed to the black perovskite phase upon X-ray irradiation. In addition, the recovery of the aged perovskite films from a yellow intermediate phase back to the black perovskite was shown to be viable via heating and X-ray irradiation.

77 FR 4522 - National Emission Standards for Hazardous Air Pollutants for Chemical Manufacturing Area Sources

Federal Register 2010, 2011, 2012, 2013, 2014

2012-01-30

... Manufacturing, Industrial Organic Chemical Manufacturing, Inorganic Pigments Manufacturing, Miscellaneous Organic Chemical Manufacturing, Plastic Materials and Resins Manufacturing, Pharmaceutical Production and... Intermediate Production, Industrial Inorganic Chemical Manufacturing, Industrial Organic Chemical Manufacturing...

Argentate(i) and (iii) complexes as intermediates in silver-mediated cross-coupling reactions.

PubMed

Weske, Sebastian; Hardin, Richard A; Auth, Thomas; O'Hair, Richard A J; Koszinowski, Konrad; Ogle, Craig A

2018-04-30

Despite the potential of silver to mediate synthetically valuable cross-coupling reactions, the operating mechanisms have remained unknown. Here, we use a combination of rapid-injection NMR spectroscopy, electrospray-ionization mass spectrometry, and quantum chemical calculations to demonstrate that these transformations involve argentate(i) and (iii) complexes as key intermediates.

Sonochemistry: what potential for conversion of lignocellulosic biomass into platform chemicals?

PubMed

Chatel, Gregory; De Oliveira Vigier, Karine; Jérôme, François

2014-10-01

This Review focuses on the use of ultrasound to produce chemicals from lignocellulosic biomass. However, the question about the potential of sonochemistry for valorization/conversion of lignocellulosic biomass into added-value chemicals is rather conceptual. Until now, this technology has been mainly used for the production of low-value chemicals such as biodiesel or as simple method for pretreatment or extraction. According to preliminary studies reported in literature, access to added-value chemicals can be easily and sometimes solely obtained by the use of ultrasound. The design of sonochemical parameters offers many opportunities to develop new eco-friendly and efficient processes. The goal of this Review is to understand why the use of ultrasound is focused rather on pretreatment or extraction of lignocellulosic biomass rather than on the production of chemicals and to understand, through the reported examples, which directions need to be followed to favor strategies based on ultrasound-assisted production of chemicals from lignocellulosic biomass. We believe that ultrasound-assisted processes represent an innovative approach and will create a growing interest in academia but also in the industry in the near future. Based on the examples reported in the literature, we critically discuss how sonochemistry could offer new strategies and give rise to new results in lignocellulosic biomass valorization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-throughput enzyme screening platform for the IPP-bypass mevalonate pathway for isopentenol production

DOE PAGES

Kang, Aram; Meadows, Corey W.; Canu, Nicolas; ...

2017-04-05

Isopentenol (or isoprenol, 3-methyl-3-buten-1-ol) is a drop-in biofuel and a precursor for commodity chemicals such as isoprene. Biological production of isopentenol via the mevalonate pathway has been optimized extensively in Escherichia coli, yielding 70% of its theoretical maximum. However, high ATP requirements and isopentenyl diphosphate (IPP) toxicity pose immediate challenges for engineering bacterial strains to overproduce commodities utilizing IPP as an intermediate. To overcome these limitations, we developed an “IPP-bypass” isopentenol pathway using the promiscuous activity of a mevalonate diphosphate decarboxylase (PMD) and demonstrated improved performance under aeration-limited conditions. However, relatively low activity of PMD toward the non-native substrate (mevalonatemore » monophosphate, MVAP) was shown to limit flux through this new pathway. By inhibiting all IPP production from the endogenous non-mevalonate pathway, we developed a high-throughput screening platform that correlated promiscuous PMD activity toward MVAP with cellular growth. Successful identification of mutants that altered PMD activity demonstrated the sensitivity and specificity of the screening platform. Strains with evolved PMD mutants and the novel IPP-bypass pathway increased titers up to 2.4-fold. Further enzymatic characterization of the evolved PMD variants suggested that higher isopentenol titers could be achieved either by altering residues directly interacting with substrate and cofactor or by altering residues on nearby α-helices. These altered residues could facilitate the production of isopentenol by tuning either k cat or K i of PMD for the non-native substrate. The synergistic modification made on PMD for the IPP-bypass mevalonate pathway is expected to significantly facilitate the industrial scale production of isopentenol.« less

High-throughput enzyme screening platform for the IPP-bypass mevalonate pathway for isopentenol production

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

Kang, Aram; Meadows, Corey W.; Canu, Nicolas

Isopentenol (or isoprenol, 3-methyl-3-buten-1-ol) is a drop-in biofuel and a precursor for commodity chemicals such as isoprene. Biological production of isopentenol via the mevalonate pathway has been optimized extensively in Escherichia coli, yielding 70% of its theoretical maximum. However, high ATP requirements and isopentenyl diphosphate (IPP) toxicity pose immediate challenges for engineering bacterial strains to overproduce commodities utilizing IPP as an intermediate. To overcome these limitations, we developed an “IPP-bypass” isopentenol pathway using the promiscuous activity of a mevalonate diphosphate decarboxylase (PMD) and demonstrated improved performance under aeration-limited conditions. However, relatively low activity of PMD toward the non-native substrate (mevalonatemore » monophosphate, MVAP) was shown to limit flux through this new pathway. By inhibiting all IPP production from the endogenous non-mevalonate pathway, we developed a high-throughput screening platform that correlated promiscuous PMD activity toward MVAP with cellular growth. Successful identification of mutants that altered PMD activity demonstrated the sensitivity and specificity of the screening platform. Strains with evolved PMD mutants and the novel IPP-bypass pathway increased titers up to 2.4-fold. Further enzymatic characterization of the evolved PMD variants suggested that higher isopentenol titers could be achieved either by altering residues directly interacting with substrate and cofactor or by altering residues on nearby α-helices. These altered residues could facilitate the production of isopentenol by tuning either k cat or K i of PMD for the non-native substrate. The synergistic modification made on PMD for the IPP-bypass mevalonate pathway is expected to significantly facilitate the industrial scale production of isopentenol.« less

Porous Ionic Polymers as a Robust and Efficient Platform for Capture and Chemical Fixation of Atmospheric CO2.

PubMed

Sun, Qi; Jin, Yingyin; Aguila, Briana; Meng, Xiangju; Ma, Shengqian; Xiao, Feng-Shou

2017-03-22

Direct use of atmospheric CO 2 as a C 1 source to synthesize high-value chemicals through environmentally benign processes is of great interest, yet challenging. Porous heterogeneous catalysts that are capable of simultaneously capturing and converting CO 2 are promising candidates for such applications. Herein, a family of organic ionic polymers with nanoporous structure, large surface area, strong affinity for CO 2 , and very high density of catalytic active sites (halide ions) was synthesized through the free-radical polymerization of vinylfunctionalized quaternary phosphonium salts. The resultant porous ionic polymers (PIPs) exhibit excellent activities in the cycloaddition of epoxides with atmospheric CO 2 , outperforming the corresponding soluble phosphonium salt analogues and ranking among the highest of known metal-free catalytic systems. The high CO 2 uptake capacity of the PIPs facilitates the enrichment of CO 2 molecules around the catalytic centers, thereby benefiting its conversion. We have demonstrated for the first time that atmospheric CO 2 can be directly converted to cyclic carbonates at room temperature using a heterogeneous catalytic system under metal-solvent free conditions. Moreover, the catalysts proved to be robust and fully recyclable, demonstrating promising potential for practical utilization for the chemical fixation of CO 2 . Our work thereby paves a way to the advance of PIPs as a new type of platform for capture and conversion of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

NCCLC: NETWORK FOR RAPID ASSESSMENT OF CHEMICAL LIFE CYCLE IMPACT

EPA Science Inventory

The project is expected to provide a platform for chemical and material life-cycle information exchange. A wide use of CLB will enable organically growing LCA database for chemicals and materials. The project is expected to help chemical producers understand potential envir...

Effect of intermediate layers on atomic layer deposition-aluminum oxide protected silver mirrors

NASA Astrophysics Data System (ADS)

Fryauf, David M.; Diaz Leon, Juan J.; Phillips, Andrew C.; Kobayashi, Nobuhiko P.

2017-07-01

This work investigates intermediate materials deposited between silver (Ag) thin-film mirrors and an aluminum oxide (AlOx) barrier overlayer and compares the effects on mirror durability to environmental stresses. Physical vapor deposition of various fluorides, oxides, and nitrides in combination with AlOx by atomic layer deposition (ALD) is used to develop several coating recipes. Ag-AlOx samples with different intermediate materials undergo aggressive high-temperature (80°C), high-humidity (80%) (HTHH) testing for 10 days. Reflectivity of mirror samples is measured before and after HTHH testing, and image processing techniques are used to analyze the specular surface of the samples after HTHH testing. Among the seven intermediate materials used in this work, TiN, MgAl2O4, NiO, and Al2O3 intermediate layers offer more robust protection against chemical corrosion and moisture when compared with samples with no intermediate layer. In addition, results show that the performance of the ALD-AlOx barrier overlayer depends significantly on the ALD-growth process temperature. Because higher durability is observed in samples with less transparent TiN and NiO layers, we propose a figure of merit based on post-HTHH testing reflectivity change and specular reflective mirror surface area remaining after HTHH testing to judge overall barrier performance.

Reactions of Criegee Intermediates with Non-Water Greenhouse Gases: Implications for Metal Free Chemical Fixation of Carbon Dioxide.

PubMed

Kumar, Manoj; Francisco, Joseph S

2017-09-07

High-level theoretical calculations suggest that a Criegee intermediate preferably interacts with carbon dioxide compared to two other greenhouse gases, nitrous oxide and methane. The results also suggest that the interaction between Criegee intermediates and carbon dioxide involves a cycloaddition reaction, which results in the formation of a cyclic carbonate-type adduct with a barrier of 6.0-14.0 kcal/mol. These results are in contrast to a previous assumption that the reaction occurs barrierlessly. The subsequent decomposition of the cyclic adduct into formic acid and carbon dioxide follows both concerted and stepwise mechanisms. The latter mechanism has been overlooked previously. Under formic acid catalysis, the concerted decomposition of the cyclic carbonate may be favored under tropospheric conditions. Considering that there is a strong nexus between carbon dioxide levels in the atmosphere and global warming, the high reactivity of Criegee intermediates could be utilized for designing efficient carbon capture technologies.

Direct Structural and Chemical Characterization of the Photolytic Intermediates of Methylcobalamin Using Time-Resolved X-ray Absorption Spectroscopy

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

Subramanian, Ganesh; Zhang, Xiaoyi; Kodis, Gerdenis

Cobalt-carbon bond cleavage is crucial to most natural and synthetic applications of the cobalamin class of compounds, and here we present the first direct electronic and geometric structural characteristics of intermediates formed following photoexcitation of methylcobalamin (MeCbl) using time-resolved X-ray absorption spectroscopy (XAS). We catch transients corresponding to two intermediates, in the hundreds of picoseconds and a few microseconds. Highlights of the picosecond intermediate, which is reduced in comparison to the ground state, are elongation of the upper axial Co-C bond and relaxation of the corrin ring. This is not so with the recombining photocleaved products captured at a fewmore » microseconds, where the Co-C bond almost (yet not entirely) reverts to its ground state configuration and a substantially elongated lower axial Co-NIm bond is observed. The reduced cobalt site here confirms formation of methyl radical as the photoproduct.« less

The influence of chemical composition of LNG on the supercritical heat transfer in an intermediate fluid vaporizer

NASA Astrophysics Data System (ADS)

Xu, Shuangqing; Chen, Xuedong; Fan, Zhichao; Chen, Yongdong; Nie, Defu; Wu, Qiaoguo

2018-04-01

A three-dimensional transient computational fluid dynamics (CFD) model has been established for the simulations of supercritical heat transfer of real liquefied natural gas (LNG) mixture in a single tube and a tube bundle of an intermediate fluid vaporizer (IFV). The influence of chemical composition of LNG on the thermal performance has been analyzed. The results have also been compared with those obtained from the one-dimensional steady-state calculations using the distributed parameter model (DPM). It is found that the current DPM approach can give reasonable prediction accuracy for the thermal performance in the tube bundle but unsatisfactory prediction accuracy for that in a single tube as compared with the corresponding CFD data. As benchmarked against pure methane, the vaporization of an LNG containing about 90% (mole fraction) of methane would lead to an absolute deviation of 5.5 K in the outlet NG temperature and a maximum relative deviation of 11.4% in the tube side HTC in a bundle of about 816 U tubes at the inlet pressure of 12 MPa and mass flux of 200 kg·m-2·s-1. It is concluded that the influence of LNG composition on the thermal performance should be taken into consideration in order to obtain an economic and reliable design of an IFV.

Microfluidic Lab-on-a-Chip Platforms: Requirements, Characteristics and Applications

NASA Astrophysics Data System (ADS)

Mark, D.; Haeberle, S.; Roth, G.; Von Stetten, F.; Zengerle, R.

This review summarizes recent developments in microfluidic platform approaches. In contrast to isolated application-specific solutions, a microfluidic platform provides a set of fluidic unit operations, which are designed for easy combination within a well-defined fabrication technology. This allows the implementation of different application-specific (bio-) chemical processes, automated by microfluidic process integration [1]. A brief introduction into technical advances, major market segments and promising applications is followed by a detailed characterization of different microfluidic platforms, comprising a short definition, the functional principle, microfluidic unit operations, application examples as well as strengths and limitations. The microfluidic platforms in focus are lateral flow tests, linear actuated devices, pressure driven laminar flow, microfluidic large scale integration, segmented flow microfluidics, centrifugal microfluidics, electro-kinetics, electrowetting, surface acoustic waves, and systems for massively parallel analysis. The review concludes with the attempt to provide a selection scheme for microfluidic platforms which is based on their characteristics according to key requirements of different applications and market segments. Applied selection criteria comprise portability, costs of instrument and disposable, sample throughput, number of parameters per sample, reagent consumption, precision, diversity of microfluidic unit operations and the flexibility in programming different liquid handling protocols.

The Usage of an Online Discussion Forum for the Facilitation of Case-Based Learning in an Intermediate Accounting Course: A New Zealand Case

ERIC Educational Resources Information Center

Weil, Sidney; McGuigan, Nicholas; Kern, Thomas

2011-01-01

This paper describes the implementation of an online discussion forum as a means of facilitating case-based learning in an intermediate financial accounting course. The paper commences with a review of case-based learning literature and the use of online discussions as a delivery platform, linking these pedagogical approaches to the emerging needs…

Metabolic engineering of Corynebacterium glutamicum for fermentative production of chemicals in biorefinery.

PubMed

Baritugo, Kei-Anne; Kim, Hee Taek; David, Yokimiko; Choi, Jong-Il; Hong, Soon Ho; Jeong, Ki Jun; Choi, Jong Hyun; Joo, Jeong Chan; Park, Si Jae

2018-05-01

Bio-based production of industrially important chemicals provides an eco-friendly alternative to current petrochemical-based processes. Because of the limited supply of fossil fuel reserves, various technologies utilizing microbial host strains for the sustainable production of platform chemicals from renewable biomass have been developed. Corynebacterium glutamicum is a non-pathogenic industrial microbial species traditionally used for L-glutamate and L-lysine production. It is a promising species for industrial production of bio-based chemicals because of its flexible metabolism that allows the utilization of a broad spectrum of carbon sources and the production of various amino acids. Classical breeding, systems, synthetic biology, and metabolic engineering approaches have been used to improve its applications, ranging from traditional amino-acid production to modern biorefinery systems for production of value-added platform chemicals. This review describes recent advances in the development of genetic engineering tools and techniques for the establishment and optimization of metabolic pathways for bio-based production of major C2-C6 platform chemicals using recombinant C. glutamicum.

Evaluation of high throughput gene expression platforms using a genomic biomarker signature for prediction of skin sensitization.

PubMed

Forreryd, Andy; Johansson, Henrik; Albrekt, Ann-Sofie; Lindstedt, Malin

2014-05-16

Allergic contact dermatitis (ACD) develops upon exposure to certain chemical compounds termed skin sensitizers. To reduce the occurrence of skin sensitizers, chemicals are regularly screened for their capacity to induce sensitization. The recently developed Genomic Allergen Rapid Detection (GARD) assay is an in vitro alternative to animal testing for identification of skin sensitizers, classifying chemicals by evaluating transcriptional levels of a genomic biomarker signature. During assay development and biomarker identification, genome-wide expression analysis was applied using microarrays covering approximately 30,000 transcripts. However, the microarray platform suffers from drawbacks in terms of low sample throughput, high cost per sample and time consuming protocols and is a limiting factor for adaption of GARD into a routine assay for screening of potential sensitizers. With the purpose to simplify assay procedures, improve technical parameters and increase sample throughput, we assessed the performance of three high throughput gene expression platforms--nCounter®, BioMark HD™ and OpenArray®--and correlated their performance metrics against our previously generated microarray data. We measured the levels of 30 transcripts from the GARD biomarker signature across 48 samples. Detection sensitivity, reproducibility, correlations and overall structure of gene expression measurements were compared across platforms. Gene expression data from all of the evaluated platforms could be used to classify most of the sensitizers from non-sensitizers in the GARD assay. Results also showed high data quality and acceptable reproducibility for all platforms but only medium to poor correlations of expression measurements across platforms. In addition, evaluated platforms were superior to the microarray platform in terms of cost efficiency, simplicity of protocols and sample throughput. We evaluated the performance of three non-array based platforms using a limited set of

Engineering of Surface Chemistry for Enhanced Sensitivity in Nanoporous Interferometric Sensing Platforms.

PubMed

Law, Cheryl Suwen; Sylvia, Georgina M; Nemati, Madieh; Yu, Jingxian; Losic, Dusan; Abell, Andrew D; Santos, Abel

2017-03-15

We explore new approaches to engineering the surface chemistry of interferometric sensing platforms based on nanoporous anodic alumina (NAA) and reflectometric interference spectroscopy (RIfS). Two surface engineering strategies are presented, namely (i) selective chemical functionalization of the inner surface of NAA pores with amine-terminated thiol molecules and (ii) selective chemical functionalization of the top surface of NAA with dithiol molecules. The strong molecular interaction of Au 3+ ions with thiol-containing functional molecules of alkane chain or peptide character provides a model sensing system with which to assess the sensitivity of these NAA platforms by both molecular feature and surface engineering. Changes in the effective optical thickness of the functionalized NAA photonic films (i.e., sensing principle), in response to gold ions, are monitored in real-time by RIfS. 6-Amino-1-hexanethiol (inner surface) and 1,6-hexanedithiol (top surface), the most sensitive functional molecules from approaches i and ii, respectively, were combined into a third sensing strategy whereby the NAA platforms are functionalized on both the top and inner surfaces concurrently. Engineering of the surface according to this approach resulted in an additive enhancement in sensitivity of up to 5-fold compared to previously reported systems. This study advances the rational engineering of surface chemistry for interferometric sensing on nanoporous platforms with potential applications for real-time monitoring of multiple analytes in dynamic environments.

Quantum Chemical Mass Spectrometry: Verification and Extension of the Mobile Proton Model for Histidine

NASA Astrophysics Data System (ADS)

Cautereels, Julie; Blockhuys, Frank

2017-06-01

The quantum chemical mass spectrometry for materials science (QCMS2) method is used to verify the proposed mechanism for proton transfer - the Mobile Proton Model (MPM) - by histidine for ten XHS tripeptides, based on quantum chemical calculations at the DFT/B3LYP/6-311+G* level of theory. The fragmentations of the different intermediate structures in the MPM mechanism are studied within the QCMS2 framework, and the energetics of the proposed mechanism itself and those of the fragmentations of the intermediate structures are compared, leading to the computational confirmation of the MPM. In addition, the calculations suggest that the mechanism should be extended from considering only the formation of five-membered ring intermediates to include larger-ring intermediates. [Figure not available: see fulltext.

Zymomonas mobilis: a novel platform for future biorefineries

PubMed Central

2014-01-01

Biosynthesis of liquid fuels and biomass-based building block chemicals from microorganisms have been regarded as a competitive alternative route to traditional. Zymomonas mobilis possesses a number of desirable characteristics for its special Entner-Doudoroff pathway, which makes it an ideal platform for both metabolic engineering and commercial-scale production of desirable bio-products as the same as Escherichia coli and Saccharomyces cerevisiae based on consideration of future biomass biorefinery. Z. mobilis has been studied extensively on both fundamental and applied level, which will provide a basis for industrial biotechnology in the future. Furthermore, metabolic engineering of Z. mobilis for enhancing bio-ethanol production from biomass resources has been significantly promoted by different methods (i.e. mutagenesis, adaptive laboratory evolution, specific gene knock-out, and metabolic engineering). In addition, the feasibility of representative metabolites, i.e. sorbitol, bionic acid, levan, succinic acid, isobutanol, and isobutanol produced by Z. mobilis and the strategies for strain improvements are also discussed or highlighted in this paper. Moreover, this review will present some guidelines for future developments in the bio-based chemical production using Z. mobilis as a novel industrial platform for future biofineries. PMID:25024744

Zymomonas mobilis: a novel platform for future biorefineries.

PubMed

He, Ming Xiong; Wu, Bo; Qin, Han; Ruan, Zhi Yong; Tan, Fu Rong; Wang, Jing Li; Shui, Zong Xia; Dai, Li Chun; Zhu, Qi Li; Pan, Ke; Tang, Xiao Yu; Wang, Wen Guo; Hu, Qi Chun

2014-01-01

Biosynthesis of liquid fuels and biomass-based building block chemicals from microorganisms have been regarded as a competitive alternative route to traditional. Zymomonas mobilis possesses a number of desirable characteristics for its special Entner-Doudoroff pathway, which makes it an ideal platform for both metabolic engineering and commercial-scale production of desirable bio-products as the same as Escherichia coli and Saccharomyces cerevisiae based on consideration of future biomass biorefinery. Z. mobilis has been studied extensively on both fundamental and applied level, which will provide a basis for industrial biotechnology in the future. Furthermore, metabolic engineering of Z. mobilis for enhancing bio-ethanol production from biomass resources has been significantly promoted by different methods (i.e. mutagenesis, adaptive laboratory evolution, specific gene knock-out, and metabolic engineering). In addition, the feasibility of representative metabolites, i.e. sorbitol, bionic acid, levan, succinic acid, isobutanol, and isobutanol produced by Z. mobilis and the strategies for strain improvements are also discussed or highlighted in this paper. Moreover, this review will present some guidelines for future developments in the bio-based chemical production using Z. mobilis as a novel industrial platform for future biofineries.

Intermediate Chemical Precipitation Softening. Training Module 2.216.3.77.

ERIC Educational Resources Information Center

McMullen, L. D.

This document is an instructional module package prepared in objective form for use by an instructor familiar with the operation and maintenance of a chemical precipitation softening system. Included are objectives, instructor guides, student handouts and transparency masters. This is the second level of a three module series. The module considers…

The oligocene Lund Tuff, Great Basin, USA: A very large volume monotonous intermediate

USGS Publications Warehouse

Maughan, L.L.; Christiansen, E.H.; Best, M.G.; Gromme, C.S.; Deino, A.L.; Tingey, D.G.

2002-01-01

Unusual monotonous intermediate ignimbrites consist of phenocryst-rich dacite that occurs as very large volume (> 1000 km3) deposits that lack systematic compositional zonation, comagmatic rhyolite precursors, and underlying plinian beds. They are distinct from countless, usually smaller volume, zoned rhyolite-dacite-andesite deposits that are conventionally believed to have erupted from magma chambers in which thermal and compositional gradients were established because of sidewall crystallization and associated convective fractionation. Despite their great volume, or because of it, monotonous intermediates have received little attention. Documentation of the stratigraphy, composition, and geologic setting of the Lund Tuff - one of four monotonous intermediate tuffs in the middle-Tertiary Great Basin ignimbrite province - provides insight into its unusual origin and, by implication, the origin of other similar monotonous intermediates. The Lund Tuff is a single cooling unit with normal magnetic polarity whose volume likely exceeded 3000 km3. It was emplaced 29.02 ?? 0.04 Ma in and around the coeval White Rock caldera which has an unextended north-south diameter of about 50 km. The tuff is monotonous in that its phenocryst assemblage is virtually uniform throughout the deposit: plagioclase > quartz ??? hornblende > biotite > Fe-Ti oxides ??? sanidine > titanite, zircon, and apatite. However, ratios of phenocrysts vary by as much as an order of magnitude in a manner consistent with progressive crystallization in the pre-eruption chamber. A significant range in whole-rock chemical composition (e.g., 63-71 wt% SiO2) is poorly correlated with phenocryst abundance. These compositional attributes cannot have been caused wholly by winnowing of glass from phenocrysts during eruption, as has been suggested for the monotonous intermediate Fish Canyon Tuff. Pumice fragments are also crystal-rich, and chemically and mineralogically indistinguishable from bulk tuff. We

Floor Plans Rolling Platform, Tech Systems Platform, and Load ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

Floor Plans - Rolling Platform, Tech Systems Platform, and Load Platform Plans - Marshall Space Flight Center, F-1 Engine Static Test Stand, On Route 565 between Huntsville and Decatur, Huntsville, Madison County, AL

Chemical Microsensor Development for Aerospace Applications

NASA Technical Reports Server (NTRS)

Xu, Jennifer C.; Hunter, Gary W.; Lukco, Dorothy; Chen, Liangyu; Biaggi-Labiosa, Azlin M.

2013-01-01

Numerous aerospace applications, including low-false-alarm fire detection, environmental monitoring, fuel leak detection, and engine emission monitoring, would benefit greatly from robust and low weight, cost, and power consumption chemical microsensors. NASA Glenn Research Center has been working to develop a variety of chemical microsensors with these attributes to address the aforementioned applications. Chemical microsensors using different material platforms and sensing mechanisms have been produced. Approaches using electrochemical cells, resistors, and Schottky diode platforms, combined with nano-based materials, high temperature solid electrolytes, and room temperature polymer electrolytes have been realized to enable different types of microsensors. By understanding the application needs and chemical gas species to be detected, sensing materials and unique microfabrication processes were selected and applied. The chemical microsensors were designed utilizing simple structures and the least number of microfabrication processes possible, while maintaining high yield and low cost. In this presentation, an overview of carbon dioxide (CO2), oxygen (O2), and hydrogen/hydrocarbons (H2/CxHy) microsensors and their fabrication, testing results, and applications will be described. Particular challenges associated with improving the H2/CxHy microsensor contact wire-bonding pad will be discussed. These microsensors represent our research approach and serve as major tools as we expand our sensor development toolbox. Our ultimate goal is to develop robust chemical microsensor systems for aerospace and commercial applications.

Particulate representation of a chemical reaction mechanism

NASA Astrophysics Data System (ADS)

Lee, Kam-Wah Lucille

1999-09-01

A growing area of interest in chemical education has been the research associated with conceptual understanding at the particulate level. This study investigated the views of 10 university chemistry lecturers, 85 pre-service chemistry teachers and 23 Secondary 3 (equivalent to Year 9) chemistry students about the particulate level of a chemical reaction, namely the heating of copper (II) carbonate. Four characteristic views were identified on the basis of their diagrammatic representations of particles. These were: (a) formation of intermediates; (b) formation of free particles (e. g., atoms or ions); (c) combination of a and b: formation of free particles (e. g., atoms or ions) first, and then intermediates; (d) no mechanism. Both the majority of the lecturers and the pre-service teachers held an identical view about the reaction mechanism, namely that the decomposition of copper (II) carbonate goes through a transition stage by forming intermediates. In contrast, even though the students were familiar with this reaction, about half of them naïvely believed that copper (II) carbonate broke up on heating and the particles recombined directly to form copper (II) oxide and carbon dioxide, the two observed products. About one-third of the students had neither any notion of how the atoms in the copper (II) carbonate lattice interacted and were rearranged in the reaction nor any concept of bond-breaking and reformation in a chemical reaction.

I-SCAD® standoff chemical agent detector overview

NASA Astrophysics Data System (ADS)

Popa, Mirela O.; Griffin, Matthew T.

2012-06-01

This paper presents a system-level description of the I-SCAD® Standoff Chemical Agent Detector, a passive Fourier Transform InfraRed (FTIR) based remote sensing system, for detecting chemical vapor threats. The passive infrared detection system automatically searches the 7 to 14 micron region of the surrounding atmosphere for agent vapor clouds. It is capable of operating while on the move to accomplish reconnaissance, surveillance, and contamination avoidance missions. Additionally, the system is designed to meet the needs for application on air and sea as well as ground mobile and fixed site platforms. The lightweight, passive, and fully automatic detection system scans the surrounding atmosphere for chemical warfare agent vapors. It provides on-the-move, 360-deg coverage from a variety of tactical and reconnaissance platforms at distances up to 5 km. The core of the system is a rugged Michelson interferometer with a flexure spring bearing mechanism and bi-directional data acquisition capability. The modular system design facilitates interfacing to many platforms. A Reduced Field of View (RFOV) variant includes novel modifications to the scanner subcomponent assembly optical design that gives extended performance in detection range and detection probability without sacrificing existing radiometric sensitivity performance. This paper will deliver an overview of system.

An analytical platform for mass spectrometry-based identification and chemical analysis of RNA in ribonucleoprotein complexes.

PubMed

Taoka, Masato; Yamauchi, Yoshio; Nobe, Yuko; Masaki, Shunpei; Nakayama, Hiroshi; Ishikawa, Hideaki; Takahashi, Nobuhiro; Isobe, Toshiaki

2009-11-01

We describe here a mass spectrometry (MS)-based analytical platform of RNA, which combines direct nano-flow reversed-phase liquid chromatography (RPLC) on a spray tip column and a high-resolution LTQ-Orbitrap mass spectrometer. Operating RPLC under a very low flow rate with volatile solvents and MS in the negative mode, we could estimate highly accurate mass values sufficient to predict the nucleotide composition of a approximately 21-nucleotide small interfering RNA, detect post-transcriptional modifications in yeast tRNA, and perform collision-induced dissociation/tandem MS-based structural analysis of nucleolytic fragments of RNA at a sub-femtomole level. Importantly, the method allowed the identification and chemical analysis of small RNAs in ribonucleoprotein (RNP) complex, such as the pre-spliceosomal RNP complex, which was pulled down from cultured cells with a tagged protein cofactor as bait. We have recently developed a unique genome-oriented database search engine, Ariadne, which allows tandem MS-based identification of RNAs in biological samples. Thus, the method presented here has broad potential for automated analysis of RNA; it complements conventional molecular biology-based techniques and is particularly suited for simultaneous analysis of the composition, structure, interaction, and dynamics of RNA and protein components in various cellular RNP complexes.

Microarray platform affords improved product analysis in mammalian cell growth studies

PubMed Central

Li, Lingyun; Migliore, Nicole; Schaefer, Eugene; Sharfstein, Susan T.; Dordick, Jonathan S.; Linhardt, Robert J.

2014-01-01

High throughput (HT) platforms serve as cost-efficient and rapid screening method for evaluating the effect of cell culture conditions and screening of chemicals. The aim of the current study was to develop a high-throughput cell-based microarray platform to assess the effect of culture conditions on Chinese hamster ovary (CHO) cells. Specifically, growth, transgene expression and metabolism of a GS/MSX CHO cell line, which produces a therapeutic monoclonal antibody, was examined using microarray system in conjunction with conventional shake flask platform in a non-proprietary medium. The microarray system consists of 60 nl spots of cells encapsulated in alginate and separated in groups via an 8-well chamber system attached to the chip. Results show the non-proprietary medium developed allows cell growth, production and normal glycosylation of recombinant antibody and metabolism of the recombinant CHO cells in both the microarray and shake flask platforms. In addition, 10.3 mM glutamate addition to the defined base media results in lactate metabolism shift in the recombinant GS/MSX CHO cells in the shake flask platform. Ultimately, the results demonstrate that the high-throughput microarray platform has the potential to be utilized for evaluating the impact of media additives on cellular processes, such as, cell growth, metabolism and productivity. PMID:24227746

Bioelectrochemical system platform for sustainable environmental remediation and energy generation.

PubMed

Wang, Heming; Luo, Haiping; Fallgren, Paul H; Jin, Song; Ren, Zhiyong Jason

2015-01-01

The increasing awareness of the energy-environment nexus is compelling the development of technologies that reduce environmental impacts during energy production as well as energy consumption during environmental remediation. Countries spend billions in pollution cleanup projects, and new technologies with low energy and chemical consumption are needed for sustainable remediation practice. This perspective review provides a comprehensive summary on the mechanisms of the new bioelectrochemical system (BES) platform technology for efficient and low cost remediation, including petroleum hydrocarbons, chlorinated solvents, perchlorate, azo dyes, and metals, and it also discusses the potential new uses of BES approach for some emerging contaminants remediation, such as CO2 in air and nutrients and micropollutants in water. The unique feature of BES for environmental remediation is the use of electrodes as non-exhaustible electron acceptors, or even donors, for contaminant degradation, which requires minimum energy or chemicals but instead produces sustainable energy for monitoring and other onsite uses. BES provides both oxidation (anode) and reduction (cathode) reactions that integrate microbial-electro-chemical removal mechanisms, so complex contaminants with different characteristics can be removed. We believe the BES platform carries great potential for sustainable remediation and hope this perspective provides background and insights for future research and development. Copyright © 2015 Elsevier Inc. All rights reserved.

77 FR 75145 - Impact of the Implementation of the Chemical Weapons Convention (CWC) on Commercial Activities...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-12-19

... the Implementation of the Chemical Weapons Convention (CWC) on Commercial Activities Involving ``Schedule 1'' Chemicals (Including Schedule 1 Chemicals Produced as Intermediates) Through Calendar Year... Chemical Weapons Convention (CWC), through the Chemical Weapons Convention Implementation Act (CWCIA) and...

Cosmogenic nuclides application on French Mediterranean shore platform development

NASA Astrophysics Data System (ADS)

Giuliano, Jérémy; Lebourg, Thomas; Godard, Vincent; Dewez, Thomas; Braucher, Régis; Bourlès, Didier; Marçot, Nathalie

2014-05-01

Rocky shorelines are among the most common elements of the world's littoral zone, and the potential effects of rising sea level on the ever increasing populations require a better understanding of their dynamics. The sinuosity and heterogeneity of the shoreline morphology at large and intermediate wavelengths (1-100 km) results from their constant evolution under the combined influence of marine and continental forcings. This macro-scale organization is the expression of the action of elementary erosion processes acting at shorter wavelengths (<1 km) which lead to the development of shore platforms by landward retreat of cliff edges. Modern analytical techniques (laser-scaning, micro-erosion meters, aerial surveys) constitute appropriate methods to identify and quantify processes of cliff retreat to 1-100 yrs time-scales. But over this time frame, shore platform development appears imperceptible. Precise knowledge of long-term erosion rates are needed to understand rocky shore evolution, and develop quantitative modeling of platform development. Rocky coasts constitute a Quaternary sea level evolution archive that is partly preserved and progressively destroyed. One major challenges is to determine the degree to which coast morphologies are (i) contemporary, (ii) or ancient features inherited, (iii) or partly inherited from Quaternary interglacial stages. In order to fill the lack of long term coast morphodynamic data, we use cosmogenic nuclides (36Cl) to study abrasion surfaces carved in carbonates lithologies along the French Mediterranean coast, in a microtidal environment (Côte Bleue, West of Marseille). 36Cl concentration heritage influences strongly our interpretations in terms of age and denudation of the surfaces. We propose to constrain heritage in sampling oldest relic marine surfaces at 10m of altitude, and along recent cliff scarp. 36Cl concentrations show that the lowest platforms near sea level are contemporary and the highest ones (8-14 m above sea

A microfluidic perfusion platform for cultivation and screening study of motile microalgal cells

PubMed Central

Eu, Young-Jae; Park, Hye-Sun; Kim, Dong-Pyo; Wook Hong, Jong

2014-01-01

Systematic screening of algal cells is getting huge interest due to their capability of producing lipid-based biodiesel. Here, we introduce a new microfluidic platform composed of an array of perfusion chambers designed for long-term cultivation and preliminary screening of motile microalgal cells through loading and releasing of cells to and from the chambers. The chemical environment in each perfusion chamber was independently controlled for 5 days. The effect of nitrogen-depletion on the lipid production, phototaxis behavior in the absence of Ca2+, and cytotoxic effect of herbicide on microalgal cells was successfully monitored and compared with simultaneous control experiments on the platform. The present methodology could be extended to effective screening of algal cells and various cell lines for the production of biodiesel and other useful chemicals. PMID:24803962

Electrochemical sensing and biosensing platform based on chemically reduced graphene oxide.

PubMed

Zhou, Ming; Zhai, Yueming; Dong, Shaojun

2009-07-15

In this paper, the characterization and application of a chemically reduced graphene oxide modified glassy carbon (CR-GO/GC) electrode, a novel electrode system, for the preparation of electrochemical sensing and biosensing platform are proposed. Different kinds of important inorganic and organic electroactive compounds (i.e., probe molecule (potassium ferricyanide), free bases of DNA (guanine (G), adenine (A), thymine (T), and cytosine (C)), oxidase/dehydrogenase-related molecules (hydrogen peroxide (H2O2)/beta-nicotinamide adenine dinucleotide (NADH)), neurotransmitters (dopamine (DA)), and other biological molecules (ascorbic acid (AA), uric acid (UA), and acetaminophen (APAP)) were employed to study their electrochemical responses at the CR-GO/GC electrode, which shows more favorable electron transfer kinetics than graphite modified glassy carbon (graphite/GC) and glassy carbon (GC) electrodes. The greatly enhanced electrochemical reactivity of the four free bases of DNA at the CR-GO/GC electrode compared with that at graphite/GC and GC electrodes makes the CR-GO/GC electrode a better choice for the electrochemical biosensing of four DNA bases in both the single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA) at physiological pH without a prehydrolysis step. This allows us to detect a single-nucleotide polymorphism (SNP) site for short oligomers with a particular sequence at the CR-GO/GC electrode without any hybridization or labeling processes in this work, suggesting the potential applications of CR-GO in the label-free electrochemical detection of DNA hybridization or DNA damage for further research. Based on the greatly enhanced electrochemical reactivity of H2O2 and NADH at the CR-GO/GC electrode, CR-GO/GC electrode-based bioelectrodes (in connection with glucose oxidase (GOD) and alcohol dehydrogenase (ADH)) show a better analytical performance for the detection of glucose and ethanol compared with graphite/GC- or GC-based bioelectrodes. By comparing

Cluster Analysis of Time-Dependent Crystallographic Data: Direct Identification of Time-Independent Structural Intermediates

PubMed Central

Kostov, Konstantin S.; Moffat, Keith

2011-01-01

The initial output of a time-resolved macromolecular crystallography experiment is a time-dependent series of difference electron density maps that displays the time-dependent changes in underlying structure as a reaction progresses. The goal is to interpret such data in terms of a small number of crystallographically refinable, time-independent structures, each associated with a reaction intermediate; to establish the pathways and rate coefficients by which these intermediates interconvert; and thereby to elucidate a chemical kinetic mechanism. One strategy toward achieving this goal is to use cluster analysis, a statistical method that groups objects based on their similarity. If the difference electron density at a particular voxel in the time-dependent difference electron density (TDED) maps is sensitive to the presence of one and only one intermediate, then its temporal evolution will exactly parallel the concentration profile of that intermediate with time. The rationale is therefore to cluster voxels with respect to the shapes of their TDEDs, so that each group or cluster of voxels corresponds to one structural intermediate. Clusters of voxels whose TDEDs reflect the presence of two or more specific intermediates can also be identified. From such groupings one can then infer the number of intermediates, obtain their time-independent difference density characteristics, and refine the structure of each intermediate. We review the principles of cluster analysis and clustering algorithms in a crystallographic context, and describe the application of the method to simulated and experimental time-resolved crystallographic data for the photocycle of photoactive yellow protein. PMID:21244840

A modular platform for targeted RNAi therapeutics

NASA Astrophysics Data System (ADS)

Kedmi, Ranit; Veiga, Nuphar; Ramishetti, Srinivas; Goldsmith, Meir; Rosenblum, Daniel; Dammes, Niels; Hazan-Halevy, Inbal; Nahary, Limor; Leviatan-Ben-Arye, Shani; Harlev, Michael; Behlke, Mark; Benhar, Itai; Lieberman, Judy; Peer, Dan

2018-01-01

Previous studies have identified relevant genes and signalling pathways that are hampered in human disorders as potential candidates for therapeutics. Developing nucleic acid-based tools to manipulate gene expression, such as short interfering RNAs1-3 (siRNAs), opens up opportunities for personalized medicine. Yet, although major progress has been made in developing siRNA targeted delivery carriers, mainly by utilizing monoclonal antibodies (mAbs) for targeting4-8, their clinical translation has not occurred. This is in part because of the massive development and production requirements and the high batch-to-batch variability of current technologies, which rely on chemical conjugation. Here we present a self-assembled modular platform that enables the construction of a theoretically unlimited repertoire of siRNA targeted carriers. The self-assembly of the platform is based on a membrane-anchored lipoprotein that is incorporated into siRNA-loaded lipid nanoparticles that interact with the antibody crystallizable fragment (Fc) domain. We show that a simple switch of eight different mAbs redirects the specific uptake of siRNAs by diverse leukocyte subsets in vivo. The therapeutic potential of the platform is demonstrated in an inflammatory bowel disease model by targeting colon macrophages to reduce inflammatory symptoms, and in a Mantle Cell Lymphoma xenograft model by targeting cancer cells to induce cell death and improve survival. This modular delivery platform represents a milestone in the development of precision medicine.

A modular platform for targeted RNAi therapeutics.

PubMed

Kedmi, Ranit; Veiga, Nuphar; Ramishetti, Srinivas; Goldsmith, Meir; Rosenblum, Daniel; Dammes, Niels; Hazan-Halevy, Inbal; Nahary, Limor; Leviatan-Ben-Arye, Shani; Harlev, Michael; Behlke, Mark; Benhar, Itai; Lieberman, Judy; Peer, Dan

2018-03-01

Previous studies have identified relevant genes and signalling pathways that are hampered in human disorders as potential candidates for therapeutics. Developing nucleic acid-based tools to manipulate gene expression, such as short interfering RNAs 1-3 (siRNAs), opens up opportunities for personalized medicine. Yet, although major progress has been made in developing siRNA targeted delivery carriers, mainly by utilizing monoclonal antibodies (mAbs) for targeting 4-8 , their clinical translation has not occurred. This is in part because of the massive development and production requirements and the high batch-to-batch variability of current technologies, which rely on chemical conjugation. Here we present a self-assembled modular platform that enables the construction of a theoretically unlimited repertoire of siRNA targeted carriers. The self-assembly of the platform is based on a membrane-anchored lipoprotein that is incorporated into siRNA-loaded lipid nanoparticles that interact with the antibody crystallizable fragment (Fc) domain. We show that a simple switch of eight different mAbs redirects the specific uptake of siRNAs by diverse leukocyte subsets in vivo. The therapeutic potential of the platform is demonstrated in an inflammatory bowel disease model by targeting colon macrophages to reduce inflammatory symptoms, and in a Mantle Cell Lymphoma xenograft model by targeting cancer cells to induce cell death and improve survival. This modular delivery platform represents a milestone in the development of precision medicine.

Synthetic Routes to Methylerythritol Phosphate Pathway Intermediates and Downstream Isoprenoids

PubMed Central

Jarchow-Choy, Sarah K; Koppisch, Andrew T; Fox, David T

2014-01-01

Isoprenoids constitute the largest class of natural products with greater than 55,000 identified members. They play essential roles in maintaining proper cellular function leading to maintenance of human health, plant defense mechanisms against predators, and are often exploited for their beneficial properties in the pharmaceutical and nutraceutical industries. Most impressively, all known isoprenoids are derived from one of two C5-precursors, isopentenyl diphosphate (IPP) or dimethylallyl diphosphate (DMAPP). In order to study the enzyme transformations leading to the extensive structural diversity found within this class of compounds there must be access to the substrates. Sometimes, intermediates within a biological pathway can be isolated and used directly to study enzyme/pathway function. However, the primary route to most of the isoprenoid intermediates is through chemical catalysis. As such, this review provides the first exhaustive examination of synthetic routes to isoprenoid and isoprenoid precursors with particular emphasis on the syntheses of intermediates found as part of the 2C-methylerythritol 4-phosphate (MEP) pathway. In addition, representative syntheses are presented for the monoterpenes (C10), sesquiterpenes (C15), diterpenes (C20), triterpenes (C30) and tetraterpenes (C40). Finally, in some instances, the synthetic routes to substrate analogs found both within the MEP pathway and downstream isoprenoids are examined. PMID:25009443

Versatile electrophoresis-based self-test platform.

PubMed

Guijt, Rosanne M

2015-03-01

Lab on a Chip technology offers the possibility to extract chemical information from a complex sample in a simple, automated way without the need for a laboratory setting. In the health care sector, this chemical information could be used as a diagnostic tool for example to inform dosing. In this issue, the research underpinning a family of electrophoresis-based point-of-care devices for self-testing of ionic analytes in various sample matrices is described [Electrophoresis 2015, 36, 712-721.]. Hardware, software, and methodological chances made to improve the overall analytical performance in terms of accuracy, precision, detection limit, and reliability are discussed. In addition to the main focus of lithium monitoring, new applications including the use of the platform for veterinary purposes, sodium, and for creatinine measurements are included. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ceramization of low and intermediate level radioactive wastes

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

Fiquet, O.; Berson, X.

1993-12-31

A ceramic conditioning is studied for a large variety of low and intermediate level wastes. These wastes arise from several waste streams coming from all process steps of the fuel cycle. The physical properties of ceramics can advantageously be used for radioactive waste immobilization. Their chemical durability can offer a barrier against external aggression. More over, some minerals have possible host sites in their crystal structure for heavy elements which can confer the best immobilization mechanism. The general route for development studies is described giving compositions and process choices. Investigations have been conducted on clay materials and on the processmore » parameters which condition the final product properties. Two practical examples are described concerning chemical precipitation sludge resulting from liquid waste treatment and chamot used as a fluidized bed in a graphite incinerator. Important process parameters are put in evidence and the possibility of a pilot plant development is briefly mentioned. Results of investigations are promising to define a new route of conditioning.« less

Monash Chemical Yields Project (Monχey) - Element production in low- and intermediate-mass stars of metallicities Z = 0 to 0.04

NASA Astrophysics Data System (ADS)

Doherty, Carolyn Louise; Lattanzio, John; Angelou, George; Wattana Campbell, Simon; Church, Ross; Constantino, Thomas; Cristallo, Sergio; Gil-Pons, Pilar; Karakas, Amanda; Lugaro, Maria; Stancliffe, Richard James

2015-08-01

The Monχey project provides a large and homogeneous set of stellar yields for the low- and intermediate- mass stars and has applications particularly to galactic chemical evolution modelling.We present a detailed grid of stellar evolutionary models and corresponding nucleosynthetic yields for stars of initial mass 0.8 M⊙ up to the limit for core collapse supernova ≈ 10 M⊙. Our study covers a broad range of metallicities, ranging from the first, primordial stars (Z=0) to those of super-solar metallicity (Z=0.04). The models are evolved from the zero-age main-sequence until the end of the asymptotic giant branch (AGB) and the nucleosynthesis calculations include all elements from H to Bi.A major innovation of our work is the first complete grid of heavy element nucleosynthetic predictions for primordial AGB stars as well as the inclusion of extra-mixing processes (in this case thermohaline) during the red giant branch. We provide a broad overview of our results with implications for galactic chemical evolution as well as highlight interesting results such as heavy element production in dredge-out events of super-AGB stars.We briefly introduce our easy to use web-based database which provides the evolutionary tracks, structural properties, internal/surface nucleosynthetic compositions and stellar yields. Our web interface includes user- driven plotting capabilities with output available in a range of formats. Our nucleosynthetic results are available for further use in post processing calculations for dust production yields.

Nonlinear Silicon Photonics: Extending Platforms, Control, and Applications

NASA Astrophysics Data System (ADS)

Miller, Steven Andrew

Silicon photonics is a revolutionary technology that enables the control of light inside a silicon chip and holds promise to impact many applications from data center optical interconnects to optical sensing and even quantum optics. The tight confinement of light inside these chips greatly enhances light-matter interactions, making this an ideal platform for nonlinear photonics. Recently, microresonator-based Kerr frequency comb generation has become a prevalent emerging field, enabling the generation of a broadband optical pulse train by inputting a low-power continuous-wave laser into a low-loss chip-scale micro-cavity. These chip-scale combs have a wide variety of applications, including optical clocks, optical spectroscopy, and data communications. Several important applications in biological, chemical and atmospheric areas require combs generated in the visible and mid-infrared wavelength ranges, where there has been far less research and development compared with the near-infrared. Additionally, most platforms widely for combs are passive, limiting the ability to control and optimize the frequency combs. In this dissertation, we set out to address these shortcomings and introduce new tunability as well as wavelength flexibility in order to enable new applications for microresonator frequency combs. The silicon nitride platform for near-infrared combs is generally a passive platform with limited tuning capabilities. We overcome dispersion limitations in the visible range by leveraging the second-order nonlinearity of silicon nitride and demonstrate visible comb lines. We then further investigate the second-order nonlinearity of silicon nitride by measuring the linear electro-optic effect, a potential tuning mechanism. Finally, we introduce thermal tuning onto the silicon nitride platform and demonstrate tuning of the resonance extinction and dispersion of a micro-cavity using a coupled cavity design. We also address the silicon mid-infrared frequency comb

75 FR 69630 - Impact of Implementation of the Chemical Weapons Convention on Commercial Activities Involving...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-15

... Implementation of the Chemical Weapons Convention on Commercial Activities Involving ``Schedule 1'' Chemicals, Including Production of Schedule 1 Chemicals as Intermediates, Through Calendar Year 2010 AGENCY: Bureau of... (BIS) is seeking public comments on the impact that implementation of the Chemical Weapons Convention...

Storage Stability and Improvement of Intermediate Moisture Foods, Phase 3

NASA Technical Reports Server (NTRS)

Labuza, T. P.

1975-01-01

Methods were determined for the improvement of shelf-life stability of intermediate moisture foods (IMF). Microbial challenge studies showed that protection against molds and Staphylococcus aureus could be achieved by a combination of antimicrobial agents, humectants and food acids. Potassium sorbate and propylene glycol gave the best results. It was also confirmed that the maximum in heat resistance shown by vegetative pathogens at intermediate water activities also occurred in a solid food. Glycols and sorbitol both achieve browning inhibition because of their action as a medium for reaction and effect on viscosity of the adsorbed phase. Chemical availability results showed rapid lysine loss before visual discoloration occurred. This is being confirmed with a biological test using Tetrahymena pyriformis W. Accelerated temperature tests show that effectiveness of food antioxidants against rancidity development can be predicted; however, the protection factor changes with temperature. BHA was found to be the best antioxidant for iron catalyzed oxidation.

View from second floor platform looking up at subsequent platforms. ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

View from second floor platform looking up at subsequent platforms. Note the Shuttle assembly outlined by the platform edges. - Marshall Space Flight Center, Saturn V Dynamic Test Facility, East Test Area, Huntsville, Madison County, AL

Time-resolved resonance fluorescence spectroscopy for study of chemical reactions in laser-induced plasmas.

PubMed

Liu, Lei; Deng, Leimin; Fan, Lisha; Huang, Xi; Lu, Yao; Shen, Xiaokang; Jiang, Lan; Silvain, Jean-François; Lu, Yongfeng

2017-10-30

Identification of chemical intermediates and study of chemical reaction pathways and mechanisms in laser-induced plasmas are important for laser-ablated applications. Laser-induced breakdown spectroscopy (LIBS), as a promising spectroscopic technique, is efficient for elemental analyses but can only provide limited information about chemical products in laser-induced plasmas. In this work, time-resolved resonance fluorescence spectroscopy was studied as a promising tool for the study of chemical reactions in laser-induced plasmas. Resonance fluorescence excitation of diatomic aluminum monoxide (AlO) and triatomic dialuminum monoxide (Al 2 O) was used to identify these chemical intermediates. Time-resolved fluorescence spectra of AlO and Al 2 O were used to observe the temporal evolution in laser-induced Al plasmas and to study their formation in the Al-O 2 chemistry in air.

Supersensitive fingerprinting of explosives by chemically modified nanosensors arrays.

PubMed

Lichtenstein, Amir; Havivi, Ehud; Shacham, Ronen; Hahamy, Ehud; Leibovich, Ronit; Pevzner, Alexander; Krivitsky, Vadim; Davivi, Guy; Presman, Igor; Elnathan, Roey; Engel, Yoni; Flaxer, Eli; Patolsky, Fernando

2014-06-24

The capability to detect traces of explosives sensitively, selectively and rapidly could be of great benefit for applications relating to civilian national security and military needs. Here, we show that, when chemically modified in a multiplexed mode, nanoelectrical devices arrays enable the supersensitive discriminative detection of explosive species. The fingerprinting of explosives is achieved by pattern recognizing the inherent kinetics, and thermodynamics, of interaction between the chemically modified nanosensors array and the molecular analytes under test. This platform allows for the rapid detection of explosives, from air collected samples, down to the parts-per-quadrillion concentration range, and represents the first nanotechnology-inspired demonstration on the selective supersensitive detection of explosives, including the nitro- and peroxide-derivatives, on a single electronic platform. Furthermore, the ultrahigh sensitivity displayed by our platform may allow the remote detection of various explosives, a task unachieved by existing detection technologies.

Supersensitive fingerprinting of explosives by chemically modified nanosensors arrays

NASA Astrophysics Data System (ADS)

Lichtenstein, Amir; Havivi, Ehud; Shacham, Ronen; Hahamy, Ehud; Leibovich, Ronit; Pevzner, Alexander; Krivitsky, Vadim; Davivi, Guy; Presman, Igor; Elnathan, Roey; Engel, Yoni; Flaxer, Eli; Patolsky, Fernando

2014-06-01

The capability to detect traces of explosives sensitively, selectively and rapidly could be of great benefit for applications relating to civilian national security and military needs. Here, we show that, when chemically modified in a multiplexed mode, nanoelectrical devices arrays enable the supersensitive discriminative detection of explosive species. The fingerprinting of explosives is achieved by pattern recognizing the inherent kinetics, and thermodynamics, of interaction between the chemically modified nanosensors array and the molecular analytes under test. This platform allows for the rapid detection of explosives, from air collected samples, down to the parts-per-quadrillion concentration range, and represents the first nanotechnology-inspired demonstration on the selective supersensitive detection of explosives, including the nitro- and peroxide-derivatives, on a single electronic platform. Furthermore, the ultrahigh sensitivity displayed by our platform may allow the remote detection of various explosives, a task unachieved by existing detection technologies.

Developing cloud applications using the e-Science Central platform.

PubMed

Hiden, Hugo; Woodman, Simon; Watson, Paul; Cala, Jacek

2013-01-28

This paper describes the e-Science Central (e-SC) cloud data processing system and its application to a number of e-Science projects. e-SC provides both software as a service (SaaS) and platform as a service for scientific data management, analysis and collaboration. It is a portable system and can be deployed on both private (e.g. Eucalyptus) and public clouds (Amazon AWS and Microsoft Windows Azure). The SaaS application allows scientists to upload data, edit and run workflows and share results in the cloud, using only a Web browser. It is underpinned by a scalable cloud platform consisting of a set of components designed to support the needs of scientists. The platform is exposed to developers so that they can easily upload their own analysis services into the system and make these available to other users. A representational state transfer-based application programming interface (API) is also provided so that external applications can leverage the platform's functionality, making it easier to build scalable, secure cloud-based applications. This paper describes the design of e-SC, its API and its use in three different case studies: spectral data visualization, medical data capture and analysis, and chemical property prediction.

Developing cloud applications using the e-Science Central platform

PubMed Central

Hiden, Hugo; Woodman, Simon; Watson, Paul; Cala, Jacek

2013-01-01

This paper describes the e-Science Central (e-SC) cloud data processing system and its application to a number of e-Science projects. e-SC provides both software as a service (SaaS) and platform as a service for scientific data management, analysis and collaboration. It is a portable system and can be deployed on both private (e.g. Eucalyptus) and public clouds (Amazon AWS and Microsoft Windows Azure). The SaaS application allows scientists to upload data, edit and run workflows and share results in the cloud, using only a Web browser. It is underpinned by a scalable cloud platform consisting of a set of components designed to support the needs of scientists. The platform is exposed to developers so that they can easily upload their own analysis services into the system and make these available to other users. A representational state transfer-based application programming interface (API) is also provided so that external applications can leverage the platform's functionality, making it easier to build scalable, secure cloud-based applications. This paper describes the design of e-SC, its API and its use in three different case studies: spectral data visualization, medical data capture and analysis, and chemical property prediction. PMID:23230161

Strategic deployment of CHO expression platforms to deliver Pfizer's Monoclonal Antibody Portfolio.

PubMed

Scarcelli, John J; Shang, Tanya Q; Iskra, Tim; Allen, Martin J; Zhang, Lin

2017-11-01

Development of stable cell lines for expression of large-molecule therapeutics represents a significant portion of the time and effort required to advance a molecule to enabling regulatory toxicology studies and clinical evaluation. Our development strategy employs two different approaches for cell line development based on the needs of a particular project: a random integration approach for projects where high-level expression is critical, and a site-specific integration approach for projects in which speed and reduced employee time spend is a necessity. Here we describe both our random integration and site-specific integration platforms and their applications in support of monoclonal antibody development and production. We also compare product quality attributes of monoclonal antibodies produced with a nonclonal cell pool or clonal cell lines derived from the two platforms. Our data suggests that material source (pools vs. clones) does not significantly alter the examined product quality attributes. Our current practice is to leverage this observation with our site-specific integration platform, where material generated from cell pools is used for an early molecular assessment of a given candidate to make informed decisions around development strategy. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:1463-1467, 2017. © 2017 American Institute of Chemical Engineers.

Biofunctionalized 3-D Carbon Nano-Network Platform for Enhanced Fibroblast Cell Adhesion

NASA Astrophysics Data System (ADS)

Chowdhury, A. K. M. Rezaul Haque; Tavangar, Amirhossein; Tan, Bo; Venkatakrishnan, Krishnan

2017-03-01

Carbon nanomaterials have been investigated for various biomedical applications. In most cases, however, these nanomaterials must be functionalized biologically or chemically due to their biological inertness or possible cytotoxicity. Here, we report the development of a new carbon nanomaterial with a bioactive phase that significantly promotes cell adhesion. We synthesize the bioactive phase by introducing self-assembled nanotopography and altered nano-chemistry to graphite substrates using ultrafast laser. To the best of our knowledge, this is the first time that such a cytophilic bio-carbon is developed in a single step without requiring subsequent biological/chemical treatments. By controlling the nano-network concentration and chemistry, we develop platforms with different degrees of cell cytophilicity. We study quantitatively and qualitatively the cell response to nano-network platforms with NIH-3T3 fibroblasts. The findings from the in vitro study indicate that the platforms possess excellent biocompatibility and promote cell adhesion considerably. The study of the cell morphology shows a healthy attachment of cells with a well-spread shape, overextended actin filaments, and morphological symmetry, which is indicative of a high cellular interaction with the nano-network. The developed nanomaterial possesses great biocompatibility and considerably stimulates cell adhesion and subsequent cell proliferation, thus offering a promising path toward engineering various biomedical devices.

Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

2017-06-01

Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes.

Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

PubMed Central

Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

2017-01-01

Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes. PMID:28660882

Hypothalamic digoxin, hemispheric chemical dominance, and the tridosha theory.

PubMed

Kurup, Ravi Kumar; Kurup, Parameswara Achutha

2003-05-01

Ayurveda, the traditional Indian System of Medicine, deals with the theory of the three tridosha states (both physical and psychological): Vata, Pitta, and Kapha. They are the three major human constitutional types that both depend on psychological and physical characteristics. The Pitta state is described as a critical, discriminative, and rational psychological state of mind, while the Kapha state is described as being dominant for emotional stimuli. The Vata state is an intermediate unstable shifting state. The Pitta types are of average height and built with well developed musculature. The Vata types are thin individuals with low body mass index. The Kapha types are short stocky individuals that tend toward obesity, and who are sedentary. The study assessed the biochemical differences between right hemispheric dominant, bihemispheric dominant, and left hemispheric dominant individuals, and then compared this with the patterns obtained in the Vata, Pitta, and Kapha states. The isoprenoid metabolites (digoxin, dolichol, and ubiquinone), glycoconjugate metabolism, free radical metabolism, and the RBC membrane composition were studied. The hemispheric chemical dominance in various systemic diseases and psychological states was also investigated. The results showed that right hemispheric chemically dominant/Kapha state had elevated digoxin levels, increased free radical production and reduced scavenging, increased tryptophan catabolites and reduced tyrosine catabolites, increased glycoconjugate levels and increased cholesterol: phospholipid ratio of RBC membranes. Left hemispheric chemically dominant/Pitta states had the opposite biochemical patterns. The patterns were normal or intermediate in the bihemispheric chemically dominant/Vata state. This pattern could be correlated with various systemic and neuropsychiatric diseases and personality traits. Right hemispheric chemical dominance/Kapha state represents a hyperdigoxinemic state with membrane sodium

Recent Advances in Lipase-Mediated Preparation of Pharmaceuticals and Their Intermediates

PubMed Central

Carvalho, Ana Caroline Lustosa de Melo; Fonseca, Thiago de Sousa; de Mattos, Marcos Carlos; de Oliveira, Maria da Conceição Ferreira; de Lemos, Telma Leda Gomes; Molinari, Francesco; Romano, Diego; Serra, Immacolata

2015-01-01

Biocatalysis offers an alternative approach to conventional chemical processes for the production of single-isomer chiral drugs. Lipases are one of the most used enzymes in the synthesis of enantiomerically pure intermediates. The use of this type of enzyme is mainly due to the characteristics of their regio-, chemo- and enantioselectivity in the resolution process of racemates, without the use of cofactors. Moreover, this class of enzymes has generally excellent stability in the presence of organic solvents, facilitating the solubility of the organic substrate to be modified. Further improvements and new applications have been achieved in the syntheses of biologically active compounds catalyzed by lipases. This review critically reports and discusses examples from recent literature (2007 to mid-2015), concerning the synthesis of enantiomerically pure active pharmaceutical ingredients (APIs) and their intermediates in which the key step involves the action of a lipase. PMID:26690428

Platform C Installation

NASA Image and Video Library

2016-10-19

A heavy-lift crane lowers the first half of the C-level work platforms, C south, for NASA’s Space Launch System (SLS) rocket, for installation on the south side of High Bay 3 in the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. In view below Platform C are several of the previously installed platforms. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Mapping Proteome-Wide Interactions of Reactive Chemicals Using Chemoproteomic Platforms

PubMed Central

Counihan, Jessica L.; Ford, Breanna; Nomura, Daniel K.

2015-01-01

A large number of pharmaceuticals, endogenous metabolites, and environmental chemicals act through covalent mechanisms with protein targets. Yet, their specific interactions with the proteome still remain poorly defined for most of these reactive chemicals. Deciphering direct protein targets of reactive small-molecules is critical in understanding their biological action, off-target effects, potential toxicological liabilities, and development of safer and more selective agents. Chemoproteomic technologies have arisen as a powerful strategy that enable the assessment of proteome-wide interactions of these irreversible agents directly in complex biological systems. We review here several chemoproteomic strategies that have facilitated our understanding of specific protein interactions of irreversibly-acting pharmaceuticals, endogenous metabolites, and environmental electrophiles to reveal novel pharmacological, biological, and toxicological mechanisms. PMID:26647369

INTERMEDIATE STAGES OF REACTIONS FORMING CARBIDES OF TITANIUM, ZIRCONIUM, VANADIUM, NIOBIUM, AND TANTALIUM

DTIC Science & Technology

Tensimetric examination was made of the formation of the carbides TiC , ZrC, VC, NbC and TaC in a vacuum. During x-ray and chemical analysis of...for obtaining TiC , and ZrC through the stage of intermediate oxides Ti2O3, Ti3O5, TiO and Zr2O3, ZrO, respectively and also for the reaction of

Europa Science Platforms and Kinetic Energy Probes

NASA Technical Reports Server (NTRS)

Hays, C. C.; Klein, G. A.

2003-01-01

This presentation will outline a proposed mission for the Jupiter Icy Moons Orbiter (JIMO). The mission outlined will concentrate on an examination of Europa. Some of the primary science goals for the JIMO mission are: 1) to answer broad science questions, 2) improved knowledge of Jovian system; specifically, lunar geological and geophysical properties, 3) chemical composition of Jovian lunar surfaces and subterranean matter, and 4) the search for life. In order to address these issues, the experiment proposed here will deploy orbiting, surface, and subterranean science platforms.

Defensive platform size and survivability. [Platform survivability

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

Canavan, Gregory H.

1988-06-01

This report discusses the survivability of space platforms, concentrating on space based kinetic energy interceptors. It evaluates the efficacy of hardening, maneuver, self-defense, and deception in extending the survivability of platforms of varying sizes to expected threats, concluding that they should be adequate in the near and mid terms.

Geosynchronous platform definition study. Volume 5: Geosynchronous platform synthesis

NASA Technical Reports Server (NTRS)

1973-01-01

The development is described of the platform configurations, support subsystems, mission equipment, and servicing concepts. A common support module is developed; subsystem concepts are traded off; data relay, TDRS, earth observational, astro-physics, and advanced navigation and traffic control mission equipment concepts are postulated; and ancillary equipment required for delivery and on-orbit servicing interfaces with geosynchronous platforms is grossly defined. The general approach was to develop a platform concept capable of evolving through three on-orbit servicing modes: remote, EVA, and shirtsleeve. The definition of the equipment is to the assembly level. Weight, power, and volumetric data are compiled for all the platforms.

QCL-based standoff and proximal chemical detectors

NASA Astrophysics Data System (ADS)

Dupuis, Julia R.; Hensley, Joel; Cosofret, Bogdan R.; Konno, Daisei; Mulhall, Phillip; Schmit, Thomas; Chang, Shing; Allen, Mark; Marinelli, William J.

2016-05-01

The development of two longwave infrared quantum cascade laser (QCL) based surface contaminant detection platforms supporting government programs will be discussed. The detection platforms utilize reflectance spectroscopy with application to optically thick and thin materials including solid and liquid phase chemical warfare agents, toxic industrial chemicals and materials, and explosives. Operation at standoff (10s of m) and proximal (1 m) ranges will be reviewed with consideration given to the spectral signatures contained in the specular and diffusely reflected components of the signal. The platforms comprise two variants: Variant 1 employs a spectrally tunable QCL source with a broadband imaging detector, and Variant 2 employs an ensemble of broadband QCLs with a spectrally selective detector. Each variant employs a version of the Adaptive Cosine Estimator for detection and discrimination in high clutter environments. Detection limits of 5 μg/cm2 have been achieved through speckle reduction methods enabling detector noise limited performance. Design considerations for QCL-based standoff and proximal surface contaminant detectors are discussed with specific emphasis on speckle-mitigated and detector noise limited performance sufficient for accurate detection and discrimination regardless of the surface coverage morphology or underlying surface reflectivity. Prototype sensors and developmental test results will be reviewed for a range of application scenarios. Future development and transition plans for the QCL-based surface detector platforms are discussed.

Spin-locking vs. chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons

PubMed Central

Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi

2010-01-01

Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of non-equivalent chemical environments. To compare the characteristics of the CEST and SL approaches in the study of chemical exchange effects, we performed CEST and SL experiments at varied pH and concentrated metabolites with exchangeable amide, amine, and hydroxyl protons at 9.4 T. Our results show that: i) On-resonance SL is most sensitive to chemical exchanges in the intermediate exchange regime and is able to detect hydroxyl and amine protons on a millimolar concentration scale. Off-resonance SL and CEST approaches are sensitive to slow-exchanging protons when an optimal SL or saturation pulse power matches the exchanging rate, respectively. ii) Offset frequency-dependent SL and CEST spectra are very similar, and can be explained well with an SL model recently developed by Trott and Palmer. iii) The exchange rate and population of metabolite protons can be determined from offset-dependent SL or CEST spectra or from on-resonance SL relaxation dispersion measurements. iv) The asymmetry of the magnetization transfer ratio (MTRasym) is highly dependent on the choice of saturation pulse power. In the intermediate exchange regime, MTRasym becomes complicated and should be interpreted with care. PMID:21500270

Trapping and Characterization of a Reaction Intermediate in Carbapenem Hydrolysis by B. cereus Metallo-β-lactamase

PubMed Central

Tioni, Mariana F.; Llarrull, Leticia I.; Poeylaut-Palena, Andrés A.; Martí, Marcelo A.; Saggu, Miguel; Periyannan, Gopal R.; Mata, Ernesto G.; Bennett, Brian; Murgida, Daniel H.; Vila, Alejandro J.

2009-01-01

Metallo-β-lactamases hydrolyze most β-lactam antibiotics. The lack of a successful inhibitor for them is related to the previous failure to characterize a reaction intermediate with a clinically useful substrate. Stopped-flow experiments together with rapid freeze-quench EPR and Raman spectroscopies were used to characterize the reaction of Co(II)-BcII with imipenem. These studies show that Co(II)-BcII is able to hydrolyze imipenem both in the mono- and dinuclear forms. In contrast to the situation met for penicillin, the species that accumulates during turnover is an enzyme-intermediate adduct in which the β-lactam bond has already been cleaved. This intermediate is a metal-bound anionic species, with a novel resonant structure, that is stabilized by the metal ion at the DCH or Zn2 site. This species has been characterized based on its spectroscopic features. This represents a novel, previously unforeseen intermediate, that is related to the chemical nature of carbapenems, as confirmed by the finding of a similar intermediate for meropenem. Since carbapenems are the only substrates cleaved by B1, B2 and B3 lactamases, the identification of this intermediate could be exploited as a first step towards the design of transition state based inhibitors for all three classes of metallo-β-lactamases. PMID:18980308

Bioorthogonal Chemical Imaging for Biomedicine

NASA Astrophysics Data System (ADS)

Min, Wei

2017-06-01

Innovations in light microscopy have tremendously revolutionized the way researchers study biological systems with subcellular resolution. Although fluorescence microscopy is currently the method of choice for cellular imaging, it faces fundamental limitations for studying the vast number of small biomolecules. This is because relatively bulky fluorescent labels could introduce considerable perturbation to or even completely alter the native functions of vital small biomolecules. Hence, despite their immense functional importance, these small biomolecules remain largely undetectable by fluorescence microscopy. To address this challenge, we have developed a bioorthogonal chemical imaging platform. By coupling stimulated Raman scattering (SRS) microscopy, an emerging nonlinear Raman microscopy technique, with tiny and Raman-active vibrational probes (e.g., alkynes, nitriles and stable isotopes including 2H and 13C), bioorthogonal chemical imaging exhibits superb sensitivity, specificity, multiplicity and biocompatibility for imaging small biomolecules in live systems including tissues and organisms. Exciting biomedical applications such as imaging fatty acid metabolism related to lipotoxicity, glucose uptake and metabolism, drug trafficking, protein synthesis, DNA replication, protein degradation, RNA synthesis and tumor metabolism will be presented. This bioorthogonal chemical imaging platform is compatible with live-cell biology, thus allowing real-time imaging of small-molecule dynamics. Moreover, further chemical and spectroscopic strategies allow for multicolor bioorthogonal chemical imaging, a valuable technique in the era of "omics". We envision that the coupling of SRS microscopy with vibrational probes would do for small biomolecules what fluorescence microscopy of fluorophores has done for larger molecular species, bringing small molecules under the illumination of modern light microscopy.

Covering Chemical Diversity of Genetically-Modified Tomatoes Using Metabolomics for Objective Substantial Equivalence Assessment

PubMed Central

Hirai, Tadayoshi; Oikawa, Akira; Matsuda, Fumio; Fukushima, Atsushi; Arita, Masanori; Watanabe, Shin; Yano, Megumu; Hiwasa-Tanase, Kyoko; Ezura, Hiroshi; Saito, Kazuki

2011-01-01

As metabolomics can provide a biochemical snapshot of an organism's phenotype it is a promising approach for charting the unintended effects of genetic modification. A critical obstacle for this application is the inherently limited metabolomic coverage of any single analytical platform. We propose using multiple analytical platforms for the direct acquisition of an interpretable data set of estimable chemical diversity. As an example, we report an application of our multi-platform approach that assesses the substantial equivalence of tomatoes over-expressing the taste-modifying protein miraculin. In combination, the chosen platforms detected compounds that represent 86% of the estimated chemical diversity of the metabolites listed in the LycoCyc database. Following a proof-of-safety approach, we show that % had an acceptable range of variation while simultaneously indicating a reproducible transformation-related metabolic signature. We conclude that multi-platform metabolomics is an approach that is both sensitive and robust and that it constitutes a good starting point for characterizing genetically modified organisms. PMID:21359231

Effect of intermediate soil cover on municipal solid waste decomposition.

PubMed

Márquez-Benavides, L; Watson-Craik, I

2003-01-01

A complex series of chemical and microbiological reactions is initiated with the burial of refuse in a sanitary landfill. At the end of each labour day, the municipal solid wastes (MSW) are covered with native soil (or an alternative material). To investigate interaction between the intermediate cover and the MSW, five sets of columns were set up, one packed with refuse only, and four with a soil-refuse mixture (a clay loam, an organic-rich peaty soil, a well limed sandy soil and a chalky soil). The anaerobic degradation over 6 months was followed in terms of leachate volatile fatty acids, chemical oxygen demand, pH and ammoniacal-N performance. Results suggest that the organic-rich peaty soil may accelerate the end of the acidogenic phase. Clay appeared not to have a significant effect on the anaerobic degradation process.

De Novo Synthesis of Mono- and Oligosaccharides via Dihydropyran Intermediates.

PubMed

Song, Wangze; Wang, Shuojin; Tang, Weiping

2017-05-18

The importance of carbohydrates is evident by their essential role in all living systems. Their syntheses have attracted attention from chemists for over a century. Most chemical syntheses in this area focus on the preparation of carbohydrates from naturally occurring monosaccharides. De novo chemical synthesis of carbohydrates from feedstock starting materials has emerged as a complementary method for the preparation of diverse mono- and oligosaccharides. In this review, the history of de novo carbohydrate synthesis is briefly discussed and particular attention is given to methods that address the formation of glycosidic bonds for potential de novo synthesis of oligosaccharides. Almost all methods of this kind involve the formation of dihydropyran intermediates. Recent progress in forming dihydropyrans by Achmatowicz rearrangement, hetero-Diels-Alder cycloaddition, ring-closing metathesis, and other methods is also elaborated. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multidimensional profiling platforms reveal metabolic dysregulation caused by organophosphorus pesticides.

PubMed

Medina-Cleghorn, Daniel; Heslin, Ann; Morris, Patrick J; Mulvihill, Melinda M; Nomura, Daniel K

2014-02-21

We are environmentally exposed to countless synthetic chemicals on a daily basis, with an increasing number of these chemical exposures linked to adverse health effects. However, our understanding of the (patho)physiological effects of these chemicals remains poorly understood, due in part to a general lack of effort to systematically and comprehensively identify the direct interactions of environmental chemicals with biological macromolecules in mammalian systems in vivo. Here, we have used functional chemoproteomic and metabolomic platforms to broadly identify direct enzyme targets that are inhibited by widely used organophosphorus (OP) pesticides in vivo in mice and to determine metabolic alterations that are caused by these chemicals. We find that these pesticides directly inhibit over 20 serine hydrolases in vivo leading to widespread disruptions in lipid metabolism. Through identifying direct biological targets of OP pesticides, we show heretofore unrecognized modes of toxicity that may be associated with these agents and underscore the utility of using multidimensional profiling approaches to obtain a more complete understanding of toxicities associated with environmental chemicals.

Stabilized floating platforms

DOEpatents

Thomas, David G.

1976-01-01

The subject invention is directed to a floating platform for supporting nuclear reactors and the like at selected offshore sites. The platform is provided with a stabilizer mechanism which significantly reduces the effects of wave action upon the platform and which comprises a pair of relatively small floats attached by rigid booms to the platform at locations spaced therefrom for reducing wave pitch, acceleration, and the resonance period of the wave.

Nanoporous Anodic Alumina: A Versatile Platform for Optical Biosensors

PubMed Central

Santos, Abel; Kumeria, Tushar; Losic, Dusan

2014-01-01

Nanoporous anodic alumina (NAA) has become one of the most promising nanomaterials in optical biosensing as a result of its unique physical and chemical properties. Many studies have demonstrated the outstanding capabilities of NAA for developing optical biosensors in combination with different optical techniques. These results reveal that NAA is a promising alternative to other widely explored nanoporous platforms, such as porous silicon. This review is aimed at reporting on the recent advances and current stage of development of NAA-based optical biosensing devices. The different optical detection techniques, principles and concepts are described in detail along with relevant examples of optical biosensing devices using NAA sensing platforms. Furthermore, we summarise the performance of these devices and provide a future perspective on this promising research field. PMID:28788678

Platform C Installation

NASA Image and Video Library

2016-10-19

A heavy-lift crane lifts the first half of the C-level work platforms, C south, for NASA’s Space Launch System (SLS) rocket, up from the transfer aisle floor of the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida. Large Tandemloc bars have been attached to the platform to keep it level during lifting and installation. The C platform will be installed on the south side of High Bay 3. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Involving older people in intermediate care.

PubMed

Andrews, JoyAnn; Manthorpe, Jill; Watson, Roger

2004-05-01

Intermediate care has become a crucial part of the United Kingdom government's programme for improving services for older people. Older people comprise a substantial part of the user base for these services, and it is increasingly recognized that there is a need for greater user involvement in service development for intermediate care. National initiatives undertaken in intermediate care have sought to widen and deepen the remit of such services, and in this way promote greater independence and improved quality of care for older people. In particular, the government has set out clear plans for reshaping services for older people in the National Health Service Plan and the rationale for greater involvement of older people in service development. This article considers ways in which these national and local objectives may be achieved and considers some of the implications for nursing. This paper aims to explore the concept of intermediate care and to identify trends and existing evidence of user involvement in care. In this way it charts a possible way forward for the development of a more 'user sensitive' approach. The following databases were searched: Medline, Cochrane Library, the Social Science Citation Index and CINAHL. Key words were 'intermediate care', 'older people', 'formal care', 'primary care', 'social services' and 'geriatrics', used in combination. The findings from this study indicate that there is considerable scope for increased user involvement in service development for intermediate care. Such challenges may be more effectively met through greater clarity of the concept of intermediate care, and a bridging of user involvement at the practice and policy levels. Nurses are key providers of intermediate care in the community. The involvement of older people in intermediate care service development must be premised on a shared comprehension of the purpose and function of intermediate care. Nurses must be involved in shifting intermediate care from

15 CFR 742.2 - Proliferation of chemical and biological weapons.

Code of Federal Regulations, 2012 CFR

2012-01-01

... Country Chart (Supplement No. 1 to part 738 of the EAR) is indicated in the appropriate ECCN, a license is... ECCN, a license is required to all destinations except countries in Country Group A:3 (see Supplement... in ECCN 1C350 (precursor and intermediate chemicals used in the production of chemical warfare agents...

The ARGO Project: assessing NA-TECH risks on off-shore oil platforms

NASA Astrophysics Data System (ADS)

Capuano, Paolo; Basco, Anna; Di Ruocco, Angela; Esposito, Simona; Fusco, Giannetta; Garcia-Aristizabal, Alexander; Mercogliano, Paola; Salzano, Ernesto; Solaro, Giuseppe; Teofilo, Gianvito; Scandone, Paolo; Gasparini, Paolo

2017-04-01

ARGO (Analysis of natural and anthropogenic risks on off-shore oil platforms) is a 2 years project, funded by the DGS-UNMIG (Directorate General for Safety of Mining and Energy Activities - National Mining Office for Hydrocarbons and Georesources) of Italian Ministry of Economic Development. The project, coordinated by AMRA (Center for the Analysis and Monitoring of Environmental Risk), aims at providing technical support for the analysis of natural and anthropogenic risks on offshore oil platforms. In order to achieve this challenging objective, ARGO brings together climate experts, risk management experts, seismologists, geologists, chemical engineers, earth and coastal observation experts. ARGO has developed methodologies for the probabilistic analysis of industrial accidents triggered by natural events (NA-TECH) on offshore oil platforms in the Italian seas, including extreme events related to climate changes. Furthermore the environmental effect of offshore activities has been investigated, including: changes on seismicity and on the evolution of coastal areas close to offshore platforms. Then a probabilistic multi-risk framework has been developed for the analysis of NA-TECH events on offshore installations for hydrocarbon extraction.

Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

PubMed

Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán

2014-03-11

While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.

Platform C Installation

NASA Image and Video Library

2016-10-19

Inside the Vehicle Assembly Building at NASA’s Kennedy Space Center in Florida, a construction worker assist with the installation of the first half of the C-level work platforms, C south, for NASA’s Space Launch System (SLS) rocket. The large bolts that hold the platform in place on the south wall are being secured. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Platform C Installation

NASA Image and Video Library

2016-10-19

Inside the Vehicle Assembly Building at NASA’s Kennedy Space Center in Florida, construction workers assist with the installation of the first half of the C-level work platforms, C south, for NASA’s Space Launch System (SLS) rocket. The large bolts that hold the platform in place on the south wall are being secured. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Platform C Installation

NASA Image and Video Library

2016-10-19

Inside the Vehicle Assembly Building at NASA’s Kennedy Space Center in Florida, the first half of the C-level work platforms, C south, for NASA’s Space Launch System (SLS) rocket, has been installed on the south side of the high bay. In view below are several levels of previously installed platforms. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Time-resolved resonance Raman spectroscopy of intermediates of bacteriorhodopsin: The bK(590) intermediate.

PubMed

Terner, J; Hsieh, C L; Burns, A R; El-Sayed, M A

1979-07-01

We have combined microbeam and flow techniques with computer subtraction methods to obtain the resonance Raman spectrum of the short lived batho-intermediate (bK(590)) of bacteriorhodopsin. Comparison of the spectra obtained in (1)H(2)O and (2)H(2)O, as well as the fact that the bK(590) intermediate shows large optical red shifts, suggests that the Schiff base linkage of this intermediate is protonated. The fingerprint region of the spectrum of bK(590), sensitive to the isomeric configuration of the retinal chromophore, does not resemble the corresponding region of the parent bR(570) form. The resonance Raman spectrum of bK(590) as well as the spectra of all of the other main intermediates in the photoreaction cycle of bacteriorhodopsin are discussed and compared with resonance Raman spectra of published model compounds.

Novel peptide-based platform for the dual presentation of biologically active peptide motifs on biomaterials.

PubMed

Mas-Moruno, Carlos; Fraioli, Roberta; Albericio, Fernando; Manero, José María; Gil, F Javier

2014-05-14

Biofunctionalization of metallic materials with cell adhesive molecules derived from the extracellular matrix is a feasible approach to improve cell-material interactions and enhance the biointegration of implant materials (e.g., osseointegration of bone implants). However, classical biomimetic strategies may prove insufficient to elicit complex and multiple biological signals required in the processes of tissue regeneration. Thus, newer strategies are focusing on installing multifunctionality on biomaterials. In this work, we introduce a novel peptide-based divalent platform with the capacity to simultaneously present distinct bioactive peptide motifs in a chemically controlled fashion. As a proof of concept, the integrin-binding sequences RGD and PHSRN were selected and introduced in the platform. The biofunctionalization of titanium with this platform showed a positive trend towards increased numbers of cell attachment, and statistically higher values of spreading and proliferation of osteoblast-like cells compared to control noncoated samples. Moreover, it displayed statistically comparable or improved cell responses compared to samples coated with the single peptides or with an equimolar mixture of the two motifs. Osteoblast-like cells produced higher levels of alkaline phosphatase on surfaces functionalized with the platform than on control titanium; however, these values were not statistically significant. This study demonstrates that these peptidic structures are versatile tools to convey multiple biofunctionality to biomaterials in a chemically defined manner.

Methylation and demethylation of intermediates selenide and methylselenol in the metabolism of selenium

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

Ohta, Yuki; Suzuki, Kazuo T.

2008-01-15

All nutritional selenium sources are transformed into the assumed common intermediate selenide for the syntheses of selenoproteins for utilization and/or of selenosugar for excretion. Methylselenol [monomethylselenide, MMSe] is the assumed intermediate leading to other methylated metabolites, dimethylselenide (DMSe) and trimethylselenonium (TMSe) for excretion, and also to the intermediate selenide from methylselenocysteine and methylseleninic acid (MSA). Here, related methylation and demethylation reactions were studied in vitro by providing chemically reactive starting substrates ({sup 76}Se-selenide, {sup 77}Se-MMSe and {sup 82}Se-DMSe) which were prepared in situ by the reduction of the corresponding labeled proximate precursors ({sup 76}Se-selenite, {sup 77}Se-MSA and {sup 82}Se-dimethylselenoxide (DMSeO),more » respectively) with glutathione, the three substrates being incubated simultaneously in rat organ supernatants and homogenates. The resulting chemically labile reaction products were detected simultaneously by speciation analysis with HPLC-ICP-MS after converting the products and un-reacted substrates to the corresponding oxidized derivatives (selenite, MSA and DMSeO). The time-related changes in selenium isotope profiles showed that demethylation of MMSe to selenide was efficient but that of DMSe to MMSe was negligible, whereas methylation of selenide to MMSe, and MMSe to DMSe were efficient, and that of DMSe to TMSe occurred less efficiently. The present methylation and demethylation reactions on equilibrium between selenide, MMSe and DMSe without producing selenosugar and selenoproteins indicated that DMSe rather than TMSe is produced as the end product, suggesting that DMSe is to be excreted more abundantly than TMSe. Organ-dependent differences in the methylation and demethylation reactions were characterized for the liver, kidney and lung.« less

Role of Intermediate Filaments in Vesicular Traffic.

PubMed

Margiotta, Azzurra; Bucci, Cecilia

2016-04-25

Intermediate filaments are an important component of the cellular cytoskeleton. The first established role attributed to intermediate filaments was the mechanical support to cells. However, it is now clear that intermediate filaments have many different roles affecting a variety of other biological functions, such as the organization of microtubules and microfilaments, the regulation of nuclear structure and activity, the control of cell cycle and the regulation of signal transduction pathways. Furthermore, a number of intermediate filament proteins have been involved in the acquisition of tumorigenic properties. Over the last years, a strong involvement of intermediate filament proteins in the regulation of several aspects of intracellular trafficking has strongly emerged. Here, we review the functions of intermediate filaments proteins focusing mainly on the recent knowledge gained from the discovery that intermediate filaments associate with key proteins of the vesicular membrane transport machinery. In particular, we analyze the current understanding of the contribution of intermediate filaments to the endocytic pathway.

Intermediality: Bridge to Critical Media Literacy.

ERIC Educational Resources Information Center

Pailliotet, Ann Watts; Semali, Ladislaus; Rodenberg, Rita K.; Giles, Jackie K.; Macaul, Sherry L.

2000-01-01

Defines "intermediality" as the ability to critically read and write with and across varied symbol systems. Relates it to critical media literacy. Offers rationales for teaching critical media literacy in general, and intermedial instruction in particular. Identifies seven guiding intermedial elements: theory, texts, processes, contexts,…

A plant-based chemical genomics screen for the identification of flowering inducers.

PubMed

Fiers, Martijn; Hoogenboom, Jorin; Brunazzi, Alice; Wennekes, Tom; Angenent, Gerco C; Immink, Richard G H

2017-01-01

Floral timing is a carefully regulated process, in which the plant determines the optimal moment to switch from the vegetative to reproductive phase. While there are numerous genes known that control flowering time, little information is available on chemical compounds that are able to influence this process. We aimed to discover novel compounds that are able to induce flowering in the model plant Arabidopsis. For this purpose we developed a plant-based screening platform that can be used in a chemical genomics study. Here we describe the set-up of the screening platform and various issues and pitfalls that need to be addressed in order to perform a chemical genomics screening on Arabidopsis plantlets. We describe the choice for a molecular marker, in combination with a sensitive reporter that's active in plants and is sufficiently sensitive for detection. In this particular screen, the firefly Luciferase marker was used, fused to the regulatory sequences of the floral meristem identity gene APETALA1 (AP1) , which is an early marker for flowering. Using this screening platform almost 9000 compounds were screened, in triplicate, in 96-well plates at a concentration of 25 µM. One of the identified potential flowering inducing compounds was studied in more detail and named Flowering1 (F1). F1 turned out to be an analogue of the plant hormone Salicylic acid (SA) and appeared to be more potent than SA in the induction of flowering. The effect could be confirmed by watering Arabidopsis plants with SA or F1, in which F1 gave a significant reduction in time to flowering in comparison to SA treatment or the control. In this study a chemical genomics screening platform was developed to discover compounds that can induce flowering in Arabidopsis. This platform was used successfully, to identify a compound that can speed-up flowering in Arabidopsis.

Biorefineries for the production of top building block chemicals and their derivatives.

PubMed

Choi, Sol; Song, Chan Woo; Shin, Jae Ho; Lee, Sang Yup

2015-03-01

Due to the growing concerns on the climate change and sustainability on petrochemical resources, DOE selected and announced the bio-based top 12 building blocks and discussed the needs for developing biorefinery technologies to replace the current petroleum based industry in 2004. Over the last 10 years after its announcement, many studies have been performed for the development of efficient technologies for the bio-based production of these chemicals and derivatives. Now, ten chemicals among these top 12 chemicals, excluding the l-aspartic acid and 3-hydroxybutyrolactone, have already been commercialized or are close to commercialization. In this paper, we review the current status of biorefinery development for the production of these platform chemicals and their derivatives. In addition, current technological advances on industrial strain development for the production of platform chemicals using micro-organisms will be covered in detail with case studies on succinic acid and 3-hydroxypropionic acid as examples. Copyright © 2015 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Chemical vapor deposition of gallium nitride from the GaCl(3)+NH(3) system. Theoretical study of the structure and thermodynamics of potential intermediates formed in the gaseous phase.

PubMed

Kovács, Attila

2002-06-17

Quantum chemical calculations at the B3P86/6-311G(d,p) level have been performed on potential intermediate molecules in the chemical vapor deposition (CVD) of GaN from the GaCl(3) + NH(3) system. The investigated molecules included the monomer (Cl(x)GaNH(x), x = 1-3) and oligomer species (Cl(2)GaNH(2))(n) with n = 1-3 and (ClGaNH)(n) with n = 1-4 as well as the respective chain dimers and trimers. The calculations revealed the importance of intramolecular Cl...H hydrogen bonding and dipole-dipole interactions in determining the conformational properties of the larger species. Except for the ClGaNH monomer, the Ga[bond]N bonding has a single bond character with a strong ionic contribution. Our thermodynamic study of the composition of the gaseous phase supported the predominance of the Cl(3)GaNH(3) complex under equilibrium conditions. Additionally, the calculated Gibbs free energies of various GaCl(3) + NH(3) reactions imply the favored formation of "saturated" chain and cyclic oligomers below 1000 K.

Platform C Installation

NASA Image and Video Library

2016-10-19

A heavy-lift crane lifts the first half of the C-level work platforms, C south, for NASA’s Space Launch System (SLS) rocket, high up from the transfer aisle floor of the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida. The C platform will be installed on the south side of High Bay 3. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Platform C Installation

NASA Image and Video Library

2016-10-19

A heavy-lift crane lifts the first half of the C-level work platforms, C south, for NASA’s Space Launch System (SLS) rocket, high up from the transfer aisle floor of the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida. The C platform will be moved into High Bay 3 for installation on the south wall. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Expanding the chemical information science gateway.

PubMed

Bajorath, Jürgen

2017-01-01

Broadly defined, chemical information science (CIS) covers chemical structure and data analysis including biological activity data as well as processing, organization, and retrieval of any form of chemical information. The CIS Gateway (CISG) of F1000Research was created to communicate research involving the entire spectrum of chemical information, including chem(o)informatics. CISG provides a forum for high-quality publications and a meaningful alternative to conventional journals. This gateway is supported by leading experts in the field recognizing the need for open science and a flexible publication platform enabling off-the-beaten path contributions. This editorial aims to further rationalize the scope of CISG, position it within its scientific environment, and open it up to a wider audience. Chemical information science is an interdisciplinary field with high potential to interface with experimental work.

Mobility platform coupling device and method for coupling mobility platforms

DOEpatents

Shirey, David L.; Hayward, David R.; Buttz, James H.

2002-01-01

A coupling device for connecting a first mobility platform to a second mobility platform in tandem. An example mobility platform is a robot. The coupling device has a loose link mode for normal steering conditions and a locking position, tight link mode for navigation across difficult terrain and across obstacles, for traversing chasms, and for navigating with a reduced footprint in tight steering conditions.

VirtualToxLab — A platform for estimating the toxic potential of drugs, chemicals and natural products

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

Vedani, Angelo, E-mail: angelo.vedani@unibas.ch; Department of Pharmaceutical Sciences, University of Basel, Klingelbergstrasse 50, 4056 Basel; Dobler, Max

The VirtualToxLab is an in silico technology for estimating the toxic potential (endocrine and metabolic disruption, some aspects of carcinogenicity and cardiotoxicity) of drugs, chemicals and natural products. The technology is based on an automated protocol that simulates and quantifies the binding of small molecules towards a series of proteins, known or suspected to trigger adverse effects. The toxic potential, a non-linear function ranging from 0.0 (none) to 1.0 (extreme), is derived from the individual binding affinities of a compound towards currently 16 target proteins: 10 nuclear receptors (androgen, estrogen α, estrogen β, glucocorticoid, liver X, mineralocorticoid, peroxisome proliferator-activated receptormore » γ, progesterone, thyroid α, and thyroid β), four members of the cytochrome P450 enzyme family (1A2, 2C9, 2D6, and 3A4), a cytosolic transcription factor (aryl hydrocarbon receptor) and a potassium ion channel (hERG). The interface to the technology allows building and uploading molecular structures, viewing and downloading results and, most importantly, rationalizing any prediction at the atomic level by interactively analyzing the binding mode of a compound with its target protein(s) in real-time 3D. The VirtualToxLab has been used to predict the toxic potential for over 2500 compounds: the results are posted on (http://www.virtualtoxlab.org). The free platform — the OpenVirtualToxLab — is accessible (in client–server mode) over the Internet. It is free of charge for universities, governmental agencies, regulatory bodies and non-profit organizations. -- Highlights: ► In silico technology for estimating the toxic potential of drugs and chemicals. ► Simulation of binding towards 16 proteins suspected to trigger adverse effects. ► Mechanistic interpretation and real-time 3D visualization. ► Accessible over the Internet. ► Free of charge for universities, governmental agencies, regulatory bodies and NPOs.« less

Spin-locking versus chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons.

PubMed

Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi

2011-05-01

Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of nonequivalent chemical environments. To compare the characteristics of the CEST and SL approaches in the study of chemical exchange effects, we performed CEST and SL experiments at varied pH and concentrated metabolite phantoms with exchangeable amide, amine, and hydroxyl protons at 9.4 T. Our results show that: (i) on-resonance SL is most sensitive to chemical exchanges in the intermediate-exchange regime and is able to detect hydroxyl and amine protons on a millimolar concentration scale. Off-resonance SL and CEST approaches are sensitive to slow-exchanging protons when an optimal SL or saturation pulse power matches the exchanging rate, respectively. (ii) Offset frequency-dependent SL and CEST spectra are very similar and can be explained well with an SL model recently developed by Trott and Palmer (J Magn Reson 2002;154:157-160). (iii) The exchange rate and population of metabolite protons can be determined from offset-dependent SL or CEST spectra or from on-resonance SL relaxation dispersion measurements. (iv) The asymmetry of the magnetization transfer ratio (MTR(asym)) is highly dependent on the choice of saturation pulse power. In the intermediate-exchange regime, MTR(asym) becomes complicated and should be interpreted with care. Copyright © 2010 Wiley-Liss, Inc.

TriPleX: a versatile dielectric photonic platform

NASA Astrophysics Data System (ADS)

Wörhoff, Kerstin; Heideman, René G.; Leinse, Arne; Hoekman, Marcel

2015-04-01

Photonic applications based on planar waveguide technology impose stringent requirements on properties such as optical propagation losses, light coupling to optical fibers, integration density, as well as on reliability and reproducibility. The latter is correlated to a high level of control of the refractive index and waveguide geometry. In this paper, we review a versatile dielectric waveguide platform, called TriPleX, which is based on alternating silicon nitride and silicon dioxide films. Fabrication with CMOS-compatible equipment based on low-pressure chemical vapor deposition enables the realization of stable material compositions being a prerequisite to the control of waveguide properties and modal shape. The transparency window of both materials allows for the realization of low-loss waveguides over a wide wavelength range (400 nm-2.35 μm). Propagation losses as low as 5×10-4 dB/cm are reported. Three basic geometries (box shell, double stripe, and filled box) can be distinguished. A specific tapering technology is developed for on-chip, low-loss (<0.1 dB) spotsize convertors, allowing for combining efficient fiber to chip coupling with high-contrast waveguides required for increased functional complexity as well as for hybrid integration with other photonic platforms such as InP and SOI. The functionality of the TriPleX platform is captured by verified basic building blocks. The corresponding library and associated design kit is available for multi-project wafer (MPW) runs. Several applications of this platform technology in communications, biomedicine, sensing, as well as a few special fields of photonics are treated in more detail.

Refining of plant oils to chemicals by olefin metathesis.

PubMed

Chikkali, Samir; Mecking, Stefan

2012-06-11

Plant oils are attractive substrates for the chemical industry. Their scope for the production of chemicals can be expanded by sophisticated catalytic conversions. Olefin metathesis is an example, which also illustrates generic issues of "biorefining" to chemicals. Utilization on a large scale requires high catalyst activities, which influences the choice of the metathesis reaction. The mixture of different fatty acids composing a technical-grade plant oil substrate gives rise to a range of products. This decisively determines possible process schemes, and potentially provides novel chemicals and intermediates not employed to date. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Platform C North Installation

NASA Image and Video Library

2016-11-10

A heavy-lift crane lifts the second half of the C-level work platforms, C north, for NASA’s Space Launch System (SLS) rocket, high up from the transfer aisle of the Vehicle Assembly Building (VAB) at NASA's Kennedy Space Center in Florida. The C platform will be moved into High Bay 3 for installation on the north side of High Bay 3. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. In view below Platform C are several of the previously installed platforms. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Joint Chemical Agent Detector (JCAD): the future of chemical agent detection

NASA Astrophysics Data System (ADS)

Laljer, Charles E.; Owen, Jeffery L.

2002-06-01

The Joint Chemical Agent Detector (JCAD) will provide state of the art chemical warfare agent detection capability to ground vehicle operators. Intelligence sources estimate that over twenty counties have active chemical weapons programs. The spread of chemical weapons to third world nations, coupled with the potential for US involvement in these areas in an operational or support capacity, increases the probability that the Joint Services may encounter chemical agents and toxic industrial materials anywhere in the world. Currently, fielded chemical agent detectors are bulky, labor intensive, and subject to false readings. No legacy detector is sensitive enough to provide detection and warning of the low dose hazards associated with miosis contamination. The JCAD will provide a small, lightweight chemical agent detector for vehicle interiors, aircraft, individual personnel, shipboard, and fixed site locations. The system provides a common detection components across multi-service platforms. This common detector system will allow the Joint Services to use the same operational and support concept for more efficient utilization of resources. The JCAD will detect, identify, quantify, and warn of the presence of chemical agents prior to onset of miosis. Upon detection of chemical agents, the detector will provide local and remote audible and visual alarms to the operators. Advance warning will provide the vehicle crew with the time necessary to protect themselves from the lethal effects of chemical agents. The JCAD will also be capable of being upgraded to protect against future chemical agent threats. The JCAD will provide the vehicle operators with the warning necessary to survive and fight in a chemical warfare agent threat environment.

OTEC platform configuration and integration study. Volume I. Systems engineering and integration. Final report

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

None

1978-04-01

The economic success of an Ocean Thermal Energy Conversion (OTEC) system is highly dependent on a platform which provides adequate support for the power system, accommodates reliably the cold water pipe, and is most cost effective. The results of a study conducted for the Department of Energy to assess six generic types of platforms to determine the most satisfactory platform for severl potential sites are presented. The six platform configurations are ship, circular barge, semi-submersible, Tuned Sphere, submersible, and spar. These represent directional and symmetric types of platforms which operate on the surface, at the interface, and submerged. The fivemore » sites for this study were primarily New Orleans, Keahole Point (Hawaii), Brazil, and secondarily Key West and Puerto Rico. Electrical transmission of energy by submarine cable is the planned form of energy transmission for all sites except Brazil, where chemical conversion is to be the method of transmission. This study is devoted to the platform (or ocean systems) of the OTEC plant which is chiefly comprised of the hull and structure, the seawater system, the position control system, and miscellaneous support/assembly systems. The principal elements in the work breakdown structure for the commercial plants are presented. The assessment of the six platform configurations was conducted utilizing a baseline plan (100-MW(e) (Net)) and site (New Orleans) with variations from the baseline to cover the range of interested platforms and sites.« less

Carbohydrate Cluster Microarrays Fabricated on 3-Dimensional Dendrimeric Platforms for Functional Glycomics Exploration

PubMed Central

Zhou, Xichun; Turchi, Craig; Wang, Denong

2009-01-01

We reported here a novel, ready-to-use bioarray platform and methodology for construction of sensitive carbohydrate cluster microarrays. This technology utilizes a 3-dimensional (3-D) poly(amidoamine) starburst dendrimer monolayer assembled on glass surface, which is functionalized with terminal aminooxy and hydrazide groups for site-specific coupling of carbohydrates. A wide range of saccharides, including monosaccharides, oligosaccharides and polysaccharides of diverse structures, are applicable for the 3-D bioarray platform without prior chemical derivatization. The process of carbohydrate coupling is effectively accelerated by microwave radiation energy. The carbohydrate concentration required for microarray fabrication is substantially reduced using this technology. Importantly, this bioarray platform presents sugar chains in defined orientation and cluster configurations. It is, thus, uniquely useful for exploration of the structural and conformational diversities of glyco-epitope and their functional properties. PMID:19791771

Storage stability and improvement of intermediate moisture foods

NASA Technical Reports Server (NTRS)

Labuza, T. P.

1973-01-01

The rates of chemical reactions which deteriorate foods prepared to an intermediate moisture content and water activity (A sub w 0.6 to 0.9) were studied. The phenomenon of sorption hysteresis was used to prepare model systems and foods to similar A sub w's but different moisture levels so that the separate effects of water binding and water content could be elucidated. It was found that water content is the controlling factor for lipid oxidation in model systems comprised of a solid support and an oxidizable liquid. It was proposed that metal chelating agents like EDTA should give good protection to oxidation. EDTA exhibited the highest efficacy, about 10-15 times better than BHA which is a radical scavenger when studied in the model systems.

[Therapy of intermediate uveitis].

PubMed

Doycheva, D; Deuter, C; Zierhut, M

2014-12-01

Intermediate uveitis is a form of intraocular inflammation in which the vitreous body is the major site of inflammation. Intermediate uveitis is primarily treated medicinally and systemic corticosteroids are the mainstay of therapy. When recurrence of uveitis or side effects occur during corticosteroid therapy an immunosuppressive treatment is required. Cyclosporine A is the only immunosuppressive agent that is approved for therapy of uveitis in Germany; however, other immunosuppressive drugs have also been shown to be effective and well-tolerated in patients with intermediate uveitis. In severe therapy-refractory cases when conventional immunosuppressive therapy has failed, biologics can be used. In patients with unilateral uveitis or when the systemic therapy is contraindicated because of side effects, an intravitreal steroid treatment can be carried out. In certain cases a vitrectomy may be used.

Evolution of South Atlantic density and chemical stratification across the last deglaciation

PubMed Central

Skinner, Luke C.; Peck, Victoria L.; Kender, Sev; Elderfield, Henry; Waelbroeck, Claire; Hodell, David A.

2016-01-01

Explanations of the glacial–interglacial variations in atmospheric pCO2 invoke a significant role for the deep ocean in the storage of CO2. Deep-ocean density stratification has been proposed as a mechanism to promote the storage of CO2 in the deep ocean during glacial times. A wealth of proxy data supports the presence of a “chemical divide” between intermediate and deep water in the glacial Atlantic Ocean, which indirectly points to an increase in deep-ocean density stratification. However, direct observational evidence of changes in the primary controls of ocean density stratification, i.e., temperature and salinity, remain scarce. Here, we use Mg/Ca-derived seawater temperature and salinity estimates determined from temperature-corrected δ18O measurements on the benthic foraminifer Uvigerina spp. from deep and intermediate water-depth marine sediment cores to reconstruct the changes in density of sub-Antarctic South Atlantic water masses over the last deglaciation (i.e., 22–2 ka before present). We find that a major breakdown in the physical density stratification significantly lags the breakdown of the deep-intermediate chemical divide, as indicated by the chemical tracers of benthic foraminifer δ13C and foraminifer/coral 14C. Our results indicate that chemical destratification likely resulted in the first rise in atmospheric pCO2, whereas the density destratification of the deep South Atlantic lags the second rise in atmospheric pCO2 during the late deglacial period. Our findings emphasize that the physical and chemical destratification of the ocean are not as tightly coupled as generally assumed. PMID:26729858

Evolution of South Atlantic density and chemical stratification across the last deglaciation.

PubMed

Roberts, Jenny; Gottschalk, Julia; Skinner, Luke C; Peck, Victoria L; Kender, Sev; Elderfield, Henry; Waelbroeck, Claire; Vázquez Riveiros, Natalia; Hodell, David A

2016-01-19

Explanations of the glacial-interglacial variations in atmospheric pCO2 invoke a significant role for the deep ocean in the storage of CO2. Deep-ocean density stratification has been proposed as a mechanism to promote the storage of CO2 in the deep ocean during glacial times. A wealth of proxy data supports the presence of a "chemical divide" between intermediate and deep water in the glacial Atlantic Ocean, which indirectly points to an increase in deep-ocean density stratification. However, direct observational evidence of changes in the primary controls of ocean density stratification, i.e., temperature and salinity, remain scarce. Here, we use Mg/Ca-derived seawater temperature and salinity estimates determined from temperature-corrected δ(18)O measurements on the benthic foraminifer Uvigerina spp. from deep and intermediate water-depth marine sediment cores to reconstruct the changes in density of sub-Antarctic South Atlantic water masses over the last deglaciation (i.e., 22-2 ka before present). We find that a major breakdown in the physical density stratification significantly lags the breakdown of the deep-intermediate chemical divide, as indicated by the chemical tracers of benthic foraminifer δ(13)C and foraminifer/coral (14)C. Our results indicate that chemical destratification likely resulted in the first rise in atmospheric pCO2, whereas the density destratification of the deep South Atlantic lags the second rise in atmospheric pCO2 during the late deglacial period. Our findings emphasize that the physical and chemical destratification of the ocean are not as tightly coupled as generally assumed.

Chemical Frustration in the Protein Folding Landscape: Grand Canonical Ensemble Simulations of Cytochrome c

PubMed Central

Weinkam, Patrick; Romesberg, Floyd E.; Wolynes, Peter G.

2010-01-01

A grand canonical formalism is developed to combine discrete simulations for chemically distinct species in equilibrium. Each simulation is based on a perturbed funneled landscape. The formalism is illustrated using the alkaline-induced transitions of cytochrome c as observed by FTIR spectroscopy and with various other experimental approaches. The grand canonical simulation method accounts for the acid/base chemistry of deprotonation, the inorganic chemistry of heme ligation and misligation, and the minimally frustrated folding energy landscape, thus elucidating the physics of protein folding involved with an acid/base titration of a protein. The formalism combines simulations for each of the relevant chemical species, varying by protonation and ligation states. In contrast to models based on perfectly funneled energy landscapes that contain only contacts found in the native structure, the current study introduces “chemical frustration” from deprotonation and misligation that gives rise to many intermediates at alkaline pH. While the nature of these intermediates cannot be easily inferred from available experimental data, the current study provides specific structural details of these intermediates thus extending our understanding of how cytochrome c changes with increasing pH. The results demonstrate the importance of chemical frustration for understanding biomolecular energy landscapes. PMID:19199810

Expanding the chemical information science gateway

PubMed Central

Bajorath, Jürgen

2017-01-01

Broadly defined, chemical information science (CIS) covers chemical structure and data analysis including biological activity data as well as processing, organization, and retrieval of any form of chemical information. The CIS Gateway (CISG) of F1000Research was created to communicate research involving the entire spectrum of chemical information, including chem(o)informatics. CISG provides a forum for high-quality publications and a meaningful alternative to conventional journals. This gateway is supported by leading experts in the field recognizing the need for open science and a flexible publication platform enabling off-the-beaten path contributions. This editorial aims to further rationalize the scope of CISG, position it within its scientific environment, and open it up to a wider audience. Chemical information science is an interdisciplinary field with high potential to interface with experimental work. PMID:29043072

Eyeglasses based wireless electrolyte and metabolite sensor platform.

PubMed

Sempionatto, Juliane R; Nakagawa, Tatsuo; Pavinatto, Adriana; Mensah, Samantha T; Imani, Somayeh; Mercier, Patrick; Wang, Joseph

2017-05-16

The demand for wearable sensors has grown rapidly in recent years, with increasing attention being given to epidermal chemical sensing. Here, we present the first example of a fully integrated eyeglasses wireless multiplexed chemical sensing platform capable of real-time monitoring of sweat electrolytes and metabolites. The new concept has been realized by integrating an amperometric lactate biosensor and a potentiometric potassium ion-selective electrode into the two nose-bridge pads of the glasses and interfacing them with a wireless electronic backbone placed on the glasses' arms. Simultaneous real-time monitoring of sweat lactate and potassium levels with no apparent cross-talk is demonstrated along with wireless signal transduction. The electrochemical sensors were screen-printed on polyethylene terephthalate (PET) stickers and placed on each side of the glasses' nose pads in order to monitor sweat metabolites and electrolytes. The electronic backbone on the arms of the glasses' frame offers control of the amperometric and potentiometric transducers and enables Bluetooth wireless data transmission to the host device. The new eyeglasses system offers an interchangeable-sensor feature in connection with a variety of different nose-bridge amperometric and potentiometric sensor stickers. For example, the lactate bridge-pad sensor was replaced with a glucose one to offer convenient monitoring of sweat glucose. Such a fully integrated wireless "Lab-on-a-Glass" multiplexed biosensor platform can be readily expanded for the simultaneous monitoring of additional sweat electrolytes and metabolites.

Integrated chemiresistor array for small sensor platforms

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

HUGHES,ROBERT C.; CASALNUOVO,STEPHEN A.; WESSENDORF,KURT O.

2000-04-13

Chemiresistors are fabricated from materials that change their electrical resistance when exposed to certain chemical species. Composites of soluble polymers with metallic particles have shown remarkable sensitivity to many volatile organic chemicals, depending on the ability of the analyte molecules to swell the polymer matrix. These sensors can be made extremely small (< 100 square microns), operate at ambient temperatures, and require almost no power to read-out. However, the chemiresistor itself is only a part of a more complex sensor system that delivers chemical information to a user who can act on the information. The authors present the design, fabricationmore » and performance of a chemiresistor array chip with four different chemiresistor materials, heaters and a temperature sensor. They also show the design and fabrication of an integrated chemiresistor array, where the electronics to read-out the chemiresistors is on the same chip with the electrodes for the chemiresistors. The circuit was designed to perform several functions to make the sensor data more useful. This low-power, integrated chemiresistor array is small enough to be deployed on a Sandia-developed microrobot platform.« less

Calculating Shocks In Flows At Chemical Equilibrium

NASA Technical Reports Server (NTRS)

Eberhardt, Scott; Palmer, Grant

1988-01-01

Boundary conditions prove critical. Conference paper describes algorithm for calculation of shocks in hypersonic flows of gases at chemical equilibrium. Although algorithm represents intermediate stage in development of reliable, accurate computer code for two-dimensional flow, research leading up to it contributes to understanding of what is needed to complete task.

Statistics-based model for prediction of chemical biosynthesis yield from Saccharomyces cerevisiae

PubMed Central

2011-01-01

Background The robustness of Saccharomyces cerevisiae in facilitating industrial-scale production of ethanol extends its utilization as a platform to synthesize other metabolites. Metabolic engineering strategies, typically via pathway overexpression and deletion, continue to play a key role for optimizing the conversion efficiency of substrates into the desired products. However, chemical production titer or yield remains difficult to predict based on reaction stoichiometry and mass balance. We sampled a large space of data of chemical production from S. cerevisiae, and developed a statistics-based model to calculate production yield using input variables that represent the number of enzymatic steps in the key biosynthetic pathway of interest, metabolic modifications, cultivation modes, nutrition and oxygen availability. Results Based on the production data of about 40 chemicals produced from S. cerevisiae, metabolic engineering methods, nutrient supplementation, and fermentation conditions described therein, we generated mathematical models with numerical and categorical variables to predict production yield. Statistically, the models showed that: 1. Chemical production from central metabolic precursors decreased exponentially with increasing number of enzymatic steps for biosynthesis (>30% loss of yield per enzymatic step, P-value = 0); 2. Categorical variables of gene overexpression and knockout improved product yield by 2~4 folds (P-value < 0.1); 3. Addition of notable amount of intermediate precursors or nutrients improved product yield by over five folds (P-value < 0.05); 4. Performing the cultivation in a well-controlled bioreactor enhanced the yield of product by three folds (P-value < 0.05); 5. Contribution of oxygen to product yield was not statistically significant. Yield calculations for various chemicals using the linear model were in fairly good agreement with the experimental values. The model generally underestimated the ethanol production as

Blue M2: an intermediate melanoidin studied via conceptual DFT.

PubMed

Frau, Juan; Glossman-Mitnik, Daniel

2018-05-31

In this computational study, ten density functionals, viz. CAM-B3LYP, LC-ω PBE, M11, M11L, MN12L, MN12SX, N12, N12SX, ω B97X, and ω B97XD, related to the Def2TZVP basis sets, are assessed together with the SMD solvation model for calculation of the molecular properties and structure of blue-M2 intermediate melanoidin pigment. All the chemical reactivity descriptors for the system are calculated via conceptual density functional theory (DFT). The active sites suitable for nucleophilic, electrophilic, and radical attacks are selected by linking them with the Fukui function indices, electrophilic Parr functions, and condensed dual descriptors Δf(r), respectively. The prediction of the maximum absorption wavelength is considerably accurate relative to its experimental value. The study reveals that the MN12SX and N12SX density functionals are the most appropriate density functionals for predicting the chemical reactivity of the molecule under study.

Effect of Intermediate Hosts on Emerging Zoonoses.

PubMed

Cui, Jing-An; Chen, Fangyuan; Fan, Shengjie

2017-08-01

Most emerging zoonotic pathogens originate from animals. They can directly infect humans through natural reservoirs or indirectly through intermediate hosts. As a bridge, an intermediate host plays different roles in the transmission of zoonotic pathogens. In this study, we present three types of pathogen transmission to evaluate the effect of intermediate hosts on emerging zoonotic diseases in human epidemics. These types are identified as follows: TYPE 1, pathogen transmission without an intermediate host for comparison; TYPE 2, pathogen transmission with an intermediate host as an amplifier; and TYPE 3, pathogen transmission with an intermediate host as a vessel for genetic variation. In addition, we established three mathematical models to elucidate the mechanisms underlying zoonotic disease transmission according to these three types. Stability analysis indicated that the existence of intermediate hosts increased the difficulty of controlling zoonotic diseases because of more difficult conditions to satisfy for the disease to die out. The human epidemic would die out under the following conditions: TYPE 1: [Formula: see text] and [Formula: see text]; TYPE 2: [Formula: see text], [Formula: see text], and [Formula: see text]; and TYPE 3: [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] Simulation with similar parameters demonstrated that intermediate hosts could change the peak time and number of infected humans during a human epidemic; intermediate hosts also exerted different effects on controlling the prevalence of a human epidemic with natural reservoirs in different periods, which is important in addressing problems in public health. Monitoring and controlling the number of natural reservoirs and intermediate hosts at the right time would successfully manage and prevent the prevalence of emerging zoonoses in humans.

RMP Guidance for Chemical Distributors - Appendix D: OSHA Guidance on PSM

EPA Pesticide Factsheets

Guidance on the Process Safety Management standard says information (including MSDS) about chemicals, including process intermediates, must enable accurate assessment of fire/explosion characteristics, reactivity hazards, and corrosing/erosion effects.

Intermediate states and structure evolution in the free-falling process of the dislocation in graphene

NASA Astrophysics Data System (ADS)

Wang, Shaofeng; Yao, Yin; Bai, Jianhui; Wang, Rui

2017-04-01

This paper investigated the intermediate states and the structure evolution of the dislocation in graphene when it falls freely from the saddle point of the energy landscape. The O-type dislocation, an unstable equilibrium structure located at the saddle point, is obtained from the lattice theory of the dislocation structure and improved by the ab initio calculation to take the buckling into account. Intermediate states along the kinetics path in the falling process are obtained from the ab initio simulation. Once the dislocation falls from the saddle point to the energy valley, this O-type dislocation transforms into the stable structure that is referred to as the B-type dislocation, and in the meantime, it moves a distance that equals half a Burgers vector. The structure evolution and the energy variation in the free-falling process are revealed explicitly. It is observed that rather than smooth change, a platform manifests itself in the energy curve. The unusual behaviour in the energy curve is mainly originated from symmetry breaking and bond formation in the dislocation core. The results can provide deep insight in the mechanism of the brittle feature of covalent materials.

Platform C North Installation

NASA Image and Video Library

2016-11-10

A heavy-lift crane lowers the second half of the C-level work platforms, C north, for NASA’s Space Launch System (SLS) rocket, into High Bay 3 of the Vehicle Assembly Building (VAB) at NASA's Kennedy Space Center in Florida. The C platform will be installed on the north side of High Bay 3. In view below are several of the previously installed levels of platforms. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Tetra(p-tolyl)borate-functionalized solvent polymeric membrane: a facile and sensitive sensing platform for peroxidase and peroxidase mimetics.

PubMed

Wang, Xuewei; Qin, Wei

2013-07-22

The determination of peroxidase activities is the basis for enzyme-labeled bioaffinity assays, peroxidase-mimicking DNAzymes- and nanoparticles-based assays, and characterization of the catalytic functions of peroxidase mimetics. Here, a facile, sensitive, and cost-effective solvent polymeric membrane-based peroxidase detection platform is described that utilizes reaction intermediates with different pKa values from those of substrates and final products. Several key but long-debated intermediates in the peroxidative oxidation of o-phenylenediamine (o-PD) have been identified and their charge states have been estimated. By using a solvent polymeric membrane functionalized by an appropriate substituted tetraphenylborate as a receptor, those cationic intermediates could be transferred into the membrane from the aqueous phase to induce a large cationic potential response. Thus, the potentiometric indication of the o-PD oxidation catalyzed by peroxidase or its mimetics can be fulfilled. Horseradish peroxidase has been detected with a detection limit at least two orders of magnitude lower than those obtained by spectrophotometric techniques and traditional membrane-based methods. As an example of peroxidase mimetics, G-quadruplex DNAzymes were probed by the intermediate-sensitive membrane and a label-free thrombin detection protocol was developed based on the catalytic activity of the thrombin-binding G-quadruplex aptamer. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production of Putative Diterpene Carboxylic Acid Intermediates of Triptolide in Yeast

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

Forman, Victor; Callari, Roberta; Folly, Christophe

The development of medical applications exploiting the broad bioactivities of the diterpene therapeutic triptolide from Tripterygium wilfordii is limited by low extraction yields from the native plant. Furthermore, the extraordinarily high structural complexity prevents an economically attractive enantioselective total synthesis. An alternative production route of triptolide through engineered Saccharomyces cerevisiae (yeast) could provide a sustainable source of triptolide. A potential intermediate in the unknown biosynthetic route to triptolide is the diterpene dehydroabietic acid. Here, we report a biosynthetic route to dehydroabietic acid by transient expression of enzymes from T. wilfordii and Sitka spruce (Picea sitchensis) in Nicotiana benthamiana. The combinationmore » of diterpene synthases TwTPS9, TwTPS27, and cytochromes P450 PsCYP720B4 yielded dehydroabietic acid and a novel analog, tentatively identified as ‘miltiradienic acid’. This biosynthetic pathway was reassembled in a yeast strain engineered for increased yields of the pathway intermediates, the diterpene olefins miltiradiene and dehydroabietadiene. Introduction in that strain of PsCYP720B4 in combination with two alternative NADPH-dependent cytochrome P450 reductases resulted in scalable in vivo production of dehydroabietic acid and its analog from glucose. Approaching future elucidation of the remaining biosynthetic steps to triptolide, our findings may provide an independent platform for testing of additional recombinant candidate genes, and ultimately pave the way to biotechnological production of the high value diterpenoid therapeutic.« less

Production of Putative Diterpene Carboxylic Acid Intermediates of Triptolide in Yeast

DOE PAGES

Forman, Victor; Callari, Roberta; Folly, Christophe; ...

2017-06-13

The development of medical applications exploiting the broad bioactivities of the diterpene therapeutic triptolide from Tripterygium wilfordii is limited by low extraction yields from the native plant. Furthermore, the extraordinarily high structural complexity prevents an economically attractive enantioselective total synthesis. An alternative production route of triptolide through engineered Saccharomyces cerevisiae (yeast) could provide a sustainable source of triptolide. A potential intermediate in the unknown biosynthetic route to triptolide is the diterpene dehydroabietic acid. Here, we report a biosynthetic route to dehydroabietic acid by transient expression of enzymes from T. wilfordii and Sitka spruce (Picea sitchensis) in Nicotiana benthamiana. The combinationmore » of diterpene synthases TwTPS9, TwTPS27, and cytochromes P450 PsCYP720B4 yielded dehydroabietic acid and a novel analog, tentatively identified as ‘miltiradienic acid’. This biosynthetic pathway was reassembled in a yeast strain engineered for increased yields of the pathway intermediates, the diterpene olefins miltiradiene and dehydroabietadiene. Introduction in that strain of PsCYP720B4 in combination with two alternative NADPH-dependent cytochrome P450 reductases resulted in scalable in vivo production of dehydroabietic acid and its analog from glucose. Approaching future elucidation of the remaining biosynthetic steps to triptolide, our findings may provide an independent platform for testing of additional recombinant candidate genes, and ultimately pave the way to biotechnological production of the high value diterpenoid therapeutic.« less

Chemical Equilibrium and Polynomial Equations: Beware of Roots.

ERIC Educational Resources Information Center

Smith, William R.; Missen, Ronald W.

1989-01-01

Describes two easily applied mathematical theorems, Budan's rule and Rolle's theorem, that in addition to Descartes's rule of signs and intermediate-value theorem, are useful in chemical equilibrium. Provides examples that illustrate the use of all four theorems. Discusses limitations of the polynomial equation representation of chemical…

MELODI: Mining Enriched Literature Objects to Derive Intermediates

PubMed Central

Elsworth, Benjamin; Dawe, Karen; Vincent, Emma E; Langdon, Ryan; Lynch, Brigid M; Martin, Richard M; Relton, Caroline; Higgins, Julian P T; Gaunt, Tom R

2018-01-01

Abstract Background The scientific literature contains a wealth of information from different fields on potential disease mechanisms. However, identifying and prioritizing mechanisms for further analytical evaluation presents enormous challenges in terms of the quantity and diversity of published research. The application of data mining approaches to the literature offers the potential to identify and prioritize mechanisms for more focused and detailed analysis. Methods Here we present MELODI, a literature mining platform that can identify mechanistic pathways between any two biomedical concepts. Results Two case studies demonstrate the potential uses of MELODI and how it can generate hypotheses for further investigation. First, an analysis of ETS-related gene ERG and prostate cancer derives the intermediate transcription factor SP1, recently confirmed to be physically interacting with ERG. Second, examining the relationship between a new potential risk factor for pancreatic cancer identifies possible mechanistic insights which can be studied in vitro. Conclusions We have demonstrated the possible applications of MELODI, including two case studies. MELODI has been implemented as a Python/Django web application, and is freely available to use at [www.melodi.biocompute.org.uk]. PMID:29342271

MELODI: Mining Enriched Literature Objects to Derive Intermediates.

PubMed

Elsworth, Benjamin; Dawe, Karen; Vincent, Emma E; Langdon, Ryan; Lynch, Brigid M; Martin, Richard M; Relton, Caroline; Higgins, Julian P T; Gaunt, Tom R

2018-01-12

The scientific literature contains a wealth of information from different fields on potential disease mechanisms. However, identifying and prioritizing mechanisms for further analytical evaluation presents enormous challenges in terms of the quantity and diversity of published research. The application of data mining approaches to the literature offers the potential to identify and prioritize mechanisms for more focused and detailed analysis. Here we present MELODI, a literature mining platform that can identify mechanistic pathways between any two biomedical concepts. Two case studies demonstrate the potential uses of MELODI and how it can generate hypotheses for further investigation. First, an analysis of ETS-related gene ERG and prostate cancer derives the intermediate transcription factor SP1, recently confirmed to be physically interacting with ERG. Second, examining the relationship between a new potential risk factor for pancreatic cancer identifies possible mechanistic insights which can be studied in vitro. We have demonstrated the possible applications of MELODI, including two case studies. MELODI has been implemented as a Python/Django web application, and is freely available to use at [www.melodi.biocompute.org.uk]. © The Author(s) 2018. Published by Oxford University Press on behalf of the International Epidemiological Association

ADMS Evaluation Platform

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

2018-01-23

Deploying an ADMS or looking to optimize its value? NREL offers a low-cost, low-risk evaluation platform for assessing ADMS performance. The National Renewable Energy Laboratory (NREL) has developed a vendor-neutral advanced distribution management system (ADMS) evaluation platform and is expanding its capabilities. The platform uses actual grid-scale hardware, large-scale distribution system models, and advanced visualization to simulate realworld conditions for the most accurate ADMS evaluation and experimentation.

Masonry. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Thompson, Moses

Several intermediate performance objectives and corresponding criterion measures are listed for each of 13 terminal objectives for an intermediate masonry course. These materials, developed for a two-semester (3 hours daily) course, are designed to provide the student with the skills and knowledge necessary for entry level employment in the field…

Thermotropic Liquid Crystal-Assisted Chemical and Biological Sensors

PubMed Central

Honaker, Lawrence W.; Usol’tseva, Nadezhda; Mann, Elizabeth K.

2017-01-01

In this review article, we analyze recent progress in the application of liquid crystal-assisted advanced functional materials for sensing biological and chemical analytes. Multiple research groups demonstrate substantial interest in liquid crystal (LC) sensing platforms, generating an increasing number of scientific articles. We review trends in implementing LC sensing techniques and identify common problems related to the stability and reliability of the sensing materials as well as to experimental set-ups. Finally, we suggest possible means of bridging scientific findings to viable and attractive LC sensor platforms. PMID:29295530

Real-time label-free quantitative fluorescence microscopy-based detection of ATP using a tunable fluorescent nano-aptasensor platform

NASA Astrophysics Data System (ADS)

Shrivastava, Sajal; Sohn, Il-Yung; Son, Young-Min; Lee, Won-Il; Lee, Nae-Eung

2015-11-01

Although real-time label-free fluorescent aptasensors based on nanomaterials are increasingly recognized as a useful strategy for the detection of target biomolecules with high fidelity, the lack of an imaging-based quantitative measurement platform limits their implementation with biological samples. Here we introduce an ensemble strategy for a real-time label-free fluorescent graphene (Gr) aptasensor platform. This platform employs aptamer length-dependent tunability, thus enabling the reagentless quantitative detection of biomolecules through computational processing coupled with real-time fluorescence imaging data. We demonstrate that this strategy effectively delivers dose-dependent quantitative readouts of adenosine triphosphate (ATP) concentration on chemical vapor deposited (CVD) Gr and reduced graphene oxide (rGO) surfaces, thereby providing cytotoxicity assessment. Compared with conventional fluorescence spectrometry methods, our highly efficient, universally applicable, and rational approach will facilitate broader implementation of imaging-based biosensing platforms for the quantitative evaluation of a range of target molecules.Although real-time label-free fluorescent aptasensors based on nanomaterials are increasingly recognized as a useful strategy for the detection of target biomolecules with high fidelity, the lack of an imaging-based quantitative measurement platform limits their implementation with biological samples. Here we introduce an ensemble strategy for a real-time label-free fluorescent graphene (Gr) aptasensor platform. This platform employs aptamer length-dependent tunability, thus enabling the reagentless quantitative detection of biomolecules through computational processing coupled with real-time fluorescence imaging data. We demonstrate that this strategy effectively delivers dose-dependent quantitative readouts of adenosine triphosphate (ATP) concentration on chemical vapor deposited (CVD) Gr and reduced graphene oxide (r

Protein vivisection reveals elusive intermediates in folding

PubMed Central

Zheng, Zhongzhou; Sosnick, Tobin R.

2010-01-01

Although most folding intermediates escape detection, their characterization is crucial to the elucidation of folding mechanisms. Here we outline a powerful strategy to populate partially unfolded intermediates: A buried aliphatic residue is substituted with a charged residue (e.g., Leu→Glu−) to destabilize and unfold a specific region of the protein. We apply this strategy to Ubiquitin, reversibly trapping a folding intermediate in which the β5 strand is unfolded. The intermediate refolds to a native-like structure upon charge neutralization under mildly acidic conditions. Characterization of the trapped intermediate using NMR and hydrogen exchange methods identifies a second folding intermediate and reveals the order and free energies of the two major folding events on the native side of the rate-limiting step. This general strategy may be combined with other methods and have broad applications in the study of protein folding and other reactions that require trapping of high energy states. PMID:20144618

Automated Platform Management System Scheduling

NASA Technical Reports Server (NTRS)

Hull, Larry G.

1990-01-01

The Platform Management System was established to coordinate the operation of platform systems and instruments. The management functions are split between ground and space components. Since platforms are to be out of contact with the ground more than the manned base, the on-board functions are required to be more autonomous than those of the manned base. Under this concept, automated replanning and rescheduling, including on-board real-time schedule maintenance and schedule repair, are required to effectively and efficiently meet Space Station Freedom mission goals. In a FY88 study, we developed several promising alternatives for automated platform planning and scheduling. We recommended both a specific alternative and a phased approach to automated platform resource scheduling. Our recommended alternative was based upon use of exactly the same scheduling engine in both ground and space components of the platform management system. Our phased approach recommendation was based upon evolutionary development of the platform. In the past year, we developed platform scheduler requirements and implemented a rapid prototype of a baseline platform scheduler. Presently we are rehosting this platform scheduler rapid prototype and integrating the scheduler prototype into two Goddard Space Flight Center testbeds, as the ground scheduler in the Scheduling Concepts, Architectures, and Networks Testbed and as the on-board scheduler in the Platform Management System Testbed. Using these testbeds, we will investigate rescheduling issues, evaluate operational performance and enhance the platform scheduler prototype to demonstrate our evolutionary approach to automated platform scheduling. The work described in this paper was performed prior to Space Station Freedom rephasing, transfer of platform responsibility to Code E, and other recently discussed changes. We neither speculate on these changes nor attempt to predict the impact of the final decisions. As a consequence some of our

Welding. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Vincent, Kenneth

Several intermediate performance objectives and corresponding criterion measures are listed for each of nine terminal objectives for an intermediate welding course. The materials were developed for a 36-week (3 hours daily) course designed to prepare the student for employment in the field of welding. Electric welding and specialized (TIG & MIG)…

Integrated optical sensors for 2D spatial chemical mapping (Conference Presentation)

NASA Astrophysics Data System (ADS)

Flores, Raquel; Janeiro, Ricardo; Viegas, Jaime

2017-02-01

Sensors based on optical waveguides for chemical sensing have attracted increasing interest over the last two decades, fueled by potential applications in commercial lab-on-a-chip devices for medical and food safety industries. Even though the early studies were oriented for single-point detection, progress in device size reduction and device yield afforded by photonics foundries have opened the opportunity for distributed dynamic chemical sensing at the microscale. This will allow researchers to follow the dynamics of chemical species in field of microbiology, and microchemistry, with a complementary method to current technologies based on microfluorescence and hyperspectral imaging. The study of the chemical dynamics at the surface of photoelectrodes in water splitting cells are a good candidate to benefit from such optochemical sensing devices that includes a photonic integrated circuit (PIC) with multiple sensors for real-time detection and spatial mapping of chemical species. In this project, we present experimental results on a prototype integrated optical system for chemical mapping based on the interaction of cascaded resonant optical devices, spatially covered with chemically sensitive polymers and plasmon-enhanced nanostructured metal/metal-oxide claddings offering chemical selectivity in a pixelated surface. In order to achieve a compact footprint, the prototype is based in a silicon photonics platform. A discussion on the relative merits of a photonic platform based on large bandgap metal oxides and nitrides which have higher chemical resistance than silicon is also presented.

Alcoholysis: A Promising Technology for Conversion of Lignocellulose and Platform Chemicals.

PubMed

Zhu, Shanhui; Guo, Jing; Wang, Xun; Wang, Jianguo; Fan, Weibin

2017-06-22

In the catalytic conversion of lignocellulose to valuable products, the first entry point is to break down these biopolymers to sugar units or aromatic monomers, which is conventionally achieved by hydrolysis in water medium. Recent years have seen tremendous progress in the alcoholysis process, which has remarkable advantages, such as the avoidance of treating waste water, suppression of humins or chars, and enhancement of reaction rate and product yield. Advances have been focused on the alcoholysis of cellulose, hemicellulose, and lignin to alkyl glucosides, xylosides, and aromatic monomers, respectively. Alcoholysis of the platform molecule furfuryl alcohol (FAL) to alkyl levulinate (AL) and integrated alcoholysis of cellulose and furfural into AL are also summarized. This Minireview highlights the comparisons between alcoholysis and hydrolysis, the reaction mechanism of alcoholysis, and future challenges for industrial applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Platform C North Installation

NASA Image and Video Library

2016-11-10

A heavy-lift crane lifts the second half of the C-level work platforms, C north, for NASA’s Space Launch System (SLS) rocket, up from the transfer aisle floor of the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida. The C platform will be installed on the north side of High Bay 3. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

BATMAV: a 2-DOF bio-inspired flapping flight platform

NASA Astrophysics Data System (ADS)

Bunget, Gheorghe; Seelecke, Stefan

2010-04-01

Due to the availability of small sensors, Micro-Aerial Vehicles (MAVs) can be used for detection missions of biological, chemical and nuclear agents. Traditionally these devices used fixed or rotary wings, actuated with electric DC motortransmission, a system which brings the disadvantage of a heavier platform. The overall objective of the BATMAV project is to develop a biologically inspired bat-like MAV with flexible and foldable wings for flapping flight. This paper presents a flight platform that features bat-inspired wings which are able to actively fold their elbow joints. A previous analysis of the flight physics for small birds, bats and large insects, revealed that the mammalian flight anatomy represents a suitable flight platform that can be actuated efficiently using Shape Memory Alloy (SMA) artificial-muscles. A previous study of the flight styles in bats based on the data collected by Norberg [1] helped to identify the required joint angles as relevant degrees of freedom for wing actuation. Using the engineering theory of robotic manipulators, engineering kinematic models of wings with 2 and 3-DOFs were designed to mimic the wing trajectories of the natural flier Plecotus auritus. Solid models of the bat-like skeleton were designed based on the linear and angular dimensions resulted from the kinematic models. This structure of the flight platform was fabricated using rapid prototyping technologies and assembled to form a desktop prototype with 2-DOFs wings. Preliminary flapping test showed suitable trajectories for wrist and wingtip that mimic the flapping cycle of the natural flyer.

Immunocontraception: Filamentous Bacteriophage as a Platform for Vaccine Development.

PubMed

Samoylova, Tatiana I; Braden, Timothy D; Spencer, Jennifer A; Bartol, Frank F

2017-11-20

Population control of domestic, wild, invasive, and captive animal species is a global issue of importance to public health, animal welfare and the economy. There is pressing need for effective, safe, and inexpensive contraceptive technologies to address this problem. Contraceptive vaccines, designed to stimulate the immune system in order to block critical reproductive events and suppress fertility, may provide a solution. Filamentous bacteriophages can be used as platforms for development of such vaccines. In this review authors highlight structural and immunogenic properties of filamentous phages, and discuss applications of phage-peptide vaccines for advancement of immunocontraception technology in animals. Phages can be engineered to display fusion (non-phage) peptides as coat proteins. Such modifications can be accomplished via genetic manipulation of phage DNA, or by chemical conjugation of synthetic peptides to phage surface proteins. Phage fusions with antigenic determinants induce humoral as well as cell-mediated immune responses in animals, making them attractive as vaccines. Additional advantages of the phage platform include environmental stability, low cost, and safety for immunized animals and those administering the vaccines. Filamentous phages are viable platforms for vaccine development that can be engineered with molecular and organismal specificity. Phage-based vaccines can be produced in abundance at low cost, are environmentally stable, and are immunogenic when administered via multiple routes. These features are essential for a contraceptive vaccine to be operationally practical in animal applications. Adaptability of the phage platform also makes it attractive for design of human immunocontraceptive agents. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Immunocontraception: Filamentous Bacteriophage as a Platform for Vaccine Development

PubMed Central

Samoylova, Tatiana I.; Braden, Timothy D.; Spencer, Jennifer A.; Bartol, Frank F.

2017-01-01

Background: Population control of domestic, wild, invasive, and captive animal species is a global issue of importance to public health, animal welfare and the economy. There is pressing need for effective, safe, and inexpensive contraceptive technologies to ad-dress this problem. Contraceptive vaccines, designed to stimulate the immune system in order to block critical reproductive events and suppress fertility, may provide a solution. Fil-amentous bacteriophages can be used as platforms for development of such vaccines. Objective: In this review authors highlight structural and immunogenic properties of fila-mentous phages, and discuss applications of phage-peptide vaccines for advancement of immunocontraception technology in animals. Results: Phages can be engineered to display fusion (non-phage) peptides as coat proteins. Such modifications can be accomplished via genetic manipulation of phage DNA, or by chemical conjugation of synthetic peptides to phage surface proteins. Phage fusions with antigenic determinants induce humoral as well as cell-mediated immune responses in ani-mals, making them attractive as vaccines. Additional advantages of the phage platform include environmental stability, low cost, and safety for immunized animals and those ad-ministering the vaccines. Conclusion: Filamentous phages are viable platforms for vaccine development that can be engineered with molecular and organismal specificity. Phage-based vaccines can be pro-duced in abundance at low cost, are environmentally stable, and are immunogenic when administered via multiple routes. These features are essential for a contraceptive vaccine to be operationally practical in animal applications. Adaptability of the phage platform also makes it attractive for design of human immunocontraceptive agents. PMID:28901276

An engineered microbial platform for direct biofuel production from brown macroalgae.

PubMed

Wargacki, Adam J; Leonard, Effendi; Win, Maung Nyan; Regitsky, Drew D; Santos, Christine Nicole S; Kim, Peter B; Cooper, Susan R; Raisner, Ryan M; Herman, Asael; Sivitz, Alicia B; Lakshmanaswamy, Arun; Kashiyama, Yuki; Baker, David; Yoshikuni, Yasuo

2012-01-20

Prospecting macroalgae (seaweeds) as feedstocks for bioconversion into biofuels and commodity chemical compounds is limited primarily by the availability of tractable microorganisms that can metabolize alginate polysaccharides. Here, we present the discovery of a 36-kilo-base pair DNA fragment from Vibrio splendidus encoding enzymes for alginate transport and metabolism. The genomic integration of this ensemble, together with an engineered system for extracellular alginate depolymerization, generated a microbial platform that can simultaneously degrade, uptake, and metabolize alginate. When further engineered for ethanol synthesis, this platform enables bioethanol production directly from macroalgae via a consolidated process, achieving a titer of 4.7% volume/volume and a yield of 0.281 weight ethanol/weight dry macroalgae (equivalent to ~80% of the maximum theoretical yield from the sugar composition in macroalgae).

Integrated nanopore sensing platform with sub-microsecond temporal resolution

PubMed Central

Rosenstein, Jacob K; Wanunu, Meni; Merchant, Christopher A; Drndic, Marija; Shepard, Kenneth L

2012-01-01

Nanopore sensors have attracted considerable interest for high-throughput sensing of individual nucleic acids and proteins without the need for chemical labels or complex optics. A prevailing problem in nanopore applications is that the transport kinetics of single biomolecules are often faster than the measurement time resolution. Methods to slow down biomolecular transport can be troublesome and are at odds with the natural goal of high-throughput sensing. Here we introduce a low-noise measurement platform that integrates a complementary metal-oxide semiconductor (CMOS) preamplifier with solid-state nanopores in thin silicon nitride membranes. With this platform we achieved a signal-to-noise ratio exceeding five at a bandwidth of 1 MHz, which to our knowledge is the highest bandwidth nanopore recording to date. We demonstrate transient signals as brief as 1 μs from short DNA molecules as well as current signatures during molecular passage events that shed light on submolecular DNA configurations in small nanopores. PMID:22426489

Retention in porous layer pillar array planar separation platforms

DOE PAGES

Lincoln, Danielle R.; Lavrik, Nickolay V.; Kravchenko, Ivan I.; ...

2016-08-11

Here, this work presents the retention capabilities and surface area enhancement of highly ordered, high-aspect-ratio, open-platform, two-dimensional (2D) pillar arrays when coated with a thin layer of porous silicon oxide (PSO). Photolithographically prepared pillar arrays were coated with 50–250 nm of PSO via plasma-enhanced chemical vapor deposition and then functionalized with either octadecyltrichlorosilane or n-butyldimethylchlorosilane. Theoretical calculations indicate that a 50 nm layer of PSO increases the surface area of a pillar nearly 120-fold. Retention capabilities were tested by observing capillary-action-driven development under various conditions, as well as by running one-dimensional separations on varying thicknesses of PSO. Increasing the thicknessmore » of PSO on an array clearly resulted in greater retention of the analyte(s) in question in both experiments. In culmination, a two-dimensional separation of fluorescently derivatized amines was performed to further demonstrate the capabilities of these fabricated platforms.« less

Retention in porous layer pillar array planar separation platforms

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

Lincoln, Danielle R.; Lavrik, Nickolay V.; Kravchenko, Ivan I.

Here, this work presents the retention capabilities and surface area enhancement of highly ordered, high-aspect-ratio, open-platform, two-dimensional (2D) pillar arrays when coated with a thin layer of porous silicon oxide (PSO). Photolithographically prepared pillar arrays were coated with 50–250 nm of PSO via plasma-enhanced chemical vapor deposition and then functionalized with either octadecyltrichlorosilane or n-butyldimethylchlorosilane. Theoretical calculations indicate that a 50 nm layer of PSO increases the surface area of a pillar nearly 120-fold. Retention capabilities were tested by observing capillary-action-driven development under various conditions, as well as by running one-dimensional separations on varying thicknesses of PSO. Increasing the thicknessmore » of PSO on an array clearly resulted in greater retention of the analyte(s) in question in both experiments. In culmination, a two-dimensional separation of fluorescently derivatized amines was performed to further demonstrate the capabilities of these fabricated platforms.« less

Hazardous Waste Cleanup: Rutherford Chemicals, LLC in Harriman, New York

EPA Pesticide Factsheets

This facility, located in Harriman, New York, on Route 17 at Arden House Road, manufactures organic and pharmaceutical intermediate chemicals, and has been in operation since the early 1950s. The principle products are pyridine, picolines and cyanopyridine

29 CFR 452.123 - Elections of intermediate body officers.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 29 Labor 2 2011-07-01 2011-07-01 false Elections of intermediate body officers. 452.123 Section... intermediate body officers. Section 401(d) states that officers of intermediate bodies shall be elected either... intermediate bodies. Such delegates may therefore participate in the election of officers of intermediate...

29 CFR 452.123 - Elections of intermediate body officers.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 29 Labor 2 2010-07-01 2010-07-01 false Elections of intermediate body officers. 452.123 Section... intermediate body officers. Section 401(d) states that officers of intermediate bodies shall be elected either... intermediate bodies. Such delegates may therefore participate in the election of officers of intermediate...

Validation of intermediate end points in cancer research.

PubMed

Schatzkin, A; Freedman, L S; Schiffman, M H; Dawsey, S M

1990-11-21

Investigations using intermediate end points as cancer surrogates are quicker, smaller, and less expensive than studies that use malignancy as the end point. We present a strategy for determining whether a given biomarker is a valid intermediate end point between an exposure and incidence of cancer. Candidate intermediate end points may be selected from case series, ecologic studies, and animal experiments. Prospective cohort and sometimes case-control studies may be used to quantify the intermediate end point-cancer association. The most appropriate measure of this association is the attributable proportion. The intermediate end point is a valid cancer surrogate if the attributable proportion is close to 1.0, but not if it is close to 0. Usually, the attributable proportion is close to neither 1.0 nor 0; in this case, valid surrogacy requires that the intermediate end point mediate an established exposure-cancer relation. This would in turn imply that the exposure effect would vanish if adjusted for the intermediate end point. We discuss the relative advantages of intervention and observational studies for the validation of intermediate end points. This validation strategy also may be applied to intermediate end points for adverse reproductive outcomes and chronic diseases other than cancer.

METABOLISM AND METABOLIC ACTIVATION OF CHEMICALS: IN-SILICO SIMULATION

EPA Science Inventory

The role of metabolism in prioritizing chemicals according to their potential adverse health effects is extremely important because innocuous parents can be transformed into toxic metabolites. This work presents the TIssue MEtabolism Simulator (TIMES) platform for simulating met...

Properties of Intermediates in the Catalytic Cycle of Oxalate Oxidoreductase and Its Suicide Inactivation by Pyruvate

PubMed Central

2017-01-01

Oxalate:ferredoxin oxidoreductase (OOR) is an unusual member of the thiamine pyrophosphate (TPP)-dependent 2-oxoacid:ferredoxin oxidoreductase (OFOR) family in that it catalyzes the coenzyme A (CoA)-independent conversion of oxalate into 2 equivalents of carbon dioxide. This reaction is surprising because binding of CoA to the acyl-TPP intermediate of other OFORs results in formation of a CoA ester, and in the case of pyruvate:ferredoxin oxidoreductase (PFOR), CoA binding generates the central metabolic intermediate acetyl-CoA and promotes a 105-fold acceleration of the rate of electron transfer. Here we describe kinetic, spectroscopic, and computational results to show that CoA has no effect on catalysis by OOR and describe the chemical rationale for why this cofactor is unnecessary in this enzymatic transformation. Our results demonstrate that, like PFOR, OOR binds pyruvate and catalyzes decarboxylation to form the same hydroxyethylidine–TPP (HE–TPP) intermediate and one-electron transfer to generate the HE–TPP radical. However, in OOR, this intermediate remains stranded at the active site as a covalent inhibitor. These and other results indicate that, like other OFOR family members, OOR generates an oxalate-derived adduct with TPP (oxalyl-TPP) that undergoes decarboxylation and one-electron transfer to form a radical intermediate remaining bound to TPP (dihydroxymethylidene–TPP). However, unlike in PFOR, where CoA binding drives formation of the product, in OOR, proton transfer and a conformational change in the “switch loop” alter the redox potential of the radical intermediate sufficiently to promote the transfer of an electron into the iron–sulfur cluster network, leading directly to a second decarboxylation and completing the catalytic cycle. PMID:28514140

Caspase-8 Binding to Cardiolipin in Giant Unilamellar Vesicles Provides a Functional Docking Platform for Bid

PubMed Central

Perry, Mark; Granjon, Thierry; Gonzalvez, François; Gottlieb, Eyal; Ayala-Sanmartin, Jesus; Klösgen, Beate; Schwille, Petra; Petit, Patrice X.

2013-01-01

Caspase-8 is involved in death receptor-mediated apoptosis in type II cells, the proapoptotic programme of which is triggered by truncated Bid. Indeed, caspase-8 and Bid are the known intermediates of this signalling pathway. Cardiolipin has been shown to provide an anchor and an essential activating platform for caspase-8 at the mitochondrial membrane surface. Destabilisation of this platform alters receptor-mediated apoptosis in diseases such as Barth Syndrome, which is characterised by the presence of immature cardiolipin which does not allow caspase-8 binding. We used a simplified in vitro system that mimics contact sites and/or cardiolipin-enriched microdomains at the outer mitochondrial surface in which the platform consisting of caspase-8, Bid and cardiolipin was reconstituted in giant unilamellar vesicles. We analysed these vesicles by flow cytometry and confirm previous results that demonstrate the requirement for intact mature cardiolipin for caspase-8 activation and Bid binding and cleavage. We also used confocal microscopy to visualise the rupture of the vesicles and their revesiculation at smaller sizes due to alteration of the curvature following caspase-8 and Bid binding. Biophysical approaches, including Laurdan fluorescence and rupture/tension measurements, were used to determine the ability of these three components (cardiolipin, caspase-8 and Bid) to fulfil the minimal requirements for the formation and function of the platform at the mitochondrial membrane. Our results shed light on the active functional role of cardiolipin, bridging the gap between death receptors and mitochondria. PMID:23418437

Platform C North Installation

NASA Image and Video Library

2016-11-10

A heavy-lift crane lifts the second half of the C-level work platforms, C north, for NASA’s Space Launch System (SLS) rocket, high up from the transfer aisle floor of the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida. The C platform will be installed on the north side of High Bay 3. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Platform C North Installation

NASA Image and Video Library

2016-11-10

A heavy-lift crane lifts the second half of the C-level work platforms, C north, for NASA’s Space Launch System (SLS) rocket, high up from the transfer aisle of the Vehicle Assembly Building (VAB) at NASA's Kennedy Space Center in Florida. The C platform will be moved into High Bay 3 for installation on the north side of High Bay 3. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Platform C North Installation

NASA Image and Video Library

2016-11-10

A heavy-lift crane lifts the second half of the C-level work platforms, C north, for NASA’s Space Launch System (SLS) rocket, high up from the transfer aisle floor of the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida. The C platform will be moved into High Bay 3 for installation on the north wall. The C platforms are the eighth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

Platform B North Installation

NASA Image and Video Library

2016-12-16

A construction worker solders a section of steel during the installation of the second half of the B-level work platforms, B north, for NASA's Space Launch System (SLS) rocket, in High Bay 3 in the Vehicle Assembly Building (VAB) at NASA's Kennedy Space Center in Florida. Construction workers will secure the large bolts that hold the platform in place on the north wall. The B platforms are the ninth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

The "Vsoil Platform" : a tool to integrate the various physical, chemical and biological processes contributing to the soil functioning at the local scale.

NASA Astrophysics Data System (ADS)

Lafolie, François; Cousin, Isabelle; Mollier, Alain; Pot, Valérie; Moitrier, Nicolas; Balesdent, Jérome; bruckler, Laurent; Moitrier, Nathalie; Nouguier, Cédric; Richard, Guy

2014-05-01

Models describing the soil functioning are valuable tools for addressing challenging issues related to agricultural production, soil protection or biogeochemical cycles. Coupling models that address different scientific fields is actually required in order to develop numerical tools able to simulate the complex interactions and feed-backs occurring within a soil profile in interaction with climate and human activities. We present here a component-based modelling platform named "VSoil", that aims at designing, developing, implementing and coupling numerical representation of biogeochemical and physical processes in soil, from the aggregate to the profile scales. The platform consists of four softwares, i) Vsoil_Processes dedicated to the conceptual description of processes and of their inputs and outputs, ii) Vsoil_Modules devoted to the development of numerical representation of elementary processes as modules, iii) Vsoil_Models which permits the coupling of modules to create models, iv) Vsoil_Player for the run of the model and the primary analysis of results. The platform is designed to be a collaborative tool, helping scientists to share not only their models, but also the scientific knowledge on which the models are built. The platform is based on the idea that processes of any kind can be described and characterized by their inputs (state variables required) and their outputs. The links between the processes are automatically detected by the platform softwares. For any process, several numerical representations (modules) can be developed and made available to platform users. When developing modules, the platform takes care of many aspects of the development task so that the user can focus on numerical calculations. Fortran2008 and C++ are the supported languages and existing codes can be easily incorporated into platform modules. Building a model from available modules simply requires selecting the processes being accounted for and for each process a module

Design of a New Ultracompact Resonant Plasmonic Multi-Analyte Label-Free Biosensing Platform

PubMed Central

De Palo, Maripina; Ciminelli, Caterina

2017-01-01

In this paper, we report on the design of a bio-multisensing platform for the selective label-free detection of protein biomarkers, carried out through a 3D numerical algorithm. The platform includes a number of biosensors, each of them is based on a plasmonic nanocavity, consisting of a periodic metal structure to be deposited on a silicon oxide substrate. Light is strongly confined in a region with extremely small size (=1.57 μm2), to enhance the light-matter interaction. A surface sensitivity Ss = 1.8 nm/nm has been calculated together with a detection limit of 128 pg/mm2. Such performance, together with the extremely small footprint, allow the integration of several devices on a single chip to realize extremely compact lab-on-chip microsystems. In addition, each sensing element of the platform has a good chemical stability that is guaranteed by the selection of gold for its fabrication. PMID:28783075

The intermediate endpoint effect in logistic and probit regression

PubMed Central

MacKinnon, DP; Lockwood, CM; Brown, CH; Wang, W; Hoffman, JM

2010-01-01

Background An intermediate endpoint is hypothesized to be in the middle of the causal sequence relating an independent variable to a dependent variable. The intermediate variable is also called a surrogate or mediating variable and the corresponding effect is called the mediated, surrogate endpoint, or intermediate endpoint effect. Clinical studies are often designed to change an intermediate or surrogate endpoint and through this intermediate change influence the ultimate endpoint. In many intermediate endpoint clinical studies the dependent variable is binary, and logistic or probit regression is used. Purpose The purpose of this study is to describe a limitation of a widely used approach to assessing intermediate endpoint effects and to propose an alternative method, based on products of coefficients, that yields more accurate results. Methods The intermediate endpoint model for a binary outcome is described for a true binary outcome and for a dichotomization of a latent continuous outcome. Plots of true values and a simulation study are used to evaluate the different methods. Results Distorted estimates of the intermediate endpoint effect and incorrect conclusions can result from the application of widely used methods to assess the intermediate endpoint effect. The same problem occurs for the proportion of an effect explained by an intermediate endpoint, which has been suggested as a useful measure for identifying intermediate endpoints. A solution to this problem is given based on the relationship between latent variable modeling and logistic or probit regression. Limitations More complicated intermediate variable models are not addressed in the study, although the methods described in the article can be extended to these more complicated models. Conclusions Researchers are encouraged to use an intermediate endpoint method based on the product of regression coefficients. A common method based on difference in coefficient methods can lead to distorted

Intra-Platform Repeatability and Inter-Platform Comparability of MicroRNA Microarray Technology

PubMed Central

Sato, Fumiaki; Tsuchiya, Soken; Terasawa, Kazuya; Tsujimoto, Gozoh

2009-01-01

Over the last decade, DNA microarray technology has provided a great contribution to the life sciences. The MicroArray Quality Control (MAQC) project demonstrated the way to analyze the expression microarray. Recently, microarray technology has been utilized to analyze a comprehensive microRNA expression profiling. Currently, several platforms of microRNA microarray chips are commercially available. Thus, we compared repeatability and comparability of five different microRNA microarray platforms (Agilent, Ambion, Exiqon, Invitrogen and Toray) using 309 microRNAs probes, and the Taqman microRNA system using 142 microRNA probes. This study demonstrated that microRNA microarray has high intra-platform repeatability and comparability to quantitative RT-PCR of microRNA. Among the five platforms, Agilent and Toray array showed relatively better performances than the others. However, the current lineup of commercially available microRNA microarray systems fails to show good inter-platform concordance, probably because of lack of an adequate normalization method and severe divergence in stringency of detection call criteria between different platforms. This study provided the basic information about the performance and the problems specific to the current microRNA microarray systems. PMID:19436744

Thermo-Physical Properties of Intermediate Temperature Heat Pipe Fluids

NASA Technical Reports Server (NTRS)

Beach, Duane E. (Technical Monitor); Devarakonda, Angirasa; Anderson, William G.

2005-01-01

Heat pipes are among the most promising technologies for space radiator systems. The paper reports further evaluation of potential heat pipe fluids in the intermediate temperature range of 400 to 700 K in continuation of two recent reports. More thermo-physical property data are examined. Organic, inorganic, and elemental substances are considered. The evaluation of surface tension and other fluid properties are examined. Halides are evaluated as potential heat pipe fluids. Reliable data are not available for all fluids and further database development is necessary. Many of the fluids considered are promising candidates as heat pipe fluids. Water is promising as a heat pipe fluid up to 500 to 550 K. Life test data for thermo-chemical compatibility are almost non-existent.

Thermo-Physical Properties of Intermediate Temperature Heat Pipe Fluids

NASA Technical Reports Server (NTRS)

Devarakonda, Angirasa; Anderson, William G.

2004-01-01

Heat pipes are among the most promising technologies for space radiator systems. The paper reports further evaluation of potential heat pipe fluids in the intermediate temperature range of 400 to 700 K in continuation of two recent reports. More thermo-physical property data are examined. Organic, inorganic and elemental substances are considered. The evaluation of surface tension and other fluid properties are examined. Halides are evaluated as potential heat pipe fluids. Reliable data are not available for all fluids and further database development in necessary. Many of the fluids considered are promising candidates as heat pipe fluids. Water is promising as a heat pipe fluid up to 500-550 K. Life test data for thermo-chemical compatibility are almost non-existent.

Nitrenes, carbenes, diradicals, and ylides. Interconversions of reactive intermediates.

PubMed

Wentrup, Curt

2011-06-21

. It has been possible in some cases to observe them all and determine their interrelationships by means of a combination of matrix-isolation spectroscopy, photochemistry, flash vacuum thermolysis, and computational chemistry. These studies have led to a deeper understanding of the nature of reactive intermediates and chemical reactivity. Moreover, the results indicate new directions for further exploration: ring-opening reactions of carbenes, nitrenes, and cyclic cumulenes can be expected in many other systems.

Solar-to-chemical and solar-to-fuel production from CO2 by metabolically engineered microorganisms.

PubMed

Woo, Han Min

2017-06-01

Recent development of carbon capture utilization (CCU) for reduction of greenhouse gas emission are reviewed. In the case of CO 2 utilization, I describe development of solar-to-chemical and solar-to-fuel technology that refers to the use of solar energy to convert CO 2 to desired chemicals and fuels. Photoautotrophic cyanobacterial platforms have been extensively developed on this principle, producing a diverse range of alcohols, organic acids, and isoprenoids directly from CO 2 . Recent breakthroughs in the metabolic engineering of cyanobacteria were reviewed. In addition, adoption of the light harvesting mechanisms from nature, photovoltaics-derived water splitting technologies have recently been integrated with microbial biotechnology to produce desired chemicals. Studies on the integration of electrode material with next-generation microbes are showcased for alternative solar-to-chemical and solar-to-fuel platforms. Copyright © 2016 Elsevier Ltd. All rights reserved.

Nanogold as NEMS platform: past, present, and future

NASA Astrophysics Data System (ADS)

Cornejo-Monroy, Delfino; Acosta-Torres, Laura S.; Castaño, Victor M.

2012-06-01

Gold has been a biomedical material since ancient times. We shall review the historical uses of gold, in different forms as well as the properties of this metal, which make it very attractive for MEMS and NEMS applications. In particular, we will discuss the synthesis and physic-chemical characteristics of nano particles of gold, emphasizing the role of surface modification, which enables the nano gold to act as a true nano reactor or a nano platform to develop various functions at the nanoscale. Finally, we will describe the use of nano gold for drug targeting and disease detection.

Nitrogen-containing polymers as a platform for CO2 electroreduction.

PubMed

Ponnurangam, Sathish; Chernyshova, Irina V; Somasundaran, Ponisseril

2017-06-01

Heterogeneous electroreduction of CO 2 has received considerable attention in the past decade. However, none of the earlier reviews has been dedicated to nitrogen-containing polymers (N-polymers) as an emerging platform for conversion of CO 2 to industrially useful chemicals. The term 'platform' is used here to underscore that the role of N-polymers is not only to serve as direct catalysts (through loaded metals) but also as co-catalysts/promoters and stabilizing agents. This review covers the current state, advantages, challenges, and prospects of the application of N-polymer-metal composites, also referred as polymer functionalized, coated, or modified electrodes, as well as functional hybrid materials, for the electrocatalytic conversion of CO 2 . It briefly surveys the efficiencies of the N-polymer-metal electrodes already used for this application, methods of their fabrication, and proposed mechanisms of their catalytic activities. Copyright © 2016 Elsevier B.V. All rights reserved.

Impact of Genomics Platform and Statistical Filtering on Transcriptional Benchmark Doses (BMD) and Multiple Approaches for Selection of Chemical Point of Departure (PoD)

PubMed Central

Webster, A. Francina; Chepelev, Nikolai; Gagné, Rémi; Kuo, Byron; Recio, Leslie; Williams, Andrew; Yauk, Carole L.

2015-01-01

Many regulatory agencies are exploring ways to integrate toxicogenomic data into their chemical risk assessments. The major challenge lies in determining how to distill the complex data produced by high-content, multi-dose gene expression studies into quantitative information. It has been proposed that benchmark dose (BMD) values derived from toxicogenomics data be used as point of departure (PoD) values in chemical risk assessments. However, there is limited information regarding which genomics platforms are most suitable and how to select appropriate PoD values. In this study, we compared BMD values modeled from RNA sequencing-, microarray-, and qPCR-derived gene expression data from a single study, and explored multiple approaches for selecting a single PoD from these data. The strategies evaluated include several that do not require prior mechanistic knowledge of the compound for selection of the PoD, thus providing approaches for assessing data-poor chemicals. We used RNA extracted from the livers of female mice exposed to non-carcinogenic (0, 2 mg/kg/day, mkd) and carcinogenic (4, 8 mkd) doses of furan for 21 days. We show that transcriptional BMD values were consistent across technologies and highly predictive of the two-year cancer bioassay-based PoD. We also demonstrate that filtering data based on statistically significant changes in gene expression prior to BMD modeling creates more conservative BMD values. Taken together, this case study on mice exposed to furan demonstrates that high-content toxicogenomics studies produce robust data for BMD modelling that are minimally affected by inter-technology variability and highly predictive of cancer-based PoD doses. PMID:26313361

Platform B North Installation

NASA Image and Video Library

2016-12-16

Construction workers wearing safety harnesses and tethered lines assist with the installation of the second half of the B-level work platforms, B north, for NASA’s Space Launch System (SLS) rocket, high up in the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida. They are securing the large bolts that hold the platform securely in place on the north side of High Bay 3. The B platforms are the ninth of 10 levels of work platforms that will surround and provide access to the SLS rocket and Orion spacecraft for Exploration Mission 1. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3, including installation of the new work platforms, to prepare for NASA’s Journey to Mars.

One-Pot Conversion of Carbohydrates into Pyrrole-2-carbaldehydes as Sustainable Platform Chemicals.

PubMed

Adhikary, Nirmal Das; Kwon, Sunjeong; Chung, Wook-Jin; Koo, Sangho

2015-08-07

A practical conversion method of carbohydrates into N-substituted 5-(hydroxymethyl)pyrrole-2-carbaldehydes (pyrralines) was developed by the reaction with primary amines and oxalic acid in DMSO at 90 °C. Further cyclization of the highly functionalized pyrralines afforded the pyrrole-fused poly-heterocyclic compounds as potential intermediates for drugs, food flavors, and functional materials. The mild Maillard variant of carbohydrates and amino esters in heated DMSO with oxalic acid expeditiously produced the pyrrole-2-carbaldehyde skeleton, which can be concisely transformed into the pyrrole alkaloid natural products, 2-benzyl- and 2-methylpyrrolo[1,4]oxazin-3-ones 8 and 9, lobechine 10, and (-)-hanishin 11 in 23-32% overall yields from each carbohydrate.

Consequence and Resilience Modeling for Chemical Supply Chains

NASA Technical Reports Server (NTRS)

Stamber, Kevin L.; Vugrin, Eric D.; Ehlen, Mark A.; Sun, Amy C.; Warren, Drake E.; Welk, Margaret E.

2011-01-01

The U.S. chemical sector produces more than 70,000 chemicals that are essential material inputs to critical infrastructure systems, such as the energy, public health, and food and agriculture sectors. Disruptions to the chemical sector can potentially cascade to other dependent sectors, resulting in serious national consequences. To address this concern, the U.S. Department of Homeland Security (DHS) tasked Sandia National Laboratories to develop a predictive consequence modeling and simulation capability for global chemical supply chains. This paper describes that capability , which includes a dynamic supply chain simulation platform called N_ABLE(tm). The paper also presents results from a case study that simulates the consequences of a Gulf Coast hurricane on selected segments of the U.S. chemical sector. The case study identified consequences that include impacted chemical facilities, cascading impacts to other parts of the chemical sector. and estimates of the lengths of chemical shortages and recovery . Overall. these simulation results can DHS prepare for and respond to actual disruptions.

Stability and anti-glycation properties of intermediate moisture apple products fortified with green tea.

PubMed

Lavelli, Vera; Corey, Mark; Kerr, William; Vantaggi, Claudia

2011-07-15

Intermediate moisture products made from blanched apple flesh and green tea extract (about 6mg of monomeric flavan 3-ols added per g of dry apple) or blanched apple flesh (control) were produced, and their quality attributes were investigated over storage for two months at water activity (a(w)) levels of 0.55 and 0.75, at 30°C. Products were evaluated for colour (L(∗), a(∗), and b(∗) Hunter's parameters), phytochemical contents (flavan 3-ols, chlorogenic acid, dihydrochalcones, ascorbic acid and total polyphenols), ferric reducing antioxidant potential, 2,2-diphenyl-1-(2,4,6-trinitrophenyl)hydrazyl radical-scavenging activity and ability to inhibit formation of fructose-induced advanced glycation end-products. During storage of the fortified and unfortified intermediate moisture apples, water availability was sufficient to support various chemical reactions involving phytochemicals, which degraded at different rates: ascorbic acid>flavan 3-ols>dihydrochalcones and chlorogenic acid. Colour variations occurred at slightly slower rates after green tea addition. In the intermediate moisture apple, antioxidant and anti-glycoxidative properties decreased at similar rates (half-life was about 80d at a(w) of 0.75, 30°C). In the green tea-fortified intermediate moisture apple, the antioxidant activity decreased at a slow rate (half-life was 165d at a(w) of 0.75, 30°C) and the anti-glycoxidative properties did not change, indicating that flavan 3-ol degradation involved the formation of derivatives that retained the properties of their parent compounds. Since these properties are linked to oxidative- and advanced glycation end-product-related diseases, these results suggest that green tea fortification of intermediate moisture apple products could be a valuable means of product innovation, to address consumers' nutritional needs. Copyright © 2011 Elsevier Ltd. All rights reserved.

An Aurivillius Oxide Based Cathode with Excellent CO2 Tolerance for Intermediate-Temperature Solid Oxide Fuel Cells.

PubMed

Zhu, Yinlong; Zhou, Wei; Chen, Yubo; Shao, Zongping

2016-07-25

The Aurivillius oxide Bi2 Sr2 Nb2 MnO12-δ (BSNM) was used as a cobalt-free cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). To the best of our knowledge, the BSNM oxide is the only alkaline-earth-containing cathode material with complete CO2 tolerance that has been reported thus far. BSNM not only shows favorable activity in the oxygen reduction reaction (ORR) at intermediate temperatures but also exhibits a low thermal expansion coefficient, excellent structural stability, and good chemical compatibility with the electrolyte. These features highlight the potential of the new BSNM material as a highly promising cathode material for IT-SOFCs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Integrated Platform for Expedited Synthesis–Purification–Testing of Small Molecule Libraries

PubMed Central

2017-01-01

The productivity of medicinal chemistry programs can be significantly increased through the introduction of automation, leading to shortened discovery cycle times. Herein, we describe a platform that consolidates synthesis, purification, quantitation, dissolution, and testing of small molecule libraries. The system was validated through the synthesis and testing of two libraries of binders of polycomb protein EED, and excellent correlation of obtained data with results generated through conventional approaches was observed. The fully automated and integrated platform enables batch-supported compound synthesis based on a broad array of chemical transformations with testing in a variety of biochemical assay formats. A library turnaround time of between 24 and 36 h was achieved, and notably, each library synthesis produces sufficient amounts of compounds for further evaluation in secondary assays thereby contributing significantly to the shortening of medicinal chemistry discovery cycles. PMID:28435537

SAW Sensors for Chemical Vapors and Gases

PubMed Central

Devkota, Jagannath; Ohodnicki, Paul R.; Greve, David W.

2017-01-01

Surface acoustic wave (SAW) technology provides a sensitive platform for sensing chemicals in gaseous and fluidic states with the inherent advantages of passive and wireless operation. In this review, we provide a general overview on the fundamental aspects and some major advances of Rayleigh wave-based SAW sensors in sensing chemicals in a gaseous phase. In particular, we review the progress in general understanding of the SAW chemical sensing mechanism, optimization of the sensor characteristics, and the development of the sensors operational at different conditions. Based on previous publications, we suggest some appropriate sensing approaches for particular applications and identify new opportunities and needs for additional research in this area moving into the future. PMID:28397760

SAW Sensors for Chemical Vapors and Gases.

PubMed

Devkota, Jagannath; Ohodnicki, Paul R; Greve, David W

2017-04-08

Surface acoustic wave (SAW) technology provides a sensitive platform for sensing chemicals in gaseous and fluidic states with the inherent advantages of passive and wireless operation. In this review, we provide a general overview on the fundamental aspects and some major advances of Rayleigh wave-based SAW sensors in sensing chemicals in a gaseous phase. In particular, we review the progress in general understanding of the SAW chemical sensing mechanism, optimization of the sensor characteristics, and the development of the sensors operational at different conditions. Based on previous publications, we suggest some appropriate sensing approaches for particular applications and identify new opportunities and needs for additional research in this area moving into the future.

Catalysis for biomass and CO2 use through solar energy: opening new scenarios for a sustainable and low-carbon chemical production.

PubMed

Lanzafame, Paola; Centi, Gabriele; Perathoner, Siglinda

2014-11-21

The use of biomass, bio-waste and CO2 derived raw materials, the latter synthesized using H2 produced using renewable energy sources, opens new scenarios to develop a sustainable and low carbon chemical production, particularly in regions such as Europe lacking in other resources. This tutorial review discusses first this new scenario with the aim to point out, between the different possible options, those more relevant to enable this new future scenario for the chemical production, commenting in particular the different drivers (economic, technological and strategic, environmental and sustainability and socio-political) which guide the selection. The case of the use of non-fossil fuel based raw materials for the sustainable production of light olefins is discussed in more detail, but the production of other olefins and polyolefins, of drop-in intermediates and other platform molecules are also analysed. The final part discusses the role of catalysis in establishing this new scenario, summarizing the development of catalysts with respect to industrial targets, for (i) the production of light olefins by catalytic dehydration of ethanol and by CO2 conversion via FTO process, (ii) the catalytic synthesis of butadiene from ethanol, butanol and butanediols, and (iii) the catalytic synthesis of HMF and its conversion to 2,5-FDCA, adipic acid, caprolactam and 1,6-hexanediol.

Polyamines are traps for reactive intermediates in furan metabolism

PubMed Central

Peterson, Lisa A.; Phillips, Martin B.; Lu, Ding; Sullivan, Mathilde M.

2011-01-01

Furan is toxic and carcinogenic in rodents. Because of the large potential for human exposure, furan is classified as a possible human carcinogen. The detailed mechanism by which furan causes toxicity and cancer is not yet known. Since furan toxicity requires cytochrome P450-catalyzed oxidation of furan, we have characterized the urinary and hepatocyte metabolites of furan to gain insight into the chemical nature of the reactive intermediate. Previous studies in hepatocytes indicated that furan is oxidized to the reactive α,β-unsaturated dialdehyde, cis-2-butene-1,4-dial (BDA), which reacts with glutathione (GSH) to form 2-(S-glutathionyl)-succinaldehyde (GSH-BDA). This intermediate forms pyrrole cross-links with cellular amines such as lysine and glutamine. In this report, we demonstrate that GSH-BDA also forms cross-links with ornithine, putrescine and spermidine when furan is incubated with rat hepatocytes. The relative levels of these metabolites are not completely explained by hepatocellular levels of the amines or by their reactivity with GSH-BDA. Mercapturic acid derivatives of the spermidine cross-links were detected in the urine of furan-treated rats, which indicates that this metabolic pathway occurs in vivo. Their detection in furan-treated hepatocytes and in urine from furan-treated rats indicates that polyamines may play an important role in the toxicity of furan PMID:21842885

Dynamic Gaming Platform (DGP)

DTIC Science & Technology

2009-04-01

GAMING PLATFORM (DGP) Lockheed Martin Corporation...YYYY) APR 09 2. REPORT TYPE Final 3. DATES COVERED (From - To) Jul 07 – Mar 09 4. TITLE AND SUBTITLE DYNAMIC GAMING PLATFORM (DGP) 5a...CMU Carnegie Mellon University DGP Dynamic Gaming Platform GA Genetic Algorithm IARPA Intelligence Advanced Research Projects Activity LM ATL Lockheed Martin Advanced Technology Laboratories PAINT ProActive INTelligence

FIELD SCREENING METHODS FOR HAZARDOUS WASTES AND TOXIC CHEMICALS

EPA Science Inventory

The purpose of this document is to present the technical papers that were presented at the Second International Symposium on Field Screening Methods for Hazardous Wastes and Toxic Chemicals. ixty platform presentations were made and included in one of ten sessions: hemical sensor...

The dichotomy between strong and ultra-weak magnetic fields among intermediate-mass stars

NASA Astrophysics Data System (ADS)

Lignières, François; Petit, Pascal; Aurière, Michel; Wade, Gregg A.; Böhm, Torsten

2014-08-01

Until recently, the detection of magnetic fields at the surface of intermediate-mass main-sequence stars has been limited to Ap/Bp stars, a class of chemically peculiar stars. This class represents no more than 5-10% of the stars in this mass range. This small fraction is not explained by the fossil field paradigm that describes the Ap/Bp type magnetism as a remnant of an early phase of the star-life. Also, the limitation of the field measurements to a small and special group of stars is obviously a problem to study the effect of the magnetic fields on the stellar evolution of a typical intermediate-mass star. Thanks to the improved sensitivity of a new generation of spectropolarimeters, a lower bound to the magnetic fields of Ap/Bp stars, a two orders of magnitude desert in the longitudinal magnetic field and a new type of sub-gauss magnetism first discovered on Vega have been identified. These advances provide new clues to understand the origin of intermediate-mass magnetism as well as its influence on stellar evolution. In particular, a scenario has been proposed whereby the magnetic dichotomy between Ap/Bp and Vega-like magnetism originate from the bifurcation between stable and unstable large scale magnetic configurations in differentially rotating stars. In this paper, we review these recent observational findings and discuss this scenario.

Novel Robotic Platforms for the Accurate Sampling and Monitoring of Water Columns

PubMed Central

Fernández, Roemi; Apalkov, Andrey; Armada, Manuel

2016-01-01

The hydrosphere contains large amounts of suspended particulate material, including living and non-living material that can be found in different compositions and concentrations, and that can be composed of particles of different sizes. The study of this particulate material along water columns plays a key role in understanding a great variety of biological, chemical, and physical processes. This paper presents the conceptual design of two patented robotic platforms that have been conceived for carrying out studies of water properties at desired depths with very high accuracy in the vertical positioning. One platform has been specially designed for operating near to a reservoir bottom, while the other is intended to be used near the surface. Several experimental tests have been conducted in order to validate the proposed approaches. PMID:27589745

A mechanical cell disruption microfluidic platform based on an on-chip micropump.

PubMed

Cheng, Yinuo; Wang, Yue; Wang, Zhiyuan; Huang, Liang; Bi, Mingzhao; Xu, Wenxiao; Wang, Wenhui; Ye, Xiongying

2017-03-01

Cell disruption plays a vital role in detection of intracellular components which contain information about genetic and disease characteristics. In this paper, we demonstrate a novel microfluidic platform based on an on-chip micropump for mechanical cell disruption and sample transport. A 50  μ l cell sample can be effectively lysed through on-chip multi-disruption in 36 s without introducing any chemical agent and suffering from clogging by cellular debris. After 30 cycles of circulating disruption, 80.6% and 90.5% cell disruption rates were achieved for the HEK293 cell sample and human natural killer cell sample, respectively. Profiting from the feature of pump-on-chip, the highly integrated platform enables more convenient and cost-effective cell disruption for the analysis of intracellular components.

A mechanical cell disruption microfluidic platform based on an on-chip micropump

PubMed Central

Cheng, Yinuo; Wang, Yue; Wang, Zhiyuan; Bi, Mingzhao; Xu, Wenxiao; Ye, Xiongying

2017-01-01

Cell disruption plays a vital role in detection of intracellular components which contain information about genetic and disease characteristics. In this paper, we demonstrate a novel microfluidic platform based on an on-chip micropump for mechanical cell disruption and sample transport. A 50 μl cell sample can be effectively lysed through on-chip multi-disruption in 36 s without introducing any chemical agent and suffering from clogging by cellular debris. After 30 cycles of circulating disruption, 80.6% and 90.5% cell disruption rates were achieved for the HEK293 cell sample and human natural killer cell sample, respectively. Profiting from the feature of pump-on-chip, the highly integrated platform enables more convenient and cost-effective cell disruption for the analysis of intracellular components. PMID:28798848

A Pictet-Spengler ligation for protein chemical modification

PubMed Central

Agarwal, Paresh; van der Weijden, Joep; Sletten, Ellen M.; Rabuka, David; Bertozzi, Carolyn R.

2013-01-01

Aldehyde- and ketone-functionalized proteins are appealing substrates for the development of chemically modified biotherapeutics and protein-based materials. Their reactive carbonyl groups are typically conjugated with α-effect nucleophiles, such as substituted hydrazines and alkoxyamines, to generate hydrazones and oximes, respectively. However, the resulting C=N linkages are susceptible to hydrolysis under physiologically relevant conditions, which limits the utility of such conjugates in biological systems. Here we introduce a Pictet-Spengler ligation that is based on the classic Pictet-Spengler reaction of aldehydes and tryptamine nucleophiles. The ligation exploits the bioorthogonal reaction of aldehydes and alkoxyamines to form an intermediate oxyiminium ion; this intermediate undergoes intramolecular C–C bond formation with an indole nucleophile to form an oxacarboline product that is hydrolytically stable. We used the reaction for site-specific chemical modification of glyoxyl- and formylglycine-functionalized proteins, including an aldehyde-tagged variant of the therapeutic monoclonal antibody Herceptin. In conjunction with techniques for site-specific introduction of aldehydes into proteins, the Pictet-Spengler ligation offers a means to generate stable bioconjugates for medical and materials applications. PMID:23237853

Platform C North Arrival

NASA Image and Video Library

2016-08-30

A section of the second half of the C-level platforms, C North, for NASA’s Space Launch System (SLS) rocket, arrives at the agency’s Kennedy Space Center in Florida. The platform was offloaded from a heavy lift transport truck and secured in a staging area in the west parking lot of the Vehicle Assembly Building (VAB). The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3 to support processing of the SLS and Orion spacecraft. A total of 10 levels of new platforms, 20 platform halves altogether, will surround the SLS rocket and Orion spacecraft and provide access for testing and processing.

The Regulation of Light Sensing and Light-Harvesting Impacts the Use of Cyanobacteria as Biotechnology Platforms

PubMed Central

Montgomery, Beronda L.

2014-01-01

Light is harvested in cyanobacteria by chlorophyll-containing photosystems embedded in the thylakoid membranes and phycobilisomes (PBSs), photosystem-associated light-harvesting antennae. Light absorbed by the PBSs and photosystems can be converted to chemical energy through photosynthesis. Photosynthetically fixed carbon pools, which are constrained by photosynthetic light capture versus the dissipation of excess light absorbed, determine the available organismal energy budget. The molecular bases of the environmental regulation of photosynthesis, photoprotection, and photomorphogenesis are still being elucidated in cyanobacteria. Thus, the potential impacts of these phenomena on the efficacy of developing cyanobacteria as robust biotechnological platforms require additional attention. Current advances and persisting needs for developing cyanobacterial production platforms that are related to light sensing and harvesting include the development of tools to balance the utilization of absorbed photons for conversion to chemical energy and biomass versus light dissipation in photoprotective mechanisms. Such tools can be used to direct energy to more effectively support the production of desired bioproducts from sunlight. PMID:25023122

Quantum Chemical Investigation of the Transition States and Intermediates for the Reaction of the Nitrosonium Ion with the Pentaammineazidocobalt(III) Ion.

PubMed

Rotzinger, François P

2016-12-19

The water exchange reaction on Co(NH 3 ) 5 OH 2 3+ was investigated with various density functionals and basis sets. A Gibbs activation energy (ΔG ⧧ ) agreeing with experiment was obtained with the long-range-corrected functionals ωB97X-D3 and LC-BOP-LRD, SMD hydration, and modified Karlsruhe def2-TZVP basis sets. This computational technique was then applied to the reaction of NO + with Co(NH 3 ) 5 N 3 2+ . All of the possible pathways were investigated, NO + attack at the terminal N of Co(NH 3 ) 5 N 3 2+ via the E and the Z isomers of the transition states, and NO + attack at the bound N of azide, also via both isomers. The most favorable pathway proceeds via the attack at the bound N via the Z isomer. This leads to the intermediate with an oxatetrazole ligand bound to Co(III) at the N in the 3-position, Co(NH 3 ) 5 (cycl-N 4 O) 3+ , which undergoes N 2 elimination to yield the Co(NH 3 ) 5 N 2 O 3+ intermediate. The subsequent substitution of N 2 O by water follows the I d mechanism with retention of the configuration. No evidence for the existence of the square-pyramidal pentacoordinated intermediate Co(NH 3 ) 5 3+ was found. All of the investigated intermediates, Co(NH 3 ) 5 N 2 3+ , Co(NH 3 ) 5 [E-N(N 2 )(NO)] 3+ , Co(NH 3 ) 5 (E-ON 4 ) 3+ , Co(NH 3 ) 5 ON 2 3+ , Co(NH 3 ) 5 (cycl-N 4 O) 3+ , and Co(NH 3 ) 5 N 2 O 3+ , exhibit short lifetimes of less than ∼60 μs and react via the I d mechanism.

Appliance Services. Intermediate Course. Career Education.

ERIC Educational Resources Information Center

Killough, Joseph

Several intermediate performance objectives and corresponding criterion measures are listed for each of 16 terminal objectives for an intermediate appliance repair course. The materials were developed for a 36-week course (3 hours daily) covering the areas of refrigeration, maintenance, repair, and troubleshooting of refrigerators and air…

40 CFR 86.246-94 - Intermediate temperature testing.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 19 2013-07-01 2013-07-01 false Intermediate temperature testing. 86... New Medium-Duty Passenger Vehicles; Cold Temperature Test Procedures § 86.246-94 Intermediate temperature testing. (a) This section is applicable to tests which are conducted at an intermediate...

40 CFR 86.246-94 - Intermediate temperature testing.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 19 2012-07-01 2012-07-01 false Intermediate temperature testing. 86... New Medium-Duty Passenger Vehicles; Cold Temperature Test Procedures § 86.246-94 Intermediate temperature testing. (a) This section is applicable to tests which are conducted at an intermediate...

40 CFR 86.246-94 - Intermediate temperature testing.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 18 2011-07-01 2011-07-01 false Intermediate temperature testing. 86... New Medium-Duty Passenger Vehicles; Cold Temperature Test Procedures § 86.246-94 Intermediate temperature testing. (a) This section is applicable to tests which are conducted at an intermediate...

Pressure-driven mesofluidic platform integrating automated on-chip renewable micro-solid-phase extraction for ultrasensitive determination of waterborne inorganic mercury.

PubMed

Portugal, Lindomar A; Laglera, Luis M; Anthemidis, Aristidis N; Ferreira, Sérgio L C; Miró, Manuel

2013-06-15

A dedicated pressure-driven mesofluidic platform incorporating on-chip sample clean-up and analyte preconcentration is herein reported for expedient determination of trace level concentrations of waterborne inorganic mercury. Capitalizing upon the Lab-on-a-Valve (LOV) concept, the mesofluidic device integrates on-chip micro-solid phase extraction (μSPE) in automatic disposable mode followed by chemical vapor generation and gas-liquid separation prior to in-line atomic fluorescence spectrometric detection. In contrast to prevailing chelating sorbents for Hg(II), bare poly(divinylbenzene-N-vinylpyrrolidone) copolymer sorptive beads were resorted to efficient uptake of Hg(II) in hydrochloric acid milieu (pH=2.3) without the need for metal derivatization nor pH adjustment of prior acidified water samples for preservation to near-neutral conditions. Experimental variables influencing the sorptive uptake and retrieval of target species and the evolvement of elemental mercury within the miniaturized integrated reaction chamber/gas-liquid separator were investigated in detail. Using merely <10 mg of sorbent, the limits of detection and quantification at the 3s(blank) and 10s(blank) levels, respectively, for a sample volume of 3 mL were 12 and 42 ng L(-1) Hg(II) with a dynamic range extending up to 5.0 μg L(-1). The proposed mesofluidic platform copes with the requirements of regulatory bodies (US-EPA, WHO, EU-Commission) for drinking water quality and surface waters that endorse maximum allowed concentrations of mercury spanning from 0.07 to 6.0 μg L(-1). Demonstrated with the analysis of aqueous samples of varying matrix complexity, the LOV approach afforded reliable results with relative recoveries of 86-107% and intermediate precision down to 9% in the renewable μSPE format. Copyright © 2013 Elsevier B.V. All rights reserved.

Metal-Organic Frameworks as Potential Platforms for Carbon Dioxide Capture and Chemical Transformation

NASA Astrophysics Data System (ADS)

Gao, Wenyang

field favours more than the richness of exposed nitrogen atoms for the interactions between MOFs and CO2 molecules, which provides a new perspective for future design of new MOFs and other types of porous materials for CO2 capture. Meanwhile, to address the water/moisture stability issue of MOFs, remote stabilization of copper paddlewheel clusters is achieved by strengthening the bonding between organic ligands and triangular inorganic copper trimers, which in turn enhances the stability of the whole MOF network and provides a better understanding of the mechanism promoting prospective suitable MOFs with enhanced water stability. In contrast with CO2 capture by sorbent materials, the chemical transformation of the captured CO2 into value-added products represents an alternative which is attractive and sustainable, and has been of escalating interest. The nanospace within MOFs not only provides the inner porosity for CO2 capture, but also engenders accessible room for substrate molecules for catalytic purpose. It is demonstrated that high catalytic efficiency for chemical fixation of CO2 into cyclic carbonates under ambient conditions is achieved on MOF-based nanoreactors featuring a high-density of well-oriented Lewis active sites. Furthermore, described for the first time is that CO 2 can be successfully inserted into aryl C-H bonds of a MOF to generate carboxylate groups. This proof-of-concept study contributes a different perspective to the current landscape of CO2 capture and transformation. In closing, the overarching goal of this work is not only to seek efficient MOF adsorbents for CO2 capture, but also to present a new yet attractive scenario of CO2 utilization on MOF platforms.

Real-time label-free quantitative fluorescence microscopy-based detection of ATP using a tunable fluorescent nano-aptasensor platform.

PubMed

Shrivastava, Sajal; Sohn, Il-Yung; Son, Young-Min; Lee, Won-Il; Lee, Nae-Eung

2015-12-14

Although real-time label-free fluorescent aptasensors based on nanomaterials are increasingly recognized as a useful strategy for the detection of target biomolecules with high fidelity, the lack of an imaging-based quantitative measurement platform limits their implementation with biological samples. Here we introduce an ensemble strategy for a real-time label-free fluorescent graphene (Gr) aptasensor platform. This platform employs aptamer length-dependent tunability, thus enabling the reagentless quantitative detection of biomolecules through computational processing coupled with real-time fluorescence imaging data. We demonstrate that this strategy effectively delivers dose-dependent quantitative readouts of adenosine triphosphate (ATP) concentration on chemical vapor deposited (CVD) Gr and reduced graphene oxide (rGO) surfaces, thereby providing cytotoxicity assessment. Compared with conventional fluorescence spectrometry methods, our highly efficient, universally applicable, and rational approach will facilitate broader implementation of imaging-based biosensing platforms for the quantitative evaluation of a range of target molecules.

Air Conditioning. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Long, William

Several intermediate performance objectives and corresponding criterion measures are listed for each of seven terminal objectives for an intermediate air conditioning course. The titles of the seven terminal objectives are Refrigeration Cycle, Job Requirement Skills, Air Conditioning, Trouble Shooting, Performance Test, Shop Management, and S.I.E.…

42 CFR 54.12 - Treatment of intermediate organizations.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 1 2010-10-01 2010-10-01 false Treatment of intermediate organizations. 54.12... intermediate organizations. If a nongovernmental organization (referred to here as an “intermediate organization”), acting under a contract or other agreement with the Federal Government or a State or local...

Desmosomes and Intermediate Filaments: Their Consequences for Tissue Mechanics.

PubMed

Hatzfeld, Mechthild; Keil, René; Magin, Thomas M

2017-06-01

Adherens junctions (AJs) and desmosomes connect the actin and keratin filament networks of adjacent cells into a mechanical unit. Whereas AJs function in mechanosensing and in transducing mechanical forces between the plasma membrane and the actomyosin cytoskeleton, desmosomes and intermediate filaments (IFs) provide mechanical stability required to maintain tissue architecture and integrity when the tissues are exposed to mechanical stress. Desmosomes are essential for stable intercellular cohesion, whereas keratins determine cell mechanics but are not involved in generating tension. Here, we summarize the current knowledge of the role of IFs and desmosomes in tissue mechanics and discuss whether the desmosome-keratin scaffold might be actively involved in mechanosensing and in the conversion of chemical signals into mechanical strength. Copyright © 2017 Cold Spring Harbor Laboratory Press; all rights reserved.

The vacuum platform

NASA Astrophysics Data System (ADS)

McNab, A.

2017-10-01

This paper describes GridPP’s Vacuum Platform for managing virtual machines (VMs), which has been used to run production workloads for WLCG and other HEP experiments. The platform provides a uniform interface between VMs and the sites they run at, whether the site is organised as an Infrastructure-as-a-Service cloud system such as OpenStack, or an Infrastructure-as-a-Client system such as Vac. The paper describes our experience in using this platform, in developing and operating VM lifecycle managers Vac and Vcycle, and in interacting with VMs provided by LHCb, ATLAS, ALICE, CMS, and the GridPP DIRAC service to run production workloads.

Organic waste as a sustainable feedstock for platform chemicals.

PubMed

Coma, M; Martinez-Hernandez, E; Abeln, F; Raikova, S; Donnelly, J; Arnot, T C; Allen, M J; Hong, D D; Chuck, C J

2017-09-21

Biorefineries have been established since the 1980s for biofuel production, and there has been a switch lately from first to second generation feedstocks in order to avoid the food versus fuel dilemma. To a lesser extent, many opportunities have been investigated for producing chemicals from biomass using by-products of the present biorefineries, simple waste streams. Current facilities apply intensive pre-treatments to deal with single substrate types such as carbohydrates. However, most organic streams such as municipal solid waste or algal blooms present a high complexity and variable mixture of molecules, which makes specific compound production and separation difficult. Here we focus on flexible anaerobic fermentation and hydrothermal processes that can treat complex biomass as a whole to obtain a range of products within an integrated biorefinery concept.

Organic waste as a sustainable feedstock for platform chemicals

PubMed Central

Martinez-Hernandez, E.; Abeln, F.; Raikova, S.; Donnelly, J.; Arnot, T. C.; Allen, M. J.; Hong, D. D.; Chuck, C. J.

2017-01-01

Biorefineries have been established since the 1980s for biofuel production, and there has been a switch lately from first to second generation feedstocks in order to avoid the food versus fuel dilemma. To a lesser extent, many opportunities have been investigated for producing chemicals from biomass using by-products of the present biorefineries, simple waste streams. Current facilities apply intensive pre-treatments to deal with single substrate types such as carbohydrates. However, most organic streams such as municipal solid waste or algal blooms present a high complexity and variable mixture of molecules, which makes specific compound production and separation difficult. Here we focus on flexible anaerobic fermentation and hydrothermal processes that can treat complex biomass as a whole to obtain a range of products within an integrated biorefinery concept. PMID:28654113

Recent advancements in chemical luminescence-based lab-on-chip and microfluidic platforms for bioanalysis.

PubMed

Mirasoli, Mara; Guardigli, Massimo; Michelini, Elisa; Roda, Aldo

2014-01-01

Miniaturization of analytical procedures through microchips, lab-on-a-chip or micro total analysis systems is one of the most recent trends in chemical and biological analysis. These systems are designed to perform all the steps in an analytical procedure, with the advantages of low sample and reagent consumption, fast analysis, reduced costs, possibility of extra-laboratory application. A range of detection technologies have been employed in miniaturized analytical systems, but most applications relied on fluorescence and electrochemical detection. Chemical luminescence (which includes chemiluminescence, bioluminescence, and electrogenerated chemiluminescence) represents an alternative detection principle that offered comparable (or better) analytical performance and easier implementation in miniaturized analytical devices. Nevertheless, chemical luminescence-based ones represents only a small fraction of the microfluidic devices reported in the literature, and until now no review has been focused on these devices. Here we review the most relevant applications (since 2009) of miniaturized analytical devices based on chemical luminescence detection. After a brief overview of the main chemical luminescence systems and of the recent technological advancements regarding their implementation in miniaturized analytical devices, analytical applications are reviewed according to the nature of the device (microfluidic chips, microchip electrophoresis, lateral flow- and paper-based devices) and the type of application (micro-flow injection assays, enzyme assays, immunoassays, gene probe hybridization assays, cell assays, whole-cell biosensors). Copyright © 2013 Elsevier B.V. All rights reserved.

Dataset from chemical gas sensor array in turbulent wind tunnel.

PubMed

Fonollosa, Jordi; Rodríguez-Luján, Irene; Trincavelli, Marco; Huerta, Ramón

2015-06-01

The dataset includes the acquired time series of a chemical detection platform exposed to different gas conditions in a turbulent wind tunnel. The chemo-sensory elements were sampling directly the environment. In contrast to traditional approaches that include measurement chambers, open sampling systems are sensitive to dispersion mechanisms of gaseous chemical analytes, namely diffusion, turbulence, and advection, making the identification and monitoring of chemical substances more challenging. The sensing platform included 72 metal-oxide gas sensors that were positioned at 6 different locations of the wind tunnel. At each location, 10 distinct chemical gases were released in the wind tunnel, the sensors were evaluated at 5 different operating temperatures, and 3 different wind speeds were generated in the wind tunnel to induce different levels of turbulence. Moreover, each configuration was repeated 20 times, yielding a dataset of 18,000 measurements. The dataset was collected over a period of 16 months. The data is related to "On the performance of gas sensor arrays in open sampling systems using Inhibitory Support Vector Machines", by Vergara et al.[1]. The dataset can be accessed publicly at the UCI repository upon citation of [1]: http://archive.ics.uci.edu/ml/datasets/Gas+sensor+arrays+in+open+sampling+settings.

Construction of a Linux based chemical and biological information system.

PubMed

Molnár, László; Vágó, István; Fehér, András

2003-01-01

A chemical and biological information system with a Web-based easy-to-use interface and corresponding databases has been developed. The constructed system incorporates all chemical, numerical and textual data related to the chemical compounds, including numerical biological screen results. Users can search the database by traditional textual/numerical and/or substructure or similarity queries through the web interface. To build our chemical database management system, we utilized existing IT components such as ORACLE or Tripos SYBYL for database management and Zope application server for the web interface. We chose Linux as the main platform, however, almost every component can be used under various operating systems.

Top value platform chemicals: bio-based production of organic acids.

PubMed

Becker, Judith; Lange, Anna; Fabarius, Jonathan; Wittmann, Christoph

2015-12-01

Driven by the quest for sustainability, recent years have seen a tremendous progress in bio-based production routes from renewable raw materials to commercial goods. Particularly, the production of organic acids has crystallized as a competitive and fast-evolving field, related to the broad applicability of organic acids for direct use, as polymer building blocks, and as commodity chemicals. Here, we review recent advances in metabolic engineering and industrial market scenarios with focus on organic acids as top value products from biomass, accessible through fermentation and biotransformation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Platform C South Arrival

NASA Image and Video Library

2016-08-04

A heavy load transport truck from Tillett Heavy Hauling in Titusville, Florida, arrives at the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida, carrying a section of the first half of the C-level work platforms, C south, for the agency’s Space Launch System (SLS) rocket. The platform will be delivered to the VAB staging area in the west parking lot. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3 to support processing of the SLS and Orion spacecraft. A total of 10 levels of new platforms, 20 platform halves altogether, will surround the SLS rocket and Orion spacecraft and provide access for testing and processing.

Remote platform power conserving system

NASA Technical Reports Server (NTRS)

Kurvin, C. W. (Inventor)

1974-01-01

A system is described where an unattended receiver and transmitter equipped data collection platform is interrogated by a substantially polar orbiting satellite. The method and apparatus involve physically representing the orbit of the satellite and the spin of the planetary body with timers, and using these representations to turn on the platform's receiver only when the satellite should be in radio range of the platform, whereby battery power at the platform is conserved.

Metabolic Engineering of a Glycerol-Oxidative Pathway in Lactobacillus panis PM1 for Utilization of Bioethanol Thin Stillage: Potential To Produce Platform Chemicals from Glycerol

PubMed Central

Kang, Tae Sun; Korber, Darren R.

2014-01-01

Lactobacillus panis PM1 has the ability to produce 1,3-propanediol (1,3-PDO) from thin stillage (TS), which is the major waste material after bioethanol production, and is therefore of significance. However, the fact that L. panis PM1 cannot use glycerol as a sole carbon source presents a considerable problem in terms of utilization of this strain in a wide range of industrial applications. Accordingly, L. panis PM1 was genetically engineered to directly utilize TS as a fermentable substrate for the production of valuable platform chemicals without the need for exogenous nutrient supplementation (e.g., sugars and nitrogen sources). An artificial glycerol-oxidative pathway, comprised of glycerol facilitator, glycerol kinase, glycerol 3-phosphate dehydrogenase, triosephosphate isomerase, and NADPH-dependent aldehyde reductase genes of Escherichia coli, was introduced into L. panis PM1 in order to directly utilize glycerol for the production of energy for growth and value-added chemicals. A pH 6.5 culture converted glycerol to mainly lactic acid (85.43 mM), whereas a significant amount of 1,3-propanediol (59.96 mM) was formed at pH 7.5. Regardless of the pH, ethanol (82.16 to 83.22 mM) was produced from TS fermentations, confirming that the artificial pathway metabolized glycerol for energy production and converted it into lactic acid or 1,3-PDO and ethanol in a pH-dependent manner. This study demonstrates the cost-effective conversion of TS to value-added chemicals by the engineered PM1 strain cultured under industrial conditions. Thus, application of this strain or these research findings can contribute to reduced costs of bioethanol production. PMID:25281374

14 CFR 398.8 - Number of intermediate stops.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Number of intermediate stops. 398.8 Section 398.8 Aeronautics and Space OFFICE OF THE SECRETARY, DEPARTMENT OF TRANSPORTATION (AVIATION... Number of intermediate stops. (a) Except in Alaska, no more than one intermediate stop is permitted in...

14 CFR 398.8 - Number of intermediate stops.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 14 Aeronautics and Space 4 2014-01-01 2014-01-01 false Number of intermediate stops. 398.8 Section 398.8 Aeronautics and Space OFFICE OF THE SECRETARY, DEPARTMENT OF TRANSPORTATION (AVIATION... Number of intermediate stops. (a) Except in Alaska, no more than one intermediate stop is permitted in...

Line-scan Raman imaging and spectroscopy platform for surface and subsurface evaluation of food safety and quality

USDA-ARS?s Scientific Manuscript database

Both surface and subsurface food inspection is important since interesting safety and quality attributes can be at different sample locations. This paper presents a multipurpose line-scan Raman platform for food safety and quality research, which can be configured for Raman chemical imaging (RCI) mo...

Dielectrophoretic investigation of Bi₂Te₃ nanowires-a microfabricated thermoelectric characterization platform for measuring the thermoelectric and structural properties of single nanowires.

PubMed

Wang, Zhi; Kojda, Danny; Peranio, Nicola; Kroener, Michael; Mitdank, Rüdiger; Toellner, William; Nielsch, Kornelius; Fischer, Saskia F; Gutsch, Sebastian; Zacharias, Margit; Eibl, Oliver; Woias, Peter

2015-03-27

In this article a microfabricated thermoelectric nanowire characterization platform to investigate the thermoelectric and structural properties of single nanowires is presented. By means of dielectrophoresis (DEP), a method to manipulate and orient nanowires in a controlled way to assemble them onto our measurement platform is introduced. The thermoelectric platform fabricated with optimally designed DEP electrodes results in a yield of nanowire assembly of approximately 90% under an applied peak-to-peak ac signal Vpp = 10 V and frequency f = 20 MHz within a series of 200 experiments. Ohmic contacts between the aligned single nanowire and the electrodes on the platform are established by electron beam-induced deposition. The Seebeck coefficient and electrical conductivity of electrochemically synthesized Bi2Te3 nanowires are measured to be -51 μV K(-1) and (943 ± 160)/(Ω(-1) cm(-1)), respectively. Chemical composition and crystallographic structure are obtained using transmission electron microscopy. The selected nanowire is observed to be single crystalline over its entire length and no grain boundaries are detected. At the surface of the nanowire, 66.1 ± 1.1 at.% Te and 34.9 ± 1.1 at.% Bi are observed. In contrast, chemical composition of 64.2 at.% Te and 35.8 at.% Bi is detected in the thick center of the nanowire.

Diesel Mechanics. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Tidwell, Joseph

Several intermediate performance objectives and corresponding criterion measures are listed for each of six terminal objectives for an intermediate diesel mechanics course (two semesters, 3 hours daily) designed for high school students who upon completion would be ready for an on-the-job training experience in diesel service and repair. Through…

Big Data Analytics in Chemical Engineering.

PubMed

Chiang, Leo; Lu, Bo; Castillo, Ivan

2017-06-07

Big data analytics is the journey to turn data into insights for more informed business and operational decisions. As the chemical engineering community is collecting more data (volume) from different sources (variety), this journey becomes more challenging in terms of using the right data and the right tools (analytics) to make the right decisions in real time (velocity). This article highlights recent big data advancements in five industries, including chemicals, energy, semiconductors, pharmaceuticals, and food, and then discusses technical, platform, and culture challenges. To reach the next milestone in multiplying successes to the enterprise level, government, academia, and industry need to collaboratively focus on workforce development and innovation.

Chemical vapor deposition of epitaxial silicon

DOEpatents

Berkman, Samuel

1984-01-01

A single chamber continuous chemical vapor deposition (CVD) reactor is described for depositing continuously on flat substrates, for example, epitaxial layers of semiconductor materials. The single chamber reactor is formed into three separate zones by baffles or tubes carrying chemical source material and a carrier gas in one gas stream and hydrogen gas in the other stream without interaction while the wafers are heated to deposition temperature. Diffusion of the two gas streams on heated wafers effects the epitaxial deposition in the intermediate zone and the wafers are cooled in the final zone by coolant gases. A CVD reactor for batch processing is also described embodying the deposition principles of the continuous reactor.

Hydroxyacetone production from C 3 Criegee intermediates

DOE PAGES

Taatjes, Craig A.; Liu, Fang; Rotavera, Brandon; ...

2016-12-21

Hydroxyacetone (CH 3C(O)CH 2OH) is observed as a stable end product from reactions of the (CH 3) 2COO Criegee intermediate, acetone oxide, in a flow tube coupled with multiplexed photoionization mass spectrometer detection. In the experiment, the isomers at m/z = 74 are distinguished by their different photoionization spectra and reaction times. Hydroxyacetone is observed as a persistent signal at longer reaction times at a higher photoionization threshold of ca. 9.7 eV than Criegee intermediate and definitively identified by comparison with the known photoionization spectrum. Complementary electronic structure calculations reveal multiple possible reaction pathways for hydroxyacetone formation, including unimolecular isomerizationmore » via hydrogen atom transfer and –OH group migration as well as self-reaction of Criegee intermediates. Varying the concentration of Criegee intermediates suggests contributions from both unimolecular and self-reaction pathways to hydroxyacetone. As a result, the hydroxyacetone end product can provide an effective, stable marker for the production of transient Criegee intermediates in future studies of alkene ozonolysis.« less

Radio and Television Servicing. Intermediate Course.

ERIC Educational Resources Information Center

Campbell, Guy; And Others

Several intermediate performance objectives and corresponding criterion measures are listed for each of 32 terminal objectives for an intermediate (second year) radio/TV servicing course. This 1-year course (3 hours daily) was designed to provide the student with the basic skills and knowledges necessary for entry level employment in the Radio/TV…

Chemical addressability of potato virus X for its applications in bio/nanotechnology.

PubMed

Le, Duc H T; Hu, He; Commandeur, Ulrich; Steinmetz, Nicole F

2017-12-01

Potato virus X (PVX), a type member of the plant virus potexvirus group, offers a unique nanotechnology platform based on its high aspect ratio and flexible filamentous shape. The PVX platform has already been engineered and studied for its uses in imaging, drug delivery, and immunotherapies. While genetic engineering procedures are well established for PVX, there is limited information about chemical conjugation strategies for functionalizing PVX, partly due to the lack of structural information of PVX at high resolution. To overcome these challenges, we built a structural model of the PVX particle based on the available structures from pepino mosaic virus (PepMV), a close cousin of PVX. Using the model and a series of chemical conjugation experiments, we identified and probed the addressability of cysteine side chains. Chemical reactivity of cysteines was confirmed using Michael-addition and thiol-selective probes, including fluorescent dyes and biotin tags. LC/MS/MS was used to map Cys 121 as having the highest selectivity for modification. Finally, building on the availability of two reactive groups, the newly identified Cys and previously established Lys side chains, we prepared multifunctional PVX nanoparticles by conjugating Gd-DOTA for magnetic resonance imaging (MRI) to lysines and fluorescent dyes for optical imaging to cysteines. The resulting functionalized nanofilament could have applications in dual-modal optical-MRI imaging applications. These results further extend the understanding of the chemical properties of PVX and enable development of novel multifunctional platforms in bio/nanotechnology. Copyright © 2017 Elsevier Inc. All rights reserved.

SAW Sensors for Chemical Vapors and Gases

DOE PAGES

Devkota, Jagannath; Ohodnicki, Paul R.; Greve, David W.

2017-04-08

Here, surface acoustic wave (SAW) technology provides a sensitive platform for sensing chemicals in gaseous and fluidic states with the inherent advantages of passive and wireless operation. In this review, we provide a general overview on the fundamental aspects and some major advances of Rayleigh wave-based SAW sensors in sensing chemicals in a gaseous phase. In particular, we review the progress in general understanding of the SAW chemical sensing mechanism, optimization of the sensor characteristics, and the development of the sensors operational at different conditions. Based on previous publications, we suggest some appropriate sensing approaches for particular applications and identifymore » new opportunities and needs for additional research in this area moving into the future.« less

Cross-platform learning: on the nature of children's learning from multiple media platforms.

PubMed

Fisch, Shalom M

2013-01-01

It is increasingly common for an educational media project to span several media platforms (e.g., TV, Web, hands-on materials), assuming that the benefits of learning from multiple media extend beyond those gained from one medium alone. Yet research typically has investigated learning from a single medium in isolation. This paper reviews several recent studies to explore cross-platform learning (i.e., learning from combined use of multiple media platforms) and how such learning compares to learning from one medium. The paper discusses unique benefits of cross-platform learning, a theoretical mechanism to explain how these benefits might arise, and questions for future research in this emerging field. Copyright © 2013 Wiley Periodicals, Inc., A Wiley Company.

Electro-oxidation of methanol on gold in alkaline media: Adsorption characteristics of reaction intermediates studied using time resolved electro-chemical impedance and surface plasmon resonance techniques

NASA Astrophysics Data System (ADS)

Assiongbon, K. A.; Roy, D.

2005-12-01

Electro-catalytic oxidation of methanol is the anode reaction in direct methanol fuel cells. We have studied the adsorption characteristics of the intermediate reactants of this multistep reaction on a gold film electrode in alkaline solutions by combining surface plasmon resonance (SPR) measurements with Fourier transform electro-chemical impedance spectroscopy (FT-EIS). Methanol oxidation in this system shows no significant effects of "site poisoning" by chemisorbed CO. Our results suggest that OH - chemisorbed onto Au acts as a stabilizing agent for the surface species of electro-active methanol. Double layer charging/discharging and adsorption/desorption of OH - show more pronounced effects than adsorption/oxidation of methanol in controlling the surface charge density of the Au substrate. These effects are manifested in both the EIS and the SPR data, and serve as key indicators of the surface reaction kinetics. The data presented here describe the important role of adsorbed OH - in electro-catalysis of methanol on Au, and demonstrate how SPR and FT-EIS can be combined for quantitative probing of catalytically active metal-solution interfaces.

Expanding the biomass derived chemical space

PubMed Central

Brun, Nicolas; Hesemann, Peter

2017-01-01

Biorefinery aims at the conversion of biomass and renewable feedstocks into fuels and platform chemicals, in analogy to conventional oil refinery. In the past years, the scientific community has defined a number of primary building blocks that can be obtained by direct biomass decomposition. However, the large potential of this “renewable chemical space” to contribute to the generation of value added bio-active compounds and materials still remains unexplored. In general, biomass derived building blocks feature a diverse range of chemical functionalities. In order to be integrated into value-added compounds, they require additional functionalization and/or covalent modification thereby generating secondary building blocks. The latter can be thus regarded as functional components of bio-active molecules or materials and represent an expansion of the renewable chemical space. This perspective highlights the most recent developments and opportunities for the synthesis of secondary biomass derived building blocks and their application to the preparation of value added products. PMID:28959397

Structure and antimicrobial activity of platypus 'intermediate' defensin-like peptide.

PubMed

Torres, Allan M; Bansal, Paramjit; Koh, Jennifer M S; Pagès, Guilhem; Wu, Ming J; Kuchel, Philip W

2014-05-02

The three-dimensional structure of a chemically synthesized peptide that we have called 'intermediate' defensin-like peptide (Int-DLP), from the platypus genome, was determined by nuclear magnetic resonance (NMR) spectroscopy; and its antimicrobial activity was investigated. The overall structural fold of Int-DLP was similar to that of the DLPs and β-defensins, however the presence of a third antiparallel β-strand makes its structure more similar to the β-defensins than the DLPs. Int-DLP displayed potent antimicrobial activity against Staphylococcus aureus and Pseudomonas aeruginosa. The four arginine residues at the N-terminus of Int-DLP did not affect the overall fold, but were important for its antimicrobial potency. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

Synthesis of Metal Oxide Nanomaterials for Chemical Sensors by Molecular Beam Epitaxy

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

Nandasiri, Manjula I.; Kuchibhatla, Satyanarayana V N T; Thevuthasan, Suntharampillai

2013-12-01

Since the industrial revolution, detection and monitoring of toxic matter, chemical wastes, and air pollutants has become an important environmental issue. Thus, it leads to the development of chemical sensors for various environmental applications. The recent disastrous oil spills over the near-surface of ocean due to the offshore drilling emphasize the use of chemical sensors for prevention and monitoring of the processes that might lead to these mishaps.1, 2 Chemical sensors operated on a simple principle that the sensing platform undergoes a detectable change when exposed to the target substance to be sensed. Among all the types of chemical sensors,more » solid state gas sensors have attracted a great deal of attention due to their advantages such as high sensitivity, greater selectivity, portability, high stability and low cost.3, 4 Especially, semiconducting metal oxides such as SnO2, TiO2, and WO3 have been widely used as the active sensing platforms in solid state gas sensors.5 For the enhanced properties of solid state gas sensors, finding new sensing materials or development of existing materials will be needed. Thus, nanostructured materials such as nanotubes,6-8 nanowires,9-11 nanorods,12-15 nanobelts,16, 17 and nano-scale thin films18-23 have been synthesized and studied for chemical sensing applications.« less

Platform C South Arrival

NASA Image and Video Library

2016-08-04

A heavy load transport truck from Tillett Heavy Hauling in Titusville, Florida, arrives at the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida, carrying a section of the first half of the C-level work platforms, C South, for the agency’s Space Launch System (SLS) rocket. The platform is being lifted and transferred onto support stands in the VAB staging area in the west parking lot. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3 to support processing of the SLS and Orion spacecraft. A total of 10 levels of new platforms, 20 platform halves altogether, will surround the SLS rocket and Orion spacecraft and provide access for testing and processing.

Platform C South Arrival

NASA Image and Video Library

2016-08-05

A heavy load transport truck from Tillett Heavy Hauling in Titusville, Florida, arrives at the Vehicle Assembly Building (VAB) at NASA’s Kennedy Space Center in Florida, carrying the second section of the first half of the C-level work platforms, C South, for the agency’s Space Launch System (SLS) rocket. The platform will be offloaded in the VAB staging area in the west parking lot. The Ground Systems Development and Operations Program is overseeing upgrades and modifications to VAB High Bay 3 to support processing of the SLS and Orion spacecraft. A total of 10 levels of new platforms, 20 platform halves altogether, will surround the SLS rocket and Orion spacecraft and provide access for testing and processing.

19 CFR 122.84 - Intermediate airport.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 19 Customs Duties 1 2011-04-01 2011-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the: (1...

19 CFR 122.84 - Intermediate airport.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 19 Customs Duties 1 2010-04-01 2010-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the: (1...

19 CFR 122.84 - Intermediate airport.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 19 Customs Duties 1 2012-04-01 2012-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the: (1...

19 CFR 122.84 - Intermediate airport.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 19 Customs Duties 1 2014-04-01 2014-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the: (1...

19 CFR 122.84 - Intermediate airport.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 19 Customs Duties 1 2013-04-01 2013-04-01 false Intermediate airport. 122.84 Section 122.84... Intermediate airport. (a) Application. The provisions of this section apply at any U.S. airport to which an... aircraft arrives at the next airport, the aircraft commander or agent shall make entry by filing the: (1...

Nucleation via an unstable intermediate phase.

PubMed

Sear, Richard P

2009-08-21

The pathway for crystallization from dilute vapors and solutions is often observed to take a detour via a liquid or concentrated-solution phase. For example, in moist subzero air, droplets of liquid water form, which then freeze. In this example and in many others, an intermediate phase (here liquid water) is dramatically accelerating the kinetics of a phase transition between two other phases (water vapor and ice). Here we study this phenomenon via exact computer simulations of a simple lattice model. Surprisingly, we find that the rate of nucleation of the new equilibrium phase is actually fastest when the intermediate phase is slightly unstable in the bulk, i.e., has a slightly higher free energy than the phase we start in. Nucleation occurs at a concave part of the surface and microscopic amounts of the intermediate phase can form there even before the phase is stable in the bulk. As the nucleus of the equilibrium phase is microscopic, this allows nucleation to occur effectively in the intermediate phase before it is stable in the bulk.

Chemical degradation and morphological instabilities during focused ion beam prototyping of polymers.

PubMed

Orthacker, A; Schmied, R; Chernev, B; Fröch, J E; Winkler, R; Hobisch, J; Trimmel, G; Plank, H

2014-01-28

Focused ion beam processing of low melting materials, such as polymers or biological samples, often leads to chemical and morphological instabilities which prevent the straight-forward application of this versatile direct-write structuring method. In this study the behaviour of different polymer classes under ion beam exposure is investigated using different patterning parameters and strategies with the aim of (i) correlating local temperatures with the polymers' chemistry and its morphological consequences; and (ii) finding a way of processing sensitive polymers with lowest chemical degradation while maintaining structuring times. It is found that during processing of polymers three temperature regimes can be observed: (1) at low temperatures all polymers investigated show stable chemical and morphological behaviour; (2) very high temperatures lead to strong chemical degradation which entails unpredictable morphologies; and (3) in the intermediate temperature regime the behaviour is found to be strongly material dependent. A detailed look reveals that polymers which rather cross-link in the proximity of the beam show stable morphologies in this intermediate regime, while polymers that rather undergo chain scission show tendencies to develop a creeping phase, where material follows the ion beam movement leading to instable and unpredictable morphologies. Finally a simple, alternative patterning strategy is suggested, which allows stable processing conditions with lowest chemical damage even for challenging polymers undergoing chain scission.

Metathesis Activity Encoded in the Metallacyclobutane Carbon-13 NMR Chemical Shift Tensors

PubMed Central

2017-01-01

Metallacyclobutanes are an important class of organometallic intermediates, due to their role in olefin metathesis. They can have either planar or puckered rings associated with characteristic chemical and physical properties. Metathesis active metallacyclobutanes have short M–Cα/α′ and M···Cβ distances, long Cα/α′–Cβ bond length, and isotropic 13C chemical shifts for both early d0 and late d4 transition metal compounds for the α- and β-carbons appearing at ca. 100 and 0 ppm, respectively. Metallacyclobutanes that do not show metathesis activity have 13C chemical shifts of the α- and β-carbons at typically 40 and 30 ppm, respectively, for d0 systems, with upfield shifts to ca. −30 ppm for the α-carbon of metallacycles with higher dn electron counts (n = 2 and 6). Measurements of the chemical shift tensor by solid-state NMR combined with an orbital (natural chemical shift, NCS) analysis of its principal components (δ11 ≥ δ22 ≥ δ33) with two-component calculations show that the specific chemical shift of metathesis active metallacyclobutanes originates from a low-lying empty orbital lying in the plane of the metallacyclobutane with local π*(M–Cα/α′) character. Thus, in the metathesis active metallacyclobutanes, the α-carbons retain some residual alkylidene character, while their β-carbon is shielded, especially in the direction perpendicular to the ring. Overall, the chemical shift tensors directly provide information on the predictive value about the ability of metallacyclobutanes to be olefin metathesis intermediates. PMID:28776018

Fast screening of analytes for chemical reactions by reactive low-temperature plasma ionization mass spectrometry.

PubMed

Zhang, Wei; Huang, Guangming

2015-11-15

Approaches for analyte screening have been used to aid in the fine-tuning of chemical reactions. Herein, we present a simple and straightforward analyte screening method for chemical reactions via reactive low-temperature plasma ionization mass spectrometry (reactive LTP-MS). Solution-phase reagents deposited on sample substrates were desorbed into the vapor phase by action of the LTP and by thermal desorption. Treated with LTP, both reagents reacted through a vapor phase ion/molecule reaction to generate the product. Finally, protonated reagents and products were identified by LTP-MS. Reaction products from imine formation reaction, Eschweiler-Clarke methylation and the Eberlin reaction were detected via reactive LTP-MS. Products from the imine formation reaction with reagents substituted with different functional groups (26 out of 28 trials) were successfully screened in a time of 30 s each. Besides, two short-lived reactive intermediates of Eschweiler-Clarke methylation were also detected. LTP in this study serves both as an ambient ionization source for analyte identification (including reagents, intermediates and products) and as a means to produce reagent ions to assist gas-phase ion/molecule reactions. The present reactive LTP-MS method enables fast screening for several analytes from several chemical reactions, which possesses good reagent compatibility and the potential to perform high-throughput analyte screening. In addition, with the detection of various reactive intermediates (intermediates I and II of Eschweiler-Clarke methylation), the present method would also contribute to revealing and elucidating reaction mechanisms. Copyright © 2015 John Wiley & Sons, Ltd.

National Community Solar Platform

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

Rupert, Bart

This project was created to provide a National Community Solar Platform (NCSP) portal known as Community Solar Hub, that is available to any entity or individual who wants to develop community solar. This has been done by providing a comprehensive portal to make CEC’s solutions, and other proven community solar solutions, externally available for everyone to access – making the process easy through proven platforms to protect subscribers, developers and utilities. The successful completion of this project provides these tools via a web platform and integration APIs, a wide spectrum of community solar projects included in the platform, multiple groupsmore » of customers (utilities, EPCs, and advocates) using the platform to develop community solar, and open access to anyone interested in community solar. CEC’s Incubator project includes web-based informational resources, integrated systems for project information and billing systems, and engagement with customers and users by community solar experts. The combined effort externalizes much of Clean Energy Collective’s industry-leading expertise, allowing third parties to develop community solar without duplicating expensive start-up efforts. The availability of this platform creates community solar projects that are cheaper to build and cheaper to participate in, furthering the goals of DOE’s SunShot Initiative. Final SF 425 Final SF 428 Final DOE F 2050.11 Final Report Narrative« less

Quantum-chemical insights from deep tensor neural networks

PubMed Central

Schütt, Kristof T.; Arbabzadah, Farhad; Chmiela, Stefan; Müller, Klaus R.; Tkatchenko, Alexandre

2017-01-01

Learning from data has led to paradigm shifts in a multitude of disciplines, including web, text and image search, speech recognition, as well as bioinformatics. Can machine learning enable similar breakthroughs in understanding quantum many-body systems? Here we develop an efficient deep learning approach that enables spatially and chemically resolved insights into quantum-mechanical observables of molecular systems. We unify concepts from many-body Hamiltonians with purpose-designed deep tensor neural networks, which leads to size-extensive and uniformly accurate (1 kcal mol−1) predictions in compositional and configurational chemical space for molecules of intermediate size. As an example of chemical relevance, the model reveals a classification of aromatic rings with respect to their stability. Further applications of our model for predicting atomic energies and local chemical potentials in molecules, reliable isomer energies, and molecules with peculiar electronic structure demonstrate the potential of machine learning for revealing insights into complex quantum-chemical systems. PMID:28067221

Quantum-chemical insights from deep tensor neural networks.

PubMed

Schütt, Kristof T; Arbabzadah, Farhad; Chmiela, Stefan; Müller, Klaus R; Tkatchenko, Alexandre

2017-01-09

Learning from data has led to paradigm shifts in a multitude of disciplines, including web, text and image search, speech recognition, as well as bioinformatics. Can machine learning enable similar breakthroughs in understanding quantum many-body systems? Here we develop an efficient deep learning approach that enables spatially and chemically resolved insights into quantum-mechanical observables of molecular systems. We unify concepts from many-body Hamiltonians with purpose-designed deep tensor neural networks, which leads to size-extensive and uniformly accurate (1 kcal mol -1 ) predictions in compositional and configurational chemical space for molecules of intermediate size. As an example of chemical relevance, the model reveals a classification of aromatic rings with respect to their stability. Further applications of our model for predicting atomic energies and local chemical potentials in molecules, reliable isomer energies, and molecules with peculiar electronic structure demonstrate the potential of machine learning for revealing insights into complex quantum-chemical systems.

Microbial synthesis of medium-chain chemicals from renewables.

PubMed

Sarria, Stephen; Kruyer, Nicholas S; Peralta-Yahya, Pamela

2017-12-01

Linear, medium-chain (C8-C12) hydrocarbons are important components of fuels as well as commodity and specialty chemicals. As industrial microbes do not contain pathways to produce medium-chain chemicals, approaches such as overexpression of endogenous enzymes or deletion of competing pathways are not available to the metabolic engineer; instead, fatty acid synthesis and reversed β-oxidation are manipulated to synthesize medium-chain chemical precursors. Even so, chain lengths remain difficult to control, which means that purification must be used to obtain the desired products, titers of which are typically low and rarely exceed milligrams per liter. By engineering the substrate specificity and activity of the pathway enzymes that generate the fatty acyl intermediates and chain-tailoring enzymes, researchers can boost the type and yield of medium-chain chemicals. Development of technologies to both manipulate chain-tailoring enzymes and to assay for products promises to enable the generation of g/L yields of medium-chain chemicals.

Quantum-chemical insights from deep tensor neural networks

NASA Astrophysics Data System (ADS)

Schütt, Kristof T.; Arbabzadah, Farhad; Chmiela, Stefan; Müller, Klaus R.; Tkatchenko, Alexandre

2017-01-01

Learning from data has led to paradigm shifts in a multitude of disciplines, including web, text and image search, speech recognition, as well as bioinformatics. Can machine learning enable similar breakthroughs in understanding quantum many-body systems? Here we develop an efficient deep learning approach that enables spatially and chemically resolved insights into quantum-mechanical observables of molecular systems. We unify concepts from many-body Hamiltonians with purpose-designed deep tensor neural networks, which leads to size-extensive and uniformly accurate (1 kcal mol-1) predictions in compositional and configurational chemical space for molecules of intermediate size. As an example of chemical relevance, the model reveals a classification of aromatic rings with respect to their stability. Further applications of our model for predicting atomic energies and local chemical potentials in molecules, reliable isomer energies, and molecules with peculiar electronic structure demonstrate the potential of machine learning for revealing insights into complex quantum-chemical systems.

Adolescents' Use of Basic, Intermediate, and Advanced Device Types for Vaping.

PubMed

Pepper, Jessica K; MacMonegle, Anna J; Nonnemaker, James M

2017-12-23

Advanced models of electronic vaping products (EVPs) likely pose a greater risk to adolescent health than basic or intermediate models because advanced models deliver nicotine more effectively and heat e-liquid to higher temperatures, producing more harmful chemical emissions. However, little is known about adolescents' risk factors for using different device types. We used social media to recruit an online sample of 1,508 U.S. adolescents aged 15-17 who reported past 30-day use of e-cigarettes. We assessed tobacco use, beliefs and knowledge about EVPs, and EVP use behavior, including the device type participants use most frequently. We used multinomial logistic regression to examine differences between adolescents who usually use intermediate versus basic and advanced versus basic devices. Most respondents usually used modifiable advanced devices (56.8%) rather than basic "cigalike" (14.5%) or pen-style intermediate (28.7%) devices. Use of multiple device types was common, particularly among those who primarily used basic devices. Younger age and less frequent vaping were associated with mainly using basic devices. Adolescents who were older, male, personally bought their main device, and had ever mixed e-liquids were at elevated risk for usually using advanced devices. Adolescents who primarily use basic devices may be newer users who are experimenting with multiple devices. Future research should examine which adolescents are most likely to transition to advanced devices in order to develop targeted interventions. Regulators should consider strategies to reduce access to all types of EVPs, such as better enforcement of the current ban on sales to minors. This research addresses two gaps in research on adolescent electronic vaping product use: (1) characterizing use of advanced devices as distinct from intermediate devices rather than grouping them together and (2) examining factors associated with use of specific device types. This study suggests that there

30 CFR 250.911 - If my platform is subject to the Platform Verification Program, what must I do?

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 2 2012-07-01 2012-07-01 false If my platform is subject to the Platform Verification Program, what must I do? 250.911 Section 250.911 Mineral Resources BUREAU OF SAFETY AND... CONTINENTAL SHELF Platforms and Structures Platform Verification Program § 250.911 If my platform is subject...

30 CFR 250.911 - If my platform is subject to the Platform Verification Program, what must I do?

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 2 2013-07-01 2013-07-01 false If my platform is subject to the Platform Verification Program, what must I do? 250.911 Section 250.911 Mineral Resources BUREAU OF SAFETY AND... CONTINENTAL SHELF Platforms and Structures Platform Verification Program § 250.911 If my platform is subject...

30 CFR 250.911 - If my platform is subject to the Platform Verification Program, what must I do?

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 2 2014-07-01 2014-07-01 false If my platform is subject to the Platform Verification Program, what must I do? 250.911 Section 250.911 Mineral Resources BUREAU OF SAFETY AND... CONTINENTAL SHELF Platforms and Structures Platform Verification Program § 250.911 If my platform is subject...

Mass Spectrometry-Based Screening Platform Reveals Orco Interactome in Drosophila melanogaster.

PubMed

Yu, Kate E; Kim, Do-Hyoung; Kim, Yong-In; Jones, Walton D; Lee, J Eugene

2018-02-28

Animals use their odorant receptors to receive chemical information from the environment. Insect odorant receptors differ from the G protein-coupled odorant receptors in vertebrates and nematodes, and very little is known about their protein-protein interactions. Here, we introduce a mass spectrometric platform designed for the large-scale analysis of insect odorant receptor protein-protein interactions. Using this platform, we obtained the first Orco interactome from Drosophila melanogaster . From a total of 1,186 identified proteins, we narrowed the interaction candidates to 226, of which only two-thirds have been named. These candidates include the known olfactory proteins Or92a and Obp51a. Around 90% of the proteins having published names likely function inside the cell, and nearly half of these intracellular proteins are associated with the endomembrane system. In a basic loss-of-function electrophysiological screen, we found that the disruption of eight (i.e., Rab5, CG32795, Mpcp, Tom70, Vir-1, CG30427, Eaat1, and CG2781) of 28 randomly selected candidates affects olfactory responses in vivo . Thus, because this Orco interactome includes physiologically meaningful candidates, we anticipate that our platform will help guide further research on the molecular mechanisms of the insect odorant receptor family.

Microfluidic platform for assessing pancreatic islet functionality through dielectric spectroscopy

PubMed Central

Heileman, K.; Daoud, J.; Hasilo, C.; Gasparrini, M.; Paraskevas, S.; Tabrizian, M.

2015-01-01

Human pancreatic islets are seldom assessed for dynamic responses to external stimuli. Thus, the elucidation of human islet functionality would provide insights into the progression of diabetes mellitus, evaluation of preparations for clinical transplantation, as well as for the development of novel therapeutics. The objective of this study was to develop a microfluidic platform for in vitro islet culture, allowing the multi-parametric investigation of islet response to chemical and biochemical stimuli. This was accomplished through the fabrication and implementation of a microfluidic platform that allowed the perifusion of islet culture while integrating real-time monitoring using impedance spectroscopy, through microfabricated, interdigitated electrodes located along the microchamber arrays. Real-time impedance measurements provide important dielectric parameters, such as cell membrane capacitance and cytoplasmic conductivity, representing proliferation, differentiation, viability, and functionality. The perifusion of varying glucose concentrations and monitoring of the resulting impedance of pancreatic islets were performed as proof-of-concept validation of the lab-on-chip platform. This novel technique to elucidate the underlying mechanisms that dictate islet functionality is presented, providing new information regarding islet function that could improve the evaluation of islet preparations for transplantation. In addition, it will lead to a better understanding of fundamental diabetes-related islet dysfunction and the development of therapeutics through evaluation of potential drug effects. PMID:26339324

The Emory Chemical Biology Discovery Center: leveraging academic innovation to advance novel targets through HTS and beyond.

PubMed

Johns, Margaret A; Meyerkord-Belton, Cheryl L; Du, Yuhong; Fu, Haian

2014-03-01

The Emory Chemical Biology Discovery Center (ECBDC) aims to accelerate high throughput biology and translation of biomedical research discoveries into therapeutic targets and future medicines by providing high throughput research platforms to scientific collaborators worldwide. ECBDC research is focused at the interface of chemistry and biology, seeking to fundamentally advance understanding of disease-related biology with its HTS/HCS platforms and chemical tools, ultimately supporting drug discovery. Established HTS/HCS capabilities, university setting, and expertise in diverse assay formats, including protein-protein interaction interrogation, have enabled the ECBDC to contribute to national chemical biology efforts, empower translational research, and serve as a training ground for young scientists. With these resources, the ECBDC is poised to leverage academic innovation to advance biology and therapeutic discovery.

Cytoplasmic peptidoglycan intermediate levels in Staphylococcus aureus.

PubMed

Vemula, Harika; Ayon, Navid J; Gutheil, William G

2016-02-01

Intracellular cytoplasmic peptidoglycan (PG) intermediate levels were determined in Staphylococcus aureus during log-phase growth in enriched media. Levels of UDP-linked intermediates were quantitatively determined using ion pairing LC-MS/MS in negative mode, and amine intermediates were quantitatively determined stereospecifically as their Marfey's reagent derivatives in positive mode. Levels of UDP-linked intermediates in S. aureus varied from 1.4 μM for UDP-GlcNAc-Enolpyruvyate to 1200 μM for UDP-MurNAc. Levels of amine intermediates (L-Ala, D-Ala, D-Ala-D-Ala, L-Glu, D-Glu, and L-Lys) varied over a range of from 860 μM for D-Ala-D-Ala to 30-260 mM for the others. Total PG was determined from the D-Glu content of isolated PG, and used to estimate the rate of PG synthesis (in terms of cytoplasmic metabolite flux) as 690 μM/min. The total UDP-linked intermediates pool (2490 μM) is therefore sufficient to sustain growth for 3.6 min. Comparison of UDP-linked metabolite levels with published pathway enzyme characteristics demonstrates that enzymes on the UDP-branch range from >80% saturation for MurA, Z, and C, to <5% saturation for MurB. Metabolite levels were compared with literature values for Escherichia coli, with the major difference in UDP-intermediates being the level of UDP-MurNAc, which was high in S. aureus (1200 μM) and low in E. coli (45 μM). Copyright © 2015 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

A platform for the discovery of new macrolide antibiotics

NASA Astrophysics Data System (ADS)

Seiple, Ian B.; Zhang, Ziyang; Jakubec, Pavol; Langlois-Mercier, Audrey; Wright, Peter M.; Hog, Daniel T.; Yabu, Kazuo; Allu, Senkara Rao; Fukuzaki, Takehiro; Carlsen, Peter N.; Kitamura, Yoshiaki; Zhou, Xiang; Condakes, Matthew L.; Szczypiński, Filip T.; Green, William D.; Myers, Andrew G.

2016-05-01

The chemical modification of structurally complex fermentation products, a process known as semisynthesis, has been an important tool in the discovery and manufacture of antibiotics for the treatment of various infectious diseases. However, many of the therapeutics obtained in this way are no longer effective, because bacterial resistance to these compounds has developed. Here we present a practical, fully synthetic route to macrolide antibiotics by the convergent assembly of simple chemical building blocks, enabling the synthesis of diverse structures not accessible by traditional semisynthetic approaches. More than 300 new macrolide antibiotic candidates, as well as the clinical candidate solithromycin, have been synthesized using our convergent approach. Evaluation of these compounds against a panel of pathogenic bacteria revealed that the majority of these structures had antibiotic activity, some efficacious against strains resistant to macrolides in current use. The chemistry we describe here provides a platform for the discovery of new macrolide antibiotics and may also serve as the basis for their manufacture.

Porous-Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis.

PubMed

Haikal, Rana R; Wang, Xia; Hassan, Youssef S; Parida, Manas R; Murali, Banavoth; Mohammed, Omar F; Pellechia, Perry J; Fontecave, Marc; Alkordi, Mohamed H

2016-08-10

A number of permanently porous polymers containing Ru(bpy)n photosensitizer or a cobaloxime complex, as a proton-reduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multitopic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity toward hydrogen-evolution reaction (HER) with remarkable recyclability. We further demonstrated, in two cases, the ability to affect the excited-state lifetime of the covalently immobilized Ru(bpy)3 complex attained through deliberate utilization of the organic linkers of variable dimensions. Overall, this approach facilitates construction of tunable porous solids, with hybrid composition and pronounced chemical and physical stability, based on the well-known Ru(bpy)nor the cobaloxime complexes.

A testing platform for durability studies of polymers and fiber-reinforced polymer composites under concurrent hygrothermo-mechanical stimuli.

PubMed

Gomez, Antonio; Pires, Robert; Yambao, Alyssa; La Saponara, Valeria

2014-12-11

The durability of polymers and fiber-reinforced polymer composites under service condition is a critical aspect to be addressed for their robust designs and condition-based maintenance. These materials are adopted in a wide range of engineering applications, from aircraft and ship structures, to bridges, wind turbine blades, biomaterials and biomedical implants. Polymers are viscoelastic materials, and their response may be highly nonlinear and thus make it challenging to predict and monitor their in-service performance. The laboratory-scale testing platform presented herein assists the investigation of the influence of concurrent mechanical loadings and environmental conditions on these materials. The platform was designed to be low-cost and user-friendly. Its chemically resistant materials make the platform adaptable to studies of chemical degradation due to in-service exposure to fluids. An example of experiment was conducted at RT on closed-cell polyurethane foam samples loaded with a weight corresponding to ~50% of their ultimate static and dry load. Results show that the testing apparatus is appropriate for these studies. Results also highlight the larger vulnerability of the polymer under concurrent loading, based on the higher mid-point displacements and lower residual failure loads. Recommendations are made for additional improvements to the testing apparatus.

A Testing Platform for Durability Studies of Polymers and Fiber-reinforced Polymer Composites under Concurrent Hygrothermo-mechanical Stimuli

PubMed Central

Gomez, Antonio; Pires, Robert; Yambao, Alyssa; La Saponara, Valeria

2014-01-01

The durability of polymers and fiber-reinforced polymer composites under service condition is a critical aspect to be addressed for their robust designs and condition-based maintenance. These materials are adopted in a wide range of engineering applications, from aircraft and ship structures, to bridges, wind turbine blades, biomaterials and biomedical implants. Polymers are viscoelastic materials, and their response may be highly nonlinear and thus make it challenging to predict and monitor their in-service performance. The laboratory-scale testing platform presented herein assists the investigation of the influence of concurrent mechanical loadings and environmental conditions on these materials. The platform was designed to be low-cost and user-friendly. Its chemically resistant materials make the platform adaptable to studies of chemical degradation due to in-service exposure to fluids. An example of experiment was conducted at RT on closed-cell polyurethane foam samples loaded with a weight corresponding to ~50% of their ultimate static and dry load. Results show that the testing apparatus is appropriate for these studies. Results also highlight the larger vulnerability of the polymer under concurrent loading, based on the higher mid-point displacements and lower residual failure loads. Recommendations are made for additional improvements to the testing apparatus. PMID:25548950

IVAG: An Integrative Visualization Application for Various Types of Genomic Data Based on R-Shiny and the Docker Platform.

PubMed

Lee, Tae-Rim; Ahn, Jin Mo; Kim, Gyuhee; Kim, Sangsoo

2017-12-01

Next-generation sequencing (NGS) technology has become a trend in the genomics research area. There are many software programs and automated pipelines to analyze NGS data, which can ease the pain for traditional scientists who are not familiar with computer programming. However, downstream analyses, such as finding differentially expressed genes or visualizing linkage disequilibrium maps and genome-wide association study (GWAS) data, still remain a challenge. Here, we introduce a dockerized web application written in R using the Shiny platform to visualize pre-analyzed RNA sequencing and GWAS data. In addition, we have integrated a genome browser based on the JBrowse platform and an automated intermediate parsing process required for custom track construction, so that users can easily build and navigate their personal genome tracks with in-house datasets. This application will help scientists perform series of downstream analyses and obtain a more integrative understanding about various types of genomic data by interactively visualizing them with customizable options.

The COMET Sleep Research Platform.

PubMed

Nichols, Deborah A; DeSalvo, Steven; Miller, Richard A; Jónsson, Darrell; Griffin, Kara S; Hyde, Pamela R; Walsh, James K; Kushida, Clete A

2014-01-01

The Comparative Outcomes Management with Electronic Data Technology (COMET) platform is extensible and designed for facilitating multicenter electronic clinical research. Our research goals were the following: (1) to conduct a comparative effectiveness trial (CET) for two obstructive sleep apnea treatments-positive airway pressure versus oral appliance therapy; and (2) to establish a new electronic network infrastructure that would support this study and other clinical research studies. The COMET platform was created to satisfy the needs of CET with a focus on creating a platform that provides comprehensive toolsets, multisite collaboration, and end-to-end data management. The platform also provides medical researchers the ability to visualize and interpret data using business intelligence (BI) tools. COMET is a research platform that is scalable and extensible, and which, in a future version, can accommodate big data sets and enable efficient and effective research across multiple studies and medical specialties. The COMET platform components were designed for an eventual move to a cloud computing infrastructure that enhances sustainability, overall cost effectiveness, and return on investment.

The COMET Sleep Research Platform

PubMed Central

Nichols, Deborah A.; DeSalvo, Steven; Miller, Richard A.; Jónsson, Darrell; Griffin, Kara S.; Hyde, Pamela R.; Walsh, James K.; Kushida, Clete A.

2014-01-01

Introduction: The Comparative Outcomes Management with Electronic Data Technology (COMET) platform is extensible and designed for facilitating multicenter electronic clinical research. Background: Our research goals were the following: (1) to conduct a comparative effectiveness trial (CET) for two obstructive sleep apnea treatments—positive airway pressure versus oral appliance therapy; and (2) to establish a new electronic network infrastructure that would support this study and other clinical research studies. Discussion: The COMET platform was created to satisfy the needs of CET with a focus on creating a platform that provides comprehensive toolsets, multisite collaboration, and end-to-end data management. The platform also provides medical researchers the ability to visualize and interpret data using business intelligence (BI) tools. Conclusion: COMET is a research platform that is scalable and extensible, and which, in a future version, can accommodate big data sets and enable efficient and effective research across multiple studies and medical specialties. The COMET platform components were designed for an eventual move to a cloud computing infrastructure that enhances sustainability, overall cost effectiveness, and return on investment. PMID:25848590

Methods for conversion of carbohydrates in ionic liquids to value-added chemicals

DOEpatents

Zhao, Haibo [The Woodlands, TX; Holladay, Johnathan E [Kennewick, WA; Zhang, Zongchao C [Norwood, NJ

2011-05-10

Methods are described for converting carbohydrates including, e.g., monosaccharides, disaccharides, and polysaccharides in ionic liquids to value-added chemicals including furans, useful as chemical intermediates and/or feedstocks. Fructose is converted to 5-hydroxylmethylfurfural (HMF) in the presence of metal halide and acid catalysts. Glucose is effectively converted to HMF in the presence of chromium chloride catalysts. Yields of up to about 70% are achieved with low levels of impurities such as levulinic acid.

Metabolic engineering of a glycerol-oxidative pathway in Lactobacillus panis PM1 for utilization of bioethanol thin stillage: potential to produce platform chemicals from glycerol.

PubMed

Kang, Tae Sun; Korber, Darren R; Tanaka, Takuji

2014-12-01

Lactobacillus panis PM1 has the ability to produce 1,3-propanediol (1,3-PDO) from thin stillage (TS), which is the major waste material after bioethanol production, and is therefore of significance. However, the fact that L. panis PM1 cannot use glycerol as a sole carbon source presents a considerable problem in terms of utilization of this strain in a wide range of industrial applications. Accordingly, L. panis PM1 was genetically engineered to directly utilize TS as a fermentable substrate for the production of valuable platform chemicals without the need for exogenous nutrient supplementation (e.g., sugars and nitrogen sources). An artificial glycerol-oxidative pathway, comprised of glycerol facilitator, glycerol kinase, glycerol 3-phosphate dehydrogenase, triosephosphate isomerase, and NADPH-dependent aldehyde reductase genes of Escherichia coli, was introduced into L. panis PM1 in order to directly utilize glycerol for the production of energy for growth and value-added chemicals. A pH 6.5 culture converted glycerol to mainly lactic acid (85.43 mM), whereas a significant amount of 1,3-propanediol (59.96 mM) was formed at pH 7.5. Regardless of the pH, ethanol (82.16 to 83.22 mM) was produced from TS fermentations, confirming that the artificial pathway metabolized glycerol for energy production and converted it into lactic acid or 1,3-PDO and ethanol in a pH-dependent manner. This study demonstrates the cost-effective conversion of TS to value-added chemicals by the engineered PM1 strain cultured under industrial conditions. Thus, application of this strain or these research findings can contribute to reduced costs of bioethanol production. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Near-field observation platform

NASA Astrophysics Data System (ADS)

Schlemmer, Harry; Baeurle, Constantin; Vogel, Holger

2008-04-01

A miniaturized near-field observation platform is presented comprising a sensitive daylight camera and an uncooled micro-bolometer thermal imager each equipped with a wide angle lens. Both cameras are optimised for a range between a few meters and 200 m. The platform features a stabilised line of sight and can therefore be used also on a vehicle when it is in motion. The line of sight either can be directed manually or the platform can be used in a panoramic mode. The video output is connected to a control panel where algorithms for moving target indication or tracking can be applied in order to support the observer. The near-field platform also can be netted with the vehicle system and the signals can be utilised, e.g. to designate a new target to the main periscope or the weapon sight.

Field programmable chemistry: integrated chemical and electronic processing of informational molecules towards electronic chemical cells.

PubMed

Wagler, Patrick F; Tangen, Uwe; Maeke, Thomas; McCaskill, John S

2012-07-01

The topic addressed is that of combining self-constructing chemical systems with electronic computation to form unconventional embedded computation systems performing complex nano-scale chemical tasks autonomously. The hybrid route to complex programmable chemistry, and ultimately to artificial cells based on novel chemistry, requires a solution of the two-way massively parallel coupling problem between digital electronics and chemical systems. We present a chemical microprocessor technology and show how it can provide a generic programmable platform for complex molecular processing tasks in Field Programmable Chemistry, including steps towards the grand challenge of constructing the first electronic chemical cells. Field programmable chemistry employs a massively parallel field of electrodes, under the control of latched voltages, which are used to modulate chemical activity. We implement such a field programmable chemistry which links to chemistry in rather generic, two-phase microfluidic channel networks that are separated into weakly coupled domains. Electric fields, produced by the high-density array of electrodes embedded in the channel floors, are used to control the transport of chemicals across the hydrodynamic barriers separating domains. In the absence of electric fields, separate microfluidic domains are essentially independent with only slow diffusional interchange of chemicals. Electronic chemical cells, based on chemical microprocessors, exploit a spatially resolved sandwich structure in which the electronic and chemical systems are locally coupled through homogeneous fine-grained actuation and sensor networks and play symmetric and complementary roles. We describe how these systems are fabricated, experimentally test their basic functionality, simulate their potential (e.g. for feed forward digital electrophoretic (FFDE) separation) and outline the application to building electronic chemical cells. Copyright © 2012 Elsevier Ireland Ltd. All rights

Direct single-molecule dynamic detection of chemical reactions.

PubMed

Guan, Jianxin; Jia, Chuancheng; Li, Yanwei; Liu, Zitong; Wang, Jinying; Yang, Zhongyue; Gu, Chunhui; Su, Dingkai; Houk, Kendall N; Zhang, Deqing; Guo, Xuefeng

2018-02-01

Single-molecule detection can reveal time trajectories and reaction pathways of individual intermediates/transition states in chemical reactions and biological processes, which is of fundamental importance to elucidate their intrinsic mechanisms. We present a reliable, label-free single-molecule approach that allows us to directly explore the dynamic process of basic chemical reactions at the single-event level by using stable graphene-molecule single-molecule junctions. These junctions are constructed by covalently connecting a single molecule with a 9-fluorenone center to nanogapped graphene electrodes. For the first time, real-time single-molecule electrical measurements unambiguously show reproducible large-amplitude two-level fluctuations that are highly dependent on solvent environments in a nucleophilic addition reaction of hydroxylamine to a carbonyl group. Both theoretical simulations and ensemble experiments prove that this observation originates from the reversible transition between the reactant and a new intermediate state within a time scale of a few microseconds. These investigations open up a new route that is able to be immediately applied to probe fast single-molecule physics or biophysics with high time resolution, making an important contribution to broad fields beyond reaction chemistry.

Direct single-molecule dynamic detection of chemical reactions

PubMed Central

Guan, Jianxin; Jia, Chuancheng; Li, Yanwei; Liu, Zitong; Wang, Jinying; Yang, Zhongyue; Gu, Chunhui; Su, Dingkai; Houk, Kendall N.; Zhang, Deqing; Guo, Xuefeng

2018-01-01

Single-molecule detection can reveal time trajectories and reaction pathways of individual intermediates/transition states in chemical reactions and biological processes, which is of fundamental importance to elucidate their intrinsic mechanisms. We present a reliable, label-free single-molecule approach that allows us to directly explore the dynamic process of basic chemical reactions at the single-event level by using stable graphene-molecule single-molecule junctions. These junctions are constructed by covalently connecting a single molecule with a 9-fluorenone center to nanogapped graphene electrodes. For the first time, real-time single-molecule electrical measurements unambiguously show reproducible large-amplitude two-level fluctuations that are highly dependent on solvent environments in a nucleophilic addition reaction of hydroxylamine to a carbonyl group. Both theoretical simulations and ensemble experiments prove that this observation originates from the reversible transition between the reactant and a new intermediate state within a time scale of a few microseconds. These investigations open up a new route that is able to be immediately applied to probe fast single-molecule physics or biophysics with high time resolution, making an important contribution to broad fields beyond reaction chemistry. PMID:29487914

Vitrified chemically bonded phosphate ceramics for immobilization of radioisotopes

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

Wagh, Arun S.

2016-04-05

A method of immobilizing a radioisotope and vitrified chemically bonded phosphate ceramic (CBPC) articles formed by the method are described. The method comprises combining a radioisotope-containing material, MgO, a source of phosphate, and optionally, a reducing agent, in water at a temperature of less than 100.degree. C. to form a slurry; curing the slurry to form a solid intermediate CBPC article comprising the radioisotope therefrom; comminuting the intermediate CBPC article, mixing the comminuted material with glass frits, and heating the mixture at a temperature in the range of about 900 to about 1500.degree. C. to form a vitrified CBPC articlemore » comprising the radioisotope immobilized therein.« less

Characterization of the Environmentally Induced Chemical Transformations of Uranium Tetrafluoride

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

Wellons, M.

A key challenge with nuclear safeguards environmental sampling is identification of the materials post release due to subsequent chemical reactions with ambient water and oxygen. Uranium Tetrafluoride (UF4) is of interest as an intermediate in both the upstream and downstream portions of uranium feedstock and metal production processes used in nuclear fuel production; however minimal published research exists relating to UF4 hydrolysis. FY16 efforts were dedicated to in-situ Raman spectroscopy and X-ray diffraction characterization of UF4 during exposure to various relative humidity conditions. This effort mapped several hydrolysis reaction pathways and identified both intermediate, and terminal progeny species.

Geostationary multipurpose platforms

NASA Technical Reports Server (NTRS)

Bekey, I.; Bowman, R. M.

1981-01-01

In addition to the advantages generally associated with orbital platforms, such as improved reliability, economies of scale, simple connectivity of elements, reduced tracking demands and the restraint of orbital object population growth, geostationary platforms yield: (1) continuous access by fixed ground antennas for communications services; (2) continuous monitoring of phenomena over chosen regions of the earth's surface; (3) a preferred location for many solar-terrestrial physics experiments. The geostationary platform also offers a low-risk and economical solution to the impending saturation of the orbital arc/frequency spectrum, maximizing the capacity of individual slots and increasing the utility of the entire arc. It also allows the use of many small, simple and inexpensive earth stations through complexity inversion and high power per beam. Block diagram and operational flowcharts are provided.

Turbine engine airfoil and platform assembly

DOEpatents

Campbell, Christian X [Oviedo, FL; James, Allister W [Chuluota, FL; Morrison, Jay A [Oviedo, FL

2012-07-31

A turbine airfoil (22A) is formed by a first process using a first material. A platform (30A) is formed by a second process using a second material that may be different from the first material. The platform (30A) is assembled around a shank (23A) of the airfoil. One or more pins (36A) extend from the platform into holes (28) in the shank (23A). The platform may be formed in two portions (32A, 34A) and placed around the shank, enclosing it. The two platform portions may be bonded to each other. Alternately, the platform (30B) may be cast around the shank (23B) using a metal alloy with better castability than that of the blade and shank, which may be specialized for thermal tolerance. The pins (36A-36D) or holes for them do not extend to an outer surface (31) of the platform, avoiding stress concentrations.

Isoporphyrin Intermediate in Heme Oxygenase Catalysis

PubMed Central

Evans, John P.; Niemevz, Fernando; Buldain, Graciela; de Montellano, Paul Ortiz

2008-01-01

Human heme oxygenase-1 (hHO-1) catalyzes the O2- and NADPH-dependent oxidation of heme to biliverdin, CO, and free iron. The first step involves regiospecific insertion of an oxygen atom at the α-meso carbon by a ferric hydroperoxide and is predicted to proceed via an isoporphyrin π-cation intermediate. Here we report spectroscopic detection of a transient intermediate during oxidation by hHO-1 of α-meso-phenylheme-IX, α-meso-(p-methylphenyl)-mesoheme-III, and α-meso-(p-trifluoromethylphenyl)-mesoheme-III. In agreement with previous experiments (Wang, J., Niemevz, F., Lad, L., Huang, L., Alvarez, D. E., Buldain, G., Poulos, T. L., and Ortiz de Montellano, P. R. (2004) J. Biol. Chem. 279, 42593–42604), only the α-biliverdin isomer is produced with concomitant formation of the corresponding benzoic acid. The transient intermediate observed in the NADPH-P450 reductase-catalyzed reaction accumulated when the reaction was supported by H2O2 and exhibited the absorption maxima at 435 and 930 nm characteristic of an isoporphyrin. Product analysis by reversed phase high performance liquid chromatography and liquid chromatography electrospray ionization mass spectrometry of the product generated with H2O2 identified it as an isoporphyrin that, on quenching, decayed to benzoylbiliverdin. In the presence of H218O2, one labeled oxygen atom was incorporated into these products. The hHO-1-isoporphyrin complexes were found to have half-lives of 1.7 and 2.4 h for the p-trifluoromethyl- and p-methyl-substituted phenylhemes, respectively. The addition of NADPH-P450 reductase to the H2O2-generated hHO-1-isoporphyrin complex produced α-biliverdin, confirming its role as a reaction intermediate. Identification of an isoporphyrin intermediate in the catalytic sequence of hHO-1, the first such intermediate observed in hemoprotein catalysis, completes our understanding of the critical first step of heme oxidation. PMID:18487208

Cyanobacterial metabolic engineering for biofuel and chemical production.

PubMed

Oliver, Neal J; Rabinovitch-Deere, Christine A; Carroll, Austin L; Nozzi, Nicole E; Case, Anna E; Atsumi, Shota

2016-12-01

Rising levels of atmospheric CO 2 are contributing to the global greenhouse effect. Large scale use of atmospheric CO 2 may be a sustainable and renewable means of chemical and liquid fuel production to mitigate global climate change. Photosynthetic organisms are an ideal platform for efficient, natural CO 2 conversion to a broad range of chemicals. Cyanobacteria are especially attractive for these purposes, due to their genetic malleability and relatively fast growth rate. Recent years have yielded a range of work in the metabolic engineering of cyanobacteria and have led to greater knowledge of the host metabolism. Understanding of endogenous and heterologous carbon regulation mechanisms leads to the expansion of productive capacity and chemical variety. This review discusses the recent progress in metabolic engineering of cyanobacteria for biofuel and bulk chemical production since 2014. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemical vapor deposition reactor. [providing uniform film thickness

NASA Technical Reports Server (NTRS)

Chern, S. S.; Maserjian, J. (Inventor)

1977-01-01

An improved chemical vapor deposition reactor is characterized by a vapor deposition chamber configured to substantially eliminate non-uniformities in films deposited on substrates by control of gas flow and removing gas phase reaction materials from the chamber. Uniformity in the thickness of films is produced by having reactive gases injected through multiple jets which are placed at uniformally distributed locations. Gas phase reaction materials are removed through an exhaust chimney which is positioned above the centrally located, heated pad or platform on which substrates are placed. A baffle is situated above the heated platform below the mouth of the chimney to prevent downdraft dispersion and scattering of gas phase reactant materials.

PR-PR: cross-platform laboratory automation system.

PubMed

Linshiz, Gregory; Stawski, Nina; Goyal, Garima; Bi, Changhao; Poust, Sean; Sharma, Monica; Mutalik, Vivek; Keasling, Jay D; Hillson, Nathan J

2014-08-15

To enable protocol standardization, sharing, and efficient implementation across laboratory automation platforms, we have further developed the PR-PR open-source high-level biology-friendly robot programming language as a cross-platform laboratory automation system. Beyond liquid-handling robotics, PR-PR now supports microfluidic and microscopy platforms, as well as protocol translation into human languages, such as English. While the same set of basic PR-PR commands and features are available for each supported platform, the underlying optimization and translation modules vary from platform to platform. Here, we describe these further developments to PR-PR, and demonstrate the experimental implementation and validation of PR-PR protocols for combinatorial modified Golden Gate DNA assembly across liquid-handling robotic, microfluidic, and manual platforms. To further test PR-PR cross-platform performance, we then implement and assess PR-PR protocols for Kunkel DNA mutagenesis and hierarchical Gibson DNA assembly for microfluidic and manual platforms.

Helicopter Flight Simulation Motion Platform Requirements

NASA Technical Reports Server (NTRS)

Schroeder, Jeffery Allyn

1999-01-01

To determine motion fidelity requirements, a series of piloted simulations was performed. Several key results were found. First, lateral and vertical translational platform cues had significant effects on fidelity. Their presence improved performance and reduced pilot workload. Second, yaw and roll rotational platform cues were not as important as the translational platform cues. In particular, the yaw rotational motion platform cue did not appear at all useful in improving performance or reducing workload. Third, when the lateral translational platform cue was combined with visual yaw rotational cues, pilots believed the platform was rotating when it was not. Thus, simulator systems can be made more efficient by proper combination of platform and visual cues. Fourth, motion fidelity specifications were revised that now provide simulator users with a better prediction of motion fidelity based upon the frequency responses of their motion control laws. Fifth, vertical platform motion affected pilot estimates of steady-state altitude during altitude repositioning. Finally, the combined results led to a general method for configuring helicopter motion systems and for developing simulator tasks that more likely represent actual flight. The overall results can serve as a guide to future simulator designers and to today's operators.

Remission of Intermediate Uveitis: Incidence and Predictive Factors.

PubMed

Kempen, John H; Gewaily, Dina Y; Newcomb, Craig W; Liesegang, Teresa L; Kaçmaz, R Oktay; Levy-Clarke, Grace A; Nussenblatt, Robert B; Rosenbaum, James T; Sen, H Nida; Suhler, Eric B; Thorne, Jennifer E; Foster, C Stephen; Jabs, Douglas A; Payal, Abhishek; Fitzgerald, Tonetta D

2016-04-01

To evaluate the incidence of remission among patients with intermediate uveitis; to identify factors potentially predictive of remission. Retrospective cohort study. Involved eyes of patients with primary noninfectious intermediate uveitis at 4 academic ocular inflammation subspecialty practices, followed sufficiently long to meet the remission outcome definition, were studied retrospectively by standardized chart review data. Remission of intermediate uveitis was defined as a lack of inflammatory activity at ≥2 visits spanning ≥90 days in the absence of any corticosteroid or immunosuppressant medications. Factors potentially predictive of intermediate uveitis remission were evaluated using survival analysis. Among 849 eyes (of 510 patients) with intermediate uveitis followed over 1934 eye-years, the incidence of intermediate uveitis remission was 8.6/100 eye-years (95% confidence interval [CI], 7.4-10.1). Factors predictive of disease remission included prior pars plana vitrectomy (PPV) (hazard ratio [HR] [vs no PPV] = 2.39; 95% CI, 1.42-4.00), diagnosis of intermediate uveitis within the last year (HR [vs diagnosis >5 years ago] =3.82; 95% CI, 1.91-7.63), age ≥45 years (HR [vs age <45 years] = 1.79; 95% CI, 1.03-3.11), female sex (HR = 1.61; 95% CI, 1.04-2.49), and Hispanic race/ethnicity (HR [vs white race] = 2.81; 95% CI, 1.23-6.41). Presence/absence of a systemic inflammatory disease, laterality of uveitis, and smoking status were not associated with differential incidence. Our results suggest that intermediate uveitis is a chronic disease with an overall low rate of remission. Recently diagnosed patients and older, female, and Hispanic patients were more likely to remit. With regard to management, pars plana vitrectomy was associated with increased probability of remission. Copyright © 2016 Elsevier Inc. All rights reserved.

Remission of Intermediate Uveitis: Incidence and Predictive Factors

PubMed Central

Kempen, John H.; Gewaily, Dina Y.; Newcomb, Craig W.; Liesegang, Teresa L.; Kaçmaz, R. Oktay; Levy-Clarke, Grace A.; Nussenblatt, Robert B.; Rosenbaum, James T.; Sen, H. Nida; Suhler, Eric B.; Thorne, Jennifer E.; Foster, C. Stephen; Jabs, Douglas A.; Payal, Abhishek; Fitzgerald, Tonetta D.

2016-01-01

Purpose To evaluate the incidence of remission among patients with intermediate uveitis; to identify factors potentially predictive of remission. Design Retrospective cohort study. Methods Involved eyes of patients with primary non-infectious intermediate uveitis at 4 academic ocular inflammation subspecialty practices, followed sufficiently long to meet the remission outcome definition, were studied retrospectively by standardized chart review data. Remission of intermediate uveitis was defined as a lack of inflammatory activity at ≥2 visits spanning ≥90 days in the absence of any corticosteroid or immunosuppressant medications. Factors potentially predictive of intermediate uveitis remission were evaluated using survival analysis. Results Among 849 eyes (of 510 patients) with intermediate uveitis followed over 1,934 eye-years, the incidence of intermediate uveitis remission was 8.6/100 eye-years (95% confidence interval (CI), 7.4–10.1). Factors predictive of disease remission included prior pars plana vitrectomy (PPV) (HR (vs. no PPV)=2.39; 95% CI, 1.42–4.00), diagnosis of intermediate uveitis within the last year (vs. diagnosis >5 years ago)=3.82; 95% CI, 1.91–7.63), age ≥45 years (HR (vs. age <45 years)=1.79; 95% CI, 1.03–3.11), female sex (HR=1.61; 95% CI, 1.04–2.49), and Hispanic race/ethnicity (HR (vs. white race)=2.81; 95% CI, 1.23–6.41). Presence/absence of a systemic inflammatory disease, laterality of uveitis, and smoking status were not associated with differential incidence. Conclusions Our results suggest that intermediate uveitis is a chronic disease with an overall low rate of remission. Recently diagnosed cases, and older, female and Hispanic cases were more likely to remit. With regards to management, pars plana vitrectomy was associated with increased probability of remission. PMID:26772874

Marine Engine Mechanics. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Jones, Marion

Several intermediate performance objectives and corresponding criterion measures are presented for each of ten terminal objectives for a two-semester course (3 hours daily). This 540-hour intermediate course includes advanced troubleshooting techniques on outboard marine engines, inboard-outboard marine engines, inboard marine engines, boat…

A Label-Free, Quantitative Fecal Hemoglobin Detection Platform for Colorectal Cancer Screening

PubMed Central

Soraya, Gita V.; Nguyen, Thanh C.; Abeyrathne, Chathurika D.; Huynh, Duc H.; Chan, Jianxiong; Nguyen, Phuong D.; Nasr, Babak; Chana, Gursharan; Kwan, Patrick; Skafidas, Efstratios

2017-01-01

The early detection of colorectal cancer is vital for disease management and patient survival. Fecal hemoglobin detection is a widely-adopted method for screening and early diagnosis. Fecal Immunochemical Test (FIT) is favored over the older generation chemical based Fecal Occult Blood Test (FOBT) as it does not require dietary or drug restrictions, and is specific to human blood from the lower digestive tract. To date, no quantitative FIT platforms are available for use in the point-of-care setting. Here, we report proof of principle data of a novel low cost quantitative fecal immunochemical-based biosensor platform that may be further developed into a point-of-care test in low-resource settings. The label-free prototype has a lower limit of detection (LOD) of 10 µg hemoglobin per gram (Hb/g) of feces, comparable to that of conventional laboratory based quantitative FIT diagnostic systems. PMID:28475117

Cretaceous tropical carbonate platform changes used as paleoclimatic and paleoceanic indicators: the three lower Cretaceous platform crises

NASA Astrophysics Data System (ADS)

Arnaud-Vanneau, A.; Vrielynck, B.

2009-04-01

Carbonate platform sediments are of biogenic origin. More commonly the bioclasts are fragments of shells and skeletons. The bioclastic composition of a limestone may reflect the nature of biota inhabiting the area and a carbonate platform can be estimated as a living factory, which reflects the prevailing ecological factors. The rate of carbonate production is highest in the tropics, in oligotrophic environments, and in the photic zone. The rate of carbonate production varies greatly with temperature and nutrient input. Three types of biotic carbonate platform can be distinguished. The highest carbonate production is linked to oligotrophic carbonate platform characterized by the presence of assemblages with hermatypic corals. This type of platform is developed in shallow marine environment, nutrient poor water and warm tropical sea. A less efficient production of carbonate platform is related to mesotrophic environments in cooler and/or deeper water and associated to nutrient flux with, sometime, detrital input. The biota includes red algae, solitary coral and branching ahermatypic corals, common bryozoans, crinoids and echinoids. The less productive carbonate platform is the eutrophic muddy platform where the mud is due to the intense bacterial activity, probably related to strong nutrient flux. All changes of type of carbonate platform can be related to climatic and oceanic changes. Three platform crises occurred during lower Cretaceous time. They are followed by important turnover of microfauna (large benthic foraminifers) and microflora (marine algae). They start with the demise of the previous oligotrophic platform, they continue with oceanic perturbations, expression of which was the widespread deposition of organic-rich sediments, well expressed during Late Aptian/Albian and Cenomanian Turonian boundary and the replacement of previous oligotrophic platforms by mesotrophic to eutrophic platforms. The first crisis occurred during Valanginian and Hauterivian

A novel hydrogel based piezoresistive pressure sensor platform for chemical sensing

NASA Astrophysics Data System (ADS)

Orthner, Michael P.

New hydrogel-based micropressure sensor arrays for use in the fields of chemical sensing, physiological monitoring, and medical diagnostics are developed and demonstrated. This sensor technology provides reliable, linear, and accurate measurements of hydrogel swelling pressures, a function of ambient chemical concentrations. For the first time, perforations were implemented into the pressure sensors piezoresistive diaphragms, used to simultaneously increase sensor sensitivity and permit diffusion of analytes into the hydrogel cavity. It was shown through analytical and numerical (finite element) methods that pore shape, location, and size can be used to modify the diaphragm mechanics and concentrate stress within the piezoresistors, thus improving electrical output (sensitivity). An optimized pore pattern was chosen based on these numerical calculations. Fabrication was performed using a 14-step semiconductor fabrication process implementing a combination of potassium hydroxide (KOH) and deep reactive ion etching (DRIE) to create perforations. The sensor arrays (2x2) measure approximately 3 x 5 mm2 and used to measure full scale pressures of 50, 25, and 5 kPa, respectively. These specifications were defined by the various swelling pressures of ionic strength, pH and glucose specific hydrogels that were targeted in this work. Initial characterization of the sensor arrays was performed using a custom built bulge testing apparatus that simultaneously measured deflection (optical profilometry), pressure, and electrical output. The new perforated diaphragm sensors were found to be fully functional with sensitivities ranging from 23 to 252 muV/V-kPa with full scale output (FSO) ranging from 5 to 80 mV. To demonstrate proof of concept, hydrogels sensitive to changes in ionic strength were synthesized using hydroxypropyl-methacrylate (HPMA), N,N-dimethylaminoethyl-methacrylate (DMA) and a tetra-ethyleneglycol-dimethacrylate (TEGDMA) crosslinker. This hydrogel quickly and

Femtosecond laser fabrication of fiber based optofluidic platform for flow cytometry applications

NASA Astrophysics Data System (ADS)

Serhatlioglu, Murat; Elbuken, Caglar; Ortac, Bulend; Solmaz, Mehmet E.

2017-02-01

Miniaturized optofluidic platforms play an important role in bio-analysis, detection and diagnostic applications. The advantages of such miniaturized devices are extremely low sample requirement, low cost development and rapid analysis capabilities. Fused silica is advantageous for optofluidic systems due to properties such as being chemically inert, mechanically stable, and optically transparent to a wide spectrum of light. As a three dimensional manufacturing method, femtosecond laser scanning followed by chemical etching shows great potential to fabricate glass based optofluidic chips. In this study, we demonstrate fabrication of all-fiber based, optofluidic flow cytometer in fused silica glass by femtosecond laser machining. 3D particle focusing was achieved through a straightforward planar chip design with two separately fabricated fused silica glass slides thermally bonded together. Bioparticles in a fluid stream encounter with optical interrogation region specifically designed to allocate 405nm single mode fiber laser source and two multi-mode collection fibers for forward scattering (FSC) and side scattering (SSC) signals detection. Detected signal data collected with oscilloscope and post processed with MATLAB script file. We were able to count number of events over 4000events/sec, and achieve size distribution for 5.95μm monodisperse polystyrene beads using FSC and SSC signals. Our platform shows promise for optical and fluidic miniaturization of flow cytometry systems.

Helicopter flight simulation motion platform requirements

NASA Astrophysics Data System (ADS)

Schroeder, Jeffery Allyn

Flight simulators attempt to reproduce in-flight pilot-vehicle behavior on the ground. This reproduction is challenging for helicopter simulators, as the pilot is often inextricably dependent on external cues for pilot-vehicle stabilization. One important simulator cue is platform motion; however, its required fidelity is unknown. To determine the required motion fidelity, several unique experiments were performed. A large displacement motion platform was used that allowed pilots to fly tasks with matched motion and visual cues. Then, the platform motion was modified to give cues varying from full motion to no motion. Several key results were found. First, lateral and vertical translational platform cues had significant effects on fidelity. Their presence improved performance and reduced pilot workload. Second, yaw and roll rotational platform cues were not as important as the translational platform cues. In particular, the yaw rotational motion platform cue did not appear at all useful in improving performance or reducing workload. Third, when the lateral translational platform cue was combined with visual yaw rotational cues, pilots believed the platform was rotating when it was not. Thus, simulator systems can be made more efficient by proper combination of platform and visual cues. Fourth, motion fidelity specifications were revised that now provide simulator users with a better prediction of motion fidelity based upon the frequency responses of their motion control laws. Fifth, vertical platform motion affected pilot estimates of steady-state altitude during altitude repositionings. This refutes the view that pilots estimate altitude and altitude rate in simulation solely from visual cues. Finally, the combined results led to a general method for configuring helicopter motion systems and for developing simulator tasks that more likely represent actual flight. The overall results can serve as a guide to future simulator designers and to today's operators.

High-resolution experiments on chemical oxidation of DNAPL in variable-aperture fractures

NASA Astrophysics Data System (ADS)

Arshadi, Masoud; Rajaram, Harihar; Detwiler, Russell L.; Jones, Trevor

2015-04-01

Chemical oxidation of dense nonaqueous-phase liquids (DNAPLs) by permanganate has emerged as an effective remediation strategy in fractured rock. We present high-resolution experimental investigations in transparent analog variable-aperture fractures to improve understanding of chemical oxidation of residual entrapped trichloroethylene (TCE) in fractures. Four experiments were performed with different permanganate concentrations, flow rates, and initial TCE phase geometry. The initial aperture field and evolving entrapped-phase geometry were quantified for each experiment. The integrated mass transfer rate from the TCE phase for all experiments exhibited three time regimes: an early-time regime with slower mass transfer rates limited by low specific interfacial area; an intermediate-time regime with higher mass transfer rates resulting from breakup of large TCE blobs, which greatly increases specific interfacial area; and a late-time regime with low mass transfer rates due to the deposition of MnO2 precipitates. In two experiments, mass balance analyses suggested that TCE mass removal rates exceeded the maximum upper bound mass removal rates derived by assuming that oxidation and dissolution are the only mechanisms for TCE mass removal. We propose incomplete oxidation by permanganate and TCE solubility enhancement by intermediate reaction products as potential mechanisms to explain this behavior. We also speculate that some intermediate reaction products with surfactant-like properties may play a role in lowering the TCE-water interfacial tension, thus causing breakup of large TCE blobs. Our quantitative experimental measurements will be useful in the context of developing accurate computational models for chemical oxidation of TCE in fractures.

Tailoring protein nanomechanics with chemical reactivity

PubMed Central

Beedle, Amy E. M.; Mora, Marc; Lynham, Steven; Stirnemann, Guillaume; Garcia-Manyes, Sergi

2017-01-01

The nanomechanical properties of elastomeric proteins determine the elasticity of a variety of tissues. A widespread natural tactic to regulate protein extensibility lies in the presence of covalent disulfide bonds, which significantly enhance protein stiffness. The prevalent in vivo strategy to form disulfide bonds requires the presence of dedicated enzymes. Here we propose an alternative chemical route to promote non-enzymatic oxidative protein folding via disulfide isomerization based on naturally occurring small molecules. Using single-molecule force-clamp spectroscopy, supported by DFT calculations and mass spectrometry measurements, we demonstrate that subtle changes in the chemical structure of a transient mixed-disulfide intermediate adduct between a protein cysteine and an attacking low molecular-weight thiol have a dramatic effect on the protein's mechanical stability. This approach provides a general tool to rationalize the dynamics of S-thiolation and its role in modulating protein nanomechanics, offering molecular insights on how chemical reactivity regulates protein elasticity. PMID:28585528

PR-PR: Cross-Platform Laboratory Automation System

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

Linshiz, G; Stawski, N; Goyal, G

To enable protocol standardization, sharing, and efficient implementation across laboratory automation platforms, we have further developed the PR-PR open-source high-level biology-friendly robot programming language as a cross-platform laboratory automation system. Beyond liquid-handling robotics, PR-PR now supports microfluidic and microscopy platforms, as well as protocol translation into human languages, such as English. While the same set of basic PR-PR commands and features are available for each supported platform, the underlying optimization and translation modules vary from platform to platform. Here, we describe these further developments to PR-PR, and demonstrate the experimental implementation and validation of PR-PR protocols for combinatorial modified Goldenmore » Gate DNA assembly across liquid-handling robotic, microfluidic, and manual platforms. To further test PR-PR cross-platform performance, we then implement and assess PR-PR protocols for Kunkel DNA mutagenesis and hierarchical Gibson DNA assembly for microfluidic and manual platforms.« less

Electron microscopic observations of mouse sperm whole mounts after extraction for nuclear matrix and intermediate filaments.

PubMed

Markova, M D

2001-01-01

Nuclear matrix and intermediate filaments (NM-IF) can be isolated by sequential treatment with non-ionic detergent, high salt. and nuclease. Extracted cells are easily observed by unembedded whole-mount transmission electron microscopy. Different somatic cell types have been subjected to this procedure and retained their essential architecture. To our knowledge, this work describes the first application of NM-IF extraction to sperm. After chemical dissection the general appearance of mouse sperm cells was preserved, except for head-from-neck separation in some cases. The cell membrane, acrosome and mitochondria were not present. The nucleus showed no apparent changes and revealed no details excepting pore complexes in the posterior part. Tissue-specific cytoskeletal elements (perforatorium, postacrosomal sheath, capitulum, segmented columns, outer dense fibers, submitochondrial reticulum, annulus, and fibrous sheath) were retained, which permitted a parallel between them and intermediate filaments of somatic cells. Tail microtubules were also relatively well preserved, showing high intrinsic stability. Cell structures could be observed well, with some details in the tail even better visible than in ultrathin sections. Observation of mouse sperm whole mounts after NM-IF extraction not only revealed intermediate filament-like properties of their cytoskeletal elements but also offered an additional viewpoint to sperm ultrastructure.

The second national audit of intermediate care.

PubMed

Young, John; Gladman, John R F; Forsyth, Duncan R; Holditch, Claire

2015-03-01

Intermediate care services have developed internationally to expedite discharge from hospital and to provide an alternative to an emergency hospital admission. Inconsistencies in the evidence base and under-developed governance structures led to concerns about the care quality, outcomes and provision of intermediate care in the NHS. The National Audit of Intermediate Care was therefore established by an interdisciplinary group. The second national audit reported in 2013 and included crisis response teams, home-based and bed-based services in approximately a half of the NHS. The main findings were evidence of weak local strategic planning, considerable under-provision, delays in accessing the services and lack of mental health involvement in care. There was a very high level of positive patient experience reported across all types of intermediate care, though reported involvement with care decisions was less satisfactory. © The Author 2014. Published by Oxford University Press on behalf of the British Geriatrics Society. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Antibiotic Algae by Chemical Surface Engineering.

PubMed

Kerschgens, Isabel P; Gademann, Karl

2018-03-02

Chemical cell-surface engineering is a tool for modifying and altering cellular functions. Herein, we report the introduction of an antibiotic phenotype to the green alga Chlamydomonas reinhardtii by chemically modifying its cell surface. Flow cytometry and confocal microscopy studies demonstrated that a hybrid of the antibiotic vancomycin and a 4-hydroxyproline oligomer binds reversibly to the cell wall without affecting the viability or motility of the cells. The modified cells were used to inhibit bacterial growth of Gram-positive Bacillus subtilis cultures. Delivery of the antibiotic from the microalgae to the bacterial cells was verified by microscopy. Our studies provide compelling evidence that 1) chemical surface engineering constitutes a useful tool for the introduction of new, previously unknown functionality, and 2) living microalgae can serve as new platforms for drug delivery. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Large-Scale Chemical Similarity Networks for Target Profiling of Compounds Identified in Cell-Based Chemical Screens

PubMed Central

Lo, Yu-Chen; Senese, Silvia; Li, Chien-Ming; Hu, Qiyang; Huang, Yong; Damoiseaux, Robert; Torres, Jorge Z.

2015-01-01

Target identification is one of the most critical steps following cell-based phenotypic chemical screens aimed at identifying compounds with potential uses in cell biology and for developing novel disease therapies. Current in silico target identification methods, including chemical similarity database searches, are limited to single or sequential ligand analysis that have limited capabilities for accurate deconvolution of a large number of compounds with diverse chemical structures. Here, we present CSNAP (Chemical Similarity Network Analysis Pulldown), a new computational target identification method that utilizes chemical similarity networks for large-scale chemotype (consensus chemical pattern) recognition and drug target profiling. Our benchmark study showed that CSNAP can achieve an overall higher accuracy (>80%) of target prediction with respect to representative chemotypes in large (>200) compound sets, in comparison to the SEA approach (60–70%). Additionally, CSNAP is capable of integrating with biological knowledge-based databases (Uniprot, GO) and high-throughput biology platforms (proteomic, genetic, etc) for system-wise drug target validation. To demonstrate the utility of the CSNAP approach, we combined CSNAP's target prediction with experimental ligand evaluation to identify the major mitotic targets of hit compounds from a cell-based chemical screen and we highlight novel compounds targeting microtubules, an important cancer therapeutic target. The CSNAP method is freely available and can be accessed from the CSNAP web server (http://services.mbi.ucla.edu/CSNAP/). PMID:25826798

Urinary Loss of Tricarboxylic Acid Cycle Intermediates As Revealed by Metabolomics Studies: An Underlying Mechanism to Reduce Lipid Accretion by Whey Protein Ingestion?

PubMed Central

2015-01-01

Whey protein intake is associated with the modulation of energy metabolism and altered body composition both in human subjects and in animals, but the underlying mechanisms are not yet elucidated. We fed obesity-prone C57BL/6J mice high-fat diets with either casein (HF casein) or whey (HF whey) for 6 weeks. At equal energy intake and apparent fat and nitrogen digestibility, mice fed HF whey stored less energy as lipids, evident both as lower white adipose tissue mass and as reduced liver lipids, compared with HF-casein-fed mice. Explorative analyses of 48 h urine, both by 1H NMR and LC–MS metabolomic platforms, demonstrated higher urinary excretion of tricarboxylic acid (TCA) cycle intermediates citric acid and succinic acid (identified by both platforms), and cis-aconitic acid and isocitric acid (identified by LC–MS platform) in the HF whey, relative to in the HF-casein-fed mice. Targeted LC–MS analyses revealed higher citric acid and cis-aconitic acid concentrations in fed state plasma, but not in liver of HF-whey-fed mice. We propose that enhanced urinary loss of TCA cycle metabolites drain available substrates for anabolic processes, such as lipogenesis, thereby leading to reduced lipid accretion in HF-whey-fed compared to HF-casein-fed mice. PMID:24702026

Vertical silicon nanowires as a universal platform for delivering biomolecules into living cells

PubMed Central

Shalek, Alex K.; Robinson, Jacob T.; Karp, Ethan S.; Lee, Jin Seok; Ahn, Dae-Ro; Yoon, Myung-Han; Sutton, Amy; Jorgolli, Marsela; Gertner, Rona S.; Gujral, Taranjit S.; MacBeath, Gavin; Yang, Eun Gyeong; Park, Hongkun

2010-01-01

A generalized platform for introducing a diverse range of biomolecules into living cells in high-throughput could transform how complex cellular processes are probed and analyzed. Here, we demonstrate spatially localized, efficient, and universal delivery of biomolecules into immortalized and primary mammalian cells using surface-modified vertical silicon nanowires. The method relies on the ability of the silicon nanowires to penetrate a cell’s membrane and subsequently release surface-bound molecules directly into the cell’s cytosol, thus allowing highly efficient delivery of biomolecules without chemical modification or viral packaging. This modality enables one to assess the phenotypic consequences of introducing a broad range of biological effectors (DNAs, RNAs, peptides, proteins, and small molecules) into almost any cell type. We show that this platform can be used to guide neuronal progenitor growth with small molecules, knock down transcript levels by delivering siRNAs, inhibit apoptosis using peptides, and introduce targeted proteins to specific organelles. We further demonstrate codelivery of siRNAs and proteins on a single substrate in a microarray format, highlighting this technology’s potential as a robust, monolithic platform for high-throughput, miniaturized bioassays. PMID:20080678

Automotive Body Repair. Performance Objectives. Intermediate Course.

ERIC Educational Resources Information Center

Lang, Thomas

Several intermediate performance objectives and corresponding criterion measures are listed for each of 10 terminal objectives for an intermediate automotive body repair and refinishing course. The materials were developed for a two-semester (3 hours daily) course for specialized classrooms, shop, and practical experiences designed to enable the…

Intermediate scale plasma density irregularities in the polar ionosphere inferred from radio occultation

NASA Astrophysics Data System (ADS)

Shume, E. B.; Komjathy, A.; Langley, R. B.; Verkhoglyadova, O. P.; Butala, M.; Mannucci, A. J.

2014-12-01

In this research, we report intermediate scale plasma density irregularities in the high-latitude ionosphere inferred from high-resolution radio occultation (RO) measurements in the CASSIOPE (CAScade Smallsat and IOnospheric Polar Explorer) - GPS (Global Positioning System) satellites radio link. The high inclination of the CASSIOPE satellite and high rate of signal receptionby the occultation antenna of the GPS Attitude, Positioning and Profiling (GAP) instrument on the Enhanced Polar Outflow Probe platform on CASSIOPE enable a high temporal and spatial resolution investigation of the dynamics of the polar ionosphere, magnetosphere-ionospherecoupling, solar wind effects, etc. with unprecedented details compared to that possible in the past. We have carried out high spatial resolution analysis in altitude and geomagnetic latitude of scintillation-producing plasma density irregularities in the polar ionosphere. Intermediate scale, scintillation-producing plasma density irregularities, which corresponds to 2 to 40 km spatial scales were inferred by applying multi-scale spectral analysis on the RO phase delay measurements. Using our multi-scale spectral analysis approach and Polar Operational Environmental Satellites (POES) and Defense Meteorological Satellite Program (DMSP) observations, we infer that the irregularity scales and phase scintillations have distinct features in the auroral oval and polar cap regions. In specific terms, we found that large length scales and and more intense phase scintillations are prevalent in the auroral oval compared to the polar cap region. Hence, the irregularity scales and phase scintillation characteristics are a function of the solar wind and the magnetospheric forcing. Multi-scale analysis may become a powerful diagnostic tool for characterizing how the ionosphere is dynamically driven by these factors.

Cyclohexane isomerization. Unimolecular dynamics of the twist-boat intermediate.

PubMed

Kakhiani, Khatuna; Lourderaj, Upakarasamy; Hu, Wenfang; Birney, David; Hase, William L

2009-04-23

Direct dynamics simulations were performed at the HF/6-31G level of theory to investigate the intramolecular and unimolecuar dynamics of the twist-boat (TB) intermediate on the cyclohexane potential energy surface (PES). Additional calculations were performed at the MP2/aug-cc-pVDZ level of theory to further characterize the PES's stationary points. The trajectories were initiated at the C(1) and C(2) half-chair transition states (TSs) connecting a chair conformer with a TB intermediate, via an intrinsic reaction coordinate (IRC). Energy was added in accord with a microcanonical ensemble at the average energy for experiments at 263 K. Important nontransition state theory (TST), non-IRC, and non-RRKM dynamics were observed in the simulations. Trajectories initially directed toward the chair conformer had a high probability of recrossing the TS, with approximately 30% forming a TB intermediate instead of accessing the potential energy well for the conformer. The TB intermediate initially formed was not necessarily the one connected to the TS via the IRC. Of the trajectories initiated at the C(2) half-chair TS and initially directed toward the chair conformer, 35% formed a TB intermediate instead of the chair conformer. Also, of the trajectories forming a TB intermediate, only 16% formed the TB intermediate connected with the C(2) TS via the IRC. Up to eight consecutive TB --> TB isomerizations were followed, and non-RRKM behavior was observed in their dynamics. A TB can isomerize to two different TBs, one by a clockwise rotation of C-C-C-C dihedral angles and the other by a counterclockwise rotation. In contrast to RRKM theory, which predicts equivalent probabilities for these rotations, the trajectory dynamics show they are not equivalent and depend on whether the C(1) or C(2) half-chair TS is initially excited. Non-RRKM dynamics is also observed in the isomerization of the TB intermediates to the chair conformers. RRKM theory assumes equivalent probabilities for

Platform options for the Space Station program

NASA Technical Reports Server (NTRS)

Mangano, M. J.; Rowley, R. W.

1986-01-01

Platforms for polar and 28.5 deg orbits were studied to determine the platform requirements and characteristics necessary to support the science objectives. Large platforms supporting the Earth-Observing System (EOS) were initially studied. Co-orbiting platforms were derived from these designs. Because cost estimates indicated that the large platform approach was likely to be too expensive, require several launches, and generally be excessively complex, studies of small platforms were undertaken. Results of these studies show the small platform approach to be technically feasible at lower overall cost. All designs maximized hardware inheritance from the Space Station program to reduce costs. Science objectives as defined at the time of these studies are largely achievable.

High-Level, First-Principles, Full-Dimensional Quantum Calculation of the Ro-vibrational Spectrum of the Simplest Criegee Intermediate (CH2OO).

PubMed

Li, Jun; Carter, Stuart; Bowman, Joel M; Dawes, Richard; Xie, Daiqian; Guo, Hua

2014-07-03

The ro-vibrational spectrum of the simplest Criegee intermediate (CH2OO) has been determined quantum mechanically based on nine-dimensional potential energy and dipole surfaces for its ground electronic state. The potential energy surface is fitted to more than 50 000 high-level ab initio points with a root-mean-square error of 25 cm(-1), using a recently proposed permutation invariant polynomial neural network method. The calculated rotational constants, vibrational frequencies, and spectral intensities of CH2OO are in excellent agreement with experiment. The potential energy surface provides a valuable platform for studying highly excited vibrational and unimolecular reaction dynamics of this important molecule.

Intermediate-energy nuclear chemistry workshop

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

Butler, G.W.; Giesler, G.C.; Liu, L.C.

1981-05-01

This report contains the proceedings of the LAMPF Intermediate-Energy Nuclear Chemistry Workshop held in Los Alamos, New Mexico, June 23-27, 1980. The first two days of the Workshop were devoted to invited review talks highlighting current experimental and theoretical research activities in intermediate-energy nuclear chemistry and physics. Working panels representing major topic areas carried out indepth appraisals of present research and formulated recommendations for future research directions. The major topic areas were Pion-Nucleus Reactions, Nucleon-Nucleus Reactions and Nuclei Far from Stability, Mesonic Atoms, Exotic Interactions, New Theoretical Approaches, and New Experimental Techniques and New Nuclear Chemistry Facilities.

Membrane Fission: Model for Intermediate Structures

PubMed Central

Kozlovsky, Yonathan; Kozlov, Michael M.

2003-01-01

Membrane budding-fission is a fundamental process generating intracellular carriers of proteins. Earlier works were focused only on formation of coated buds connected to the initial membrane by narrow membrane necks. We present the theoretical analysis of the whole pathway of budding-fission, including the crucial stage where the membrane neck undergoes fission and the carrier separates from the donor membrane. We consider two successive intermediates of the reaction: 1), a constricted membrane neck coming out of aperture of the assembling protein coat, and 2), hemifission intermediate resulting from self-fusion of the inner monolayer of the neck, while its outer monolayer remains continuous. Transformation of the constricted neck into the hemifission intermediate is driven by the membrane stress produced in the neck by the protein coat. Although apparently similar to hemifusion, the fission is predicted to have an opposite dependence on the monolayer spontaneous curvature. Analysis of the further stages of the process demonstrates that in all practically important cases the hemifission intermediate decays spontaneously into two separate membranes, thereby completing the fission process. We formulate the “job description” for fission proteins by calculating the energy they have to deliver and the radii of the protein coat aperture which have to be reached to drive the fission process. PMID:12829467

The ARES High-level Intermediate Representation