Sample records for absorbed water molecules

  1. A Raman spectroscopy study on the effects of intermolecular hydrogen bonding on water molecules absorbed by borosilicate glass surface

    NASA Astrophysics Data System (ADS)

    Li, Fabing; Li, Zhanlong; Wang, Ying; Wang, Shenghan; Wang, Xiaojun; Sun, Chenglin; Men, Zhiwei

    2018-05-01

    The structural forms of water/deuterated water molecules located on the surface of borosilicate capillaries have been first investigated in this study on the basis of the Raman spectral data obtained at different temperatures and under atmospheric pressure for molecules in bulk and also for molecules absorbed by borosilicate glass surface. The strongest two fundamental bands locating at 3063 cm-1 (2438 cm-1) in the recorded Raman spectra are assigned here to the Osbnd H (Osbnd D) bond stretching vibrations and they are compared with the corresponding bands observed at 3124 cm-1 (2325 cm-1) in the Raman spectrum of ice Ih. Our spectroscopic observations have indicated that the structure of water and deuterated water molecules on borosilicate surface is similar to that of ice Ih (hexagonal phase of ice). These observations have also indicated that water molecules locate on the borosilicate surface so as to construct a bilayer structure and that strong and weak intermolecular hydrogen bonds are formed between water/deuterated molecules and silanol groups on borosilicate surface. In accordance with these findings, water and deuterated water molecules at the interface of capillary have a higher melting temperature.

  2. Liposomogenic UV Absorbers are Water-Resistant on Pig Skin-A Model Study With Relevance for Sunscreens.

    PubMed

    Herzog, Bernd; Hüglin, Dietmar; Luther, Helmut

    2017-02-01

    An important property of sunscreens is their water resistance after the application on human skin. In this work, the hypothesis that UV absorber molecules which are able to form liposomes, so-called liposomogenic UV absorbers, show better water resistance on a pig skin model than UV-absorbing molecules lacking this ability was tested. The assumption behind is that molecules which can form liposomes are able to integrate into the stratum corneum lipids of the skin. Three different liposomogenic UV absorbers were synthesized and their behavior investigated, leading to the confirmation of the hypothesis. With one of the liposomogenic UV absorbers, it was possible to show the integration of the UV absorber molecules into the bilayers of another liposome consisting of phosphatidylcholine, supporting the assumption that liposomogenic UV absorbers exhibit improved water resistance because they integrate into the skin lipids. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  3. Dual band metamaterial perfect absorber based on artificial dielectric "molecules".

    PubMed

    Liu, Xiaoming; Lan, Chuwen; Li, Bo; Zhao, Qian; Zhou, Ji

    2016-07-13

    Dual band metamaterial perfect absorbers with two absorption bands are highly desirable because of their potential application areas such as detectors, transceiver system, and spectroscopic imagers. However, most of these dual band metamaterial absorbers proposed were based on resonances of metal patterns. Here, we numerically and experimentally demonstrate a dual band metamaterial perfect absorber composed of artificial dielectric "molecules" with high symmetry. The artificial dielectric "molecule" consists of four "atoms" of two different sizes corresponding to two absorption bands with near unity absorptivity. Numerical and experimental absorptivity verify that the dual-band metamaterial absorber is polarization insensitive and can operate in wide-angle incidence.

  4. Ultraviolet light absorbers having two different chromophors in the same molecule

    DOEpatents

    Vogl, O.; Li, S.

    1983-10-06

    This invention relates to novel ultraviolet light absorbers having two chromophors in the same molecule, and more particularly to benzotriazole substituted dihydroxybenzophenones and acetophenones. More particularly, this invention relates to 3,5-(di(2H-benzotriazole-2-yl))-2,4-dihydroxybenzophenone and 3,5-(di(2H-benzotriazole-2-yl))-2,4-dihydroxyacetophenone which are particularly useful as an ultraviolet light absorbers.

  5. Kevlar based nanofibrous particles as robust, effective and recyclable absorbents for water purification.

    PubMed

    Nie, Chuanxiong; Peng, Zihang; Yang, Ye; Cheng, Chong; Ma, Lang; Zhao, Changsheng

    2016-11-15

    Developing robust and recyclable absorbents for water purification is of great demand to control water pollution and to provide sustainable water resources. Herein, for the first time, we reported the fabrication of Kevlar nanofiber (KNF) based composite particles for water purification. Both the KNF and KNF-carbon nanotube composite particles can be produced in large-scale by automatic injection of casting solution into ethanol. The resulted nanofibrous particles showed high adsorption capacities towards various pollutants, including metal ions, phenylic compounds and various dyes. Meanwhile, the adsorption process towards dyes was found to fit well with the pseudo-second-order model, while the adsorption speed was controlled by intraparticle diffusion. Furthermore, the adsorption capacities of the nanofibrous particles could be easily recovered by washing with ethanol. In general, the KNF based particles integrate the advantages of easy production, robust and effective adsorption performances, as well as good recyclability, which can be used as robust absorbents to remove toxic molecules and forward the application of absorbents in water purification. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Super water-absorbing new material from chitosan, EDTA and urea.

    PubMed

    Narayanan, Abathodharanan; Dhamodharan, Raghavachari

    2015-12-10

    A new, super water-absorbing, material is synthesized by the reaction between chitosan, EDTA and urea and named as CHEDUR. CHEDUR is probably formed through the crosslinking of chitosan molecules (CH) with the EDTA-urea (EDUR) adduct that is formed during the reaction. CHEDUR as well as the other products formed in control reactions are characterized extensively. CHEDUR exhibits a very high water uptake capacity when compared with chitosan, chitosan-EDTA adduct, as well as a commercial diaper material. A systematic study was done to find the optimum composition as well as reaction conditions for maximum water absorbing capacity. CHEDUR can play a vital role in applications that demand the rapid absorption and slow release of water such as agriculture, as a three in one new material for the slow release of urea, water and other metal ions that can be attached through the EDTA component. The other potential advantage of CHEDUR is that it can be expected to degrade in soil based on its chitosan backbone. The new material with rapid and high water uptake could also find potential applications as biodegradable active ingredient of the diaper material. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Chemical structure-nonlinear optical property relationships for a series of two-photon absorbing fluorene molecules

    NASA Astrophysics Data System (ADS)

    Hales, Joel Mccajah

    This dissertation reports on the investigation of two-photon absorption (2PA) in a series of fluorenyl molecules. Several current and emerging technologies exploit this optical nonlinearity including two-photon fluorescence imaging, three-dimensional microfabrication, site-specific photodynamic cancer therapy and biological caging studies. The two key features of this nonlinearity which make it an ideal candidate for the above applications are its quadratic dependence on the incident irradiance and the improved penetration into absorbing media that it affords. As a consequence of the burgeoning field which exploits 2PA, it is a goal to find materials that exhibit strong two-photon absorbing capabilities. Organic materials are promising candidates for 2PA applications because their material properties can be tailored through molecular engineering thereby facilitating optimization of their nonlinear optical properties. Fluorene derivatives are particularly interesting since they possess high photochemical stability for organic molecules and are generally strongly fluorescent. By systematically altering the structural properties in a series of fluorenyl molecules, we have determined how these changes affect their two-photon absorbing capabilities. This was accomplished through characterization of both the strength and location of their 2PA spectra. In order to ensure the validity of these results, three separate nonlinear characterization techniques were employed: two-photon fluorescence spectroscopy, white-light continuum pump-probe spectroscopy, and the Z-scan technique. In addition, full linear spectroscopic characterization was performed on these molecules along with supplementary quantum chemical calculations to obtain certain molecular properties that might impact the nonlinearity. Different designs in chemical architecture allowed investigation of the effects of symmetry, solvism, donor-acceptor strengths, conjugation length, and multi-branched geometries on

  8. Metamaterial Absorber for Electromagnetic Waves in Periodic Water Droplets

    PubMed Central

    Yoo, Young Joon; Ju, Sanghyun; Park, Sang Yoon; Ju Kim, Young; Bong, Jihye; Lim, Taekyung; Kim, Ki Won; Rhee, Joo Yull; Lee, YoungPak

    2015-01-01

    Perfect metamaterial absorber (PMA) can intercept electromagnetic wave harmful for body in Wi-Fi, cell phones and home appliances that we are daily using and provide stealth function that military fighter, tank and warship can avoid radar detection. We reported new concept of water droplet-based PMA absorbing perfectly electromagnetic wave with water, an eco-friendly material which is very plentiful on the earth. If arranging water droplets with particular height and diameter on material surface through the wettability of material surface, meta-properties absorbing electromagnetic wave perfectly in GHz wide-band were shown. It was possible to control absorption ratio and absorption wavelength band of electromagnetic wave according to the shape of water droplet–height and diameter– and apply to various flexible and/or transparent substrates such as plastic, glass and paper. In addition, this research examined how electromagnetic wave can be well absorbed in water droplets with low electrical conductivity unlike metal-based metamaterials inquiring highly electrical conductivity. Those results are judged to lead broad applications to variously civilian and military products in the future by providing perfect absorber of broadband in all products including transparent and bendable materials. PMID:26354891

  9. Metamaterial Absorber for Electromagnetic Waves in Periodic Water Droplets

    NASA Astrophysics Data System (ADS)

    Yoo, Young Joon; Ju, Sanghyun; Park, Sang Yoon; Ju Kim, Young; Bong, Jihye; Lim, Taekyung; Kim, Ki Won; Rhee, Joo Yull; Lee, Youngpak

    2015-09-01

    Perfect metamaterial absorber (PMA) can intercept electromagnetic wave harmful for body in Wi-Fi, cell phones and home appliances that we are daily using and provide stealth function that military fighter, tank and warship can avoid radar detection. We reported new concept of water droplet-based PMA absorbing perfectly electromagnetic wave with water, an eco-friendly material which is very plentiful on the earth. If arranging water droplets with particular height and diameter on material surface through the wettability of material surface, meta-properties absorbing electromagnetic wave perfectly in GHz wide-band were shown. It was possible to control absorption ratio and absorption wavelength band of electromagnetic wave according to the shape of water droplet-height and diameter- and apply to various flexible and/or transparent substrates such as plastic, glass and paper. In addition, this research examined how electromagnetic wave can be well absorbed in water droplets with low electrical conductivity unlike metal-based metamaterials inquiring highly electrical conductivity. Those results are judged to lead broad applications to variously civilian and military products in the future by providing perfect absorber of broadband in all products including transparent and bendable materials.

  10. Metamaterial Absorber for Electromagnetic Waves in Periodic Water Droplets.

    PubMed

    Yoo, Young Joon; Ju, Sanghyun; Park, Sang Yoon; Ju Kim, Young; Bong, Jihye; Lim, Taekyung; Kim, Ki Won; Rhee, Joo Yull; Lee, YoungPak

    2015-09-10

    Perfect metamaterial absorber (PMA) can intercept electromagnetic wave harmful for body in Wi-Fi, cell phones and home appliances that we are daily using and provide stealth function that military fighter, tank and warship can avoid radar detection. We reported new concept of water droplet-based PMA absorbing perfectly electromagnetic wave with water, an eco-friendly material which is very plentiful on the earth. If arranging water droplets with particular height and diameter on material surface through the wettability of material surface, meta-properties absorbing electromagnetic wave perfectly in GHz wide-band were shown. It was possible to control absorption ratio and absorption wavelength band of electromagnetic wave according to the shape of water droplet-height and diameter- and apply to various flexible and/or transparent substrates such as plastic, glass and paper. In addition, this research examined how electromagnetic wave can be well absorbed in water droplets with low electrical conductivity unlike metal-based metamaterials inquiring highly electrical conductivity. Those results are judged to lead broad applications to variously civilian and military products in the future by providing perfect absorber of broadband in all products including transparent and bendable materials.

  11. Fluorescence of bioaerosols: mathematical model including primary fluorescing and absorbing molecules in bacteria.

    PubMed

    Hill, Steven C; Pan, Yong-Le; Williamson, Chatt; Santarpia, Joshua L; Hill, Hanna H

    2013-09-23

    This paper describes a mathematical model of fluorescent biological particles composed of bacteria, viruses, or proteins. The fluorescent and/or light absorbing molecules included in the model are amino acids (tryptophan, etc.); nucleic acids (DNA, RNA, etc.); coenzymes (nicotinamide adenine dinucleotides, flavins, and vitamins B₆ and K and variants of these); and dipicolinates. The concentrations, absorptivities, and fluorescence quantum yields are estimated from the literature, often with large uncertainties. The bioparticles in the model are spherical and homogeneous. Calculated fluorescence cross sections for particles excited at 266, 280, and 355 nm are compared with measured values from the literature for several bacteria, bacterial spores and albumins. The calculated 266- and 280-nm excited fluorescence is within a factor of 3.2 of the measurements for the vegetative cells and proteins, but overestimates the fluorescence of spores by a factor of 10 or more. This is the first reported modeling of the fluorescence of bioaerosols in which the primary fluorophores and absorbing molecules are included.

  12. Finding a Single Molecule in a Haystack: Optical Detection and Spectroscopy of Single Absorbers in Solids

    DTIC Science & Technology

    1989-08-18

    CODES 18 SUBJECT TERMS (Continue on reverse if necessary and identify by block number) FIELD GROUP SUB-GROUP Single Molecule Detection Pentacene in p...and 10 additional pentacene molecules. This may be accomplished by- a combination of laser FM spectroscopy and either Stark or ultrasonic double...6099 408-927-2426 ABSTRACT: Single-absorber optical spectroscopy in solids is described for the case of finding a single pentacene molecule in a

  13. Analysis of solar water heater with parabolic dish concentrator and conical absorber

    NASA Astrophysics Data System (ADS)

    Rajamohan, G.; Kumar, P.; Anwar, M.; Mohanraj, T.

    2017-06-01

    This research focuses on developing novel technique for a solar water heating system. The novel solar system comprises a parabolic dish concentrator, conical absorber and water heater. In this system, the conical absorber tube directly absorbs solar radiation from the sun and the parabolic dish concentrator reflects the solar radiations towards the conical absorber tube from all directions, therefore both radiations would significantly improve the thermal collector efficiency. The working fluid water is stored at the bottom of the absorber tubes. The absorber tubes get heated and increases the temperature of the working fluid inside of the absorber tube and causes the working fluid to partially evaporate. The partially vaporized working fluid moves in the upward direction due to buoyancy effect and enters the heat exchanger. When fresh water passes through the heat exchanger, temperature of the vapour decreases through heat exchange. This leads to condensation of the vapour and forms liquid phase. The working fluid returns to the bottom of the collector absorber tube by gravity. Hence, this will continue as a cyclic process inside the system. The proposed investigation shows an improvement of collector efficiency, enhanced heat transfer and a quality water heating system.

  14. Water Molecule Hops on Ceres

    NASA Image and Video Library

    2016-12-15

    This graphic shows a theoretical path of a water molecule on Ceres. Some water molecules fall into cold, dark craters at high latitudes called "cold traps," where very little of the ice turns into vapor, even over the course of a billion years. Other water molecules that do not land in cold traps are lost to space as they hop around the dwarf planet. http://photojournal.jpl.nasa.gov/catalog/PIA21083

  15. Size-dependent fluorescence of bioaerosols: Mathematical model using fluorescing and absorbing molecules in bacteria

    DOE PAGES

    Hill, Steven C.; Williamson, Chatt C.; Doughty, David C.; ...

    2015-02-02

    This paper uses a mathematical model of fluorescent biological particles composed of bacteria and/or proteins (mostly as in Hill et al., 2013 [23]) to investigate the size-dependence of the total fluorescence emitted in all directions. The model applies to particles which have negligible reabsorption of fluorescence within the particle. The specific particles modeled here are composed of ovalbumin and of a generic Bacillus. The particles need not be spherical, and in some cases need not be homogeneous. However, the results calculated in this paper are for spherical homogeneous particles. Light absorbing and fluorescing molecules included in the model are aminomore » acids, nucleic acids, and several coenzymes. Here the excitation wavelength is 266 nm. The emission range, 300 to 370 nm, encompasses the fluorescence of tryptophan. The fluorescence cross section (C F) is calculated and compared with one set of published measured values. We investigate power law (Ad y) approximations to C F, where d is diameter, and A and y are parameters adjusted to fit the data, and examine how y varies with d and composition, including the fraction as water. The particle's fluorescence efficiency (Q F=C F/geometric-cross-section) can be written for homogeneous particles as Q absR F, where Q abs is the absorption efficiency, and R F, the fraction of the absorbed light emitted as fluorescence, is independent of size and shape. When Q F is plotted vs. m id or mi(m r-1)d, where m=m r+im i is the complex refractive index, the plots for different fractions of water in the particle tend to overlap.« less

  16. Conserved water molecules in bacterial serine hydroxymethyltransferases.

    PubMed

    Milano, Teresa; Di Salvo, Martino Luigi; Angelaccio, Sebastiana; Pascarella, Stefano

    2015-10-01

    Water molecules occurring in the interior of protein structures often are endowed with key structural and functional roles. We report the results of a systematic analysis of conserved water molecules in bacterial serine hydroxymethyltransferases (SHMTs). SHMTs are an important group of pyridoxal-5'-phosphate-dependent enzymes that catalyze the reversible conversion of l-serine and tetrahydropteroylglutamate to glycine and 5,10-methylenetetrahydropteroylglutamate. The approach utilized in this study relies on two programs, ProACT2 and WatCH. The first software is able to categorize water molecules in a protein crystallographic structure as buried, positioned in clefts or at the surface. The other program finds, in a set of superposed homologous proteins, water molecules that occur approximately in equivalent position in each of the considered structures. These groups of molecules are referred to as 'clusters' and represent structurally conserved water molecules. Several conserved clusters of buried or cleft water molecules were found in the set of 11 bacterial SHMTs we took into account for this work. The majority of these clusters were not described previously. Possible structural and functional roles for the conserved water molecules are envisaged. This work provides a map of the conserved water molecules helpful for deciphering SHMT mechanism and for rational design of molecular engineering experiments. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  17. Kinetic analysis of an anion exchange absorbent for CO2 capture from ambient air.

    PubMed

    Shi, Xiaoyang; Li, Qibin; Wang, Tao; Lackner, Klaus S

    2017-01-01

    This study reports a preparation method of a new moisture swing sorbent for CO2 capture from air. The new sorbent components include ion exchange resin (IER) and polyvinyl chloride (PVC) as a binder. The IER can absorb CO2 when surrounding is dry and release CO2 when surrounding is wet. The manuscript presents the studies of membrane structure, kinetic model of absorption process, performance of desorption process and the diffusivity of water molecules in the CO2 absorbent. It has been proved that the kinetic performance of CO2 absorption/desorption can be improved by using thin binder and hot water treatment. The fast kinetics of P-100-90C absorbent is due to the thin PVC binder, and high diffusion rate of H2O molecules in the sample. The impressive is this new CO2 absorbent has the fastest CO2 absorption rate among all absorbents which have been reported by other up-to-date literatures.

  18. Kinetic analysis of an anion exchange absorbent for CO2 capture from ambient air

    PubMed Central

    Shi, Xiaoyang; Li, Qibin; Lackner, Klaus S.

    2017-01-01

    This study reports a preparation method of a new moisture swing sorbent for CO2 capture from air. The new sorbent components include ion exchange resin (IER) and polyvinyl chloride (PVC) as a binder. The IER can absorb CO2 when surrounding is dry and release CO2 when surrounding is wet. The manuscript presents the studies of membrane structure, kinetic model of absorption process, performance of desorption process and the diffusivity of water molecules in the CO2 absorbent. It has been proved that the kinetic performance of CO2 absorption/desorption can be improved by using thin binder and hot water treatment. The fast kinetics of P-100-90C absorbent is due to the thin PVC binder, and high diffusion rate of H2O molecules in the sample. The impressive is this new CO2 absorbent has the fastest CO2 absorption rate among all absorbents which have been reported by other up-to-date literatures. PMID:28640914

  19. Neural network consistent empirical physical formula construction for density functional theory based nonlinear vibrational absorbance and intensity of 6-choloronicotinic acid molecule

    NASA Astrophysics Data System (ADS)

    Yildiz, Nihat; Karabacak, Mehmet; Kurt, Mustafa; Akkoyun, Serkan

    2012-05-01

    Being directly related to the electric charge distributions in a molecule, the vibrational spectra intensities are both experimentally and theoretically important physical quantities. However, these intensities are inherently highly nonlinear and of complex pattern. Therefore, in particular for unknown detailed spatial molecular structures, it is difficult to make ab initio intensity calculations to compare with new experimental data. In this respect, we very recently initiated entirely novel layered feedforward neural network (LFNN) approach to construct empirical physical formulas (EPFs) for density functional theory (DFT) vibrational spectra of some molecules. In this paper, as a new and far improved contribution to our novel molecular vibrational spectra LFNN-EPF approach, we constructed LFFN-EPFs for absorbances and intensities of 6-choloronicotinic acid (6-CNA) molecule. The 6-CNA data, borrowed from our previous study, was entirely different and much larger than the vibrational intensity data of our formerly used LFNN-EPF molecules. In line with our another previous work which theoretically proved the LFNN relevance to EPFs, although the 6-CNA DFT absorbance and intensity were inherently highly nonlinear and sharply fluctuating in character, still the optimally constructed train set LFFN-EPFs very successfully fitted the absorbances and intensities. Moreover, test set (i.e. yet-to-be measured experimental data) LFNN-EPFs consistently and successfully predicted the absorbance and intensity data. This simply means that the physical law embedded in the 6-CNA vibrational data was successfully extracted by the LFNN-EPFs. In conclusion, these vibrational LFNN-EPFs are of explicit form. Therefore, by various suitable operations of mathematical analysis, they can be used to estimate the electronic charge distributions of the unknown molecule of the significant complexity. Additionally, these estimations can be combined with those of theoretical DFT atomic polar

  20. Neural network consistent empirical physical formula construction for density functional theory based nonlinear vibrational absorbance and intensity of 6-choloronicotinic acid molecule.

    PubMed

    Yildiz, Nihat; Karabacak, Mehmet; Kurt, Mustafa; Akkoyun, Serkan

    2012-05-01

    Being directly related to the electric charge distributions in a molecule, the vibrational spectra intensities are both experimentally and theoretically important physical quantities. However, these intensities are inherently highly nonlinear and of complex pattern. Therefore, in particular for unknown detailed spatial molecular structures, it is difficult to make ab initio intensity calculations to compare with new experimental data. In this respect, we very recently initiated entirely novel layered feedforward neural network (LFNN) approach to construct empirical physical formulas (EPFs) for density functional theory (DFT) vibrational spectra of some molecules. In this paper, as a new and far improved contribution to our novel molecular vibrational spectra LFNN-EPF approach, we constructed LFFN-EPFs for absorbances and intensities of 6-choloronicotinic acid (6-CNA) molecule. The 6-CNA data, borrowed from our previous study, was entirely different and much larger than the vibrational intensity data of our formerly used LFNN-EPF molecules. In line with our another previous work which theoretically proved the LFNN relevance to EPFs, although the 6-CNA DFT absorbance and intensity were inherently highly nonlinear and sharply fluctuating in character, still the optimally constructed train set LFFN-EPFs very successfully fitted the absorbances and intensities. Moreover, test set (i.e. yet-to-be measured experimental data) LFNN-EPFs consistently and successfully predicted the absorbance and intensity data. This simply means that the physical law embedded in the 6-CNA vibrational data was successfully extracted by the LFNN-EPFs. In conclusion, these vibrational LFNN-EPFs are of explicit form. Therefore, by various suitable operations of mathematical analysis, they can be used to estimate the electronic charge distributions of the unknown molecule of the significant complexity. Additionally, these estimations can be combined with those of theoretical DFT atomic polar

  1. Embedded dielectric water "atom" array for broadband microwave absorber based on Mie resonance

    NASA Astrophysics Data System (ADS)

    Gogoi, Dhruba Jyoti; Bhattacharyya, Nidhi Saxena

    2017-11-01

    A wide band microwave absorber at X-band frequency range is demonstrated numerically and experimentally by embedding a simple rectangular structured dielectric water "atom" in flexible silicone substrate. The absorption peak of the absorber is tuned by manipulating the size of the dielectric water "atom." The frequency dispersive permittivity property of the water "atom" shows broadband absorption covering the entire X-band above 90% efficiency with varying the size of the water "atom." Mie resonance of the proposed absorber provides the desired impedance matching condition at the air-absorber interface across a wide frequency range in terms of electric and magnetic resonances. Multipole decomposition of induced current densities is used to identify the nature of observed resonances. Numerical absorptivity verifies that the designed absorber is polarization insensitive for normal incidence and can maintain an absorption bandwidth of more than 2 GHz in a wide-angle incidence. Additionally, the tunability of absorption property with temperature is shown experimentally.

  2. What is the minimum number of water molecules required to dissolve a potassium chloride molecule?

    PubMed

    Sen, Anik; Ganguly, Bishwajit

    2010-12-01

    This work answers an unsolved question that consists of determining the least number of water molecules necessary to separate a potassium chloride molecule. The answer based on accurate quantum chemical calculations suggests that tetramers are the smallest clusters necessary to dissociate KCl molecules. The study was made with Møller-Plesset second-order perturbation theory modified with the cluster theory having single, double, and perturbative triple excitations. With this extensive study, the dissociation of KCl molecule in different water clusters was evaluated. The calculated results show that four water molecules stabilize a solvent separated K(+)/Cl(-) ion-pair in prismatic structure and with six water molecules further dissociation was observed. Attenuated total reflection infrared spectroscopy of KCl dissolved in water establishes that clusters are made of closely bound ions with a mean of five water molecules per ion-pair [K(+)(H(2)O)(5)Cl(-)]. (Max and Chapados, Appl Spectrosc 1999, 53, 1601; Max and Chapados, J Chem Phys 2001, 115, 2664.) The calculated results tend to support that five water molecules leads toward the formation of contact ion-pair. The structures, energies, and infrared spectra of KCl molecules in different water clusters are also discussed. © 2010 Wiley Periodicals, Inc.

  3. Water-assisted dehalogenation of thionyl chloride in the presence of water molecules.

    PubMed

    Yeung, Chi Shun; Ng, Ping Leung; Guan, Xiangguo; Phillips, David Lee

    2010-04-01

    A second-order Møller-Plesset perturbation theory (MP2) and density functional theory (DFT) investigation of the dehalogenation reactions of thionyl chloride is reported, in which water molecules (up to seven) were explicitly involved in the reaction complex. The dehalogenation processes of thionyl chloride were found to be dramatically catalyzed by water molecules. The reaction rate became significantly faster as more water molecules became involved in the reaction complex. The dehalogenation processes can be reasonably simulated by the gas-phase water cluster models, which reveals that water molecules can help to solvate the thionyl chloride molecules and activate the release of the Cl(-) leaving group. The computed activation energies were used to compare the calculations to available experimental data.

  4. Thermo-responsive gels that absorb moisture and ooze water.

    PubMed

    Matsumoto, Kazuya; Sakikawa, Nobuki; Miyata, Takashi

    2018-06-13

    The water content of thermo-responsive hydrogels can be drastically altered by small changes in temperature because their polymer chains change from hydrophilic to hydrophobic above their low critical solution temperature (LCST). In general, such smart hydrogels have been utilized in aqueous solutions or in their wet state, and no attempt has been made to determine the phase-transition behavior of the gels in their dried states. Here we demonstrate an application of the thermo-responsive behavior of an interpenetrating polymer network (IPN) gel comprising thermo-responsive poly(N-isopropylacrylamide) and hydrophilic sodium alginate networks in their dried states. The dried IPN gel absorbs considerable moisture from air at temperatures below its LCST and oozes the absorbed moisture as liquid water above its LCST. These phenomena provide energy exchange systems in which moisture from air can be condensed to liquid water using the controllable hydrophilic/hydrophobic properties of thermo-responsive gels with a small temperature change.

  5. Water-absorbing capacitor system for measuring relative humidity

    NASA Technical Reports Server (NTRS)

    Laue, Eric G. (Inventor)

    1987-01-01

    A method and apparatus using a known water-absorbent polymer as a capacitor which is operated at a dc voltage for measuring relative humidity is presented. When formed as a layer between porous electrically-conductive electrodes and operated in an RC oscillator circuit, the oscillator frequency varies inversely with the partial pressure of the moisture to be measured. In a preferred embodiment, the capacitor is formed from Nafion and is operated at a low dc voltage with a resistor as an RC circuit in an RC oscillator. At the low voltage, the leakage current is proper for oscillation over a satisfactory range. The frequency of oscillation varies in an essentially linear fashion with relative humidity which is represented by the moisture being absorbed into the Nafion. The oscillation frequency is detected by a frequency detector.

  6. Sequential evaporation of water molecules from protonated water clusters: measurement of the velocity distributions of the evaporated molecules and statistical analysis.

    PubMed

    Berthias, F; Feketeová, L; Abdoul-Carime, H; Calvo, F; Farizon, B; Farizon, M; Märk, T D

    2018-06-22

    Velocity distributions of neutral water molecules evaporated after collision induced dissociation of protonated water clusters H+(H2O)n≤10 were measured using the combined correlated ion and neutral fragment time-of-flight (COINTOF) and velocity map imaging (VMI) techniques. As observed previously, all measured velocity distributions exhibit two contributions, with a low velocity part identified by statistical molecular dynamics (SMD) simulations as events obeying the Maxwell-Boltzmann statistics and a high velocity contribution corresponding to non-ergodic events in which energy redistribution is incomplete. In contrast to earlier studies, where the evaporation of a single molecule was probed, the present study is concerned with events involving the evaporation of up to five water molecules. In particular, we discuss here in detail the cases of two and three evaporated molecules. Evaporation of several water molecules after CID can be interpreted in general as a sequential evaporation process. In addition to the SMD calculations, a Monte Carlo (MC) based simulation was developed allowing the reconstruction of the velocity distribution produced by the evaporation of m molecules from H+(H2O)n≤10 cluster ions using the measured velocity distributions for singly evaporated molecules as the input. The observed broadening of the low-velocity part of the distributions for the evaporation of two and three molecules as compared to the width for the evaporation of a single molecule results from the cumulative recoil velocity of the successive ion residues as well as the intrinsically broader distributions for decreasingly smaller parent clusters. Further MC simulations were carried out assuming that a certain proportion of non-ergodic events is responsible for the first evaporation in such a sequential evaporation series, thereby allowing to model the entire velocity distribution.

  7. On the Several Molecules and Nanostructures of Water

    PubMed Central

    Whitney, Cynthia Kolb

    2012-01-01

    This paper investigates the water molecule from a variety of viewpoints. Water can involve different isotopes of Hydrogen and Oxygen, it can form differently shaped isomer molecules, and, when frozen, it occupies space differently than most other substances do. The tool for conducting the investigation of all this is called ‘Algebraic Chemistry’. This tool is a quantitative model for predicting the energy budget for all sorts of changes between different ionization states of atoms that are involved in chemical reactions and in changes of physical state. The model is based on consistent patterns seen in empirical data about ionization potentials, together with rational scaling laws that can interpolate and extrapolate for situations where no data are available. The results of the investigation of the water molecule include comments, both positive and negative, about technologies involving heavy water, poly water, Brown’s gas, and cold fusion. PMID:22312305

  8. On the several molecules and nanostructures of water.

    PubMed

    Whitney, Cynthia Kolb

    2012-01-01

    This paper investigates the water molecule from a variety of viewpoints. Water can involve different isotopes of Hydrogen and Oxygen, it can form differently shaped isomer molecules, and, when frozen, it occupies space differently than most other substances do. The tool for conducting the investigation of all this is called 'Algebraic Chemistry'. This tool is a quantitative model for predicting the energy budget for all sorts of changes between different ionization states of atoms that are involved in chemical reactions and in changes of physical state. The model is based on consistent patterns seen in empirical data about ionization potentials, together with rational scaling laws that can interpolate and extrapolate for situations where no data are available. The results of the investigation of the water molecule include comments, both positive and negative, about technologies involving heavy water, poly water, Brown's gas, and cold fusion.

  9. Dynamics of bound water molecules in fullerenol at different hydration levels

    NASA Astrophysics Data System (ADS)

    Wang, Yilin; Robey, Steven; Reutt-Robey, Janice

    Fullerenols, polyhydroxylated fullerenes, are of great interest as promising materials in medical application because of their high water solubility and biocompatibility. Fullerenols are highly responsive to their environment, for example, they readily undergo hydration under ambient conditions. Understanding the dynamics of water molecules bound to fullerenols, and the interplay between water molecules and fullerenols is important in realizing biological function. Here, broadband dielectric spectroscopy (BDS), was performed on a fullerenol with 44 hydroxyl groups, C60(OH)44, between 300 K and 340 K. At room temperature and under ambient conditions, C60(OH)44 is hydrated, releasing bound water molecules with increasing temperature, as quantified by thermal gravimetric analysis (TGA) measurements. At room temperature, a dielectric band due to collective bulk-like dynamics of the bound water molecules is observed. The relaxation peak of the water molecules shifts to higher frequency with increasing of temperature, reflecting the dynamics of bound water. Upon loss of water molecules, either thermally induced or vacuum induced, the relaxation peak shifts to lower frequency. The stoichiometric relationship between the dielectric properties of the hydrated fullerenol and the interplay between the bound water molecules and C60(OH)44 will be discussed. This work was supported by the National Science Foundation (NSF) under Award Number 1310380.

  10. Free enthalpies of replacing water molecules in protein binding pockets.

    PubMed

    Riniker, Sereina; Barandun, Luzi J; Diederich, François; Krämer, Oliver; Steffen, Andreas; van Gunsteren, Wilfred F

    2012-12-01

    Water molecules in the binding pocket of a protein and their role in ligand binding have increasingly raised interest in recent years. Displacement of such water molecules by ligand atoms can be either favourable or unfavourable for ligand binding depending on the change in free enthalpy. In this study, we investigate the displacement of water molecules by an apolar probe in the binding pocket of two proteins, cyclin-dependent kinase 2 and tRNA-guanine transglycosylase, using the method of enveloping distribution sampling (EDS) to obtain free enthalpy differences. In both cases, a ligand core is placed inside the respective pocket and the remaining water molecules are converted to apolar probes, both individually and in pairs. The free enthalpy difference between a water molecule and a CH(3) group at the same location in the pocket in comparison to their presence in bulk solution calculated from EDS molecular dynamics simulations corresponds to the binding free enthalpy of CH(3) at this location. From the free enthalpy difference and the enthalpy difference, the entropic contribution of the displacement can be obtained too. The overlay of the resulting occupancy volumes of the water molecules with crystal structures of analogous ligands shows qualitative correlation between experimentally measured inhibition constants and the calculated free enthalpy differences. Thus, such an EDS analysis of the water molecules in the binding pocket may give valuable insight for potency optimization in drug design.

  11. Free enthalpies of replacing water molecules in protein binding pockets

    NASA Astrophysics Data System (ADS)

    Riniker, Sereina; Barandun, Luzi J.; Diederich, François; Krämer, Oliver; Steffen, Andreas; van Gunsteren, Wilfred F.

    2012-12-01

    Water molecules in the binding pocket of a protein and their role in ligand binding have increasingly raised interest in recent years. Displacement of such water molecules by ligand atoms can be either favourable or unfavourable for ligand binding depending on the change in free enthalpy. In this study, we investigate the displacement of water molecules by an apolar probe in the binding pocket of two proteins, cyclin-dependent kinase 2 and tRNA-guanine transglycosylase, using the method of enveloping distribution sampling (EDS) to obtain free enthalpy differences. In both cases, a ligand core is placed inside the respective pocket and the remaining water molecules are converted to apolar probes, both individually and in pairs. The free enthalpy difference between a water molecule and a CH3 group at the same location in the pocket in comparison to their presence in bulk solution calculated from EDS molecular dynamics simulations corresponds to the binding free enthalpy of CH3 at this location. From the free enthalpy difference and the enthalpy difference, the entropic contribution of the displacement can be obtained too. The overlay of the resulting occupancy volumes of the water molecules with crystal structures of analogous ligands shows qualitative correlation between experimentally measured inhibition constants and the calculated free enthalpy differences. Thus, such an EDS analysis of the water molecules in the binding pocket may give valuable insight for potency optimization in drug design.

  12. Organic molecules and nanoparticles in inorganic crystals: Vitamin C in CaCO3 as an ultraviolet absorber

    NASA Astrophysics Data System (ADS)

    Sato, H.; Ikeya, M.

    2004-03-01

    Organic molecules and nanoparticles embedded in inorganic crystalline lattices have been studied to add different properties and functions to composite materials. Calcium carbonate was precipitated by dropping an aqueous solution of CaCl2 into that of Na2CO3 containing dissolved vitamin C (ascorbic acid). The optical absorption ascribed to divalent ascorbate anions in the lattice was observed in the ultraviolet B (wavelength: 280-315 nm) region, while solid vitamin C exhibited absorption in the ultraviolet C (100-280 nm) region. The divalent ascorbate anion is only stable in CaCO3 due to the absence of oxygen molecules. Doping CaCO3 with nanoparticles of ZnO also enhanced the absorption in the ultraviolet A (315-380 nm) region. These composite materials are suggested for use as UV absorbers.

  13. Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

    ERIC Educational Resources Information Center

    Barlag, Rebecca; Nyasulu, Frazier

    2011-01-01

    The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

  14. Absorbent product to absorb fluids. [for collection of human wastes

    NASA Technical Reports Server (NTRS)

    Dawn, F. S.; Correale, J. V. (Inventor)

    1982-01-01

    A multi-layer absorbent product for use in contact with the skin to absorb fluids is discussed. The product utilizes a water pervious facing layer for contacting the skin, overlayed by a first fibrous wicking layer, the wicking layer preferably being of the one-way variety in which fluid or liquid is moved away from the facing layer. The product further includes a first container section defined by inner and outer layer of a water pervious wicking material between which is disposed a first absorbent mass. A second container section defined by inner and outer layers between which is disposed a second absorbent mass and a liquid impermeable/gas permeable layer. Spacesuit applications are discussed.

  15. Use of a New Simltaneous Absorbance-Fluorescene Instrument to Monitor Hydraluic Fracture Mining Waste Water to Prevent Drinking Water Contamination

    NASA Astrophysics Data System (ADS)

    Gilmore, A. M.

    2013-05-01

    Recently, the issue of waste water effuse from oil and gas mining, especially that including hydraulic fracturing, has resurfaced on the news and the political atmosphere as an area of concern. One of the key concerns is drinking water contamination from the hydraulic fracturing chemicals and chemicals contained in the water introduced into the well at high-pressure and the flowback and produced water associate with the petroleum product extraction. The key to successfully meeting drinking water safety requirements lies in the drinking water treatment plant's ability to deal with often dramatic source-water variations in natural organic matter (NOM) content that can react during disinfection with high levels of chloride and bromide found in hydraulic facture waste water to form toxc disinfection by-products (DBPs). Importantly, the brominated DBP species are particularly dangerous. Whereas the regulated levels of NOM can roughly determined by measuring total organic carbon (TOC), often this parameter does not provide rapid or cost-effective qualitative or quantitative assessment of the various humic, fulvic and other aromatic NOM components associated with DBP formation. However, two main optical techniques namely UV absorbance and fluorescence excitation-emission mapping can be used for rapid assessment with precise identification of humic and fulvic components that cause DBPs. This study presents data from a new type of instrument which simultaneously measures the UV-VIS absorbance spectrum and EEM. The rapid absorbance-EEM is facilitated by a single system that is more than 100 time faster than conventional scanning absorbance and fluorescence optical benches. The new system can continuously collect EEMs and absorbance spectra at a rate often greater than 1 per min with the extra capacity to monitor the UV254 absorbance and fluorescence emission spectrum excited at 254 nm in 4 ms intervals (an equivalent scan rate of 5.5 million nm/min). The EEM spectral data is

  16. A series of fluorene-based two-photon absorbing molecules: synthesis, linear and nonlinear characterization, and bioimaging

    PubMed Central

    Andrade, Carolina D.; Yanez, Ciceron O.; Rodriguez, Luis; Belfield, Kevin D.

    2010-01-01

    The synthesis, structural, and photophysical characterization of a series of new fluorescent donor–acceptor and acceptor-acceptor molecules, based on the fluorenyl ring system, with two-photon absorbing properties is described. These new compounds exhibited large Stokes shifts, high fluorescent quantum yields, and, significantly, high two-photon absorption cross sections, making them well suited for two-photon fluorescence microscopy (2PFM) imaging. Confocal and two-photon fluorescence microscopy imaging of COS-7 and HCT 116 cells incubated with probe I showed endosomal selectivity, demonstrating the potential of this class of fluorescent probes in multiphoton fluorescence microscopy. PMID:20481596

  17. Femtosecond spectroscopic study of the solvation of amphiphilic molecules by water

    NASA Astrophysics Data System (ADS)

    Rezus, Y. L. A.; Bakker, H. J.

    2008-06-01

    We use polarization-resolved mid-infrared pump-probe spectroscopy to study the aqueous solvation of proline and N-methylacetamide. These molecules serve as models to study the solvation of proteins. We monitor the orientational dynamics of partly deuterated water molecules (HDO) that are present at a low concentration in the water. We find that the OD vibration of HDO relaxes via an intermediate level, that is characterized by a hydrogen-bond that is stronger than in the ground state. With increasing concentration the lifetime of the excited state increases from 1.8 ps to 2.4 ps and the lifetime of the intermediate level from 0.6 ps to 1.0 ps. Regarding the orientational dynamics we observe biexponential behavior, which finds its origin in the presence of two classes of water molecules. There is a fraction of water molecules that has bulk-like orientational dynamics ( τrot = 2.5 ps) and a fraction of immobilized water molecules ( τrot > 10 ps). The relative abundance of the two fractions is determined by the nature and concentration of the solute. We find that the hydrophobic solute groups are responsible for the immobilization of water molecules. Every methyl group causes the immobilization of approximately 4 water OH groups. The hydrophilic solute groups, on the other hand, do not hinder the reorientation and the water molecules solvating them reorient with the same rate as in the bulk liquid.

  18. Effect of water pressure on absorbency of hydroentangled greige cotton nonwoven fabrics

    USDA-ARS?s Scientific Manuscript database

    A studied has been conducted to determine the effect of water pressure in a commercial-grade Fleissner MiniJet hydroentanglement system on the absorbency of greige (non-bleached) cotton lint-based nonwoven fabric. The study has shown that a water pressure of 125 Bar or higher on only two high-pressu...

  19. Water-injected all-dielectric ultra-wideband and prominent oblique incidence metamaterial absorber in microwave regime

    NASA Astrophysics Data System (ADS)

    Huang, Xiaojun; Yang, Helin; Shen, Zhaoyang; Chen, Jiao; Lin, Hail; Yu, Zetai

    2017-09-01

    We present a water-injected all-dielectric metamaterial that can offer an extremely wide bandwidth of electromagnetic absorption and prominent wide incident angle range. Different from conventional metal-dielectric based metamaterial absorbers, the absorption mechanism of the proposed all-dielectric metamaterial absorber is to take advantage of the dispersion of water, rather than electric or/and magnetic resonance, which thoroughly overcomes the defects of narrow bandwidth and oblique incidence from metal-dielectric based metamaterial absorber. The simulated absorption was over 90% in 8.1-22.9 GHz with the relative bandwidth of 95.5% when the incident angle reaches 60°, and the corresponding microwave experiment is performed to support the simulations. The obtained excellent absorption performance reveals a possible application of the proposed absorber, which can be exploited for electromagnetic stealth purposes, especially for electromagnetic stealth of sea targets.

  20. Study of thermal effects and optical properties of an innovative absorber in integrated collector storage solar water heater

    NASA Astrophysics Data System (ADS)

    Taheri, Yaser; Alimardani, Kazem; Ziapour, Behrooz M.

    2015-10-01

    Solar passive water heaters are potential candidates for enhanced heat transfer. Solar water heaters with an integrated water tank and with the low temperature energy resource are used as the simplest and cheapest recipient devices of the solar energy for heating and supplying hot water in the buildings. The solar thermal performances of one primitive absorber were determined by using both the experimental and the simulation model of it. All materials applied for absorber such as the cover glass, the black colored sands and the V shaped galvanized plate were submerged into the water. The water storage tank was manufactured from galvanized sheet of 0.0015 m in thickness and the effective area of the collector was 0.67 m2. The absorber was installed on a compact solar water heater. The constructed flat-plate collectors were tested outdoors. However the simulation results showed that the absorbers operated near to the gray materials and all experimental results showed that the thermal efficiencies of the collector are over than 70 %.

  1. Analytical model for three-dimensional Mercedes-Benz water molecules.

    PubMed

    Urbic, T

    2012-06-01

    We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature.

  2. Analytical model for three-dimensional Mercedes-Benz water molecules

    NASA Astrophysics Data System (ADS)

    Urbic, T.

    2012-06-01

    We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature.

  3. Analytical model for three-dimensional Mercedes-Benz water molecules

    PubMed Central

    Urbic, T.

    2013-01-01

    We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature. PMID:23005100

  4. The Investigation of Property of Radiation and Absorbed of Infrared Lights of the Biological Tissues

    NASA Astrophysics Data System (ADS)

    Pang, Xiao-Feng; Deng, Bo; Xiao, He-Lan; Cai, Guo-Ping

    2010-04-01

    The properties of absorption of infrared light for collagen, hemoglobin, bivine serum albumen (BSA) protein molecules with α- helix structure and water in the living systems as well as the infrared transmission spectra for person’s skins and finger hands of human body in the region of 400-4000 cm-1 (i.e., wavelengths of 2-20 μm) have been collected and determined by using a Nicolet Nexus 670 FT-IR Spectrometer, a Perkin Elmer GX FT-IR spectrometer, an OMA (optical multichannel analysis) and an infrared probe systems, respectively. The experimental results obtained show that the protein molecules and water can all absorb the infrared lights in the ranges of 600-1900 cm-1 and 2900-3900 cm-l, but their properties of absorption are somewhat different due to distinctions of their structure and conformation and molecular weight. We know from the transmission spectra of person’s finger hands and skin that the infrared lights with wavelengths of 2 μm-7 μm can not only transmit over the person’s skin and finger hands, but also be absorbed by the above proteins and water in the living systems. Thus, we can conclude from this study that the human beings and animals can absorb the infrared lights with wavelengths of 2 μm-7 μm.

  5. Rapid and accurate prediction and scoring of water molecules in protein binding sites.

    PubMed

    Ross, Gregory A; Morris, Garrett M; Biggin, Philip C

    2012-01-01

    Water plays a critical role in ligand-protein interactions. However, it is still challenging to predict accurately not only where water molecules prefer to bind, but also which of those water molecules might be displaceable. The latter is often seen as a route to optimizing affinity of potential drug candidates. Using a protocol we call WaterDock, we show that the freely available AutoDock Vina tool can be used to predict accurately the binding sites of water molecules. WaterDock was validated using data from X-ray crystallography, neutron diffraction and molecular dynamics simulations and correctly predicted 97% of the water molecules in the test set. In addition, we combined data-mining, heuristic and machine learning techniques to develop probabilistic water molecule classifiers. When applied to WaterDock predictions in the Astex Diverse Set of protein ligand complexes, we could identify whether a water molecule was conserved or displaced to an accuracy of 75%. A second model predicted whether water molecules were displaced by polar groups or by non-polar groups to an accuracy of 80%. These results should prove useful for anyone wishing to undertake rational design of new compounds where the displacement of water molecules is being considered as a route to improved affinity.

  6. Reverse Mössbauer effect as a possible source of “hot” molecules absorbed in crystalline solids at low temperature

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

    Demontis, Pierfranco; Suffritti, Giuseppe B., E-mail: pino@uniss.it

    2016-09-07

    As an attempt to explain some of the many anomalies and unresolved problems which have been reported about the dynamic behavior of particles and molecules absorbed in crystalline solids, the “reverse Mössbauer effect” (RME) is proposed. RME theory posits that a particle in non-equilibrium state with respect to a crystal (colliding with the crystal or absorbed in it, but set out of thermal equilibrium by some external cause) is scattered by the whole crystal with a momentum proportional to a vector representing a reciprocal lattice point. The scattering is expected to occur with a well-defined probability and the momentum transferablemore » to the particle is expected to follow a predictable distribution. The RME theory, in practice, is an extension of the Bragg–von Laue scattering law to high-energy colliding particles, in general, and can be applied to any particle or molecule colliding with the surface of a crystalline solid or absorbed in it, but not in thermal equilibrium with the crystal lattice. We verified the RME theory by considering a well-defined unresolved problem. In an experimental study about methane adsorbed in the zeolite Na-ZSM-5 [H. Jobic, Chem. Phys. Lett. 170, 217 (1990)] reporting neutron inelastic-scattering spectra (recoiled bands) at 10 K, the translational kinetic energy of methane resulted to be much higher than equilibrium expected value, namely, about 85 K (or 7.3 meV). The author concluded that “the interpretation of this unusual behavior has yet to be found.” In the present study, on the basis of the RME, an explanation of this behavior is put forward.« less

  7. Influence of Molecular Oxygen on Ortho-Para Conversion of Water Molecules

    NASA Astrophysics Data System (ADS)

    Valiev, R. R.; Minaev, B. F.

    2017-07-01

    The mechanism of influence of molecular oxygen on the probability of ortho-para conversion of water molecules and its relation to water magnetization are considered within the framework of the concept of paramagnetic spin catalysis. Matrix elements of the hyperfine ortho-para interaction via the Fermi contact mechanism are calculated, as well as the Maliken spin densities on water protons in H2O and O2 collisional complexes. The mechanism of penetration of the electron spin density into the water molecule due to partial spin transfer from paramagnetic oxygen is considered. The probability of ortho-para conversion of the water molecules is estimated by the quantum chemistry methods. The results obtained show that effective ortho-para conversion of the water molecules is possible during the existence of water-oxygen dimers. An external magnetic field affects the ortho-para conversion rate given that the wave functions of nuclear spin sublevels of the water protons are mixed in the complex with oxygen.

  8. Lipid-absorbing Polymers

    NASA Technical Reports Server (NTRS)

    Marsh, H. E., Jr.; Wallace, C. J.

    1973-01-01

    The removal of bile acids and cholesterol by polymeric absorption is discussed in terms of micelle-polymer interaction. The results obtained with a polymer composed of 75 parts PEO and 25 parts PB plus curing ingredients show an absorption of 305 to 309%, based on original polymer weight. Particle size effects on absorption rate are analyzed. It is concluded that crosslinked polyethylene oxide polymers will absorb water, crosslinked polybutadiene polymers will absorb lipids; neither polymer will absorb appreciable amounts of lipids from micellar solutions of lipids in water.

  9. Different effects of water molecules on CO oxidation with different reaction mechanisms.

    PubMed

    Liu, Shan Ping; Zhao, Ming; Sun, Guo En; Gao, Wang; Jiang, Qing

    2018-03-28

    The effects of water molecules (promotion/prohibition) on CO oxidation remain debated. Herein, using density functional theory calculations, we demonstrate that water molecules can facilitate the CO + O/O 2 oxidation process, but prohibit the CO + OH oxidation process, which is consistent with the experimental finding that water molecules have two distinct effects on CO oxidation. For the CO + O/O 2 oxidation mechanisms, we find that the reactants were pushed towards each other due to the steric effect of the water molecules, which decreases the reaction barriers and promotes the CO + O/O 2 oxidation process. For the CO + OH oxidation mechanisms, water molecules increase the stability of the COOH* intermeditae by H-bonds and van der Waals forces, which increase the barriers of the COOH* transformation process and the COOH*-tra dissociation process, and prohibit the CO + OH oxidation process. These results clarify the different effects of water molecules on CO oxidation and shed light on catalyst usage in the CO oxidation industry.

  10. Origin of the blueshift of water molecules at interfaces of hydrophilic cyclic compounds

    PubMed Central

    Tomobe, Katsufumi; Yamamoto, Eiji; Kojić, Dušan; Sato, Yohei; Yasui, Masato; Yasuoka, Kenji

    2017-01-01

    Water molecules at interfaces of materials exhibit enigmatic properties. A variety of spectroscopic studies have observed a high-frequency motion in these water molecules, represented by a blueshift, at both hydrophobic and hydrophilic interfaces. However, the molecular mechanism behind this blueshift has remained unclear. Using Raman spectroscopy and ab initio molecular dynamics simulations, we reveal the molecular mechanism of the blueshift of water molecules around six monosaccharide isomers. In the first hydration shell, we found weak hydrogen-bonded water molecules that cannot have a stable tetrahedral water network. In the water molecules, the vibrational state of the OH bond oriented toward the bulk solvent strongly contributes to the observed blueshift. Our work suggests that the blueshift in various solutions originates from the vibrational motions of these observed water molecules. PMID:29282448

  11. The role of water molecules in computational drug design.

    PubMed

    de Beer, Stephanie B A; Vermeulen, Nico P E; Oostenbrink, Chris

    2010-01-01

    Although water molecules are small and only consist of two different atom types, they play various roles in cellular systems. This review discusses their influence on the binding process between biomacromolecular targets and small molecule ligands and how this influence can be modeled in computational drug design approaches. Both the structure and the thermodynamics of active site waters will be discussed as these influence the binding process significantly. Structurally conserved waters cannot always be determined experimentally and if observed, it is not clear if they will be replaced upon ligand binding, even if sufficient space is available. Methods to predict the presence of water in protein-ligand complexes will be reviewed. Subsequently, we will discuss methods to include water in computational drug research. Either as an additional factor in automated docking experiments, or explicitly in detailed molecular dynamics simulations, the effect of water on the quality of the simulations is significant, but not easily predicted. The most detailed calculations involve estimates of the free energy contribution of water molecules to protein-ligand complexes. These calculations are computationally demanding, but give insight in the versatility and importance of water in ligand binding.

  12. Quantum Behavior of Water Molecules Confined to Nanocavities in Gemstones.

    PubMed

    Gorshunov, Boris P; Zhukova, Elena S; Torgashev, Victor I; Lebedev, Vladimir V; Shakurov, Gil'man S; Kremer, Reinhard K; Pestrjakov, Efim V; Thomas, Victor G; Fursenko, Dimitry A; Dressel, Martin

    2013-06-20

    When water is confined to nanocavities, its quantum mechanical behavior can be revealed by terahertz spectroscopy. We place H2O molecules in the nanopores of a beryl crystal lattice and observe a rich and highly anisotropic set of absorption lines in the terahertz spectral range. Two bands can be identified, which originate from translational and librational motions of the water molecule isolated within the cage; they correspond to the analogous broad bands in liquid water and ice. In the present case of well-defined and highly symmetric nanocavities, the observed fine structure can be explained by macroscopic tunneling of the H2O molecules within a six-fold potential caused by the interaction of the molecule with the cavity walls.

  13. Interplay between translational diffusion and large-amplitude angular jumps of water molecules

    NASA Astrophysics Data System (ADS)

    Liu, Chao; Zhang, Yangyang; Zhang, Jian; Wang, Jun; Li, Wenfei; Wang, Wei

    2018-05-01

    Understanding the microscopic mechanism of water molecular translational diffusion is a challenging topic in both physics and chemistry. Here, we report an investigation on the interplay between the translational diffusion and the large-amplitude angular jumps of water molecules in bulk water using molecular dynamics simulations. We found that large-amplitude angular jumps are tightly coupled to the translational diffusions. Particularly, we revealed that concurrent rotational jumps of spatially neighboring water molecules induce inter-basin translational jumps, which contributes to the fast component of the water translational diffusion. Consequently, the translational diffusion shows positional heterogeneity; i.e., the neighbors of the water molecules with inter-basin translational jumps have larger probability to diffuse by inter-basin translational jumps. Our control simulations showed that a model water molecule with moderate hydrogen bond strength can diffuse much faster than a simple Lennard-Jones particle in bulk water due to the capability of disturbing the hydrogen bond network of the surrounding water molecules. Our results added to the understanding of the microscopic picture of the water translational diffusion and demonstrated the unique features of water diffusion arising from their hydrogen bond network structure compared with those of the simple liquids.

  14. Protein-bound water molecules in primate red- and green-sensitive visual pigments.

    PubMed

    Katayama, Kota; Furutani, Yuji; Imai, Hiroo; Kandori, Hideki

    2012-02-14

    Protein-bound water molecules play crucial roles in the structure and function of proteins. The functional role of water molecules has been discussed for rhodopsin, the light sensor for twilight vision, on the basis of X-ray crystallography, Fourier transform infrared (FTIR) spectroscopy, and a radiolytic labeling method, but nothing is known about the protein-bound waters in our color visual pigments. Here we apply low-temperature FTIR spectroscopy to monkey red (MR)- and green (MG)-sensitive color pigments at 77 K and successfully identify water vibrations using D(2)O and D(2)(18)O in the whole midinfrared region. The observed water vibrations are 6-8 for MR and MG, indicating that several water molecules are present near the retinal chromophore and change their hydrogen bonds upon retinal photoisomerization. In this sense, color visual pigments possess protein-bound water molecules essentially similar to those of rhodopsin. The absence of strongly hydrogen-bonded water molecules (O-D stretch at <2400 cm(-1)) is common between rhodopsin and color pigments, which greatly contrasts with the case of proton-pumping microbial rhodopsins. On the other hand, two important differences are observed in water signal between rhodopsin and color pigments. First, the water vibrations are identical between the 11-cis and 9-cis forms of rhodopsin, but different vibrational bands are observed at >2550 cm(-1) for both MR and MG. Second, strongly hydrogen-bonded water molecules (2303 cm(-1) for MR and 2308 cm(-1) for MG) are observed for the all-trans form after retinal photoisomerization, which is not the case for rhodopsin. These specific features of MR and MG can be explained by the presence of water molecules in the Cl(-)-biding site, which are located near positions C11 and C9 of the retinal chromophore. The averaged frequencies of the observed water O-D stretching vibrations for MR and MG are lower as the λ(max) is red-shifted, suggesting that water molecules are involved in

  15. Thermally Tunable Ultra-wideband Metamaterial Absorbers based on Three-dimensional Water-substrate construction.

    PubMed

    Shen, Yang; Zhang, Jieqiu; Pang, Yongqiang; Zheng, Lin; Wang, Jiafu; Ma, Hua; Qu, Shaobo

    2018-03-13

    Distilled water has frequency dispersive characteristic and high value of imaginary part in permittivity, which can be seen as a good candidate of broadband metamaterial absorbers(MAs) in microwave. Here, an interesting idea based on the combination of water-substrate and metallic metamaterial in the three-dimensional construction is proposed, which can achieve outstanding broadband absorption. As a proof, the distilled water is filled into the dielectric reservoir as ultra-thin water-substrate, and then the water-substrates are arranged on the metal backplane periodically as three-dimensional water-substrate array(TWA). Simulation shows that the TWA achieves broadband absorption with the efficiency more than 90% from 8.3 to 21.0 GHz. Then, the trigonal metallic fishbone structure is introduced here between the water-substrate and the dielectric reservoir periodically as three-dimensional water-substrate metamaterial absorber(TWMA). The proposed TWMA could achieve ultra-broadband absorption from 2.6 to 16.8 GHz, which has increase by 64.8% in relative absorption bandwidth. Meanwhile, due to the participation of distilled water, the thermally tunable property also deserves to be discussed here. In view of the outstanding performance, it is worth to expect a wide range of applications to emerge inspired from the proposed construction.

  16. Absorbent product and articles made therefrom

    NASA Technical Reports Server (NTRS)

    Dawn, F. S.; Correale, J. V. (Inventor)

    1982-01-01

    A multilayer absorbent product for use in contact with the skin to absorb fluids is described. The product has a water pervious facing layer for contacting the skin, and a first fibrous wicking layer overlaying the water pervious layer. A first container section is defined by inner and outer layers of a water pervious wicking material in between a first absorbent mass and a second container section defined by inner and outer layers of a water pervious wicking material between what is disposed a second absorbent mass, and a liquid impermeable/gas permeable layer overlaying the second fibrous wicking layer.

  17. Internally bridging water molecule in transmembrane alpha-helical kink.

    PubMed

    Miyano, Masashi; Ago, Hideo; Saino, Hiromichi; Hori, Tetsuya; Ida, Koh

    2010-08-01

    There are hundreds of membrane protein atomic coordinates in the Protein Data Bank (PDB), and high-resolution structures of better than 2.5 A enable the visualization of a sizable number of amphiphiles (lipid and/or detergent) and bound water molecules as essential parts of the structure. Upon scrutinizing these high-resolution structures, water molecules were found to 'wedge' and stabilize large kink angle (30-40 degrees) in a simple cylindrical model at the transmembrane helical kinks so as to form an inter-helical cavity to accommodate a ligand binding or active site as a crucial structural feature in alpha-helical integral membrane proteins. Furthermore, some of these water molecules are proposed to play a pivotal role of their conformational change to exert their functional regulation. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  18. Adsorption of Small Molecules at Water--Hexane and Water--Membrane Interfaces

    NASA Astrophysics Data System (ADS)

    Wilson, Michael A.

    1996-03-01

    The interaction of solutes with aqueous interfaces plays a significant role in a variety of physical processes, including general anesthesia and atmospheric chemistry. We present molecular dynamics results for the transfer of several small solutes across water liquid--vapor, water--hexane and water--GMO bilayer membrane interfaces. (A. Pohorille and M. A. Wilson, J. Chem. Phys. (in press, 1995).)^, (A. Pohorille, P. CIeplak, and M. A. Wilson, Chem. Phys. (in press, 1995).) The free energies of transferring small polar molecules across the interface exhibit fairly deep minima while those of nonpolar molecules do not. This is due to a balance between nonelectrostatic contributions --- primarily the work required to create a cavity large enough to accommodate the solute --- and the solute--solvent electrostatic interactions.^1 The surface excess of solute is calculated and compared with experimental results from the Gibbs adsorption isotherm. The interfacial solubilities correlate with measured anesthetic potencies of these compounds, implying that the binding sites for anesthetics are located near the water--membrane interface.

  19. A graphite calorimeter for absolute measurements of absorbed dose to water: application in medium-energy x-ray filtered beams.

    PubMed

    Pinto, M; Pimpinella, M; Quini, M; D'Arienzo, M; Astefanoaei, I; Loreti, S; Guerra, A S

    2016-02-21

    The Italian National Institute of Ionizing Radiation Metrology (ENEA-INMRI) has designed and built a graphite calorimeter that, in a water phantom, has allowed the determination of the absorbed dose to water in medium-energy x-rays with generating voltages from 180 to 250 kV. The new standard is a miniaturized three-bodies calorimeter, with a disc-shaped core of 21 mm diameter and 2 mm thickness weighing 1.134 g, sealed in a PMMA waterproof envelope with air-evacuated gaps. The measured absorbed dose to graphite is converted into absorbed dose to water by means of an energy-dependent conversion factor obtained from Monte Carlo simulations. Heat-transfer correction factors were determined by FEM calculations. At a source-to-detector distance of 100 cm, a depth in water of 2 g cm(-2), and at a dose rate of about 0.15 Gy min(-1), results of calorimetric measurements of absorbed dose to water, D(w), were compared to experimental determinations, D wK, obtained via an ionization chamber calibrated in terms of air kerma, according to established dosimetry protocols. The combined standard uncertainty of D(w) and D(wK) were estimated as 1.9% and 1.7%, respectively. The two absorbed dose to water determinations were in agreement within 1%, well below the stated measurement uncertainties. Advancements are in progress to extend the measurement capability of the new in-water-phantom graphite calorimeter to other filtered medium-energy x-ray qualities and to reduce the D(w) uncertainty to around 1%. The new calorimeter represents the first implementation of in-water-phantom graphite calorimetry in the kilovoltage range and, allowing independent determinations of D(w), it will contribute to establish a robust system of absorbed dose to water primary standards for medium-energy x-ray beams.

  20. Free energy barriers for escape of water molecules from protein hydration layer.

    PubMed

    Roy, Susmita; Bagchi, Biman

    2012-03-08

    Free energy barriers separating interfacial water molecules from the hydration layer at the surface of a protein to the bulk are obtained by using the umbrella sampling method of free energy calculation. We consider hydration layer of chicken villin head piece (HP-36) which has been studied extensively by molecular dynamics simulations. The free energy calculations reveal a strong sensitivity to the secondary structure. In particular, we find a region near the junction of first and second helix that contains a cluster of water molecules which are slow in motion, characterized by long residence times (of the order of 100 ps or more) and separated by a large free energy barrier from the bulk water. However, these "slow" water molecules constitute only about 5-10% of the total number of hydration layer water molecules. Nevertheless, they play an important role in stabilizing the protein conformation. Water molecules near the third helix (which is the important helix for biological function) are enthalpically least stable and exhibit the fastest dynamics. Interestingly, barrier height distributions of interfacial water are quite broad for water surrounding all the three helices (and the three coils), with the smallest barriers found for those near the helix-3. For the quasi-bound water molecules near the first and second helices, we use well-known Kramers' theory to estimate the residence time from the free energy surface, by estimating the friction along the reaction coordinate from the diffusion coefficient by using Einstein relation. The agreement found is satisfactory. We discuss the possible biological function of these slow, quasi-bound (but transient) water molecules on the surface.

  1. Quantum Electric Dipole Lattice - Water Molecules Confined to Nanocavities in Beryl

    NASA Astrophysics Data System (ADS)

    Dressel, Martin; Zhukova, Elena S.; Thomas, Victor G.; Gorshunov, Boris P.

    2018-02-01

    Water is subject to intense investigations due to its importance in biological matter but keeps many of its secrets. Here, we unveil an even other aspect by confining H2O molecules to nanosize cages. Our THz and infrared spectra of water in the gemstone beryl evidence quantum tunneling of H2O molecules in the crystal lattice. The water molecules are spread out when confined in a nanocage. In combination with low-frequency dielectric measurements, we were also able to show that dipolar coupling among the H2O molecules leads towards a ferroelectric state at low temperatures. Upon cooling, a ferroelectric soft mode shifts through the THz range. Only quantum fluctuations prevent perfect macroscopic order to be fully achieved. Beside the significance to life science and possible application, nanoconfined water may become the prime example of a quantum electric dipolar lattice.

  2. What Can Interfacial Water Molecules Tell Us About Solute Structure?

    NASA Astrophysics Data System (ADS)

    Willard, Adam

    The molecular structure of bulk liquid water reflects a molecular tendency to engage in tetrahedrally coordinated hydrogen bonding. At a solute interface waters preferred three-dimensional hydrogen bonding network must conform to a locally anisotropy interfacial environment. Interfacial water molecules adopt configurations that balance water-solute and water-water interactions. The arrangements of interfacial water molecules, therefore encode information about the effective solute-water interactions. This solute-specific information is difficult to extract, however, because interfacial structure also reflects waters collective response to an anisotropic hydrogen bonding environment. Here I present a methodology for characterizing the molecular-level structure of liquid water interface from simulation data. This method can be used to explore waters static and/or dynamic response to a wide range of chemically and topologically heterogeneous solutes such as proteins.

  3. Structures of water molecules in carbon nanotubes under electric fields

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

    Winarto,; Takaiwa, Daisuke; Yamamoto, Eiji

    2015-03-28

    Carbon nanotubes (CNTs) are promising for water transport through membranes and for use as nano-pumps. The development of CNT-based nanofluidic devices, however, requires a better understanding of the properties of water molecules in CNTs because they can be very different from those in the bulk. Using all-atom molecular dynamics simulations, we investigate the effect of axial electric fields on the structure of water molecules in CNTs having diameters ranging from (7,7) to (10,10). The water dipole moments were aligned parallel to the electric field, which increases the density of water inside the CNTs and forms ordered ice-like structures. The electricmore » field induces the transition from liquid to ice nanotubes in a wide range of CNT diameters. Moreover, we found an increase in the lifetime of hydrogen bonds for water structures in the CNTs. Fast librational motion breaks some hydrogen bonds, but the molecular pairs do not separate and the hydrogen bonds reform. Thus, hydrogen bonds maintain the water structure in the CNTs, and the water molecules move collectively, decreasing the axial diffusion coefficient and permeation rate.« less

  4. Characterization of metal oxide absorbents for regenerative carbon dioxide and water vapor removal for advanced portable life support systems

    NASA Technical Reports Server (NTRS)

    Kast, Timothy P.; Nacheff-Benedict, Maurena S.; Chang, Craig H.; Cusick, Robert J.

    1990-01-01

    Characterization of the performance of a silver-oxide-based absorbent in terms of its ability to remove both gaseous CO2 and water vapor in an astronaut portable life support systems (PLSS) is discussed. Attention is focused on regeneration of the absorbent from the carbonite state of the oxide state, preconditioning of the absorbent using a humidified gas stream, and absorption breakthrough testing. Based on the results of bench-scale experiments, a test plan is carried out to further characterize the silver-oxide-based absorbent on a larger scale; it calls for examination of the absorbent in both an adiabatic packed bed and a near-isothermal cooled bed configuration. It is demonstrated that the tested absorbent can be utilized in a way that removes substantial amounts of CO2 and water vapor during an 8-hour extravehicular activity mission, and that applying the absorbent to PLSS applications can simplify the ventilation loop.

  5. Bound states of water in gelatin discriminated by near-infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Otsuka, Yukiko; Shirakashi, Ryo; Hirakawa, Kazuhiko

    2017-11-01

    By near-infrared spectroscopy, we classified water molecules in hydrated gelatin membranes in a drying process. Absorbance spectra in the frequency range of 4500-5500 cm-1 were resolved into three peaks, S0, S1, and S2, that correspond to water molecules with different hydrogen bond states. From the areas of the absorbance peaks as a function of the water content of gelatin, together with the information on the freezing properties of water measured by differential scanning calorimetry, we found that, when the water content is less than 20%, free water disappears and only weakly and strongly bound waters remain. We also found that the weakly bound water consists of S0, S1, and S2 water molecules with a simple composition of \\text{S}0:\\text{S}1:\\text{S}2 ≈ 1:2:0. Using this information, most of the freezable water was determined to be free water. Our classification provides a simple method of estimating the retention and freezing properties of processed foods or drugs by infrared spectroscopy.

  6. Water dynamics in rigid ionomer networks.

    PubMed

    Osti, N C; Etampawala, T N; Shrestha, U M; Aryal, D; Tyagi, M; Diallo, S O; Mamontov, E; Cornelius, C J; Perahia, D

    2016-12-14

    The dynamics of water within ionic polymer networks formed by sulfonated poly(phenylene) (SPP), as revealed by quasi-elastic neutron scattering (QENS), is presented. These polymers are distinguished from other ionic macromolecules by their rigidity and therefore in their network structure. QENS measurements as a function of temperature as the fraction of ionic groups and humidity were varied have shown that the polymer molecules are immobile while absorbed water molecules remain dynamic. The water molecules occupy multiple sites, either bound or loosely constrained, and bounce between the two. With increasing temperature and hydration levels, the system becomes more dynamic. Water molecules remain mobile even at subzero temperatures, illustrating the applicability of the SPP membrane for selective transport over a broad temperature range.

  7. Orbeez: the magic water absorbing bead--risk of pediatric bowel obstruction?

    PubMed

    Darracq, Michael A; Cullen, Jennifer; Rentmeester, Landen; Cantrell, F Lee; Ly, Binh T

    2015-06-01

    In December 2012, the U.S. Consumer Product Safety Commission recalled the water-absorbing toy WaterBalz after reports of small intestine obstruction after ingestion by children. Orbeez, another water-absorbing bead, remains available and is marketed as a children's toy. We sought to determine the extent to which Orbeez enlarge in various liquid media and the potential risk for bowel obstruction. Three Orbeez beads were added to 210 mL of the following liquid media: room temperature tap water, whole milk, simulated gastric fluid, GoLytely (polyethelyelene glycol, 3350 and electrolytes), and vodka (40% ethanol by volume). Diameters before exposure to media were measured using a caliper to the nearest 0.1 mm and again at 1, 2, 4, 6, 12, and 24 hours. Ten beads were then added to the beads already immersed in simulated gastric fluid and water and observed for an additional 72 hours (96 hours total) for clumping or increase in diameter. Clumping was defined as two or more beads remaining persistently adherent to one another despite gentle circular movement (swirling) of the liquid. Growth in each of the media was observed. Growth in simulated gastric fluid was minimal, whereas the beads were observed to be the largest after 24 hours in vodka. Clumping of the beads was not observed to occur. Orbeez beads enlarge to a different extent in different liquid media. It is unlikely that Orbeez beads would expand to sizes or demonstrate clumping that would be concerning for intestinal obstruction.

  8. Multistep Cylindrical Structure Analysis at Normal Incidence Based on Water-Substrate Broadband Metamaterial Absorbers

    NASA Astrophysics Data System (ADS)

    Fang, Chonghua

    2018-01-01

    A new multistep cylindrical structure based on water-substrate broadband metamaterial absorbers is designed to reduce the traditional radar cross-section (RCS) of a rod-shaped object. The proposed configuration consists of two distinct parts. One of these components is formed by a four-step cylindrical metal structure, whereas the other one is formed by a new water-substrate broadband metamaterial absorber. The designed structure can significantly reduce the radar cross section more than 10 dB from 4.58 to 18.42 GHz which is the 86.5 % bandwidth of from C-band to 20 GHz. The results of measurement show reasonably good accordance with the simulated ones, which verifies the ability and effect of the proposed design.

  9. The role of water molecules in stereoselectivity of glucose/galactose-binding protein

    NASA Astrophysics Data System (ADS)

    Kim, Minsup; Cho, Art E.

    2016-11-01

    Using molecular dynamics (MD) simulation methods, we attempted to explain the experimental results on ligand specificity of glucose/galactose-binding protein (GGBP) to β-D-glucose and β-D-galactose. For the simulation, a three-dimensional structure of GGBP was prepared, and homology modeling was performed to generate variant structures of GGBP with mutations at Asp14. Then, docking was carried out to find a reasonable β-D-glucose and β-D-galactose binding conformations with GGBP. Subsequent molecular dynamics simulations of β-D-glucose-GGBP and β-D-galactose-GGBP complexes and estimation of the orientation and stability of water molecules at the binding site revealed how water molecules influence ligand specificity. In our simulation, water molecules mediated interactions of β-D-glucose or β-D-galactose with residue 14 of GGBP. In this mechanism, the Phe16Ala mutant leaves both sugar molecules free to move, and the specific role of water molecules were eliminated, while the wild type, Asp14Asn mutant, and Asp14Glu mutant make hydrogen bond interactions with β-D-glucose more favorable. Our results demonstrate that bound water molecules at the binding site of GGBP are related to localized conformational change, contributing to ligand specificity of GGBP for β-D-glucose over β-D-galactose.

  10. Hydration of polar and nonpolar molecules at the surface of amorphous solid water

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

    Souda, Ryutaro

    2004-10-15

    On the basis of time-of-flight secondary ion mass spectrometry, properties of amorphous solid water above the glass transition temperature (136 K) and the hydration of polar (HCOOH,C{sub 3}H{sub 7}OH) and nonpolar (C{sub 6}H{sub 14},C{sub 6}F{sub 14}) molecules on the D{sub 2}O-ice surface have been investigated. No evidence was obtained for the irreversible transition of the amorphous solid water into the crystalline phase: the self-diffusion of water molecules occurs above 140 K irrespective of the preparation temperatures of the water-ice film ranging from 15 K to 165 K, whereas the morphology of the film changes drastically at 165 K due tomore » the evolution of liquidlike water. It is also demonstrated that the change in conformation of the hydrated HCOOH molecule, as well as the occurrence of hydrophilic/hydrophobic hydration of the C{sub 3}H{sub 7}OH molecule, can be analyzed successfully from the temperature evolutions of the secondary-ion intensities. These polar molecules basically stay on the surface and tend to quench the morphological change of the water film due to the reduction of surface tension. The nonpolar C{sub 6}H{sub 14} and C{sub 6}F{sub 14} molecules readily dissolve in the D{sub 2}O layer below 100 K and dehydration of the incorporated molecules occurs at 165 K concomitantly with the evolution of the liquidlike water. It is thus concluded that the hydrophobic hydration of nonpolar molecules is intimately related to the properties of water films.« less

  11. Structurally conserved water molecules in ribonuclease T1.

    PubMed

    Malin, R; Zielenkiewicz, P; Saenger, W

    1991-03-15

    In the high resolution (1.7-1.9 A) crystal structures of ribonuclease T1 (RNase T1) in complex with guanosine, guanosine 2'-phosphate, guanylyl 2',5'-guanosine, and vanadate, there are 30 water sites in nearly identical (+/- 1 A) positions that are considered conserved. One water is tightly bound to Asp76(O delta), Thr93(O gamma), Cys6(O), and Asn9(N); another bridges two loops by hydrogen-bonding to Tyr68(O eta) and to Ser35(N), Asn36(N); a loop structure is stabilized by two waters coordinated to Gly31(O) and His27(N delta), and by water bound to cis-Pro39(O). Most notable is a hydrogen-bonded chain of 10 water molecules. Waters 1-5 of this chain are inaccessible to solvent, are anchored at Trp59(N), and stitch together the loop formed by segments 60-68; waters 5-8 coordinate to Ca2+, and waters 9 and 10 hydrogen-bond to N-terminal side chains of the alpha-helix. The water chain and two conserved water molecules are bound to amino acids adjacent to the active site residues His40, Glu58, Arg77, and His92; they are probably involved in maintaining their spatial orientation required for catalysis. Water sites must be considered in genetic engineering; the mutation Trp59Tyr, which probably influences the 10-water chain, doubles the catalytic activity of RNase T1.

  12. Ultrasensitive Laser Spectroscopy in Solids: Single-Molecule Detection

    DTIC Science & Technology

    1989-10-25

    spite of detection intensity constraints necessary to avoid power broadening, the optical absorption spectrum of single molecules of pentacene In p...molecule detection, or SMD) would provide a useful tool for the study of local host-absorber interactions where tihe absorbing ,ontor is essentially at...modulation techniques 7. 8 for the model system composed of pentacene substitutional impurities in p-terphenyl crystals at 1.5K. The pontacene molecules can

  13. Confinement of water molecule inside (2, 2) graphyne nanotube

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

    Deb, Jyotirmoy; Bhattacharya, Barnali; Sarkar, Utpal, E-mail: utpalchemiitkgp@yahoo.com

    2016-05-23

    Using density functional theory (DFT) calculations with generalized gradient approximation, the interaction between H{sub 2}O molecule and (2, 2) graphyne nanotube (GNT) has been investigated. The stable configuration due to the insertion of H{sub 2}O molecule inside (2, 2) GNT is determined on the basis of binding energy. The band gap of the GNT decreases due to the confinement of H{sub 2}O molecule. The charge analysis reveals that electrons are shifted from the H{sub 2}O molecule to the GNT. The electronic property of the GNT is highly influenced by the presence of H{sub 2}O molecule; thus, we may design amore » GNT based sensor for the detection of water molecule.« less

  14. The Effect of Water Molecules on Mechanical Properties of Cell Walls

    NASA Astrophysics Data System (ADS)

    Rahbar, Nima; Youssefian, Sina

    The unique properties of bamboo fibers come from their natural composite structures that comprise mainly cellulose nanofibrils in a matrix of intertwined hemicellulose and lignin called lignin-carbohydrate complex (LCC). Here, we have utilized atomistic simulations to investigate the mechanical properties and mechanisms of interactions between these materials, in the presence of water molecules. The role of hemicellulose found to be enhancing the mechanical properties and lignin found to be providing the strength of bamboo fibers. The abundance of Hbonds in hemicellulose chains is responsible for improving the mechanical behavior of LCC. The strong van der Waals forces between lignin molecules and cellulose nanofibrils are responsible for higher adhesion energy between LCC/cellulose nanofibrils. We also found out that the amorphous regions of cellulose nanofibrils is the weakest interface in bamboo Microfibrils. In presence of water, the elastic modulus of lignin increases at low water content and decreases in higher water content, whereas the hemicellulose elastic modulus constantly decreases. The variations of Radial Distribution Function and Free Fractional Volume of these materials with water suggest that water molecules enhance the mechanical properties of lignin by filling voids in the system and creating Hbond bridges between polymer chains. For hemicellulose, however, the effect is always regressive due to the destructive effect of water molecules on the Hbond of its dense structure.

  15. Water in the presence of inert Lennard-Jones obstacles

    NASA Astrophysics Data System (ADS)

    Kurtjak, Mario; Urbic, Tomaz

    2014-04-01

    Water confined by the presence of a 'sea' of inert obstacles was examined. In the article, freely mobile two-dimensional Mercedes-Benz (MB) water put to a disordered, but fixed, matrix of Lennard-Jones disks was studied by the Monte Carlo computer simulations. For the MB water molecules in the matrix of Lennard-Jones disks, we explored the structures, hydrogen-bond-network formation and thermodynamics as a function of temperature and size and density of matrix particles. We found that the structure of model water is perturbed by the presence of the obstacles. Density of confined water, which was in equilibrium with the bulk water, was smaller than the density of the bulk water and the temperature dependence of the density of absorbed water did not show the density anomaly in the studied temperature range. The behaviour observed as a consequence of confinement is similar to that of increasing temperature, which can for a matrix lead to a process similar to capillary evaporation. At the same occupancy of space, smaller matrix molecules cause higher destruction effect on the absorbed water molecules than the bigger ones. We have also tested the hypothesis that at low matrix densities the obstacles induce an increased ordering and 'hydrogen bonding' of the MB model molecules, relative to pure fluid, while at high densities the obstacles reduce MB water structuring, as they prevent the fluid to form good 'hydrogen-bonding' networks. However, for the size of matrix molecules similar to that of water, we did not observe this effect.

  16. Hydration in drug design. 3. Conserved water molecules at the ligand-binding sites of homologous proteins

    NASA Astrophysics Data System (ADS)

    Poornima, C. S.; Dean, P. M.

    1995-12-01

    Water molecules are known to play an important rôle in mediating protein-ligand interactions. If water molecules are conserved at the ligand-binding sites of homologous proteins, such a finding may suggest the structural importance of water molecules in ligand binding. Structurally conserved water molecules change the conventional definition of `binding sites' by changing the shape and complementarity of these sites. Such conserved water molecules can be important for site-directed ligand/drug design. Therefore, five different sets of homologous protein/protein-ligand complexes have been examined to identify the conserved water molecules at the ligand-binding sites. Our analysis reveals that there are as many as 16 conserved water molecules at the FAD binding site of glutathione reductase between the crystal structures obtained from human and E. coli. In the remaining four sets of high-resolution crystal structures, 2-4 water molecules have been found to be conserved at the ligand-binding sites. The majority of these conserved water molecules are either bound in deep grooves at the protein-ligand interface or completely buried in cavities between the protein and the ligand. All these water molecules, conserved between the protein/protein-ligand complexes from different species, have identical or similar apolar and polar interactions in a given set. The site residues interacting with the conserved water molecules at the ligand-binding sites have been found to be highly conserved among proteins from different species; they are more conserved compared to the other site residues interacting with the ligand. These water molecules, in general, make multiple polar contacts with protein-site residues.

  17. Hydrogen isotope separation from water

    DOEpatents

    Jensen, R.J.

    1975-09-01

    A process for separating tritium from tritium-containing water or deuterium enrichment from water is described. The process involves selective, laser-induced two-photon excitation and photodissociation of those water molecules containing deuterium or tritium followed by immediate reaction of the photodissociation products with a scavenger gas which does not substantially absorb the laser light. The reaction products are then separated from the undissociated water. (auth)

  18. Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

    NASA Astrophysics Data System (ADS)

    Prisk, T. R.; Hoffmann, C.; Kolesnikov, A. I.; Mamontov, E.; Podlesnyak, A. A.; Wang, X.; Kent, P. R. C.; Anovitz, L. M.

    2018-05-01

    Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factor reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10-100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.

  19. Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

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

    Prisk, Timothy; Hoffmann, Christina; Kolesnikov, Alexander I.

    Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less

  20. Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

    DOE PAGES

    Prisk, Timothy; Hoffmann, Christina; Kolesnikov, Alexander I.; ...

    2018-05-09

    Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less

  1. Transport of water molecules through noncylindrical pores in multilayer nanoporous graphene.

    PubMed

    Shahbabaei, Majid; Kim, Daejoong

    2017-08-09

    In this study, molecular dynamics (MD) simulations are used to examine the water transport properties through asymmetric hourglass-shaped pores in multilayer nanoporous graphene with a constant interlayer separation of 6 Å. The properties of the tested asymmetric hourglass-shaped pores [with the models having long cone (l 1 , -P) and short cone (l 2 , +P) entrances] are compared to a symmetric pore model. The study findings indicate that the water occupancy increases across the asymmetric pore (l 1 , -P) compared to (l 2 , +P), because of the length effect. The asymmetric pore, (l 1 , -P), yields higher flux compared to (l 2 , +P) and even the symmetric model, which can be attributed to the increase in the hydrogen bonds. In addition, the single-file water molecules across the narrowest pore diameter inside the (l 2 , +P) pore exhibit higher viscosity compared to those in the (l 1 , -P) pore because of the increase in the water layering effect. Moreover, it is found that the permeability inside the multilayer hourglass-shaped pore depends on the length of the flow path of the water molecules before approaching the layer with the smallest pore diameter. The probability of dipole orientation exhibits wider distribution inside the (l 1 , -P) system compared to (l 2 , +P), implying an enhanced formation of hydrogen bonding of water molecules. This results in the fast flow of water molecules. The MD trajectory shows that the dipole orientation across the single-layer graphene has frequently flipped compared to the dipole orientation across the pores in multilayer graphene, which is maintained during the whole simulation time (although the dipole orientation has flipped for a few picoseconds at the beginning of the simulation). This can be attributed to the energy barrier induced by the individual layer. The diffusion coefficient of water molecules inside the (l 2 , +P) system increases with pressure difference, however, it decreases inside the (l 1 , -P) system because

  2. Incipient ferroelectricity of water molecules confined to nano-channels of beryl

    NASA Astrophysics Data System (ADS)

    Gorshunov, B. P.; Torgashev, V. I.; Zhukova, E. S.; Thomas, V. G.; Belyanchikov, M. A.; Kadlec, C.; Kadlec, F.; Savinov, M.; Ostapchuk, T.; Petzelt, J.; Prokleška, J.; Tomas, P. V.; Pestrjakov, E. V.; Fursenko, D. A.; Shakurov, G. S.; Prokhorov, A. S.; Gorelik, V. S.; Kadyrov, L. S.; Uskov, V. V.; Kremer, R. K.; Dressel, M.

    2016-09-01

    Water is characterized by large molecular electric dipole moments and strong interactions between molecules; however, hydrogen bonds screen the dipole-dipole coupling and suppress the ferroelectric order. The situation changes drastically when water is confined: in this case ordering of the molecular dipoles has been predicted, but never unambiguously detected experimentally. In the present study we place separate H2O molecules in the structural channels of a beryl single crystal so that they are located far enough to prevent hydrogen bonding, but close enough to keep the dipole-dipole interaction, resulting in incipient ferroelectricity in the water molecular subsystem. We observe a ferroelectric soft mode that causes Curie-Weiss behaviour of the static permittivity, which saturates below 10 K due to quantum fluctuations. The ferroelectricity of water molecules may play a key role in the functioning of biological systems and find applications in fuel and memory cells, light emitters and other nanoscale electronic devices.

  3. Incipient ferroelectricity of water molecules confined to nano-channels of beryl

    PubMed Central

    Gorshunov, B. P.; Torgashev, V. I.; Zhukova, E. S.; Thomas, V. G.; Belyanchikov, M. A.; Kadlec, C.; Kadlec, F.; Savinov, M.; Ostapchuk, T.; Petzelt, J.; Prokleška, J.; Tomas, P. V.; Pestrjakov, E. V.; Fursenko, D. A.; Shakurov, G. S.; Prokhorov, A. S.; Gorelik, V. S.; Kadyrov, L. S.; Uskov, V. V.; Kremer, R. K.; Dressel, M.

    2016-01-01

    Water is characterized by large molecular electric dipole moments and strong interactions between molecules; however, hydrogen bonds screen the dipole–dipole coupling and suppress the ferroelectric order. The situation changes drastically when water is confined: in this case ordering of the molecular dipoles has been predicted, but never unambiguously detected experimentally. In the present study we place separate H2O molecules in the structural channels of a beryl single crystal so that they are located far enough to prevent hydrogen bonding, but close enough to keep the dipole–dipole interaction, resulting in incipient ferroelectricity in the water molecular subsystem. We observe a ferroelectric soft mode that causes Curie–Weiss behaviour of the static permittivity, which saturates below 10 K due to quantum fluctuations. The ferroelectricity of water molecules may play a key role in the functioning of biological systems and find applications in fuel and memory cells, light emitters and other nanoscale electronic devices. PMID:27687693

  4. Water-based metamaterial absorbers for optical transparency and broadband microwave absorption

    NASA Astrophysics Data System (ADS)

    Pang, Yongqiang; Shen, Yang; Li, Yongfeng; Wang, Jiafu; Xu, Zhuo; Qu, Shaobo

    2018-04-01

    Naturally occurring water is a promising candidate for achieving broadband absorption. In this work, by virtue of the optically transparent character of the water, the water-based metamaterial absorbers (MAs) are proposed to achieve the broadband absorption at microwave frequencies and optical transparence simultaneously. For this purpose, the transparent indium tin oxide (ITO) and polymethyl methacrylate (PMMA) are chosen as the constitutive materials. The water is encapsulated between the ITO backed plate and PMMA, serving as the microwave loss as well as optically transparent material. Numerical simulations show that the broadband absorption with the efficiency over 90% in the frequency band of 6.4-30 GHz and highly optical transparency of about 85% in the visible region can be achieved and have been well demonstrated experimentally. Additionally, the proposed water-based MA displays a wide-angle absorption performance for both TE and TM waves and is also robust to the variations of the structure parameters, which is much desired in a practical application.

  5. Vibrational states of a water molecule in a nano-cavity of beryl crystal lattice

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

    Zhukova, Elena S., E-mail: zhukovaelenka@gmail.com; Gorshunov, Boris P.; 1. Physikalisches Institut, Universität Stuttgart, Pfaffenwaldring 57, 70550 Stuttgart

    2014-06-14

    Low-energy excitations of a single water molecule are studied when confined within a nano-size cavity formed by the ionic crystal lattice. Optical spectra are measured of manganese doped beryl single crystal Mn:Be{sub 3}Al{sub 2}Si{sub 6}O{sub 18}, that contains water molecules individually isolated in 0.51 nm diameter voids within the crystal lattice. Two types of orientation are distinguished: water-I molecules have their dipole moments aligned perpendicular to the c axis and dipole moments of water-II molecules are parallel to the c-axis. The optical conductivity σ(ν) and permittivity ε{sup ′}(ν) spectra are recorded in terahertz and infrared ranges, at frequencies from severalmore » wavenumbers up to ν = 7000 cm{sup −1}, at temperatures 5–300 K and for two polarizations, when the electric vector E of the radiation is parallel and perpendicular to the c-axis. Comparative experiments on as-grown and on dehydrated samples allow to identify the spectra of σ(ν) and ε{sup ′}(ν) caused exclusively by water molecules. In the infrared range, well-known internal modes ν{sub 1}, ν{sub 2}, and ν{sub 3} of the H{sub 2}O molecule are observed for both polarizations, indicating the presence of water-I and water-II molecules in the crystal. Spectra recorded below 1000 cm{sup −1} reveal a rich set of highly anisotropic features in the low-energy response of H{sub 2}O molecule in a crystalline nano-cavity. While for E∥c only two absorption peaks are detected, at ∼90 cm{sup −1} and ∼160 cm{sup −1}, several absorption bands are discovered for E⊥c, each consisting of narrower resonances. The bands are assigned to librational (400–500 cm{sup −1}) and translational (150–200 cm{sup −1}) vibrations of water-I molecule that is weakly coupled to the nano-cavity “walls.” A model is presented that explains the “fine structure” of the bands by a splitting of the energy levels due to quantum tunneling between the minima in a six

  6. Detection of magnetic dipolar coupling of water molecules at the nanoscale using quantum magnetometry

    NASA Astrophysics Data System (ADS)

    Yang, Zhiping; Shi, Fazhan; Wang, Pengfei; Raatz, Nicole; Li, Rui; Qin, Xi; Meijer, Jan; Duan, Changkui; Ju, Chenyong; Kong, Xi; Du, Jiangfeng

    2018-05-01

    It is a crucial issue to study interactions among water molecules and hydrophobic interfacial water at the nanoscale. Here we succeed in measuring the nuclear magnetic resonance spectrum of a diamond-water interfacial ice with a detection volume of about 2.2 ×10-22 L. More importantly, the magnetic dipolar coupling between the two protons of a water molecule is resolved by measuring the signal contributed from about 7000 water molecules at the nanoscale. The resolved intramolecule magnetic dipolar interactions are about 15 and 33 kHz with spectral resolution of 5 kHz. This work provides a platform for hydrophobic interfacial water study under ambient conditions, with further applications in more general nanoscale structural analysis.

  7. Development of novel two-photon absorbing chromophores

    NASA Astrophysics Data System (ADS)

    Rogers, Joy E.; Slagle, Jonathan E.; McLean, Daniel G.; Sutherland, Richard L.; Krein, Douglas M.; Cooper, Thomas M.; Brant, Mark; Heinrichs, James; Kannan, Ramamurthi; Tan, Loon-Seng; Urbas, Augustine M.; Fleitz, Paul A.

    2006-08-01

    There has been much interest in the development of two-photon absorbing materials and many efforts to understand the nonlinear absorption properties of these dyes but this area is still not well understood. A computational model has been developed in our lab to understand the nanosecond nonlinear absorption properties that incorporate all of the measured one-photon photophysical parameters of a class of materials called AFX. We have investigated the nonlinear and photophysical properties of the AFX chromophores including the two-photon absorption cross-section, the excited state cross-section, the intersystem crossing quantum yield, and the singlet and triplet excited state lifetimes using a variety of experimental techniques that include UV-visible, fluorescence and phosphorescence spectroscopy, time correlated single photon counting, ultrafast transient absorption, and nanosecond laser flash photolysis. The model accurately predicts the nanosecond nonlinear transmittance data using experimentally measured parameters. Much of the strong nonlinear absorption has been shown to be due to excited state absorption from both the singlet and triplet excited states. Based on this understanding of the nonlinear absorption and the importance of singlet and triplet excited states we have begun to develop new two-photon absorbing molecules within the AFX class as well as linked to other classes of nonlinear absorbing molecules. This opens up the possibilities of new materials with unique and interesting properties. Specifically we have been working on a new class of two-photon absorbing molecules linked to platinum poly-ynes. In the platinum poly-yne chromophores the photophysics are more complicated and we have just started to understand what drives both the linear and non-linear photophysical properties.

  8. Investigation of the Hydantoin Monomer and its Interaction with Water Molecules

    NASA Astrophysics Data System (ADS)

    Gruet, Sébastien; Perez, Cristobal; Schnell, Melanie

    2017-06-01

    Hydantoin (Imidazolidine-2,4-dione, C_3H_4N_2O_2) is a five-membered heterocyclic compound of astrobiological interest. This molecule has been detected in carbonaceous chondrites [1], and its formation can rise from the presence of glycolic acid and urea, two prebiotic molecules [2]. The hydrolysis of hydantoin under acidic conditions can also produce glycine [3], an amino acid actively searched for in the interstellar medium. Spectroscopic data of hydantoin is very limited and mostly dedicated to the solid phase. The high resolution study in gas phase is restricted to the work recently published by Ozeki et al. reporting the pure rotational spectra of the ground state and two vibrational states of the molecule in the millimeter-wave region (90-370 GHz)[4]. Using chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy, we recorded the jet-cooled rotational spectra of hydantoin with water between 2 to 8 GHz. We observed the ground state of hydantoin monomer and several water complexes with one or two water molecules. All the observed species exhibit a hyperfine structure due to the two nitrogen atoms present in the molecule, which were fully resolved and analyzed. Additional experiments with a ^{18}O enriched water sample were realized to determine the oxygen-atom positions of the water monomers. These experiments yielded accurate structural information on the preferred water binding sites. The observed complexes and the interactions that hold them together, mainly strong directional hydrogen bonds, will be presented and discussed. [1] Shimoyama, A. and Ogasawara, R., Orig. Life Evol. Biosph., 32, 165-179, 2002. DOI:10.1023/A:1016015319112. [2] Menor-Salván, C. and Marín-Yaseli, M.R., Chem. Soc. Rev., 41(16), 5404-5415, 2012. DOI:10.1039/c2cs35060b. [3] De Marcellus P., Bertrand M., Nuevo M., Westall F. and Le Sergeant d'Hendecourt L., Astrobiology. 11(9), 847-854, 2011. DOI:10.1089/ast.2011.0677. [4] Ozeki, H., Miyahara R., Ihara H., Todaka S., Kobayashi

  9. Degradation process by effect of water molecules during negative bias temperature stress in amorphous-InGaZnO thin-film transistor

    NASA Astrophysics Data System (ADS)

    Lee, Yeol-Hyeong; Cho, Yong-Jung; Kim, Woo-Sic; Park, Jeong Ki; Kim, Geon Tae; Kim, Ohyun

    2017-10-01

    We explained how H2O degrades amorphous-InGaZnO thin-film transistors. H2O caused serious degradation only during negative bias temperature stress (NBTS). Degradation was caused by molecules that were absorbed or diffused from the outside. We suggest that degradation under NBTS is caused by the migration of hydrogen ions among oxygen vacancies. Under illumination, the soaking time t S did not affect the threshold voltage shift ΔV th. We consider that this independence occurred because illumination caused ionization from the oxygen vacancy VO state to VO 2+, which impeded hydrogen migration induced by electric field and thereby protected the device from degradation after exposure to water.

  10. Using LiF:Mg,Cu,P TLDs to estimate the absorbed dose to water in liquid water around an 192Ir brachytherapy source.

    PubMed

    Lucas, P Avilés; Aubineau-Lanièce, I; Lourenço, V; Vermesse, D; Cutarella, D

    2014-01-01

    The absorbed dose to water is the fundamental reference quantity for brachytherapy treatment planning systems and thermoluminescence dosimeters (TLDs) have been recognized as the most validated detectors for measurement of such a dosimetric descriptor. The detector response in a wide energy spectrum as that of an (192)Ir brachytherapy source as well as the specific measurement medium which surrounds the TLD need to be accounted for when estimating the absorbed dose. This paper develops a methodology based on highly sensitive LiF:Mg,Cu,P TLDs to directly estimate the absorbed dose to water in liquid water around a high dose rate (192)Ir brachytherapy source. Different experimental designs in liquid water and air were constructed to study the response of LiF:Mg,Cu,P TLDs when irradiated in several standard photon beams of the LNE-LNHB (French national metrology laboratory for ionizing radiation). Measurement strategies and Monte Carlo techniques were developed to calibrate the LiF:Mg,Cu,P detectors in the energy interval characteristic of that found when TLDs are immersed in water around an (192)Ir source. Finally, an experimental system was designed to irradiate TLDs at different angles between 1 and 11 cm away from an (192)Ir source in liquid water. Monte Carlo simulations were performed to correct measured results to provide estimates of the absorbed dose to water in water around the (192)Ir source. The dose response dependence of LiF:Mg,Cu,P TLDs with the linear energy transfer of secondary electrons followed the same variations as those of published results. The calibration strategy which used TLDs in air exposed to a standard N-250 ISO x-ray beam and TLDs in water irradiated with a standard (137)Cs beam provided an estimated mean uncertainty of 2.8% (k = 1) in the TLD calibration coefficient for irradiations by the (192)Ir source in water. The 3D TLD measurements performed in liquid water were obtained with a maximum uncertainty of 11% (k = 1) found at 1 cm

  11. Pigmentation and spectral absorbance signatures in deep-water corals from the Trondheimsfjord, Norway.

    PubMed

    Elde, Anette C; Pettersen, Ragnhild; Bruheim, Per; Järnegren, Johanna; Johnsen, Geir

    2012-06-01

    The pigmentation and corresponding in vivo and in vitro absorption characteristics in three different deep-water coral species: white and orange Lophelia pertusa, Paragorgia arborea and Primnoa resedaeformis, collected from the Trondheimsfjord are described. Pigments were isolated and characterized by High-Performance Liquid Chromatography (HPLC) analysis and High-Performance Liquid Chromatography Time-Of-Flight Mass Spectrometer (LC-TOF MS). The main carotenoids identified for all three coral species were astaxanthin and a canthaxanthin-like carotenoid. Soft tissue and skeleton of orange L. pertusa contained 2 times more astaxanthin g(-1) wet weight compared to white L. pertusa. White and orange L. pertusa were characterized with in vivo absorbance peaks at 409 and 473 nm, respectively. In vivo absorbance maxima for P. arborea and P. resedaeformis was typically at 475 nm. The shapes of the absorbance spectra (400-700 nm) were species-specific, indicated by in vivo, in vitro and the corresponding difference spectra. The results may provide important chemotaxonomic information for pigment when bonded to their proteins in vivo, bio-prospecting, and for in situ identification, mapping and monitoring of corals.

  12. Thermodynamics of hydrogen bond patterns in supramolecular assemblies of water molecules.

    PubMed

    Henry, Marc

    2002-07-02

    The PACHA (Partial Atomic Charges and Hardnesses Analysis) formalism is applied to various supramolecular assemblies of water molecules. After a detailed study of all available crystal structures for ice polymorphs, we shown that the hydrogen bond strength is roughly constant below 1 GPa and considerably weakened above that value. New hydrogen bond patterns are proposed for ice IV, V, and VI after (EB) (electrostatic balance) minimization. For other polymorphs, there is an almost perfect coincidence between experimental and predicted hydrogen bond patterns. The evolution of hydrogen bond energy as a function of molecular geometry in water clusters with up to 280 water molecules and in large supramolecular compounds is quantitatively described. Intermolecular hydrogen bonds are found to lie between -9 and -32 kJ mol-1, the stronger interaction occurs within the spherical fully disordered water droplet buried at the heart of Müller's superfullerene keplerate. The weakest one occurs in a chiral molecular snub cube built from six calix[4]resorcinarene and eight water molecules. Intramolecular hydrogen bonds are found in the range -10-100 kJ mol-1 and can thus be considerably stronger than intermolecular bonds. Finally, through the investigation of a clathrate type I compound, it was possible to obtain a deep insight of the host-guest interactions and self-assembly rules of water cages in these materials.

  13. Water: a responsive small molecule.

    PubMed

    Shultz, Mary Jane; Vu, Tuan Hoang; Meyer, Bryce; Bisson, Patrick

    2012-01-17

    Unique among small molecules, water forms a nearly tetrahedral yet flexible hydrogen-bond network. In addition to its flexibility, this network is dynamic: bonds are formed or broken on a picosecond time scale. These unique features make probing the local structure of water challenging. Despite the challenges, there is intense interest in developing a picture of the local water structure due to water's fundamental importance in many fields of chemistry. Understanding changes in the local network structure of water near solutes likely holds the key to unlock problems from analyzing parameters that determine the three dimensional structure of proteins to modeling the fate of volatile materials released into the atmosphere. Pictures of the local structure of water are heavily influenced by what is known about the structure of ice. In hexagonal I(h) ice, the most stable form of solid water under ordinary conditions, water has an equal number of donor and acceptor bonds; a kind of symmetry. This symmetric tetrahedral coordination is only approximately preserved in the liquid. The most obvious manifestation of this altered tetrahedral bonding is the greater density in the liquid compared with the solid. Formation of an interface or addition of solutes further modifies the local bonding in water. Because the O-H stretching frequency is sensitive to the environment, vibrational spectroscopy provides an excellent probe for the hydrogen-bond structure in water. In this Account, we examine both local interactions between water and small solutes and longer range interactions at the aqueous surface. Locally, the results suggest that water is not a symmetric donor or acceptor, but rather has a propensity to act as an acceptor. In interactions with hydrocarbons, action is centered at the water oxygen. For soluble inorganic salts, interaction is greater with the cation than the anion. The vibrational spectrum of the surface of salt solutions is altered compared with that of neat

  14. Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation

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

    Ye, ChuanXiang; Zhao, Yi, E-mail: yizhao@xmu.edu.cn, E-mail: liangwz@xmu.edu.cn; Liang, WanZhen, E-mail: yizhao@xmu.edu.cn, E-mail: liangwz@xmu.edu.cn

    2015-10-21

    The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra withmore » respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT.« less

  15. High-order above-threshold dissociation of molecules

    NASA Astrophysics Data System (ADS)

    Lu, Peifen; Wang, Junping; Li, Hui; Lin, Kang; Gong, Xiaochun; Song, Qiying; Ji, Qinying; Zhang, Wenbin; Ma, Junyang; Li, Hanxiao; Zeng, Heping; He, Feng; Wu, Jian

    2018-03-01

    Electrons bound to atoms or molecules can simultaneously absorb multiple photons via the above-threshold ionization featured with discrete peaks in the photoelectron spectrum on account of the quantized nature of the light energy. Analogously, the above-threshold dissociation of molecules has been proposed to address the multiple-photon energy deposition in the nuclei of molecules. In this case, nuclear energy spectra consisting of photon-energy spaced peaks exceeding the binding energy of the molecular bond are predicted. Although the observation of such phenomena is difficult, this scenario is nevertheless logical and is based on the fundamental laws. Here, we report conclusive experimental observation of high-order above-threshold dissociation of H2 in strong laser fields where the tunneling-ionized electron transfers the absorbed multiphoton energy, which is above the ionization threshold to the nuclei via the field-driven inelastic rescattering. Our results provide an unambiguous evidence that the electron and nuclei of a molecule as a whole absorb multiple photons, and thus above-threshold ionization and above-threshold dissociation must appear simultaneously, which is the cornerstone of the nowadays strong-field molecular physics.

  16. High-order above-threshold dissociation of molecules.

    PubMed

    Lu, Peifen; Wang, Junping; Li, Hui; Lin, Kang; Gong, Xiaochun; Song, Qiying; Ji, Qinying; Zhang, Wenbin; Ma, Junyang; Li, Hanxiao; Zeng, Heping; He, Feng; Wu, Jian

    2018-02-27

    Electrons bound to atoms or molecules can simultaneously absorb multiple photons via the above-threshold ionization featured with discrete peaks in the photoelectron spectrum on account of the quantized nature of the light energy. Analogously, the above-threshold dissociation of molecules has been proposed to address the multiple-photon energy deposition in the nuclei of molecules. In this case, nuclear energy spectra consisting of photon-energy spaced peaks exceeding the binding energy of the molecular bond are predicted. Although the observation of such phenomena is difficult, this scenario is nevertheless logical and is based on the fundamental laws. Here, we report conclusive experimental observation of high-order above-threshold dissociation of H 2 in strong laser fields where the tunneling-ionized electron transfers the absorbed multiphoton energy, which is above the ionization threshold to the nuclei via the field-driven inelastic rescattering. Our results provide an unambiguous evidence that the electron and nuclei of a molecule as a whole absorb multiple photons, and thus above-threshold ionization and above-threshold dissociation must appear simultaneously, which is the cornerstone of the nowadays strong-field molecular physics. Copyright © 2018 the Author(s). Published by PNAS.

  17. Method 415.3, Rev. 1.2: Determination of Total Organic Carbon and Specific UV Absorbance at 254 nm in Source Water and Drinking Water

    EPA Science Inventory

    This method provides procedures for the determination of total organic carbon (TOC), dissolved organic carbon (DOC), and UV absorption at 254 nm (UVA) in source waters and drinking waters. The DOC and UVA determinations are used in the calculation of the Specific UV Absorbance (S...

  18. Quantum Tunneling of Water in Beryl. A New State of the Water Molecule

    DOE PAGES

    Kolesnikov, Alexander I.; Reiter, George F.; Choudhury, Narayani; ...

    2016-04-22

    When using neutron scattering and ab initio simulations, we document the discovery of a new “quantum tunneling state” of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. We observed a number of peaks in the inelastic neutron scattering spectra that were uniquely assigned to water quantum tunneling. Additionally, the water proton momentum distribution was measured with deep inelastic neutron scattering, which directly revealed coherent delocalization of the protons in the ground state.

  19. Quantum Tunneling of Water in Beryl. A New State of the Water Molecule

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

    Kolesnikov, Alexander I.; Reiter, George F.; Choudhury, Narayani

    When using neutron scattering and ab initio simulations, we document the discovery of a new “quantum tunneling state” of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. We observed a number of peaks in the inelastic neutron scattering spectra that were uniquely assigned to water quantum tunneling. Additionally, the water proton momentum distribution was measured with deep inelastic neutron scattering, which directly revealed coherent delocalization of the protons in the ground state.

  20. On the dynamics of water molecules at the protein solute interfaces.

    PubMed

    Bernini, A; Spiga, O; Ciutti, A; Chiellini, S; Menciassi, N; Venditti, V; Niccolai, N

    2004-10-01

    Proteins, with the large variety of chemical groups they present at their molecular surface, are a class of molecules which can be very informative on most of the possible solute-solvent interactions. Hen egg white lysozyme has been used as a probe to investigate the complex solvent dynamics occurring at the protein surface, by analysing the results obtained from Nuclear Magnetic Resonance, X-ray diffractometry and Molecular Dynamics simulations. A consistent overall picture for the dynamics of water molecules close to the protein is obtained, suggesting that a rapid exchange occurs, in a picosecond timescale, among all the possible hydration surface sites both in solution and the solid state, excluding the possibility that solvent molecules can form liquid-crystal-like supramolecular adducts, which have been proposed as a molecular basis of 'memory of water'.

  1. Thermodynamics of water sorption in high performance glassy thermoplastic polymers

    PubMed Central

    Scherillo, Giuseppe; Petretta, Mauro; Galizia, Michele; La Manna, Pietro; Musto, Pellegrino; Mensitieri, Giuseppe

    2014-01-01

    Sorption thermodynamics of water in two glassy polymers, polyetherimide (PEI) and polyetheretherketone (PEEK), is investigated by coupling gravimetry and on line FTIR spectroscopy in order to gather information on the total amount of sorbed water as well as on the different species of water molecules absorbed within the polymers, addressing the issue of cross- and self-interactions occurring in the polymer/water systems. Water sorption isotherms have been determined at temperatures ranging from 30 to 70°C while FTIR spectroscopy has been performed only at 30°C. The experimental analysis provided information on the groups present on the polymer backbones involved in hydrogen bonding interactions with absorbed water molecules. Moreover, it also supplied qualitative indications about the different “populations” of water molecules present within the PEEK and a quantitative assessment of these “populations” in the case of PEI. The results of the experimental analysis have been interpreted using an equation of state theory based on a compressible lattice fluid model for the Gibbs energy of the polymer-water mixture, developed by extending to the case of out of equilibrium glassy polymers a previous model intended for equilibrium rubbery polymers. The model accounts for the non-equilibrium nature of glassy polymers as well as for mean field and for hydrogen bonding interactions, providing a satisfactory quantitative interpretation of the experimental data. PMID:24860802

  2. Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

    DOE PAGES

    Chen, Ying; Bylaska, Eric J.; Weare, John H.

    2017-03-31

    Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite (α-Fe(OOH). Ab-initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Here, several exchange correlation functionals were employed (PBE96, PBE96+Grimme, and PBE0) in the simulations of a (3 x 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a=30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

  3. Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

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

    Chen, Ying; Bylaska, Eric J.; Weare, John H.

    Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite (α-Fe(OOH). Ab-initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Here, several exchange correlation functionals were employed (PBE96, PBE96+Grimme, and PBE0) in the simulations of a (3 x 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a=30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

  4. Pigmentation and Spectral Absorbance Signatures in Deep-Water Corals from the Trondheimsfjord, Norway

    PubMed Central

    Elde, Anette C.; Pettersen, Ragnhild; Bruheim, Per; Järnegren, Johanna; Johnsen, Geir

    2012-01-01

    The pigmentation and corresponding in vivo and in vitro absorption characteristics in three different deep-water coral species: white and orange Lophelia pertusa, Paragorgia arborea and Primnoa resedaeformis, collected from the Trondheimsfjord are described. Pigments were isolated and characterized by High-Performance Liquid Chromatography (HPLC) analysis and High-Performance Liquid Chromatography Time-Of-Flight Mass Spectrometer (LC-TOF MS). The main carotenoids identified for all three coral species were astaxanthin and a canthaxanthin-like carotenoid. Soft tissue and skeleton of orange L. pertusa contained 2 times more astaxanthin g−1 wet weight compared to white L. pertusa. White and orange L. pertusa were characterized with in vivo absorbance peaks at 409 and 473 nm, respectively. In vivo absorbance maxima for P. arborea and P. resedaeformis was typically at 475 nm. The shapes of the absorbance spectra (400–700 nm) were species-specific, indicated by in vivo, in vitro and the corresponding difference spectra. The results may provide important chemotaxonomic information for pigment when bonded to their proteins in vivo, bio-prospecting, and for in situ identification, mapping and monitoring of corals. PMID:22822381

  5. Comparison of absorbed-dose-to-water units for Co-60 and high-energy x-rays between PTB and LNE-LNHB

    NASA Astrophysics Data System (ADS)

    Delaunay, F.; Kapsch, R.-P.; Gouriou, J.; Illemann, J.; Krauss, A.; Le Roy, M.; Ostrowsky, A.; Sommier, L.; Vermesse, D.

    2012-10-01

    During the Euramet project JRP7 ‘External Beam Cancer Therapy’, PTB and LNE-LNHB used primary standards to determine the absorbed dose to water under IMRT conditions (in small fields). PTB used a water calorimeter to determine the absorbed-dose-to-water references in 6 MV and 10 MV beams for field sizes of 10 cm × 10 cm and 3 cm × 3 cm while LNE-LNHB used graphite calorimeters in 6 MV and 12 MV beams for field sizes of 10 cm × 10 cm, 4 cm × 4 cm and 2 cm × 2 cm. The purpose of this study is to compare PTB and LNE-LNHB new absorbed-dose-to-water references. LNE-LNHB sent an Exradin A1SL ionization chamber traceable to its primary standard to the PTB for calibration in 60Co and in linac beams and PTB sent a PTW 31010 ionization chamber traceable to its primary standard to LNE-LNHB for calibration in 60Co and in linac beams. Calculated Sw,air will be used as beam quality specifier for the ionization chamber comparison at different field sizes. The standard uncertainties (k = 1) of PTB and LNE-LNHB calibration coefficients lie respectively between 0.25% (60Co) and 0.40% (linac) and between 0.29% and 0.46%. PTB and LNE-LNHB absorbed-dose-to-water references developed for this project, based respectively on water calorimetry and on graphite calorimetry, agree within 1.5 standard deviations for field size of 10 cm × 10 cm down to 2 cm × 2 cm and for beams of 6 MV to 10 MV.

  6. Reversible geminate recombination of hydrogen-bonded water molecule pair

    NASA Astrophysics Data System (ADS)

    Markovitch, Omer; Agmon, Noam

    2008-08-01

    The (history independent) autocorrelation function for a hydrogen-bonded water molecule pair, calculated from classical molecular dynamics trajectories of liquid water, exhibits a t-3/2 asymptotic tail. Its whole time dependence agrees quantitatively with the solution for reversible diffusion-influenced geminate recombination derived by Agmon and Weiss [J. Chem. Phys. 91, 6937 (1989)]. Agreement with diffusion theory is independent of the precise definition of the bound state. Given the water self-diffusion constant, this theory enables us to determine the dissociation and bimolecular recombination rate parameters for a water dimer. (The theory is indispensable for obtaining the bimolecular rate coefficient.) Interestingly, the activation energies obtained from the temperature dependence of these rate coefficients are similar, rather than differing by the hydrogen-bond (HB) strength. This suggests that recombination requires displacing another water molecule, which meanwhile occupied the binding site. Because these activation energies are about twice the HB strength, cleavage of two HBs may be required to allow pair separation. The autocorrelation function without the HB angular restriction yields a recombination rate coefficient that is larger than that for rebinding to all four tetrahedral water sites (with angular restrictions), suggesting the additional participation of interstitial sites. Following dissociation, the probability of the pair to be unbound but within the reaction sphere rises more slowly than expected, possibly because binding to the interstitial sites delays pair separation. An extended diffusion model, which includes an additional binding site, can account for this behavior.

  7. Bias-dependent local structure of water molecules at an electrochemical interface

    NASA Astrophysics Data System (ADS)

    Pedroza, Luana; Brandimarte, Pedro; Rocha, Alexandre R.; Fernandez-Serra, Marivi

    2015-03-01

    Following the need for new - and renewable - sources of energy worldwide, fuel cells using electrocatalysts can be thought of as a viable option. Understanding the local structure of water molecules at the interfaces of the metallic electrodes is a key problem. Notably the system is under an external potential bias, which makes the task of simulating this setup difficult. A first principle description of all components of the system is the most appropriate methodology in order to advance understanding of electrochemical processes. There, the metal is usually charged. To correctly compute the effect of an external bias potential applied to electrodes, we combine density functional theory (DFT) and non-equilibrium Green's functions methods (NEGF), with and without van der Waals interactions. In this work, we apply this methodology to study the electronic properties and forces of one water molecule and water monolayer at the interface of gold electrodes. We find that the water molecule has a different torque direction depending on the sign of the bias applied. We also show that it changes the position of the most stable configuration indicating that the external bias plays an important role in the structural properties of the interface. We acknowledge financial support from FAPESP.

  8. Advances in the treatment of explicit water molecules in docking and binding free energy calculations.

    PubMed

    Hu, Xiao; Maffucci, Irene; Contini, Alessandro

    2018-05-13

    The inclusion of direct effects mediated by water during the ligand-receptor recognition is a hot-topic of modern computational chemistry applied to drug discovery and development. Docking or virtual screening with explicit hydration is still debatable, despite the successful cases that have been presented in the last years. Indeed, how to select the water molecules that will be included in the docking process or how the included waters should be treated remain open questions. In this review, we will discuss some of the most recent methods that can be used in computational drug discovery and drug development when the effect of a single water, or of a small network of interacting waters, needs to be explicitly considered. Here, we analyse software to aid the selection, or to predict the position, of water molecules that are going to be explicitly considered in later docking studies. We also present software and protocols able to efficiently treat flexible water molecules during docking, including examples of applications. Finally, we discuss methods based on molecular dynamics simulations that can be used to integrate docking studies or to reliably and efficiently compute binding energies of ligands in presence of interfacial or bridging water molecules. Software applications aiding the design of new drugs that exploit water molecules, either as displaceable residues or as bridges to the receptor, are constantly being developed. Although further validation is needed, workflows that explicitly consider water will probably become a standard for computational drug discovery soon. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  9. Visualizing water molecules in transmembrane proteins using radiolytic labeling methods†

    PubMed Central

    Orban, Tivadar; Gupta, Sayan; Palczewski, Krzysztof; Chance, Mark R.

    2010-01-01

    Essential to cells and their organelles, water is both shuttled to where it is needed and trapped within cellular compartments and structures. Moreover, ordered waters within protein structures often co-localize with strategically placed polar or charged groups critical for protein function. Yet it is unclear if these ordered water molecules provide structural stabilization, mediate conformational changes in signaling, neutralize charged residues, or carry out a combination of all these functions. Structures of many integral membrane proteins, including G protein-coupled receptors (GPCRs), reveal the presence of ordered water molecules that may act like prosthetic groups in a manner quite unlike bulk water. Identification of ‘ordered’ waters within a crystalline protein structure requires sufficient occupancy of water to enable its detection in the protein's X-ray diffraction pattern and thus the observed waters likely represent a subset of tightly-bound functional waters. In this review, we highlight recent studies that suggest the structures of ordered waters within GPCRs are as conserved (and thus as important) as conserved side chains. In addition, methods of radiolysis, coupled to structural mass spectrometry (protein footprinting), reveal dynamic changes in water structure that mediate transmembrane signaling. The idea of water as a prosthetic group mediating chemical reaction dynamics is not new in fields such as catalysis. However, the concept of water as a mediator of conformational dynamics in signaling is just emerging, owing to advances in both crystallographic structure determination and new methods of protein footprinting. Although oil and water do not mix, understanding the roles of water is essential to understanding the function of membrane proteins. PMID:20047303

  10. Energy absorber for sodium-heated heat exchanger

    DOEpatents

    Essebaggers, J.

    1975-12-01

    A heat exchanger is described in which water-carrying tubes are heated by liquid sodium and in which the results of accidental contact between the water and the sodium caused by failure of one or more of the water tubes is minimized. An energy absorbing chamber contains a compressible gas and is connected to the body of flowing sodium by a channel so that, in the event of a sodium-water reaction, products of the reaction will partially fill the energy absorbing chamber to attenuate the rise in pressure within the heat exchanger.

  11. Effectiveness of a water-saving super-absorbent polymer in soil water conservation for corn (Zea mays L.) based on eco-physiological parameters.

    PubMed

    Islam, M Robiul; Hu, Yuegao; Mao, Sishuai; Mao, Jinzhu; Eneji, A Egrinya; Xue, Xuzhang

    2011-08-30

    The objective was to study soil water conservation and physiological growth of corn (Zea mays L.) using water-saving super-absorbent polymer (SAP) at 30 kg ha(-1). The effectiveness of SAP was studied under three irrigation levels (adequate, moderate and deficit) using a new type of negative hydraulic pressure controlled auto-irrigator in the years 2009 and 2010 in a greenhouse at Beijing, P.R. China. Eight weeks after sowing, plant height and leaf area increased significantly by 41.6 and 79.6% under deficit irrigation for SAP treatment. The SAP had little effect on shoot dry mass under adequate and moderate irrigation but increased it significantly by 133.5% under deficit irrigation. Similarly, the efficiency of water use also increased by 97.1%. Leaf water potential under adequate and moderate irrigation differs slightly for SAP application, whereas under deficit irrigation the values were exceeded significantly by 27.8%. The superior growth and water use efficiency of corn treated with SAP under deficit irrigation was ascribed to maintenance of higher relative water contents in leaves as well as intercellular carbon dioxide concentration, net photosynthesis and transpiration rate. Our results suggested that plant growth and different physiological activities are restricted by drought stress and the application of super-absorbent polymer could conserve soil water, making same available to plants for increased growth and biomass accumulation especially under severe water stress. Thus, application of SAP is a suitable soil management practice for the locations characterised by severe water stress. Copyright © 2011 Society of Chemical Industry.

  12. Electric dipole moments of nanosolvated acid molecules in water clusters.

    PubMed

    Guggemos, Nicholas; Slavíček, Petr; Kresin, Vitaly V

    2015-01-30

    The electric dipole moments of (H2O)nDCl (n=3-9) clusters have been measured by the beam-deflection method. Reflecting the (dynamical) charge distribution within the system, the dipole moment contributes information about the microscopic structure of nanoscale solvation. The addition of a DCl molecule to a water cluster results in a strongly enhanced susceptibility. There is evidence for a noticeable rise in the dipole moment occurring at n≈5-6. This size is consistent with predictions for the onset of ionic dissociation. Additionally, a molecular-dynamics model suggests that even with a nominally bound impurity an enhanced dipole moment can arise due to the thermal and zero-point motion of the proton and the water molecules. The experimental measurements and the calculations draw attention to the importance of fluctuations in defining the polarity of water-based nanoclusters and generally to the essential role played by motional effects in determining the response of fluxional nanoscale systems under realistic conditions.

  13. Neuroscience of water molecules: a salute to professor Linus Carl Pauling.

    PubMed

    Nakada, Tsutomu

    2009-04-01

    More than 35 years ago double Nobel laureate Linus Carl Pauling published a powerful model of the molecular mechanism of general anesthesia, generally referred to as the hydrate-microcrystal (aqueous-phase) theory. This hypothesis, based on the molecular behavior of water molecules, did not receive serious attention during Pauling's life time, when scientific tools for examining complex systems such as the brain were still in their infancy. The situation has since drastically changed, and, now, in the twenty first century, many scientific tools are available for examining different types of complex systems. The discovery of aquaporin-4, a subtype of water channel abundantly expressed in glial systems, further highlighted the concept that the dynamics of water molecules in the cerebral cortex play an important role in important physiological brain functions including consciousness and information processing.

  14. Influence of Aromatic Molecules on the Structure and Spectroscopy of Water Clusters

    NASA Astrophysics Data System (ADS)

    Tabor, Daniel P.; Sibert, Edwin; Walsh, Patrick S.; Zwier, Timothy S.

    2016-06-01

    Isomer-specific resonant ion-dip infrared spectra are presented for benzene-(water)_n, 1-2-diphenoxyethane-(water)_n, and tricyclophane-(water)_n clusters. The IR spectra are modeled with a local mode Hamiltonian that was originally formulated for the analysis of benzene-(water)_n clusters with up to seven waters. The model accounts for stretch-bend Fermi coupling, which can complicate the IR spectra in the 3150-3300 cm-1 region. When the water clusters interact with each of the solutes, the hydrogen bond lengths between the water molecules change in a characteristic way, reflecting the strength of the solute-water interaction. These structural effects are also reflected spectroscopically in the shifts of the local mode OH stretch frequencies. When diphenoxyethane is the solute, the water clusters distort more significantly than when bound to benzene. Tricyclophane's structure provides an aromatic-rich binding pocket for the water clusters. The local mode model is used to extract Hamiltonians for individual water molecules. These monomer Hamiltonians divide into groups based on their local H-bonding architecture, allowing for further classification of the wide variety of water environments encountered in this study.

  15. Geometry-dependent distributed polarizability models for the water molecule

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

    Loboda, Oleksandr; Ingrosso, Francesca; Ruiz-López, Manuel F.

    2016-01-21

    Geometry-dependent distributed polarizability models have been constructed by fits to ab initio calculations at the coupled cluster level of theory with up to noniterative triple excitations in an augmented triple-zeta quality basis set for the water molecule in the field of a point charge. The investigated models include (i) charge-flow polarizabilities between chemically bonded atoms, (ii) isotropic or anisotropic dipolar polarizabilities on oxygen atom or on all atoms, and (iii) combinations of models (i) and (ii). For each model, the polarizability parameters have been optimized to reproduce the induction energy of a water molecule polarized by a point charge successivelymore » occupying a grid of points surrounding the molecule. The quality of the models is ascertained by examining their ability to reproduce these induction energies as well as the molecular dipolar and quadrupolar polarizabilities. The geometry dependence of the distributed polarizability models has been explored by changing bond lengths and HOH angle to generate 125 molecular structures (reduced to 75 symmetry-unique ones). For each considered model, the distributed polarizability components have been fitted as a function of the geometry by a Taylor expansion in monomer coordinate displacements up to the sum of powers equal to 4.« less

  16. Clustering of water molecules in ultramicroporous carbon: In-situ small-angle neutron scattering

    DOE PAGES

    Bahadur, Jitendra; Contescu, Cristian I.; Rai, Durgesh K.; ...

    2016-10-19

    The adsorption of water is central to most of the applications of microporous carbon as adsorbent material. We report early kinetics of water adsorption in the microporous carbon using in-situ small-angle neutron scattering. It is observed that adsorption of water occurs via cluster formation of molecules. Interestingly, the cluster size remains constant throughout the adsorption process whereas number density of clusters increases with time. The role of surface chemistry of microporous carbon on the early kinetics of adsorption process was also investigated. Lastly, the present study provides direct experimental evidence for cluster assisted adsorption of water molecules in microporous carbonmore » (Do-Do model).« less

  17. Investigation of the local structure variance of water molecules in laser-induced thermal desorption process

    NASA Astrophysics Data System (ADS)

    Ju, Shin-Pon; Weng, Cheng-I.

    2004-05-01

    This paper presents the use of molecular dynamics simulation in the study of laser-induced thermal desorption (LITD) of water molecules adjacent to a laser-heated Au substrate. The local structure of the water molecules is investigated by considering the densities of the oxygen and hydrogen atoms, the average number of neighbors, nNN, and the average number of H-bonds, nHB. At an equilibrium temperature of 300 K, the simulation results show that three adsorption water layers are formed in the immediate vicinity of the Au surface, and that each four-fold hollow site on the uppermost Au(0 0 1) surface is occupied by a single water molecule. Following laser-induced heating of the Au substrate with a sub-picosecond laser pulse of 350 fs, the substrate temperature increases to 1000 K. This causes a gradual heating of the adjacent water film, which is accompanied by a decrease in the values of nNN and nHB. Hence, it can be concluded that an increase in the water film temperature destroys the hydrogen-bonding network throughout the water film. Although the maximum local temperature of the water film occurs in the region immediately adjacent to the Au substrate, it is determined that the attractive energy between the Au atoms and the water molecules in this region causes the water molecules to aggregate together to form three-dimensional water clusters. Furthermore, this energy prevents the hydrogen bonds in this region from breaking apart as violently as those within the phase explosion region. Finally, it is observed that the phase explosion phenomenon occurs in the region of the water film where the values of nNN and nHB are at a minimum.

  18. Effect of UV-C radiation and vapor released from a water hyacinth root absorbent containing bergamot oil to control mold on storage of brown rice.

    PubMed

    Songsamoe, Sumethee; Matan, Narumol; Matan, Nirundorn

    2016-03-01

    The aims of this study were to develop absorbent material from a water hyacinth root containing bergamot oil and to improve its antifungal activity by using ultraviolet C (UV-C) against the growth of A. flavus on the brown rice. Process optimization was studied by the immersion of a water hyacinth root into a water and bergamot oil (300, 500 and 700 μl ml(-1)). The root (absorbent material) was dried at 50, 70, and 90 °C for 10 min. Then, ultraviolet C (UV-C) was used for enhancing the antifungal activity of bergamot oil for 10, 15, and 20 min. The shelf-life of the brown rice with the absorbent after incubation at 25 ° C with 100 % RH for 12 weeks was also investigated. A microscope and a Fourier transform infrared spectroscopy (FTIR) were used to find out possible mode of action. Results indicated that the absorbent material produced from the water hyacinth root containing bergamot oil at 500 μl ml(-1) in the water solution, dried at 70 ° C and UV for 15 min showed the highest antifungal activity in a vapor phase against A. flavus on the brown rice. A microscopy investigation confirmed that the water hyacinth root could absorb bergamot oil from an outside water solution into root cells. Limonene in vapor phase was shown to be a stronger inhibitor than essential oil after UV-C radiation and should be the key factor in boosting bergamot oil antifungal activity. A vapor phase of bergamot oil could be released and inhibit natural mold on the surface of the brown rice for up to 12 weeks; without the absorbent, mold covered the brown rice in only 4 weeks.

  19. Amphiphilic Bio-molecules/ZnO Interface: Enhancement of Bio-affinity and Dispersibility

    NASA Astrophysics Data System (ADS)

    Meng, Xiu-Qing; Fang, Yun-Zhang; Wu, Feng-Min

    2012-01-01

    The dispersibility of bio-molecules such as lecithins on the surface of ZnO nanowires are investigated for biosensor applications. Lecithins can be absorbed on an as-synthesized ZnO nanowire surface in the form of sub-micro sized clusters, while scattering well on those annealed under oxygen atmosphere. Wettability analysis reveals that the as-synthesized ZnO nanowires bear a super-hydrophobic surface, which convents to superhydrophilic after oxygen annealing. First-principles calculations indicate that the adsorption energy of ZnO with water is about 0.2 eV at a distance of 2 Å when it is superhydrophilic, suggesting that lecithin can be absorbed on the hydrophilic surface stably at this distance and the bio-affinity can be enhanced under this condition.

  20. Different Structural Changes Occur in the Blue- and Green-Absorbing Proteorhodopsin During the Primary Photoreaction†

    PubMed Central

    Amsden, Jason J.; Kralj, Joel M.; Bergo, Vladislav B.; Spudich, Elena N.; Spudich, John L.; Rothschild, Kenneth J.

    2013-01-01

    We examine the structural changes during the primary photoreaction in blue-absorbing proteorhodopsin (BPR), a light-driven retinylidene proton pump, using low-temperature FTIR difference spectroscopy. Comparison of the light induced BPR difference spectrum recorded at 80 K to that of green-absorbing proteorhodopsin (GPR) reveals that there are several differences in the BPR and GPR primary photoreactions despite the similar structure of the retinal chromophore and all-trans → 13-cis isomerization. Strong bands near 1700 cm−1 assigned previously to a change in hydrogen bonding of Asn230 in GPR are still present in BPR but in addition bands in the same region are assigned on the basis of site-directed mutagenesis to changes occurring in Gln105. In the amide II region bands are assigned on the basis of total-N15 labeling to structural changes of the protein backbone, although no such bands were previously observed for GPR. A band at 3642 cm−1 in BPR, assigned to the OH stretching mode of a water molecule on the basis of H218O substitution, appears at a different frequency than a band at 3626 cm−1 previously assigned to a water molecule in GPR. However, the substitution of Gln105 for Leu105 in BPR leads to the appearance of both bands at 3642 and 3626 cm−1 indicating the waters assigned in BPR and GPR exist in separate distinct locations and can coexist in the GPR-like Q105L mutant of BPR. These results indicate that there exist significant differences in the conformational changes occurring in these two types proteorhodopsin during the initial photoreaction despite their similar chromophores structures, which might reflect a different arrangement of water in the active site as well as substitution of a hydrophilic for hydrophobic residue at residue 105. PMID:18842006

  1. The molecular inventory around protostars: water, organic molecules, and the missing oxygen problem

    NASA Astrophysics Data System (ADS)

    Neufeld, David A.

    2018-06-01

    Massive star formation is accompanied by significant chemical evolution in the surrounding interstellar gas. Here, grains are heated up and icy mantles evaporate, releasing a rich inventory of water and organic molecules into the gas-phase within “hot core” regions surrounding massive protostars. Because molecules on the grain surface present broad infrared features without rotational structure, only the most abundant molecules can be identified unambiguously in the solid phase; once released into the gas-phase, however, where they are free to rotate, the constituents of grain mantles can be identified easily by means of rotational spectroscopy at millimeter and submillimeter wavelengths or through rovibrational spectroscopy in the mid-infrared. While observations of pure-rotational emission lines provide a broad view of hot core chemistry, absorption line spectroscopy of rovibrational transitions can probe the very hottest material closest to the protostar. With access to the mid-infrared spectral region from above 99% of Earth’s water vapor, SOFIA provides a unique platform for high-resolution rovibrational spectroscopy of water and organic molecules, many of which have vibrational transitions in the 5 – 8 micron spectral region that is unobservable from the ground. High spectral resolution is essential for disentangling the rotational structure and providing reliable measurements of the molecular column densities and temperatures. Future SOFIA observations will help elucidate the inventory of water and organic molecules around young protostars, and can address a puzzle related to the “oxygen budget” in the interstellar medium: surprisingly, the main interstellar reservoirs of the third-most abundant element in the Universe have yet to be identified.

  2. Trapping and desorption of complex organic molecules in water at 20 K

    NASA Astrophysics Data System (ADS)

    Burke, Daren J.; Puletti, Fabrizio; Woods, Paul M.; Viti, Serena; Slater, Ben; Brown, Wendy A.

    2015-10-01

    The formation, chemical, and thermal processing of complex organic molecules (COMs) is currently a topic of much interest in interstellar chemistry. The isomers glycolaldehyde, methyl formate, and acetic acid are particularly important because of their role as pre-biotic species. It is becoming increasingly clear that many COMs are formed within interstellar ices which are dominated by water. Hence, the interaction of these species with water ice is crucially important in dictating their behaviour. Here, we present the first detailed comparative study of the adsorption and thermal processing of glycolaldehyde, methyl formate, and acetic acid adsorbed on and in water ices at astrophysically relevant temperatures (20 K). We show that the functional group of the isomer dictates the strength of interaction with water ice, and hence the resulting desorption and trapping behaviour. Furthermore, the strength of this interaction directly affects the crystallization of water, which in turn affects the desorption behaviour. Our detailed coverage and composition dependent data allow us to categorize the desorption behaviour of the three isomers on the basis of the strength of intermolecular and intramolecular interactions, as well as the natural sublimation temperature of the molecule. This categorization is extended to other C, H, and O containing molecules in order to predict and describe the desorption behaviour of COMs from interstellar ices.

  3. Estimation of the degree of hydrogen bonding between quinoline and water by ultraviolet-visible absorbance spectroscopy in sub- and supercritical water

    NASA Astrophysics Data System (ADS)

    Osada, Mitsumasa; Toyoshima, Katsunori; Mizutani, Takakazu; Minami, Kimitaka; Watanabe, Masaru; Adschiri, Tadafumi; Arai, Kunio

    2003-03-01

    UV-visible spectra of quinoline was measured in sub- and supercritical water (25 °Cwater was estimated from solvatochromic shifts in the π-π* absorbance band. Hydrogen bonding decreased with increasing temperature from 25 to 360 °C. At supercritical conditions (380 °Cwater was large (0.5<ρr<1.5). In this condition, local density around quinoline was lower than bulk density, namely negative solvation, and it led to the cleavage of hydrogen bonding between quinoline and water.

  4. Water-mediated influence of a crowded environment on internal vibrations of a protein molecule.

    PubMed

    Kuffel, Anna; Zielkiewicz, Jan

    2016-02-14

    The influence of crowding on the protein inner dynamics is examined by putting a single protein molecule close to one or two neighboring protein molecules. The presence of additional molecules influences the amplitudes of protein fluctuations. Also, a weak dynamical coupling of collective velocities of surface atoms of proteins separated by a layer of water is detected. The possible mechanisms of these phenomena are described. The cross-correlation function of the collective velocities of surface atoms of two proteins was decomposed into the Fourier series. The amplitude spectrum displays a peak at low frequencies. Also, the results of principal component analysis suggest that the close presence of an additional protein molecule influences the high-amplitude, low-frequency modes in the most prominent way. This part of the spectrum covers biologically important protein motions. The neighbor-induced changes in the inner dynamics of the protein may be connected with the changes in the velocity power spectrum of interfacial water. The additional protein molecule changes the properties of solvation water and in this way it can influence the dynamics of the second protein. It is suggested that this phenomenon may be described, at first approximation, by a damped oscillator driven by an external random force. This model was successfully applied to conformationally rigid Choristoneura fumiferana antifreeze protein molecules.

  5. Sticking of Molecules on Nonporous Amorphous Water Ice

    NASA Astrophysics Data System (ADS)

    He, Jiao; Acharyya, Kinsuk; Vidali, Gianfranco

    2016-05-01

    Accurate modeling of physical and chemical processes in the interstellar medium (ISM) requires detailed knowledge of how atoms and molecules adsorb on dust grains. However, the sticking coefficient, a number between 0 and 1 that measures the first step in the interaction of a particle with a surface, is usually assumed in simulations of ISM environments to be either 0.5 or 1. Here we report on the determination of the sticking coefficient of H2, D2, N2, O2, CO, CH4, and CO2 on nonporous amorphous solid water. The sticking coefficient was measured over a wide range of surface temperatures using a highly collimated molecular beam. We showed that the standard way of measuring the sticking coefficient—the King-Wells method—leads to the underestimation of trapping events in which there is incomplete energy accommodation of the molecule on the surface. Surface scattering experiments with the use of a pulsed molecular beam are used instead to measure the sticking coefficient. Based on the values of the measured sticking coefficient, we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy. We use this formula in a simulation of ISM gas-grain chemistry to find the effect of sticking on the abundance of key molecules both on grains and in the gas phase.

  6. Hydrophilic absorbable copolyester exhibiting zero-order drug release.

    PubMed

    Andjelić, Sasa; Yuan, Jenny; Jamiolkowski, Dennis D; Diluccio, Robert; Bezwada, Rao; Zhang, Hua; Mijović, Jovan

    2006-04-01

    A novel absorbable hydrophilic copolyester developed in our laboratory, amorphous 40/60 poly(ethylene diglycolate-co-glycolide), exhibits outstanding physical properties. Films made from this material appear fully transparent, colorless, soft and slightly elastic, but relatively strong and durable materials so that they can be potentially used as stand-alone devices in various in-vivo medical applications. In this study, in-vitro drug release characteristics of this copolyester were examined. High Performance Liquid Chromatography was used to generate release profiles on selected non-steroidal anti-inflammatory agents, NSAIDs. In addition, dielectric relaxation spectroscopy, as well as mid- and near infrared spectroscopy, were used to study specific polymer chain interactions in water and buffer solution as a function of aging time at 37 degrees C. This copolyester, compression molded into a film, exhibited nearly constant in-vitro release of various hydrophilic and hydrophobic drugs. The release profile showed minimal or, in most cases, no burst effect. The effect was observed with the three NSAIDs that were tested as model compounds; however, this system may prove generally useful for other drug entities. In-vitro hydrolysis conducted at 37 degrees C on this hydrophilic copolyester revealed an unusually long induction period (no hydrolysis for up to 6 days), followed by the relatively rapid hydrolysis. Data from dipole relaxation spectroscopy indicated that the water molecules do not structurally associate with the polymer chains in phosphate buffer during initial hydrolysis period. The results suggest unique dynamics of water diffusion through the polymer matrix that may play a critical role in achieving controlled release properties. Furthermore, we suspect that the molecular interactions associated with this new synthetic absorbable material may find a critical utility in important medical applications.

  7. Hyperfine coupling constants on inner-sphere water molecules of Gd(III)-based MRI contrast agents.

    PubMed

    Esteban-Gómez, David; de Blas, Andrés; Rodríguez-Blas, Teresa; Helm, Lothar; Platas-Iglesias, Carlos

    2012-11-12

    Herein we present a theoretical investigation of the hyperfine coupling constants (HFCCs) on the inner-sphere water molecules of [Gd(H(2)O)(8)](3+) and different Gd(III)-based magnetic resonance imaging contrast agents such as [Gd(DOTA)(H(2)O)](-), [Gd(DTPA)(H(2)O)](2-), [Gd(DTPA-BMA)(H(2)O)] and [Gd(HP-DO3A)(H(2)O)]. DFT calculations performed on the [Gd(H(2)O)(8)](3+) model system show that both hybrid-GGA functionals (BH&HLYP, B3PW91 and PBE1PBE) and the hybrid meta-GGA functional TPSSh provide (17)O HFCCs in close agreement with the experimental data. The use of all-electron relativistic approaches based on the DKH2 approximation and the use of relativistic effective core potentials (RECP) provide results of essentially the same quality. The accurate calculation of HFCCs on the [Gd(DOTA)(H(2)O)](-), [Gd(DTPA)(H(2)O)](2-), [Gd(DTPA-BMA)(H(2)O)] and [Gd(HP-DO3A)(H(2)O)] complexes requires an adequate description of solvent effects. This was achieved by using a mixed cluster/continuum approach that includes explicitly two second-sphere water molecules. The calculated isotropic (17)O HFCCs (A(iso)) fall within the range 0.40-0.56 MHz, and show deviations from the corresponding experimental values typically lower than 0.05 MHz. The A(iso) values are significantly affected by the distance between the oxygen atom of the coordinated water molecule and the Gd(III) ion, as well as by the orientation of the water molecule plane with respect to the Gd-O vector. (1)H HFCCs of coordinated water molecules and (17)O HFCCs of second-sphere water molecules take values close to zero. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations.

    PubMed

    Chen, Ying; Bylaska, Eric J; Weare, John H

    2017-03-31

    Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick). The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe 3+ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe 3+ . The water molecules capping surface Fe 3+ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe 3+ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe 3+ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe 3+ , those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe 3+ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism. Water molecules adjacent to the surface were found to only weakly interact with the surface and as a

  9. Building better water models using the shape of the charge distribution of a water molecule

    NASA Astrophysics Data System (ADS)

    Dharmawardhana, Chamila Chathuranga; Ichiye, Toshiko

    2017-11-01

    The unique properties of liquid water apparently arise from more than just the tetrahedral bond angle between the nuclei of a water molecule since simple three-site models of water are poor at mimicking these properties in computer simulations. Four- and five-site models add partial charges on dummy sites and are better at modeling these properties, which suggests that the shape of charge distribution is important. Since a multipole expansion of the electrostatic potential describes a charge distribution in an orthogonal basis set that is exact in the limit of infinite order, multipoles may be an even better way to model the charge distribution. In particular, molecular multipoles up to the octupole centered on the oxygen appear to describe the electrostatic potential from electronic structure calculations better than four- and five-site models, and molecular multipole models give better agreement with the temperature and pressure dependence of many liquid state properties of water while retaining the computational efficiency of three-site models. Here, the influence of the shape of the molecular charge distribution on liquid state properties is examined by correlating multipoles of non-polarizable water models with their liquid state properties in computer simulations. This will aid in the development of accurate water models for classical simulations as well as in determining the accuracy needed in quantum mechanical/molecular mechanical studies and ab initio molecular dynamics simulations of water. More fundamentally, this will lead to a greater understanding of how the charge distribution of a water molecule leads to the unique properties of liquid water. In particular, these studies indicate that p-orbital charge out of the molecular plane is important.

  10. Identifying Few-Molecule Water Clusters with High Precision on Au(111) Surface.

    PubMed

    Dong, Anning; Yan, Lei; Sun, Lihuan; Yan, Shichao; Shan, Xinyan; Guo, Yang; Meng, Sheng; Lu, Xinghua

    2018-06-01

    Revealing the nature of a hydrogen-bond network in water structures is one of the imperative objectives of science. With the use of a low-temperature scanning tunneling microscope, water clusters on a Au(111) surface were directly imaged with molecular resolution by a functionalized tip. The internal structures of the water clusters as well as the geometry variations with the increase of size were identified. In contrast to a buckled water hexamer predicted by previous theoretical calculations, our results present deterministic evidence for a flat configuration of water hexamers on Au(111), corroborated by density functional theory calculations with properly implemented van der Waals corrections. The consistency between the experimental observations and improved theoretical calculations not only renders the internal structures of absorbed water clusters unambiguously, but also directly manifests the crucial role of van der Waals interactions in constructing water-solid interfaces.

  11. Reaction Kinetics of Water Molecules with Oxygen Vacancies on Rutile TiO 2(110)

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

    Petrik, Nikolay G.; Kimmel, Gregory A.

    2015-09-16

    The formation of bridging hydroxyls (OHb) via reactions of water molecules with oxygen vacancies (VO) on reduced TiO 2(110) surfaces is studied using infrared reflection-absorption spectroscopy (IRAS), electron-stimulated desorption (ESD), and photon-stimulated desorption (PSD). Narrow IRAS peaks at 2737 cm-1 and 3711 cm -1 are observed for stretching vibrations of OD b and OH b on TiO 2(110), respectively. IRAS measurements with s- and p-polarized light demonstrate that the bridging hydroxyls are oriented normal to the (110) surface. The IR peaks disappear after the sample is exposed to O 2 or annealed in the temperature range of 400 – 600more » K (correlating with the temperature at which pairs of OHb’s reform water and then desorb), which is consistent with their identification as bridging hydroxyls. We have studied the kinetics of water reacting with the vacancies by monitoring the formation of bridging hydroxyls (using IRAS) as a function of the annealing temperature for a small amount of water initially dosed on the TiO 2(110) at low temperature. Separate experiments have also monitored the loss of water molecules (using water ESD) and vacancies (using the CO photooxidation reaction) due to the reactions of water molecules with the vacancies. All three techniques show that the reaction rate becomes appreciable for T > 150 K and that the reactions largely complete for T > 250 K. The temperature-dependent water-VO reaction kinetics are consistent with a Gaussian distribution of activation energies with E a = 0.545 eV, ΔE a(FWHM) = 0.125 eV, and a “normal” prefactor, v = 10 12 s -1. In contrast, a single activation energy with a physically reasonable prefactor does not fit the data well. Our experimental activation energy is close to theoretical estimates for the diffusion of water molecules along the Ti 5c rows on the reduced TiO 2(110) surface, which suggests that the diffusion of water controls the water – V O reaction rate.« less

  12. Performance of a Multifunctional Space Evaporator- Absorber-Radiator (SEAR)

    NASA Technical Reports Server (NTRS)

    Izenson, Michael G.; Chen, Weibo; Bue, Grant; Quinn, Gregory

    2013-01-01

    The Space Evaporator-Absorber-Radiator (SEAR) is a nonventing thermal control subsystem that combines a Space Water Membrane Evaporator (SWME) with a Lithium Chloride Absorber Radiator (LCAR). The LCAR is a heat pump radiator that absorbs water vapor produced in the SWME. Because of the very low water vapor pressure at equilibrium with lithium chloride solution, the LCAR can absorb water vapor at a temperature considerably higher than the SWME, enabling heat rejection by thermal radiation from a relatively small area radiator. Prior SEAR prototypes used a flexible LCAR that was designed to be installed on the outer surface of a portable life support system (PLSS) backpack. This paper describes a SEAR subsystem that incorporates a very compact LCAR. The compact, multifunctional LCAR is built in the form of thin panels that can also serve as the PLSS structural shell. We designed and assembled a 2 sq ft prototype LCAR based on this design and measured its performance in thermal vacuum tests when supplied with water vapor by a SWME. These tests validated our models for SEAR performance and showed that there is enough area available on the PLSS backpack shell to enable heat rejection from the LCAR.

  13. New measurements on water ice photodesorption and product formation under ultraviolet irradiation

    NASA Astrophysics Data System (ADS)

    Cruz-Diaz, Gustavo A.; Martín-Doménech, Rafael; Moreno, Elena; Muñoz Caro, Guillermo M.; Chen, Yu-Jung

    2018-03-01

    The photodesorption of icy grain mantles has been claimed to be responsible for the abundance of gas-phase molecules towards cold regions. Being water a ubiquitous molecule, it is crucial to understand its role in photochemistry and its behaviour under an ultraviolet field. We report new measurements on the ultraviolet (UV) photodesorption of water ice and its H2, OH, and O2 photoproducts using a calibrated quadrupole mass spectrometer. Solid water was deposited under ultra-high-vacuum conditions and then UV-irradiated at various temperatures starting from 8 K with a microwave discharged hydrogen lamp. Deuterated water was used for confirmation of the results. We found a photodesorption yield of 1.3 × 10-3 molecules per incident photon for water and 0.7 × 10-3 molecules per incident photon for deuterated water at the lowest irradiation temperature, 8 K. The photodesorption yield per absorbed photon is given and comparison with astrophysical scenarios, where water ice photodesorption could account for the presence of gas-phase water towards cold regions in the absence of a thermal desorption process, is addressed.

  14. Measurements of water molecule density by tunable diode laser absorption spectroscopy in dielectric barrier discharges with gas-water interface

    NASA Astrophysics Data System (ADS)

    Tachibana, Kunihide; Nakamura, Toshihiro; Kawasaki, Mitsuo; Morita, Tatsuo; Umekawa, Toyofumi; Kawasaki, Masahiro

    2018-01-01

    We measured water molecule (H2O) density by tunable diode-laser absorption spectroscopy (TDLAS) for applications in dielectric barrier discharges (DBDs) with a gas-water interface. First, the effects of water temperature and presence of gas flow were tested using a Petri dish filled with water and a gas injection nozzle. Second, the TDLAS system was applied to the measurements of H2O density in two types of DBDs; one was a normal (non-inverted) type with a dielectric-covered electrode above a water-filled counter electrode and the other was an inverted type with a water-suspending mesh electrode above a dielectric-covered counter electrode. The H2O density in the normal DBD was close to the density estimated from the saturated vapor pressure, whereas the density in the inverted DBD was about half of that in the former type. The difference is attributed to the upward gas flow in the latter type, that pushes the water molecules up towards the gas-water interface.

  15. STICKING OF MOLECULES ON NONPOROUS AMORPHOUS WATER ICE

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

    He, Jiao; Vidali, Gianfranco; Acharyya, Kinsuk, E-mail: gvidali@syr.edu

    2016-05-20

    Accurate modeling of physical and chemical processes in the interstellar medium (ISM) requires detailed knowledge of how atoms and molecules adsorb on dust grains. However, the sticking coefficient, a number between 0 and 1 that measures the first step in the interaction of a particle with a surface, is usually assumed in simulations of ISM environments to be either 0.5 or 1. Here we report on the determination of the sticking coefficient of H{sub 2}, D{sub 2}, N{sub 2}, O{sub 2}, CO, CH{sub 4}, and CO{sub 2} on nonporous amorphous solid water. The sticking coefficient was measured over a widemore » range of surface temperatures using a highly collimated molecular beam. We showed that the standard way of measuring the sticking coefficient—the King–Wells method—leads to the underestimation of trapping events in which there is incomplete energy accommodation of the molecule on the surface. Surface scattering experiments with the use of a pulsed molecular beam are used instead to measure the sticking coefficient. Based on the values of the measured sticking coefficient, we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy. We use this formula in a simulation of ISM gas–grain chemistry to find the effect of sticking on the abundance of key molecules both on grains and in the gas phase.« less

  16. Different catalytic effects of a single water molecule: the gas-phase reaction of formic acid with hydroxyl radical in water vapor.

    PubMed

    Anglada, Josep M; Gonzalez, Javier

    2009-12-07

    The effect of a single water molecule on the reaction mechanism of the gas-phase reaction between formic acid and the hydroxyl radical was investigated with high-level quantum mechanical calculations using DFT-B3LYP, MP2 and CCSD(T) theoretical approaches in concert with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction between HCOOH and HO has a very complex mechanism involving a proton-coupled electron transfer process (pcet), two hydrogen-atom transfer reactions (hat) and a double proton transfer process (dpt). The hydroxyl radical predominantly abstracts the acidic hydrogen of formic acid through a pcet mechanism. A single water molecule affects each one of these reaction mechanisms in different ways, depending on the way the water interacts. Very interesting is also the fact that our calculations predict that the participation of a single water molecule results in the abstraction of the formyl hydrogen of formic acid through a hydrogen atom transfer process (hat).

  17. Studies of Water V. Five Phonons in Protonic Semiconductor Lattice Model of Pure Liquid Water

    NASA Astrophysics Data System (ADS)

    Jie, Binbin; Sah, Chihtang

    2017-07-01

    We report physics based confirmation (~1% RMS deviation), by existing experimental data, of proton-prohol (proton-hole) ion product (pH) and mobilities in pure liquid water (0-100{}{{o}}C, 1-atm pressure) anticipated from our melted-ice Hexagonal-Close-Packed (H{}2O){}4 Lattice Model. Five phonons are identified. (1) A propagating protonic phonon (520.9 meV from lone-pair-blue-shifted stretching mode of isolated water molecule) absorbed to generate a proton-prohol pair or detrap a tightly-bound proton. (2) Two (173.4 and 196.6 meV) bending-breathing protonic-proholic or protonic phonons absorbed during de-trapping-limited proton or proton-prohol mobilities. (3) Two propagating oxygenic-wateric Debye-Dispersive phonons (30.3 and 27.5 meV) absorbed during scattering-limited proton or proton-prohol mobilities. Summer School in Theoretical Physics funded by the National Natural Science Foundation of China, on Soft Materials Physics, hosted by the Physics Department of Xiamen University, China, during August 1 to 14, 2016. This was also just presented at the 2017 March Meeting (March 14 to 16) of the American Physical Society in New Orleans, USA.

  18. Geometry-dependent atomic multipole models for the water molecule.

    PubMed

    Loboda, O; Millot, C

    2017-10-28

    Models of atomic electric multipoles for the water molecule have been optimized in order to reproduce the electric potential around the molecule computed by ab initio calculations at the coupled cluster level of theory with up to noniterative triple excitations in an augmented triple-zeta quality basis set. Different models of increasing complexity, from atomic charges up to models containing atomic charges, dipoles, and quadrupoles, have been obtained. The geometry dependence of these atomic multipole models has been investigated by changing bond lengths and HOH angle to generate 125 molecular structures (reduced to 75 symmetry-unique ones). For several models, the atomic multipole components have been fitted as a function of the geometry by a Taylor series of fourth order in monomer coordinate displacements.

  19. Geometry-dependent atomic multipole models for the water molecule

    NASA Astrophysics Data System (ADS)

    Loboda, O.; Millot, C.

    2017-10-01

    Models of atomic electric multipoles for the water molecule have been optimized in order to reproduce the electric potential around the molecule computed by ab initio calculations at the coupled cluster level of theory with up to noniterative triple excitations in an augmented triple-zeta quality basis set. Different models of increasing complexity, from atomic charges up to models containing atomic charges, dipoles, and quadrupoles, have been obtained. The geometry dependence of these atomic multipole models has been investigated by changing bond lengths and HOH angle to generate 125 molecular structures (reduced to 75 symmetry-unique ones). For several models, the atomic multipole components have been fitted as a function of the geometry by a Taylor series of fourth order in monomer coordinate displacements.

  20. Surgical suite environmental control system. [using halothane absorbing filter

    NASA Technical Reports Server (NTRS)

    Higginbotham, E. J.; Jacobs, M. L.

    1974-01-01

    Theoretical and experimental work for a systems analysis approach to the problem of surgical suit exhaust systems centered on evaluation of halothane absorbing filters. An activated charcoal-alumina-charcoal combination proved to be the best filter for eliminating halothane through multilayer absorption of gas molecules.

  1. Moving beyond the limits of mass transport in liquid absorbent microfilms through the implementation of surface-induced vortices

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

    Bigham, S; Yu, DZ; Chugh, D

    2014-02-01

    The slow diffusion of an absorbate molecule into an absorbent often makes the absorption process a rate-limiting step in many applications. In cases involving an absorbate with a high heat of phase change, such as water absorption into a LiBr (lithium bromide) solution, the absorption rate is further slowed due to significant heating of the absorbent. Recently, it has been demonstrated that constraining a LiBr solution film by a hydrophobic porous structure enables manipulation of the solution flow thermohydraulic characteristics. Here, it is shown that mass transport mode in a constrained laminar solution flow can be changed from diffusive tomore » advective. This change in mode is accomplished through stretching and folding the laminar streamlines within the solution film via the implementation of micro-scale features on the flow channel surface. The process induces vortices within the solution film, which continuously bring concentrated solution from the bottom and middle of the solution channel to its interface with the vapor phase, thus leading to a significant enhancement in the absorption rate. The detailed physics of the involved transport processes is elucidated using the LBM (Lattice Boltzmann Method). Published by Elsevier Ltd.« less

  2. Plumbing system shock absorbers as a source of Legionella pneumophila.

    PubMed

    Memish, Z A; Oxley, C; Contant, J; Garber, G E

    1992-12-01

    Water distribution systems have been demonstrated to be a major source of nosocomial legionellosis. We describe an outbreak in our institution in which a novel source of Legionella pneumophila was identified in the plumbing system. After an outbreak of 10 cases of legionellosis in our hospital, recommended measures including superheating of the hot water to 80 degrees C, hyperchlorination to 2 ppm, and flushing resulted in no new cases in the following 5 years. Recently, despite these control measures, three new cases occurred. Surveillance cultures of shower heads and water tanks were negative; cultures of tap water samples remained positive. This prompted a search for another reservoir. Shock absorbers installed within water pipes to decrease noise were suspected. One hundred twenty-five shock absorbers were removed and cultured. A total of 13 (10%) yielded heavy growth of L. pneumophila (serogroup 1). Since their removal, no new cases have been found and the percentage of positive results of random tap water culture has dropped from 20% to 5%. This is the first report that identifies shock absorbers as a possible reservoir for L. pneumophila. We recommend that institutions with endemic legionellosis assess the water system for possible removal of shock absorbers.

  3. Water molecule-enhanced CO{sub 2} insertion in lanthanide coordination polymers

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

    Luo Liushan; Huang Xiaoyuan; Wang Ning

    2009-08-15

    Two new lanthanide coordination polymers H{sub 2}N(CH{sub 3}){sub 2}.[Eu{sup III}{sub 2}(L{sub 1}){sub 3}(L{sub 2})] (1, L{sub 1}=isophthalic acid dianion, L{sub 2}=formic acid anion) and [La{sup III}(2,5-PDC)(L{sub 2})](2, 2,5-PDC=2,5-pyridinedicarboxylate dianion) were synthesized under solvothermal conditions. It is of interest that the formic ligand (L{sub 2}) is not contained in the stating materials, but arises from the water molecule-enhanced CO{sub 2} insertion during the solvothermal process. Both of the two compounds exhibit complicated three dimensional sandwich-like frameworks. - Graphical abstract: Two new lanthanide coordination polymers involving water molecule-enhanced CO{sub 2} insertion resulting in the formation of formic anion and dimethylammonium cation weremore » synthesized under solvothermal conditions.« less

  4. Identification of Carboxylate, Phosphate, and Phenoxide Functionalities in Deprotonated Molecules Related to Drug Metabolites via Ion-Molecule Reactions with water and Diethylhydroxyborane

    NASA Astrophysics Data System (ADS)

    Zhu, Hanyu; Ma, Xin; Kong, John Y.; Zhang, Minli; Kenttämaa, Hilkka I.

    2017-10-01

    Tandem mass spectrometry based on ion-molecule reactions has emerged as a powerful tool for structural elucidation of ionized analytes. However, most currently used reagents were designed to react with protonated analytes, making them suboptimal for acidic analytes that are preferentially detected in negative ion mode. In this work we demonstrate that the phenoxide, carboxylate, and phosphate functionalities can be identified in deprotonated molecules by use of a combination of two reagents, diethylmethoxyborane (DEMB) and water. A novel reagent introduction setup that allowed DEMB and water to be separately introduced into the ion trap region of the mass spectrometer was developed to facilitate fundamental studies of this reaction. A new reagent, diethylhydroxyborane (DEHB), was generated inside the ion trap by hydrolysis of DEMB on introduction of water. Most carboxylates and phenoxides formed a DEHB adduct, followed by addition of one water molecule and subsequent ethane elimination (DEHB adduct +H2O - CH3CH3) as the major product ion. Phenoxides with a hydroxy group adjacent to the deprotonation site and phosphates formed a DEHB adduct, followed by ethane elimination (DEHB adduct - CH3CH3). Deprotonated molecules with strong intramolecular hydrogen bonds or without the aforementioned functionalities, including sulfates, were unreactive toward DEHB/H2O. Reaction mechanisms were explored via isotope labeling experiments and quantum chemical calculations. The mass spectrometry method allowed the differentiation of phenoxide-, carboxylate-, phosphate-, and sulfate-containing analytes. Finally, it was successfully coupled with high-performance liquid chromatography for the analysis of a mixture containing hymecromone, a biliary spasm drug, and its three possible metabolites. [Figure not available: see fulltext.

  5. Control of unidirectional transport of single-file water molecules through carbon nanotubes in an electric field.

    PubMed

    Su, Jiaye; Guo, Hongxia

    2011-01-25

    The transport of water molecules through nanopores is not only crucial to biological activities but also useful for designing novel nanofluidic devices. Despite considerable effort and progress that has been made, a controllable and unidirectional water flow is still difficult to achieve and the underlying mechanism is far from being understood. In this paper, using molecular dynamics simulations, we systematically investigate the effects of an external electric field on the transport of single-file water molecules through a carbon nanotube (CNT). We find that the orientation of water molecules inside the CNT can be well-tuned by the electric field and is strongly coupled to the water flux. This orientation-induced water flux is energetically due to the asymmetrical water-water interaction along the CNT axis. The wavelike water density profiles are disturbed under strong field strengths. The frequency of flipping for the water dipoles will decrease as the field strength is increased, and the flipping events vanish completely for the relatively large field strengths. Most importantly, a critical field strength E(c) related to the water flux is found. The water flux is increased as E is increased for E ≤ E(c), while it is almost unchanged for E > E(c). Thus, the electric field offers a level of governing for unidirectional water flow, which may have some biological applications and provides a route for designing efficient nanopumps.

  6. Metamaterial absorber for molecular detection and identification (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Tanaka, Takuo

    2017-03-01

    Metamaterial absorber was used for a background-suppressed surface-enhanced molecular detection technique. By utilizing the resonant coupling between plasmonic modes of a metamaterial absorber and infrared (IR) vibrational modes of a self-assembled monolayer (SAM), attomole level molecular sensitivity was experimentally demonstrated. IR absorption spectroscopy of molecular vibrations is of importance in chemical, material, medical science and so on, since it provides essential information of the molecular structure, composition, and orientation. In the vibrational spectroscopic techniques, in addition to the weak signals from the molecules, strong background degrades the signal-to-noise ratio, and suppression of the background is crucial for the further improvement of the sensitivity. Here, we demonstrate low-background resonant Surface enhanced IR absorption (SEIRA) by using the metamaterial IR absorber that offers significant background suppression as well as plasmonic enhancement. By using mask-less laser lithography technique, metamaterial absorber which consisted of 1D array of Au micro-ribbons on a thick Au film separated by a transparent gap layer made of MgF2 was fabricated. This metamaterial structure was designed to exhibit an anomalous IR absorption at 3000 cm-1, which spectrally overlapped with C-H stretching vibrational modes. 16-Mercaptohexadecanoic acid (16-MHDA) was used as a test molecule, which formed a 2-nm thick SAM with their thiol head-group chemisorbed on the Au surface. In the FTIR measurements, the symmetric and asymmetric C-H stretching modes were clearly observed as reflection peaks within a broad plasmonic absorption of the metamaterial, and 1.8 attomole molecular sensitivity was experimentally demonstrated.

  7. Cavity mutants of Savinase. Crystal structures and differential scanning calorimetry experiments give hints of the function of the buried water molecules in subtilisins.

    PubMed

    Pedersen, J T; Olsen, O H; Betzel, C; Eschenburg, S; Branner, S; Hastrup, S

    1994-09-23

    The subtilisin molecule possesses several internal water molecules, which may be characterised as an integral part of the protein structure. We have introduced specific mutations (T71I, T71S, T71V, T71A and T71G) at position 71 in the subtilisin variant Savinase from Bacillus lentus. This position is involved in a hydrogen bonded network with several internal water molecules, forming a water channel. The water channel and most of the other internal water molecules are positioned in the interface between two half-domains of the subtilisin molecule. The data presented here indicate that the internal water molecules are structural, and may be the result of trapping during the folding process.

  8. Determination of absorbed dose to water around a clinical HDR (192)Ir source using LiF:Mg,Ti TLDs demonstrates an LET dependence of detector response.

    PubMed

    Carlsson Tedgren, Asa; Elia, Rouba; Hedtjarn, Hakan; Olsson, Sara; Alm Carlsson, Gudrun

    2012-02-01

    Experimental radiation dosimetry with thermoluminescent dosimeters (TLDs), calibrated in a (60)Co or megavoltage (MV) photon beam, is recommended by AAPM TG-43U1for verification of Monte Carlo calculated absorbed doses around brachytherapy sources. However, it has been shown by Carlsson Tedgren et al. [Med. Phys. 38, 5539-5550 (2011)] that for TLDs of LiF:Mg,Ti, detector response was 4% higher in a (137)Cs beam than in a (60)Co one. The aim of this work was to investigate if similar over-response exists when measuring absorbed dose to water around (192)Ir sources, using LiF:Mg,Ti dosimeters calibrated in a 6 MV photon beam. LiF dosimeters were calibrated to measure absorbed dose to water in a 6 MV photon beam and used to measure absorbed dose to water at distances of 3, 5, and 7 cm from a clinical high dose rate (HDR) (192)Ir source in a polymethylmethacrylate (PMMA) phantom. Measured values were compared to values of absorbed dose to water calculated using a treatment planning system (TPS) including corrections for the difference in energy absorption properties between calibration quality and the quality in the users' (192)Ir beam and for the use of a PMMA phantom instead of the water phantom underlying dose calculations in the TPS. Measured absorbed doses to water around the (192)Ir source were overestimated by 5% compared to those calculated by the TPS. Corresponding absorbed doses to water measured in a previous work with lithium formate electron paramagnetic resonance (EPR) dosimeters by Antonovic et al. [Med. Phys. 36, 2236-2247 (2009)], using the same irradiation setup and calibration procedure as in this work, were 2% lower than those calculated by the TPS. The results obtained in the measurements in this work and those obtained using the EPR lithium formate dosimeters were, within the expanded (k = 2) uncertainty, in agreement with the values derived by the TPS. The discrepancy between the results using LiF:Mg,Ti TLDs and the EPR lithium formate

  9. Intercomparison of standards of absorbed dose between the USSR and the UK

    NASA Astrophysics Data System (ADS)

    Berlyand, V. A.; Bregadze, J. I.; Burns, J. E.; Dusautoy, A. R.; Sharpe, P. H. G.

    1991-05-01

    A comparison of national standards of absorbed dose was carried out between the All-Union Research Institute for Physical Technical and Radiotechnical Measurements (VNIIFTRI), USSR, and the National Physical Laboratotry (NPL), UK (United Kingdom). Absorbed dose to water for cobalt 60 gamma radiation was compared by means of Fricke dosimeters and ionization chambers in 1985 and 1986. The primary standards used to derive absorbed dose to water were cavity ionization chambers at NPL and a graphite calorimeter at VNIIFTRI. The ratio of absorbed dose to water, NPL to VNIIFTRI, using Fricke dosimeters was 1.008; using ionization chambers it was 1.007. This agreement is within the estimated uncertainties of the standards and measurement methods.

  10. Self-monitoring of water quality in sewer systems using absorbance of ultraviolet and visible light.

    PubMed

    Ruban, G; Ruperd, Y; Laveau, B; Lucas, E

    2001-01-01

    Continuous pollution measurement is interesting to optimize the operation of sanitary facilities as well as to minimize the stormwater discharges. An experimental study was carried out for the determination of Suspended Solids (SS) and Chemical Oxygen Demand (COD) concentrations in combined sewers using ultraviolet and visible absorbances. The maintenance of the measurement system requires six hours a month for the cleaning of the hydraulic feeding system and adjustment of the optical device. The feeding system developed increased the representativeness and reliability of the pollution measurement, but needs to be validated on other measurement sites. The determination of SS concentrations from visible absorbances requires 2 calibration curves for dry and rainy weather respectively. The corresponding accuracies appear satisfactory when compared with the results of standard sampling/laboratory analysis. The accuracy of COD determination from ultraviolet absorbance is less satisfactory, but could perhaps be improved taking into account another parameter. Then the optical measurement of SS and COD is interesting to determine average or long term pollution loads, for example the yearly impact of urban stormwater discharges. With this kind of continuous and on-line measurement, it is possible to react with short delay to unexpected phenomena which could damage the environment or water treatment efficiency.

  11. What Gives an Insulin Hexamer Its Unique Shape and Stability? Role of Ten Confined Water Molecules.

    PubMed

    Mukherjee, Saumyak; Mondal, Sayantan; Deshmukh, Ashish Anilrao; Gopal, Balasubramanian; Bagchi, Biman

    2018-02-08

    Self-assembly of proteins often gives rise to interesting quasi-stable structures that serve important biological purposes. Insulin hexamer is such an assembly. While monomer is the biologically active form of insulin, hexamer serves as the storehouse of the hormone. The hexamer also prevents the formation of higher order aggregates. While several studies explored the role of bivalent metal ions like Zn 2+ , Ca 2+ , etc., in the stabilization of the hexameric form, the role of water molecules has been ignored. We combine molecular dynamics simulations, quantum calculations, and X-ray analyses to discover that a team of approximately 10 water molecules confined inside a barrel-shaped nanocavity at the center of insulin hexamer is one of the major causes that account for the unusual stability of the biomolecular assembly. These cavity water molecules exhibit interesting dynamical features like intermittent escape and reentrance. We find that these water molecules are dynamically slower than the bulk and weave an intricate hydrogen bond network among themselves and with neighboring protein residues to generate a robust backbone at the center of the hexamer that holds the association strongly from inside and maintains the barrel shape.

  12. Performance of a Multifunctional Space Evaporator-Absorber-Radiator (SEAR)

    NASA Technical Reports Server (NTRS)

    Izenson, Michael G.; Chen, Weibo; Phillips, Scott; Chepko, Ariane; Bue, Grant; Quinn, Gregory

    2014-01-01

    The Space Evaporator-Absorber-Radiator (SEAR) is a nonventing thermal control subsystem that combines a Space Water Membrane Evaporator (SWME) with a Lithium Chloride Absorber Radiator (LCAR). The LCAR is a heat pump radiator that absorbs water vapor produced in the SWME. Because of the very low water vapor pressure at equilibrium with lithium chloride solution, the LCAR can absorb water vapor at a temperature considerably higher than the SWME, enabling heat rejection sufficient for most EVA activities by thermal radiation from a relatively small area radiator. Prior SEAR prototypes used a flexible LCAR that was designed to be installed on the outer surface of a portable life support system (PLSS) backpack. This paper describes a SEAR subsystem that incorporates a very compact LCAR. The compact, multifunctional LCAR is built in the form of thin panels that can also serve as the PLSS structural shell. We designed and assembled a 2 ft² prototype LCAR based on this design and measured its performance in thermal vacuum tests when supplied with water vapor by a SWME. These tests validated our models for SEAR performance and showed that there is enough area available on the PLSS backpack shell to enable rejection of metabolic heat from the LCAR. We used results of these tests to assess future performance potential and suggest approaches for integrating the SEAR system with future space suits.

  13. Specific intermolecular interactions of conserved water molecules with amino acids in the Galectin-1 carbohydrate recognition domain

    NASA Astrophysics Data System (ADS)

    Di Lella, Santiago; Petruk, Ariel A.; Armiño, Diego J. Alonso de; Álvarez, Rosa M. S.

    2010-08-01

    Water molecules, rigidly associated to protein surfaces, play a key role in stabilizing biomolecules and participating in their biological functions. Recent studies on the solvation properties of the carbohydrate recognition domain of Galectin-1 by means of molecular dynamic simulations have revealed the existence of several water sites which were well correlated to both the bound water molecules observed in the crystal structure of the protein in the free state and to some of the hydroxyl groups of the carbohydrate ligand observed in the crystal structure of the complexed protein. In this work, we present a study using quantum mechanical methods (B3LYP/6-311++G(3df,3dp)//B3LYP/6-31+G(d)) to determine the energy involved in the binding of these water molecules to specific amino acids in the carbohydrate recognition domain of the protein. By modeling the hydroxyl groups of the carbohydrate by methanol, the energies associated to the local interactions between the ligand and the protein have been evaluated by replacing specific water molecules with methanol. The values of the binding energies have been compared to those previously obtained by the molecular dynamic method.

  14. Water Molecules and Hydrogen-Bonded Networks in Bacteriorhodopsin—Molecular Dynamics Simulations of the Ground State and the M-Intermediate

    PubMed Central

    Grudinin, Sergei; Büldt, Georg; Gordeliy, Valentin; Baumgaertner, Artur

    2005-01-01

    Protein crystallography provides the structure of a protein, averaged over all elementary cells during data collection time. Thus, it has only a limited access to diffusive processes. This article demonstrates how molecular dynamics simulations can elucidate structure-function relationships in bacteriorhodopsin (bR) involving water molecules. The spatial distribution of water molecules and their corresponding hydrogen-bonded networks inside bR in its ground state (G) and late M intermediate conformations were investigated by molecular dynamics simulations. The simulations reveal a much higher average number of internal water molecules per monomer (28 in the G and 36 in the M) than observed in crystal structures (18 and 22, respectively). We found nine water molecules trapped and 19 diffusive inside the G-monomer, and 13 trapped and 23 diffusive inside the M-monomer. The exchange of a set of diffusive internal water molecules follows an exponential decay with a 1/e time in the order of 340 ps for the G state and 460 ps for the M state. The average residence time of a diffusive water molecule inside the protein is ∼95 ps for the G state and 110 ps for the M state. We have used the Grotthuss model to describe the possible proton transport through the hydrogen-bonded networks inside the protein, which is built up in the picosecond-to-nanosecond time domains. Comparing the water distribution and hydrogen-bonded networks of the two different states, we suggest possible pathways for proton hopping and water movement inside bR. PMID:15731388

  15. The Effect of Water Molecules on Mechanical Properties of Bamboo Microfibrils

    NASA Astrophysics Data System (ADS)

    Rahbar, Nima

    Bamboo fibers have higher strength-to-weight ratios than steel and concrete. The unique properties of bamboo fibers come from their natural composite structures that comprise mainly cellulose nanofibrils in a matrix of intertwined hemicellulose and lignin called lignin-carbohydrate complex (LCC). Here, we have utilized atomistic simulations to investigate the mechanical properties and mechanisms of interactions between these materials, in the presence of water molecules. Our results suggest that hemicellulose exhibits better mechanical properties and lignin shows greater tendency to adhere to cellulose nanofibrils. Consequently, the role of hemicellulose found to be enhancing the mechanical properties and lignin found to be providing the strength of bamboo fibers. The abundance of Hbonds in hemicellulose chains is responsible for improving the mechanical behavior of LCC. The strong van der Waals forces between lignin molecules and cellulose nanofibrils is responsible for higher adhesion energy between LCC/cellulose nanofibrils. We also found out that the amorphous regions of cellulose nanofibrils is the weakest interface in bamboo Microfibrils. In presence of water, the elastic modulus of lignin increases at low water content (less than 10 NSF CAREER Grant No. 1261284.

  16. [Interactions of DNA bases with individual water molecules. Molecular mechanics and quantum mechanics computation results vs. experimental data].

    PubMed

    Gonzalez, E; Lino, J; Deriabina, A; Herrera, J N F; Poltev, V I

    2013-01-01

    To elucidate details of the DNA-water interactions we performed the calculations and systemaitic search for minima of interaction energy of the systems consisting of one of DNA bases and one or two water molecules. The results of calculations using two force fields of molecular mechanics (MM) and correlated ab initio method MP2/6-31G(d, p) of quantum mechanics (QM) have been compared with one another and with experimental data. The calculations demonstrated a qualitative agreement between geometry characteristics of the most of local energy minima obtained via different methods. The deepest minima revealed by MM and QM methods correspond to water molecule position between two neighbor hydrophilic centers of the base and to the formation by water molecule of hydrogen bonds with them. Nevertheless, the relative depth of some minima and peculiarities of mutual water-base positions in' these minima depend on the method used. The analysis revealed insignificance of some differences in the results of calculations performed via different methods and the importance of other ones for the description of DNA hydration. The calculations via MM methods enable us to reproduce quantitatively all the experimental data on the enthalpies of complex formation of single water molecule with the set of mono-, di-, and trimethylated bases, as well as on water molecule locations near base hydrophilic atoms in the crystals of DNA duplex fragments, while some of these data cannot be rationalized by QM calculations.

  17. On the Role of Water Models in Quantifying the Binding Free Energy of Highly Conserved Water Molecules in Proteins: The Case of Concanavalin A.

    PubMed

    Fadda, Elisa; Woods, Robert J

    2011-10-11

    The ability of ligands to displace conserved water molecules in protein binding sites is of significant interest in drug design and is particularly pertinent in the case of glycomimetic drugs. This concept was explored in previous work [ Clarke et al. J. Am. Chem. Soc. 2001 , 123 , 12238 - 12247 and Kadirvelraj et al. J. Am. Chem. Soc. 2008 , 130 , 16933 - 16942 ] for a highly conserved water molecule located in the binding site of the prototypic carbohydrate-binding protein Concanavalin A (Con A). A synthetic ligand was designed with the aim of displacing such water. While the synthetic ligand bound to Con A in an analogous manner to that of the natural ligand, crystallographic analysis demonstrated that it did not displace the conserved water. In order to quantify the affinity of this particular water for the Con A surface, we report here the calculated standard binding free energy for this water in both ligand-bound and free Con A, employing three popular water models: TIP3P, TIP4P, and TIP5P. Although each model was developed to perform well in simulations of bulk-phase water, the computed binding energies for the isolated water molecule displayed a high sensitivity to the model. Both molecular dynamics simulation and free energy results indicate that the choice of water model may greatly influence the characterization of surface water molecules as conserved (TIP5P) or not (TIP3P) in protein binding sites, an observation of considerable significance to rational drug design. Structural and theoretical aspects at the basis of the different behaviors are identified and discussed.

  18. Magnetically driven floating foams for the removal of oil contaminants from water.

    PubMed

    Calcagnile, Paola; Fragouli, Despina; Bayer, Ilker S; Anyfantis, George C; Martiradonna, Luigi; Cozzoli, P Davide; Cingolani, Roberto; Athanassiou, Athanassia

    2012-06-26

    In this study, we present a novel composite material based on commercially available polyurethane foams functionalized with colloidal superparamagnetic iron oxide nanoparticles and submicrometer polytetrafluoroethylene particles, which can efficiently separate oil from water. Untreated foam surfaces are inherently hydrophobic and oleophobic, but they can be rendered water-repellent and oil-absorbing by a solvent-free, electrostatic polytetrafluoroethylene particle deposition technique. It was found that combined functionalization of the polytetrafluoroethylene-treated foam surfaces with colloidal iron oxide nanoparticles significantly increases the speed of oil absorption. Detailed microscopic and wettability studies reveal that the combined effects of the surface morphology and of the chemistry of the functionalized foams greatly affect the oil-absorption dynamics. In particular, nanoparticle capping molecules are found to play a major role in this mechanism. In addition to the water-repellent and oil-absorbing capabilities, the functionalized foams exhibit also magnetic responsivity. Finally, due to their light weight, they float easily on water. Hence, by simply moving them around oil-polluted waters using a magnet, they can absorb the floating oil from the polluted regions, thereby purifying the water underneath. This low-cost process can easily be scaled up to clean large-area oil spills in water.

  19. Combining solvent thermodynamic profiles with functionality maps of the Hsp90 binding site to predict the displacement of water molecules.

    PubMed

    Haider, Kamran; Huggins, David J

    2013-10-28

    Intermolecular interactions in the aqueous phase must compete with the interactions between the two binding partners and their solvating water molecules. In biological systems, water molecules in protein binding sites cluster at well-defined hydration sites and can form strong hydrogen-bonding interactions with backbone and side-chain atoms. Displacement of such water molecules is only favorable when the ligand can form strong compensating hydrogen bonds. Conversely, water molecules in hydrophobic regions of protein binding sites make only weak interactions, and the requirements for favorable displacement are less stringent. The propensity of water molecules for displacement can be identified using inhomogeneous fluid solvation theory (IFST), a statistical mechanical method that decomposes the solvation free energy of a solute into the contributions from different spatial regions and identifies potential binding hotspots. In this study, we employed IFST to study the displacement of water molecules from the ATP binding site of Hsp90, using a test set of 103 ligands. The predicted contribution of a hydration site to the hydration free energy was found to correlate well with the observed displacement. Additionally, we investigated if this correlation could be improved by using the energetic scores of favorable probe groups binding at the location of hydration sites, derived from a multiple copy simultaneous search (MCSS) method. The probe binding scores were not highly predictive of the observed displacement and did not improve the predictivity when used in combination with IFST-based hydration free energies. The results show that IFST alone can be used to reliably predict the observed displacement of water molecules in Hsp90. However, MCSS can augment IFST calculations by suggesting which functional groups should be used to replace highly displaceable water molecules. Such an approach could be very useful in improving the hit-to-lead process for new drug targets.

  20. Aqueous heterogeneity at the air/water interface revealed by 2D-HD-SFG spectroscopy.

    PubMed

    Hsieh, Cho-Shuen; Okuno, Masanari; Hunger, Johannes; Backus, Ellen H G; Nagata, Yuki; Bonn, Mischa

    2014-07-28

    Water molecules interact strongly with each other through hydrogen bonds. This efficient intermolecular coupling causes strong delocalization of molecular vibrations in bulk water. We study intermolecular coupling at the air/water interface and find intermolecular coupling 1) to be significantly reduced and 2) to vary strongly for different water molecules at the interface--whereas in bulk water the coupling is homogeneous. For strongly hydrogen-bonded OH groups, coupling is roughly half of that of bulk water, due to the lower density in the near-surface region. For weakly hydrogen-bonded OH groups that absorb around 3500 cm(-1), which are assigned to the outermost, yet hydrogen-bonded OH groups pointing towards the liquid, coupling is further reduced by an additional factor of 2. Remarkably, despite the reduced structural constraints imposed by the interfacial hydrogen-bond environment, the structural relaxation is slow and the intermolecular coupling of these water molecules is weak. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The spontaneous synchronized dance of pairs of water molecules

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

    Roncaratti, Luiz F.; Instituto de Física, Universidade de Brasília, 70910-900 Brasília; Cappelletti, David, E-mail: david.cappelletti@unipg.it

    2014-03-28

    Molecular beam scattering experiments have been performed to study the effect of long-range anisotropic forces on the collision dynamics of two small polar molecules. The main focus of this paper is on water, but also ammonia and hydrogen sulphide molecules have been investigated, and some results will be anticipated. The intermolecular distances mainly probed are of the order of 1 nm and therefore much larger than the molecular dimensions. In particular, we have found that the natural electric field gradient, generated by different spatial orientations of the permanent electric dipoles, is able to promote the transformation of free rotations into coupledmore » pendular states, letting the molecular partners involved in the collision complex swinging to and fro around the field direction. This long-ranged concerted motion manifested itself as large increases of the magnitude of the total integral cross section. The experimental findings and the theoretical treatment developed to shed light on the details of the process suggest that the transformation from free rotations to pendular states depends on the rotational level of both molecules, on the impact parameter, on the relative collision velocity, on the dipole moment product and occurs in the time scale of picoseconds. The consequences of this intriguing phenomenon may be important for the interpretation and, in perspective, for the control of elementary chemical and biological processes, given by polar molecules, ions, and free radicals, occurring in several environments under various conditions.« less

  2. The spontaneous synchronized dance of pairs of water molecules

    NASA Astrophysics Data System (ADS)

    Roncaratti, Luiz F.; Cappelletti, David; Pirani, Fernando

    2014-03-01

    Molecular beam scattering experiments have been performed to study the effect of long-range anisotropic forces on the collision dynamics of two small polar molecules. The main focus of this paper is on water, but also ammonia and hydrogen sulphide molecules have been investigated, and some results will be anticipated. The intermolecular distances mainly probed are of the order of 1 nm and therefore much larger than the molecular dimensions. In particular, we have found that the natural electric field gradient, generated by different spatial orientations of the permanent electric dipoles, is able to promote the transformation of free rotations into coupled pendular states, letting the molecular partners involved in the collision complex swinging to and fro around the field direction. This long-ranged concerted motion manifested itself as large increases of the magnitude of the total integral cross section. The experimental findings and the theoretical treatment developed to shed light on the details of the process suggest that the transformation from free rotations to pendular states depends on the rotational level of both molecules, on the impact parameter, on the relative collision velocity, on the dipole moment product and occurs in the time scale of picoseconds. The consequences of this intriguing phenomenon may be important for the interpretation and, in perspective, for the control of elementary chemical and biological processes, given by polar molecules, ions, and free radicals, occurring in several environments under various conditions.

  3. Determination of absorbed dose to water around a clinical HDR {sup 192}Ir source using LiF:Mg,Ti TLDs demonstrates an LET dependence of detector response

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

    Carlsson Tedgren, Aasa; Elia, Rouba; Hedtjaern, Haakan

    2012-02-15

    Purpose: Experimental radiation dosimetry with thermoluminescent dosimeters (TLDs), calibrated in a {sup 60}Co or megavoltage (MV) photon beam, is recommended by AAPM TG-43U1for verification of Monte Carlo calculated absorbed doses around brachytherapy sources. However, it has been shown by Carlsson Tedgren et al.[Med. Phys. 38, 5539-5550 (2011)] that for TLDs of LiF:Mg,Ti, detector response was 4% higher in a {sup 137}Cs beam than in a {sup 60}Co one. The aim of this work was to investigate if similar over-response exists when measuring absorbed dose to water around {sup 192}Ir sources, using LiF:Mg,Ti dosimeters calibrated in a 6 MV photon beam.more » Methods: LiF dosimeters were calibrated to measure absorbed dose to water in a 6 MV photon beam and used to measure absorbed dose to water at distances of 3, 5, and 7 cm from a clinical high dose rate (HDR) {sup 192}Ir source in a polymethylmethacrylate (PMMA) phantom. Measured values were compared to values of absorbed dose to water calculated using a treatment planning system (TPS) including corrections for the difference in energy absorption properties between calibration quality and the quality in the users'{sup 192}Ir beam and for the use of a PMMA phantom instead of the water phantom underlying dose calculations in the TPS. Results: Measured absorbed doses to water around the {sup 192}Ir source were overestimated by 5% compared to those calculated by the TPS. Corresponding absorbed doses to water measured in a previous work with lithium formate electron paramagnetic resonance (EPR) dosimeters by Antonovic et al. [Med. Phys. 36, 2236-2247 (2009)], using the same irradiation setup and calibration procedure as in this work, were 2% lower than those calculated by the TPS. The results obtained in the measurements in this work and those obtained using the EPR lithium formate dosimeters were, within the expanded (k = 2) uncertainty, in agreement with the values derived by the TPS. The discrepancy between the

  4. High-Capacity Spacesuit Evaporator Absorber Radiator (SEAR)

    NASA Technical Reports Server (NTRS)

    Izenson, Michael G.; Chen, Weibo; Phillips, Scott; Chepko, Ariane; Bue, Grant; Quinn, Gregory

    2015-01-01

    Future human space exploration missions will require advanced life support technology that can operate across a wide range of applications and environments. Thermal control systems for space suits and spacecraft will need to meet critical requirements for water conservation and multifunctional operation. This paper describes a Space Evaporator Absorber Radiator (SEAR) that has been designed to meet performance requirements for future life support systems. A SEAR system comprises a lithium chloride absorber radiator (LCAR) for heat rejection coupled with a space water membrane evaporator (SWME) for heat acquisition. SEAR systems provide heat pumping to minimize radiator size, thermal storage to accommodate variable environmental conditions, and water absorption to minimize use of expendables. We have built and tested a flight-like, high-capacity LCAR, demonstrated its performance in thermal vacuum tests, and explored the feasibility of an ISS demonstration test of a SEAR system. The new LCAR design provides the same cooling capability as prior LCAR prototypes while enabling over 30% more heat absorbing capacity. Studies show that it should be feasible to demonstrate SEAR operation in flight by coupling with an existing EMU on the space station.

  5. High-Capacity Spacesuit Evaporator Absorber Radiator (SEAR)

    NASA Technical Reports Server (NTRS)

    Izenson, Michael G.; Chen, Weibo; Phillips, Scott; Chepko, Ariane; Bue, Grant; Quinn, Gregory

    2014-01-01

    Future human space exploration missions will require advanced life support technology that can operate across a wide range of applications and environments. Thermal control systems for space suits and spacecraft will need to meet critical requirements for water conservation and adaptability to highly variable thermal environments. This paper describes a Space Evaporator Absorber Radiator (SEAR) that has been designed to meet performance requirements for future life support systems. A SEAR system comprises a lithium chloride absorber radiator (LCAR) for heat rejection coupled with a space water membrane evaporator (SWME) for heat acquisition. SEAR systems provide heat pumping to minimize radiator size, thermal storage to accommodate variable environmental conditions, and water absorption to minimize use of expendables. We have built and tested a flightlike, high-capacity LCAR, demonstrated its performance in thermal vacuum tests, and explored the feasibility of an ISS demonstration test of a SEAR system. The new LCAR design provides the same cooling capability as prior LCAR prototypes while enabling over 30% more heat absorbing capacity. Studies show that it should be feasible to demonstrate SEAR operation in flight by coupling with an existing EMU on the space station.

  6. Determination of absorbed dose to water from a miniature kilovoltage x-ray source using a parallel-plate ionization chamber

    NASA Astrophysics Data System (ADS)

    Watson, Peter G. F.; Popovic, Marija; Seuntjens, Jan

    2018-01-01

    Electronic brachytherapy sources are widely accepted as alternatives to radionuclide-based systems. Yet, formal dosimetry standards for these devices to independently complement the dose protocol provided by the manufacturer are lacking. This article presents a formalism for calculating and independently verifying the absorbed dose to water from a kV x-ray source (The INTRABEAM System) measured in a water phantom with an ionization chamber calibrated in terms of air-kerma. This formalism uses a Monte Carlo (MC) calculated chamber conversion factor, CQ , to convert air-kerma in a reference beam to absorbed dose to water in the measurement beam. In this work CQ was determined for a PTW 34013 parallel-plate ionization chamber. Our results show that CQ was sensitive to the chamber plate separation tolerance, with differences of up to 15%. CQ was also found to have a depth dependence which varied with chamber plate separation (0 to 10% variation for the smallest and largest cavity height, over 3 to 30 mm depth). However for all chamber dimensions investigated, CQ was found to be significantly larger than the manufacturer reported value, suggesting that the manufacturer recommended method of dose calculation could be underestimating the dose to water.

  7. Experimental Analysis of the Thermo-Hydraulic Performance on a Cylindrical Parabolic Concentrating Solar Water Heater with Twisted Tape Inserts in an Absorber Tube

    NASA Astrophysics Data System (ADS)

    Kumar, Birendra; Nayak, Rajen Kumar; Singh, S. N.

    2018-05-01

    A twisted tape inserted in an absorber tube may be an excellent option to enhance the performance of a cylindrical parabolic concentrating solar collector (CPC). The present work is an experimental study of the flow and heat transfer with and without twisted tape inserts in the absorber tube of a CPC. Results are presented for mass flow rates of water, ṁ=0.0198-0.0525 kg/s, twist ratio, y=5-10 and Reynolds number, Re=2577.46-6785.55. In the present study, we found that the outlet water temperature, collector efficiency and Nusselt number (Nu) are higher in the twisted tapes as compared to those without the twisted tape inserts in the absorber tube of the CPC. For fixed mass flow rate of water ṁ, the To and η increased with the decrease in twist ratio, y, and is higher in lower twist ratio, y=5, of the twisted tapes. The whole experiment was performed at the Indian Institute of Technology (ISM) in Dhanbad, India during the months of March-April 2017. Based on the experimental data, the correlations for the Nu and friction factor were also developed.

  8. Shape-selective adsorption of aromatic molecules from water by tetramethylammonium-smectite

    USGS Publications Warehouse

    Lee, J.; Mortland, M.M.; Boyd, S.A.; Chiou, C.T.

    1989-01-01

    The adsorption of aromatic compounds by smectite exchanged with tetramethylammonium (TMA) has been studied. Aromatic compounds adsorbed by TMA-smectite are assumed to adopt a tilted orientation in a face-to-face arrangment with the TMA tetrahedra. The sorptive characteristics of TMA-smectite were influenced strongly by the presence of water. The dry TMA-smectite showed little selectivity in the uptake of benzen, toluene and xylene. In the presence of water, TMA-smectite showed a high degree of selectivity based on molecular size/shape, resulting in high uptake of benzene and progressively lower uptake of larger aromatic molecules. This selectivity appeared to result from the shrinkage of interlamellar cavities by water.

  9. The δ18O of Atmospheric Water Vapour is Recorded in the Oxygen Isotope Ratios of Leaf water and Organic Molecules at High Relative Humidity

    NASA Astrophysics Data System (ADS)

    Lehmann, M. M.; Goldsmith, G. R.; Schmid, L.; Siegwolf, R. T.; Gessler, A.; Saurer, M.

    2016-12-01

    The oxygen stable isotope ratios (δ18O) of water and organic molecules in plants hold information about plant physiology, ecohydrology, and environmental conditions. For instance, the δ18O ratio of leaf water reflects both the δ18O ratios of water in the soil and in the atmosphere. This water, which is incorporated into organic molecules at the time of synthesis, thus serves to record the environment in which the plant was growing. However, how δ18O of atmospheric water vapour affects the δ18O ratio of organic molecules remains poorly understood. In order to investigate the effects of fog and rain (e.g. high atmospheric water availability) on δ18O ratios of leaf water and organic molecules, we exposed oak tree saplings (Quercus robur) in wet and dry soil treatments to 18O-depleted water vapour at ca. 90% relative humidity for 5 h. We harvested plant material over 24 h to trace the movement of the isotopic label in water and organics throughout the plant from the leaves to the stem. The atmospheric water vapour caused a strong 18O-depletion in leaf and xylem water, as well as in leaf carbohydrates, with the most negative ratios observed at the end of the fogging. Moreover, the label was clearly observed in twig and stem phloem carbohydrates following a short delay. A detailed compound-specific isotope analysis of the leaf carbohydrates revealed that the label caused an 18O-depletion in fructose, glucose, and sucrose. Quercitol, an oak-specific alditol, did not show 18O-depletion. Clear soil moisture treatment effects were only observed for twig phloem carbohydrates, with a stronger 18O-depletion in wet plants than in dry plants, suggesting retarded leaf-to-phloem sugar export in trees under drought. We demonstrate that labelling with 18O-depleted water is a potential tool to trace the movement and incorporation of oxygen stable isotopes in plants. We clearly show that changes in δ18O of atmospheric water vapour are quickly imprinted on leaf water and

  10. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

    PubMed

    Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

    2017-07-06

    The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

  11. Physicochemical basis for water-actuated movement and stress generation in nonliving plant tissues.

    PubMed

    Bertinetti, L; Fischer, F D; Fratzl, P

    2013-12-06

    Generating stresses and strains through water uptake from atmospheric humidity is a common process in nature, e.g., in seed dispersal. Actuation depends on a balance between chemical interactions and the elastic energy required to accomplish the volume change. In order to study the poorly understood chemical interactions, we combine mechanosorption experiments with theoretical calculations of the swelling behavior to estimate the mechanical energy and extract the contribution of the chemical energy per absorbed water molecule. The latter is highest in the completely dry state and stays almost constant at about 1.2 kT for higher hydrations. This suggests that water bound to the macromolecular components of the wood tissues acquires one additional hydrogen bond per eight water molecules, thus providing energy for actuation.

  12. Role of oxygen functional groups for structure and dynamics of interfacial water on low rank coal surface: a molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    You, Xiaofang; Wei, Hengbin; Zhu, Xianchang; Lyu, Xianjun; Li, Lin

    2018-07-01

    Molecular dynamics simulations were employed to study the effects of oxygen functional groups for structure and dynamics properties of interfacial water molecules on the subbituminous coal surface. Because of complex composition and structure, the graphite surface modified by hydroxyl, carboxyl and carbonyl groups was used to represent the surface model of subbituminous coal according to XPS results, and the composing proportion for hydroxyl, carbonyl and carboxyl is 25:3:5. The hydration energy with -386.28 kJ/mol means that the adsorption process between water and coal surface is spontaneous. Density profiles for oxygen atoms and hydrogen atoms indicate that the coal surface properties affect the structural and dynamic characteristics of the interfacial water molecules. The interfacial water exhibits much more ordering than bulk water. The results of radial distribution functions, mean square displacement and local self-diffusion coefficient for water molecule related to three oxygen moieties confirmed that the water molecules prefer to absorb with carboxylic groups, and adsorption of water molecules at the hydroxyl and carbonyl is similar.

  13. Accuracy of a dose-area product compared to an absorbed dose to water at a point in a 2 cm diameter field

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

    Dufreneix, S.; Ostrowsky, A.; Rapp, B.

    Purpose: Graphite calorimeters with a core diameter larger than the beam can be used to establish dosimetric references in small fields. The dose-area product (DAP) measured can theoretically be linked to an absorbed dose at a point by the determination of a profile correction. This study aims at comparing the DAP-based protocol to the usual absorbed dose at a point protocol in a 2 cm diameter field for which both references exist. Methods: Two calorimeters were used, respectively, with a sensitive volume of 0.6 cm (for the absorbed dose at a point measurement) and 3 cm diameter (for the DAPmore » measurement). Profile correction was calculated from a 2D dose mapping using three detectors: a PinPoint chamber, a synthetic diamond, and EBT3 films. A specific protocol to read EBT3 films was implemented and the dose-rate and energy dependences were studied to assure a precise measurement, especially in the penumbra and out-of-field regions. Results: EBT3 films were found independent on dose rates over the range studied but showed a strong under-response (18%) at low energies. Depending on the dosimeter used for calculating the profile correction, a deviation of 0.8% (PinPoint chamber), 0.9% (diamond), or 1.9% (EBT3 films) was observed between the calibration coefficient derived from DAP measurements and the one directly established in terms of absorbed dose to water at a point. Conclusions: The DAP method can currently be linked to the classical dosimetric reference system based in an absorbed dose at a point only with a confidence interval of 95% (k = 2). None of the detectors studied can be used to determine an absorbed dose to water at a point from a DAP measurement with an uncertainty smaller than 1.2%.« less

  14. Prediction of Ordered Water Molecules in Protein Binding Sites from Molecular Dynamics Simulations: The Impact of Ligand Binding on Hydration Networks.

    PubMed

    Rudling, Axel; Orro, Adolfo; Carlsson, Jens

    2018-02-26

    Water plays a major role in ligand binding and is attracting increasing attention in structure-based drug design. Water molecules can make large contributions to binding affinity by bridging protein-ligand interactions or by being displaced upon complex formation, but these phenomena are challenging to model at the molecular level. Herein, networks of ordered water molecules in protein binding sites were analyzed by clustering of molecular dynamics (MD) simulation trajectories. Locations of ordered waters (hydration sites) were first identified from simulations of high resolution crystal structures of 13 protein-ligand complexes. The MD-derived hydration sites reproduced 73% of the binding site water molecules observed in the crystal structures. If the simulations were repeated without the cocrystallized ligands, a majority (58%) of the crystal waters in the binding sites were still predicted. In addition, comparison of the hydration sites obtained from simulations carried out in the absence of ligands to those identified for the complexes revealed that the networks of ordered water molecules were preserved to a large extent, suggesting that the locations of waters in a protein-ligand interface are mainly dictated by the protein. Analysis of >1000 crystal structures showed that hydration sites bridged protein-ligand interactions in complexes with different ligands, and those with high MD-derived occupancies were more likely to correspond to experimentally observed ordered water molecules. The results demonstrate that ordered water molecules relevant for modeling of protein-ligand complexes can be identified from MD simulations. Our findings could contribute to development of improved methods for structure-based virtual screening and lead optimization.

  15. Improving of enzyme immunoassay for detection and quantification of the target molecules using silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Syrvatka, Vasyl J.; Slyvchuk, Yurij I.; Rozgoni, Ivan I.; Gevkan, Ivan I.; Overchuk, Marta O.

    2014-02-01

    Modern routine enzyme immunoassays for detection and quantification of biomolecules have several disadvantages such as high cost, insufficient sensitivity, complexity and long-term execution. The surface plasmon resonance of silver nanoparticles gives reasons of creating new in the basis of simple, highly sensitive and low cost colorimetric assays that can be applied to the detection of small molecules, DNA, proteins and pollutants. The main aim of the study was the improving of enzyme immunoassay for detection and quantification of the target molecules using silver nanoparticles. For this purpose we developed method for synthesis of silver nanoparticles with hyaluronic acid and studied possibility of use these nanoparticles in direct determination of target molecules concentration (in particular proteins) and for improving of enzyme immunoassay. As model we used conventional enzyme immunoassays for determination of progesterone and estradiol concentration. We obtained the possibility to produce silver nanoparticles with hyaluronan homogeneous in size between 10 and 12 nm, soluble and stable in water during long term of storage using modified procedure of silver nanoparticles synthesis. New method allows to obtain silver nanoparticles with strong optical properties at the higher concentrations - 60-90 μg/ml with the peak of absorbance at the wavelength 400 nm. Therefore surface plasmon resonance of silver nanoparticles with hyaluronan and ultraviolet-visible spectroscopy provide an opportunity for rapid determination of target molecules concentration (especial protein). We used silver nanoparticles as enzyme carriers and signal enhancers. Our preliminary data show that silver nanoparticles increased absorbance of samples that allows improving upper limit of determination of estradiol and progesterone concentration.

  16. The binding energies of one and two water molecules to the first transition-row metal positive ions. II

    NASA Technical Reports Server (NTRS)

    Rosi, Marzio; Bauschlicher, Charles W., Jr.

    1990-01-01

    The present investigation of H2O's binding energy to transition-metal ions proceeds from the D(2h) structure and bends the two water molecules out of plane. The molecule is constrained to have C(2v) symmetry, so that each water molecule and metal ion lies on a plane. The ground states are bent only for Mn(H2O)2(+) and Zn(H2O)2(+), where only 4s4p hybridization is energetically favorable; 4s4p hybridization reduces repulsion.

  17. Construction of Nontoxic Polymeric UV-Absorber with Great Resistance to UV-Photoaging

    PubMed Central

    Huang, Zhong; Ding, Aishun; Guo, Hao; Lu, Guolin; Huang, Xiaoyu

    2016-01-01

    In this article, we developed a series of new nontoxic polymeric UV-absorbers through covalently attaching a benzophenone derivative onto the main chain of poly(vinyl chloride) (PVC) via mild and quantitative click chemistry. Azide groups were firstly introduced into the backbone of PVC via a nucleophilic reaction without affecting polymeric skeleton. Copper-catalyzed Husigen-Click cycloaddition reaction was performed between the pendant azide groups of PVC and alkynyl of (2-hydroxy-4-(prop-2-ynyloxy)phenyl)(phenyl)methanone at ambient temperature for affording the desired PVC-based UV-absorbers (PVC-UV) with different amounts of benzophenone moieties, which displayed great resistance to photoaging without degradation while exposed to UV irradiation. These polymeric UV-absorbers also showed good solubilities in common organic solvents and no cytotoxicity vs. HaCat cell. Small amounts of PVC-UV were homogeneously mixed with PVC as additive for stabilizing PVC against UV-photoaging without degradation and releasing small molecule even after 200 h while keeping thermal stability. This route of polymeric additive clearly paved an efficient way for solving the puzzle of separation of small molecule additive. PMID:27138547

  18. Development of an innovative solar absorber

    NASA Astrophysics Data System (ADS)

    Goodchild, Gavin

    Solar thermal systems have great potential to replace or reduce the dependence of conventional fossil fuel based heating technologies required for space and water heating. Specifically solar domestic hot water systems can contribute 50-75% of the annual thermal load. To date residential users have been slow to purchase and install systems, primarily due to the large monetary investment required to purchase and install a system. Recent innovations in materials design and manufacturing techniques, offer opportunities for the development of absorber plate designs that have the potential to reduce cost, increase efficiency and reduce payback periods. Consequently, this design study was conducted in conjunction with industrial partners to develop an improved absorber based on roll bond manufacturing that can be produced at reduced cost with comparable or greater thermal efficiency.

  19. "Nanofiltration" Enabled by Super-Absorbent Polymer Beads for Concentrating Microorganisms in Water Samples.

    PubMed

    Xie, Xing; Bahnemann, Janina; Wang, Siwen; Yang, Yang; Hoffmann, Michael R

    2016-02-15

    Detection and quantification of pathogens in water is critical for the protection of human health and for drinking water safety and security. When the pathogen concentrations are low, large sample volumes (several liters) are needed to achieve reliable quantitative results. However, most microbial identification methods utilize relatively small sample volumes. As a consequence, a concentration step is often required to detect pathogens in natural waters. Herein, we introduce a novel water sample concentration method based on superabsorbent polymer (SAP) beads. When SAP beads swell with water, small molecules can be sorbed within the beads, but larger particles are excluded and, thus, concentrated in the residual non-sorbed water. To illustrate this approach, millimeter-sized poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) beads are synthesized and successfully applied to concentrate water samples containing two model microorganisms: Escherichia coli and bacteriophage MS2. Experimental results indicate that the size of the water channel within water swollen P(AM-co-IA) hydrogel beads is on the order of several nanometers. The millimeter size coupled with a negative surface charge of the beads are shown to be critical in order to achieve high levels of concentration. This new concentration procedure is very fast, effective, scalable, and low-cost with no need for complex instrumentation.

  20. Space Evaporator Absorber Radiator (SEAR) for Thermal Storage on Manned Spacecraft

    NASA Technical Reports Server (NTRS)

    Izenson, Michael G.; Chen, Weibo; Chepko, Ariane; Bue, Grant; Quinn, Gregory

    2014-01-01

    Future manned exploration spacecraft will need to operate in challenging thermal environments. State-of the- art technology for active thermal control relies on sublimating water ice and venting the vapor overboard in very hot environments. This approach can lead to large loss of water and a significant mass penalty for the spacecraft. This paper describes an innovative thermal control system that uses a Space Evaporator Absorber Radiator (SEAR) to control spacecraft temperatures in highly variable environments without venting water. SEAR uses heat pumping and energy storage by LiCl/water absorption to enable effective cooling during hot periods and regeneration during cool periods. The LiCl absorber technology has the potential to absorb over 800 kJ per kg of system mass, compared to phase change heat sink systems that typically achieve approx. 50 kJ/kg. The optimal system is based on a trade-off between the mass of water saved and extra power needed to regenerate the LiCl absorber. This paper describes analysis models and the predicted performance and optimize the size of the SEAR system, estimated size and mass of key components, and power requirements for regeneration. We also present a concept design for an ISS test package to demonstrate operation of a subscale system in zero gravity.

  1. SU-E-T-204: Comparison of Absorbed-Dose to Water in High-Energy Photon Beams Based On Addendum AAPM TG-51, IAEA TRS-398, and JSMP 12

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

    Kinoshita, N; Kita, A; Yoshioka, C

    Purpose: Several clinical reference dosimetry protocols for absorbed-dose to water have recently been published: The American Association of Physicists in Medicine (AAPM) published an Addendum to the AAPM’s TG-51 (Addendum TG-51) in April 2014, and the Japan Society of Medical Physics (JSMP) published the Japan Society of Medical Physics 12 (JSMP12), a clinical reference dosimetry protocol, in September 2012. This investigation compared and evaluated the absorbed-dose to water of high-energy photon beams according to Addendum TG-51, International Atomic Energy Agency Technical Report Series No. 398 (TRS-398), and JSMP12. Methods: Differences in the respective beam quality conversion factors with Addendum TG-51,more » TRS-398, and JSMP12 were analyzed and the absorbed-dose to water using 6- and 10-MV photon beams was measured according to the protocols recommended in Addendum TG-51, TRS-398, and JSMP12. The measurements were conducted using two Farmer-type ionization chambers, Exradin A12 and PTW 30013. Results: The beam quality conversion factors for both the 6- and 10-MV photon beams with Addendum TG-51 were within 0.6%, in agreement with the beam quality conversion factors with TRS-398 and JSMP12. The Exradin A12 provided an absorbed-dose to water ratio from 1.003 to 1.006 with TRS-398 / Addendum TG-51 and from 1.004 to 1.005 with JSMP 12 / Addendum TG-51, whereas the PTW 30013 provided a ratio of 1.001 with TRS-398 / Addendum TG-51 and a range from 0.997 to 0.999 with JSMP 12 / Addendum TG-51. Conclusion: Despite differences in the beam quality conversion factor, no major differences were seen in the absorbed-dose to water with Addendum TG-51, TRS-398, and JSMP12. However, Addendum TG-51 provides the most recent data for beam quality conversion factors based on Monte Carlo simulation and greater detail for the measurement protocol. Therefore, the absorbed-dose to water measured with Addendum TG-51 is an estimate with less uncertainty.« less

  2. Tuning Transpiration by Interfacial Solar Absorber-Leaf Engineering.

    PubMed

    Zhuang, Shendong; Zhou, Lin; Xu, Weichao; Xu, Ning; Hu, Xiaozhen; Li, Xiuqiang; Lv, Guangxin; Zheng, Qinghui; Zhu, Shining; Wang, Zhenlin; Zhu, Jia

    2018-02-01

    Plant transpiration, a process of water movement through a plant and its evaporation from aerial parts especially leaves, consumes a large component of the total continental precipitation (≈48%) and significantly influences global water distribution and climate. To date, various chemical and/or biological explorations have been made to tune the transpiration but with uncertain environmental risks. In recent years, interfacial solar steam/vapor generation is attracting a lot of attention for achieving high energy transfer efficiency. Various optical and thermal designs at the solar absorber-water interface for potential applications in water purification, seawater desalination, and power generation appear. In this work, the concept of interfacial solar vapor generation is extended to tunable plant transpiration by showing for the first time that the transpiration efficiency can also be enhanced or suppressed through engineering the solar absorber-leaf interface. By tuning the solar absorption of membrane in direct touch with green leaf, surface temperature of green leaf will change accordingly because of photothermal effect, thus the transpiration efficiency as well as temperature and relative humidity in the surrounding environment will be tuned. This tunable transpiration by interfacial absorber-leaf engineering can open an alternative avenue to regulate local atmospheric temperature, humidity, and eventually hydrologic cycle.

  3. UV-visible absorbance spectroscopy as a proxy for peatland dissolved organic carbon (DOC) quantity and quality: considerations on wavelength and absorbance degradation.

    PubMed

    Peacock, Mike; Evans, Chris D; Fenner, Nathalie; Freeman, Chris; Gough, Rachel; Jones, Timothy G; Lebron, Inma

    2014-05-01

    Absorbance in the UV or visible spectrum (UV-vis) is commonly used as a proxy for DOC concentrations in waters draining upland catchments. To determine the appropriateness of different UV-vis measurements we used surface and pore water samples from two Welsh peatlands in four different experiments: (i) an assessment of single wavelength proxies (1 nm increments between 230-800 nm) for DOC concentration demonstrated that 254 nm was more accurate than 400 nm. The highest R(2) values between absorbance and DOC concentration were generated using 263 nm for one sample set (R(2) = 0.91), and 230 nm for the other three sample sets (respective R(2) values of 0.86, 0.81, and 0.93). (ii) A comparison of different DOC concentration proxies, including single wavelength proxies, a two wavelength model, a proxy using phenolic concentration, and a proxy using the area under a UV spectrum at 250-350 nm. It was found that both a single wavelength proxy (≤263 nm) and a two wavelength model performed well for both pore water and surface water. (iii) An evaluation of the E2 : E3, E2 : E4, E4 : E6 ratios, and SUVA (absorbance at 254 nm normalised to DOC concentration) as indicators of DOC quality showed that the E4 : E6 ratio was subject to extensive variation over time, and was highly correlated between surface water and pore water, suggesting that it is a useful metric to determine temporal changes in DOC quality. (iv) A repeated weekly analysis over twelve weeks showed no consistent change in UV-vis absorbance, and therefore an inferred lack of degradation of total DOC in samples that were filtered and stored in the dark at 4 °C.

  4. Preparation of pure chitosan film using ternary solvents and its super absorbency.

    PubMed

    Wang, Xuejun; Lou, Tao; Zhao, Wenhua; Song, Guojun

    2016-11-20

    Chemical modification and graft copolymerization were commonly adopted to prepare super absorbent materials. However, physical microstructure of pure chitosan film was optimized to improve the water uptake capacity in this study. Chitosan films with micro-nanostructure were prepared by a ternary solvent system. The optimal process parameters are 1% acetic acid water solution: dioxane: dimethyl sulfoxide=90: 2.5: 7.5 (v/v/v) with chitosan concentration at 1.25% (w/v). The water uptake capacity of the chitosan film prepared under the optimal process parameters was 896g/g. The prepared chitosan films also exhibited high water uptake capacity in response to external stimuli such as temperature, pH and salt. This finding may provide another way for improving the water absorbency. The pure chitosan film may find potential applications especially in the fields of hygienic products and biomedicine due to its super water absorbency and nontoxicity. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Relationship between diffusivity of water molecules inside hydrating tablets and their drug release behavior elucidated by magnetic resonance imaging.

    PubMed

    Kikuchi, Shingo; Onuki, Yoshinori; Kuribayashi, Hideto; Takayama, Kozo

    2012-01-01

    We reported previously that sustained release matrix tablets showed zero-order drug release without being affected by pH change. To understand drug release mechanisms more fully, we monitored the swelling and erosion of hydrating tablets using magnetic resonance imaging (MRI). Three different types of tablets comprised of polyion complex-forming materials and a hydroxypropyl methylcellulose (HPMC) were used. Proton density- and diffusion-weighted images of the hydrating tablets were acquired at intervals. Furthermore, apparent self-diffusion coefficient maps were generated from diffusion-weighted imaging to evaluate the state of hydrating tablets. Our findings indicated that water penetration into polyion complex tablets was faster than that into HPMC matrix tablets. In polyion complex tablets, water molecules were dispersed homogeneously and their diffusivity was relatively high, whereas in HPMC matrix tablets, water molecule movement was tightly restricted within the gel. An optimal tablet formulation determined in a previous study had water molecule penetration and diffusivity properties that appeared intermediate to those of polyion complex and HPMC matrix tablets; water molecules were capable of penetrating throughout the tablets and relatively high diffusivity was similar to that in the polyion complex tablet, whereas like the HPMC matrix tablet, it was well swollen. This study succeeded in characterizing the tablet hydration process. MRI provides profound insight into the state of water molecules in hydrating tablets; thus, it is a useful tool for understanding drug release mechanisms at a molecular level.

  6. Rotational spectra of tetracyclic quinolizidine alkaloids: does a water molecule flip sparteine?

    PubMed

    Lesarri, Alberto; Pinacho, Ruth; Enríquez, Lourdes; Rubio, José E; Jaraíz, Martín; Abad, José L; Gigosos, Marco A

    2017-07-21

    Sparteine is a quinolizidine alkaloid used as a chiral auxiliary in asymmetric synthesis. We examine whether hydration by a single molecule can flip sparteine from the most stable trans conformation to the bidentate cis arrangement observed in catalytic complexation to a metal center. Sparteine and the sparteine-water dimer were generated in a supersonic jet expansion with H 2 16 O and H 2 18 O, and characterized by broadband chirped-pulse microwave spectroscopy. Even though the bidentate water dimer was predicted with larger binding energy, a single isomer was observed for the monohydrated cluster, with sparteine retaining the trans conformation observed for the free molecule. The absence of the bidentate dimer is attributed to the kinetic control of cluster formation, favoring the pre-expansion most abundant monomer. The structural properties of the O-HN hydrogen bond in the dimer are compared with those of complexes of other secondary and tertiary amines.

  7. The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs)

    NASA Astrophysics Data System (ADS)

    Hogan, Greg Anthony

    The process of molecular transport and intercalation has been widely studied for many years, resulting in the discovery of molecular frameworks that are capable of hosting guest molecules or ions. Layered and porous metal-organic frameworks (MOFs) have been found to have applications in the field of catalysis, storage, separations, and ion-exchange. More recently, molecular components with peripheral hydrogen-bonding moieties have been used to affect the synthesis of hydrogen-bonded metal-organic frameworks (HMOFs) as an alternative to MOFs, which are interconnected via coordinate-covalent bonds. While MOFs are perhaps stronger materials, HMOFs have the advantage of being easily modifiable and more flexible. Because HMOFs have not been extensively studied for their ability to host molecules, and because their ability to withstand guest loss and guest exchange is essentially unknown, here we report the synthesis and molecular transport properties of both close-packed and porous HMOFs. Layered materials can mimic the behavior of naturally occurring clays, where guest molecules are absorbed and the layer will expand to accommodate the entering guest molecule. We have created a clay mimic composed of a metal pyridine-dicarboxylates and ammonium counterions (a layered HMOF), which is suitable for studying the ability of such materials to absorb guest molecules. We can control the distance of the interlayer region, as well as the chemical nature (hydrophobic or hydrophilic) by varying the organic amine. The metal complex contains axial water ligands that are replaceable, and such ligand exchange has precedence in coordination polymer (MOF) systems, and has been termed "coordinative intercalation". Using the synthesized layered material we examined the process of intercalation, having chosen a variety of guest molecules ranging from alkyl to aryl molecules, each of which have substituents varying in size, shape and electronics. The first set of guest molecules are non

  8. Energy-switching potential energy surface for the water molecule revisited: A highly accurate singled-sheeted form.

    PubMed

    Galvão, B R L; Rodrigues, S P J; Varandas, A J C

    2008-07-28

    A global ab initio potential energy surface is proposed for the water molecule by energy-switching/merging a highly accurate isotope-dependent local potential function reported by Polyansky et al. [Science 299, 539 (2003)] with a global form of the many-body expansion type suitably adapted to account explicitly for the dynamical correlation and parametrized from extensive accurate multireference configuration interaction energies extrapolated to the complete basis set limit. The new function mimics also the complicated Sigma/Pi crossing that arises at linear geometries of the water molecule.

  9. Highly Absorbent Antibacterial Hemostatic Dressing for Healing Severe Hemorrhagic Wounds

    PubMed Central

    Li, Ting-Ting; Lou, Ching-Wen; Chen, An-Pang; Lee, Mong-Chuan; Ho, Tsing-Fen; Chen, Yueh-Sheng; Lin, Jia-Horng

    2016-01-01

    To accelerate healing of severe hemorrhagic wounds, a novel highly absorbent hemostatic dressing composed of a Tencel®/absorbent-cotton/polylactic acid nonwoven base and chitosan/nanosilver antibacterial agent was fabricated by using a nonwoven processing technique and a freeze-drying technique. This study is the first to investigate the wicking and water-absorbing properties of a nonwoven base by measuring the vertical wicking height and water absorption ratio. Moreover, blood agglutination and hemostatic second tests were conducted to evaluate the hemostatic performance of the resultant wound dressing. The blending ratio of fibers, areal weight, punching density, and fiber orientation, all significantly influenced the vertical moisture wicking property. However, only the first two parameters markedly affected the water absorption ratio. After the nonwoven base absorbed blood, scanning electron microscope (SEM) observation showed that erythrocytes were trapped between the fibrin/clot network and nonwoven fibers when coagulation pathways were activated. Prothrombin time (PT) and activated partial thromboplastin time (APTT) blood agglutination of the resultant dressing decreased to 14.34 and 50.94 s, respectively. In the femoral artery of the rate bleeding model, hemostatic time was saved by 87.2% compared with that of cotton cloth. Therefore, the resultant antibacterial wound dressing demonstrated greater water and blood absorption, as well as hemostatic performance, than the commercially available cotton cloth, especially for healing severe hemorrhagic wounds. PMID:28773912

  10. Investigation of N-acyl homoserine lactone (AHL) molecule production in Gram-negative bacteria isolated from cooling tower water and biofilm samples.

    PubMed

    Haslan, Ezgi; Kimiran-Erdem, Ayten

    2013-09-01

    In this study, 99 Gram-negative rod bacteria were isolated from cooling tower water, and biofilm samples were examined for cell-to-cell signaling systems, N-acyl homoserine lactone (AHL) signal molecule types, and biofilm formation capacity. Four of 39 (10 %) strains isolated from water samples and 14 of 60 (23 %) strains isolated from biofilm samples were found to be producing a variety of AHL signal molecules. It was determined that the AHL signal molecule production ability and the biofilm formation capacity of sessile bacteria is higher than planktonic bacteria, and there was a statistically significant difference between the AHL signal molecule production of these two groups (p < 0.05). In addition, it was found that bacteria belonging to the same species isolated from cooling tower water and biofilm samples produced different types of AHL signal molecules and that there were different types of AHL signal molecules in an AHL extract of bacteria. In the present study, it was observed that different isolates of the same strains did not produce the same AHLs or did not produce AHL molecules, and bacteria known as AHL producers did not produce AHL. These findings suggest that detection of signal molecules in bacteria isolated from cooling towers may contribute to prevention of biofilm formation, elimination of communication among bacteria in water systems, and blockage of quorum-sensing controlled virulence of these bacteria.

  11. Direct numerical solution of the Ornstein-Zernike integral equation and spatial distribution of water around hydrophobic molecules

    NASA Astrophysics Data System (ADS)

    Ikeguchi, Mitsunori; Doi, Junta

    1995-09-01

    The Ornstein-Zernike integral equation (OZ equation) has been used to evaluate the distribution function of solvents around solutes, but its numerical solution is difficult for molecules with a complicated shape. This paper proposes a numerical method to directly solve the OZ equation by introducing the 3D lattice. The method employs no approximation the reference interaction site model (RISM) equation employed. The method enables one to obtain the spatial distribution of spherical solvents around solutes with an arbitrary shape. Numerical accuracy is sufficient when the grid-spacing is less than 0.5 Å for solvent water. The spatial water distribution around a propane molecule is demonstrated as an example of a nonspherical hydrophobic molecule using iso-value surfaces. The water model proposed by Pratt and Chandler is used. The distribution agrees with the molecular dynamics simulation. The distribution increases offshore molecular concavities. The spatial distribution of water around 5α-cholest-2-ene (C27H46) is visualized using computer graphics techniques and a similar trend is observed.

  12. Dynamic properties of individual water molecules in a hydrophobic pore lined with acyl chains: a molecular dynamics study.

    PubMed

    Qi, Z; Sokabe, M

    1998-03-30

    Recently, a certain class of synthetic molecules has been shown to form ion channels, the pore of which is lined with hydrophobic acyl chains [M. Sokabe, in: F. Oosawa, H. Hayashi, T. Yoshioka (Eds.), Transmembrane Signaling and Sensation, JSSP/VNU Science Press BV, Tokyo, 1984, p. 119; F. Hayashi, M. Sokabe, M. Takagi, K. Hayashi, U. Kishimoto, Biochim. Biophys. Acta, 510 (1978) 305; M.J. Pregel, L. Jullien, J. Canceill, L. Lacombe, J.M. Lehn, J. Chem. Soc. Perkin Trans., 2 (1995) 417; Y. Tanaka, Y. Kobuke, M. Sokabe, Angew. Chem. Int. Ed. Engl., 34 (1995) 693; M. Sokabe, Z. Qi, K. Donowaki, H. Ishida, K. Okubo, Biophys. J., 70 (1996) A201; H. Ishida, K. Donowaki, Y. Inoue, Z. Qi, M. Sokabe, Chem. Lett. (1997) p. 953]. As an initial step towards understanding the physical mechanisms of ion permeation across such a hydrophobic pore, systematic molecular dynamics simulations were performed to investigate dynamic and energetic properties of water molecules inside the pore using a dimer of alanine-N'-acylated cyclic peptide as a channel model. Dynamic energy profiles for water molecules indicated that the energy barrier at the middle region of the pore is approximately 2-3 kcal/mol higher than that in the cap water region which was defined as a vicinity region of the channel entrance. Energetics analyses demonstrated that the mutual interactions among intrapore water molecules are the major factor to give favorable interaction (negative energy contribution) for themselves. The pore, despite being lined with acyl chains, has a favorable van der Waals interaction with intrapore water molecules. These results may help to explain why water-filled channels can be formed by the hydrophobic helices in natural channels.

  13. Structural analysis on mutation residues and interfacial water molecules for human TIM disease understanding

    PubMed Central

    2013-01-01

    Background Human triosephosphate isomerase (HsTIM) deficiency is a genetic disease caused often by the pathogenic mutation E104D. This mutation, located at the side of an abnormally large cluster of water in the inter-subunit interface, reduces the thermostability of the enzyme. Why and how these water molecules are directly related to the excessive thermolability of the mutant have not been investigated in structural biology. Results This work compares the structure of the E104D mutant with its wild type counterparts. It is found that the water topology in the dimer interface of HsTIM is atypical, having a "wet-core-dry-rim" distribution with 16 water molecules tightly packed in a small deep region surrounded by 22 residues including GLU104. These water molecules are co-conserved with their surrounding residues in non-archaeal TIMs (dimers) but not conserved across archaeal TIMs (tetramers), indicating their importance in preserving the overall quaternary structure. As the structural permutation induced by the mutation is not significant, we hypothesize that the excessive thermolability of the E104D mutant is attributed to the easy propagation of atoms' flexibility from the surface into the core via the large cluster of water. It is indeed found that the B factor increment in the wet region is higher than other regions, and, more importantly, the B factor increment in the wet region is maintained in the deeply buried core. Molecular dynamics simulations revealed that for the mutant structure at normal temperature, a clear increase of the root-mean-square deviation is observed for the wet region contacting with the large cluster of interfacial water. Such increase is not observed for other interfacial regions or the whole protein. This clearly suggests that, in the E104D mutant, the large water cluster is responsible for the subunit interface flexibility and overall thermolability, and it ultimately leads to the deficiency of this enzyme. Conclusions Our study

  14. 3D metamaterial absorber for attomole molecular detection (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Tanaka, Takuo; Ishikawa, Atsushi

    2016-09-01

    3D Metamaterial absorber was used for a background-suppressed surface-enhanced molecular detection technique. By utilizing the resonant coupling of plasmonic modes of a metamaterial absorber and infrared (IR) vibrational modes of a self-assembled monolayer (SAM), attomole level molecular sensitivity was experimentally demonstrated. IR absorption spectroscopy of molecular vibrations is of importance in chemical, material, medical science and so on, since it provides essential information of the molecular structure, composition, and orientation. In the vibrational spectroscopic techniques, in addition to the weak signals from the molecules, strong background degrades the signal-to-noise ratio, and suppression of the background is crucial for the further improvement of the sensitivity. Here, we demonstrate low-background resonant Surface enhanced IR absorption (SEIRA) by using the metamaterial IR absorber that offers significant background suppression as well as plasmonic enhancement. The fabricated metamaterial consisted of 1D array of Au micro-ribbons on a thick Au film separated by a transparent gap layer made of MgF2. The surface structures were designed to exhibit an anomalous IR absorption at 3000 cm-1, which spectrally overlapped with C-H stretching vibrational modes. 16-Mercaptohexadecanoic acid (16-MHDA) was used as a test molecule, which formed a 2-nm thick SAM with their thiol head-group chemisorbed on the Au surface. In the FTIR measurements, the symmetric and asymmetric C-H stretching modes were clearly observed as reflection peaks within a broad plasmonic absorption of the metamaterial.

  15. Effect of ultraviolet light absorbers on photostabilization of azadirachtin-A in solution (part: II).

    PubMed

    Deota, P T; Upadhyay, P R; Valodkar, V B

    2003-01-01

    The effect of photostabilization of azadirachtin-A (Aza-A) was examined in solutions when exposed to UV radiation, in the presence of four structurally different UV absorbers namely, p-aminobenzoic acid, 2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone and phenyl salicylate. The percentages of Aza-A recovered from the solutions after 6 h exposed to UV radiation in the presence and absence of UV absorbers indicated that the order of stabilization of Aza-A by these absorbers was similar to that obtained in the solid phase experiments in accordance with our previous observations. It is observed that the addition of phenyl salicylate in Aza-A (in 1:1 mole ratio) provides the excellent photostabilization of Aza-A molecule in solid phase as well as in solution among the four absorbers studied.

  16. Structure and dynamics of water and lipid molecules in charged anionic DMPG lipid bilayer membranes

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

    Rønnest, A. K.; Peters, G. H.; Hansen, F. Y., E-mail: flemming@kemi.dtu.dk

    2016-04-14

    Molecular dynamics simulations have been used to investigate the influence of the valency of counter-ions on the structure of freestanding bilayer membranes of the anionic 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG) lipid at 310 K and 1 atm. At this temperature, the membrane is in the fluid phase with a monovalent counter-ion and in the gel phase with a divalent counter-ion. The diffusion constant of water as a function of its depth in the membrane has been determined from mean-square-displacement calculations. Also, calculated incoherent quasielastic neutron scattering functions have been compared to experimental results and used to determine an average diffusion constant for allmore » water molecules in the system. On extrapolating the diffusion constants inferred experimentally to a temperature of 310 K, reasonable agreement with the simulations is obtained. However, the experiments do not have the sensitivity to confirm the diffusion of a small component of water bound to the lipids as found in the simulations. In addition, the orientation of the dipole moment of the water molecules has been determined as a function of their depth in the membrane. Previous indirect estimates of the electrostatic potential within phospholipid membranes imply an enormous electric field of 10{sup 8}–10{sup 9} V m{sup −1}, which is likely to have great significance in controlling the conformation of translocating membrane proteins and in the transfer of ions and molecules across the membrane. We have calculated the membrane potential for DMPG bilayers and found ∼1 V (∼2 ⋅ 10{sup 8} V m{sup −1}) when in the fluid phase with a monovalent counter-ion and ∼1.4 V (∼2.8 ⋅ 10{sup 8} V m{sup −1}) when in the gel phase with a divalent counter-ion. The number of water molecules for a fully hydrated DMPG membrane has been estimated to be 9.7 molecules per lipid in the gel phase and 17.5 molecules in the fluid phase, considerably smaller than inferred

  17. Degradation of bromophenol blue molecule during argon plasma jet irradiation

    NASA Astrophysics Data System (ADS)

    Matinzadeh, Ziba; Shahgoli, Farhad; Abbasi, Hamed; Ghoranneviss, Mahmood; Salem, Mohammad Kazem

    2017-06-01

    The aim of this paper is to study degradation of a bromophenol blue molecule (C19H10Br4O5S) using direct irradiation of cold atmospheric argon plasma jet. The pH of the bromophenol blue solution has been measured as well as its absorbance spectra and conductivity before and after the irradiation of non-thermal plasma jet in various time durations. The results indicated that the lengths of conjugated systems in the molecular structure of bromophenol blue decreased, and that the bromophenol blue solution was decolorized as a result of the decomposition of bromophenol blue. This result shows that non-thermal plasma jet irradiation is capable of decomposing, and can also be used for water purification.

  18. Application of differential scanning calorimetry to measure the differential binding of ions, water and protons in the unfolding of DNA molecules.

    PubMed

    Olsen, Chris M; Shikiya, Ronald; Ganugula, Rajkumar; Reiling-Steffensmeier, Calliste; Khutsishvili, Irine; Johnson, Sarah E; Marky, Luis A

    2016-05-01

    The overall stability of DNA molecules globally depends on base-pair stacking, base-pairing, polyelectrolyte effect and hydration contributions. In order to understand how they carry out their biological roles, it is essential to have a complete physical description of how the folding of nucleic acids takes place, including their ion and water binding. To investigate the role of ions, water and protons in the stability and melting behavior of DNA structures, we report here an experimental approach i.e., mainly differential scanning calorimetry (DSC), to determine linking numbers: the differential binding of ions (Δnion), water (ΔnW) and protons (ΔnH(+)) in the helix-coil transition of DNA molecules. We use DSC and temperature-dependent UV spectroscopic techniques to measure the differential binding of ions, water, and protons for the unfolding of a variety of DNA molecules: salmon testes DNA (ST-DNA), one dodecamer, one undecamer and one decamer duplexes, nine hairpin loops, and two triplexes. These methods can be applied to any conformational transition of a biomolecule. We determined complete thermodynamic profiles, including all three linking numbers, for the unfolding of each molecule. The favorable folding of a DNA helix results from a favorable enthalpy-unfavorable entropy compensation. DSC thermograms and UV melts as a function of salt, osmolyte and proton concentrations yielded releases of ions and water. Therefore, the favorable folding of each DNA molecule results from the formation of base-pair stacks and uptake of both counterions and water molecules. In addition, the triplex with C(+)GC base triplets yielded an uptake of protons. Furthermore, the folding of a DNA duplex is accompanied by a lower uptake of ions and a similar uptake of four water molecules as the DNA helix gets shorter. In addition, the oligomer duplexes and hairpin thermodynamic data suggest ion and water binding depends on the DNA sequence rather than DNA composition. Copyright

  19. “Nanofiltration” Enabled by Super-Absorbent Polymer Beads for Concentrating Microorganisms in Water Samples

    NASA Astrophysics Data System (ADS)

    Xie, Xing; Bahnemann, Janina; Wang, Siwen; Yang, Yang; Hoffmann, Michael R.

    2016-02-01

    Detection and quantification of pathogens in water is critical for the protection of human health and for drinking water safety and security. When the pathogen concentrations are low, large sample volumes (several liters) are needed to achieve reliable quantitative results. However, most microbial identification methods utilize relatively small sample volumes. As a consequence, a concentration step is often required to detect pathogens in natural waters. Herein, we introduce a novel water sample concentration method based on superabsorbent polymer (SAP) beads. When SAP beads swell with water, small molecules can be sorbed within the beads, but larger particles are excluded and, thus, concentrated in the residual non-sorbed water. To illustrate this approach, millimeter-sized poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) beads are synthesized and successfully applied to concentrate water samples containing two model microorganisms: Escherichia coli and bacteriophage MS2. Experimental results indicate that the size of the water channel within water swollen P(AM-co-IA) hydrogel beads is on the order of several nanometers. The millimeter size coupled with a negative surface charge of the beads are shown to be critical in order to achieve high levels of concentration. This new concentration procedure is very fast, effective, scalable, and low-cost with no need for complex instrumentation.

  20. “Nanofiltration” Enabled by Super-Absorbent Polymer Beads for Concentrating Microorganisms in Water Samples

    PubMed Central

    Xie, Xing; Bahnemann, Janina; Wang, Siwen; Yang, Yang; Hoffmann, Michael R.

    2016-01-01

    Detection and quantification of pathogens in water is critical for the protection of human health and for drinking water safety and security. When the pathogen concentrations are low, large sample volumes (several liters) are needed to achieve reliable quantitative results. However, most microbial identification methods utilize relatively small sample volumes. As a consequence, a concentration step is often required to detect pathogens in natural waters. Herein, we introduce a novel water sample concentration method based on superabsorbent polymer (SAP) beads. When SAP beads swell with water, small molecules can be sorbed within the beads, but larger particles are excluded and, thus, concentrated in the residual non-sorbed water. To illustrate this approach, millimeter-sized poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) beads are synthesized and successfully applied to concentrate water samples containing two model microorganisms: Escherichia coli and bacteriophage MS2. Experimental results indicate that the size of the water channel within water swollen P(AM-co-IA) hydrogel beads is on the order of several nanometers. The millimeter size coupled with a negative surface charge of the beads are shown to be critical in order to achieve high levels of concentration. This new concentration procedure is very fast, effective, scalable, and low-cost with no need for complex instrumentation. PMID:26876979

  1. Spacesuit Evaporator-Absorber-Radiator (SEAR)

    NASA Technical Reports Server (NTRS)

    Hodgson, Ed; Izenson, Mike; Chan, Weibo; Bue, Grant C.

    2012-01-01

    For decades advanced spacesuit developers have pursued a regenerable, robust nonventing system for heat rejection. Toward this end, this paper investigates linking together two previously developed technologies, namely NASA s Spacesuit Water Membrane Evaporator (SWME), and Creare s Lithium Chloride Absorber Radiator (LCAR). Heat from a liquid cooled garment is transported to SWME that provides cooling through evaporation. This water vapor is then captured by solid LiCl in the LCAR with a high enthalpy of absorption, resulting in sufficient temperature lift to reject heat to space by radiation. After the sortie, the LCAR would be heated up and dried in a regenerator to drive off and recover the absorbed evaporant. A engineering development prototype was built and tested in vacuum conditions at a sink temperature of 250 K. The LCAR was able to stably reject 75 W over a 7-hour period. A conceptual design of a full-scale radiator is proposed. Excess heat rejection above 240 W would be accomplished through venting of the evaporant. Loop closure rates were predicted for various exploration environment scenarios.

  2. Reactions of water and C1 molecules on carbide and metal-modified carbide surfaces

    DOE PAGES

    Wan, Weiming; Tackett, Brian M.; Chen, Jingguang G.

    2017-02-23

    The formation of carbides can significantly modify the physical and chemical properties of the parent metals. In the current review, we summarize the general trends in the reactions of water and C1 molecules over transition metal carbide (TMC) and metal-modified TMC surfaces and thin films. Although the primary focus of the current review is on the theoretical and experimental studies of reactions of C1 molecules (CO, CO 2, CH 3OH, etc.), the reactions of water will also be reviewed because water plays an important role in many of the C1 transformation reactions. This review is organized by discussing separately thermalmore » reactions and electrochemical reactions, which provides insights into the application of TMCs in heterogeneous catalysis and electrocatalysis, respectively. In thermal reactions, we discuss the thermal decomposition of water and methanol, as well as the reactions of CO and CO 2 over TMC surfaces. In electrochemical reactions, we summarize recent studies in the hydrogen evolution reaction, electrooxidation of methanol and CO, and electroreduction of CO 2. Lastly, future research opportunities and challenges associated with using TMCs as catalysts and electrocatalysts are also discussed.« less

  3. Evaluation of factors to convert absorbed dose calibrations from graphite to water for the NPL high-energy photon calibration service.

    PubMed

    Nutbrown, R F; Duane, S; Shipley, D R; Thomas, R A S

    2002-02-07

    The National Physical Laboratory (NPL) provides a high-energy photon calibration service using 4-19 MV x-rays and 60Co gamma-radiation for secondary standard dosemeters in terms of absorbed dose to water. The primary standard used for this service is a graphite calorimeter and so absorbed dose calibrations must be converted from graphite to water. The conversion factors currently in use were determined prior to the launch of this service in 1988. Since then, it has been found that the differences in inherent filtration between the NPL LINAC and typical clinical machines are large enough to affect absorbed dose calibrations and, since 1992, calibrations have been performed in heavily filtered qualities. The conversion factors for heavily filtered qualities were determined by interpolation and extrapolation of lightly filtered results as a function of tissue phantom ratio 20,10 (TPR20,10). This paper aims to evaluate these factors for all mega-voltage photon energies provided by the NPL LINAC for both lightly and heavily filtered qualities and for 60Co y-radiation in two ways. The first method involves the use of the photon fluence-scaling theorem. This states that if two blocks of different material are irradiated by the same photon beam, and if all dimensions are scaled in the inverse ratio of the electron densities of the two media, then, assuming that all photon interactions occur by Compton scatter the photon attenuation and scatter factors at corresponding scaled points of measurement in the phantom will be identical. The second method involves making in-phantom measurements of chamber response at a constant target-chamber distance. Monte Carlo techniques are then used to determine the corresponding dose to the medium in order to determine the chamber calibration factor directly. Values of the ratio of absorbed dose calibration factors in water and in graphite determined in these two ways agree with each other to within 0.2% (1sigma uncertainty). The best fit

  4. Graphene oxide papers with high water adsorption capacity for air dehumidification.

    PubMed

    Liu, Renlong; Gong, Tao; Zhang, Kan; Lee, Changgu

    2017-08-29

    Graphene oxide (GO) has shown a high potential to adsorb and store water molecules due to the oxygen-containing functional groups on its hydrophilic surface. In this study, we characterized the water absorbing properties of graphene oxide in the form of papers. We fabricated three kinds of graphene oxide papers, two with rich oxygen functional groups and one with partial chemical reduction, to vary the oxygen/carbon ratio and found that the paper with high oxygen content has higher moisture adsorption capability. For the GO paper with reduction, the overall moisture absorbance was reduced. However, the absorbance at high humidity was significantly improved due to direct formation of multilayer water vapor in the system, which derived from the weak interaction between the adsorbent and the adsorbate. To demonstrate one application of GO papers as a desiccant, we tested grape fruits with and without GO paper. The fruits with a GO paper exhibited longer-term preservation with delayed mold gathering because of desiccation effect from the paper. Our results suggest that GO will find numerous practical applications as a desiccant and is a promising material for moisture desiccation and food preservation.

  5. Removal of persistent organic pollutants from micro-polluted drinking water by triolein embedded absorbent.

    PubMed

    Liu, Huijuan; Ru, Jia; Qu, Jiuhui; Dai, Ruihua; Wang, Zijian; Hu, Chun

    2009-06-01

    A new biomimetic absorbent, cellulose acetate (CA) embedded with triolein (CA-triolein), was prepared and applied for the removal of persistent organic pollutants (POPs) from micro-polluted aqueous solution. The comparison of CA-triolein, CA and granular activated carbon (GAC) for dieldrin removal was investigated. Results showed that CA-triolein absorbent gave a lowest residual concentration after 24 h although GAC had high removal rate in the first 4 h adsorption. Then the removal efficiency of mixed POPs (e.g. aldrin, dieldrin, endrin and heptachlor epoxide), absorption isotherm, absorbent regeneration and initial column experiments of CA-triolein were studied in detail. The linear absorption isotherm and the independent absorption in binary isotherm indicated that the selected POPs are mainly absorbed onto CA-triolein absorbent by a partition mechanism. The absorption constant, K, was closely related to the hydrophobic property of the compound. Thermodynamic calculations showed that the absorption was spontaneous, with a high affinity and the absorption was an endothermic reaction. Rinsing with hexane the CA-triolein absorbent can be regenerated after absorption of POPs. No significant decrease in the dieldrin removal efficiency was observed even when the absorption-regeneration process was repeated for five times. The results of initial column experiments showed that the CA-triolein absorbent did not reach the breakthrough point at a breakthrough empty-bed volume (BV) of 3200 when the influent concentration was 1-1.5 microg/L and the empty-bed contact time (EBCT) was 20 min.

  6. Optical Detection and Spectroscopy of Single Molecules in a Solid.

    DTIC Science & Technology

    1989-03-23

    the optical absorption spectrum of single dopant molecules of pentacene in a p-terphenyl host crystal at liquid-helium temperatures. To achieve this...dopant molecules of pentacene in a p-terphenyl host crystal at liquid-helium temperatures. To achieve this, frequency-modulation spectroscopy was combined...solid would provide an important new tool for the study of local absorber-host interactions that would be uncomplicated by the normal averaging over

  7. KEY COMPARISON: Comparison of the standards for absorbed dose to water of the ENEA-INMRI (Italy) and the BIPM for 60Co γ rays

    NASA Astrophysics Data System (ADS)

    Kessler, C.; Allisy-Roberts, P. J.; Burns, D. T.; Guerra, A. S.; Laitano, R. F.; Pimpinella, M.

    2010-01-01

    A comparison of the standards for absorbed dose to water of the Istituto Nazionale di Metrologia delle Radiazioni Ionizzanti of the Ente per le Nuove Tecnologie, l'Energia e l'Ambiente, Italy (ENEA-INMRI), and of the Bureau International des Poids et Mesures (BIPM) has been made in 60Co gamma radiation under the auspices of the key comparison BIPM.RI(I)-K4. The comparison result, based on the calibration coefficients for three transfer standards and expressed as a ratio of the ENEA and the BIPM standards for absorbed dose to water, is 0.9999 (0.0044). The present 2007 result replaces the earlier ENEA value in this key comparison. The degrees of equivalence between the ENEA and the other participants in this comparison have been calculated and the results are given in the form of a matrix for the ten national metrology institutes (NMIs) that have published results in this ongoing comparison for absorbed dose to water. A graphical presentation is also given. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCRI Section I, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

  8. Molecular conformation of linear alkane molecules: From gas phase to bulk water through the interface

    NASA Astrophysics Data System (ADS)

    Murina, Ezequiel L.; Fernández-Prini, Roberto; Pastorino, Claudio

    2017-08-01

    We studied the behavior of long chain alkanes (LCAs) as they were transferred from gas to bulk water, through the liquid-vapor interface. These systems were studied using umbrella sampling molecular dynamics simulation and we have calculated properties like free energy profiles, molecular orientation, and radius of gyration of the LCA molecules. The results show changes in conformation of the solutes along the path. LCAs adopt pronounced molecular orientations and the larger ones extend appreciably when partially immersed in the interface. In bulk water, their conformations up to dodecane are mainly extended. However, larger alkanes like eicosane present a more stable collapsed conformation as they approach bulk water. We have characterized the more probable configurations in all interface and bulk regions. The results obtained are of interest for the study of biomatter processes requiring the transfer of hydrophobic matter, especially chain-like molecules like LCAs, from gas to bulk aqueous systems through the interface.

  9. Adsorption Study of a Water Molecule on Vacancy-Defected Nonpolar CdS Surfaces

    PubMed Central

    2017-01-01

    A detailed understanding of the water–semiconductor interface is of major importance for elucidating the molecular interactions at the photocatalyst’s surface. Here, we studied the effect of vacancy defects on the adsorption of a water molecule on the (101̅0) and (112̅0) CdS surfaces, using spin-polarized density functional theory. We observed that the local spin polarization did not persist for most of the cationic vacancies on the surfaces, unlike in bulk, owing to surface reconstructions caused by displaced S atoms. This result suggests that cationic vacancies on these surfaces may not be the leading cause of the experimentally observed magnetism in CdS nanostructures. The surface vacancies are predominantly nonmagnetic except for one case, where a magnetic cationic vacancy is relatively stable due to constraints posed by the (101̅0) surface geometry. At this particular magnetic defect site, we found a very strong interaction with the H2O molecule leading to a case of chemisorption, where the local spin polarization vanishes concurrently. At the same defect site, adsorption of an O2 molecule was also simulated, and the results were found to be consistent with experimental electron paramagnetic resonance findings for powdered CdS. The anion vacancies on these surfaces were always found to be nonmagnetic and did not affect the water adsorption at these surfaces. PMID:28539988

  10. Validation of polyethylene glycol 3350 as a poorly absorbable marker for intestinal perfusion studies.

    PubMed

    Schiller, L R; Santa Ana, C A; Porter, J; Fordtran, J S

    1997-01-01

    Polyethylene glycol (PEG) has been used as a poorly absorbable marker in intestinal perfusion studies, but there is controversy about the absorbability of PEG, particularly when glucose-sodium cotransport is occurring. Total intestinal perfusion studies were done in five normal humans using three solutions containing 1 g/liter PEG 3350 and designed to produce low rates of water absorption, high rates of water absorption, or high rates of glucose-sodium cotransport. Water absorption rates were calculated by traditional nonabsorbable marker equations and by a novel balance technique in which absorption was taken as the difference between the volumes of solution infused and recovered during steady-state conditions. Effluent PEG recovery was 99 +/- 4%, 109 +/- 2%, and 104 +/- 6% of the amount infused with each solution. Water absorption rates measured by use of PEG concentrations were similar to those calculated by the balance technique (r = 0.99). The complete recovery of PEG confirms the poor absorbability of PEG 3350, and the excellent agreement between techniques validates PEG as a poorly absorbed marker, even when glucose-sodium cotransport is occurring.

  11. Simultaneous flame ionization and absorbance detection of volatile and nonvolatile compounds by reversed-phase liquid chromatography with a water mobile phase.

    PubMed

    Bruckner, C A; Ecker, S T; Synovec, R E

    1997-09-01

    A flame ionization detector (FID) is used to detect volatile organic compounds that have been separated by water-only reversed-phase liquid chromatography (WRP-LC). The mobile phase is 100% water at room temperature, without use of organic solvent modifiers. An interface between the LC and detector is presented, whereby a helium stream samples the vapor of volatile components from individual drops of the LC eluent, and the vapor-enriched gas stream is sent to the FID. The design of the drop headspace cell is simple because the water-only nature of the LC separation obviates the need to do any organic solvent removal prior to gas phase detection. Despite the absence of organic modifier, hydrophobic compounds can be separated in a reasonable time due to the low phase volume ratio of the WRP-LC columns. The drop headspace interface easily handles LC flows of 1 mL/min, and, in fact, compound detection limits are improved at faster liquid flow rates. The transfer efficiency of the headspace interface was estimated at 10% for toluene in water at 1 mL/min but varies depending on the volatility of each analyte. The detection system is linear over more than 5 orders of 1-butanol concentration in water and is able to detect sub-ppb amounts of o-xylene and other aromatic compounds in water. In order to analyze volatile and nonvolatile analytes simultaneously, the FID is coupled in series to a WRP-LC system with UV absorbance detection. WRP-LC improves UV absorbance detection limits because the absence of organic modifier allows the detector to be operated in the short-wavelength UV region, where analytes generally have significantly larger molar absorptivities. The selectivity the headspace interface provides for flame ionization detection of volatiles is demonstrated with a separation of 1-butanol, 1,1,2-trichloroethane (TCE), and chlorobenzene in a mixture of benzoic acid in water. Despite coelution of butanol and TCE with the benzoate anion, the nonvolatile benzoate anion

  12. Identifying the perfect absorption of metamaterial absorbers

    NASA Astrophysics Data System (ADS)

    Duan, G.; Schalch, J.; Zhao, X.; Zhang, J.; Averitt, R. D.; Zhang, X.

    2018-01-01

    We present a detailed analysis of the conditions that result in unity absorption in metamaterial absorbers to guide the design and optimization of this important class of functional electromagnetic composites. Multilayer absorbers consisting of a metamaterial layer, dielectric spacer, and ground plane are specifically considered. Using interference theory, the dielectric spacer thickness and resonant frequency for unity absorption can be numerically determined from the functional dependence of the relative phase shift of the total reflection. Further, using transmission line theory in combination with interference theory we obtain analytical expressions for the unity absorption resonance frequency and corresponding spacer layer thickness in terms of the bare resonant frequency of the metamaterial layer and metallic and dielectric losses within the absorber structure. These simple expressions reveal a redshift of the unity absorption frequency with increasing loss that, in turn, necessitates an increase in the thickness of the dielectric spacer. The results of our analysis are experimentally confirmed by performing reflection-based terahertz time-domain spectroscopy on fabricated absorber structures covering a range of dielectric spacer thicknesses with careful control of the loss accomplished through water absorption in a semiporous polyimide dielectric spacer. Our findings can be widely applied to guide the design and optimization of the metamaterial absorbers and sensors.

  13. Influence of the water molecules near surface of viral protein on virus activation process

    NASA Astrophysics Data System (ADS)

    Shepelenko, S. O.; Salnikov, A. S.; Rak, S. V.; Goncharova, E. P.; Ryzhikov, A. B.

    2009-06-01

    The infection of a cell with influenza virus comprises the stages of receptor binding to the cell membrane, endocytosis of virus particle, and fusion of the virus envelope and cell endosome membrane, which is determined by the conformational changes in hemagglutinin, a virus envelope protein, caused by pH decrease within the endosome. The pH value that induces conformation rearrangements of hemagglutinin molecule considerably varies for different influenza virus strains, first and foremost, due to the differences in amino acid structure of the corresponding proteins. The main goal of this study was to construct a model making it possible to assess the critical pH value characterizing the fusogenic activity of influenza virus hemagglutinin from the data on hemagglutinin structure and experimental verification of this model. Under this model, we assume that when the electrostatic force between interacting hemagglutinin molecules in the virus envelop exceeds a certain value, the hemagglutinin HA1 subunits are arranged so that they form a cavity sufficient for penetration of water molecules. This event leads to an irreversible hydration of the inner fragments of hemagglutinin molecule in a trimer and to the completion of conformational changes. The geometry of electrostatic field in hemagglutinin trimer was calculated taking into account the polarization effects near the interface of two dielectrics, aqueous medium and protein macromolecule. The critical pH values for the conformational changes in hemagglutinin were measured by the erythrocyte hemolysis induced by influenza virus particles when decreasing pH. The critical pH value conditionally separating the pH range into the regions with and without the conformational changes was calculated for several influenza virus H1N1 and H3N2 strains based on the data on the amino acid structure of the corresponding hemagglutinin molecules. Comparison of the theoretical and experimental values of critical pH values for

  14. Orbiting Water Molecules Dance to Tune Of Galaxy's "Central Engine," Astronomers Say

    NASA Astrophysics Data System (ADS)

    2000-01-01

    A disk of water molecules orbiting a supermassive black hole at the core of a galaxy 60 million light-years away is "reverberating" in response to variations in the energy output from the galaxy's powerful "central engine" close to the black hole, astronomers say. The team of astronomers used the National Science Foundation's (NSF) Very Large Array (VLA) radio telescope in New Mexico and the 100-meter-diameter radio telescope of the Max Planck Institute for Radio Astronomy at Effelsberg, Germany, to observe the galaxy NGC 1068 in the constellation Cetus. They announced their findings today at the American Astronomical Society's meeting in Atlanta. The water molecules, in a disk some 5 light-years in diameter, are acting as a set of giant cosmic radio-wave amplifiers, called masers. Using energy radiated by the galaxy's "central engine," the molecules strengthen, or brighten, radio emission at a particular frequency as seen from Earth. "We have seen variations in the radio 'brightness' of these cosmic amplifiers that we believe were caused by variations in the energy output of the central engine," said Jack Gallimore, an astronomer at the National Radio Astronomy Observatory (NRAO) in Charlottesville, VA. "This could provide us with a valuable new tool for learning about the central engine itself," he added. Gallimore worked with Stefi Baum of the Space Telescope Science Institute in Baltimore, MD; Christian Henkel of the Max Planck Institute for Radio Astronomy in Bonn, Germany; Ian Glass of the South African Astronomical Observatory; Mark Claussen of the NRAO in Socorro, NM; and Almudena Prieto of the European Southern Observatory in Munich, Germany. "Our observations show that NGC 1068 is the second-known case of a giant disk of water molecules orbiting a supermassive black hole at a galaxy's core," Gallimore said. The first case was the galaxy NGC 4258 (Messier 106), whose disk of radio-amplifying water molecules was measured by the NSF's Very Long Baseline

  15. 10.4% Efficient triple organic solar cells containing near infrared absorbers

    NASA Astrophysics Data System (ADS)

    Meerheim, Rico; Körner, Christian; Oesen, Benjamin; Leo, Karl

    2016-03-01

    The efficiency of organic solar cells can be increased by serially stacked subcells with spectrally different absorber materials. For the triple junction devices presented here, we use the small molecule donor materials DCV5T-Me for the green region and Tol2-benz-bodipy or Ph2-benz-bodipy as near infrared absorbers. The broader spectral response allows an efficiency increase from a pure DCV5T-Me triple cell to a triple junction containing a Ph2-benz-bodipy subcell, reaching 10.4%. As often observed for organic photovoltaics, the efficiency is further increased at low light intensities to 11%, which allows improved energy harvesting under real outdoor conditions and better performance indoor.

  16. Simulating Carbon Flux Dynamics with the Product of PAR Absorbed by Chlorophyll (fAPARchl)

    NASA Astrophysics Data System (ADS)

    Yao, T.; Zhang, Q.

    2016-12-01

    A common way to estimate the gross primary production (GPP) is to use the fraction of photosynthetically radiation (PAR) absorbed by vegetation (FPAR). However, only the PAR absorbed by chlorophyll of the canopy, not the PAR absorbed by the foliage or by the entire canopy, is used for photosynthesis. MODIS fAPARchl product, which refers to the fraction of PAR absorbed by chlorophyll of the canopy, is derived from Moderate Resolution Imaging Spectroradiometer (MODIS) surface reflectance by using an advanced leaf-canopy-soil-water-snow coupled radiative transfer model PROSAIL4. PROSAIL4 can retrieve surface water cover fraction, snow cover fraction, and physiologically active canopy chemistry components (chlorophyll concentration and water content), fraction of photosynthetically active radiation (PAR) absorbed by a canopy (fAPARcanopy), fraction of PAR absorbed by photosynthetic vegetation (PV) component (mainly chlorophyll) throughout the canopy (fAPARPV, i.e., fAPARchl) and fraction of PAR absorbed by non-photosynthetic vegetation (NPV) component of the canopy (fAPARNPV). We have successfully retrieved these vegetation parameters for selected areas with PROSAIL4 and the MODIS images, or simulated spectrally MODIS-like images. In this study, the product of PAR absorbed by chlorophyll (fAPARchl) has been used to simulate carbon flux over different kinds of vegetation types. The results show that MODIS fAPARchl product has the ability to better characterize phenology than current phenology model in the Community Land Model and it also will likely be able to increase the accuracy of carbon fluxes simulations.

  17. Role of water molecules in structure and energetics of Pseudomonas aeruginosa lectin I interacting with disaccharides.

    PubMed

    Nurisso, Alessandra; Blanchard, Bertrand; Audfray, Aymeric; Rydner, Lina; Oscarson, Stefan; Varrot, Annabelle; Imberty, Anne

    2010-06-25

    Calcium-dependent lectin I from Pseudomonas aeruginosa (PA-IL) binds specifically to oligosaccharides presenting an alpha-galactose residue at their nonreducing end, such as the disaccharides alphaGal1-2betaGalOMe, alphaGal1-3betaGalOMe, and alphaGal1-4betaGalOMe. This provides a unique model for studying the effect of the glycosidic linkage of the ligands on structure and thermodynamics of the complexes by means of experimental and theoretical tools. The structural features of PA-IL in complex with the three disaccharides were established by docking and molecular dynamics simulations and compared with those observed in available crystal structures, including PA-IL.alphaGal1-2betaGalOMe complex, which was solved at 2.4 A resolution and reported herein. The role of a structural bridge water molecule in the binding site of PA-IL was also elucidated through molecular dynamics simulations and free energy calculations. This water molecule establishes three very stable hydrogen bonds with O6 of nonreducing galactose, oxygen from Pro-51 main chain, and nitrogen from Gln-53 main chain of the lectin binding site. Binding free energies for PA-IL in complex with the three disaccharides were investigated, and the results were compared with the experimental data determined by titration microcalorimetry. When the bridge water molecule was included in the free energy calculations, the simulations predicted the correct binding affinity trends with the 1-2-linked disaccharide presenting three times stronger affinity ligand than the other two. These results highlight the role of the water molecule in the binding site of PA-IL and indicate that it should be taken into account when designing glycoderivatives active against P. aeruginosa adhesion.

  18. Origins of Protons in C-H Bond Insertion Products of Phenols: Proton-Self-Sufficient Function via Water Molecules.

    PubMed

    Luo, Zhoujie; Gao, Ya; Zhu, Tong; Zhang, John Zenghui; Xia, Fei

    2017-08-31

    Water molecules can serve as proton shuttles for proton transfer in the C-H bond insertion reactions catalyzed by transition metal complexes. Recently, the control experiments performed for C-H bond insertion of phenol and anisol by gold carbenes show that large discrepancy exists in the yields of hydrogenated and deuterated products. Thus, we conducted a detailed theoretical analysis on the function of water molecules in the C-H bond insertion reactions. The comparison of calculated results and control experiments indicates that the solution water molecules play a crucial role of proton shuttle in C-H bond insertion. In particular, it was found that the hydroxyl groups in phenols were capable of donating protons via water shuttles for the production of C-H products, which had a substantial influence on the yields of inserted products. The hydroxyl groups instead of C-H bonds in phenols function like "proton reservoirs" in the C-H bond insertion, which we call the "proton self-sufficient" (PSS) function of phenol. The PSS function of phenol indicates that the substrates with and without proton reservoirs will lead to different C-H bond insertion products.

  19. Freshwater DOM quantity and quality from a two-component model of UV absorbance

    USGS Publications Warehouse

    Carter, Heather T.; Tipping, Edward; Koprivnjak, Jean-Francois; Miller, Matthew P.; Cookson, Brenda; Hamilton-Taylor, John

    2012-01-01

    We present a model that considers UV-absorbing dissolved organic matter (DOM) to consist of two components (A and B), each with a distinct and constant spectrum. Component A absorbs UV light strongly, and is therefore presumed to possess aromatic chromophores and hydrophobic character, whereas B absorbs weakly and can be assumed hydrophilic. We parameterised the model with dissolved organic carbon concentrations [DOC] and corresponding UV spectra for c. 1700 filtered surface water samples from North America and the United Kingdom, by optimising extinction coefficients for A and B, together with a small constant concentration of non-absorbing DOM (0.80 mg DOC L-1). Good unbiased predictions of [DOC] from absorbance data at 270 and 350 nm were obtained (r2 = 0.98), the sum of squared residuals in [DOC] being reduced by 66% compared to a regression model fitted to absorbance at 270 nm alone. The parameterised model can use measured optical absorbance values at any pair of suitable wavelengths to calculate both [DOC] and the relative amounts of A and B in a water sample, i.e. measures of quantity and quality. Blind prediction of [DOC] was satisfactory for 9 of 11 independent data sets (181 of 213 individual samples).

  20. MOCCA: A 4k-Pixel Molecule Camera for the Position- and Energy-Resolving Detection of Neutral Molecule Fragments at CSR

    NASA Astrophysics Data System (ADS)

    Gamer, L.; Schulz, D.; Enss, C.; Fleischmann, A.; Gastaldo, L.; Kempf, S.; Krantz, C.; Novotný, O.; Schwalm, D.; Wolf, A.

    2016-08-01

    We present the design of MOCCA, a large-area particle detector that is developed for the position- and energy-resolving detection of neutral molecule fragments produced in electron-ion interactions at the Cryogenic Storage Ring at the Max Planck Institute for Nuclear Physics in Heidelberg. The detector is based on metallic magnetic calorimeters and consists of 4096 particle absorbers covering a total detection area of 44.8 mathrm {mm} × 44.8 mathrm {mm}. Groups of four absorbers are thermally coupled to a common paramagnetic temperature sensor where the strength of the thermal link is different for each absorber. This allows attributing a detector event within this group to the corresponding absorber by discriminating the signal rise times. A novel readout scheme further allows reading out all 1024 temperature sensors that are arranged in a 32 × 32 square array using only 16+16 current-sensing superconducting quantum interference devices. Numerical calculations taking into account a simplified detector model predict an energy resolution of Δ E_mathrm {FWHM} le 80 mathrm {eV} for all pixels of this detector.

  1. Far-infrared self-broadening in methylcyanide - Absorber-perturber resonance

    NASA Technical Reports Server (NTRS)

    Buffa, G.; Tarrini, O.; De Natale, P.; Inguscio, M.; Pavone, F. S.; Prevedelli, M.; Evenson, K. M.; Zink, L. R.; Schwaab, G. W.

    1992-01-01

    Using tunable far-infrared spectrometers with high-frequency stability and accuracy, the self-pressure broadening and shift of CH3CN are measured. Evidence of absorber-perturber resonance effects on the collisional line shape are obtained. This tests the theoretical model and its possible improvements and also allows predictions of broadening and shift for a large class of molecules. Moreover, the resonance effect produces a theoretical temperature dependence of self-broadening that is different from what is commonly assumed.

  2. Enhancing Localized Evaporation through Separated Light Absorbing Centers and Scattering Centers

    PubMed Central

    Zhao, Dengwu; Duan, Haoze; Yu, Shengtao; Zhang, Yao; He, Jiaqing; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

    2015-01-01

    This report investigates the enhancement of localized evaporation via separated light absorbing particles (plasmonic absorbers) and scattering particles (polystyrene nanoparticles). Evaporation has been considered as one of the most important phase-change processes in modern industries. To improve the efficiency of evaporation, one of the most feasible methods is to localize heat at the top water layer rather than heating the bulk water. In this work, the mixture of purely light absorptive plasmonic nanostructures such as gold nanoparticles and purely scattering particles (polystyrene nanoparticles) are employed to confine the incident light at the top of the solution and convert light to heat. Different concentrations of both the light absorbing centers and the light scattering centers were evaluated and the evaporation performance can be largely enhanced with the balance between absorbing centers and scattering centers. The findings in this study not only provide a new way to improve evaporation efficiency in plasmonic particle-based solution, but also shed lights on the design of new solar-driven localized evaporation systems. PMID:26606898

  3. Two-dimensional description of surface-bounded exospheres with application to the migration of water molecules on the Moon

    NASA Astrophysics Data System (ADS)

    Schorghofer, Norbert

    2015-05-01

    On the Moon, water molecules and other volatiles are thought to migrate along ballistic trajectories. Here, this migration process is described in terms of a two-dimensional partial differential equation for the surface concentration, based on the probability distribution of thermal ballistic hops. A random-walk model, a corresponding diffusion coefficient, and a continuum description are provided. In other words, a surface-bounded exosphere is described purely in terms of quantities on the surface, which can provide computational and conceptual advantages. The derived continuum equation can be used to calculate the steady-state distribution of the surface concentration of volatile water molecules. An analytic steady-state solution is obtained for an equatorial ring; it reveals the width and mass of the pileup of molecules at the morning terminator.

  4. Change of the isoelectric point of hemoglobin at the air/water interface probed by the orientational flip-flop of water molecules.

    PubMed

    Devineau, Stéphanie; Inoue, Ken-Ichi; Kusaka, Ryoji; Urashima, Shu-Hei; Nihonyanagi, Satoshi; Baigl, Damien; Tsuneshige, Antonio; Tahara, Tahei

    2017-04-19

    Elucidation of the molecular mechanisms of protein adsorption is of essential importance for further development of biotechnology. Here, we use interface-selective nonlinear vibrational spectroscopy to investigate protein charge at the air/water interface by probing the orientation of interfacial water molecules. We measured the Im χ (2) spectra of hemoglobin, myoglobin, serum albumin and lysozyme at the air/water interface in the CH and OH stretching regions using heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy, and we deduced the isoelectric point of the protein by monitoring the orientational flip-flop of water molecules at the interface. Strikingly, our measurements indicate that the isoelectric point of hemoglobin is significantly lowered (by about one pH unit) at the air/water interface compared to that in the bulk. This can be predominantly attributed to the modifications of the protein structure at the air/water interface. Our results also suggest that a similar mechanism accounts for the modification of myoglobin charge at the air/water interface. This effect has not been reported for other model proteins at interfaces probed by conventional VSFG techniques, and it emphasizes the importance of the structural modifications of proteins at the interface, which can drastically affect their charge profiles in a protein-specific manner. The direct experimental approach using HD-VSFG can unveil the changes of the isoelectric point of adsorbed proteins at various interfaces, which is of major relevance to many biological applications and sheds new light on the effect of interfaces on protein charge.

  5. Clay-Alcohol-Water Dispersions: Anomalous Viscosity Changes Due to Network Formation of Clay Nanosheets Induced by Alcohol Clustering.

    PubMed

    Kimura, Yuji; Haraguchi, Kazutoshi

    2017-05-16

    Clay-alcohol-water ternary dispersions were compared with alcohol-water binary mixtures in terms of viscosity and optical absorbance. Aqueous clay dispersions to which lower alcohols (ethanol, 1-propanol, 2-propanol, and tert-butanol) were added exhibited significant viscosity anomalies (maxima) when the alcohol content was 30-55 wt %, as well as optical absorbance anomalies (maxima). The maximum viscosity (η max ) depended strongly on the clay content and varied between 300 and 8000 mPa·s, making it remarkably high compared with the viscosity anomalies (2 mPa·s) observed in alcohol-water binary mixtures. The alcohol content at η max decreased as the hydrophobicity of the alcohol increased. The ternary dispersions with viscosity anomalies exhibited thixotropic behaviors. The effects of other hydrophilic solvents (glycols) and other kinds of clays were also clarified. Based on these findings and the average particle size changes, the viscosity anomalies in the ternary dispersions were explained by alcohol-clustering-induced network formation of the clay nanosheets. It was estimated that 0.9, 1.7, and 2.5 H 2 O molecules per alcohol molecule were required to stabilize the ethanol, 2-propanol, and tert-butanol, respectively, in the clay-alcohol-water dispersions.

  6. Observation of conformational changes in ethylene glycol–water complexes by FTIR–ATR spectroscopy and computational studies

    NASA Astrophysics Data System (ADS)

    Guo, Yu-Cong; Cai, Chen; Zhang, Yun-Hong

    2018-05-01

    Attenuated total reflectance - Fourier transform infrared (ATR-FTIR) spectra of ethylene glycol-water (abbreviated as EG-H2O) mixtures were measured at 298 K with the ethylene glycol molar ratio ranging from 0.01 to 1400. The two bands at 1033 and 1082 cm-1 were assigned to be the C-C stretching vibration modes related to the trans- and gauche- conformation of EG. The absorbance of the two bands was found to be sensitive to the molar ratios. We made theoretical calculation for ten conformations of the EG molecules to understand the conformational transformation of EG molecules changing with EG-H2O molar ratios. The absorbance ratio (A1033/A1082) was used to determine the trans- and gauche- conformation ratio with the calculated (AνO-C-C-O-T/AνO-C-C-O-G) as standard. When the molar ratio of water and EG (xH2O/xEG) is smaller than 0.4, strong associations formed by the intermolecular hydrogen bonds were dominant in the solutions and the proportion of gauche- conformation was about 0.5. Within the region of 0.4< xH2O/xEG < 20, the intermolecular hydrogen bonds structure between EG molecules were broken by the water molecules and the structure of most EG molecules changed from trans- to gauche- conformation. The blue shift of the peaks indicated the increasing hydrogen bonding between water and EG. When xH2O/xEG is larger than 20, the monomers of molecules started to appear in the EG-H2O solution. The gauche- conformation was the dominated conformation in the dilute EG-H2O solution with proportion of 0.87. In the CH2 rocking vibration (δC-H) region, the computational results showed that the majority bands in this region were influenced by the gauche- conformation which can be divided into group G1 or G2. The transformation between the gauche- conformations of EG molecules can be studied by combining the experimental results and the computational results, The proportion of G1 for the EG-rich solution was about 0.71 while it decreased to 0.55 for the H2O-rich solution.

  7. Influence of the target molecule on the oxygen radical absorbance capacity index: a comparison between alizarin red- and fluorescein-based methodologies.

    PubMed

    Martin, I; Aspée, A; Torres, P; Lissi, E; López-Alarcón, C

    2009-12-01

    A comparison of alizarin red (AR) and fluorescein (FL) as target molecules in oxygen radical absorbance capacity (ORAC)-like methods is reported. Galangin, apigenin, ferulic acid, and coumaric acid decreased AR initial consumption rate, whereas quercetin, kaempferol, luteolin, caffeic acid, and sinapic acid inhibited its consumption through an induction time, associated with a repair mechanism. On the other hand, all compounds protected FL with a clear induction time. AR was more selective and provides ORAC-AR values considerably smaller for compounds of low reactivity. The ORAC-AR value for luteolin was nearly 200 times that of coumaric acid. However, the ratio of ORAC-FL values for luteolin and coumaric acid was only 1.2. This different selectivity implies that AR provides ORAC values more related to reactivity than FL. ORAC-AR values of infusions were considerably smaller than the corresponding ORAC-FL values. These differences are interpreted in terms of the capacity of FL to generate induction times, irrespective of the reactivity of the additive. It is proposed that comparison of ORAC-AR and ORAC-FL values could afford a rough estimation of the average reactivity of the antioxidants titrated by the ORAC-FL methodology.

  8. An ab initio MO study on the hydrolysis of methyl chloride with explicit consideration of 13 water molecules

    NASA Astrophysics Data System (ADS)

    Yamataka, Hiroshi; Aida, Misako

    1998-06-01

    Ab initio MO calculations (HF/3-21G, HF/6-31G, HF/6-31+G* and MP2/6-31+G*) were carried out on the hydrolysis of CH 3Cl in which up to 13 water solvent molecules were explicitly considered. For n⩾3, three important stationary points ( cmp1, TS, and cmp2) were detected in the course of the reaction. The calculations for the n=13 system at the HF/6-31+G* level reproduced the experimental activation enthalpy and the secondary deuterium kinetic isotope effect. The two reacting bond lengths in the transition state are 1.975 Å (O-C) and 2.500 Å (C-Cl), and CH 3Cl is surrounded by 13 water molecules without any apparent vacant space. The proton transfer from the attacking water to the water cluster occurs after TS is reached.

  9. Colorful solar selective absorber integrated with different colored units.

    PubMed

    Chen, Feiliang; Wang, Shao-Wei; Liu, Xingxing; Ji, Ruonan; Li, Zhifeng; Chen, Xiaoshuang; Chen, Yuwei; Lu, Wei

    2016-01-25

    Solar selective absorbers are the core part for solar thermal technologies such as solar water heaters, concentrated solar power, solar thermoelectric generators and solar thermophotovoltaics. Colorful solar selective absorber can provide new freedom and flexibility beyond energy performance, which will lead to wider utilization of solar technologies. In this work, we present a monolithic integration of colored solar absorber array with different colors on a single substrate based on a multilayered structure of Cu/TiN(x)O(y)/TiO(2)/Si(3)N(4)/SiO(2). A colored solar absorber array with 16 color units is demonstrated experimentally by using combinatorial deposition technique via changing the thickness of SiO(2) layer. The solar absorptivity and thermal emissivity of all the color units is higher than 92% and lower than 5.5%, respectively. The colored solar selective absorber array can have colorful appearance and designable patterns while keeping high energy performance at the same time. It is a new candidate for a number of solar applications, especially for architecture integration and military camouflage.

  10. Large magnetoresistance in Fe3O4/molecule nanoparticles

    NASA Astrophysics Data System (ADS)

    Wang, S.; Yue, F. J.; Lin, L.; Shi, Y. J.; Wu, D.

    2010-08-01

    In this work, we successfully fabricate Fe3O4 nanoparticles self-assembled with molecules to explore a new approach of studying the molecular spintronics. Fourier transform infrared spectroscopy measurements indicate that one monolayer molecules chemically bonds to the Fe3O4 nanoparticles and the physically absorbed molecules do not exist in the samples. The magnetoresistance (MR) of molecule fully coated ~10 nm size nanoparticles is up to 7.3% at room temperature and 17.5% at 115 K under a field of 5.8 kOe. And the MR ratio is more than two times larger than that of pure Fe3O4 nanoparticles. This enhanced MR is likely arising from weak spin scattering while carriers transport through the molecules. Moreover, a very large low field magnetoresistance is also observed with ~500nm ferromagnetic Fe3O4 nanoparticles coated with acetic acid molecules. Those features open a door for the development of future spin-based molecular electronics.

  11. An aspartate and a water molecule mediate efficient acid-base catalysis in a tailored antibody pocket

    PubMed Central

    Debler, Erik W.; Müller, Roger; Hilvert, Donald; Wilson, Ian A.

    2009-01-01

    Design of catalysts featuring multiple functional groups is a desirable, yet formidable goal. Antibody 13G5, which accelerates the cleavage of unactivated benzisoxazoles, is one of few artificial enzymes that harness an acid and a base to achieve efficient proton transfer. X-ray structures of the Fab-hapten complexes of wild-type 13G5 and active-site variants now afford detailed insights into its mechanism. The parent antibody preorganizes AspH35 and GluL34 to abstract a proton from substrate and to orient a water molecule for leaving group stabilization, respectively. Remodeling the environment of the hydrogen bond donor with a compensatory network of ordered waters, as seen in the GluL34 to alanine mutant, leads to an impressive 109-fold rate acceleration over the nonenzymatic reaction with acetate, illustrating the utility of buried water molecules in bifunctional catalysis. Generalization of these design principles may aid in creation of catalysts for other important chemical transformations. PMID:19846764

  12. An aspartate and a water molecule mediate efficient acid-base catalysis in a tailored antibody pocket.

    PubMed

    Debler, Erik W; Müller, Roger; Hilvert, Donald; Wilson, Ian A

    2009-11-03

    Design of catalysts featuring multiple functional groups is a desirable, yet formidable goal. Antibody 13G5, which accelerates the cleavage of unactivated benzisoxazoles, is one of few artificial enzymes that harness an acid and a base to achieve efficient proton transfer. X-ray structures of the Fab-hapten complexes of wild-type 13G5 and active-site variants now afford detailed insights into its mechanism. The parent antibody preorganizes Asp(H35) and Glu(L34) to abstract a proton from substrate and to orient a water molecule for leaving group stabilization, respectively. Remodeling the environment of the hydrogen bond donor with a compensatory network of ordered waters, as seen in the Glu(L34) to alanine mutant, leads to an impressive 10(9)-fold rate acceleration over the nonenzymatic reaction with acetate, illustrating the utility of buried water molecules in bifunctional catalysis. Generalization of these design principles may aid in creation of catalysts for other important chemical transformations.

  13. Dynamics of water around the complex structures formed between the KH domains of far upstream element binding protein and single-stranded DNA molecules

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

    Chakraborty, Kaushik; Bandyopadhyay, Sanjoy, E-mail: sanjoy@chem.iitkgp.ernet.in

    2015-07-28

    Single-stranded DNA (ss-DNA) binding proteins specifically bind to the single-stranded regions of the DNA and protect it from premature annealing, thereby stabilizing the DNA structure. We have carried out atomistic molecular dynamics simulations of the aqueous solutions of two DNA binding K homology (KH) domains (KH3 and KH4) of the far upstream element binding protein complexed with two short ss-DNA segments. Attempts have been made to explore the influence of the formation of such complex structures on the microscopic dynamics and hydrogen bond properties of the interfacial water molecules. It is found that the water molecules involved in bridging themore » ss-DNA segments and the protein domains form a highly constrained thin layer with extremely retarded mobility. These water molecules play important roles in freezing the conformational oscillations of the ss-DNA oligomers and thereby forming rigid complex structures. Further, it is demonstrated that the effect of complexation on the slow long-time relaxations of hydrogen bonds at the interface is correlated with hindered motions of the surrounding water molecules. Importantly, it is observed that the highly restricted motions of the water molecules bridging the protein and the DNA components in the complexed forms originate from more frequent hydrogen bond reformations.« less

  14. One-step fabrication of novel superhydrophobic and superoleophilic sponge with outstanding absorbency and flame-retardancy for the selective removal of oily organic solvent from water

    NASA Astrophysics Data System (ADS)

    Xiang, Yuqian; Pang, Youyou; Jiang, Xiaomei; Huang, Jie; Xi, Fengna; Liu, Jiyang

    2018-01-01

    Absorbent materials integrated with superhydrophobicity, superoleophilicity and flame-retardancy are highly desired in the adsorption/removal of flammable oils/organic compounds as well as reducing the risk of fire and explosion. Here, one-step fabrication of novel superhydrophobic and superoleophilic sponge with outstanding absorbency and flame-retardancy was presented. Using raw melamine (ME) sponge as the supporting matrix, the formation of polydopamine (PDA) nanoaggregates via in-situ self-polymerization of high-concentrated dopamine and the covalent grafting of hydrophobic n-dodecylthiol (DT) onto PDA were combined in a feasible alkaline water/ethanol medium. As investigated by scanning electron microscopy (SEM) and X-ray energy-dispersive spectroscopy (EDS), the as-prepared ME/PDA/DT sponge possessed hierarchical structure with submicron PDA nanoaggregates containing DT motif (low surface energy) on 3D interconnected porous network. It exhibited superhydrophobic (water contact angle 157.7°) and superoleophilic (oily/organic solvent contact angle 0° properties. Owing to the highly porous structure, superhydrophobic property, chemical and mechanical stability, the ME/PDA/DT sponge exhibited outstanding absorbency properties of oily organic solvents including fast absorption kinetics, high absorption capacity, and easy reusability. Also, the ME/PDA/DT sponge could be used for one-line continuous organic solvent/water separation. More interestingly, the ME/PDA/DT sponge demonstrated improved flame-retardant property as compared to the intrinsic flame-retardant nature of the raw melamine sponge. Consequently, the risk of fire and explosion was expected to reduce when the fabricated sponge was used as an absorbent for flammable oils and organic compounds. The ease of the one-step superhydrophobic/superoleophilic modification and the promising feature of the obtained materials exhibit great potential for application in oils/organic solvents clean-up.

  15. A far wing line shape theory and its application to the water continuum absorption in the infrared region. I

    NASA Technical Reports Server (NTRS)

    Ma, Q.; Tipping, R. H.

    1991-01-01

    The present theory for the continuous absorption that is due to the far-wing contribution of allowed lines is based on the quasistatic approximation for the far wing limit and the binary collision approximation of one absorber molecule and one bath molecule. The validity of the theory is discussed, and numerical results of the water-continuum absorption in the IR region are presented for comparison with experimental data. Good agreement is obtained for both the magnitude and temperature dependence of the absorption coefficients.

  16. Absorbed dose to water based dosimetry versus air kerma based dosimetry for high-energy photon beams: an experimental study.

    PubMed

    Palmans, Hugo; Nafaa, Laila; De, Jans Jo; Gillis, Sofie; Hoornaert, Marie-Thérèse; Martens, Chantal; Piessens, Marleen; Thierens, Hubert; Van der Plaetsen, Ann; Vynckier, Stefaan

    2002-02-07

    In recent years, a change has been proposed from air kerma based reference dosimetry to absorbed dose based reference dosimetry for all radiotherapy beams of ionizing radiation. In this paper, a dosimetry study is presented in which absorbed dose based dosimetry using recently developed formalisms was compared with air kerma based dosimetry using older formalisms. Three ionization chambers of each of three different types were calibrated in terms of absorbed dose to water and air kerma and sent to five hospitals. There, reference dosimetry with all the chambers was performed in a total of eight high-energy clinical photon beams. The selected chamber types were the NE2571, the PTW-30004 and the Wellhöfer-FC65G (previously Wellhöfer-IC70). Having a graphite wall, they exhibit a stable volume and the presence of an aluminium electrode ensures the robustness of these chambers. The data were analysed with the most important recommendations for clinical dosimetry: IAEA TRS-398, AAPM TG-51, IAEA TRS-277, NCS report-2 (presently recommended in Belgium) and AAPM TG-21. The necessary conversion factors were taken from those protocols, or calculated using the data in the different protocols if data for a chamber type are lacking. Polarity corrections were within 0.1% for all chambers in all beams. Recombination corrections were consistent with theoretical predictions, did not vary within a chamber type and only slightly between different chamber types. The maximum chamber-to-chamber variations of the dose obtained with the different formalisms within the same chamber type were between 0.2% and 0.6% for the NE2571, between 0.2% and 0.6% for the PTW-30004 and 0.1% and 0.3% for the Wellhöfer-FC65G for the different beams. The absorbed dose results for the NE2571 and Wellhöfer-FC65G chambers were in good agreement for all beams and all formalisms. The PTW-30004 chambers gave a small but systematically higher result compared to the result for the NE2571 chambers (on the

  17. Syntheses, structures and photoelectrochemical properties of three water-stable, visible light absorbing mental-organic frameworks based on tetrakis(4-carboxyphenyl)silane and 1,4-bis(pyridyl)benzene mixed ligands

    NASA Astrophysics Data System (ADS)

    Guo, Tiantian; Yang, Xiaowei; Li, Ruyan; Liu, Xiaoyu; Gao, Yanling; Dai, Zhihui; Fang, Min; Liu, Hong-Ke; Wu, Yong

    2017-09-01

    Photovoltaics (PV), which directly convert solar energy into electricity generally using semiconductors, offer a practical and sustainable solution to the current energy shortage and environmental pollution crisis. Photovoltaic applications of metal-organic frameworks (MOFs) belong to a relatively new area of research. Given that UV light accounts for only 4% while visible light contributes 43% of solar energy, it is rather imperative to develop semiconductors with narrow band gaps so that they could absorb visible light. In this work, three water-stable, narrow band semiconducting MOFs of [Cu(H2TCS)(H2O)] (1), [Co(H2TCS)(BPB)] (2) and [Ni(H2TCS)(BPB)] (3) were synthesized using tetrakis(4-carboxyphenyl)silane (H4TCS) and 1,4-bis (pyridyl)benzene (BPB) in water, and structurally characterized by single-crystal X-ray diffractions. MOF 1 has a 2D structure. MOF 2 and 3 are isostructrual and have 3D frameworks formed by interwoven 2D layers. All three MOFs are stable in acidic water solutions and can be stable in water for 7 days. MOFs 1-3 absorb UV and visible light and have band gaps of 0.50, 1.77 and 1.49 eV, respectively. Rapid and stable photocurrent responses of MOFs 1-3 under UV and visible light illuminations are observed. This work demonstrates that using electron rich Cu2+, Co2+, or Ni2+ as metal nodes can effectively decrease the band gaps of MOFs to make them absorbing visible light. To increase the conjugation in the linker is generally considered to be the method to decrease the band gap of MOFs. The conjugation in H4TCS is not significant and this ligand basically only absorbs UV light. However, by using electron rich Cu2+ ions as metal nodes, the prepared [Cu(H2TCS)(H2O)]·H2O (1) absorbs broadly in the visible light region. Thus, this work suggests that by using electron rich Cu2+, many narrow-band semiconductor MOFs can be prepared even by using ligands which only absorbs UV light.

  18. Space Evaporator Absorber Radiator (SEAR) for Thermal Storage on Manned Spacecraft

    NASA Technical Reports Server (NTRS)

    Izenson, Michael G.; Chen, Weibo; Chepko, Ariane; Bue, Grant; Quinn, Gregory

    2015-01-01

    Future manned exploration spacecraft will need to operate in challenging thermal environments. State-of-the-art technology for active thermal control relies on sublimating water ice and venting the vapor overboard in very hot environments, and or heavy phase change material heat exchangers for thermal storage. These approaches can lead to large loss of water and a significant mass penalties for the spacecraft. This paper describes an innovative thermal control system that uses a Space Evaporator Absorber Radiator (SEAR) to control spacecraft temperatures in highly variable environments without venting water. SEAR uses heat pumping and energy storage by LiCl/water absorption to enable effective cooling during hot periods and regeneration during cool periods. The LiCl absorber technology has the potential to absorb over 800 kJ per kg of system mass, compared to phase change heat sink systems that typically achieve approx. 50 kJ/kg. This paper describes analysis models to predict performance and optimize the size of the SEAR system, estimated size and mass of key components, and an assessment of potential mass savings compared with alternative thermal management approaches. We also describe a concept design for an ISS test package to demonstrate operation of a subscale system in zero gravity.

  19. Sampling and Analysis of Organic Molecules in the Plumes of Enceladus

    NASA Astrophysics Data System (ADS)

    Monroe, A. A.; Williams, P.; Anbar, A. D.; Tsou, P.

    2012-12-01

    The recent detection of organic molecules in the plumes of Enceladus, which also contain water and nitrogen (Waite et al., 2006; Matson et al., 2007), suggests that the geologically active South polar region contains habitable, subsurface water (McKay et al., 2008). Characterizing these molecules will be a high priority for any future mission to Enceladus. Sample return is highly desirable, but can it capture useful samples at Enceladus? Using Stardust mission parameters for comparison, we consider the survival of complex organic molecules during collection to assess the feasibility of one aspect of a sample return mission. A successful sample return mission must include the capability to capture and recover intact or partly intact molecules of particular astrobiological interest: lipids, amino and nucleic acids, polypeptides, and polynucleotides. The Stardust mission to comet Wild 2 successfully captured amino acids, amines, and PAHs using a combination of aerogel and Al foil (Sandford et al., 2006, 2010). For larger and more fragile molecules, particularly polypeptides and polynucleotides, low collisional damage is achieved by impact on low molecular weight surfaces. A particularly intriguing possibility is a capture surface pre-coated with organic matrices identified as ideal for analysis of various biomolecules using MALDI-MS (matrix-assisted laser desorption/ionization mass spectrometry) (Hillenkamp and Karas, 2007). MALDI is a standard technique with attomole sensitivity, exceptional mass resolution, and (bio)molecular specificity (Vestal, 2011). Capture surfaces appropriate for MALDI-MS analysis could be analyzed directly without post-return manipulation, minimizing post-capture damage to these molecules and the risk of contamination during handling. A hypothetical sample collection encounter speed of ~ 5 km/s corresponds to ~0.13 eV kinetic energy per amu. Studies of molecule survival and fragmentation exist for free hexapeptides impacting hydrocarbon

  20. Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules.

    PubMed

    Lee, Yong-Min; Bang, Suhee; Yoon, Heejung; Bae, Seong Hee; Hong, Seungwoo; Cho, Kyung-Bin; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2015-07-20

    Redox-inactive metal ions play important roles in tuning chemical properties of metal-oxygen intermediates. Herein we report the effect of water molecules on the redox properties of a nonheme iron(III)-peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn(2+) ion in (TMC)Fe(III) -(O2 )-Zn(CF3 SO3 )2 (1-Zn(2+) ) decreases the Lewis acidity of the Zn(2+) ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn(2+) . This further changes the reactivities of 1-Zn(2+) in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn(2+) , whereas 1-Zn(2+) coordinating two water molecules, (TMC)Fe(III) -(O2 )-Zn(CF3 SO3 )2 -(OH2 )2 [1-Zn(2+) -(OH2 )2 ], releases the O2 unit in the oxidation reaction. In the reduction reactions, 1-Zn(2+) was converted to its corresponding iron(IV)-oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn(2+) -(OH2 )2 . The present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal-oxygen intermediates. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules

    DOE PAGES

    Lee, Yong-Min; Bang, Suhee; Yoon, Heejung; ...

    2015-06-19

    Here we report redox-inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. We describe the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn 2+ ion in (TMC)Fe III-(O 2)-Zn(CF 3SO 3) 2 (1-Zn 2+) decreases the Lewis acidity of the Zn 2+ ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn 2+. This further changes the reactivities of 1-Zn 2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidantmore » (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn 2+, whereas 1-Zn 2+ coordinating two water molecules, (TMC)Fe III-(O 2)-Zn(CF 3SO 3) 2-(OH 2) 2 [1-Zn 2+-(OH 2) 2], releases the O 2 unit in the oxidation reaction. In the reduction reactions, 1-Zn 2+ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn 2+-(OH 2) 2. Finally, the present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates.« less

  2. Peptide-based ambidextrous bifunctional gelator: applications in oil spill recovery and removal of toxic organic dyes for waste water management.

    PubMed

    Basu, Kingshuk; Nandi, Nibedita; Mondal, Biplab; Dehsorkhi, Ashkan; Hamley, Ian W; Banerjee, Arindam

    2017-12-06

    A low molecular weight peptide-based ambidextrous gelator molecule has been discovered for efficient control of water pollution. The gelator molecules can gel various organic solvents with diverse polarity, e.g. n -hexane, n -octane, petroleum ether, petrol, diesel, aromatic solvents like chlorobenzene, toluene, benzene, o -xylene and even aqueous phosphate buffer of pH 7.5. These gels have been thoroughly characterized using various techniques including field emission scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray powder diffraction analysis, small angle X-ray scattering and rheological experiments. Interestingly, hydrogel obtained from the gelator molecule has been found to absorb toxic organic dyes (both cationic and anionic dyes) from dye-contaminated water. The gelator molecule can be reused for several cycles, indicating its possible future use in waste water management. Moreover, this gelator can selectively gel petrol, diesel, pump oil from an oil-water mixture in the presence of a carrier solvent, ethyl acetate, suggesting its efficient application for oil spill recovery. These results indicate that the peptide-based ambidextrous gelator produces soft materials (gels) with dual function: (i) removal of toxic organic dyes in waste water treatment and (ii) oil spill recovery.

  3. Effects of enhanced ultraviolet-B radiation, water deficit, and their combination on UV-absorbing compounds and osmotic adjustment substances in two different moss species.

    PubMed

    Hui, Rong; Zhao, Ruiming; Song, Guang; Li, Yixuan; Zhao, Yang; Wang, Yanli

    2018-05-01

    A simulation experiment was conducted to explore the influence of enhanced ultraviolet-B (UV-B) radiation, water deficit, and their combination on UV-absorbing compounds and osmotic adjustment substances of mosses Bryum argenteum and Didymodon vinealis isolated from biological soil crusts (BSCs) growing in a revegetated area of the Tengger Desert, China. Four levels of UV-B radiation and two gradients of water regime were employed. Compared with their controls, amounts of total flavonoids, chlorophyll, carotenoids, soluble sugars, and soluble proteins significantly decreased (p < 0.05), but proline content significantly increased (p < 0.05), when exposed to either enhanced UV-B or water deficit. The negative effects of enhanced UV-B were alleviated when water deficit was applied. There were increases in UV-absorbing compounds and osmotic adjustment substances when exposed to a combination of enhanced UV-B and water deficit compared with single stresses, except for the proline content in D. vinealis. In addition, our results also indicated interspecific differences in response to enhanced UV-B, water deficit, and their combination. Compared with B. argenteum, D. vinealis was more resistant to enhanced UV-B and water deficit singly and in combination. These results suggest that the damage of enhanced UV-B on both species might be alleviated by water deficit. This alleviation is important for understanding the response of BSCs to UV-B radiation in future global climate change. This also provides novel insights into assessment damages of UV-B to BSC stability in arid and semiarid regions.

  4. Hydrogen bonding directed self-assembly of small-molecule amphiphiles in water.

    PubMed

    Xu, Jiang-Fei; Niu, Li-Ya; Chen, Yu-Zhe; Wu, Li-Zhu; Tung, Chen-Ho; Yang, Qing-Zheng

    2014-08-01

    Compounds comprising one or two quadruply hydrogen bonding units, 2-ureido-4[1H]-pyrimidinone (UPy) and tris(tetraethylene glycol monomethyl ether) moieties, were reported to form highly stable hydrogen-bonded assemblies in water. Compound 1, containing one UPy, assembles into vesicles, and compound 2, containing two UPy units, forms micelles. The aggregates disassemble reversibly when the solution pH is raised to 9.0 or above. The results demonstrate the utility of hydrogen bonding to direct the self-assembly of small-molecule building blocks in aqueous media.

  5. Finding a Single Molecule in a Haystack: Laser Spectroscopy of Solids from Sqrt. N to N = 1

    DTIC Science & Technology

    1991-01-02

    low-temperature inhomogeneously broadened 0-0 S, +- S electronic transition of pentacene dopant molecules in p-terphenyl crystals have yielded both (1...absorber, single-miolecule detection, or SMDI) wvould provide a-- useful tool for the study of local host-absorber interactions wiherte the absorbing...molecular impurity is-a truly local probe of the minute details of a single local environment in a solid. l’he use of powerful spectroscopic methods as

  6. Crospovidone interactions with water. II. Dynamic vapor sorption analysis of the effect of Polyplasdone particle size on its uptake and distribution of water.

    PubMed

    Saripella, Kalyan K; Mallipeddi, Rama; Neau, Steven H

    2014-11-20

    Polyplasdone of different particle size was used to study the sorption, desorption, and distribution of water, and to seek evidence that larger particles can internalize water. The three samples were Polyplasdone® XL, XL-10, and INF-10. Moisture sorption and desorption isotherms at 25 °C at 5% intervals from 0 to 95% relative humidity (RH) were generated by dynamic vapor sorption analysis. The three products provided similar data, judged to be Type III with a small hysteresis that appears when RH is below 65%. An absent rounded knee in the sorption curve suggests that multilayers form before the monolayer is completed. The hysteresis indicates that internally absorbed moisture is trapped as the water is desorbed and the polymer sample shrinks, thus requiring a lower level of RH to continue desorption. The fit of the Guggenheim-Anderson-de Boer (GAB) and the Young and Nelson equations was accomplished in the data analysis. The W(m), C(G), and K values from GAB analysis are similar across the three samples, revealing 0.962 water molecules per repeating unit in the monolayer. A small amount of absorbed water is identified, but this is consistent across the three particle sizes. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. SU-F-19A-02: Comparison of Absorbed Dose to Water Standards for HDR Ir-192 Brachytherapy Between the LCR, Brazil and NRC, Canada

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

    Salata, C; David, M; Almeida, C de

    2014-06-15

    Purpose: To compare absorbed dose to water standards for HDR brachytherapy dosimetry developed by the Radiological Science Laboratory of Rio de Janeiro State University (LCR) and the National Research Council, Canada (NRC). Methods: The two institutions have separately developed absorbed dose standards based on the Fricke dosimetry system. There are important differences between the two standards, including: preparation and read-out of the Fricke solution, irradiation geometry of the Fricke holder in relation to the Ir-192 source, and determination of the G-value to be used at Ir-192 energies. All measurements for both standards were made directly at the NRC laboratory (i.e.,more » no transfer instrument was used) using a single Ir-192 source (microSelectron v2). In addition, the NRC group has established a self-consistent method to determine the G-value for Ir-192, based on an interpolation between G-values obtained at Co-60 and 250kVp X-rays, and this measurement was repeated using the LCR Fricke solution to investigate possible systematic uncertainties. Results: G-values for Co-60 and 250 kVp x-rays, obtained using the LCR Fricke system, agreed with the NRC values within 0.5 % and 1 % respectively, indicating that the general assumption of universal G-values is appropriate in this case. The standard uncertainty in the determination of G for Ir-192 is estimated to be 0.6 %. For the comparison of absorbed dose measurements at the reference point for Ir-192 (1 cm depth in water, perpendicular to the seed long-axis), the ratio Dw(NRC)/Dw(LCR) was found to be 1.011 with a combined standard uncertainty of 1.7 %, k=1. Conclusion: The agreement in the absorbed dose to water values for the LCR and NRC systems is very encouraging. Combined with the lower uncertainty in this approach compared to the present air-kerma approach, these results reaffirm the use of Fricke solution as a potential primary standard for HDR Ir-192 brachytherapy.« less

  8. Hexavalent Chromium Removal from Model Water and Car Shock Absorber Factory Effluent by Nanofiltration and Reverse Osmosis Membrane

    PubMed Central

    Bejaoui, Imen; Mouelhi, Meral; Hamrouni, Béchir

    2017-01-01

    Nanofiltration and reverse osmosis are investigated as a possible alternative to the conventional methods of Cr(VI) removal from model water and industrial effluent. The influences of feed concentration, water recovery, pH, and the coexisting anions were studied. The results have shown that retention rates of hexavalent chromium can reach 99.7% using nanofiltration membrane (NF-HL) and vary from 85 to 99.9% using reverse osmosis membrane (RO-SG) depending upon the composition of the solution and operating conditions. This work was also extended to investigate the separation of Cr(VI) from car shock absorber factory effluent. The use of these membranes is very promising for Cr(VI) water treatment and desalting industry effluent. Spiegler-Kedem model was applied to experimental results in the aim to determine phenomenological parameters, the reflection coefficient of the membrane (σ), and the solute permeability coefficient (Ps). The convective and diffusive parts of the mass transfer were quantified with predominance of the diffusive contribution. PMID:28819360

  9. Combined quantum mechanics/molecular mechanics (QM/MM) simulations for protein-ligand complexes: free energies of binding of water molecules in influenza neuraminidase.

    PubMed

    Woods, Christopher J; Shaw, Katherine E; Mulholland, Adrian J

    2015-01-22

    The applicability of combined quantum mechanics/molecular mechanics (QM/MM) methods for the calculation of absolute binding free energies of conserved water molecules in protein/ligand complexes is demonstrated. Here, we apply QM/MM Monte Carlo simulations to investigate binding of water molecules to influenza neuraminidase. We investigate five different complexes, including those with the drugs oseltamivir and peramivir. We investigate water molecules in two different environments, one more hydrophobic and one hydrophilic. We calculate the free-energy change for perturbation of a QM to MM representation of the bound water molecule. The calculations are performed at the BLYP/aVDZ (QM) and TIP4P (MM) levels of theory, which we have previously demonstrated to be consistent with one another for QM/MM modeling. The results show that the QM to MM perturbation is significant in both environments (greater than 1 kcal mol(-1)) and larger in the more hydrophilic site. Comparison with the same perturbation in bulk water shows that this makes a contribution to binding. The results quantify how electronic polarization differences in different environments affect binding affinity and also demonstrate that extensive, converged QM/MM free-energy simulations, with good levels of QM theory, are now practical for protein/ligand complexes.

  10. Thermodynamic properties of water molecules in the presence of cosolute depend on DNA structure: a study using grid inhomogeneous solvation theory.

    PubMed

    Nakano, Miki; Tateishi-Karimata, Hisae; Tanaka, Shigenori; Tama, Florence; Miyashita, Osamu; Nakano, Shu-Ichi; Sugimoto, Naoki

    2015-12-02

    In conditions that mimic those of the living cell, where various biomolecules and other components are present, DNA strands can adopt many structures in addition to the canonical B-form duplex. Previous studies in the presence of cosolutes that induce molecular crowding showed that thermal stabilities of DNA structures are associated with the properties of the water molecules around the DNAs. To understand how cosolutes, such as ethylene glycol, affect the thermal stability of DNA structures, we investigated the thermodynamic properties of water molecules around a hairpin duplex and a G-quadruplex using grid inhomogeneous solvation theory (GIST) with or without cosolutes. Our analysis indicated that (i) cosolutes increased the free energy of water molecules around DNA by disrupting water-water interactions, (ii) ethylene glycol more effectively disrupted water-water interactions around Watson-Crick base pairs than those around G-quartets or non-paired bases, (iii) due to the negative electrostatic potential there was a thicker hydration shell around G-quartets than around Watson-Crick-paired bases. Our findings suggest that the thermal stability of the hydration shell around DNAs is one factor that affects the thermal stabilities of DNA structures under the crowding conditions. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

  11. Parasitic oscillation suppression in solid state lasers using absorbing thin films

    DOEpatents

    Zapata, Luis E.

    1994-01-01

    A thin absorbing film is bonded onto at least certain surfaces of a solid state laser gain medium. An absorbing metal-dielectric multilayer film is optimized for a broad range of incidence angles, and is resistant to the corrosive/erosive effects of a coolant such as water, used in the forced convection cooling of the film. Parasitic oscillations hamper the operation of solid state lasers by causing the decay of stored energy to amplified rays trapped within the gain medium by total and partial internal reflections off the gain medium facets. Zigzag lasers intended for high average power operation require the ASE absorber.

  12. Effects of protonation state of Asp181 and position of active site water molecules on the conformation of PTP1B.

    PubMed

    Ozcan, Ahmet; Olmez, Elif Ozkirimli; Alakent, Burak

    2013-05-01

    In protein tyrosine phosphatase 1B (PTP1B), the flexible WPD loop adopts a closed conformation (WPDclosed ) in the active state of PTP1B, bringing the catalytic Asp181 close to the active site pocket, while WPD loop is in an open conformation (WPDopen ) in the inactive state. Previous studies showed that Asp181 may be protonated at physiological pH, and ordered water molecules exist in the active site. In the current study, molecular dynamics simulations are employed at different Asp181 protonation states and initial positions of active site water molecules, and compared with the existing crystallographic data of PTP1B. In WPDclosed conformation, the active site is found to maintain its conformation only in the protonated state of Asp181 in both free and liganded states, while Asp181 is likely to be deprotonated in WPDopen conformation. When the active site water molecule network that is a part of the free WPDclosed crystal structure is disrupted, intermediate WPD loop conformations, similar to that in the PTPRR crystal structure, are sampled in the MD simulations. In liganded PTP1B, one active site water molecule is found to be important for facilitating the orientation of Cys215 and the phosphate ion, thus may play a role in the reaction. In conclusion, conformational stability of WPD loop, and possibly catalytic activity of PTP1B, is significantly affected by the protonation state of Asp181 and position of active site water molecules, showing that these aspects should be taken into consideration both in MD simulations and inhibitor design. Copyright © 2013 Wiley Periodicals, Inc.

  13. Docking ligands into flexible and solvated macromolecules. 7. Impact of protein flexibility and water molecules on docking-based virtual screening accuracy.

    PubMed

    Therrien, Eric; Weill, Nathanael; Tomberg, Anna; Corbeil, Christopher R; Lee, Devin; Moitessier, Nicolas

    2014-11-24

    The use of predictive computational methods in the drug discovery process is in a state of continual growth. Over the last two decades, an increasingly large number of docking tools have been developed to identify hits or optimize lead molecules through in-silico screening of chemical libraries to proteins. In recent years, the focus has been on implementing protein flexibility and water molecules. Our efforts led to the development of Fitted first reported in 2007 and further developed since then. In this study, we wished to evaluate the impact of protein flexibility and occurrence of water molecules on the accuracy of the Fitted docking program to discriminate active compounds from inactive compounds in virtual screening (VS) campaigns. For this purpose, a total of 171 proteins cocrystallized with small molecules representing 40 unique enzymes and receptors as well as sets of known ligands and decoys were selected from the Protein Data Bank (PDB) and the Directory of Useful Decoys (DUD), respectively. This study revealed that implementing displaceable crystallographic or computationally placed particle water molecules and protein flexibility can improve the enrichment in active compounds. In addition, an informed decision based on library diversity or research objectives (hit discovery vs lead optimization) on which implementation to use may lead to significant improvements.

  14. Ultrahigh-throughput–directed enzyme evolution by absorbance-activated droplet sorting (AADS)

    PubMed Central

    Gielen, Fabrice; Hours, Raphaelle; Emond, Stephane; Fischlechner, Martin; Schell, Ursula

    2016-01-01

    Ultrahigh-throughput screening, in which members of enzyme libraries compartmentalized in water-in-oil emulsion droplets are assayed, has emerged as a powerful format for directed evolution and functional metagenomics but is currently limited to fluorescence readouts. Here we describe a highly efficient microfluidic absorbance-activated droplet sorter (AADS) that extends the range of assays amenable to this approach. Using this module, microdroplets can be sorted based on absorbance readout at rates of up to 300 droplets per second (i.e., >1 million droplets per hour). To validate this device, we implemented a miniaturized coupled assay for NAD+-dependent amino acid dehydrogenases. The detection limit (10 μM in a coupled assay producing a formazan dye) enables accurate kinetic readouts sensitive enough to detect a minimum of 1,300 turnovers per enzyme molecule, expressed in a single cell, and released by lysis within a droplet. Sorting experiments showed that the AADS successfully enriched active variants up to 2,800-fold from an overwhelming majority of inactive ones at ∼100 Hz. To demonstrate the utility of this module for protein engineering, two rounds of directed evolution were performed to improve the activity of phenylalanine dehydrogenase toward its native substrate. Fourteen hits showed increased activity (improved >4.5-fold in lysate; kcat increased >2.7-fold), soluble protein expression levels (up 60%), and thermostability (Tm, 12 °C higher). The AADS module makes the most widely used optical detection format amenable to screens of unprecedented size, paving the way for the implementation of chromogenic assays in droplet microfluidics workflows. PMID:27821774

  15. Role of interfacial water molecules in proline-rich ligand recognition by the Src homology 3 domain of Abl.

    PubMed

    Palencia, Andres; Camara-Artigas, Ana; Pisabarro, M Teresa; Martinez, Jose C; Luque, Irene

    2010-01-22

    The interaction of Abl-Src homology 3 domain (SH3) with the high affinity peptide p41 is the most notable example of the inconsistency existing between the currently accepted description of SH3 complexes and their binding thermodynamic signature. We had previously hypothesized that the presence of interfacial water molecules is partially responsible for this thermodynamic behavior. We present here a thermodynamic, structural, and molecular dynamics simulation study of the interaction of p41 with Abl-SH3 and a set of mutants designed to alter the water-mediated interaction network. Our results provide a detailed description of the dynamic properties of the interfacial water molecules and a molecular interpretation of the thermodynamic effects elicited by the mutations in terms of the modulation of the water-mediated hydrogen bond network. In the light of these results, a new dual binding mechanism is proposed that provides a better description of proline-rich ligand recognition by Abl-SH3 and that has important implications for rational design.

  16. Ultraviolet absorbance as a proxy for total dissolved mercury in streams

    USGS Publications Warehouse

    Dittman, J.A.; Shanley, J.B.; Driscoll, C.T.; Aiken, G.R.; Chalmers, A.T.; Towse, J.E.

    2009-01-01

    Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THgd), DOC concentration and DOC composition, and UV254 absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THgd to DOC (r2 = 0.87), but progressively stronger correlations of THgd with the hydrophobic acid fraction (HPOA) of DOC (r2 = 0.91) and with UV254 absorbance (r2 = 0.92). The strength of the UV254 absorbance-THgd relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THgd concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THgd flux in drainage waters. ?? 2009 Elsevier Ltd.

  17. Air kerma and absorbed dose standards for reference dosimetry in brachytherapy

    PubMed Central

    2014-01-01

    This article reviews recent developments in primary standards for the calibration of brachytherapy sources, with an emphasis on the currently most common photon-emitting radionuclides. The introduction discusses the need for reference dosimetry in brachytherapy in general. The following section focuses on the three main quantities, i.e. reference air kerma rate, air kerma strength and absorbed dose rate to water, which are currently used for the specification of brachytherapy photon sources and which can be realized with primary standards from first principles. An overview of different air kerma and absorbed dose standards, which have been independently developed by various national metrology institutes over the past two decades, is given in the next two sections. Other dosimetry techniques for brachytherapy will also be discussed. The review closes with an outlook on a possible transition from air kerma to absorbed dose to water-based calibrations for brachytherapy sources in the future. PMID:24814696

  18. Analytical and numerical solution for wave reflection from a porous wave absorber

    NASA Astrophysics Data System (ADS)

    Magdalena, Ikha; Roque, Marian P.

    2018-03-01

    In this paper, wave reflection from a porous wave absorber is investigated theoretically and numerically. The equations that we used are based on shallow water type model. Modification of motion inside the absorber is by including linearized friction term in momentum equation and introducing a filtered velocity. Here, an analytical solution for wave reflection coefficient from a porous wave absorber over a flat bottom is derived. Numerically, we solve the equations using the finite volume method on a staggered grid. To validate our numerical model, comparison of the numerical reflection coefficient is made against the analytical solution. Further, we implement our numerical scheme to study the evolution of surface waves pass through a porous absorber over varied bottom topography.

  19. Experimental investigation and model verification for a GAX absorber

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

    Palmer, S.C.; Christensen, R.N.

    1996-12-31

    In the ammonia-water generator-absorber heat exchange (GAX) absorption heat pump, the heat and mass transfer processes which occur between the generator and absorber are the most crucial in assuring that the heat pump will achieve COPs competitive with those of current technologies. In this study, a model is developed for the heat and mass transfer processes that occur in a counter-current vertical fluted tube absorber (VFTA) with inserts. Correlations for heat and mass transfer in annuli are used to model the processes in the VTA. Experimental data is used to validate the model for three different insert geometries. Comparison ofmore » model results with experimental data provides insight into model corrections necessary to bring the model into agreement with the physical phenomena observed in the laboratory.« less

  20. Interacting dark resonances with plasmonic meta-molecules

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

    Jha, Pankaj K.; Mrejen, Michael; Kim, Jeongmin

    2014-09-15

    Dark state physics has led to a variety of remarkable phenomena in atomic physics, quantum optics, and information theory. Here, we investigate interacting dark resonance type physics in multi-layered plasmonic meta-molecules. We theoretically demonstrate that these plasmonic meta-molecules exhibit sub-natural spectral response, analogous to conventional atomic four-level configuration, by manipulating the evanescent coupling between the bright and dark elements (plasmonic atoms). Using cascaded coupling, we show nearly 4-fold reduction in linewidth of the hybridized resonance compared to a resonantly excited single bright plasmonic atom with same absorbance. In addition, we engineered the geometry of the meta-molecules to realize efficient intramolecularmore » excitation transfer with nearly 80%, on resonant excitation, of the total absorption being localized at the second dark plasmonic atom. An analytical description of the spectral response of the structure is presented with full electrodynamics simulations to corroborate our results. Such multilayered meta-molecules can bring a new dimension to higher quality factor plasmonic resonance, efficient excitation transfer, wavelength demultiplexing, and enhanced non-linearity at nanoscale.« less

  1. Intuitive, but not simple: including explicit water molecules in protein-protein docking simulations improves model quality.

    PubMed

    Parikh, Hardik I; Kellogg, Glen E

    2014-06-01

    Characterizing the nature of interaction between proteins that have not been experimentally cocrystallized requires a computational docking approach that can successfully predict the spatial conformation adopted in the complex. In this work, the Hydropathic INTeractions (HINT) force field model was used for scoring docked models in a data set of 30 high-resolution crystallographically characterized "dry" protein-protein complexes and was shown to reliably identify native-like models. However, most current protein-protein docking algorithms fail to explicitly account for water molecules involved in bridging interactions that mediate and stabilize the association of the protein partners, so we used HINT to illuminate the physical and chemical properties of bridging waters and account for their energetic stabilizing contributions. The HINT water Relevance metric identified the "truly" bridging waters at the 30 protein-protein interfaces and we utilized them in "solvated" docking by manually inserting them into the input files for the rigid body ZDOCK program. By accounting for these interfacial waters, a statistically significant improvement of ∼24% in the average hit-count within the top-10 predictions the protein-protein dataset was seen, compared to standard "dry" docking. The results also show scoring improvement, with medium and high accuracy models ranking much better than incorrect ones. These improvements can be attributed to the physical presence of water molecules that alter surface properties and better represent native shape and hydropathic complementarity between interacting partners, with concomitantly more accurate native-like structure predictions. © 2013 Wiley Periodicals, Inc.

  2. Thermodynamic properties of water molecules in the presence of cosolute depend on DNA structure: a study using grid inhomogeneous solvation theory

    PubMed Central

    Nakano, Miki; Tateishi-Karimata, Hisae; Tanaka, Shigenori; Tama, Florence; Miyashita, Osamu; Nakano, Shu-ichi; Sugimoto, Naoki

    2015-01-01

    In conditions that mimic those of the living cell, where various biomolecules and other components are present, DNA strands can adopt many structures in addition to the canonical B-form duplex. Previous studies in the presence of cosolutes that induce molecular crowding showed that thermal stabilities of DNA structures are associated with the properties of the water molecules around the DNAs. To understand how cosolutes, such as ethylene glycol, affect the thermal stability of DNA structures, we investigated the thermodynamic properties of water molecules around a hairpin duplex and a G-quadruplex using grid inhomogeneous solvation theory (GIST) with or without cosolutes. Our analysis indicated that (i) cosolutes increased the free energy of water molecules around DNA by disrupting water–water interactions, (ii) ethylene glycol more effectively disrupted water–water interactions around Watson–Crick base pairs than those around G-quartets or non-paired bases, (iii) due to the negative electrostatic potential there was a thicker hydration shell around G-quartets than around Watson–Crick-paired bases. Our findings suggest that the thermal stability of the hydration shell around DNAs is one factor that affects the thermal stabilities of DNA structures under the crowding conditions. PMID:26538600

  3. The properties of residual water molecules in ionic liquids: a comparison between direct and inverse Kirkwood-Buff approaches.

    PubMed

    Kobayashi, Takeshi; Reid, Joshua E S J; Shimizu, Seishi; Fyta, Maria; Smiatek, Jens

    2017-07-26

    We study the properties of residual water molecules at different mole fractions in dialkylimidazolium based ionic liquids (ILs), namely 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM/BF 4 ) and 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM/BF 4 ) by means of atomistic molecular dynamics (MD) simulations. The corresponding Kirkwood-Buff (KB) integrals for the water-ion and ion-ion correlation behavior are calculated by a direct evaluation of the radial distribution functions. The outcomes are compared to the corresponding KB integrals derived by an inverse approach based on experimental data. Our results reveal a quantitative agreement between both approaches, which paves a way towards a more reliable comparison between simulation and experimental results. The simulation outcomes further highlight that water even at intermediate mole fractions has a negligible influence on the ion distribution in the solution. More detailed analysis on the local/bulk partition coefficients and the partial structure factors reveal that water molecules at low mole fractions mainly remain in the monomeric state. A non-linear increase of higher order water clusters can be found at larger water concentrations. For both ILs, a more pronounced water coordination around the cations when compared to the anions can be observed, which points out that the IL cations are mainly responsible for water pairing mechanisms. Our simulations thus provide detailed insights in the properties of dialkylimidazolium based ILs and their effects on water binding.

  4. Polariton condensation with saturable molecules dressed by vibrational modes

    DOE PAGES

    Cwik, Justyna A.; Reja, Sahinur; Littlewood, Peter B.; ...

    2014-02-01

    Here, polaritons, mixed light-matter quasiparticles, undergo a transition to a condensed, macroscopically coherent state at low temperatures or high densities. Recent experiments show that coupling light to organic molecules inside a microcavity allows condensation at room temperature. The molecules act as saturable absorbers with transitions dressed by molecular vibrational modes. Motivated by this, we calculate the phase diagram and spectrum of a modified Tavis-Cummings model, describing vibrationally dressed two-level systems, coupled to a cavity mode. Coupling to vibrational modes can induce re-entrance, i.e. a normal-condensed-normal sequence with decreasing temperature and can drive the transition first-order.

  5. Aqueous solvation of polyalanine α-helices with specific water molecules and with the CPCM and SM5.2 aqueous continuum models using density functional theory.

    PubMed

    Marianski, Mateusz; Dannenberg, J J

    2012-02-02

    We present density functional theory (DFT) calculations at the X3LYP/D95(d,p) level on the solvation of polyalanine α-helices in water. The study includes the effects of discrete water molecules and the CPCM and AMSOL SM5.2 solvent continuum model both separately and in combination. We find that individual water molecules cooperatively hydrogen-bond to both the C- and N-termini of the helix, which results in increases in the dipole moment of the helix/water complex to more than the vector sum of their individual dipole moments. These waters are found to be more stable than in bulk solvent. On the other hand, individual water molecules that interact with the backbone lower the dipole moment of the helix/water complex to below that of the helix itself. Small clusters of waters at the termini increase the dipole moments of the helix/water aggregates, but the effect diminishes as more waters are added. We discuss the somewhat complex behavior of the helix with the discrete waters in the continuum models.

  6. Parasitic oscillation suppression in solid state lasers using absorbing thin films

    DOEpatents

    Zapata, L.E.

    1994-08-02

    A thin absorbing film is bonded onto at least certain surfaces of a solid state laser gain medium. An absorbing metal-dielectric multilayer film is optimized for a broad range of incidence angles, and is resistant to the corrosive/erosive effects of a coolant such as water, used in the forced convection cooling of the film. Parasitic oscillations hamper the operation of solid state lasers by causing the decay of stored energy to amplified rays trapped within the gain medium by total and partial internal reflections off the gain medium facets. Zigzag lasers intended for high average power operation require the ASE absorber. 16 figs.

  7. Gibbs Free Energy of Hydrolytic Water Molecule in Acyl-Enzyme Intermediates of a Serine Protease: A Potential Application for Computer-Aided Discovery of Mechanism-Based Reversible Covalent Inhibitors.

    PubMed

    Masuda, Yosuke; Yamaotsu, Noriyuki; Hirono, Shuichi

    2017-01-01

    In order to predict the potencies of mechanism-based reversible covalent inhibitors, the relationships between calculated Gibbs free energy of hydrolytic water molecule in acyl-trypsin intermediates and experimentally measured catalytic rate constants (k cat ) were investigated. After obtaining representative solution structures by molecular dynamics (MD) simulations, hydration thermodynamics analyses using WaterMap™ were conducted. Consequently, we found for the first time that when Gibbs free energy of the hydrolytic water molecule was lower, logarithms of k cat were also lower. The hydrolytic water molecule with favorable Gibbs free energy may hydrolyze acylated serine slowly. Gibbs free energy of hydrolytic water molecule might be a useful descriptor for computer-aided discovery of mechanism-based reversible covalent inhibitors of hydrolytic enzymes.

  8. Hydrophobic fluorine mediated switching of the hydrogen bonding site as well as orientation of water molecules in the aqueous mixture of monofluoroethanol: IR, molecular dynamics and quantum chemical studies.

    PubMed

    Mondal, Saptarsi; Biswas, Biswajit; Nandy, Tonima; Singh, Prashant Chandra

    2017-09-20

    The local structures between water-water, alcohol-water and alcohol-alcohol have been investigated for aqueous mixtures of ethanol (ETH) and monofluoroethanol (MFE) by the deconvolution of IR bands in the OH stretching region, molecular dynamics simulation and quantum chemical calculations. It has been found that the addition of a small amount of ETH into the aqueous medium increases the strength of the hydrogen bonds between water molecules. In an aqueous mixture of MFE, the substitution of a single fluorine induces a change in the orientation as well as the hydrogen bonding site of water molecules from the oxygen to the fluorine terminal of MFE. The switching of the hydrogen bonding site of water in the aqueous mixture of MFE results in comparatively strong hydrogen bonds between MFE and water molecules as well as less clustering of water molecules, unlike the case of the aqueous mixture of ETH. These findings about the modification of a hydrogen bond network by the hydrophobic fluorine group probably make fluorinated molecules useful for pharmaceutical as well as biological applications.

  9. Effect of pH value of probe molecule on the graphene oxide-based surface enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Cui, Shao-li; Du, Xiao-qing; Zeng, Chao; Li, Lu; Bao, Jun

    2017-06-01

    The dependence of graphene oxide (GO)-based surface enhanced Raman scattering (SERS) on the pH value of probe molecule was investigated. Water-soluble copper phthalocyanine (TSCuPc) was used as probe molecule and its pH value was adjusted with HCl and NaOH solution. The Raman spectra of TSCuPc with pH equaling 3, 8, and 11 on GO base were tested, respectively. The results show that both Raman enhanced intensity and full width at half maximum (FWHM) of characteristic peaks vary with the pH value of TSCuPc. It is shown that there is no obvious spectral widening of TSCuPc characteristic peaks when TSCuPc is neutral or acidic, and the chemical enhancement intensity of neutral TSCuPc on GO is biggest. In contrast, when TSCuPc is alkaline, the characteristic Raman peaks between 1350 and 1600 cm-1 of TSCuPc on GO are much wider and the intensities of characteristic peaks decrease considerably. The reasons for the pH dependence of GO-based Raman spectra were explored by comparing the wettability of molecule droplet on GO and the absorbance of different pH-adjusted TSCuPc films. It is found that the effect of molecule's pH value on SERS can be contributed to the differences of concentration and distributions on GO surface for varied pH-treated molecule.

  10. Insight into unusual impurity absorbability of GeO(2) in GeO(2)∕Ge stacks.

    PubMed

    Ogawa, Shingo; Suda, Taichi; Yamamoto, Takashi; Kutsuki, Katsuhiro; Hideshima, Iori; Hosoi, Takuji; Shimura, Takayoshi; Watanabe, Heiji

    2011-10-03

    Adsorbed species and its diffusion behaviors in GeO(2)∕Ge stacks, which are future alternative metal-oxide-semiconductor (MOS) materials, have been investigated using various physical analyses. We clarified that GeO(2) rapidly absorbs moisture in air just after its exposure. After the absorbed moisture in GeO(2) reaches a certain limit, the GeO(2) starts to absorb some organic molecules, which is accompanied by a structural change in GeO(2) to form a partial carbonate or hydroxide. We also found that the hydrogen distribution in GeO(2) shows intrinsic characteristics, indicative of different diffusion behaviors at the surface and at the GeO(2)∕Ge interface. Because the impurity absorbability of GeO(2) has a great influence on the electrical properties in Ge-MOS devices, these results provide valuable information in realizing high quality GeO(2)∕Ge stacks for the actual use of Ge-MOS technologies.

  11. Externally tuned vibration absorber

    DOEpatents

    Vincent, Ronald J.

    1987-09-22

    A vibration absorber unit or units are mounted on the exterior housing of a hydraulic drive system of the type that is powered from a pressure wave generated, e.g., by a Stirling engine. The hydraulic drive system employs a piston which is hydraulically driven to oscillate in a direction perpendicular to the axis of the hydraulic drive system. The vibration absorbers each include a spring or other resilient member having one side affixed to the housing and another side to which an absorber mass is affixed. In a preferred embodiment, a pair of vibration absorbers is employed, each absorber being formed of a pair of leaf spring assemblies, between which the absorber mass is suspended.

  12. Tunable allosteric library of caspase-3 identifies coupling between conserved water molecules and conformational selection

    PubMed Central

    Maciag, Joseph J.; Mackenzie, Sarah H.; Tucker, Matthew B.; Schipper, Joshua L.; Swartz, Paul; Clark, A. Clay

    2016-01-01

    The native ensemble of caspases is described globally by a complex energy landscape where the binding of substrate selects for the active conformation, whereas targeting an allosteric site in the dimer interface selects an inactive conformation that contains disordered active-site loops. Mutations and posttranslational modifications stabilize high-energy inactive conformations, with mostly formed, but distorted, active sites. To examine the interconversion of active and inactive states in the ensemble, we used detection of related solvent positions to analyze 4,995 waters in 15 high-resolution (<2.0 Å) structures of wild-type caspase-3, resulting in 450 clusters with the most highly conserved set containing 145 water molecules. The data show that regions of the protein that contact the conserved waters also correspond to sites of posttranslational modifications, suggesting that the conserved waters are an integral part of allosteric mechanisms. To test this hypothesis, we created a library of 19 caspase-3 variants through saturation mutagenesis in a single position of the allosteric site of the dimer interface, and we show that the enzyme activity varies by more than four orders of magnitude. Altogether, our database consists of 37 high-resolution structures of caspase-3 variants, and we demonstrate that the decrease in activity correlates with a loss of conserved water molecules. The data show that the activity of caspase-3 can be fine-tuned through globally desolvating the active conformation within the native ensemble, providing a mechanism for cells to repartition the ensemble and thus fine-tune activity through conformational selection. PMID:27681633

  13. Tunable allosteric library of caspase-3 identifies coupling between conserved water molecules and conformational selection.

    PubMed

    Maciag, Joseph J; Mackenzie, Sarah H; Tucker, Matthew B; Schipper, Joshua L; Swartz, Paul; Clark, A Clay

    2016-10-11

    The native ensemble of caspases is described globally by a complex energy landscape where the binding of substrate selects for the active conformation, whereas targeting an allosteric site in the dimer interface selects an inactive conformation that contains disordered active-site loops. Mutations and posttranslational modifications stabilize high-energy inactive conformations, with mostly formed, but distorted, active sites. To examine the interconversion of active and inactive states in the ensemble, we used detection of related solvent positions to analyze 4,995 waters in 15 high-resolution (<2.0 Å) structures of wild-type caspase-3, resulting in 450 clusters with the most highly conserved set containing 145 water molecules. The data show that regions of the protein that contact the conserved waters also correspond to sites of posttranslational modifications, suggesting that the conserved waters are an integral part of allosteric mechanisms. To test this hypothesis, we created a library of 19 caspase-3 variants through saturation mutagenesis in a single position of the allosteric site of the dimer interface, and we show that the enzyme activity varies by more than four orders of magnitude. Altogether, our database consists of 37 high-resolution structures of caspase-3 variants, and we demonstrate that the decrease in activity correlates with a loss of conserved water molecules. The data show that the activity of caspase-3 can be fine-tuned through globally desolvating the active conformation within the native ensemble, providing a mechanism for cells to repartition the ensemble and thus fine-tune activity through conformational selection.

  14. An optical conveyor for molecules.

    PubMed

    Weinert, Franz M; Braun, Dieter

    2009-12-01

    Trapping single ions under vacuum allows for precise spectroscopy in atomic physics. The confinement of biological molecules in bulk water is hindered by the lack of comparably strong forces. Molecules have been immobilized to surfaces, however often with detrimental effects on their function. Here, we optically trap molecules by creating the microscale analogue of a conveyor belt: a bidirectional flow is combined with a perpendicular thermophoretic molecule drift. Arranged in a toroidal geometry, the conveyor accumulates a hundredfold excess of 5-base DNA within seconds. The concentrations of the trapped DNA scale exponentially with length, reaching trapping potential depths of 14 kT for 50 bases. The mechanism does not require microfluidics, electrodes, or surface modifications. As a result, the trap can be dynamically relocated. The optical conveyor can be used to enhance diffusion-limited surface reactions, redirect cellular signaling, observe individual biomolecules over a prolonged time, or approach single-molecule chemistry in bulk water.

  15. Crystal Structures of Fatty Acid Amide Hydrolase Bound to the Carbamate Inhibitor URB597: Discovery of a Deacylating Water Molecule and Insight into Enzyme Inactivation

    PubMed Central

    Mileni, Mauro; Kamtekar, Satwik; Wood, David C.; Benson, Timothy E.; Cravatt, Benjamin F.; Stevens, Raymond C.

    2010-01-01

    The endocannabinoid system regulates a wide range of physiological processes including pain, inflammation, and cognitive/emotional states. URB597 is one of the best characterized covalent inhibitors of the endocannabinoid-degrading enzyme fatty acid amide hydrolase (FAAH). Here, we report the structure of the FAAH-URB597 complex at 2.3 Å resolution. The structure provides insights into mechanistic details of enzyme inactivation and experimental evidence of a previously uncharacterized active site water molecule that likely is involved in substrate deacylation. This water molecule is part of an extensive hydrogen-bonding network, and is coordinated indirectly to residues lining the cytosolic port of the enzyme. In order to corroborate our hypothesis concerning the role of this water molecule in FAAH’s catalytic mechanism, we determined the structure of FAAH conjugated to a urea-based inhibitor, PF-3845, to a higher resolution (2.4 Å) than previously reported. The higher resolution structure confirms the presence of the water molecule in a virtually identical location in the active site. Examination of the structures of serine hydrolases that are non-homologous to FAAH, such as elastase, trypsin, or chymotrypsin, shows a similarly positioned hydrolytic water molecule and suggest a functional convergence between the amidase signature enzymes and serine proteases. PMID:20493882

  16. Crystal structure of fatty acid amide hydrolase bound to the carbamate inhibitor URB597: discovery of a deacylating water molecule and insight into enzyme inactivation.

    PubMed

    Mileni, Mauro; Kamtekar, Satwik; Wood, David C; Benson, Timothy E; Cravatt, Benjamin F; Stevens, Raymond C

    2010-07-23

    The endocannabinoid system regulates a wide range of physiological processes including pain, inflammation, and cognitive/emotional states. URB597 is one of the best characterized covalent inhibitors of the endocannabinoid-degrading enzyme fatty acid amide hydrolase (FAAH). Here, we report the structure of the FAAH-URB597 complex at 2.3 A resolution. The structure provides insights into mechanistic details of enzyme inactivation and experimental evidence of a previously uncharacterized active site water molecule that likely is involved in substrate deacylation. This water molecule is part of an extensive hydrogen-bonding network and is coordinated indirectly to residues lining the cytosolic port of the enzyme. In order to corroborate our hypothesis concerning the role of this water molecule in FAAH's catalytic mechanism, we determined the structure of FAAH conjugated to a urea-based inhibitor, PF-3845, to a higher resolution (2.4 A) than previously reported. The higher-resolution structure confirms the presence of the water molecule in a virtually identical location in the active site. Examination of the structures of serine hydrolases that are non-homologous to FAAH, such as elastase, trypsin, or chymotrypsin, shows a similarly positioned hydrolytic water molecule and suggests a functional convergence between the amidase signature enzymes and serine proteases. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  17. Frequency-dependent absorbance of broadband terahertz wave in dense plasma sheet

    NASA Astrophysics Data System (ADS)

    Peng, Yan; Qi, Binbin; Jiang, Xiankai; Zhu, Zhi; Zhao, Hongwei; Zhu, Yiming

    2018-05-01

    Due to the ability of accurate fingerprinting and low-ionization for different substances, terahertz (THz) technology has a lot of crucial applications in material analysis, information transfer, and safety inspection, etc. However, the spectral characteristic of atmospheric gas and ionized gas has not been widely investigated, which is important for the remote sensing application. Here, in this paper, we investigate the absorbance of broadband terahertz wave in dense plasma sheet generated by femtosecond laser pulses. It was found that as the terahertz wave transmits through the plasma sheet formed, respectively, in carbon dioxide, oxygen, argon and nitrogen, spectrum presents completely different and frequency-dependent absorbance. The reasons for these absorption peaks are related to the molecular polarity, electric charge, intermolecular and intramolecular interactions, and collisional absorption of gas molecules. These results have significant implications for the remote sensing of gas medium.

  18. On Spectral Invariance of Single Scattering Albedo for Water Droplets and Ice Crystals at Weakly Absorbing Wavelengths

    NASA Technical Reports Server (NTRS)

    Marshak, Alexander; Knyazikhin, Yuri; Chiu, J. Christine; Wiscombe, Warren J.

    2012-01-01

    The single scattering albedo omega(sub O lambda) in atmospheric radiative transfer is the ratio of the scattering coefficient to the extinction coefficient. For cloud water droplets both the scattering and absorption coefficients, thus the single scattering albedo, are functions of wavelength lambda and droplet size r. This note shows that for water droplets at weakly absorbing wavelengths, the ratio omega(sub O lambda)(r)/omega(sub O lambda)(r (sub O)) of two single scattering albedo spectra is a linear function of omega(sub O lambda)(r). The slope and intercept of the linear function are wavelength independent and sum to unity. This relationship allows for a representation of any single scattering albedo spectrum omega(sub O lambda)(r) via one known spectrum omega(sub O lambda)(r (sub O)). We provide a simple physical explanation of the discovered relationship. Similar linear relationships were found for the single scattering albedo spectra of non-spherical ice crystals.

  19. The mechanism and properties of bio-photon emission and absorption in protein molecules in living systems

    NASA Astrophysics Data System (ADS)

    Pang, Xiao-feng

    2012-05-01

    The mechanism and properties of bio-photon emission and absorption in bio-tissues were studied using Pang's theory of bio-energy transport, in which the energy spectra of protein molecules are obtained from the discrete dynamic equation. From the energy spectra, it was determined that the protein molecules could both radiate and absorb bio-photons with wavelengths of <3 μm and 5-7 μm, consistent with the energy level transitions of the excitons. These results were consistent with the experimental data; this consisted of infrared absorption data from collagen, bovine serum albumin, the protein-like molecule acetanilide, plasma, and a person's finger, and the laser-Raman spectra of acidity I-type collagen in the lungs of a mouse, and metabolically active Escherichia coli. We further elucidated the mechanism responsible for the non-thermal biological effects produced by the infrared light absorbed by the bio-tissues, using the above results. No temperature rise was observed; instead, the absorbed infrared light promoted the vibrations of amides as well the transport of the bio-energy from one place to other in the protein molecules, which changed their conformations. These experimental results, therefore, not only confirmed the validity of the mechanism of bio-photon emission, and the newly developed theory of bio-energy transport mentioned above, but also explained the mechanism and properties of the non-thermal biological effects produced by the absorption of infrared light by the living systems.

  20. Photo-electrochemical Oxidation of Organic C1 Molecules over WO3 Films in Aqueous Electrolyte: Competition Between Water Oxidation and C1 Oxidation.

    PubMed

    Reichert, Robert; Zambrzycki, Christian; Jusys, Zenonas; Behm, R Jürgen

    2015-11-01

    To better understand organic-molecule-assisted photo-electrochemical water splitting, photo-electrochemistry and on-line mass spectrometry measurements are used to investigate the photo-electrochemical oxidation of the C1 molecules methanol, formaldehyde, and formic acid over WO3 film anodes in aqueous solution and its competition with O2 evolution from water oxidation O2 (+) and CO2 (+) ion currents show that water oxidation is strongly suppressed by the organic species. Photo-electro-oxidation of formic acid is dominated by formation of CO2 , whereas incomplete oxidation of formaldehyde and methanol prevails, with the selectivity for CO2 formation increasing with increasing potential and light intensity. The mechanistic implications for the photo-electro-oxidation of the organic molecules and its competition with water oxidation, which could be derived from this novel approach, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Small molecule absorption by PDMS in the context of drug response bioassays.

    PubMed

    van Meer, B J; de Vries, H; Firth, K S A; van Weerd, J; Tertoolen, L G J; Karperien, H B J; Jonkheijm, P; Denning, C; IJzerman, A P; Mummery, C L

    2017-01-08

    The polymer polydimethylsiloxane (PDMS) is widely used to build microfluidic devices compatible with cell culture. Whilst convenient in manufacture, PDMS has the disadvantage that it can absorb small molecules such as drugs. In microfluidic devices like "Organs-on-Chip", designed to examine cell behavior and test the effects of drugs, this might impact drug bioavailability. Here we developed an assay to compare the absorption of a test set of four cardiac drugs by PDMS based on measuring the residual non-absorbed compound by High Pressure Liquid Chromatography (HPLC). We showed that absorption was variable and time dependent and not determined exclusively by hydrophobicity as claimed previously. We demonstrated that two commercially available lipophilic coatings and the presence of cells affected absorption. The use of lipophilic coatings may be useful in preventing small molecule absorption by PDMS. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

  2. Methods for absorbing neutrons

    DOEpatents

    Guillen, Donna P [Idaho Falls, ID; Longhurst, Glen R [Idaho Falls, ID; Porter, Douglas L [Idaho Falls, ID; Parry, James R [Idaho Falls, ID

    2012-07-24

    A conduction cooled neutron absorber may include a metal matrix composite that comprises a metal having a thermal neutron cross-section of at least about 50 barns and a metal having a thermal conductivity of at least about 1 W/cmK. Apparatus for providing a neutron flux having a high fast-to-thermal neutron ratio may include a source of neutrons that produces fast neutrons and thermal neutrons. A neutron absorber positioned adjacent the neutron source absorbs at least some of the thermal neutrons so that a region adjacent the neutron absorber has a fast-to-thermal neutron ratio of at least about 15. A coolant in thermal contact with the neutron absorber removes heat from the neutron absorber.

  3. Role of Interfacial Water Molecules in Proline-rich Ligand Recognition by the Src Homology 3 Domain of Abl*

    PubMed Central

    Palencia, Andres; Camara-Artigas, Ana; Pisabarro, M. Teresa; Martinez, Jose C.; Luque, Irene

    2010-01-01

    The interaction of Abl-Src homology 3 domain (SH3) with the high affinity peptide p41 is the most notable example of the inconsistency existing between the currently accepted description of SH3 complexes and their binding thermodynamic signature. We had previously hypothesized that the presence of interfacial water molecules is partially responsible for this thermodynamic behavior. We present here a thermodynamic, structural, and molecular dynamics simulation study of the interaction of p41 with Abl-SH3 and a set of mutants designed to alter the water-mediated interaction network. Our results provide a detailed description of the dynamic properties of the interfacial water molecules and a molecular interpretation of the thermodynamic effects elicited by the mutations in terms of the modulation of the water-mediated hydrogen bond network. In the light of these results, a new dual binding mechanism is proposed that provides a better description of proline-rich ligand recognition by Abl-SH3 and that has important implications for rational design. PMID:19906645

  4. Displacement of disordered water molecules from hydrophobic pocket creates enthalpic signature: binding of phosphonamidate to the S₁'-pocket of thermolysin.

    PubMed

    Englert, L; Biela, A; Zayed, M; Heine, A; Hangauer, D; Klebe, G

    2010-11-01

    Prerequisite for the design of tight binding protein inhibitors and prediction of their properties is an in-depth understanding of the structural and thermodynamic details of the binding process. A series of closely related phosphonamidates was studied to elucidate the forces underlying their binding affinity to thermolysin. The investigated inhibitors are identical except for the parts penetrating into the hydrophobic S₁'-pocket. A correlation of structural, kinetic and thermodynamic data was carried out by X-ray crystallography, kinetic inhibition assay and isothermal titration calorimetry. Binding affinity increases with larger ligand hydrophobic P₁'-moieties accommodating the S₁'-pocket. Surprisingly, larger P₁'-side chain modifications are accompanied by an increase in the enthalpic contribution to binding. In agreement with other studies, it is suggested that the release of largely disordered waters from an imperfectly hydrated pocket results in an enthalpically favourable integration of these water molecules into bulk water upon inhibitor binding. This enthalpically favourable process contributes more strongly to the binding energetics than the entropy increase resulting from the release of water molecules from the S₁'-pocket or the formation of apolar interactions between protein and inhibitor. Displacement of highly disordered water molecules from a rather imperfectly hydrated and hydrophobic specificity pocket can reveal an enthalpic signature of inhibitor binding. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. Composition for absorbing hydrogen

    DOEpatents

    Heung, L.K.; Wicks, G.G.; Enz, G.L.

    1995-05-02

    A hydrogen absorbing composition is described. The composition comprises a porous glass matrix, made by a sol-gel process, having a hydrogen-absorbing material dispersed throughout the matrix. A sol, made from tetraethyl orthosilicate, is mixed with a hydrogen-absorbing material and solidified to form a porous glass matrix with the hydrogen-absorbing material dispersed uniformly throughout the matrix. The glass matrix has pores large enough to allow gases having hydrogen to pass through the matrix, yet small enough to hold the particles dispersed within the matrix so that the hydrogen-absorbing particles are not released during repeated hydrogen absorption/desorption cycles.

  6. Composition for absorbing hydrogen

    DOEpatents

    Heung, Leung K.; Wicks, George G.; Enz, Glenn L.

    1995-01-01

    A hydrogen absorbing composition. The composition comprises a porous glass matrix, made by a sol-gel process, having a hydrogen-absorbing material dispersed throughout the matrix. A sol, made from tetraethyl orthosilicate, is mixed with a hydrogen-absorbing material and solidified to form a porous glass matrix with the hydrogen-absorbing material dispersed uniformly throughout the matrix. The glass matrix has pores large enough to allow gases having hydrogen to pass through the matrix, yet small enough to hold the particles dispersed within the matrix so that the hydrogen-absorbing particles are not released during repeated hydrogen absorption/desorption cycles.

  7. Tuning dissociation using isoelectronically doped graphene and hexagonal boron nitride: Water and other small molecules

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

    Al-Hamdani, Yasmine S.; Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ; Alfè, Dario

    2016-04-21

    Novel uses for 2-dimensional materials like graphene and hexagonal boron nitride (h-BN) are being frequently discovered especially for membrane and catalysis applications. Still however, a great deal remains to be understood about the interaction of environmentally and industrially relevant molecules such as water with these materials. Taking inspiration from advances in hybridising graphene and h-BN, we explore using density functional theory, the dissociation of water, hydrogen, methane, and methanol on graphene, h-BN, and their isoelectronic doped counterparts: BN doped graphene and C doped h-BN. We find that doped surfaces are considerably more reactive than their pristine counterparts and by comparingmore » the reactivity of several small molecules, we develop a general framework for dissociative adsorption. From this a particularly attractive consequence of isoelectronic doping emerges: substrates can be doped to enhance their reactivity specifically towards either polar or non-polar adsorbates. As such, these substrates are potentially viable candidates for selective catalysts and membranes, with the implication that a range of tuneable materials can be designed.« less

  8. Tuning dissociation using isoelectronically doped graphene and hexagonal boron nitride: Water and other small molecules

    NASA Astrophysics Data System (ADS)

    Al-Hamdani, Yasmine S.; Alfè, Dario; von Lilienfeld, O. Anatole; Michaelides, Angelos

    2016-04-01

    Novel uses for 2-dimensional materials like graphene and hexagonal boron nitride (h-BN) are being frequently discovered especially for membrane and catalysis applications. Still however, a great deal remains to be understood about the interaction of environmentally and industrially relevant molecules such as water with these materials. Taking inspiration from advances in hybridising graphene and h-BN, we explore using density functional theory, the dissociation of water, hydrogen, methane, and methanol on graphene, h-BN, and their isoelectronic doped counterparts: BN doped graphene and C doped h-BN. We find that doped surfaces are considerably more reactive than their pristine counterparts and by comparing the reactivity of several small molecules, we develop a general framework for dissociative adsorption. From this a particularly attractive consequence of isoelectronic doping emerges: substrates can be doped to enhance their reactivity specifically towards either polar or non-polar adsorbates. As such, these substrates are potentially viable candidates for selective catalysts and membranes, with the implication that a range of tuneable materials can be designed.

  9. Cu-In Halide Perovskite Solar Absorbers.

    PubMed

    Zhao, Xin-Gang; Yang, Dongwen; Sun, Yuanhui; Li, Tianshu; Zhang, Lijun; Yu, Liping; Zunger, Alex

    2017-05-17

    The long-term chemical instability and the presence of toxic Pb in otherwise stellar solar absorber APbX 3 made of organic molecules on the A site and halogens for X have hindered their large-scale commercialization. Previously explored ways to achieve Pb-free halide perovskites involved replacing Pb 2+ with other similar M 2+ cations in ns 2 electron configuration, e.g., Sn 2+ or by Bi 3+ (plus Ag + ), but unfortunately this showed either poor stability (M = Sn) or weakly absorbing oversized indirect gaps (M = Bi), prompting concerns that perhaps stability and good optoelectronic properties might be contraindicated. Herein, we exploit the electronic structure underpinning of classic Cu[In,Ga]Se 2 (CIGS) chalcopyrite solar absorbers to design Pb-free halide perovskites by transmuting 2Pb to the pair [B IB + C III ] such as [Cu + Ga] or [Ag + In] and combinations thereof. The resulting group of double perovskites with formula A 2 BCX 6 (A = K, Rb, Cs; B = Cu, Ag; C = Ga, In; X = Cl, Br, I) benefits from the ionic, yet narrow-gap character of halide perovskites, and at the same time borrows the advantage of the strong Cu(d)/Se(p) → Ga/In(s/p) valence-to-conduction-band absorption spectra known from CIGS. This constitutes a new group of CuIn-based Halide Perovskite (CIHP). Our first-principles calculations guided by such design principles indicate that the CIHPs class has members with clear thermodynamic stability, showing direct band gaps, and manifesting a wide-range of tunable gap values (from zero to about 2.5 eV) and combination of light electron and heavy-light hole effective masses. Materials screening of candidate CIHPs then identifies the best-of-class Rb 2 [CuIn]Cl 6 , Rb 2 [AgIn]Br 6 , and Cs 2 [AgIn]Br 6 , having direct band gaps of 1.36, 1.46, and 1.50 eV, and theoretical spectroscopic limited maximal efficiency comparable to chalcopyrites and CH 3 NH 3 PbI 3 . Our finding offers a new routine for designing new-type Pb-free halide perovskite solar

  10. Changes in the hydrogen-bonding strength of internal water molecules and cysteine residues in the conductive state of channelrhodopsin-1

    NASA Astrophysics Data System (ADS)

    Lórenz-Fonfría, Víctor A.; Muders, Vera; Schlesinger, Ramona; Heberle, Joachim

    2014-12-01

    Water plays an essential role in the structure and function of proteins, particularly in the less understood class of membrane proteins. As the first of its kind, channelrhodopsin is a light-gated cation channel and paved the way for the new and vibrant field of optogenetics, where nerve cells are activated by light. Still, the molecular mechanism of channelrhodopsin is not understood. Here, we applied time-resolved FT-IR difference spectroscopy to channelrhodopsin-1 from Chlamydomonas augustae. It is shown that the (conductive) P2380 intermediate decays with τ ≈ 40 ms and 200 ms after pulsed excitation. The vibrational changes between the closed and the conductive states were analyzed in the X-H stretching region (X = O, S, N), comprising vibrational changes of water molecules, sulfhydryl groups of cysteine side chains and changes of the amide A of the protein backbone. The O-H stretching vibrations of "dangling" water molecules were detected in two different states of the protein using H218O exchange. Uncoupling experiments with a 1:1 mixture of H2O:D2O provided the natural uncoupled frequencies of the four O-H (and O-D) stretches of these water molecules, each with a very weakly hydrogen-bonded O-H group (3639 and 3628 cm-1) and with the other O-H group medium (3440 cm-1) to moderately strongly (3300 cm-1) hydrogen-bonded. Changes in amide A and thiol vibrations report on global and local changes, respectively, associated with the formation of the conductive state. Future studies will aim at assigning the respective cysteine group(s) and at localizing the "dangling" water molecules within the protein, providing a better understanding of their functional relevance in CaChR1.

  11. Interferometer-Based Calorimetric Measurements of Absorbed Dose to Water in External Beam Radiotherapy

    NASA Astrophysics Data System (ADS)

    Flores-Martinez, Everardo

    Calorimetry is often used to establish high-energy photon absorbed dose to water (ADW) primary standards as calorimetry is a direct measurement of the energy imparted to the water by ionizing radiation. Current calorimeters use thermistors to establish national standards but there is the possibility of systematic errors in these instruments because thermistors overheat due to their low heat capacity. For this reason, there has been renewed interest in using alternative temperature measurement techniques, especially those that do not require a mechanical probe. Interferometer-based thermometry is a technique that exploits the temperature dependence of the refractive index of water and can be used as an alternative method for temperature measurement in radiation calorimetry. A distinctive advantage of the use of interferometry for radiation calorimetry is the capability of obtaining 2D or 3D temperature/dose distributions. Compared to thermistor-based measurements, the use of interferometer-based ADW measurements has been limited by the low measurement resolution. Optimized setups with higher accuracy and precision are necessary to perform measurements at clinically relevant dose rates. A calorimeter for thermistor-based ADW measurements was developed. The instrument was used to measure thermal drifts and noise were measured using the instrument in a water phantom. Residual thermal drifts were accounted for by using a three-step measurement protocol. Additionally, the instrument was used to measure ADW from a 6MV photon beam from a medical linear accelerator. A Michelson-type interferometer was built, characterized, and placed inside the calorimeter with the water phantom at the reference arm. Interferometer and phantom temperature fluctuations were minimized by means of the passive thermal control provide by the calorimeter enclosure, leading to increased fringe pattern stability. The interferometer characterization included phase shift measurements induced by

  12. The relationship between absorbency and density of bioplastic film made from hydrolyzed starch

    NASA Astrophysics Data System (ADS)

    Singan, Grace; Chiang, Liew Kang

    2017-12-01

    Water absorption in polymer blends such as starch-based bioplastic films is important to evaluate the stability characteristics of such films in water that will affect their long-term performance in final products. In this study, the absorbency of starch-based bioplastic films made from potato, cassava, and corn starches that have went through the hydrolysis process first to alter its characteristics and properties in terms of granular swelling and hydrophilicity behaviour. The final results showed that hydrolyzed cassava bioplastic film has the ability to absorb more water compared to hydrolyzed potato and corn bioplastic films. The reading of hydrolyzed cassava bioplastic film on the seventh day of immersion for all ratios were between 87.83 % to 131.29 %, while for hydrolyzed potato bioplastic films was 69.48 % to 92.41 % and hydrolyzed corn bioplastic films was 66.28 % to 74.18 %. Meanwhile, the density analysis was evaluated to determine its physical properties towards moisture condition. The results showed that the hydrolyzed cassava bioplastic films have higher density compared to the other two, which indicated that it is a more favourable raw material to produce biodegradable planting pot due to its ability to absorb more water. Hence, still manage to retain its shape with low brittle surface.

  13. Enhanced absorption in a reverse saturable absorbing dye blended with carbon nanotubes.

    PubMed

    Webster, Scott; Reyes-Reyes, Marisol; Williams, Richard; Carroll, David L

    2008-12-01

    Using nonlinear absorption at 532 nm in the nanosecond temporal regime, we have measured the low fluence nonlinear transmittance properties of the reverse saturable absorbing carbocyanine dye, 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide (HITCI), blended with well dispersed carbon nanotubes. The nonlinear optical properties of the blends are strongly dependent on the ratio of dye to nanotubes in solution. In the case where the nanotubes per dye molecule ratio is large, we see a distinctive enhancement in optical fluence limiting properties of the system, suggesting enhanced absorption of the excited states. However, when the nanotube to dye ratio decreases, the system's response is dominated by the behavior of the dye. We suggest that this can be understood as a two component system in which sensitized dye molecules associated with the nanotubes have an effectively different optical cross-section from the dye molecules far from the nanotubes. From classical antennae considerations, this is expected.

  14. Preheating Water In The Covers Of Solar Water Heaters

    NASA Technical Reports Server (NTRS)

    Bhandari, Pradeep

    1995-01-01

    Solar water heaters that include glass covers over absorber plates redesigned to increase efficiencies according to proposal. Redesign includes modification of single-layer glass cover into double-layer glass cover and addition of plumbing so cool water to be heated made to flow between layers of cover before entering absorber plate.

  15. Experimental study on the cool storage performance of super absorbent polymers for cool storage clothes

    NASA Astrophysics Data System (ADS)

    Li, Shidong; Mo, Caisong; Wang, Junze; Zheng, Jingfu; Tian, Ruhong

    2017-11-01

    In this paper, a kind of cool storage clothes which can cool the human body in high temperature condition is put forward. super absorbent polymers was selected as a cold storage material, through at the normal and extreme environment simulation, the cold storage materials were prepared with different composition, and their performance was tested. Test results show that:under normal temperature conditions, the 1:50 concentration of super absorbent polymers continued to release the longest cooling time, compared with pure water, cooling time extended 43 minutes by about 30%; under the condition of 37°C, the 1:100 concentration of super absorbent polymers continued to release the longest cooling time, compared with pure water, cooling time extended 105 minutes by about 50%.

  16. The advantages of absorbed-dose calibration factors.

    PubMed

    Rogers, D W

    1992-01-01

    A formalism for clinical external beam dosimetry based on use of ion chamber absorbed-dose calibration factors is outlined in the context and notation of the AAPM TG-21 protocol. It is shown that basing clinical dosimetry on absorbed-dose calibration factors ND leads to considerable simplification and reduced uncertainty in dose measurement. In keeping with a protocol which is used in Germany, a quantity kQ is defined which relates an absorbed-dose calibration factor in a beam of quality Q0 to that in a beam of quality Q. For 38 cylindrical ion chambers, two sets of values are presented for ND/NX and Ngas/ND and for kQ for photon beams with beam quality specified by the TPR20(10) ratio. One set is based on TG-21's protocol to allow the new formalism to be used while maintaining equivalence to the TG-21 protocol. To demonstrate the magnitude of the overall error in the TG-21 protocol, the other set uses corrected versions of the TG-21 equations and the more consistent physical data of the IAEA Code of Practice. Comparisons are made to procedures based on air-kerma or exposure calibration factors and it is shown that accuracy and simplicity are gained by avoiding the determination of Ngas from NX. It is also shown that the kQ approach simplifies the use of plastic phantoms in photon beams since kQ values change by less than 0.6% compared to those in water although an overall correction factor of 0.973 is needed to go from absorbed dose in water calibration factors to those in PMMA or polystyrene. Values of kQ calculated using the IAEA Code of Practice are presented but are shown to be anomalous because of the way the effective point of measurement changes for 60Co beams. In photon beams the major difference between the IAEA Code of Practice and the corrected AAPM TG-21 protocol is shown to be the Prepl correction factor. Calculated kQ curves and three parameter equations for them are presented for each wall material and are shown to represent accurately the kQ curve

  17. AFM investigation of effect of absorbed water layer structure on growth mechanism of octadecyltrichlorosilane self-assembled monolayer on oxidized silicon

    NASA Astrophysics Data System (ADS)

    Li, Shaowei; Zheng, Yanjun; Chen, Changfeng

    2016-06-01

    The growth mechanism of an octadecyltrichlorosilane (OTS) self-assembled monolayer on a silicon oxide surface at various relative humidities has been investigated. Atomic force microscopy images show that excess water may actually hinder the nucleation and growth of OTS islands. A moderate amount of water is favorable for the nucleation and growth of OTS islands in the initial stage; however, the completion of the monolayer is very slow in the final stage. The growth of OTS islands on a low-water-content surface maintains a relatively constant speed and requires the least amount of time. The mobility of water molecules is thought to play an important role in the OTS monolayers, and a low-mobility water layer provides a steady condition for OTS monolayer growth.

  18. KEY COMPARISON: Comparison of the standards for absorbed dose to water of the VNIIFTRI, Russia and the BIPM in 60Co γ rays

    NASA Astrophysics Data System (ADS)

    Allisy-Roberts, P. J.; Kessler, C.; Burns, D. T.; Berlyand, V.; Berlyand, A.

    2010-01-01

    A new comparison of the standards for absorbed dose to water of the All-Russian Scientific Research Institute for Physical-Technical and Radiotechnical Measurements (VNIIFTRI), Russia and of the Bureau International des Poids et Mesures (BIPM) has been made in 60Co gamma radiation in 2009. The results show that the VNIIFTRI and the BIPM standards for absorbed dose to water are in agreement, yielding a mean ratio of 0.9976 for the calibration coefficients of the transfer chambers, the difference from unity being within the combined standard uncertainty (0.0043) for this result. This result is consistent with the earlier 2001 comparison result of 0.9967 (43). The updated degrees of equivalence for the VNIIFTRI are compared with those of the other national metrology institutes as presented in the BIPM key comparison database. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCRI Section I, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

  19. Electromagnetic-radiation absorption by water.

    PubMed

    Lunkenheimer, P; Emmert, S; Gulich, R; Köhler, M; Wolf, M; Schwab, M; Loidl, A

    2017-12-01

    Why does a microwave oven work? How does biological tissue absorb electromagnetic radiation? Astonishingly, we do not have a definite answer to these simple questions because the microscopic processes governing the absorption of electromagnetic waves by water are largely unclarified. This absorption can be quantified by dielectric loss spectra, which reveal a huge peak at a frequency of the exciting electric field of about 20 GHz and a gradual tailing off toward higher frequencies. The microscopic interpretation of such spectra is highly controversial and various superpositions of relaxation and resonance processes ascribed to single-molecule or molecule-cluster motions have been proposed for their analysis. By combining dielectric, microwave, THz, and far-infrared spectroscopy, here we provide nearly continuous temperature-dependent broadband spectra of water. Moreover, we find that corresponding spectra for aqueous solutions reveal the same features as pure water. However, in contrast to the latter, crystallization in these solutions can be avoided by supercooling. As different spectral contributions tend to disentangle at low temperatures, this enables us to deconvolute them when approaching the glass transition under cooling. We find that the overall spectral development, including the 20 GHz feature (employed for microwave heating), closely resembles the behavior known for common supercooled liquids. Thus water's absorption of electromagnetic waves at room temperature is not unusual but very similar to that of glass-forming liquids at elevated temperatures, deep in the low-viscosity liquid regime, and should be interpreted along similar lines.

  20. Electromagnetic-radiation absorption by water

    NASA Astrophysics Data System (ADS)

    Lunkenheimer, P.; Emmert, S.; Gulich, R.; Köhler, M.; Wolf, M.; Schwab, M.; Loidl, A.

    2017-12-01

    Why does a microwave oven work? How does biological tissue absorb electromagnetic radiation? Astonishingly, we do not have a definite answer to these simple questions because the microscopic processes governing the absorption of electromagnetic waves by water are largely unclarified. This absorption can be quantified by dielectric loss spectra, which reveal a huge peak at a frequency of the exciting electric field of about 20 GHz and a gradual tailing off toward higher frequencies. The microscopic interpretation of such spectra is highly controversial and various superpositions of relaxation and resonance processes ascribed to single-molecule or molecule-cluster motions have been proposed for their analysis. By combining dielectric, microwave, THz, and far-infrared spectroscopy, here we provide nearly continuous temperature-dependent broadband spectra of water. Moreover, we find that corresponding spectra for aqueous solutions reveal the same features as pure water. However, in contrast to the latter, crystallization in these solutions can be avoided by supercooling. As different spectral contributions tend to disentangle at low temperatures, this enables us to deconvolute them when approaching the glass transition under cooling. We find that the overall spectral development, including the 20 GHz feature (employed for microwave heating), closely resembles the behavior known for common supercooled liquids. Thus water's absorption of electromagnetic waves at room temperature is not unusual but very similar to that of glass-forming liquids at elevated temperatures, deep in the low-viscosity liquid regime, and should be interpreted along similar lines.

  1. Internal absorber solar collector

    DOEpatents

    Sletten, Carlyle J.; Herskovitz, Sheldon B.; Holt, F. S.; Sletten, E. J.

    1981-01-01

    Thin solar collecting panels are described made from arrays of small rod collectors consisting of a refracting dielectric rod lens with an absorber imbedded within it and a reflecting mirror coated on the back side of the dielectric rod. Non-tracking collector panels on vertical walls or roof tops receive approximately 90% of solar radiation within an acceptance zone 60.degree. in elevation angle by 120.degree. or more in the azimuth sectors with a collector concentration ratio of approximately 3.0. Miniaturized construction of the circular dielectric rods with internal absorbers reduces the weight per area of glass, plastic and metal used in the collector panels. No external parts or insulation are needed as heat losses are low due to partial vacuum or low conductivity gas surrounding heated portions of the collector. The miniature internal absorbers are generally made of solid copper with black selective surface and the collected solar heat is extracted at the collector ends by thermal conductivity along the absorber rods. Heat is removed from end fittings by use of liquid circulants. Several alternate constructions are provided for simplifying collector panel fabrication and for preventing the thermal expansion and contraction of the heated absorber or circulant tubes from damaging vacuum seals. In a modified version of the internal absorber collector, oil with temperature dependent viscosity is pumped through a segmented absorber which is now composed of closely spaced insulated metal tubes. In this way the circulant is automatically diverted through heated portions of the absorber giving higher collector concentration ratios than theoretically possible for an unsegmented absorber.

  2. Absorber modeling for NGCC carbon capture with aqueous piperazine.

    PubMed

    Zhang, Yue; Freeman, Brice; Hao, Pingjiao; Rochelle, Gary T

    2016-10-20

    A hybrid system combining amine scrubbing with membrane technology for carbon capture from natural gas combined cycle (NGCC) power plants is proposed in this paper. In this process, the CO 2 in the flue gas can be enriched from 4% to 18% by the membrane, and the amine scrubbing system will have lower capture costs. Aqueous piperazine (PZ) is chosen as the solvent. Different direct contact cooler (DCC) options, multiple absorber operating conditions, optimal intercooling designs, and different cooling options have been evaluated across a wide range of inlet CO 2 . Amine scrubbing without DCC is a superior design for NGCC carbon capture. Pump-around cooling at the bottom of the absorber can effectively manage the temperature of the hot flue gas, and still be effective for CO 2 absorption. The absorber gas inlet must be designed to avoid excessive localized temperature and solvent evaporation. When the inlet CO 2 increases from 4% to 18%, total absorber CAPEX decreases by 60%; another 10% of the total absorber CAPEX can be saved by eliminating the DCC. In-and-out intercooling works well for high CO 2 , while pump-around intercooling is more effective for low CO 2 . Dry cooling requires more packing and energy but appears to be technically and economically feasible if cooling water availability is limited.

  3. Photoionization of water molecules by a train of attosecond pulses assisted by a near-infrared laser: delay and polarization control

    NASA Astrophysics Data System (ADS)

    Martini, Lara; Boll, Diego I. R.; Fojón, Omar A.

    2017-08-01

    Basic reactions involving water molecules are essential to understand the interaction between radiation and the biological tissue because living cells are composed mostly by water. Therefore, the knowledge of ionization of the latter is crucial in many domains of Biology and Physics. So, we study theoretically the photoionization of water molecules by extreme ultraviolet attopulse trains assisted by lasers in the near-infrared range. We use a separable Coulomb-Volkov model in which the temporal evolution of the system can be divided into three stages allowing spatial and temporal separation for the Coulomb and Volkov final state wavefunctions. First, we analyze photoelectron angular distributions for different delays between the attopulse train and the assistant laser field. We compare our results for water and Ne atoms as they belong to the same isoelectronic series. Moreover, we contrast our calculations with previous theoretical and experimental work for Ar atoms due to the similarities of the orbitals involved in the reaction. Second, we study the effect of varying the relative orientations of the attopulse and laser field polarizations and we compare our predictions with other theories and experiments. We expect these studies contribute to the improvement of polarization experiments and the development of the attopulse trains and assistant laser fields technologies. Finally, we hope our work promote progress on the control of the chemical reactivity of water molecules since this could be useful in different fields such as radiobiology and medical physics.

  4. WScore: A Flexible and Accurate Treatment of Explicit Water Molecules in Ligand-Receptor Docking.

    PubMed

    Murphy, Robert B; Repasky, Matthew P; Greenwood, Jeremy R; Tubert-Brohman, Ivan; Jerome, Steven; Annabhimoju, Ramakrishna; Boyles, Nicholas A; Schmitz, Christopher D; Abel, Robert; Farid, Ramy; Friesner, Richard A

    2016-05-12

    We have developed a new methodology for protein-ligand docking and scoring, WScore, incorporating a flexible description of explicit water molecules. The locations and thermodynamics of the waters are derived from a WaterMap molecular dynamics simulation. The water structure is employed to provide an atomic level description of ligand and protein desolvation. WScore also contains a detailed model for localized ligand and protein strain energy and integrates an MM-GBSA scoring component with these terms to assess delocalized strain of the complex. Ensemble docking is used to take into account induced fit effects on the receptor conformation, and protein reorganization free energies are assigned via fitting to experimental data. The performance of the method is evaluated for pose prediction, rank ordering of self-docked complexes, and enrichment in virtual screening, using a large data set of PDB complexes and compared with the Glide SP and Glide XP models; significant improvements are obtained.

  5. Maximizing T2-exchange in Dy3+DOTA-(amide)X chelates: Fine-tuning the water molecule exchange rate for enhanced T2 contrast in MRI

    PubMed Central

    Soesbe, Todd C.; Ratnakar, S. James; Milne, Mark; Zhang, Shanrong; Do, Quyen N.; Kovacs, Zoltan; Sherry, A. Dean

    2014-01-01

    Purpose The water molecule exchange rates in a series of DyDOTA-(amide)X chelates were fine-tuned to maximize the effects of T2-exchange line broadening and improve T2 contrast. Methods Four DyDOTA-(amide)X chelates having a variable number of glycinate side-arms were prepared and characterized as T2-exchange agents. The non-exchanging DyTETA chelate was also used to measure the bulk water T2 reduction due solely to T2*. The total transverse relaxivity (r2tot) at 22, 37, and 52 °C for each chelate was measured in vitro at 9.4 T (400 MHz) by fitting plots of total T2−1 versus concentration. The water molecule exchange rates for each complex were measured by fitting 17O line-width versus temperature data taken at 9.4 T (54.3 MHz). Results The measured transverse relaxivities due to water molecule exchange (r2ex) and bound water lifetimes (τM) were in excellent agreement with Swift-Connick theory, with DyDOTA-(gly)3 giving the largest r2ex = 11.8 s−1 mM−1 at 37 °C. Conclusion By fine-tuning the water molecule exchange rate at 37 °C, the transverse relaxivity has been increased by 2 to 30 times compared to previously studied Dy3+-based chelates. Polymerization or dendrimerization of the optimal chelate could yield a highly sensitive, molecule-sized T2 contrast agent for improved molecular imaging applications. PMID:24390729

  6. Absorber for terahertz radiation management

    DOEpatents

    Biallas, George Herman; Apeldoorn, Cornelis; Williams, Gwyn P.; Benson, Stephen V.; Shinn, Michelle D.; Heckman, John D.

    2015-12-08

    A method and apparatus for minimizing the degradation of power in a free electron laser (FEL) generating terahertz (THz) radiation. The method includes inserting an absorber ring in the FEL beam path for absorbing any irregular THz radiation and thus minimizes the degradation of downstream optics and the resulting degradation of the FEL output power. The absorber ring includes an upstream side, a downstream side, and a plurality of wedges spaced radially around the absorber ring. The wedges form a scallop-like feature on the innermost edges of the absorber ring that acts as an apodizer, stopping diffractive focusing of the THz radiation that is not intercepted by the absorber. Spacing between the scallop-like features and the shape of the features approximates the Bartlett apodization function. The absorber ring provides a smooth intensity distribution, rather than one that is peaked on-center, thereby eliminating minor distortion downstream of the absorber.

  7. Complex absorbing potential based Lorentzian fitting scheme and time dependent quantum transport.

    PubMed

    Xie, Hang; Kwok, Yanho; Jiang, Feng; Zheng, Xiao; Chen, GuanHua

    2014-10-28

    Based on the complex absorbing potential (CAP) method, a Lorentzian expansion scheme is developed to express the self-energy. The CAP-based Lorentzian expansion of self-energy is employed to solve efficiently the Liouville-von Neumann equation of one-electron density matrix. The resulting method is applicable for both tight-binding and first-principles models and is used to simulate the transient currents through graphene nanoribbons and a benzene molecule sandwiched between two carbon-atom chains.

  8. Manipulating surface wettability and oil absorbency of diatomite depending on processing and ambient conditions

    NASA Astrophysics Data System (ADS)

    Özen, İlhan; Şimşek, Süleyman; Okyay, Gamze

    2015-03-01

    In this study, a diatomite sample, which is a natural inorganic mineral with inherently high water and oil absorption capacity, was subjected to grinding before surface modification. Afterwards, the diatomite surface was modified via facile methods using a fluorocarbon (FC) chemical and stearic acid (SA) in addition to the sol-gel fluorosilanization (FS) process. The water and oil wettability, and oil absorbency properties of the unmodified and modified diatomites were investigated in addition to diatomite characterizations such as chemical content, surface area, particle size distribution, morphology, and modification efficiency. It was revealed that the wettability was changed completely depending on the surface modification agent and the media used, while the oil absorbency property surprisingly did not change. On the other hand, the oil absorbency was worsened by the grinding process, whereas the wettability was not affected.

  9. Impact of natural photosensitizer extraction solvent upon light absorbance in dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Suhaimi, Suriati; Mohamed Siddick, Siti Zubaidah; Ahmad Hambali, Nor Azura Malini; Retnasamy, Vithyacharan; Abdul Wahid, Mohamad Halim; Mohamad Shahimin, Mukhzeer

    2017-02-01

    Natural pigmentations of Ardisia, Bawang Sabrang, Harum Manis mango, Oxalis Triangularis and Rosella were used to study the general trend in performance of dyes as a photosensitizer in the application of dye-sensitized solar cells (DSSCs) based on optical light absorbance and photoelectrochemical characteristics. From the Ultraviolet-Visible Spectrophotometer with the recorded absorption measurements in the range between 400 nm to 800 nm, the dyes extracted from Rosella and Oxalis Triangularis in water solvent exhibited the conversion efficiency up to 0.68% and 0.67%, respectively. The light absorbance peak for dye extracted from Ardisia, Bawang Sabrang, Oxalis Triangularis and Rosella in water and ethanol solvent resulted in the range between 500 nm to 650 nm, while the Harum Manis mango resulted in the broader spectra in both water and ethanol solvent. The light absorbance spectra of each the dyes shows shifted wavelength spectrum when the extracted dye is adsorbed onto TiO2 film surface that might influenced the absorption of light by TiO2 particle in the visible region. The capabilities of the dyes to absorb light when bonded onto the TiO2 photoanode was found to be significant with the current-voltage conversion of the cell. The results demonstrates just the tip of the vastness of natural dyes' (native to tropical region) feasibility and applicability as a photosensitizer.

  10. Heaving buoys, point absorbers and arrays.

    PubMed

    Falnes, Johannes; Hals, Jørgen

    2012-01-28

    Absorption of wave energy may be considered as a phenomenon of interference between incident and radiated waves generated by an oscillating object; a wave-energy converter (WEC) that displaces water. If a WEC is very small in comparison with one wavelength, it is classified as a point absorber (PA); otherwise, as a 'quasi-point absorber'. The latter may be a dipole-mode radiator, for instance an immersed body oscillating in the surge mode or pitch mode, while a PA is so small that it should preferably be a source-mode radiator, for instance a heaving semi-submerged buoy. The power take-off capacity, the WEC's maximum swept volume and preferably also its full physical volume should be reasonably matched to the wave climate. To discuss this matter, two different upper bounds for absorbed power are applied in a 'Budal diagram'. It appears that, for a single WEC unit, a power capacity of only about 0.3 MW matches well to a typical offshore wave climate, and the full physical volume has, unfortunately, to be significantly larger than the swept volume, unless phase control is used. An example of a phase-controlled PA is presented. For a sizeable wave-power plant, an array consisting of hundreds, or even thousands, of mass-produced WEC units is required.

  11. AFM investigation of effect of absorbed water layer structure on growth mechanism of octadecyltrichlorosilane self-assembled monolayer on oxidized silicon

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

    Li, Shaowei; Zheng, Yanjun, E-mail: zhengyj@cup.edu.cn; Chen, Changfeng

    2016-06-28

    The growth mechanism of an octadecyltrichlorosilane (OTS) self-assembled monolayer on a silicon oxide surface at various relative humidities has been investigated. Atomic force microscopy images show that excess water may actually hinder the nucleation and growth of OTS islands. A moderate amount of water is favorable for the nucleation and growth of OTS islands in the initial stage; however, the completion of the monolayer is very slow in the final stage. The growth of OTS islands on a low-water-content surface maintains a relatively constant speed and requires the least amount of time. The mobility of water molecules is thought tomore » play an important role in the OTS monolayers, and a low-mobility water layer provides a steady condition for OTS monolayer growth.« less

  12. Optimization of Multilayer Laminated Film and Absorbent of Vacuum Insulation Panel for Use at High Temperature

    NASA Astrophysics Data System (ADS)

    Araki, Kuninari; Echigoya, Wataru; Tsuruga, Toshimitsu; Kamoto, Daigorou; Matsuoka, Shin-Ichi

    For the energy saving regulation and larger capacity, Vacuum Insulation Panel (VIP) has been used in refrigerators with urethane foam in recent years. VIP for low temperature is constructed by laminated plastic film, using heat welding of each neighboring part for keeping vacuum, so that the performance decrement is very large under high temperature. But recently high efficiency insulation material is desired for high temperature water holding devices (automatic vending machine, heat pump water heater, electric hot-water pot water, etc.), and we especially focused on cost and ability of the laminated plastic film and absorbent for high temperature VIP. We measured the heatproof temperature of plastic films and checked the amount of water vapor and out coming gas on temperature-programmed adsorption in absorbent. These results suggest the suitable laminated film and absorbent system for VIP use at high temperature, and the long-term reliability was evaluated by measuring thermal conductivity of high temperature. As a result it was found that high-retort pouch of CPP (cast polypropylene film) and adding of aluminum coating are the most suitable materials for use in the welded layers of high-temperature VIPs (105°C).

  13. Water pumps

    PubMed Central

    Loo, Donald D F; Wright, Ernest M; Zeuthen, Thomas

    2002-01-01

    The transport of water across epithelia has remained an enigma ever since it was discovered over 100 years ago that water was transported across the isolated small intestine in the absence of osmotic and hydrostatic pressure gradients. While it is accepted that water transport is linked to solute transport, the actual mechanisms are not well understood. Current dogma holds that active ion transport sets up local osmotic gradients in the spaces between epithelial cells, the lateral intercellular spaces, and this in turn drives water transport by local osmosis. In the case of the small intestine, which in humans absorbs about 8 l of water a day, there is no direct evidence for either local osmosis or aquaporin gene expression in enterocytes. Intestinal water absorption is greatly enhanced by glucose, and this is the basis for oral rehydration therapy in patients with secretory diarrhoea. In our studies of the intestinal brush border Na+-glucose cotransporter we have obtained evidence that there is a direct link between the transport of Na+, glucose and water transport, i.e. there is cotransport of water along with Na+ and sugar, that will account for about 50 % of the total water transport across the human intestinal brush border membrane. In this short review we summarize the evidence for water cotransport and propose how this occurs during the enzymatic turnover of the transporter. This is a general property of cotransporters and so we expect that this may have wider implications in the transport of water and other small polar molecules across cell membranes in animals and plants. PMID:12096049

  14. Water pumps.

    PubMed

    Loo, Donald D F; Wright, Ernest M; Zeuthen, Thomas

    2002-07-01

    The transport of water across epithelia has remained an enigma ever since it was discovered over 100 years ago that water was transported across the isolated small intestine in the absence of osmotic and hydrostatic pressure gradients. While it is accepted that water transport is linked to solute transport, the actual mechanisms are not well understood. Current dogma holds that active ion transport sets up local osmotic gradients in the spaces between epithelial cells, the lateral intercellular spaces, and this in turn drives water transport by local osmosis. In the case of the small intestine, which in humans absorbs about 8 l of water a day, there is no direct evidence for either local osmosis or aquaporin gene expression in enterocytes. Intestinal water absorption is greatly enhanced by glucose, and this is the basis for oral rehydration therapy in patients with secretory diarrhoea. In our studies of the intestinal brush border Na+-glucose cotransporter we have obtained evidence that there is a direct link between the transport of Na+, glucose and water transport, i.e. there is cotransport of water along with Na+ and sugar, that will account for about 50 % of the total water transport across the human intestinal brush border membrane. In this short review we summarize the evidence for water cotransport and propose how this occurs during the enzymatic turnover of the transporter. This is a general property of cotransporters and so we expect that this may have wider implications in the transport of water and other small polar molecules across cell membranes in animals and plants.

  15. Molecular dynamics approach to probe PKCβII-ligand interactions and influence of crystal water molecules on these interactions.

    PubMed

    Grewal, Baljinder K; Bhat, Jyotsna; Sobhia, Masilamani Elizabeth

    2015-01-01

    PKCβII is a potential target for therapeutic intervention against pandemic diabetic complications. Present study probes the molecular interactions of PKCβII with its clinically important ligands, viz. ruboxistaurin, enzastaurin and co-crystallized ligand, 2-methyl-1H-indol-3-yl-BIM-1. The essentials of PKCβII-ligand interaction, crystal water-induced alterations in these interactions and key interacting flexible residues are analyzed. Computational methodologies, viz. molecular docking and molecular simulation coupled with molecular mechanics-Poisson-Boltzmann surface area and generalized born surface area (MM-PB[GB]SA) are employed. The structural changes in the presence and absence of crystal water molecules in PKCβII ATP binding site residues, and its interaction with bound ligand, are identified. Difference in interaction of selective and nonselective ligand with ATP binding site residues of PKCβII is reported. The study showed that the nonbonding interactions contribute significantly in PKCβII-ligand binding and presence of crystal water molecules affects the interactions. The findings of present work may integrate the new aspects in the drug design process of PKCβII inhibitors.

  16. Candidate chemical systems for air cooled solar powered, absorption air conditioner design. Part I. Organic absorbent systems

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

    Biermann, W. J.

    1978-01-01

    All the available experimental evidence suggests that the optimum ''organic'' absorbent/refrigerant combination would be a methane derivative with a single hydrogen atom with chlorine and fluorine atoms in the other sites, as refrigerant. This would be hydrogen bonded to an absorbent molecule containing the group =NC/sup -/O, with the substituent groups being such that no steric hindrance took place. Cycle analyses showed that the ratio of internal heat transfer to cooling would be large, probably impractically so in view of the high coefficient of performance needed for solar driven cooling and the additional handicap of heat rejection to the atmosphere.more » A more promising approach would be to reduce the internal heat transfer per unit of space cooling by selecting a refrigerant with a high latent heat of vaporization and selecting an absorbent with suitable properties.« less

  17. Soft and broadband infrared metamaterial absorber based on gold nanorod/liquid crystal hybrid with tunable total absorption

    PubMed Central

    Su, Zhaoxian; Yin, Jianbo; Zhao, Xiaopeng

    2015-01-01

    We design a soft infrared metamaterial absorber based on gold nanorods dispersed in liquid crystal (LC) placed on a gold film and theoretically investigate its total absorption character. Because the nanorods align with the LC molecule, the gold nanorods/LC hybrid exhibits different permittivity as a function of tilt angle of LC. At a certain tilt angle, the absorber shows an omnidirectional total absorption effect. By changing the tilt angle of LC by an external electric field, the total absorption character can be adjusted. The total absorption character also depends on the concentration, geometric dimension of nanorods, and defect of nanorod arrangement in LC. When the LC contains different size of gold nanorods, a broadband absorption can be easily realized. The characteristics including flexibility, omnidirectional, broadband and tunablility make the infrared metamaterial absorber possess potential use in smart metamaterial devices. PMID:26576660

  18. MO-FG-CAMPUS-IeP1-05: New Ionization Chamber Dosimetry of Absorbed Dose to Water in Diagnostic KV X-Ray Beams

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

    Araki, F; Ohno, T

    Purpose: To develop new ionization chamber dosimetry of absorbed dose to water in diagnostic kV x-ray beams, by using a beam quality conversion factor, kQ, for Co-60 to kV x-ray and an ionization conversion factor for a water-substitute plastic phantom. Methods: kQ was calculated for aluminum half value-layers (Al-HVLs) of 1.5 mm to 8 mm which were generated by kV x-ray beams of 50 to 120 kVp. Twenty-two energy spectra for ten effective energies (Eeff) were calculated by a SpecCalc program. Depth doses in water were calculated at 5 × 5 to 30 × 30 cm{sup 2} fields. Output factorsmore » were also obtained from the dose ratio for a 10 × 10 cm{sup 2} field. kQ was obtained for a PTW30013 Former ion chamber. In addition, an ionization conversion factor of the PWDT phantom to water was calculated. All calculations were performed with EGSnrc/cavity code and egs-chamber codes. Results: The x-ray beam energies for 1.5 mm to 8 mm Al-HVLs ranged in Eeff of 25.7 to 54.3 keV. kQ for 1.5 mm to 8 mm Al-HVLs were 0.831 to 0.897, at 1 and 2 cm depths for a 10 × 10 cm2 field. Similarly, output factors for 5 × 5 to 30 × 30 cm{sup 2} fields were 0.937 to 1.033 for 25.7 keV and 0.857 to 1.168 for 54.3 keV. The depth dose in a PWDT phantom decreased up to 5% compared to that in water at depth of ten percent of maximum dose for 1.5 mm Al-HVL. The ionization ratios of water/PWDT phantoms for the PTW30013 chamber were 1.012 to 1.007 for 1.5 mm to 8 mm Al-HVLs at 1 cm depth. Conclusion: It became possible to directly measure the absorbed dose to water with the ionization chamber in diagnostic kV x-ray beams, by using kQ and the PWDT phantom.« less

  19. A novel catalytic ceramic membrane fabricated with CuMn2O4 particles for emerging UV absorbers degradation from aqueous and membrane fouling elimination.

    PubMed

    Guo, Yang; Song, Zilong; Xu, Bingbing; Li, Yanning; Qi, Fei; Croue, Jean-Philippe; Yuan, Donghai

    2018-02-15

    A novel catalytic ceramic membrane (CM) for improving ozonation and filtration performance was fabricated by surface coating CuMn 2 O 4 particles on a tubular CM. The degradation of ultraviolet (UV) absorbers, reduction of toxicity, elimination of membrane fouling and catalytic mechanism were investigated. The characterization results suggested the particles were well-fixed on membrane surface. The modified membrane showed improved benzophenone-3 removal performance (from 28% to 34%), detoxification (EC 50 as 12.77%) and the stability of catalytic activity. In the degradation performance of model UV absorbers, the developed membrane significantly decreased the UV254 and DOC values in effluent. Compared with a virgin CM, this CM ozonation increased water flux as 29.9% by in-situ degrade effluent organic matters. The CuMn 2 O 4 modified membrane enhanced the ozone self-decompose to generate O 2 - and initiated the chain reaction of ozone decomposition, and subsequently reacted with molecule ozone to produce OH. Additionally, CM was able to promote the interaction between ozone and catalyst/organic chemicals to form H 2 O 2 that promoted the formation of OH. This catalytic ceramic membrane combining with ozonation showed potential applications in emerging pollutant degradation and membrane fouling elimination, and acted as a novel ternary technology for wastewater treatment and water reuse. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Thermodynamic analysis of water molecules at the surface of proteins and applications to binding site prediction and characterization.

    PubMed

    Beuming, Thijs; Che, Ye; Abel, Robert; Kim, Byungchan; Shanmugasundaram, Veerabahu; Sherman, Woody

    2012-03-01

    Water plays an essential role in determining the structure and function of all biological systems. Recent methodological advances allow for an accurate and efficient estimation of the thermodynamic properties of water molecules at the surface of proteins. In this work, we characterize these thermodynamic properties and relate them to various structural and functional characteristics of the protein. We find that high-energy hydration sites often exist near protein motifs typically characterized as hydrophilic, such as backbone amide groups. We also find that waters around alpha helices and beta sheets tend to be less stable than waters around loops. Furthermore, we find no significant correlation between the hydration site-free energy and the solvent accessible surface area of the site. In addition, we find that the distribution of high-energy hydration sites on the protein surface can be used to identify the location of binding sites and that binding sites of druggable targets tend to have a greater density of thermodynamically unstable hydration sites. Using this information, we characterize the FKBP12 protein and show good agreement between fragment screening hit rates from NMR spectroscopy and hydration site energetics. Finally, we show that water molecules observed in crystal structures are less stable on average than bulk water as a consequence of the high degree of spatial localization, thereby resulting in a significant loss in entropy. These findings should help to better understand the characteristics of waters at the surface of proteins and are expected to lead to insights that can guide structure-based drug design efforts. Copyright © 2011 Wiley Periodicals, Inc.

  1. New biochemical insight of conserved water molecules at catalytic and structural Zn2+ ions in human matrix metalloproteinase-I: a study by MD-simulation.

    PubMed

    Chakrabarti, Bornali; Bairagya, Hridoy R; Mukhopadhyay, Bishnu P; Sekar, K

    2017-02-01

    Human matrix metalloproteinase (MMP)-1 or collagenase-1 plays a significant role in embryonic development, tissue remodeling, and is also involved in several diseases like arthritis, metastasis, etc. Molecular dynamics simulation studies on hMMP-1 X-ray structures (PDB Id. 1CGE, 1CGF, 1CGL, 1HFC, and 2TCL) suggest that the three conserved water molecules (W H/1 , W I , W S ) are coordinated with catalytic zinc (Zn C ), and one water molecule (W) is associated at structural zinc ion (Zn S ). Transition of the coordination geometry around Zn C from tetrahedral to octahedral and tetrahedral to trigonal bipyramidal at Zn S are also observed during the dynamics. Recognition of two zinc ions through water mediated bridges (Zn C - W H (W 1 )…W 2 ….H 183 - Zn S ) and stabilization of secondary coordination zone around the metal ions indicates the possibility of Zn C …Zn S coupled catalytic mechanism in hMMP-I. This study not only reveals a functionally important role of conserved water molecules in hMMP-I but also highlights the involvement of other non catalytic residues, such as S172 and D170 in the catalytic mechanism. The results obtained in this study could be relevant for importance of conserved water mediated recognition site of the sequence residue id. 202(RWTNNFREY)210, interaction of W(tryptophan)203 to zinc bound histidine, their influence on the water molecules that are involved in bridging between Zn C and Zn S , and structure-based design of specific hMMP inhibitors. Graphical abstract Water mediated recognition of structural and catalytic zinc ions of hMMP-1 structure (MD simulatated conformation).

  2. Comparison of the IAEA TRS-398 and AAPM TG-51 absorbed dose to water protocols in the dosimetry of high-energy photon and electron beams

    NASA Astrophysics Data System (ADS)

    Saiful Huq, M.; Andreo, Pedro; Song, Haijun

    2001-11-01

    The International Atomic Energy Agency (IAEA TRS-398) and the American Association of Physicists in Medicine (AAPM TG-51) have published new protocols for the calibration of radiotherapy beams. These protocols are based on the use of an ionization chamber calibrated in terms of absorbed dose to water in a standards laboratory's reference quality beam. This paper compares the recommendations of the two protocols in two ways: (i) by analysing in detail the differences in the basic data included in the two protocols for photon and electron beam dosimetry and (ii) by performing measurements in clinical photon and electron beams and determining the absorbed dose to water following the recommendations of the two protocols. Measurements were made with two Farmer-type ionization chambers and three plane-parallel ionization chamber types in 6, 18 and 25 MV photon beams and 6, 8, 10, 12, 15 and 18 MeV electron beams. The Farmer-type chambers used were NE 2571 and PTW 30001, and the plane-parallel chambers were a Scanditronix-Wellhöfer NACP and Roos, and a PTW Markus chamber. For photon beams, the measured ratios TG-51/TRS-398 of absorbed dose to water Dw ranged between 0.997 and 1.001, with a mean value of 0.999. The ratios for the beam quality correction factors kQ were found to agree to within about +/-0.2% despite significant differences in the method of beam quality specification for photon beams and in the basic data entering into kQ. For electron beams, dose measurements were made using direct ND,w calibrations of cylindrical and plane-parallel chambers in a 60Co gamma-ray beam, as well as cross-calibrations of plane-parallel chambers in a high-energy electron beam. For the direct ND,w calibrations the ratios TG-51/TRS-398 of absorbed dose to water Dw were found to lie between 0.994 and 1.018 depending upon the chamber and electron beam energy used, with mean values of 0.996, 1.006, and 1.017, respectively, for the cylindrical, well-guarded and not well-guarded plane

  3. MO-AB-BRA-03: Calorimetry-Based Absorbed Dose to Water Measurements Using Interferometry

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

    Flores-Martinez, E; Malin, M; DeWerd, L

    2015-06-15

    Purpose: Interferometry-based calorimetry is a novel technique to measure radiation-induced temperature changes allowing the measurement of absorbed dose to water (ADW). There are no mechanical components in the field. This technique also has the possibility of obtaining 2D dose distributions. The goal of this investigation is to calorimetrically-measure doses between 2.5 and 5 Gy over a single projection in a photon beam using interferometry and compare the results with doses calculated using the TG-51 linac calibration. Methods: ADW was determined by measuring radiation-induced phase shifts (PSs) of light passing through water irradiated with a 6 MV photon beam. A 9×9×9more » cm{sup 3} glass phantom filled with water and placed in an arm of a Michelson interferometer was irradiated with 300, 400, 500 and 600 monitor units. The whole system was thermally insulated to achieve sufficient passive temperature control. The depth of measurement was 4.5 cm with a field size of 7×7 cm{sup 2}. The intensity of the fringe pattern was monitored with a photodiode and used to calculate the time-dependent PS curve. Data was acquired 60 s before and after the irradiation. The radiation-induced PS was calculated by taking the difference in the pre- and post-irradiation drifts extrapolated to the midpoint of the irradiation. Results were compared to computed doses. Results: Average comparison of calculated ADW values with interferometry-measured values showed an agreement to within 9.5%. k=1 uncertainties were 4.3% for calculations and 14.7% for measurements. The dominant source of uncertainty for the measurements was a temperature drift of about 30 µK/s caused by heat conduction from the interferometer’s surroundings. Conclusion: This work presented the first absolute ADW measurements using interferometry in the dose range of linac-based radiotherapy. Future work to improve measurements’ reproducibility includes the implementation of active thermal control techniques.« less

  4. Handling of computational in vitro/in vivo correlation problems by Microsoft Excel: V. Predictive absorbability models.

    PubMed

    Langenbucher, Frieder

    2007-08-01

    This paper discusses Excel applications related to the prediction of drug absorbability from physicochemical constants. PHDISSOC provides a generalized model for pH profiles of electrolytic dissociation, water solubility, and partition coefficient. SKMODEL predicts drug absorbability, based on a log-log plot of water solubility and O/W partitioning; augmented by additional features such as electrolytic dissociation, melting point, and the dose administered. GIABS presents a mechanistic model of g.i. drug absorption. BIODATCO presents a database compiling relevant drug data to be used for quantitative predictions.

  5. Grand canonical Monte Carlo simulation of the adsorption isotherms of water molecules on model soot particles

    NASA Astrophysics Data System (ADS)

    Moulin, F.; Picaud, S.; Hoang, P. N. M.; Jedlovszky, P.

    2007-10-01

    The grand canonical Monte Carlo method is used to simulate the adsorption isotherms of water molecules on different types of model soot particles. The soot particles are modeled by graphite-type layers arranged in an onionlike structure that contains randomly distributed hydrophilic sites, such as OH and COOH groups. The calculated water adsorption isotherm at 298K exhibits different characteristic shapes depending both on the type and the location of the hydrophilic sites and also on the size of the pores inside the soot particle. The different shapes of the adsorption isotherms result from different ways of water aggregation in or/and around the soot particle. The present results show the very weak influence of the OH sites on the water adsorption process when compared to the COOH sites. The results of these simulations can help in interpreting the experimental isotherms of water adsorbed on aircraft soot.

  6. Optimization of water absorbing exopolysaccharide production on local cheap substrates by Bacillus strain CMG1403 using one variable at a time approach.

    PubMed

    Muhammadi; Afzal, Muhammad

    2014-01-01

    Optimum culture conditions, and carbon and nitrogen sources for production of water absorbing exopolysaccharide by Bacillus strain CMG1403 on local cheap substrates were determined using one variable at a time approach. Carbon source was found to be sole substrate for EPS biosynthesis in the presence of yeast extract that supported the growth only and hence, indirectly enhanced the EPS yield. Whereas, urea only coupled with carbon source could enhance the EPS production but no effect on growth. The maximum yield of EPS was obtained when Bacillus strain CMG1403 was grown statically in neutral minimal medium with 25% volumetric aeration at 30°C for 10 days. Under these optimum conditions, a maximum yield of 2.71±0.024, 3.82±0.005, 4.33±0.021, 4.73±0.021, 4.85±0.024, and 5.52±0.016 g/L culture medium was obtained with 20 g (sugar) of sweet whey, glucose, fructose, sucrose, cane molasses and sugar beet the most efficient one respectively as carbon sources. Thus, the present study showed that under optimum culture conditions, the local cheap substrates could be superior and efficient alternatives to synthetic carbon sources providing way for an economical production of water absorbing EPS by indigenous soil bacterium Bacillus strain CMG1403.

  7. Reflection measurements of microwave absorbers

    NASA Astrophysics Data System (ADS)

    Baker, Dirk E.; van der Neut, Cornelis A.

    1988-12-01

    A swept-frequency interferometer is described for making rapid, real-time assessments of localized inhomogeneities in planar microwave absorber panels. An aperture-matched exponential horn is used to reduce residual reflections in the system to about -37 dB. This residual reflection is adequate for making comparative measurements on planar absorber panels whose reflectivities usually fall in the -15 to -25 dB range. Reflectivity measurements on a variety of planar absorber panels show that multilayer Jaumann absorbers have the greatest inhomogeneity, while honeycomb absorbers generally have excellent homogeneity within a sheet and from sheet to sheet. The test setup is also used to measure the center frequencies of resonant absorbers. With directional couplers and aperture-matched exponential horns, the technique can be easily applied in the standard 2 to 40 GHz waveguide bands.

  8. Detection of water molecules in inert gas based plasma by the ratios of atomic spectral lines

    NASA Astrophysics Data System (ADS)

    Bernatskiy, A. V.; Ochkin, V. N.

    2017-01-01

    A new approach is considered to detect the water leaks in inert plasma-forming gas present in the reactor chamber. It is made up of the intensity ratio of D α and H α spectral lines in combination with O, Ar and Xe lines intensity. The concentrations of H2O, O, H and D particles have been measured with high sensitivity. At the D2 admixture pressure {{p}{{\\text{D}\\text{2}}}}   =  0.025 mbar, we used the acquisition time of 10 s to measure the rate of water molecules injected from the outside, Γ0  =  1.4 · 10-9 mbar · m3 · s-1, and the incoming water molecules to plasma, Γ  =  5 ·10-11 mbar · m3 · s-1. The scaling proves that at small D2 admixtures (10-4 mbar), the leaks with the rates Γ0  ≈  6 · 10-12 mbar · m3 · s-1 and Γ  ≈  2 · 10-13 mbar · m3 · s-1 can be detected and measured. The difference between Γ0 and Γ values is due to the high degree of H2O dissociation, which can be up to 97-98%.

  9. Diamond detector in absorbed dose measurements in high-energy linear accelerator photon and electron beams.

    PubMed

    Ravichandran, Ramamoorthy; Binukumar, John Pichy; Al Amri, Iqbal; Davis, Cheriyathmanjiyil Antony

    2016-03-08

    Diamond detectors (DD) are preferred in small field dosimetry of radiation beams because of small dose profile penumbras, better spatial resolution, and tissue-equivalent properties. We investigated a commercially available 'microdiamond' detector in realizing absorbed dose from first principles. A microdiamond detector, type TM 60019 with tandem electrometer is used to measure absorbed doses in water, nylon, and PMMA phantoms. With sensitive volume 0.004 mm3, radius 1.1mm, thickness 1 x10(-3) mm, the nominal response is 1 nC/Gy. It is assumed that the diamond detector could collect total electric charge (nC) developed during irradiation at 0 V bias. We found that dose rate effect is less than 0.7% for changing dose rate by 500 MU/min. The reproducibility in obtaining readings with diamond detector is found to be ± 0.17% (1 SD) (n = 11). The measured absorbed doses for 6 MV and 15 MV photons arrived at using mass energy absorption coefficients and stop-ping power ratios compared well with Nd, water calibrated ion chamber measured absorbed doses within 3% in water, PMMA, and nylon media. The calibration factor obtained for diamond detector confirmed response variation is due to sensitivity due to difference in manufacturing process. For electron beams, we had to apply ratio of electron densities of water to carbon. Our results qualify diamond dosimeter as a transfer standard, based on long-term stability and reproducibility. Based on micro-dimensions, we recommend these detectors for pretreatment dose verifications in small field irradiations like stereotactic treatments with image guidance.

  10. Corrosion resistant neutron absorbing coatings

    DOEpatents

    Choi, Jor-Shan [El Cerrito, CA; Farmer, Joseph C [Tracy, CA; Lee, Chuck K [Hayward, CA; Walker, Jeffrey [Gaithersburg, MD; Russell, Paige [Las Vegas, NV; Kirkwood, Jon [Saint Leonard, MD; Yang, Nancy [Lafayette, CA; Champagne, Victor [Oxford, PA

    2012-05-29

    A method of forming a corrosion resistant neutron absorbing coating comprising the steps of spray or deposition or sputtering or welding processing to form a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material. Also a corrosion resistant neutron absorbing coating comprising a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material.

  11. Corrosion resistant neutron absorbing coatings

    DOEpatents

    Choi, Jor-Shan; Farmer, Joseph C; Lee, Chuck K; Walker, Jeffrey; Russell, Paige; Kirkwood, Jon; Yang, Nancy; Champagne, Victor

    2013-11-12

    A method of forming a corrosion resistant neutron absorbing coating comprising the steps of spray or deposition or sputtering or welding processing to form a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material. Also a corrosion resistant neutron absorbing coating comprising a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material.

  12. Long term measurements of light absorbing particles on tropical glaciers

    NASA Astrophysics Data System (ADS)

    Schmitt, C. G.; Sanchez Rodriguez, W.; Arnott, W. P.; All, J.; Schwarz, J. P.

    2016-12-01

    We present results of six years of measurements of light absorbing particles (LAP) on glaciers of the Cordillera Blanca mountain range in Peru. Tropical glaciers are important sources of water for human consumption, agriculture, and hydroelectric power in the region. Regular measurements in the dry season show that light absorbing particle concentrations are generally low (equivalent to the absorption equivalent of 5-30 nanograms of black carbon per gram of snow) during non-El Nino years while values increase substantially during the recent El Nino. Two years of monthly measurements at two glaciers show that fresh snow LAP concentration are very low while LAP levels increase dramatically during snow-less periods.

  13. Polydimethylsiloxane (PDMS) modulates CD38 expression, absorbs retinoic acid and may perturb retinoid signalling.

    PubMed

    Futrega, Kathryn; Yu, Jianshi; Jones, Jace W; Kane, Maureen A; Lott, William B; Atkinson, Kerry; Doran, Michael R

    2016-04-21

    Polydimethylsiloxane (PDMS) is the most commonly used material in the manufacture of customized cell culture devices. While there is concern that uncured PDMS oligomers may leach into culture medium and/or hydrophobic molecules may be absorbed into PDMS structures, there is no consensus on how or if PDMS influences cell behaviour. We observed that human umbilical cord blood (CB)-derived CD34(+) cells expanded in standard culture medium on PDMS exhibit reduced CD38 surface expression, relative to cells cultured on tissue culture polystyrene (TCP). All-trans retinoic acid (ATRA) induces CD38 expression, and we reasoned that this hydrophobic molecule might be absorbed by PDMS. Through a series of experiments we demonstrated that ATRA-mediated CD38 expression was attenuated when cultures were maintained on PDMS. Medium pre-incubated on PDMS for extended durations resulted in a time-dependant reduction of ATRA in the medium and increasingly attenuated CD38 expression. This indicated a time-dependent absorption of ATRA into the PDMS. To better understand how PDMS might generally influence cell behaviour, Ingenuity Pathway Analysis (IPA) was used to identify potential upstream regulators. This analysis was performed for differentially expressed genes in primary cells including CD34(+) haematopoietic progenitor cells, mesenchymal stromal cells (MSC), and keratinocytes, and cell lines including prostate cancer epithelial cells (LNCaP), breast cancer epithelial cells (MCF-7), and myeloid leukaemia cells (KG1a). IPA predicted that the most likely common upstream regulator of perturbed pathways was ATRA. We demonstrate here that ATRA is absorbed by PDMS in a time-dependent manner and results in the concomitant reduced expression of CD38 on the cell surface of CB-derived CD34(+) cells.

  14. Flight of a cytidine deaminase complex with an imperfect transition state analogue inhibitor: mass spectrometric evidence for the presence of a trapped water molecule.

    PubMed

    Schroeder, Gottfried K; Zhou, Li; Snider, Mark J; Chen, Xian; Wolfenden, Richard

    2012-08-14

    Cytidine deaminase (CDA) binds the inhibitor zebularine as its 3,4-hydrate (K(d) ~ 10(-12) M), capturing all but ~5.6 kcal/mol of the free energy of binding expected of an ideal transition state analogue (K(tx) ~ 10(-16) M). On the basis of its entropic origin, that shortfall was tentatively ascribed to the trapping of a water molecule in the enzyme-inhibitor complex, as had been observed earlier for product uridine [Snider, M. J., and Wolfenden, R. (2001) Biochemistry 40, 11364-11371]. Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) of CDA nebularized in the presence of saturating 5-fluorozebularine reveals peaks corresponding to the masses of E(2)Zn(2)W(2) (dimeric Zn-CDA with two water molecules), E(2)Zn(2)W(2)Fz, and E(2)Zn(2)W(2)Fz(2), where Fz represents the 3,4-hydrate of 5-fluorozebularine. In the absence of an inhibitor, E(2)Zn(2) is the only dimeric species detected, with no additional water molecules. Experiments conducted in H(2)(18)O indicate that the added mass W represents a trapped water molecule rather than an isobaric ammonium ion. This appears to represent the first identification of an enzyme-bound water molecule at a subunit interface (active site) using FTICR-MS. The presence of a 5-fluoro group appears to retard the decomposition of the inhibitory complex kinetically in the vapor phase, as no additional dimeric complexes (other than E(2)Zn(2)) are observed when zebularine is used in place of 5-fluorozebularine. Substrate competition assays show that in solution zebularine is released from CDA (k(off) > 0.14 s(-1)) much more rapidly than is 5-fluorozebularine (k(off) = 0.014 s(-1)), despite the greater thermodynamic stability of the zebularine complex.

  15. Real Time Monitoring of Dissolved Organic Carbon Concentration and Disinfection By-Product Formation Potential in a Surface Water Treatment Plant with Simulaneous UV-VIS Absorbance and Fluorescence Excitation-Emission Mapping

    NASA Astrophysics Data System (ADS)

    Gilmore, A. M.

    2015-12-01

    This study describes a method based on simultaneous absorbance and fluorescence excitation-emission mapping for rapidly and accurately monitoring dissolved organic carbon concentration and disinfection by-product formation potential for surface water sourced drinking water treatment. The method enables real-time monitoring of the Dissolved Organic Carbon (DOC), absorbance at 254 nm (UVA), the Specific UV Absorbance (SUVA) as well as the Simulated Distribution System Trihalomethane (THM) Formation Potential (SDS-THMFP) for the source and treated water among other component parameters. The method primarily involves Parallel Factor Analysis (PARAFAC) decomposition of the high and lower molecular weight humic and fulvic organic component concentrations. The DOC calibration method involves calculating a single slope factor (with the intercept fixed at 0 mg/l) by linear regression for the UVA divided by the ratio of the high and low molecular weight component concentrations. This method thus corrects for the changes in the molecular weight component composition as a function of the source water composition and coagulation treatment effects. The SDS-THMFP calibration involves a multiple linear regression of the DOC, organic component ratio, chlorine residual, pH and alkalinity. Both the DOC and SDS-THMFP correlations over a period of 18 months exhibited adjusted correlation coefficients with r2 > 0.969. The parameters can be reported as a function of compliance rules associated with required % removals of DOC (as a function of alkalinity) and predicted maximum contaminant levels (MCL) of THMs. The single instrument method, which is compatible with continuous flow monitoring or grab sampling, provides a rapid (2-3 minute) and precise indicator of drinking water disinfectant treatability without the need for separate UV photometric and DOC meter measurements or independent THM determinations.

  16. Deuterated water in low-mass protostars

    NASA Astrophysics Data System (ADS)

    Coutens, Audrey; Vastel, Charlotte; Chess Collaboration; Wish Collaboration; Hexos Collaboration

    2013-07-01

    In addition to its dominant role in the cooling of warm gas and in the oxygen chemistry, water is a primordial species in the emergence of life, and comets may have brought a large fraction to Earth to form the oceans. Observations of deuterated water are an important complement for studies of H2O to understand how water forms and how it has evolved from cold prestellar cores to protoplanetary disks and consequently oceans for the Earth's specific, but probably not isolated, case. Several deuterated water transitions were observed with the Herschel/HIFI (Heterodyne Instrument for Far Infrared) instrument towards three low-mass protostars: IRAS 16293-2422, NGC1333 IRAS4A and NGC1333 IRAS4B. In the first source, both HDO and D2O lines are detected, thanks to the unbiased spectral survey carried out by the CHESS key program (Vastel et al. 2010, Coutens et al. 2013a). In the framework of a collaboration between the CHESS, WISH and HEXOS programs, two HDO key lines were observed towards the two other protostars. In addition, complementary observations were carried out with several ground-based single-dish telescopes (IRAM-30m, JCMT, APEX). We used the non-LTE RATRAN spherical model (Hogerheijde & van der Tak 2000) to determine the HDO abundance distribution throughout the protostellar envelope. An abundance jump at 100 K is required to reproduce the line profiles. Indeed, water molecules trapped in the icy grain mantles thermally desorb in the hot corinos, the inner warm regions of the protostellar envelopes. We also obtain that it is necessary to add a water-rich external absorbing layer to reproduce the absorbing components of the HDO and D2O fundamental transitions in all sources (Coutens et al. 2012, 2013a,b). The results derived for the different sources will be then presented and discussed.

  17. Multiple-Path-Length Optical Absorbance Cell

    NASA Technical Reports Server (NTRS)

    2001-01-01

    An optical absorbance cell that offers a selection of multiple optical path lengths has been developed as part of a portable spectrometric instrument that measures absorption spectra of small samples of water and that costs less than does a conventional, non-portable laboratory spectrometer. The instrument is intended, more specifically, for use in studying colored dissolved organic matter (CDOM) in seawater, especially in coastal regions. Accurate characterization of CDOM is necessary for building bio-optical mathematical models of seawater. The multiple path lengths of the absorption cell afford a wide range of sensitivity needed for measuring the optical absorbances associated with the wide range of concentrations of CDOM observed in nature. The instrument operates in the wavelength range of 370 to 725 nm. The major subsystems of the instrument (see figure) include a color-balanced light source; the absorption cell; a peristaltic pump; a high-precision, low-noise fiber optic spectrometer; and a laptop or other personal computer. A fiber-optic cable transmits light from the source to the absorption cell. Other optical fibers transmit light from the absorption cell to the spectrometer,

  18. Stable high-power saturable absorber based on polymer-black-phosphorus films

    NASA Astrophysics Data System (ADS)

    Mao, Dong; Li, Mingkun; Cui, Xiaoqi; Zhang, Wending; Lu, Hua; Song, Kun; Zhao, Jianlin

    2018-01-01

    Black phosphorus (BP), a rising two-dimensional material with a layer-number-dependent direct bandgap of 0.3-1.5 eV, is very interesting for optoelectronics applications from near- to mid-infrared wavebands. In the atmosphere, few-layer BP tends to be oxidized or degenerated during interacting with lasers. Here, we fabricate few-layer BP nanosheets based on a liquid exfoliation method using N-methylpyrrolidone as the dispersion liquid. By incorporating BP nanosheets with polymers (polyvinyl alcohol or high-melting-point polyimide), two flexible filmy BP saturable absorbers are fabricated to realize passive mode locking in erbium-doped fiber lasers. The polymer-BP saturable absorber, especially the polyimide-BP saturable absorber, can prevent the oxidation or water-induced etching under high-power laser illuminations, providing a promising candidate for Q-switchers, mode lockers, and light modulators.

  19. Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks

    NASA Astrophysics Data System (ADS)

    Byun, Jeehye; Patel, Hasmukh A.; Thirion, Damien; Yavuz, Cafer T.

    2016-11-01

    Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow.

  20. Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks

    PubMed Central

    Byun, Jeehye; Patel, Hasmukh A.; Thirion, Damien; Yavuz, Cafer T.

    2016-01-01

    Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow. PMID:27830697

  1. Counterflow absorber for an absorption refrigeration system

    DOEpatents

    Reimann, Robert C.

    1984-01-01

    An air-cooled, vertical tube absorber for an absorption refrigeration system is disclosed. Strong absorbent solution is supplied to the top of the absorber and refrigerant vapor is supplied to the bottom of the absorber to create a direct counterflow of refrigerant vapor and absorbent solution in the absorber. The refrigeration system is designed so that the volume flow rate of refrigerant vapor in the tubes of the absorber is sufficient to create a substantially direct counterflow along the entire length of each tube in the absorber. This provides several advantages for the absorber such as higher efficiency and improved heat transfer characteristics, and allows improved purging of non-condensibles from the absorber.

  2. Hyperfine coupling constants on inner-sphere water molecules of a triazacyclononane-based Mn(II) complex and related systems relevant as MRI contrast agents.

    PubMed

    Patinec, Véronique; Rolla, Gabriele A; Botta, Mauro; Tripier, Raphaël; Esteban-Gómez, David; Platas-Iglesias, Carlos

    2013-10-07

    We report the synthesis of the ligand H2MeNO2A (1,4-bis(carboxymethyl)-7-methyl-1,4,7-triazacyclononane) and a detailed experimental and computational study of the hyperfine coupling constants (HFCCs) on the inner-sphere water molecules of [Mn(MeNO2A)] and related Mn(2+) complexes relevant as potential contrast agents in magnetic resonance imaging (MRI). Nuclear magnetic relaxation dispersion (NMRD) profiles, (17)O NMR chemical shifts, and transverse relaxation rates of aqueous solutions of [Mn(MeNO2A)] were recorded to determine the parameters governing the relaxivity in this complex and the (17)O and (1)H HFCCs. DFT calculations (TPSSh model) performed in aqueous solution (PCM model) on the [Mn(MeNO2A)(H2O)]·xH2O and [Mn(EDTA)(H2O)](2-)·xH2O (x = 0-4) systems were used to determine theoretically the (17)O and (1)H HFCCs responsible for the (17)O NMR chemical shifts and the scalar contributions to (17)O and (1)H NMR relaxation rates. The use of a mixed cluster/continuum approach with the explicit inclusion of a few second-sphere water molecules is critical for an accurate calculation of HFCCs of coordinated water molecules. The impact of complex dynamics on the calculated HFCCs was evaluated with the use of molecular dynamics simulations within the atom-centered density matrix propagation (ADMP) approach. The (17)O and (1)H HFCCs calculated for these complexes and related systems show an excellent agreement with the experimental data. Both the (1)H and (17)O HFCCs (A(iso) values) are dominated by the spin delocalization mechanism. The A(iso) values are significantly affected by the distance between the oxygen atom of the coordinated water molecule and the Mn(2+) ion, as well as by the orientation of the water molecule plane with respect to the Mn-O vector.

  3. Environmentally friendly and breathable wet-laid hydroentangled nonwovens for personal hygiene care with excellent water absorbency and flushability

    NASA Astrophysics Data System (ADS)

    Deng, Chao; Liu, Wanjun; Zhang, Yinjiang; Huang, Chen; Zhao, Yi; Jin, Xiangyu

    2018-04-01

    Developing wet-laid papers with a good wet strength remains a longstanding challenge in the papermaking industry. In this study, hydroentanglement, a mechanical bonding technique is developed to consolidate the wet-laid fibre web. The results indicate that wet tensile strength, ductile stretching property, softness, air permeability and water absorbency of the wet-laid fibre web are significantly improved by hydroentanglement. In addition, the abrasion test shows that the dusting off rate of wet-laid fibre web can be effectively reduced through hydroentanglement. Moreover, the disintegration experiment proves that wet-laid hydroentangled nonwovens could be easily dispersed when compared with conventional carded hydroentangled nonwovens. Therefore, the new wet-laid hydroentangled nonwovens can maintain excellent performance in a wet state, showing a great potential for personal hygiene applications.

  4. Environmentally friendly and breathable wet-laid hydroentangled nonwovens for personal hygiene care with excellent water absorbency and flushability.

    PubMed

    Deng, Chao; Liu, Wanjun; Zhang, Yinjiang; Huang, Chen; Zhao, Yi; Jin, Xiangyu

    2018-04-01

    Developing wet-laid papers with a good wet strength remains a longstanding challenge in the papermaking industry. In this study, hydroentanglement, a mechanical bonding technique is developed to consolidate the wet-laid fibre web. The results indicate that wet tensile strength, ductile stretching property, softness, air permeability and water absorbency of the wet-laid fibre web are significantly improved by hydroentanglement. In addition, the abrasion test shows that the dusting off rate of wet-laid fibre web can be effectively reduced through hydroentanglement. Moreover, the disintegration experiment proves that wet-laid hydroentangled nonwovens could be easily dispersed when compared with conventional carded hydroentangled nonwovens. Therefore, the new wet-laid hydroentangled nonwovens can maintain excellent performance in a wet state, showing a great potential for personal hygiene applications.

  5. Water and complex organic molecules in the warm inner regions of solar-type protostars

    NASA Astrophysics Data System (ADS)

    Coutens, A.; Jørgensen, J. K.; Persson, M. V.; Lykke, J. M.; Taquet, V.; van Dishoeck, E. F.; Vastel, C.; Wampfler, S. F.

    2015-12-01

    Water and complex organic molecules play an important role in the emergence of Life. They have been detected in different types of astrophysical environments (protostars, prestellar cores, outflows, protoplanetary disks, comets, etc). In particular, they show high abundances towards the warm inner regions of protostars, where the icy grain mantles thermally desorb. Can a part of the molecular content observed in these regions be preserved during the star formation process and incorporated into asteroids and comets, that can deliver it to planetary embryos through impacts? By comparison with cometary studies, interferometric observations of solar-type protostars can help to address this important question. We present recent results obtained with the Plateau de Bure interferometer about water deuteration, glycolaldehyde and ethylene glycol towards the low-mass protostar NGC 1333 IRAS2A.

  6. Wave energy extraction by coupled resonant absorbers.

    PubMed

    Evans, D V; Porter, R

    2012-01-28

    In this article, a range of problems and theories will be introduced that will build towards a new wave energy converter (WEC) concept, with the acronym 'ROTA' standing for resonant over-topping absorber. First, classical results for wave power absorption for WECs constrained to operate in a single degree of freedom will be reviewed and the role of resonance in their operation highlighted. Emphasis will then be placed on how the introduction of further resonances can improve power take-off characteristics by extending the range of frequencies over which the efficiency is close to a theoretical maximum. Methods for doing this in different types of WECs will be demonstrated. Coupled resonant absorbers achieve this by connecting a WEC device equipped with its own resonance (determined from a hydrodynamic analysis) to a new system having separate mass/spring/damper characteristics. It is shown that a coupled resonant effect can be realized by inserting a water tank into a WEC, and this idea forms the basis of the ROTA device. In essence, the idea is to exploit the coupling between the natural sloshing frequencies of the water in the internal tank and the natural resonance of a submerged buoyant circular cylinder device that is tethered to the sea floor, allowing a rotary motion about its axis of attachment.

  7. Nonstationary behavior of a high-spin molecule in a bifrequency alternating current magnetic field

    NASA Astrophysics Data System (ADS)

    Tokman, I. D.; Vugalter, G. A.

    2002-07-01

    An interaction of a high-spin molecule with a bifrequency ac magnetic field, occurring at times much shorter than the molecule relaxation times, has been considered. The molecule is subjected to a dc magnetic field perpendicular to the easy anisotropy axis of the molecule. The bifrequency ac field is a superposition of two ac fields, one of which is perpendicular to the easy anisotropy axis and causes resonant transitions between the lower states of the fundamental and first excited doublets. The other ac field is parallel to the easy anisotropy axis and has a frequency much smaller than the frequency of the first ac field. It has been shown that, first, the molecule can absorb or emit energy, depending on the frequency of the low-frequency ac field, second, the bifrequency ac magnetic field induces tunneling of the molecule magnetization with the Rabi frequency. The conditions of observation of the effects predicted are discussed.

  8. Relative Sizes of Organic Molecules

    NASA Technical Reports Server (NTRS)

    2000-01-01

    This computer graphic depicts the relative complexity of crystallizing large proteins in order to study their structures through x-ray crystallography. Insulin is a vital protein whose structure has several subtle points that scientists are still trying to determine. Large molecules such as insuline are complex with structures that are comparatively difficult to understand. For comparison, a sugar molecule (which many people have grown as hard crystals in science glass) and a water molecule are shown. These images were produced with the Macmolecule program. Photo credit: NASA/Marshall Space Flight Center (MSFC)

  9. Combination gas producing and waste-water disposal well

    DOEpatents

    Malinchak, Raymond M.

    1984-01-01

    The present invention is directed to a waste-water disposal system for use in a gas recovery well penetrating a subterranean water-containing and methane gas-bearing coal formation. A cased bore hole penetrates the coal formation and extends downwardly therefrom into a further earth formation which has sufficient permeability to absorb the waste water entering the borehole from the coal formation. Pump means are disposed in the casing below the coal formation for pumping the water through a main conduit towards the water-absorbing earth formation. A barrier or water plug is disposed about the main conduit to prevent water flow through the casing except for through the main conduit. Bypass conduits disposed above the barrier communicate with the main conduit to provide an unpumped flow of water to the water-absorbing earth formation. One-way valves are in the main conduit and in the bypass conduits to provide flow of water therethrough only in the direction towards the water-absorbing earth formation.

  10. Self-Regulating Shock Absorber

    NASA Technical Reports Server (NTRS)

    Wesselski, Clarence J.

    1995-01-01

    Mechanical shock absorber keeps frictional damping force within tolerable limit. Its damping force does not increase with coefficient of friction between energy-absorbing components; rather, frictional damping force varies only slightly. Relatively insensitive to manufacturing variations and environmental conditions altering friction. Does not exhibit high breakaway friction and consequent sharp increase followed by sharp decrease in damping force at beginning of stroking. Damping force in absorber does not vary appreciably with speed of stroking. In addition, not vulnerable to leakage of hydraulic fluid.

  11. Quantification of the Intracellular Life Time of Water Molecules to Measure Transport Rates of Human Aquaglyceroporins.

    PubMed

    Palmgren, Madelene; Hernebring, Malin; Eriksson, Stefanie; Elbing, Karin; Geijer, Cecilia; Lasič, Samo; Dahl, Peter; Hansen, Jesper S; Topgaard, Daniel; Lindkvist-Petersson, Karin

    2017-12-01

    Orthodox aquaporins are transmembrane channel proteins that facilitate rapid diffusion of water, while aquaglyceroporins facilitate the diffusion of small uncharged molecules such as glycerol and arsenic trioxide. Aquaglyceroporins play important roles in human physiology, in particular for glycerol metabolism and arsenic detoxification. We have developed a unique system applying the strain of the yeast Pichia pastoris, where the endogenous aquaporins/aquaglyceroporins have been removed and human aquaglyceroporins AQP3, AQP7, and AQP9 are recombinantly expressed enabling comparative permeability measurements between the expressed proteins. Using a newly established Nuclear Magnetic Resonance approach based on measurement of the intracellular life time of water, we propose that human aquaglyceroporins are poor facilitators of water and that the water transport efficiency is similar to that of passive diffusion across native cell membranes. This is distinctly different from glycerol and arsenic trioxide, where high glycerol transport efficiency was recorded.

  12. Diamond detector in absorbed dose measurements in high‐energy linear accelerator photon and electron beams

    PubMed Central

    Binukumar, John Pichy; Amri, Iqbal Al; Davis, Cheriyathmanjiyil Antony

    2016-01-01

    Diamond detectors (DD) are preferred in small field dosimetry of radiation beams because of small dose profile penumbras, better spatial resolution, and tissue‐equivalent properties. We investigated a commercially available ‘microdiamond’ detector in realizing absorbed dose from first principles. A microdiamond detector, type TM 60019 with tandem electrometer is used to measure absorbed doses in water, nylon, and PMMA phantoms. With sensitive volume 0.004 mm3, radius 1.1 mm, thickness 1×10−3mm, the nominal response is 1 nC/Gy. It is assumed that the diamond detector could collect total electric charge (nC) developed during irradiation at 0 V bias. We found that dose rate effect is less than 0.7% for changing dose rate by 500 MU/min. The reproducibility in obtaining readings with diamond detector is found to be ±0.17% (1 SD) (n=11). The measured absorbed doses for 6 MV and 15 MV photons arrived at using mass energy absorption coefficients and stopping power ratios compared well with Nd, water calibrated ion chamber measured absorbed doses within 3% in water, PMMA, and nylon media. The calibration factor obtained for diamond detector confirmed response variation is due to sensitivity due to difference in manufacturing process. For electron beams, we had to apply ratio of electron densities of water to carbon. Our results qualify diamond dosimeter as a transfer standard, based on long‐term stability and reproducibility. Based on micro‐dimensions, we recommend these detectors for pretreatment dose verifications in small field irradiations like stereotactic treatments with image guidance. PACS number(s): 87.56.Da PMID:27074452

  13. Mechanical energy absorber

    NASA Technical Reports Server (NTRS)

    Wesselski, Clarence J. (Inventor)

    1993-01-01

    An energy absorbing system for controlling the force where a moving object engages a stationary stop and where the system utilized telescopic tubular members, energy absorbing diaphragm elements, force regulating disc springs, and a return spring to return the telescoping member to its start position after stroking is presented. The energy absorbing system has frusto-conical diaphragm elements frictionally engaging the shaft and are opposed by a force regulating set of disc springs. In principle, this force feedback mechanism serves to keep the stroking load at a reasonable level even if the friction coefficient increases greatly. This force feedback device also serves to desensitize the singular and combined effects of manufacturing tolerances, sliding surface wear, temperature changes, dynamic effects, and lubricity.

  14. Structure and functions of water-membrane interfaces and their role in proto-biological evolution

    NASA Technical Reports Server (NTRS)

    Pohorille, A.; Wilson, M.; Macelroy, R. D.

    1991-01-01

    Among the most important developments in proto-biological evolution was the emergence of membrane-like structures. These are formed by spontaneous association of relatively simple amphiphilic molecules that would have been readily available in the primordial environment. The resulting interfacial regions between water and nonpolar interior of the membrane have several properties which made them uniquely suitable for promoting subsequent evolution. They can (1) selectively attract organic material and mediate its transport, (2) serve as simple catalysts for chemical reactions, and (3) promote the formation of trans-membrane electrical and chemical gradients which could provide energy sources for proto-cells. Understanding the structure of interfaces, their interactions with organic molecules and molecular mechanisms of their functions is an essential step to understanding proto-biological evolution. In our computer simulation studies, we showed that the structure of water at interfaces with nonpolar media is significantly different from that in the bulk. In particular, the average surface dipole density points from the vapor to the liquid. As a result, negative ions can approach the interface more easily than positive ions. Amphiphilic molecules composed of hydrocarbon conjugated rings and polar substituents (e.g., phenol) assume at the interface rigid orientations in which polar groups are buried in water while hydrocarbon parts are located in the nonpolar environment. These orientational differences are of special interest in connection with the ability of some of these molecules to efficiently absorb photons. Flexible molecules with polar substituents often adopt at interfaces conformations different from those in the bulk aquaeous solution and in the gas phase. As a result, in many instances both specificity and kinetics of chemical reactions in which these molecules can participate is modified by the presence of surfaces. Of special interest is the mechanism by

  15. Site-specific binding of a water molecule to the sulfa drugs sulfamethoxazole and sulfisoxazole: a laser-desorption isomer-specific UV and IR study.

    PubMed

    Uhlemann, Thomas; Seidel, Sebastian; Müller, Christian W

    2018-03-07

    To determine the preferred water molecule binding sites of the polybasic sulfa drugs sulfamethoxazole (SMX) and sulfisoxazole (SIX), we have studied their monomers and monohydrated complexes through laser-desorption conformer-specific UV and IR spectroscopy. Both the SMX and SIX monomer adopt a single conformer in the molecular beam. On the basis of their conformer-specific IR spectra in the NH stretch region, these conformers were assigned to the SMX and SIX global minimum structures, both exhibiting a staggered sulfonamide group and an intramolecular C-HO[double bond, length as m-dash]S hydrogen bond. The SMX-H 2 O and SIX-H 2 O complexes each adopt a single isomer in the molecular beam. Their isomeric structures were determined based on their isomer-specific IR spectra in the NH/OH stretch region. Quantum Theory of Atoms in Molecules analysis of the calculated electron densities revealed that in the SMX-H 2 O complex the water molecule donates an O-HN hydrogen bond to the heterocycle nitrogen atom and accepts an N-HO hydrogen bond from the sulfonamide NH group. In the SIX-H 2 O complex, however, the water molecule does not bind to the heterocycle but instead donates an O-HO[double bond, length as m-dash]S hydrogen bond to the sulfonamide group and accepts an N-HO hydrogen bond from the sulfonamide NH group. Both water complexes are additionally stabilized by a C ph -HOH 2 hydrogen bond. Interacting Quantum Atoms analysis suggests that all intermolecular hydrogen bonds are dominated by the short-range exchange-correlation contribution.

  16. Optimization of sound absorbing performance for gradient multi-layer-assembled sintered fibrous absorbers

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Zhang, Weiyong; Zhu, Jian

    2012-04-01

    The transfer matrix method, based on plane wave theory, of multi-layer equivalent fluid is employed to evaluate the sound absorbing properties of two-layer-assembled and three-layer-assembled sintered fibrous sheets (generally regarded as a kind of compound absorber or structures). Two objective functions which are more suitable for the optimization of sound absorption properties of multi-layer absorbers within the wider frequency ranges are developed and the optimized results of using two objective functions are also compared with each other. It is found that using the two objective functions, especially the second one, may be more helpful to exert the sound absorbing properties of absorbers at lower frequencies to the best of their abilities. Then the calculation and optimization of sound absorption properties of multi-layer-assembled structures are performed by developing a simulated annealing genetic arithmetic program and using above-mentioned objective functions. Finally, based on the optimization in this work the thoughts of the gradient design over the acoustic parameters- the porosity, the tortuosity, the viscous and thermal characteristic lengths and the thickness of each samples- of porous metals are put forth and thereby some useful design criteria upon the acoustic parameters of each layer of porous fibrous metals are given while applying the multi-layer-assembled compound absorbers in noise control engineering.

  17. Aqueous Solvation of Polyalanine α-Helices with Specific Water Molecules and with the CPCM and SM5.2 Aqueous Continuum Models using Density Functional Theory

    PubMed Central

    Marianski, Mateusz

    2012-01-01

    We present density functional theory (DFT) calculations at the X3LYP/D95(d,p) level on the solvation of polyalanine α-helices in water. The study includes the effects of discrete water molecules and the CPCM and AMSOL SM5.2 solvent continuum model both separately and in combination. We find that individual water molecules cooperatively hydrogen-bond to both the C- and N-termini of the helix, which results in increases in the dipole moment of the helix/water complex to more than the vector sum of their individual dipole moments. These waters are found to be more stable than in bulk solvent. On the other hand, individual water that interact with the backbone lower the dipole moment of the helix/water complex to below that of the helix, itself. Small clusters of waters at the termini increase the dipole moments of the helix/water aggregates, but the effect diminishes as more waters are added. We discuss the somewhat complex behavior of the helix with the discrete waters in the continuum models. PMID:22201227

  18. Sound Absorbers

    NASA Astrophysics Data System (ADS)

    Fuchs, H. V.; Möser, M.

    Sound absorption indicates the transformation of sound energy into heat. It is, for instance, employed to design the acoustics in rooms. The noise emitted by machinery and plants shall be reduced before arriving at a workplace; auditoria such as lecture rooms or concert halls require a certain reverberation time. Such design goals are realised by installing absorbing components at the walls with well-defined absorption characteristics, which are adjusted for corresponding demands. Sound absorbers also play an important role in acoustic capsules, ducts and screens to avoid sound immission from noise intensive environments into the neighbourhood.

  19. Absorbed Dose and Dose Equivalent Calculations for Modeling Effective Dose

    NASA Technical Reports Server (NTRS)

    Welton, Andrew; Lee, Kerry

    2010-01-01

    While in orbit, Astronauts are exposed to a much higher dose of ionizing radiation than when on the ground. It is important to model how shielding designs on spacecraft reduce radiation effective dose pre-flight, and determine whether or not a danger to humans is presented. However, in order to calculate effective dose, dose equivalent calculations are needed. Dose equivalent takes into account an absorbed dose of radiation and the biological effectiveness of ionizing radiation. This is important in preventing long-term, stochastic radiation effects in humans spending time in space. Monte carlo simulations run with the particle transport code FLUKA, give absorbed and equivalent dose data for relevant shielding. The shielding geometry used in the dose calculations is a layered slab design, consisting of aluminum, polyethylene, and water. Water is used to simulate the soft tissues that compose the human body. The results obtained will provide information on how the shielding performs with many thicknesses of each material in the slab. This allows them to be directly applicable to modern spacecraft shielding geometries.

  20. Water solvent effects using continuum and discrete models: The nitromethane molecule, CH3NO2.

    PubMed

    Modesto-Costa, Lucas; Uhl, Elmar; Borges, Itamar

    2015-11-15

    The first three valence transitions of the two nitromethane conformers (CH3NO2) are two dark n → π* transitions and a very intense π → π* transition. In this work, these transitions in gas-phase and solvated in water of both conformers were investigated theoretically. The polarizable continuum model (PCM), two conductor-like screening (COSMO) models, and the discrete sequential quantum mechanics/molecular mechanics (S-QM/MM) method were used to describe the solvation effect on the electronic spectra. Time dependent density functional theory (TDDFT), configuration interaction including all single substitutions and perturbed double excitations (CIS(D)), the symmetry-adapted-cluster CI (SAC-CI), the multistate complete active space second order perturbation theory (CASPT2), and the algebraic-diagrammatic construction (ADC(2)) electronic structure methods were used. Gas-phase CASPT2, SAC-CI, and ADC(2) results are in very good agreement with published experimental and theoretical spectra. Among the continuum models, PCM combined either with CASPT2, SAC-CI, or B3LYP provided good agreement with available experimental data. COSMO combined with ADC(2) described the overall trends of the transition energy shifts. The effect of increasing the number of explicit water molecules in the S-QM/MM approach was discussed and the formation of hydrogen bonds was clearly established. By including explicitly 24 water molecules corresponding to the complete first solvation shell in the S-QM/MM approach, the ADC(2) method gives more accurate results as compared to the TDDFT approach and with similar computational demands. The ADC(2) with S-QM/MM model is, therefore, the best compromise for accurate solvent calculations in a polar environment. © 2015 Wiley Periodicals, Inc.

  1. Promotion of Homogeneous Ice Nucleation by Soluble Molecules.

    PubMed

    Mochizuki, Kenji; Qiu, Yuqing; Molinero, Valeria

    2017-11-29

    Atmospheric aerosols nucleate ice in clouds, strongly impacting precipitation and climate. The prevailing consensus is that ice nucleation is promoted heterogeneously by the surface of ice nucleating particles in the aerosols. However, recent experiments indicate that water-soluble molecules, such as polysaccharides of pollen and poly(vinyl alcohol) (PVA), increase the ice freezing temperature. This poses the question of how do flexible soluble molecules promote the formation of water crystals, as they do not expose a well-defined surface to ice. Here we use molecular simulations to demonstrate that PVA promotes ice nucleation through a homogeneous mechanism: PVA increases the nucleation rate by destabilizing water in the solution. This work demonstrates a novel paradigm for understanding ice nucleation by soluble molecules and provides a new handle to design additives that promote crystallization.

  2. Reversed phase liquid chromatography with UV absorbance and flame ionization detection using a water mobile phase and a cyano propyl stationary phase Analysis of alcohols and chlorinated hydrocarbons.

    PubMed

    Quigley, W W; Ecker, S T; Vahey, P G; Synovec, R E

    1999-10-01

    The development of liquid chromatography with a commercially available cyano propyl stationary phase and a 100% water mobile phase is reported. Separations were performed at ambient temperature, simplifying instrumental requirements. Excellent separation efficiency using a water mobile phase was achieved, for example N=18 800, or 75 200 m(-1), was obtained for resorcinol, at a retention factor of k'=4.88 (retention time of 9.55 min at 1 ml min(-1) for a 25 cmx4.6 mm i.d. column, packed with 5 mum diameter particles with the cyano propyl stationary phase). A separation via reversed phase liquid chromatography (RP-LC) with a 100% water mobile phase of six phenols and related compounds was compared to a separation of the same compounds by traditional RP-LC, using octadecylsilane (ODS), i.e. C18, bound to silica and an aqueous mobile phase modified with acetonitrile. Nearly identical analysis time was achieved for the separation of six phenols and related compounds using the cyano propyl stationary phase with a 100% water mobile phase, as compared to traditional RP-LC requiring a relatively large fraction of organic solvent modifier in the mobile phase (25% acetonitrile:75% water). Additional understanding of the retention mechanism with the 100% water mobile phase was obtained by relating measured retention factors of aliphatic alcohols, phenols and related compounds, and chlorinated hydrocarbons to their octanol:water partition coefficients. The retention mechanism is found to be consistent with a RP-LC mechanism coupled with an additional retention effect due to residual hydroxyl groups on the cyano propyl stationary phase. Advantages due to a 100% water mobile phase for the chemical analysis of alcohol mixtures and chlorinated hydrocarbons are reported. By placing an absorbance detector in-series and preceding a novel drop interface to a flame ionization detector (FID), selective detection of a separated mixture of phenols and related compounds and aliphatic

  3. The Ortho-to-para Ratio of Water Molecules Desorbed from Ice Made from Para-water Monomers at 11 K

    NASA Astrophysics Data System (ADS)

    Hama, Tetsuya; Kouchi, Akira; Watanabe, Naoki

    2018-04-01

    Water has two nuclear-spin isomers: ortho- and para-H2O. Some observations of interstellar space and cometary comae have reported the existence of gaseous H2O molecules with anomalous ortho-to-para ratios (OPRs) less than the statistical value of three. This has been often used to estimate the formation temperature of ice on dust, which is inferred to be below 50 K. The relation between the nuclear-spin dynamics of H2O in ice at low temperatures and the OPR of gaseous H2O desorbed from the ice has yet to be explored in a laboratory. Consequently, the true meaning of the observed OPRs remains debated. We measure the OPR of H2O photodesorbed from ice made from para-H2O monomers at 11 K, which was prepared by the sublimation of Ne from a para-H2O/Ne matrix. The photodesorbed H2O molecules from the ice have the statistical OPR value of three, demonstrating the immediate nuclear-spin-state mixing of H2O toward the statistical value of ice even at 11 K. The OPR of H2O thermally desorbed from the ice also shows the expected statistical value. Our results indicate that the OPR of H2O desorbed from interstellar ice should be the statistical value regardless of the formation process of the ice, which cannot be used to deduce the ice-formation temperature. This study highlights the importance of interstellar gas-phase processes in understanding anomalous abundance ratios of nuclear-spin isomers of molecules in space.

  4. Infrared spectral marker bands characterizing a transient water wire inside a hydrophobic membrane protein.

    PubMed

    Wolf, Steffen; Freier, Erik; Cui, Qiang; Gerwert, Klaus

    2014-12-14

    Proton conduction along protein-bound "water wires" is an essential feature in membrane proteins. Here, we analyze in detail a transient water wire, which conducts protons via a hydrophobic barrier within a membrane protein to create a proton gradient. It is formed only for a millisecond out of three water molecules distributed at inactive positions in a polar environment in the ground state. The movement into a hydrophobic environment causes characteristic shifts of the water bands reflecting their different chemical properties. These band shifts are identified by time-resolved Fourier Transform Infrared difference spectroscopy and analyzed by biomolecular Quantum Mechanical/Molecular Mechanical simulations. A non-hydrogen bonded ("dangling") O-H stretching vibration band and a broad continuum absorbance caused by a combined vibration along the water wire are identified as characteristic marker bands of such water wires in a hydrophobic environment. The results provide a basic understanding of water wires in hydrophobic environments.

  5. Effects of a Single Water Molecule on the Reaction Barrier of Interstellar CO2 Formation Reaction.

    PubMed

    Tachikawa, Hiroto; Kawabata, Hiroshi

    2016-08-25

    The mechanism by which CO2 is formed in the interstellar space remains a mystery. The most likely reaction is collision between CO and OH; however, previous theoretical works have shown that the activation barrier for CO2 formation is high enough to prevent the reaction at the low thermal conditions of space (∼10 K). The effects of single water molecule on the reaction barrier of CO2 formation from reaction between CO and OH have been investigated here by means of ab initio calculation. The barrier height along the lowest-energy pathway in the reaction between CO and OH in the absence of the H2O molecule was calculated to be 2.3 kcal/mol when CCSD(T) energy corrections are combined with the MP2 basis set limit. In the case of the hydrated (H2O-CO-OH) system, the inclusion of a single H2O molecule into the system significantly decreased the barrier height to 0.2 kcal/mol. This suggests that CO2 can be formed when CO and OH react in the presence of H2O, even under thermal conditions as low as 10 K.

  6. High Selective Gas Detection for small molecules based on Germanium selenide monolayer

    NASA Astrophysics Data System (ADS)

    Liu, Lian; Yang, Qun; Wang, Zeping; Ye, Huaiyu; Chen, Xianping; Fan, Xuejun; Zhang, Guoqi

    2018-03-01

    Predictive calculations based on density functional theory (DFT) are used here to study the electronic and optical properties of GeSe monolayer after adsorbing gas molecules (O2, NH3, SO2, H2, CO2, H2S, NO2, CH4, H2O, NO, CO). Our results reveal that for all the gas molecules considered, only NH3 is adsorbed on GeSe monolayer by physisorption. Whereas SO2 and NO2 are chemisorbed on GeSe monolayer with strong adsorption energies. In addition, the adsorption of O2, NO and NO2 distinctly enhances the optical absorbance and broaden the absorbance range of GeSe monolayer in visible light region. Also, it is found that the adsorption of H2S, NO and NH3 can reduce the work function of the GeSe monolayer. The results indicate that GeSe monolayer is not only a promising candidate for the sensing, capture, and storage of NH3, but also an anticipated disposable gas sensor or metal-free catalyst for detecting and catalyzing SO2 and NO2. Furthermore, it has excellent potential to be applied to optical sensors, solar cells, nanoelectronics or optoelectronics devices.

  7. Deprotonation states of the two active site water molecules regulate the binding of protein phosphatase 5 with its substrate: A molecular dynamics study.

    PubMed

    Wang, Lingyun; Yan, Feng

    2017-10-01

    Protein phosphatase 5 (PP5), mainly localized in human brain, can dephosphorylate tau protein whose high level of phosphorylation is related to Alzheimer's disease. Similar to other protein phosphatases, PP5 has a conserved motif in the catalytic domain that contains two binding sites for manganese (Mn 2+ ) ions. Structural data indicate that two active site water molecules, one bridging the two Mn 2+ ions and the other terminally coordinated with one of the Mn 2+ ions (Mn1), are involved in catalysis. Recently, a density functional theory study revealed that the two water molecules can be both deprotonated to keep a neutral active site for catalysis. The theoretical study gives us an insight into the catalytic mechanism of PP5, but the knowledge of how the deprotonation states of the two water molecules affect the binding of PP5 with its substrate is still lacking. To approach this problem, molecular dynamics simulations were performed to model the four possible deprotonation states. Through structural, dynamical and energetic analyses, the results demonstrate that the deprotonation states of the two water molecules affect the structure of the active site including the distance between the two Mn 2+ ions and their coordination, impact the interaction energy of residues R275, R400 and H304 which directly interact with the substrate phosphoserine, and mediate the dynamics of helix αJ which is involved in regulation of the enzyme's activity. Furthermore, the deprotonation state that is preferable for PP5 binding of its substrate has been identified. These findings could provide new design strategy for PP5 inhibitor. © 2017 The Protein Society.

  8. Super-hydrophilic copper sulfide films as light absorbers for efficient solar steam generation under one sun illumination

    NASA Astrophysics Data System (ADS)

    Guo, Zhenzhen; Ming, Xin; Wang, Gang; Hou, Baofei; Liu, Xinghang; Mei, Tao; Li, Jinhua; Wang, Jianying; Wang, Xianbao

    2018-02-01

    Solar steam technology is one of the simplest, most direct and effective ways to harness solar energy through water evaporation. Here, we report the development using super-hydrophilic copper sulfide (CuS) films with double-layer structures as light absorbers for solar steam generation. In the double-layer structure system, a porous mixed cellulose ester (MCE) membrane is used as a supporting layer, which enables water to get into the CuS light absorbers through a capillary action to provide continuous water during solar steam generation. The super-hydrophilic property of the double-layer system (CuS/MCE) leads to a thinner water film close to the air-water interface where the surface temperature is sufficiently high, leading to more efficient evaporation (˜80 ± 2.5%) under one sun illumination. Furthermore, the evaporation efficiencies still keep a steady value after 15 cycles of testing. The super-hydrophilic CuS film is promising for practical application in water purification and evaporation as a light absorption material.

  9. Angular motion of a PAH molecule in interstellar environment

    NASA Technical Reports Server (NTRS)

    Rouan, D.; Leger, Alain; Omont, A.; Giard, Martin

    1989-01-01

    Polycyclic aromatic hydrocarbon (PAH) molecules have recently been proposed as an important and hitherto undetected component of the Interstellar Medium (ISM). The theory was based on an explanation of the Unidentified IR Emission Bands by Leger et al. It has already led to a verified prediction on extended galactic and extragalactic emissions measured by IRAS, or by a recent balloon borne experiment. The physics that rules the motion of such molecules in the ISM was studied, taking into account their coupling with the ambient gas, the radiation field (absorption and emission) and the static magnetic field. This is important for many implications of the PAH theory such as the radio emission by these molecules or the expected polarization of their IR emission. A reflection nebulae is considered where the situation is rather well known. Every day life of a mean PAH molecule in such a region is as follows: every 3 hrs a UV photon is absorbed heating the molecule to a thousand degs; the temperature decay due to cooling by IR emission follows then within a few seconds. A collision with a molecule of gas occurs typically once a week, while an H atom is ejected or captured at the same rate. A typical cooling cycle after a heat impulse is given. The PAH molecules studied as representative of the family has typically 50 atoms, a radius of 4.5 A, is circular and has a molecular mass of M = 300; its permanent dipole moment is 3 Debye.

  10. The effects of metabolite molecules produced by drinking water-isolated bacteria on their single and multispecies biofilms.

    PubMed

    Simões, Lúcia Chaves; Simões, Manuel; Vieira, Maria João

    2011-08-01

    The elucidation of the mechanisms by which diverse species survive and interact in drinking water (DW) biofilm communities may allow the identification of new biofilm control strategies. The purpose of the present study was to investigate the effects of metabolite molecules produced by bacteria isolated from DW on biofilm formation. Six opportunistic bacteria, viz. Acinetobacter calcoaceticus, Burkholderia cepacia, Methylobacterium sp., Mycobacterium mucogenicum, Sphingomonas capsulata and Staphylococcus sp. isolated from a drinking water distribution systems (DWDS) were used to form single and multispecies biofilms in the presence and absence of crude cell-free supernatants produced by the partner bacteria. Biofilms were characterized in terms of mass and metabolic activity. Additionally, several physiological aspects regulating interspecies interactions (sessile growth rates, antimicrobial activity of cell-free supernatants, and production of iron chelators) were studied to identify bacterial species with biocontrol potential in DWDS. Biofilms of Methylobacterium sp. had the highest growth rate and M. mucogenicum biofilms the lowest. Only B. cepacia was able to produce extracellular iron-chelating molecules. A. calcoaceticus, B. cepacia, Methylobacterium sp. and M. mucogenicum biofilms were strongly inhibited by crude cell-free supernatants from the other bacteria. The crude cell-free supernatants of M. mucogenicum and S. capsulata demonstrated a high potential for inhibiting the growth of counterpart biofilms. Multispecies biofilm formation was strongly inhibited in the absence of A. calcoaceticus. Only crude cell-free supernatants produced by B. cepacia and A. calcoaceticus had no inhibitory effects on multispecies biofilm formation, while metabolite molecules of M. mucogenicum showed the most significant biocontrol potential.

  11. In vitro isolation of small-molecule-binding aptamers with intrinsic dye-displacement functionality

    PubMed Central

    Yu, Haixiang; Yang, Weijuan; Alkhamis, Obtin; Canoura, Juan; Yang, Kyung-Ae; Xiao, Yi

    2018-01-01

    Abstract Aptamer-based sensors offer a powerful tool for molecular detection, but the practical implementation of these biosensors is hindered by costly and laborious sequence engineering and chemical modification procedures. We report a simple strategy for directly isolating signal-reporting aptamers in vitro through systematic evolution of ligands by exponential enrichment (SELEX) that transduce binding events into a detectable change of absorbance via target-induced displacement of a small-molecule dye. We first demonstrate that diethylthiatricarbocyanine (Cy7) can stack into DNA three-way junctions (TWJs) in a sequence-independent fashion, greatly altering the dye's absorbance spectrum. We then design a TWJ-containing structured library and isolate an aptamer against 3,4-methylenedioxypyrovalerone (MDPV), a synthetic cathinone that is an emerging drug of abuse. This aptamer intrinsically binds Cy7 within its TWJ domain, but MDPV efficiently displaces the dye, resulting in a change in absorbance within seconds. This assay is label-free, and detects nanomolar concentrations of MDPV. It also recognizes other synthetic cathinones, offering the potential to detect newly-emerging designer drugs, but does not detect structurally-similar non-cathinone compounds or common cutting agents. Moreover, we demonstrate that the Cy7-displacement colorimetric assay is more sensitive than a conventional strand-displacement fluorescence assay. We believe our strategy offers an effective generalized approach for the development of sensitive dye-displacement colorimetric assays for other small-molecule targets. PMID:29361056

  12. Transfer of lipid molecules and polycyclic aromatic hydrocarbons to open marine waters by dense water cascading events

    NASA Astrophysics Data System (ADS)

    Salvadó, Joan A.; Grimalt, Joan O.; López, Jordi F.; Palanques, Albert; Heussner, Serge; Pasqual, Catalina; Sanchez-Vidal, Anna; Canals, Miquel

    2017-12-01

    Settling particles were collected by a set of moored sediment traps deployed during one year in the western Gulf of Lion along Cap de Creus and Lacaze-Duthiers submarine canyons and on the adjacent southern open slope. These traps collected particles during periods of pelagic settling and also during events of deep water flushing by dense shelf water cascading (DSWC). Analyses of lipid biomarkers (n-alkanes, n-alkan-1-ols, sterols and C37-C38 alkenones) and polycyclic aromatic hydrocarbons (PAHs) showed much higher transfer of terrestrial lipids and PAHs to open deep waters during DSWC than in the absence of cascading. The area of highest lateral fluxes was mostly located at 1000 m depth but also at 1500 m depth and extended along the canyons and to the adjacent slope. Higher fluxes were observed near the bottom (30 m above bottom; mab) than at intermediate waters (500 mab) which is consistent with the formation and sinking of dense water over the continental shelf, and its transport through the canyons towards the continental slope and deep basin. DSWC involved the highest settling fluxes of terrestrial lipids and PAHs ever described in marine continental slopes and the pelagic domain, as illustrated by peak values of C23-C33 odd carbon numbered alkanes (405 ng m-2 d-1), C22-C32 even carbon numbered alkan-1-ols (850 ng m-2 d-1), β-sitosterol+sitostanol (4800 ng m-2 d-1) and PAHs (55 μg m-2 d-1). The algal lipids also showed higher transfer to deep waters during DSWC but to a lower extent than the terrigenous compounds. However, the C37-C38 alkenones constituted an exception and their settling fluxes were not influenced by DSWC. The lack of influence of the DSWC on the C37-C38 alkenone settling is consistent with absence of haptophyte algal inputs from the continental shelf and reinforces the reliability of these molecules for palaeothermometry and palaeoproductivity measurements in pelagic systems.

  13. How water molecules affect the catalytic activity of hydrolases--a XANES study of the local structures of peptide deformylase.

    PubMed

    Cui, Peixin; Wang, Yu; Chu, Wangsheng; Guo, Xiaoyun; Yang, Feifei; Yu, Meijuan; Zhao, Haifeng; Dong, Yuhui; Xie, Yaning; Gong, Weimin; Wu, Ziyu

    2014-12-12

    Peptide deformylase (PDF) is a prokaryotic enzyme that catalyzes the deformylation of nascent peptides generated during protein synthesis and water molecules play a key role in these hydrolases. Using X-ray absorption near edge spectroscopy (XANES) and ab initio calculations we accurately probe the local atomic environment of the metal ion binding in the active site of PDF at different pH values and with different metal ions. This new approach is an effective way to monitor existing correlations among functions and structural changes. We show for the first time that the enzymatic activity depends on pH values and metal ions via the bond length of the nearest coordinating water (Wat1) to the metal ion. Combining experimental and theoretical data we may claim that PDF exhibits an enhanced enzymatic activity only when the distance of the Wat1 molecule with the metal ion falls in the limited range from 2.15 to 2.55 Å.

  14. Metal-shearing energy absorber

    NASA Technical Reports Server (NTRS)

    Fay, R. J.; Wittrock, E. P.

    1971-01-01

    Device, consisting of tongue of thin aluminum alloy strip, pull tab, slotted steel plate which serves as cutter, and steel buckle, absorbs mechanical energy when its ends are subjected to tensile loading. Device is applicable as auxiliary shock absorbing anchor for automobile and airplane safety belts.

  15. Intrascleral outflow after deep sclerectomy with absorbable and non-absorbable implants in the rabbit eye.

    PubMed

    Kałużny, Jakub J; Grzanka, Dariusz; Wiśniewska, Halina; Niewińska, Alicja; Kałużny, Bartłomiej J; Grzanka, Alina

    2012-10-01

    The purpose of the study is an analysis of intrascleral drainage vessels formed in rabbits' eyes after non-penetrating deep sclerectomy (NPDS) with absorbable and non-absorbable implants, and comparison to eyes in which surgery was performed without implanted material. NPDS was carried out in 12 rabbits, with implantation of non-absorbable methacrylic hydrogel (N=10 eyes) or absorbable cross-linked sodium hyaluronate (N=6 eyes), or without any implant (N=8 eyes). All the animals were euthanized 1 year after surgery. Twenty-one eyeballs were prepared for light microscopy and 3 were prepared for transmission electron microscope (TEM) analysis. Aqueous humour pathways were stained with ferritin in 6 eyeballs. By light microscopy, small vessels adjacent to the areas of scarring were the most common abnormality. Vessel density was significantly higher in operated sclera compared to normal, healthy tissue, regardless of the type of implant used. The average vessel densities were 2.18±1.48 vessels/mm2 in non-implanted sclera, 2.34±1.69 vessels/mm2 in eyes with absorbable implants, and 3.64±1.78 vessels/mm2 in eyes with non-absorbable implants. Analysis of iron distribution in ferritin-injected eyes showed a positive reaction inside new aqueous draining vessels in all groups. TEM analysis showed that the ultrastructure of new vessels matched the features of the small veins. Aqueous outflow after NPDS can be achieved through the newly formed network of small intrascleral veins. Use of non-absorbable implants significantly increases vessel density in the sclera adjacent to implanted material compared to eyes in which absorbable implants or no implants were used.

  16. Optimizing electrostatic field calculations with the Adaptive Poisson-Boltzmann Solver to predict electric fields at protein-protein interfaces II: explicit near-probe and hydrogen-bonding water molecules.

    PubMed

    Ritchie, Andrew W; Webb, Lauren J

    2014-07-17

    We have examined the effects of including explicit, near-probe solvent molecules in a continuum electrostatics strategy using the linear Poisson-Boltzmann equation with the Adaptive Poisson-Boltzmann Solver (APBS) to calculate electric fields at the midpoint of a nitrile bond both at the surface of a monomeric protein and when docked at a protein-protein interface. Results were compared to experimental vibrational absorption energy measurements of the nitrile oscillator. We examined three methods for selecting explicit water molecules: (1) all water molecules within 5 Å of the nitrile nitrogen; (2) the water molecule closest to the nitrile nitrogen; and (3) any single water molecule hydrogen-bonding to the nitrile. The correlation between absolute field strengths with experimental absorption energies were calculated and it was observed that method 1 was only an improvement for the monomer calculations, while methods 2 and 3 were not significantly different from the purely implicit solvent calculations for all protein systems examined. Upon taking the difference in calculated electrostatic fields and comparing to the difference in absorption frequencies, we typically observed an increase in experimental correlation for all methods, with method 1 showing the largest gain, likely due to the improved absolute monomer correlations using that method. These results suggest that, unlike with quantum mechanical methods, when calculating absolute fields using entirely classical models, implicit solvent is typically sufficient and additional work to identify hydrogen-bonding or nearest waters does not significantly impact the results. Although we observed that a sphere of solvent near the field of interest improved results for relative field calculations, it should not be consider a panacea for all situations.

  17. Techno-Economic Analysis of Solar Water Heating Systems inTurkey.

    PubMed

    Ertekin, Can; Kulcu, Recep; Evrendilek, Fatih

    2008-02-25

    In this study, solar water heater was investigated using meteorological and geographical data of 129 sites over Turkey. Three different collector types were compared in terms of absorber material (copper, galvanized sheet and selective absorber). Energy requirement for water heating, collector performances, and economical indicators were calculated with formulations using observed data. Results showed that selective absorbers were most appropriate in terms of coverage rate of energy requirement for water-heating all over Turkey. The prices of selective, copper and galvanized absorber type's heating systems in Turkey were 740.49, 615.69 and 490.89 USD, respectively. While payback periods (PBPs) of the galvanized absorber were lower, net present values (NPVs) of the selective absorber were higher than the rest. Copper absorber type collectors did not appear to be appropriate based on economical indicators.

  18. Advanced neutron absorber materials

    DOEpatents

    Branagan, Daniel J.; Smolik, Galen R.

    2000-01-01

    A neutron absorbing material and method utilizing rare earth elements such as gadolinium, europium and samarium to form metallic glasses and/or noble base nano/microcrystalline materials, the neutron absorbing material having a combination of superior neutron capture cross sections coupled with enhanced resistance to corrosion, oxidation and leaching.

  19. Activation of a water molecule using a mononuclear Mn complex: from Mn-aquo, to Mn-hydroxo, to Mn-oxyl via charge compensation.

    PubMed

    Lassalle-Kaiser, Benedikt; Hureau, Christelle; Pantazis, Dimitrios A; Pushkar, Yulia; Guillot, Régis; Yachandra, Vittal K; Yano, Junko; Neese, Frank; Anxolabéhère-Mallart, Elodie

    2010-07-01

    Activation of a water molecule by the electrochemical oxidation of a Mn-aquo complex accompanied by the loss of protons is reported. The sequential (2 × 1 electron/1 proton) and direct (2 electron/2 proton) proton-coupled electrochemical oxidation of a non-porphyrinic six-coordinated Mn(II)OH 2 complex into a mononuclear Mn(O) complex is described. The intermediate Mn(III)OH 2 and Mn(III)OH complexes are electrochemically prepared and analysed. Complete deprotonation of the coordinated water molecule in the Mn(O) complex is confirmed by electrochemical data while the analysis of EXAFS data reveals a gradual shortening of an Mn-O bond upon oxidation from Mn(II)OH 2 to Mn(III)OH and Mn(O). Reactivity experiments, DFT calculations and XANES pre-edge features provide strong evidence that the bonding in Mn(O) is best characterized by a Mn(III)-oxyl description. Such oxyl species could play a crucial role in natural and artificial water splitting reactions. We provide here a synthetic example for such species, obtained by electrochemical activation of a water ligand.

  20. Activation of a water molecule using a mononuclear Mn complex: from Mn-aquo, to Mn-hydroxo, to Mn-oxyl via charge compensation†

    PubMed Central

    Lassalle-Kaiser, Benedikt; Hureau, Christelle; Pantazis, Dimitrios A.; Pushkar, Yulia; Guillot, Régis; Yachandra, Vittal K.; Yano, Junko; Neese, Frank; Anxolabéhère-Mallart, Elodie

    2014-01-01

    Activation of a water molecule by the electrochemical oxidation of a Mn-aquo complex accompanied by the loss of protons is reported. The sequential (2 × 1 electron/1 proton) and direct (2 electron/2 proton) proton-coupled electrochemical oxidation of a non-porphyrinic six-coordinated Mn(II)OH2 complex into a mononuclear Mn(O) complex is described. The intermediate Mn(III)OH2 and Mn(III)OH complexes are electrochemically prepared and analysed. Complete deprotonation of the coordinated water molecule in the Mn(O) complex is confirmed by electrochemical data while the analysis of EXAFS data reveals a gradual shortening of an Mn–O bond upon oxidation from Mn(II)OH2 to Mn(III)OH and Mn(O). Reactivity experiments, DFT calculations and XANES pre-edge features provide strong evidence that the bonding in Mn(O) is best characterized by a Mn(III)-oxyl description. Such oxyl species could play a crucial role in natural and artificial water splitting reactions. We provide here a synthetic example for such species, obtained by electrochemical activation of a water ligand. PMID:24772190

  1. Effect of synthetic and natural water-absorbing soil amendments on photosynthesis characteristics and tuber nutritional quality of potato in a semi-arid region.

    PubMed

    Xu, Shengtao; Zhang, Lei; McLaughlin, Neil B; Mi, Junzhen; Chen, Qin; Liu, Jinghui

    2016-02-01

    The effect of water-absorbing soil amendments on photosynthesis characteristics and tuber nutritional quality was investigated in a field experiment in a semi-arid region in northern China in 2010-2012. Treatments included two synthetic water-absorbing amendments, potassium polyacrylate (PAA) and polyacrylamide (PAM), and one natural amendment, humic acid (HA), both as single amendments and compound amendments (HA combined with PAA or PAM), and a no amendment control. Soil amendments had a highly significant effect (P ≤ 0.01) on photosynthesis characteristics, dry biomass, crop root/shoot (R/S) ratio and tuber nutritional quality. They improved both dry biomass above ground and dry biomass underground in the whole growing season by 4.6-31.2 and 1.1-83.1% respectively in all three years. Crop R/S ratio was reduced in the early growing season by 2.0-29.4% and increased in the later growing season by 2.3-32.6%. Soil amendments improved leaf soil plant analysis development value, net photosynthesis rate, stomatal conductance and transpiration rate by 1.4-17.0, 5.1-45.9, 2.4-90.6 and 2.0-22.6% respectively and reduced intercellular CO2 concentration by 2.1-19.5% in all three years. Amendment treatment with PAM + HA always had the greatest effect on photosynthesis characteristics and tuber nutritional quality among all amendment treatments and thus merits further research. © 2015 Society of Chemical Industry.

  2. Burnable absorber arrangement for fuel bundle

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

    Crowther, R.L.; Townsend, D.B.

    1986-12-16

    This patent describes a boiling water reactor core whose operation is characterized by a substantial proportion of steam voids with concomitantly reduced moderation toward the top of the core when the reactor is in its hot operating condition. The reduced moderation leads to slower burnup and greater conversion ratio in an upper core region so that when the reactor is in its cold shut down condition the resulting relatively increased moderation in the upper core region is accompanied by a reactivity profile that peaks in the upper core region. A fuel assembly is described comprising; a component of fissile materialmore » distributed over a substantial axial extent of the fuel assembly; and a component of neutron absorbing material having an axial distribution characterized by an enhancement in an axial zone of the fuel assembly, designated the cold shutdown control zone, corresponding to at least a portion of the axial region of the core when the cold shutdown reactivity peaks. The aggregate amount of neutron absorbing material in the cold shutdown zone of the fuel assembly is greater than the aggregate amount of neutron absorbing material in the axial zones of the fuel assembly immediately above and immediately below the cold shutdown control zone whereby the cold shutdown reactivity peak is reduced relative to the cold shutdown reactivity in the zones immediately above and immediately below the cold shutdown control zone. The cold shutdown zone has an axial extent measured from the bottom of the fuel assembly in the range between 68-88 percent of the height of the fissile material in the fuel assembly.« less

  3. Open-framework gallium borate with boric and metaboric acid molecules inside structural channels showing photocatalysis to water splitting.

    PubMed

    Gao, Wenliang; Jing, Yan; Yang, Jia; Zhou, Zhengyang; Yang, Dingfeng; Sun, Junliang; Lin, Jianhua; Cong, Rihong; Yang, Tao

    2014-03-03

    An open-framework gallium borate with intrinsic photocatalytic activities to water splitting has been discovered. Small inorganic molecules, H3BO3 and H3B3O6, are confined inside structural channels by multiple hydrogen bonds. It is the first example to experimentally show the structural template effect of boric acid in flux synthesis.

  4. Changes in deviation of absorbed dose to water among users by chamber calibration shift.

    PubMed

    Katayose, Tetsurou; Saitoh, Hidetoshi; Igari, Mitsunobu; Chang, Weishan; Hashimoto, Shimpei; Morioka, Mie

    2017-07-01

    The JSMP01 dosimetry protocol had adopted the provisional 60 Co calibration coefficient [Formula: see text], namely, the product of exposure calibration coefficient N C and conversion coefficient k D,X . After that, the absorbed dose to water D w  standard was established, and the JSMP12 protocol adopted the [Formula: see text] calibration. In this study, the influence of the calibration shift on the measurement of D w among users was analyzed. The intercomparison of the D w using an ionization chamber was annually performed by visiting related hospitals. Intercomparison results before and after the calibration shift were analyzed, the deviation of D w among users was re-evaluated, and the cause of deviation was estimated. As a result, the stability of LINAC, calibration of the thermometer and barometer, and collection method of ion recombination were confirmed. The statistical significance of standard deviation of D w was not observed, but that of difference of D w among users was observed between N C and [Formula: see text] calibration. Uncertainty due to chamber-to-chamber variation was reduced by the calibration shift, consequently reducing the uncertainty among users regarding D w . The result also pointed out uncertainty might be reduced by accurate and detailed instructions on the setup of an ionization chamber.

  5. Molecular dynamics simulations of amphiphilic graft copolymer molecules at a water/air interface.

    PubMed

    Anderson, Philip M; Wilson, Mark R

    2004-11-01

    Fully atomistic molecular dynamics simulations of amphiphilic graft copolymer molecules have been performed at a range of surface concentrations at a water/air interface. These simulations are compared to experimental results from a corresponding system over a similar range of surface concentrations. Neutron reflectivity data calculated from the simulation trajectories agrees well with experimentally acquired profiles. In particular, excellent agreement in neutron reflectivity is found for lower surface concentration simulations. A simulation of a poly(ethylene oxide) (PEO) chain in aqueous solution has also been performed. This simulation allows the conformational behavior of the free PEO chain and those tethered to the interface in the previous simulations to be compared. (c) 2004 American Institute of Physics.

  6. Spacesuit Evaporator-Absorber-Radiator (SEAR)

    NASA Technical Reports Server (NTRS)

    Bue, Grant C.; Hodgson, Ed; Izenso, Mike; Chan, Weibo; Cupples, Scott

    2011-01-01

    For decades advanced spacesuit developers have pursued a regenerable, robust non-venting system for heat rejection. Toward this end, this paper investigates linking together two previously developed technologies, namely NASA's Spacesuit Water Membrane Evaporator (SWME), and Creare's lithium chloride Heat Pump Radiator (HPR). Heat from a liquid cooled garment is transported to SWME that provides cooling through evaporation. The SEAR is evacuated at the onset of operations and thereafter, the water vapor absorption rate of the HPR maintains a low pressure environment for the SWME to evaporate effectively. This water vapor captured by solid LiCl in the HPR with a high enthalpy of absorption, results in sufficient temperature lift to reject most of the heat to space by radiation. After the sortie, the HPR would be heated up in a regenerator to drive off and recover the absorbed evaporant. A one-fourth scale prototype was built and tested in vacuum conditions at a sink temperature of 250 K. The HPR was able to stably reject 60 W over a 7-hour period. A conceptual design of a full-scale radiator is proposed. Excess heat rejection above 240 W would be accomplished through venting of the evaporant. Loop closure rates were predicted for various exploration environment scenarios.

  7. Techno-Economic Analysis of Solar Water Heating Systems in Turkey

    PubMed Central

    Ertekin, Can; Kulcu, Recep; Evrendilek, Fatih

    2008-01-01

    In this study, solar water heater was investigated using meteorological and geographical data of 129 sites over Turkey. Three different collector types were compared in terms of absorber material (copper, galvanized sheet and selective absorber). Energy requirement for water heating, collector performances, and economical indicators were calculated with formulations using observed data. Results showed that selective absorbers were most appropriate in terms of coverage rate of energy requirement for water-heating all over Turkey. The prices of selective, copper and galvanized absorber type's heating systems in Turkey were 740.49, 615.69 and 490.89 USD, respectively. While payback periods (PBPs) of the galvanized absorber were lower, net present values (NPVs) of the selective absorber were higher than the rest. Copper absorber type collectors did not appear to be appropriate based on economical indicators. PMID:27879764

  8. Optical fiber humidity sensor based on evanescent-wave scattering.

    PubMed

    Xu, Lina; Fanguy, Joseph C; Soni, Krunal; Tao, Shiquan

    2004-06-01

    The phenomenon of evanescent-wave scattering (EWS) is used to design an optical-fiber humidity sensor. Porous solgel silica (PSGS) coated on the surface of a silica optical-fiber core scatters evanescent waves that penetrate the coating layer. Water molecules in the gas phase surrounding the optical fiber can be absorbed into the inner surface of the pores of the porous silica. The absorbed water molecules form a thin layer of liquid water on the inner surface of the porous silica and enhance the EWS. The amount of water absorbed into the PSGS coating is in dynamic equilibrium with the water-vapor pressure in the gas phase. Therefore the humidity in the air can be quantitatively determined with fiber-optic EWS caused by the PSGS coating. The humidity sensor reported here is fast in response, reversible, and has a wide dynamic range. The possible interference caused by EWS to an optical-fiber gas sensor with a reagent-doped PSGS coating as a transducer is also discussed.

  9. Atomistic investigation on the detachment of oil molecules from defective alumina surface

    NASA Astrophysics Data System (ADS)

    Xie, W. K.; Sun, Y. Z.; Liu, H. T.

    2017-12-01

    The mechanism of oil detachment from defective alumina surface in aqueous solution was investigated via atomistic molecular dynamics (MD) simulations. Special attention was focused on the effect of surface defect on the oil detachment. Our simulation results suggest that compared with perfect Al2O3 surface, defective substrate surface provides much more sites for the adsorption of oil molecules, thus it has higher oil adsorption energy. However, higher oil-solid adsorption energy does not mean that oil contaminants are much more difficult to be detached. It is found that surface defect could induce the spontaneous imbibition of water molecules, effectively promoting the detachment of oil molecules. Thus, compared with perfect alumina surface, the detachment of oil molecules from defective alumina surface tends to be much easier. Moreover, surface defect could lead to the oil residues inside surface defect. In water solution, the entire detachment process of oil molecules on defective surface consists of following stages, including the early detachment of oil molecules inside surface defect induced by capillary-driven spontaneous imbibition of water molecules, the following conformational change of oil molecules on topmost surface and the final migration of detached oil molecules from solid surface. These findings may help to sufficiently enrich the removal mechanism of oil molecules adhered onto defective solid surface.

  10. Neutron absorbers and methods of forming at least a portion of a neutron absorber

    DOEpatents

    Guillen, Donna P; Porter, Douglas L; Swank, W David; Erickson, Arnold W

    2014-12-02

    Methods of forming at least a portion of a neutron absorber include combining a first material and a second material to form a compound, reducing the compound into a plurality of particles, mixing the plurality of particles with a third material, and pressing the mixture of the plurality of particles and the third material. One or more components of neutron absorbers may be formed by such methods. Neutron absorbers may include a composite material including an intermetallic compound comprising hafnium aluminide and a matrix material comprising pure aluminum.

  11. Broadband Absorbing Exciton-Plasmon Metafluids with Narrow Transparency Windows.

    PubMed

    Yang, Jihua; Kramer, Nicolaas J; Schramke, Katelyn S; Wheeler, Lance M; Besteiro, Lucas V; Hogan, Christopher J; Govorov, Alexander O; Kortshagen, Uwe R

    2016-02-10

    Optical metafluids that consist of colloidal solutions of plasmonic and/or excitonic nanomaterials may play important roles as functional working fluids or as means for producing solid metamaterial coatings. The concept of a metafluid employed here is based on the picture that a single ballistic photon, propagating through the metafluid, interacts with a large collection of specifically designed optically active nanocrystals. We demonstrate water-based metafluids that act as broadband electromagnetic absorbers in a spectral range of 200-3300 nm and feature a tunable narrow (∼100 nm) transparency window in the visible-to-near-infrared region. To define this transparency window, we employ plasmonic gold nanorods. We utilize excitonic boron-doped silicon nanocrystals as opaque optical absorbers ("optical wall") in the UV and blue-green range of the spectrum. Water itself acts as an opaque "wall" in the near-infrared to infrared. We explore the limits of the concept of a "simple" metafluid by computationally testing and validating the effective medium approach based on the Beer-Lambert law. According to our simulations and experiments, particle aggregation and the associated decay of the window effect are one example of the failure of the simple metafluid concept due to strong interparticle interactions.

  12. [Study of new blended chemical absorbents to absorb CO2].

    PubMed

    Wang, Jin-Lian; Fang, Meng-Xiang; Yan, Shui-Ping; Luo, Zhong-Yang; Cen, Ke-Fa

    2007-11-01

    Three kinds of blended absorbents were investigated on bench-scale experimental bench according to absorption rate and regeneration grade to select a reasonable additive concentration. The results show that, among methyldiethanolamine (MDEA) and piperazine (PZ) mixtures, comparing MDEA : PZ = 1 : 0.4 (m : m) with MDEA : PZ = 1 : 0.2 (m : m), the absorption rate is increased by about 70% at 0.2 mol x mol(-1). When regeneration lasting for 40 min, regeneration grade of blended absorbents with PZ concentration of 0.2, 0.4, and 0.8 is decreased to 83.06%, 77.77% and 76.67% respectively while 91.04% for PZ concentration of 0. MDEA : PZ = 1 : 0.4(m : m) is a suitable ratio for MDEA/PZ mixtures as absorption and regeneration properties of the blended absorbents are all improved. The aqueous blends with 10% primary amines and 2% tertiary amines could keep high CO2 absorption rate, and lower regeneration energy consumption. Adding 2% 2-Amino-2-methyl-1-propanol (AMP) to 10% diethanolamine (DEA), the blended amine solvents have an advantage in absorption and regeneration properties over other DEA/AMP mixtures. Blended solvents, which consist of a mixture of primary amines with a small amount of tertiary amines, have the highest absorption rate among the three. And mixed absorbents of secondary amines and a small amount of sterically hindered amines have the best regeneration property. To combine absorption and regeneration properties, blends with medium activator addition to tertiary amines are competitive.

  13. Shock absorber servicing tool

    NASA Technical Reports Server (NTRS)

    Koepler, Jack L. (Inventor); Hill, Robert L. (Inventor)

    1981-01-01

    A tool to assist in the servicing of a shock absorber wherein the shock absorber is constructed of a pair of aligned gas and liquid filled chambers. Each of the chambers is separated by a movable separator member. Maximum efficiency of the shock absorber is achieved in the locating of a precise volume of gas within the gas chamber and a precise volume of liquid within the liquid chamber. The servicing tool of this invention employs a rod which is to connect with the separator and by observation of the position of the rod with respect to the gauge body, the location of the separator is ascertained even though it is not directly observable.

  14. CHEMICAL TRANSPORT FACILITATED BY COLLOIDAL-SIZED ORGANIC MOLECULES

    EPA Science Inventory

    The fluid passing through the pores of soils and geologic materials is not just water with dissolved inorganic chemicals, but a complex mixture of organic and inorganic molecules. Large organic molecules such as humic and fulvic materials may impact the movement of contaminants. ...

  15. Parametric study of two-body floating-point wave absorber

    NASA Astrophysics Data System (ADS)

    Amiri, Atena; Panahi, Roozbeh; Radfar, Soheil

    2016-03-01

    In this paper, we present a comprehensive numerical simulation of a point wave absorber in deep water. Analyses are performed in both the frequency and time domains. The converter is a two-body floating-point absorber (FPA) with one degree of freedom in the heave direction. Its two parts are connected by a linear mass-spring-damper system. The commercial ANSYS-AQWA software used in this study performs well in considering validations. The velocity potential is obtained by assuming incompressible and irrotational flow. As such, we investigated the effects of wave characteristics on energy conversion and device efficiency, including wave height and wave period, as well as the device diameter, draft, geometry, and damping coefficient. To validate the model, we compared our numerical results with those from similar experiments. Our study results can clearly help to maximize the converter's efficiency when considering specific conditions.

  16. Chemical Recycling of Molecules in Cometary Comae

    NASA Astrophysics Data System (ADS)

    Boice, Daniel C.; Kawakita, Hideyo; Shinnaka, Yoshiharu; Kobayashi, Hitomi

    2015-08-01

    Modeling is essential to understand the important physical and chemical processes that occur in cometary comae, especially the relationship between native and sibling molecules, such as, HCN and CN. Photochemistry is a major source of ions and electrons that further initiate key gas-phase reactions, leading to the plethora of molecules and atoms observed in comets. The effects of photoelectrons that react via impacts are important to the overall ionization in the inner coma. We have found that many molecules undergo protonation reactions with primarily water, followed by electron recombination resulting in the original molecules in a vibrationally excited state. These excited molecules spontaneously emit photons back to the ground state. We identify this series of reactions as chemical “recycling.” We discuss the importance of this mechanism for HCN, NH3, and water in comets. We also identify other relevant processes in the collision-dominated, inner coma of a comet within a global modeling framework to better understand observations and in situ measurements of cometary species, especially relationships between native and sibling molecules for the Rosetta Mission to Comet 67P/Churyumov-Gerasimenko.Acknowledgements: We appreciate support from the NSF Planetary Astronomy Program under Grant No. 0908529. This program is partially supported by the MEXT Supported Program for the Strategic Research Foundation at Private Universities, 2014-2018.

  17. Absorbed dose measurements for kV-cone beam computed tomography in image-guided radiation therapy

    NASA Astrophysics Data System (ADS)

    Hioki, Kazunari; Araki, Fujio; Ohno, Takeshi; Nakaguchi, Yuji; Tomiyama, Yuuki

    2014-12-01

    In this study, we develope a novel method to directly evaluate an absorbed dose-to-water for kilovoltage-cone beam computed tomography (kV-CBCT) in image-guided radiation therapy (IGRT). Absorbed doses for the kV-CBCT systems of the Varian On-Board Imager (OBI) and the Elekta X-ray Volumetric Imager (XVI) were measured by a Farmer ionization chamber with a 60Co calibration factor. The chamber measurements were performed at the center and four peripheral points in body-type (30 cm diameter and 51 cm length) and head-type (16 cm diameter and 33 cm length) cylindrical water phantoms. The measured ionization was converted to the absorbed dose-to-water by using a 60Co calibration factor and a Monte Carlo (MC)-calculated beam quality conversion factor, kQ, for 60Co to kV-CBCT. The irradiation for OBI and XVI was performed with pelvis and head modes for the body- and the head-type phantoms, respectively. In addition, the dose distributions in the phantom for both kV-CBCT systems were calculated with MC method and were compared with measured values. The MC-calculated doses were calibrated at the center in the water phantom and compared with measured doses at four peripheral points. The measured absorbed doses at the center in the body-type phantom were 1.96 cGy for OBI and 0.83 cGy for XVI. The peripheral doses were 2.36-2.90 cGy for OBI and 0.83-1.06 cGy for XVI. The doses for XVI were lower up to approximately one-third of those for OBI. Similarly, the measured doses at the center in the head-type phantom were 0.48 cGy for OBI and 0.21 cGy for XVI. The peripheral doses were 0.26-0.66 cGy for OBI and 0.16-0.30 cGy for XVI. The calculated peripheral doses agreed within 3% in the pelvis mode and within 4% in the head mode with measured doses for both kV-CBCT systems. In addition, the absorbed dose determined in this study was approximately 4% lower than that in TG-61 but the absorbed dose by both methods was in agreement within their combined

  18. Shock Absorbing System

    NASA Technical Reports Server (NTRS)

    1982-01-01

    A lightweight, inexpensive shock-absorbing system, developed by Langley Research Center 20 years ago, is now in service as safety device for an automated railway at Duke University Medical Center. The transportation system travels at about 25 miles per hour, carrying patients, visitors, staff and cargo. At the end of each guideway of the system are "frangible," (breakable) tube "buffers." If a slowing car fails to make a complete stop at the terminal, it would bump and shatter the tubes, absorbing energy that might otherwise jolt the passengers or damage the vehicle.

  19. Phase-Transfer Energetics of Small-Molecule Alcohols Across the Water-Hexane Interface: Molecular Dynamics Simulation Using Charge Equilibration Models

    PubMed Central

    Bauer, Brad A.; Zhong, Yang; Meninger, David J.; Davis, Joseph E.; Patel, Sandeep

    2010-01-01

    We study the water-hexane interface using molecular dynamics (MD) and polarizable charge equilibration (CHEQ) force fields. Bulk densities for TIP4P-FQ water and hexane, 1.0086±0.0002 g/cm3 and 0.6378±0.0001 g/cm3, demonstrate excellent agreement with experiment. Interfacial width and interfacial tension are consistent with previously reported values. The in-plane component of the dielectric permittivity (ε∥) for water is shown to decrease from 81.7±0.04 to unity, transitioning longitudinally from bulk water to bulk hexane. ε∥ for hexane reaches a maximum in the interface, but this term represents only a small contribution to the total dielectric constant (as expected for a non-polar species). Structurally, net orientations of the molecules arise in the interfacial region such that hexane lies slightly parallel to the interface and water reorients to maximize hydrogen bonding. Interfacial potentials due to contributions of the water and hexane are calculated to be -567.9±0.13mV and 198.7±0.01mV, respectively, giving rise to a total potential in agreement with the range of values reported from previous simulations of similar systems. Potentials of mean force (PMF) calculated for methanol, ethanol, and 1-propanol for the transfer from water to hexane indicate an interfacial free energy minimum, corresponding to the amphiphilic nature of the molecules. The magnitudes of transfer free energies were further characterized from the solvation free energies of alcohols in water and hexane using thermodynamic integration. This analysis shows that solvation free energies for alcohols in hexane are 0.2-0.3 kcal/mol too unfavorable, whereas solvation of alcohols in water is approximately 1 kcal/mol too favorable. For the pure hexane-water interfacial simulations, we observe a monotonic decrease of the water dipole moment to near-vacuum values. This suggests that the electrostatic component of the desolvation free energy is not as severe for polarizable models than

  20. New approximate orientation averaging of the water molecule interacting with the thermal neutron

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

    Markovic, M.I.; Minic, D.M.; Rakic, A.D.

    1992-02-01

    This paper reports that exactly describing the time of thermal neutron collisions with water molecules, orientation averaging is performed by an exact method (EOA{sub k}) and four approximate methods (two well known and two less known). Expressions for the microscopic scattering kernel are developed. The two well-known approximate orientation averaging methods are Krieger-Nelkin (K-N) and Koppel-Young (K-Y). The results obtained by one of the two proposed approximate orientation averaging methods agree best with the corresponding results obtained by EOA{sub k}. The largest discrepancies between the EOA{sub k} results and the results of the approximate methods are obtained using the well-knowmore » K-N approximate orientation averaging method.« less

  1. Combination gas-producing and waste-water disposal well. [DOE patent application

    DOEpatents

    Malinchak, R.M.

    1981-09-03

    The present invention is directed to a waste-water disposal system for use in a gas recovery well penetrating a subterranean water-containing and methane gas-bearing coal formation. A cased bore hole penetrates the coal formation and extends downwardly therefrom into a further earth formation which has sufficient permeability to absorb the waste water entering the borehole from the coal formation. Pump means are disposed in the casing below the coal formation for pumping the water through a main conduit towards the water-absorbing earth formation. A barrier or water plug is disposed about the main conduit to prevent water flow through the casing except for through the main conduit. Bypass conduits disposed above the barrier communicate with the main conduit to provide an unpumped flow of water to the water-absorbing earth formation. One-way valves are in the main conduit and in the bypass conduits to provide flow of water therethrough only in the direction towards the water-absorbing earth formation.

  2. Carbon Absorber Retrofit Equipment (CARE)

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

    Klein, Eric

    During Project DE-FE0007528, CARE (Carbon Absorber Retrofit Equipment), Neumann Systems Group (NSG) designed, installed and tested a 0.5MW NeuStream® carbon dioxide (CO 2) capture system using the patented NeuStream® absorber equipment and concentrated (6 molal) piperazine (PZ) as the solvent at Colorado Springs Utilities’ (CSU’s) Martin Drake pulverized coal (PC) power plant. The 36 month project included design, build and test phases. The 0.5MW NeuStream® CO 2 capture system was successfully tested on flue gas from both coal and natural gas combustion sources and was shown to meet project objectives. Ninety percent CO 2 removal was achieved with greater thanmore » 95% CO 2product purity. The absorbers tested support a 90% reduction in absorber volume compared to packed towers and with an absorber parasitic power of less than 1% when configured for operation with a 550MW coal plant. The preliminary techno-economic analysis (TEA) performed by the Energy and Environmental Research Center (EERC) predicted an over-the-fence cost of $25.73/tonne of CO 2 captured from a sub-critical PC plant.« less

  3. Thermal bleaching in single fluorescent molecules under two-photon excitation regime

    NASA Astrophysics Data System (ADS)

    Chirico, Giuseppe; Cannone, Fabio; Baldini, Giancarlo; Diaspro, Alberto

    2003-07-01

    Single molecule spectroscopy often requires the immobilization of the molecules onto solid or quasi-solid substrates and the use of relatively high excitation intensity We have studied the fluorescence emission of four common dyes used for bio-imaging studies, rhodamine 6G, fluorescein, pyrene and indo-1 at the single molecule level under two-photon excitation regime. We focus on two-photon excitation thermal effects on the stability of the single molecules, influencing the internal photo-dynamics and the total duration of the fluorescent emission. Single dye molecules, spread on a glass substrate by spin coating, show a constant fluorescence output till a sudden transition to a dark state very close to the background. The bleaching time that is found to vary in the series pyrene, Indo-1, fluorescein and rhodamine 6G from the fastest to the slowest one respectively, has a Gaussian distribution suggesting that bleaching is not due to photo-bleaching. Moreover it shows a correlation to the amount of absorbed power not re-irradiated as fluorescence and to the complexity of the molecule. These observations are interpreted as thermal bleaching where the temperature increase is induced by the two-photon excitation process. This study should be extended to different trapping media of interest in single molecule basic research and applications, such as silica and polyacrylamide gels or nanosctructured polyelectrolyte matrices. We think that the observed behavior and the correlations found to the molecular chemical and physical parameters, may be of some help for the design of molecules with switching on-off behavior of longer duration.

  4. Thin film absorber for a solar collector

    DOEpatents

    Wilhelm, William G.

    1985-01-01

    This invention pertains to energy absorbers for solar collectors, and more particularly to high performance thin film absorbers. The solar collectors comprising the absorber of this invention overcome several problems seen in current systems, such as excessive hardware, high cost and unreliability. In the preferred form, the apparatus features a substantially rigid planar frame with a thin film window bonded to one planar side of the frame. An absorber in accordance with the present invention is comprised of two thin film layers that are sealed perimetrically. In a preferred embodiment, thin film layers are formed from a metal/plastic laminate. The layers define a fluid-tight planar envelope of large surface area to volume through which a heat transfer fluid flows. The absorber is bonded to the other planar side of the frame. The thin film construction of the absorber assures substantially full envelope wetting and thus good efficiency. The window and absorber films stress the frame adding to the overall strength of the collector.

  5. Solar sustained plasma/absorber conceptual design

    NASA Technical Reports Server (NTRS)

    Rodgers, R. J.; Krascella, N. L.; Kendall, J. S.

    1979-01-01

    A space power system concept was evaluated which uses concentrated solar energy to heat a working fluid to temperatures as high as 4000 K. The high temperature working fluid could be used for efficient electric power production in advanced thermal or magnetohydrodynamic conversion cycles. Energy absorber configurations utilizing particles or cesium vapor absorber material were investigaed. Results of detailed radiant heat transfer calculations indicated approximately 86 percent of the incident solar energy could be absorbed within a 12-cm-dia flowing stream of gas borne carbon particles. Calculated total energy absorption in the cesium vapor seeded absorber configuration ranged from 34 percent to 64 percent of the incident solar energy. Solar flux concentration ratios of between approximately 3000 and 10,000 will be required to sustain absorber temperatures in the range from 3000 K to 4000 K.

  6. Structured Metal Film as Perfect Absorber

    NASA Astrophysics Data System (ADS)

    Xiong, Xiang; Jiang, Shang-Chi; Peng, Ru-Wen; Wang, Mu

    2014-03-01

    With standing U-shaped resonators, fish-spear-like resonator has been designed for the first time as the building block to assemble perfect absorbers. The samples have been fabricated with two-photon polymerization process and FTIR measurement results support the effectiveness of the perfect absorber design. In such a structure the polarization-dependent resonance occurs between the tines of the spears instead of the conventional design where the resonance occurs between the metallic layers separated by a dielectric interlayer. The incident light neither transmits nor reflects back which results in unit absorbance. The power of light is trapped between the tines of spears and finally be absorbed. The whole structure is covered with a continuous metallic layer with good thermo-conductance, which provides an excellent approach to deal with heat dissipation, is enlightening in exploring metamaterial absorbers.

  7. Absorbed dose thresholds and absorbed dose rate limitations for studies of electron radiation effects on polyetherimides

    NASA Technical Reports Server (NTRS)

    Long, Edward R., Jr.; Long, Sheila Ann T.; Gray, Stephanie L.; Collins, William D.

    1989-01-01

    The threshold values of total absorbed dose for causing changes in tensile properties of a polyetherimide film and the limitations of the absorbed dose rate for accelerated-exposure evaluation of the effects of electron radiation in geosynchronous orbit were studied. Total absorbed doses from 1 kGy to 100 MGy and absorbed dose rates from 0.01 MGy/hr to 100 MGy/hr were investigated, where 1 Gy equals 100 rads. Total doses less than 2.5 MGy did not significantly change the tensile properties of the film whereas doses higher than 2.5 MGy significantly reduced elongation-to-failure. There was no measurable effect of the dose rate on the tensile properties for accelerated electron exposures.

  8. "Smart" Electromechanical Shock Absorber

    NASA Technical Reports Server (NTRS)

    Stokes, Lebarian; Glenn, Dean C.; Carroll, Monty B.

    1989-01-01

    Shock-absorbing apparatus includes electromechanical actuator and digital feedback control circuitry rather than springs and hydraulic damping as in conventional shock absorbers. Device not subject to leakage and requires little or no maintenance. Attenuator parameters adjusted in response to sensory feedback and predictive algorithms to obtain desired damping characteristic. Device programmed to decelerate slowly approaching vehicle or other large object according to prescribed damping characteristic.

  9. Determination of absorbed dose to water for high-energy photon and electron beams-comparison of the standards DIN 6800-2 (1997), IAEA TRS 398 (2000) and DIN 6800-2 (2006).

    PubMed

    Zakaria, Golam Abu; Schuette, Wilhelm

    2007-01-01

    For the determination of the absorbed dose to water for high-energy photon and electron beams the IAEA code of practice TRS-398 (2000) is applied internationally. In Germany, the German dosimetry protocol DIN 6800-2 (1997) is used. Recently, the DIN standard has been revised and published as Draft National Standard DIN 6800-2 (2006). It has adopted widely the methodology and dosimetric data of the code of practice. This paper compares these three dosimetry protocols systematically and identifies similarities as well as differences. The investigation was done with 6 and 18 MV photon as well as 5 to 21 MeV electron beams. While only cylindrical chambers were used for photon beams, measurements of electron beams were performed using cylindrical as well as plane-parallel chambers. The discrepancies in the determination of absorbed dose to water between the three protocols were 0.4% for photon beams and 1.5% for electron beams. Comparative measurements showed a deviation of less than 0.5% between our measurements following protocol DIN 6800-2 (2006) and TLD inter-comparison procedure in an external audit.

  10. Deep absorbing porphyrin small molecule for high-performance organic solar cells with very low energy losses.

    PubMed

    Gao, Ke; Li, Lisheng; Lai, Tianqi; Xiao, Liangang; Huang, Yuan; Huang, Fei; Peng, Junbiao; Cao, Yong; Liu, Feng; Russell, Thomas P; Janssen, René A J; Peng, Xiaobin

    2015-06-17

    We designed and synthesized the DPPEZnP-TEH molecule, with a porphyrin ring linked to two diketopyrrolopyrrole units by ethynylene bridges. The resulting material exhibits a very low energy band gap of 1.37 eV and a broad light absorption to 907 nm. An open-circuit voltage of 0.78 V was obtained in bulk heterojunction (BHJ) organic solar cells, showing a low energy loss of only 0.59 eV, which is the first report that small molecule solar cells show energy losses <0.6 eV. The optimized solar cells show remarkable external quantum efficiency, short circuit current, and power conversion efficiency up to 65%, 16.76 mA/cm(2), and 8.08%, respectively, which are the best values for BHJ solar cells with very low energy losses. Additionally, the morphology of DPPEZnP-TEH neat and blend films with PC61BM was studied thoroughly by grazing incidence X-ray diffraction, resonant soft X-ray scattering, and transmission electron microscopy under different fabrication conditions.

  11. Carbon dioxide absorber and regeneration assemblies useful for power plant flue gas

    DOEpatents

    Vimalchand, Pannalal; Liu, Guohai; Peng, Wan Wang

    2012-11-06

    Disclosed are apparatus and method to treat large amounts of flue gas from a pulverized coal combustion power plant. The flue gas is contacted with solid sorbents to selectively absorb CO.sub.2, which is then released as a nearly pure CO.sub.2 gas stream upon regeneration at higher temperature. The method is capable of handling the necessary sorbent circulation rates of tens of millions of lbs/hr to separate CO.sub.2 from a power plant's flue gas stream. Because pressurizing large amounts of flue gas is cost prohibitive, the method of this invention minimizes the overall pressure drop in the absorption section to less than 25 inches of water column. The internal circulation of sorbent within the absorber assembly in the proposed method not only minimizes temperature increases in the absorber to less than 25.degree. F., but also increases the CO.sub.2 concentration in the sorbent to near saturation levels. Saturating the sorbent with CO.sub.2 in the absorber section minimizes the heat energy needed for sorbent regeneration. The commercial embodiments of the proposed method can be optimized for sorbents with slower or faster absorption kinetics, low or high heat release rates, low or high saturation capacities and slower or faster regeneration kinetics.

  12. Dynamic testing of airplane shock-absorbing struts

    NASA Technical Reports Server (NTRS)

    Langer, P; Thome, W

    1932-01-01

    Measurement of perpendicular impacts of a landing gear with different shock-absorbing struts against the drum testing stand. Tests were made with pneumatic shock absorbers having various degrees of damping, liquid shock absorbers, steel-spring shock absorbers and rigid struts. Falling tests and rolling tests. Maximum impact and gradual reduction of the impacts in number and time in the falling tests. Maximum impact and number of weaker impacts in rolling tests.

  13. Impedance approach to designing efficient vibration energy absorbers

    NASA Astrophysics Data System (ADS)

    Bobrovnitskii, Y. I.; Morozov, K. D.; Tomilina, T. M.

    2017-03-01

    The concept introduced previously by the authors on the best sound absorber having the maximum allowable efficiency in absorbing the energy of an incident sound field has been extended to arbitrary linear elastic media and structures. Analytic relations have been found for the input impedance characteristics that the best vibrational energy absorber should have. The implementation of these relations is the basis of the proposed impedance method of designing efficient vibration and noise absorbers. We present the results of a laboratory experiment that confirms the validity of the obtained theoretical relations, and we construct the simplest best vibration absorber. We also calculate the parameters and demonstrate the efficiency of a dynamic vibration absorber as the best absorber.

  14. [In situ diffuse reflectance FTIR spectroscopy study of CO adsorption on Ni2P/mesoporous molecule sieve catalysts].

    PubMed

    Liu, Qian-qian; Ji, Sheng-fu; Wu, Ping-yi; Hu, Lin-hua; Huang, Xiao-fan; Zhu, Ji-qin; Li, Cheng-yue

    2009-05-01

    Abstract The supported nickel phosphate precursors were prepared by incipient wetness impregnation using nickel nitrate as nickel source, diammonium hydrogen phosphate as phosphorus source, and MCM-41, MCM-48, SBA-15 and SBA-16 as supports, respectively. Then, the supported Ni2 P catalysts were prepared by temperature-programmed reduction in flowing Hz from their nickel phosphate precursors. The in situ diffuse reflectance FTIR spectroscopy (DRIFTS) analysis with the probe molecule CO was carried out to characterize the surface properties. The results indicated that there were significant differences in the spectral features of the samples. The upsilon(CO) absorbances observed for adsorbed CO on mesoporous molecule sieve was attributed to weak physical adsorption. There are four different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2 P/MCM-41 catalyst with the following assignments: (1) the formation of Ni(CO)4 at 2055 cm(-1). (2) CO terminally bonded to cus Ni(delta+) (0absorbances observed for adsorbed CO on Ni2P/MCM-48, Ni2P/ SBA-15 and Ni2P/SBA-16 catalysts. The absorbance observed at 2051-2055 cm(-1) for CO adsorption on Ni2P/MCM-48, Ni2P/SBA-15 and Ni2P/SBA-16 catalysts is due to the formation of Ni(CO)4 species. The other upsilon absorbances observed at 2093-2096 cm(-1) was attributed to CO terminally bonded to cus Ni(delta+) (0

  15. Nonpeptide-Based Small-Molecule Probe for Fluorogenic and Chromogenic Detection of Chymotrypsin.

    PubMed

    Wu, Lei; Yang, Shu-Hou; Xiong, Hao; Yang, Jia-Qian; Guo, Jun; Yang, Wen-Chao; Yang, Guang-Fu

    2017-03-21

    We report herein a nonpeptide-based small-molecule probe for fluorogenic and chromogenic detection of chymotrypsin, as well as the primary application for this probe. This probe was rationally designed by mimicking the peptide substrate and optimized by adjusting the recognition group. The refined probe 2 exhibits good specificity toward chymotrypsin, producing about 25-fold higher enhancement in both the fluorescence intensity and absorbance upon the catalysis by chymotrypsin. Compared with the most widely used peptide substrate (AMC-FPAA-Suc) of chymotrypsin, probe 2 shows about 5-fold higher binding affinity and comparable catalytical efficiency against chymotrypsin. Furthermore, it was successfully applied for the inhibitor characterization. To the best of our knowledge, probe 2 is the first nonpeptide-based small-molecule probe for chymotrypsin, with the advantages of simple structure and high sensitivity compared to the widely used peptide-based substrates. This small-molecule probe is expected to be a useful molecular tool for drug discovery and chymotrypsin-related disease diagnosis.

  16. Interactions of Oxygen and Water Molecules with Pyrite Surface: A New Insight.

    PubMed

    Li, Yuqiong; Chen, Jianhua; Chen, Ye; Zhao, Cuihua; Zhang, Yibing; Ke, Baolin

    2018-02-06

    Pyrite is the most common sulfide in nature, and it is well-known for its roles in acid mine drainage, flotation separation of useful metal (Cu, Pb, Zn, and Mo) sulfide minerals, optoelectronic and photovoltaic application, pneumoconiosis, and even in the origin of life. However, the detailed oxidation behaviors of pyrite are still unclear and not well-understood. New oxidation pathways by O 2 on the pyrite (100) surface have been found in this work for the first time using density functional theory simulation; that is, besides Fe sites, S sites are also possible oxidation sites in the initial oxidation state of pyrite, where easier and stronger oxidation may occur. This is the first time to confirm the other researchers' conjecture on the direct oxidation of S sites, which explains the isotopic composition experiments that a minor amount of O 2 is permanently incorporated into SO 4 2- during pyrite oxidation (O in SO 4 2- is mainly derived from water). We constructed various H 2 O-O 2 coadsorption models on the pyrite surface by considering the adsorption sequence of H 2 O and O 2 . It is found that the H 2 O molecule undergoes step-wise dissociation in the presence of the O 2 molecule. Hydroxyl radical •OH is the reactive oxygen species during H 2 O dissociation. Cyclic voltammetric measurements confirm the presence of •OH. In addition, H 2 O 2 may also be formed on the surface in terms of H 2 O-then-O 2 sequence adsorption.

  17. Infrared light-induced protein crystallization. Structuring of protein interfacial water and periodic self-assembly

    NASA Astrophysics Data System (ADS)

    Kowacz, Magdalena; Marchel, Mateusz; Juknaité, Lina; Esperança, José M. S. S.; Romão, Maria João; Carvalho, Ana Luísa; Rebelo, Luís Paulo N.

    2017-01-01

    We show that a physical trigger, a non-ionizing infrared (IR) radiation at wavelengths strongly absorbed by liquid water, can be used to induce and kinetically control protein (periodic) self-assembly in solution. This phenomenon is explained by considering the effect of IR light on the structuring of protein interfacial water. Our results indicate that the IR radiation can promote enhanced mutual correlations of water molecules in the protein hydration shell. We report on the radiation-induced increase in both the strength and cooperativeness of H-bonds. The presence of a structured dipolar hydration layer can lead to attractive interactions between like-charged biomacromolecules in solution (and crystal nucleation events). Furthermore, our study suggests that enveloping the protein within a layer of structured solvent (an effect enhanced by IR light) can prevent the protein non-specific aggregation favoring periodic self-assembly. Recognizing the ability to affect protein-water interactions by means of IR radiation may have important implications for biological and bio-inspired systems.

  18. Composite neutron absorbing coatings for nuclear criticality control

    DOEpatents

    Wright, Richard N.; Swank, W. David; Mizia, Ronald E.

    2005-07-19

    Thermal neutron absorbing composite coating materials and methods of applying such coating materials to spent nuclear fuel storage systems are provided. A composite neutron absorbing coating applied to a substrate surface includes a neutron absorbing layer overlying at least a portion of the substrate surface, and a corrosion resistant top coat layer overlying at least a portion of the neutron absorbing layer. An optional bond coat layer can be formed on the substrate surface prior to forming the neutron absorbing layer. The neutron absorbing layer can include a neutron absorbing material, such as gadolinium oxide or gadolinium phosphate, dispersed in a metal alloy matrix. The coating layers may be formed by a plasma spray process or a high velocity oxygen fuel process.

  19. Single-molecule nanopore enzymology

    PubMed Central

    Wloka, Carsten; Maglia, Giovanni

    2017-01-01

    Biological nanopores are a class of membrane proteins that open nanoscale water-conduits in biological membranes. When they are reconstituted in artificial membranes and a bias voltage is applied across the membrane, the ionic current passing through individual nanopores can be used to monitor chemical reactions, to recognize individual molecules and, of most interest, to sequence DNA. More recently, proteins and enzymes have started being analysed with nanopores. Monitoring enzymatic reactions with nanopores, i.e. nanopore enzymology, has the unique advantage that it allows long-timescale observations of native proteins at the single-molecule level. Here we describe the approaches and challenges in nanopore enzymology. PMID:28630164

  20. Far-ultraviolet absorbance detection of sugars and peptides by high-performance liquid chromatography.

    PubMed

    Uchiho, Yuichi; Goto, Yusuke; Kamahori, Masao; Aota, Toshimichi; Morisaki, Atsuki; Hosen, Yusuke; Koda, Kimiyoshi

    2015-12-11

    A far-ultraviolet (FUV)-absorbance detector with a transmission flow cell was developed and applied to detect absorbance of sugars and peptides by HPLC. The main inherent limitation of FUV-absorbance detection is the strong absorptions of solvents and atmospheric oxygen in the optical system as well as dissolved oxygen in the solvent. High absorptivity of the solvent and oxygen decreases transmission-light intensity in the flow cell and hinders the absorbance measurement. To solve the above drawbacks, the transmission-light intensity in the flow cell was increased by introducing a new optical system and a nitrogen-purging unit to remove the atmospheric oxygen. The optical system has a photodiode for detecting the reference light at a position of the minus-first-order diffracted light. In addition, acetonitrile and water were selected as usable solvents because of their low absorptivity in the FUV region. As a result of these implementations, the detectable wavelength of the FUV-absorbance detector (with a flow cell having an effective optical path length of 0.5mm) can be extended down to 175nm. Three sugars (glucose, fructose, and sucrose) were successfully detected with the FUV-absorbance detector. These detection results reveal that the absorption peak of sugar in liquid phase lies at around 178nm. The detection limit (S/N=3) in absorbance with a 0.5-mm flow cell at 180nm was 21μAU, which corresponds to 33, 60 and 60μM (198, 360, and 360pmol) for fructose, glucose, and sucrose, respectively. Also, the peptide Met-enkephalin could be detected with a high sensitivity at 190nm. The estimated detection limit (S/N=3) for Met-enkephalin is 29nM (0.29pmol), which is eight times lower than that at 220nm. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Structure and energetics of model amphiphilic molecules at the water liquid-vapor interface - A molecular dynamics study

    NASA Technical Reports Server (NTRS)

    Pohorille, Andrew; Benjamin, Ilan

    1993-01-01

    A molecular dynamics study of adsorption of p-n-pentylphenol at infinite dilution at the water liquid-vapor interface is reported. The calculated free energy of adsorption is -8.8 +/- 0.7 kcal/mol, in good agreement with the experimental value of -7.3 kcal/mol. The transition between the interfacial region and the bulk solution is sharp and well-defined by energetic, conformational, and orientational criteria. At the water surface, the phenol head group is mostly immersed in aqueous solvent. The most frequent orientation of the hydrocarbon tail is parallel to the interface, due to dispersion interactions with the water surface. This arrangement of the phenol ring and the alkyl chain requires that the chain exhibits a kink. As the polar head group is being moved into the solvent, the chain length increases and the tail becomes increasingly aligned toward the surface normal, such that the nonpolar part of the molecule exposed to water is minimized. The same effect was achieved when phenol was replaced by a more polar head group, phenolate.

  2. Wide band cryogenic ultra-high vacuum microwave absorber

    DOEpatents

    Campisi, I.E.

    1992-05-12

    An absorber waveguide assembly for absorbing higher order modes of microwave energy under cryogenic ultra-high vacuum conditions, that absorbs wide-band multi-mode energy. The absorber is of a special triangular shape, made from flat tiles of silicon carbide and aluminum nitride. The leading sharp end of the absorber is located in a corner of the waveguide and tapers to a larger cross-sectional area whose center is located approximately in the center of the wave guide. The absorber is relatively short, being of less height than the maximum width of the waveguide. 11 figs.

  3. Wide band cryogenic ultra-high vacuum microwave absorber

    DOEpatents

    Campisi, Isidoro E.

    1992-01-01

    An absorber wave guide assembly for absorbing higher order modes of microwave energy under cryogenic ultra-high vacuum conditions, that absorbs wide-band multi-mode energy. The absorber is of a special triangular shape, made from flat tiles of silicon carbide and aluminum nitride. The leading sharp end of the absorber is located in a corner of the wave guide and tapers to a larger cross-sectional area whose center is located approximately in the center of the wave guide. The absorber is relatively short, being of less height than the maximum width of the wave guide.

  4. Two-dimensional QR-coded metamaterial absorber

    NASA Astrophysics Data System (ADS)

    Sui, Sai; Ma, Hua; Wang, Jiafu; Pang, Yongqiang; Zhang, Jieqiu; Qu, Shaobo

    2016-01-01

    In this paper, the design of metamaterial absorbers is proposed based on QR coding and topology optimization. Such absorbers look like QR codes and can be recognized by decoding softwares as well as mobile phones. To verify the design, two lightweight wideband absorbers are designed, which can achieve wideband absorption above 90 % in 6.68-19.30 and 7.00-19.70 GHz, respectively. More importantly, polarization-independent absorption over 90 % can be maintained under incident angle within 55°. The QR code absorber not only can achieve wideband absorption, but also can carry information such as texts and Web sites. They are of important values in applications such identification and electromagnetic protection.

  5. A proactive role of water molecules in acceptor recognition by protein O-fucosyltransferase 2.

    PubMed

    Valero-González, Jessika; Leonhard-Melief, Christina; Lira-Navarrete, Erandi; Jiménez-Osés, Gonzalo; Hernández-Ruiz, Cristina; Pallarés, María Carmen; Yruela, Inmaculada; Vasudevan, Deepika; Lostao, Anabel; Corzana, Francisco; Takeuchi, Hideyuki; Haltiwanger, Robert S; Hurtado-Guerrero, Ramon

    2016-04-01

    Protein O-fucosyltransferase 2 (POFUT2) is an essential enzyme that fucosylates serine and threonine residues of folded thrombospondin type 1 repeats (TSRs). To date, the mechanism by which this enzyme recognizes very dissimilar TSRs has been unclear. By engineering a fusion protein, we report the crystal structure of Caenorhabditis elegans POFUT2 (CePOFUT2) in complex with GDP and human TSR1 that suggests an inverting mechanism for fucose transfer assisted by a catalytic base and shows that nearly half of the TSR1 is embraced by CePOFUT2. A small number of direct interactions and a large network of water molecules maintain the complex. Site-directed mutagenesis demonstrates that POFUT2 fucosylates threonine preferentially over serine and relies on folded TSRs containing the minimal consensus sequence C-X-X-S/T-C. Crystallographic and mutagenesis data, together with atomic-level simulations, uncover a binding mechanism by which POFUT2 promiscuously recognizes the structural fingerprint of poorly homologous TSRs through a dynamic network of water-mediated interactions.

  6. Wireless device for activation of an underground shock wave absorber

    NASA Astrophysics Data System (ADS)

    Chikhradze, M.; Akhvlediani, I.; Bochorishvili, N.; Mataradze, E.

    2011-10-01

    The paper describes the mechanism and design of the wireless device for activation of energy absorber for localization of blast energy in underground openings. The statistics shows that the greatest share of accidents with fatal results associate with explosions in coal mines due to aero-methane and/or air-coal media explosion. The other significant problem is terrorist or accidental explosions in underground structures. At present there are different protective systems to reduce the blast energy. One of the main parts of protective Systems is blast Identification and Registration Module. The works conducted at G. Tsulukidze Mining Institute of Georgia enabled to construct the wireless system of explosion detection and mitigation of shock waves. The system is based on the constant control on overpressure. The experimental research continues to fulfill the system based on both threats, on the constant control on overpressure and flame parameters, especially in underground structures and coal mines. Reaching the threshold value of any of those parameters, the system immediately starts the activation. The absorber contains a pyrotechnic device ensuring the discharge of dispersed water. The operational parameters of wireless device and activation mechanisms of pyrotechnic element of shock wave absorber are discussed in the paper.

  7. Anomalous diffusion of water molecules at grain boundaries in ice Ih.

    PubMed

    Moreira, Pedro Augusto Franco Pinheiro; Veiga, Roberto Gomes de Aguiar; Ribeiro, Ingrid de Almeida; Freitas, Rodrigo; Helfferich, Julian; de Koning, Maurice

    2018-05-23

    Using ab initio and classical molecular dynamics simulations, we study pre-melting phenomena in pristine coincident-site-lattice grain boundaries (GBs) in proton-disordered hexagonal ice Ih at temperatures just below the melting point Tm. Concerning pre-melt-layer thicknesses, the results are consistent with the available experimental estimates for low-disorder impurity-free GBs. With regard to molecular mobility, the simulations provide a key new insight: the translational motion of the water molecules is found to be subdiffusive for time scales from ∼10 ns up to at least 0.1 μs. Moreover, the fact that the anomalous diffusion occurs even at temperatures just below Tm where the bulk supercooled liquid still diffuses normally suggests that it is related to the confinement of the GB pre-melt layers by the surrounding crystalline environment. Furthermore, we show that this behavior can be characterized by continuous-time random walk models in which the waiting-time distributions decay according to power-laws that are very similar to those describing dynamics in glass-forming systems.

  8. Intercalated Water and Organic Molecules for Electrode Materials of Rechargeable Batteries.

    PubMed

    Lee, Hyeon Jeong; Shin, Jaeho; Choi, Jang Wook

    2018-03-24

    The intrinsic limitations of lithium-ion batteries (LIBs) with regard to safety, cost, and the availability of raw materials have promoted research on so-called "post-LIBs". The recent intense research of post-LIBs provides an invaluable lesson that existing electrode materials used in LIBs may not perform as well in post-LIBs, calling for new material designs compliant with emerging batteries based on new chemistries. One promising approach in this direction is the development of materials with intercalated water or organic molecules, as these materials demonstrate superior electrochemical performance in emerging battery systems. The enlarged ionic channel dimensions and effective shielding of the electrostatic interaction between carrier ions and the lattice host are the origins of the observed electrochemical performance. Moreover, these intercalants serve as interlayer pillars to sustain the framework for prolonged cycles. Representative examples of such intercalated materials applied to batteries based on Li + , Na + , Mg 2+ , and Zn 2+ ions and supercapacitors are considered, along with their impact in materials research. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Fingerprinting Dissolved Organic Carbon (DOC) Sources with Specific UV Absorbance (SUVA) and Fluorescence

    NASA Astrophysics Data System (ADS)

    van Verseveld, W. J.; Lajtha, K.; McDonnell, J. J.

    2007-12-01

    DOC is an important water quality constituent because it is an important food source for stream biota, it plays a significant role in metal toxicity and transport, and protects aquatic organisms by absorbing visible and UV light. However, sources of stream DOC and changes in DOC quality at storm and seasonal scales remain poorly understood. We characterized DOC concentrations and SUVA (as an indicator of aromaticity) at the plot, hillslope and catchment scale during and between five storm events over the period Fall 2004 until Spring 2005, in WS10, H.J. Andrews, Oregon, USA. This study site has hillslopes that issue directly into the stream. This enabled us to compare a trenched hillslope response to the stream response without the influence of a riparian zone. The main result of this study was that SUVA in addition to DOC was needed to fingerprint sources of DOC. Stream water and lateral subsurface flow showed a clockwise DOC and SUVA hysteresis pattern. Both organic horizon water and transient groundwater were characterized by high DOC concentrations and SUVA values, while DOC concentrations and SUVA values in soil water decreased with depth in the soil profile. This indicates transient groundwater was an important contributor to high DOC concentrations and SUVA values during storm events. During the falling limb of the hydrograph deep soil water and seepage groundwater based on SUVA values contributed significantly to lateral subsurface flow and stream water. Preliminary results showed that fluorescence of stream water and lateral subsurface flow continuously measured with a fluorometer was significantly related to UV-absorbance during a December storm event. Finally, SUVA of lateral subsurface flow was lower than SUVA of stream water at the seasonal scale, indicating a difference in mixing of water sources at the hillslope and catchment scale. Overall, our results show that SUVA and fluorescence are useful tracers for fingerprinting DOC sources.

  10. Light Absorbers and Catalysts for Solar to Fuel Conversion

    NASA Astrophysics Data System (ADS)

    Kornienko, Nikolay I.

    Increasing fossil fuel consumption and the resulting consequences to the environment has propelled research into means of utilizing alternative, clean energy sources. Solar power is among the most promising of renewable energy sources but must be converted into an energy dense medium such as chemical bonds to render it useful for transport and energy storage. Photoelectrochemistry (PEC), the splitting of water into oxygen and hydrogen fuel or reducing CO 2 to hydrocarbon fuels via sunlight is a promising approach towards this goal. Photoelectrochemical systems are comprised of several components, including light absorbers and catalysts. These parts must all synergistically function in a working device. Therefore, the continual development of each component is crucial for the overall goal. For PEC systems to be practical for large scale use, the must be efficient, stable, and composed of cost effective components. To this end, my work focused on the development of light absorbing and catalyst components of PEC solar to fuel converting systems. In the direction of light absorbers, I focused of utilizing Indium Phosphide (InP) nanowires (NWs) as photocathodes. I first developed synthetic techniques for InP NW solution phase and vapor phase growth. Next, I developed light absorbing photocathodes from my InP NWs towards PEC water splitting cells. I studied cobalt sulfide (CoSx) as an earth abundant catalyst for the reductive hydrogen evolution half reaction. Using in situ spectroscopic techniques, I elucidated the active structure of this catalyst and offered clues to its high activity. In addition to hydrogen evolution catalysts, I established a new generation of earth abundant catalysts for CO2 reduction to CO fuel/chemical feedstock. I first worked with molecularly tunable homogeneous catalysts that exhibited high selectivity for CO2 reduction in non-aqueous media. Next, in order to retain molecular tunability while achieving stability and efficiency in aqueous

  11. Measurement of absorbed dose with a bone-equivalent extrapolation chamber.

    PubMed

    DeBlois, François; Abdel-Rahman, Wamied; Seuntjens, Jan P; Podgorsak, Ervin B

    2002-03-01

    A hybrid phantom-embedded extrapolation chamber (PEEC) made of Solid Water and bone-equivalent material was used for determining absorbed dose in a bone-equivalent phantom irradiated with clinical radiation beams (cobalt-60 gamma rays; 6 and 18 MV x rays; and 9 and 15 MeV electrons). The dose was determined with the Spencer-Attix cavity theory, using ionization gradient measurements and an indirect determination of the chamber air-mass through measurements of chamber capacitance. The collected charge was corrected for ionic recombination and diffusion in the chamber air volume following the standard two-voltage technique. Due to the hybrid chamber design, correction factors accounting for scatter deficit and electrode composition were determined and applied in the dose equation to obtain absorbed dose in bone for the equivalent homogeneous bone phantom. Correction factors for graphite electrodes were calculated with Monte Carlo techniques and the calculated results were verified through relative air cavity dose measurements for three different polarizing electrode materials: graphite, steel, and brass in conjunction with a graphite collecting electrode. Scatter deficit, due mainly to loss of lateral scatter in the hybrid chamber, reduces the dose to the air cavity in the hybrid PEEC in comparison with full bone PEEC by 0.7% to approximately 2% depending on beam quality and energy. In megavoltage photon and electron beams, graphite electrodes do not affect the dose measurement in the Solid Water PEEC but decrease the cavity dose by up to 5% in the bone-equivalent PEEC even for very thin graphite electrodes (<0.0025 cm). In conjunction with appropriate correction factors determined with Monte Carlo techniques, the uncalibrated hybrid PEEC can be used for measuring absorbed dose in bone material to within 2% for high-energy photon and electron beams.

  12. On the definition of absorbed dose

    NASA Astrophysics Data System (ADS)

    Grusell, Erik

    2015-02-01

    Purpose: The quantity absorbed dose is used extensively in all areas concerning the interaction of ionizing radiation with biological organisms, as well as with matter in general. The most recent and authoritative definition of absorbed dose is given by the International Commission on Radiation Units and Measurements (ICRU) in ICRU Report 85. However, that definition is incomplete. The purpose of the present work is to give a rigorous definition of absorbed dose. Methods: Absorbed dose is defined in terms of the random variable specific energy imparted. A random variable is a mathematical function, and it cannot be defined without specifying its domain of definition which is a probability space. This is not done in report 85 by the ICRU, mentioned above. Results: In the present work a definition of a suitable probability space is given, so that a rigorous definition of absorbed dose is possible. This necessarily includes the specification of the experiment which the probability space describes. In this case this is an irradiation, which is specified by the initial particles released and by the material objects which can interact with the radiation. Some consequences are discussed. Specific energy imparted is defined for a volume, and the definition of absorbed dose as a point function involves the specific energy imparted for a small mass contained in a volume surrounding the point. A possible more precise definition of this volume is suggested and discussed. Conclusions: The importance of absorbed dose motivates a proper definition, and one is given in the present work. No rigorous definition has been presented before.

  13. Ligand uptake in Mycobacterium tuberculosis truncated hemoglobins is controlled by both internal tunnels and active site water molecules

    PubMed Central

    Davidge, Kelly S; Singh, Sandip; Bowman, Lesley AH; Tinajero-Trejo, Mariana; Carballal, Sebastián; Radi, Rafael; Poole, Robert K; Dikshit, Kanak; Estrin, Dario A; Marti, Marcelo A; Boechi, Leonardo

    2015-01-01

    Mycobacterium tuberculosis, the causative agent of human tuberculosis, has two proteins belonging to the truncated hemoglobin (trHb) family. Mt-trHbN presents well-defined internal hydrophobic tunnels that allow O 2 and •NO to migrate easily from the solvent to the active site, whereas Mt-trHbO possesses tunnels interrupted by a few bulky residues, particularly a tryptophan at position G8. Differential ligand migration rates allow Mt-trHbN to detoxify •NO, a crucial step for pathogen survival once under attack by the immune system, much more efficiently than Mt-trHbO. In order to investigate the differences between these proteins, we performed experimental kinetic measurements, •NO decomposition, as well as molecular dynamics simulations of the wild type Mt-trHbN and two mutants, VG8F and VG8W. These mutations affect both the tunnels accessibility as well as the affinity of distal site water molecules, thus modifying the ligand access to the iron. We found that a single mutation allows Mt-trHbN to acquire ligand migration rates comparable to those observed for Mt-trHbO, confirming that ligand migration is regulated by the internal tunnel architecture as well as by water molecules stabilized in the active site. PMID:26478812

  14. Ligand uptake in Mycobacterium tuberculosis truncated hemoglobins is controlled by both internal tunnels and active site water molecules.

    PubMed

    Boron, Ignacio; Bustamante, Juan Pablo; Davidge, Kelly S; Singh, Sandip; Bowman, Lesley Ah; Tinajero-Trejo, Mariana; Carballal, Sebastián; Radi, Rafael; Poole, Robert K; Dikshit, Kanak; Estrin, Dario A; Marti, Marcelo A; Boechi, Leonardo

    2015-01-01

    Mycobacterium tuberculosis, the causative agent of human tuberculosis, has two proteins belonging to the truncated hemoglobin (trHb) family. Mt-trHbN presents well-defined internal hydrophobic tunnels that allow O 2 and • NO to migrate easily from the solvent to the active site, whereas Mt-trHbO possesses tunnels interrupted by a few bulky residues, particularly a tryptophan at position G8. Differential ligand migration rates allow Mt-trHbN to detoxify • NO, a crucial step for pathogen survival once under attack by the immune system, much more efficiently than Mt-trHbO. In order to investigate the differences between these proteins, we performed experimental kinetic measurements, • NO decomposition, as well as molecular dynamics simulations of the wild type Mt-trHbN and two mutants, VG8F and VG8W. These mutations affect both the tunnels accessibility as well as the affinity of distal site water molecules, thus modifying the ligand access to the iron. We found that a single mutation allows Mt-trHbN to acquire ligand migration rates comparable to those observed for Mt-trHbO, confirming that ligand migration is regulated by the internal tunnel architecture as well as by water molecules stabilized in the active site.

  15. Synthesis of ZnO particles using water molecules generated in esterification reaction

    NASA Astrophysics Data System (ADS)

    Šarić, Ankica; Gotić, Marijan; Štefanić, Goran; Dražić, Goran

    2017-07-01

    Zinc oxide particles were synthesized without the addition of water by autoclaving (anhydrous) zinc acetate/alcohol and zinc acetate/acetic acid/alcohol solutions at 160 °C. The solvothermal synthesis was performed in ethanol or octanol. The structural, optical and morphological characteristics of ZnO particles were investigated by X-ray diffraction (XRD), UV-Vis spectroscopy, FE-SEM and TEM/STEM microscopy. 13C NMR spectroscopy revealed the presence of ester (ethyl- or octyl-acetate) in the supernatants which directly indicate the reaction mechanism. The formation of ester in this esterification reaction generated water molecule in situ, which hydrolyzed anhydrous zinc acetate and initiated nucleation and formation of ZnO. It was found that the size and shape of ZnO particles depend on the type of alcohol used as a solvent and on the presence of acetic acid in solution. The presence of ethanol in the ;pure; system without acetic acid favoured the formation of fine and uniform spherical ZnO nanoparticles (∼20 nm). With the addition of small amount of acetic acid the size of these small nanoparticles increased significantly up to a few hundred nanometers. The addition of small amount of acetic acid in the presence of octanol caused even more radical changes in the shape of ZnO particles, favouring the growth of huge rod-like particles (∼3 μm).

  16. Magnetic field effects on microwave absorbing materials

    NASA Technical Reports Server (NTRS)

    Goldberg, Ira; Hollingsworth, Charles S.; Mckinney, Ted M.

    1991-01-01

    The objective of this program was to gather information to formulate a microwave absorber that can work in the presence of strong constant direct current (DC) magnetic fields. The program was conducted in four steps. The first step was to investigate the electrical and magnetic properties of magnetic and ferrite microwave absorbers in the presence of strong magnetic fields. This included both experimental measurements and a literature survey of properties that may be applicable to finding an appropriate absorbing material. The second step was to identify those material properties that will produce desirable absorptive properties in the presence of intense magnetic fields and determine the range of magnetic field in which the absorbers remain effective. The third step was to establish ferrite absorber designs that will produce low reflection and adequate absorption in the presence of intense inhomogeneous static magnetic fields. The fourth and final step was to prepare and test samples of such magnetic microwave absorbers if such designs seem practical.

  17. Additive manufacturing of RF absorbers

    NASA Astrophysics Data System (ADS)

    Mills, Matthew S.

    The ability of additive manufacturing techniques to fabricate integrated electromagnetic absorbers tuned for specific radio frequency bands within structural composites allows for unique combinations of mechanical and electromagnetic properties. These composites and films can be used for RF shielding of sensitive electromagnetic components through in-plane and out-of-plane RF absorption. Structural composites are a common building block of many commercial platforms. These platforms may be placed in situations in which there is a need for embedded RF absorbing properties along with structural properties. Instead of adding radar absorbing treatments to the external surface of existing structures, which adds increased size, weight and cost; it could prove to be advantageous to integrate the microwave absorbing properties directly into the composite during the fabrication process. In this thesis, a method based on additive manufacturing techniques of composites structures with prescribed electromagnetic loss, within the frequency range 1 to 26GHz, is presented. This method utilizes screen printing and nScrypt micro dispensing to pattern a carbon based ink onto low loss substrates. The materials chosen for this study will be presented, and the fabrication technique that these materials went through to create RF absorbing structures will be described. The calibration methods used, the modeling of the RF structures, and the applications in which this technology can be utilized will also be presented.

  18. Assessment of capabilities of multiangle imaging photo-polarimetry for atmospheric correction in presence of absorbing aerosols

    NASA Astrophysics Data System (ADS)

    Kalashnikova, O. V.; Garay, M. J.; Xu, F.; Seidel, F. C.; Diner, D. J.

    2015-12-01

    Satellite remote sensing of ocean color is a critical tool for assessing the productivity of marine ecosystems and monitoring changes resulting from climatic or environmental influences. Yet water-leaving radiance comprises less than 10% of the signal measured from space, making correction for absorption and scattering by the intervening atmosphere imperative. Traditional ocean color retrieval algorithms utilize a standard set of aerosol models and the assumption of negligible water-leaving radiance in the near-infrared. Modern improvements have been developed to handle absorbing aerosols such as urban particulates in coastal areas and transported desert dust over the open ocean, where ocean fertilization can impact biological productivity at the base of the marine food chain. Even so, imperfect knowledge of the absorbing aerosol optical properties or their height distribution results in well-documented sources of error. In the UV, the problem of UV-enhanced absorption and nonsphericity of certain aerosol types are amplified due to the increased Rayleigh and aerosol optical depth, especially at off-nadir view angles. Multi-angle spectro-polarimetric measurements have been advocated as an additional tool to better understand and retrieve the aerosol properties needed for atmospheric correction for ocean color retrievals. The central concern of the work to be described is the assessment of the effects of absorbing aerosol properties on water leaving radiance measurement uncertainty by neglecting UV-enhanced absorption of carbonaceous particles and by not accounting for dust nonsphericity. In addition, we evaluate the polarimetric sensitivity of absorbing aerosol properties in light of measurement uncertainties achievable for the next generation of multi-angle polarimetric imaging instruments, and demonstrate advantages and disadvantages of wavelength selection in the UV/VNIR range. The phase matrices for the spherical smoke particles were calculated using a standard

  19. Water hyacinths for removal of phenols from polluted waters

    NASA Technical Reports Server (NTRS)

    Wolverton, B. C.

    1975-01-01

    Removal of phenol by water hyacinths (Eichhornia crassipes (Mart.) Solms) in static water was investigated. 2.75 g dry weight of this aquatic plant demonstrated the ability to absorb 100 mg of phenol per plant per 72 hours from distilled water, river water, and bayou water. One hectare of water hyacinth plants is shown to be potentially capable of removing 160 kg of phenol per 72 hours from waters polluted with this chemical.

  20. Probing the dynamic nature of water molecules and their influences on ligand binding in a model binding site.

    PubMed

    Cappel, Daniel; Wahlström, Rickard; Brenk, Ruth; Sotriffer, Christoph A

    2011-10-24

    The model binding site of the cytochrome c peroxidase (CCP) W191G mutant is used to investigate the structural and dynamic properties of the water network at the buried cavity using computational methods supported by crystallographic analysis. In particular, the differences of the hydration pattern between the uncomplexed state and various complexed forms are analyzed as well as the differences between five complexes of CCP W191G with structurally closely related ligands. The ability of docking programs to correctly handle the water molecules in these systems is studied in detail. It is found that fully automated prediction of water replacement or retention upon docking works well if some additional preselection is carried out but not necessarily if the entire water network in the cavity is used as input. On the other hand, molecular interaction fields for water calculated from static crystal structures and hydration density maps obtained from molecular dynamics simulations agree very well with crystallographically observed water positions. For one complex, the docking and MD results sensitively depend on the quality of the starting structure, and agreement is obtained only after redetermination of the crystal structure and refinement at higher resolution.

  1. Warm Absorber Diagnostics of AGN Dynamics

    NASA Astrophysics Data System (ADS)

    Kallman, Timothy

    Warm absorbers and related phenomena are observable manifestations of outflows or winds from active galactic nuclei (AGN) that have great potential value. Understanding AGN outflows is important for explaining the mass budgets of the central accreting black hole, and also for understanding feedback and the apparent co-evolution of black holes and their host galaxies. In the X-ray band warm absorbers are observed as photoelectric absorption and resonance line scattering features in the 0.5-10 keV energy band; the UV band also shows resonance line absorption. Warm absorbers are common in low luminosity AGN and they have been extensively studied observationally. They may play an important role in AGN feedback, regulating the net accretion onto the black hole and providing mechanical energy to the surroundings. However, fundamental properties of the warm absorbers are not known: What is the mechanism which drives the outflow?; what is the gas density in the flow and the geometrical distribution of the outflow?; what is the explanation for the apparent relation between warm absorbers and the surprising quasi-relativistic 'ultrafast outflows' (UFOs)? We propose a focused set of model calculations that are aimed at synthesizing observable properties of warm absorber flows and associated quantities. These will be used to explore various scenarios for warm absorber dynamics in order to answer the questions in the previous paragraph. The guiding principle will be to examine as wide a range as possible of warm absorber driving mechanisms, geometry and other properties, but with as careful consideration as possible to physical consistency. We will build on our previous work, which was a systematic campaign for testing important class of scenarios for driving the outflows. We have developed a set of tools that are unique and well suited for dynamical calculations including radiation in this context. We also have state-of-the-art tools for generating synthetic spectra, which are

  2. 21 CFR 868.5300 - Carbon dioxide absorbent.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Carbon dioxide absorbent. 868.5300 Section 868...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5300 Carbon dioxide absorbent. (a) Identification. A carbon dioxide absorbent is a device intended for medical purposes that consists of an...

  3. 21 CFR 868.5300 - Carbon dioxide absorbent.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Carbon dioxide absorbent. 868.5300 Section 868...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5300 Carbon dioxide absorbent. (a) Identification. A carbon dioxide absorbent is a device intended for medical purposes that consists of an...

  4. 21 CFR 868.5300 - Carbon dioxide absorbent.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Carbon dioxide absorbent. 868.5300 Section 868...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5300 Carbon dioxide absorbent. (a) Identification. A carbon dioxide absorbent is a device intended for medical purposes that consists of an...

  5. Frequency Tuning of Vibration Absorber Using Topology Optimization

    NASA Astrophysics Data System (ADS)

    Harel, Swapnil Subhash

    A tuned mass absorber is a system for reducing the amplitude in one oscillator by coupling it to a second oscillator. If tuned correctly, the maximum amplitude of the first oscillator in response to a periodic driver will be lowered, and much of the vibration will be 'transferred' to the second oscillator. The tuned vibration absorber (TVA) has been utilized for vibration control purposes in many sectors of Civil/Automotive/Aerospace Engineering for many decades since its inception. Time and again we come across a situation in which a vibratory system is required to run near resonance. In the past, approaches have been made to design such auxiliary spring mass tuned absorbers for the safety of the structures. This research focuses on the development and optimization of continuously tuned mass absorbers as a substitute to the discretely tuned mass absorbers (spring- mass system). After conducting the study of structural behavior, the boundary condition and frequency to which the absorber is to be tuned are determined. The Modal analysis approach is used to determine mode shapes and frequencies. The absorber is designed and optimized using the topology optimization tool, which simultaneously designs, optimizes and tunes the absorber to the desired frequency. The tuned, optimized absorber, after post processing, is attached to the target structure. The number of the absorbers are increased to amplify bandwidth and thereby upgrade the safety of structure for a wide range of frequency. The frequency response analysis is carried out using various combinations of structure and number of absorber cell.

  6. Electron and fluorescence spectra of a water molecule irradiated by an x-ray free-electron laser pulse

    NASA Astrophysics Data System (ADS)

    Schäfer, Julia M.; Inhester, Ludger; Son, Sang-Kil; Fink, Reinhold F.; Santra, Robin

    2018-05-01

    With the highly intense x-ray light generated by x-ray free-electron lasers (XFELs), molecular samples can be ionized many times in a single pulse. Here we report on a computational study of molecular spectroscopy at the high x-ray intensity provided by XFELs. Calculated photoelectron, Auger electron, and x-ray fluorescence spectra are presented for a single water molecule that reaches many electronic hole configurations through repeated ionization steps. The rich details shown in the spectra depend on the x-ray pulse parameters in a nonintuitive way. We discuss how the observed trends can be explained by the competition of microscopic electronic transition processes. A detailed comparison between spectra calculated within the independent-atom model and within the molecular-orbital framework highlights the chemical sensitivity of the spectral lines of multiple-hole configurations. Our results demonstrate how x-ray multiphoton ionization-related effects such as charge-rearrangement-enhanced x-ray ionization of molecules and frustrated absorption manifest themselves in the electron and fluorescence spectra.

  7. Reflection by absorbing periodically stratified media

    NASA Astrophysics Data System (ADS)

    Lekner, John

    2014-03-01

    Existing theory gives the optical properties of a periodically stratified medium in terms of a two by two matrix. This theory is valid also for absorbing media, because the matrix remains unimodular. The main effect of absorption is that the reflection (of either polarization) becomes independent of the number of periods N, and of the substrate properties, provided N exceeds a certain value which depends on the absorption. The s and p reflections are then given by simple formulae. The stop-band structure, which gives total reflection in bands of frequency and angle of incidence in the non-absorbing case, remains influential in weakly absorbing media, causing strong variations in reflectivity. The theory is applied to the frequency dependence of the normal-incidence reflectivity of a quarter-wave stack in which the high-index and low-index layers both absorb weakly. Analytical expressions are obtained for the frequency at which the reflectivity is maximum, the maximum reflectivity, and also for the reflectivity at the band edges of the stop band of the non-absorbing stack.

  8. 21 CFR 880.5300 - Medical absorbent fiber.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Medical absorbent fiber. 880.5300 Section 880.5300...) MEDICAL DEVICES GENERAL HOSPITAL AND PERSONAL USE DEVICES General Hospital and Personal Use Therapeutic Devices § 880.5300 Medical absorbent fiber. (a) Identification. A medical absorbent fiber is a device...

  9. 21 CFR 880.5300 - Medical absorbent fiber.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Medical absorbent fiber. 880.5300 Section 880.5300...) MEDICAL DEVICES GENERAL HOSPITAL AND PERSONAL USE DEVICES General Hospital and Personal Use Therapeutic Devices § 880.5300 Medical absorbent fiber. (a) Identification. A medical absorbent fiber is a device...

  10. Electrical tree initiation in polyethylene absorbing Penning gas

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

    Shimizu, N.; Tohyama, N.; Sato, H.

    1996-12-31

    Ac tree initiation voltage was examined in untreated LDPE, vacuum degassed LDPE and LDPE absorbing He gas (He gas was absorbed after vacuum degassing). The authors have already reported that vacuum degassed LDPE shows much higher tree initiation voltage than untreated one because of absence of oxygen. Therefore they expected that LDPE absorbing He shows the same property with vacuum degassed LDPE. However tree initiation voltage of LDPE absorbing He is as low as that of untreated LDPE. LDPE absorbing Ar gas shows the same tendency. He or Ar gas does not change so much impulse tree initiation voltage. LDPEmore » absorbing He was not well dyed with methylene blue after ac voltage application, which indicates that active oxidation does not occur. Low ac tree initiation voltage in LDPE absorbing He or Ar may be caused by Penning ionization in free volume.« less

  11. Vibration analysis on compact car shock absorber

    NASA Astrophysics Data System (ADS)

    Tan, W. H.; Cheah, J. X.; Lam, C. K.; Lim, E. A.; Chuah, H. G.; Khor, C. Y.

    2017-10-01

    Shock absorber is a part of the suspension system which provides comfort experience while driving. Resonance, a phenomenon where forced frequency is coinciding with the natural frequency has significant effect on the shock absorber itself. Thus, in this study, natural frequencies of the shock absorber in a 2 degree-of-freedom system were investigated using Wolfram Mathematica 11, CATIA, and ANSYS. Both theoretical and simulation study how will the resonance affect the car shock absorber. The parametric study on the performance of shock absorber also had been conducted. It is found that the failure tends to occur on coil sprung of the shock absorber before the body of the shock absorber is fail. From mathematical modelling, it can also be seen that higher vibration level occurred on un-sprung mass compare to spring mass. This is due to the weight of sprung mass which could stabilize as compared with the weight of un-sprung mass. Besides that, two natural frequencies had been obtained which are 1.0 Hz and 9.1 Hz for sprung mass and un-sprung mass respectively where the acceleration is recorded as maximum. In conclusion, ANSYS can be used to validate with theoretical results with complete model in order to match with mathematical modelling.

  12. 21 CFR 868.5310 - Carbon dioxide absorber.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Carbon dioxide absorber. 868.5310 Section 868.5310...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5310 Carbon dioxide absorber. (a) Identification. A carbon dioxide absorber is a device that is intended for medical purposes and that is used in a...

  13. 21 CFR 868.5310 - Carbon dioxide absorber.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Carbon dioxide absorber. 868.5310 Section 868.5310...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5310 Carbon dioxide absorber. (a) Identification. A carbon dioxide absorber is a device that is intended for medical purposes and that is used in a...

  14. 21 CFR 868.5310 - Carbon dioxide absorber.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Carbon dioxide absorber. 868.5310 Section 868.5310...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5310 Carbon dioxide absorber. (a) Identification. A carbon dioxide absorber is a device that is intended for medical purposes and that is used in a...

  15. HIGH RESOLUTION SPECTROSCOPY IN THE GAS PHASE: Even Large Molecules Have Well-Defined Shapes

    NASA Astrophysics Data System (ADS)

    Pratt, David W.

    1998-10-01

    A review of recent high-resolution microwave, infrared, and optical spectroscopy experiments demonstrates that remarkable progress has been made in the past 20 years in determining the equilibrium geometries of large polyatomic molecules and their clusters in the gas phase, and how these geometries change when the photon is absorbed. A special focus is on the dynamical information that can be obtained from such studies, particularly of electronically excited states.

  16. The bubble method of water purification

    NASA Astrophysics Data System (ADS)

    Smirnov, B. M.; Babaeva, N. Yu.; Naidis, G. V.; Panov, V. A.; Saveliev, A. S.; Son, E. E.; Tereshonok, D. V.

    2018-02-01

    The processes of water purification from admixture molecules are analyzed. The purification rate is limited due to a low diffusion coefficient of the admixture molecules in water. At non-small concentrations of the admixture molecules, the water purication can proceed through association of molecules in condensed nanoparticles which fall on the bottom of the water volume. The rate of association may be increased in an external electric field, but in reality this cannot change significantly the rate of the purification process. The bubble method of water purification is considered, where air bubbles formed at the bottom of the water volume, transfer admixture molecules to the interface. This method allows one to clean small water volumes fast. This mechanism of water purification is realized experimentally and exhibits the promises of the bubble purification method.

  17. High Conduction Neutron Absorber to Simulate Fast Reactor Environment in an Existing Test Reactor

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

    Guillen, Donna; Greenwood, Lawrence R.; Parry, James

    2014-06-22

    A need was determined for a thermal neutron absorbing material that could be cooled in a gas reactor environment without using large amounts of a coolant that would thermalize the neutron flux. A new neutron absorbing material was developed that provided high conduction so a small amount of water would be sufficient for cooling thereby thermalizing the flux as little as possible. An irradiation experiment was performed to assess the effects of radiation and the performance of a new neutron absorbing material. Neutron fluence monitors were placed inside specially fabricated holders within a set of drop-in capsules and irradiated formore » up to four cycles in the Advanced Test Reactor. Following irradiation, the neutron fluence monitor wires were analyzed by gamma and x-ray spectrometry to determine the activities of the activation products. The adjusted neutron fluences were calculated and grouped into three bins – thermal, epithermal and fast to evaluate the spectral shift created by the new material. Fluence monitors were evaluated after four different irradiation periods to evaluate the effects of burn-up in the absorbing material. Additionally, activities of the three highest activity isotopes present in the specimens are given.« less

  18. PT-symmetric laser absorber

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

    Longhi, Stefano

    2010-09-15

    In a recent work, Y. D. Chong et al. [Phys. Rev. Lett. 105, 053901 (2010)] proposed the idea of a coherent perfect absorber (CPA) as the time-reversed counterpart of a laser, in which a purely incoming radiation pattern is completely absorbed by a lossy medium. The optical medium that realizes CPA is obtained by reversing the gain with absorption, and thus it generally differs from the lasing medium. Here it is shown that a laser with an optical medium that satisfies the parity-time (PT) symmetry condition {epsilon}(-r)={epsilon}*(r) for the dielectric constant behaves simultaneously as a laser oscillator (i.e., it canmore » emit outgoing coherent waves) and as a CPA (i.e., it can fully absorb incoming coherent waves with appropriate amplitudes and phases). Such a device can thus be referred to as a PT-symmetric CPA laser. The general amplification or absorption features of the PT CPA laser below lasing threshold driven by two fields are determined.« less

  19. Gold absorbing film for a composite bolometer

    NASA Technical Reports Server (NTRS)

    Dragovan, M.; Moseley, S. H.

    1984-01-01

    The principles governing the design of metal films are reviewed, with attention also given to the choice of metals. A description is then given of the characteristics of a bolometer with a gold absorbing film. It is demonstrated that gold is effective as an absorbing film for a millimeter bolometer operated at 1.5 K. At 1.5 K, gold is significantly better than bismuth since gold has a lower heat capacity for the absorbing film. At 0.3 K, gold and bismuth are both suitable. It is pointed out that at temperatures below 0.3 K, a superconducting absorbing film can have a heat capacity low enough not to dominate the heat capacity of the detector; for this reason, it may give better performance than a nonsuperconducting absorbing film.

  20. Energy absorber for the CETA

    NASA Technical Reports Server (NTRS)

    Wesselski, Clarence J.

    1994-01-01

    The energy absorber that was developed for the CETA (Crew Equipment and Translation Aid) on Space Station Freedom is a metal on metal frictional type and has a load regulating feature that prevents excessive stroking loads from occurring while in operation. This paper highlights some of the design and operating aspects and the testing of this energy absorber.

  1. Determination of absorbed dose to water for high-energy photon and electron beams-comparison of the standards DIN 6800-2 (1997), IAEA TRS 398 (2000) and DIN 6800-2 (2006)

    PubMed Central

    Zakaria, Golam Abu; Schuette, Wilhelm

    2007-01-01

    For the determination of the absorbed dose to water for high-energy photon and electron beams the IAEA code of practice TRS-398 (2000) is applied internationally. In Germany, the German dosimetry protocol DIN 6800-2 (1997) is used. Recently, the DIN standard has been revised and published as Draft National Standard DIN 6800-2 (2006). It has adopted widely the methodology and dosimetric data of the code of practice. This paper compares these three dosimetry protocols systematically and identifies similarities as well as differences. The investigation was done with 6 and 18 MV photon as well as 5 to 21 MeV electron beams. While only cylindrical chambers were used for photon beams, measurements of electron beams were performed using cylindrical as well as plane-parallel chambers. The discrepancies in the determination of absorbed dose to water between the three protocols were 0.4% for photon beams and 1.5% for electron beams. Comparative measurements showed a deviation of less than 0.5% between our measurements following protocol DIN 6800-2 (2006) and TLD inter-comparison procedure in an external audit. PMID:21217912

  2. 21 CFR 868.5310 - Carbon dioxide absorber.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Carbon dioxide absorber. 868.5310 Section 868.5310 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5310 Carbon dioxide absorber. (a) Identification. A carbon dioxide absorber is a devic...

  3. 21 CFR 868.5300 - Carbon dioxide absorbent.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Carbon dioxide absorbent. 868.5300 Section 868.5300 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5300 Carbon dioxide absorbent. (a) Identification. A carbon dioxide absorbent is a...

  4. 21 CFR 868.5300 - Carbon dioxide absorbent.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Carbon dioxide absorbent. 868.5300 Section 868.5300 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5300 Carbon dioxide absorbent. (a) Identification. A carbon dioxide absorbent is a...

  5. 21 CFR 868.5310 - Carbon dioxide absorber.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Carbon dioxide absorber. 868.5310 Section 868.5310 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5310 Carbon dioxide absorber. (a) Identification. A carbon dioxide absorber is a devic...

  6. Intermolecular interaction in nucleobases and dimethyl sulfoxide/water molecules: A DFT, NBO, AIM and NCI analysis.

    PubMed

    Venkataramanan, Natarajan Sathiyamoorthy; Suvitha, Ambigapathy; Kawazoe, Yoshiyuki

    2017-11-01

    This study aims to cast light on the physico-chemical nature and energetics of interactions between the nucleobases and water/DMSO molecules which occurs through the non-conventional CH⋯O/N-H bonds using a comprehensive quantum-chemical approach. The computed interaction energies do not show any appreciable change for all the nucleobase-solvent complexes, conforming the experimental findings on the hydration enthalpies. Compared to water, DMSO form complexes with high interaction energies. The quantitative molecular electrostatic potentials display a charge transfer during the complexation. NBO analysis shows the nucleobase-DMSO complexes, have higher stabilization energy values than the nucleobase-water complexes. AIM analysis illustrates that the in the nucleobase-DMSO complexes, SO⋯H-N type interaction have strongest hydrogen bond strength with high E HB values. Furthermore, the Laplacian of electron density and total electron density were negative indicating the partial covalent nature of bonding in these systems, while the other bonds are classified as noncovalent interactions. EDA analysis indicates, the electrostatic interaction is more pronounced in the case of nucleobase-water complexes, while the dispersion contribution is more dominant in nucleobase-DMSO complexes. NCI-RDG analysis proves the existence of strong hydrogen bonding in nucleobase-DMSO complex, which supports the AIM results. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Self-Assemblies of novel molecules, VECAR

    NASA Astrophysics Data System (ADS)

    Shrestha, Bijay; Kim, Hye-Young; Lee, Soojin; Novak, Brian; Moldovan, Dorel

    2015-03-01

    VECAR is a newly synthesized molecule, which is an amphiphilic antioxidant molecule that consists of two molecular groups, vitamin-E and Carnosine, linked by a hydrocarbon chain. The hydrocarbon chain is hydrophobic and both vitamin-E and Carnosine ends are hydrophilic. In the synthesis process, the length of the hydrophobic chain of VECAR molecules can vary from the shortest (n =0) to the longest (n =18), where n indicates the number of carbon atoms in the chain. We conducted MD simulation studies of self-assembly of VECAR molecules in water using GROMACS on LONI HPC resources. Our study shows that there is a strong correlation between the shape and atomistic structure of the self-assembled nano-structures (SANs) and the chain-length (n) of VECAR molecules. We will report the results of data analyses including the atomistic structure of each SANs and the dynamic and energetic mechanisms of their formation as function of time. In summary, both VECAR molecules of chain-length n =18 and 9 form worm-like micelles, which may be used as a drug delivery system. This research is supported by the Louisiana Board of Regents-RCS Grant (LEQSF(2012-15)-RD-A-19).

  8. Design and proof of concept of an innovative very high temperature ceramic solar absorber

    NASA Astrophysics Data System (ADS)

    Leray, Cédric; Ferriere, Alain; Toutant, Adrien; Olalde, Gabriel; Peroy, Jean-Yves; Chéreau, Patrick; Ferrato, Marc

    2017-06-01

    Hybrid solar gas-turbine (HSGT) is an attractive technology to foster market penetration of CSP. HSGT offers some major advantages like for example high solar-to-electric conversion efficiency, reduced water requirement and low capital cost. A very high temperature solar receiver is needed when elevated solar share is claimed. A few research works, as reported by Karni et al. [8] and by Buck et al. [1], have been dedicated to solar receiver technologies able to deliver pressurized air at temperature above 750°C. The present work focuses on research aiming at developing an efficient and reliable solar absorber able to provide pressurized air at temperature up to 1000°C and more. A surface absorber technology is selected and a modular design of receiver is proposed in which each absorber module is made of BOOSTEC® SiC ceramic (silicon carbide) as bulk material with straight air channels inside. Early stage experimental works done at CNRS/PROMES on lab-scale absorbers showed that the thermo-mechanical behavior of this material is a critical issue, resulting in elevated probability of failure under severe conditions like large temperature gradient or steep variation of solar flux density in situations of cloud covering. This paper reports on recent progress made at CNRS/PROMES to address this critical issue. The design of the absorber has been revised and optimized according to thermo-mechanical numerical simulations, and an experimental proof of concept has been done on a pilot-scale absorber module at Themis solar tower facility.

  9. Mushroom plasmonic metamaterial infrared absorbers

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

    Ogawa, Shinpei, E-mail: Ogawa.Shimpei@eb.MitsubishiElectric.co.jp; Fujisawa, Daisuke; Hata, Hisatoshi

    2015-01-26

    There has been a considerable amount of interest in the development of various types of electromagnetic wave absorbers for use in different wavelength ranges. In particular, infrared (IR) absorbers with wavelength selectivity can be applied to advanced uncooled IR sensors, which would be capable of identifying objects through their radiation spectrum. In the present study, mushroom plasmonic metamaterial absorbers (MPMAs) for the IR wavelength region were designed and fabricated. The MPMAs consist of a periodic array of thin metal micropatches connected to a thin metal plate with narrow silicon (Si) posts. A Si post height of 200 nm was achieved bymore » isotropic XeF{sub 2} etching of a thin Si layer sandwiched between metal plates. This fabrication procedure is relatively simple and is consistent with complementary metal oxide semiconductor technology. The absorption spectra of the fabricated MPMAs were experimentally measured. In addition, theoretical calculations of their absorption properties were conducted using rigorous coupled wave analysis. Both the calculated and measured absorbance results demonstrated that these MPMAs can realize strong selective absorption at wavelengths beyond the period of the array by varying the micropatch width. Absorbance values greater than 90% were achieved. Dual- or single-mode absorption can also be selected by varying the width of the Si posts. Pixel structures using such MPMAs could be used as high responsivity, high resolution and fast uncooled IR sensors.« less

  10. Shock absorber operates over wide range

    NASA Technical Reports Server (NTRS)

    Creasy, W. K.; Jones, J. C.

    1965-01-01

    Piston-type hydraulic shock absorber, with a metered damping system, operates over a wide range of kinetic energy loading rates. It is used for absorbing shock and vibration on mounted machinery and heavy earth-moving equipment.

  11. Design of a nonlinear torsional vibration absorber

    NASA Astrophysics Data System (ADS)

    Tahir, Ammaar Bin

    Tuned mass dampers (TMD) utilizing linear spring mechanisms to mitigate destructive vibrations are commonly used in practice. A TMD is usually tuned for a specific resonant frequency or an operating frequency of a system. Recently, nonlinear vibration absorbers attracted attention of researchers due to some potential advantages they possess over the TMDs. The nonlinear vibration absorber, or the nonlinear energy sink (NES), has an advantage of being effective over a broad range of excitation frequencies, which makes it more suitable for systems with several resonant frequencies, or for a system with varying excitation frequency. Vibration dissipation mechanism in an NES is passive and ensures that there is no energy backflow to the primary system. In this study, an experimental setup of a rotational system has been designed for validation of the concept of nonlinear torsional vibration absorber with geometrically induced cubic stiffness nonlinearity. Dimensions of the primary system have been optimized so as to get the first natural frequency of the system to be fairly low. This was done in order to excite the dynamic system for torsional vibration response by the available motor. Experiments have been performed to obtain the modal parameters of the system. Based on the obtained modal parameters, the design optimization of the nonlinear torsional vibration absorber was carried out using an equivalent 2-DOF modal model. The optimality criterion was chosen to be maximization of energy dissipation in the nonlinear absorber attached to the equivalent 2-DOF system. The optimized design parameters of the nonlinear absorber were tested on the original 5-DOF system numerically. A comparison was made between the performance of linear and nonlinear absorbers using the numerical models. The comparison showed the superiority of the nonlinear absorber over its linear counterpart for the given set of primary system parameters as the vibration energy dissipation in the former is

  12. Purifying Water by Imbibition

    NASA Technical Reports Server (NTRS)

    Lawton, E. A.

    1986-01-01

    Concept for purifying water uses absorbent material to remove organic substances. Entire bulk of material employed, not just surface. Proposed purification process uses inexpensive equipment and low energy. Material is methyl acrylate polymer. Material cheap and regenerated by rinsing with methanol or by allowing absorbed compounds to evaporate from it.

  13. Experimental and simulated study of a composite structure metamaterial absorber

    NASA Astrophysics Data System (ADS)

    Li, Shengyong; Ai, Xiaochuan; Wu, Ronghua; Chen, Jiajun

    2017-11-01

    In this paper, a high performance metamaterial absorber is designed and experimental studied. Measured results indicate that a perfect absorption band and a short-wavelength absorption peak are achieved in the near-infrared spectrum. Current strength distributions reveal that the absorption band is excited by the cavity resonance. And electric field distributions show that the short-wavelength absorption peak is excited by the horizontal coupled of localized surface plasmon (LSP) modes near hole edges. On the one hand, the absorption property of the measured metamaterial absorber can be enhanced through optimizing the structural parameters (a, w, and H). On the other hand, the absorption property is sensitive to the change of refractive index of environmental medias. A sensing scheme is proposed for refractive index detecting based on the figure of merit (FOM) value. Measured results indicate that the proposed sensing scheme can achieve high FOM value with different environmental medias (water, glucose solution).

  14. Performance evaluation of CFRP-rubber shock absorbers

    NASA Astrophysics Data System (ADS)

    Lamanna, Giuseppe; Sepe, Raffaele

    2014-05-01

    In the present work a numerical investigation on the energy absorbing capability of dedicated structural components made of a carbon fiber reinforced polymer and an emulsion polymerised styrene butadiene rubber is reported. The shock absorbers are devices designed to absorb large amounts of energy by sacrificing their own structural integrity. Their aim is to cushion the effects of an impact phenomenon with the intent to preserve other structures from global failure or local damaging. Another important role of shock absorbers is reducing the peak of the acceleration showed during an impact phenomenon. This effect is of considerable interest in the case of vehicles to preserve passengers' safety. Static and dynamic numerical results are compared with experimental ones in terms of mean crushing forces, energy and peak crushing. The global performance of the absorbers has been evaluated by referencing to a proposed quality index.

  15. Biosensing via light scattering from plasmonic core-shell nanospheres coated with DNA molecules

    NASA Astrophysics Data System (ADS)

    Xie, Huai-Yi; Chen, Minfeng; Chang, Yia-Chung; Moirangthem, Rakesh Singh

    2017-05-01

    We present both experimental and theoretical studies for investigating DNA molecules attached on metallic nanospheres. We have developed an efficient and accurate numerical method to investigate light scattering from plasmonic nanospheres on a substrate covered by a shell, based on the Green's function approach with suitable spherical harmonic basis. Next, we use this method to study optical scattering from DNA molecules attached to metallic nanoparticles placed on a substrate and compare with experimental results. We obtain fairly good agreement between theoretical predictions and the measured ellipsometric spectra. The metallic nanoparticles were used to detect the binding with DNA molecules in a microfluidic setup via spectroscopic ellipsometry (SE), and a detectable change in ellipsometric spectra was found when DNA molecules are captured on Au nanoparticles. Our theoretical simulation indicates that the coverage of Au nanosphere by a submonolayer of DNA molecules, which is modeled by a thin layer of dielectric material (which may absorb light), can lead to a small but detectable spectroscopic shift in both the Ψ and Δ spectra with more significant change in Δ spectra in agreement with experimental results. Our studies demonstrated the ultrasensitive capability of SE for sensing submonolayer coverage of DNA molecules on Au nanospheres. Hence the spectroscopic ellipsometric measurements coupled with theoretical analysis via an efficient computation method can be an effective tool for detecting DNA molecules attached on Au nanoparticles, thus achieving label-free, non-destructive, and high-sensitivity biosensing with nanoscale resolution.

  16. Estimate of the Impact of Absorbing Aerosol Over Cloud on the MODIS Retrievals of Cloud Optical Thickness and Effective Radius Using Two Independent Retrievals of Liquid Water Path

    NASA Technical Reports Server (NTRS)

    Wilcox, Eric M.; Harshvardhan; Platnick, Steven

    2009-01-01

    Two independent satellite retrievals of cloud liquid water path (LWP) from the NASA Aqua satellite are used to diagnose the impact of absorbing biomass burning aerosol overlaying boundary-layer marine water clouds on the Moderate Resolution Imaging Spectrometer (MODIS) retrievals of cloud optical thickness (tau) and cloud droplet effective radius (r(sub e)). In the MODIS retrieval over oceans, cloud reflectance in the 0.86-micrometer and 2.13-micrometer bands is used to simultaneously retrieve tau and r(sub e). A low bias in the MODIS tau retrieval may result from reductions in the 0.86-micrometer reflectance, which is only very weakly absorbed by clouds, owing to absorption by aerosols in cases where biomass burning aerosols occur above water clouds. MODIS LWP, derived from the product of the retrieved tau and r(sub e), is compared with LWP ocean retrievals from the Advanced Microwave Scanning Radiometer-EOS (AMSR-E), determined from cloud microwave emission that is transparent to aerosols. For the coastal Atlantic southern African region investigated in this study, a systematic difference between AMSR-E and MODIS LWP retrievals is found for stratocumulus clouds over three biomass burning months in 2005 and 2006 that is consistent with above-cloud absorbing aerosols. Biomass burning aerosol is detected using the ultraviolet aerosol index from the Ozone Monitoring Instrument (OMI) on the Aura satellite. The LWP difference (AMSR-E minus MODIS) increases both with increasing tau and increasing OMI aerosol index. During the biomass burning season the mean LWP difference is 14 g per square meters, which is within the 15-20 g per square meter range of estimated uncertainties in instantaneous LWP retrievals. For samples with only low amounts of overlaying smoke (OMI AI less than or equal to 1) the difference is 9.4, suggesting that the impact of smoke aerosols on the mean MODIS LWP is 5.6 g per square meter. Only for scenes with OMI aerosol index greater than 2 does the

  17. [Dynamics of Irreversible Evaporation of a Water-Protein Droplet and a Problem of Structural and Dynamical Experiments with Single Molecules].

    PubMed

    Shaitan, K V; Armeev, G A; Shaytan, A K

    2016-01-01

    We discuss the effect of isothermal and adiabatic evaporation of water on the state of a water-protein droplet. The discussed problem is of current importance due to development of techniques to perform single molecule experiments using free electron lasers. In such structure-dynamic experiments the delivery of a sample into the X-ray beam is performed using the microdroplet injector. The time between the injection and delivery is in the order of microseconds. In this paper we developed a specialized variant of all-atom molecular dynamics simulations for the study of irreversible isothermal evaporation of the droplet. Using in silico experiments we determined the parameters of isothermal evaporation of the water-protein droplet with the sodium and chloride ions in the concentration range of 0.3 M at different temperatures. The energy of irreversible evaporation determined from in silico experiments at the initial stages of evaporation virtually coincides with the specific heat of evaporation for water. For the kinetics of irreversible adiabatic evaporation an exact analytical solution was obtained in the limit of high thermal conductivity of the droplet (or up to the droplet size of -100 Å). This analytical solution incorporates parameters that are determined using in silico. experiments on isothermal droplet evaporation. We show that the kinetics of adiabatic evaporation and cooling of the droplet scales with the droplet size. Our estimates of the water-protemi droplet. freezing rate in the adiabatic regime in a vacuum chamber show that additional techniques for stabilizing the temperature inside the droplet should be used in order to study the conformational transitions of the protein in single molecules. Isothermal and quasi-isothermal conditions are most suitable for studying the conformational transitions upon object functioning. However, in this case it is necessary to take into account the effects of dehydration and rapid increase of ionic strength in an

  18. [Ortho/para spin-isomers of H2O molecules as a factor responsible for formation of two structural motifs in water].

    PubMed

    Zakharov, S D

    2013-01-01

    According to the last results obtained by small-angle X-ray scattering and X-ray spectroscopy it was suggested that water within the nanometer scale represents a fluctuating mixture of clusters with tetrahedral structure and a subphase with partially broken hydrogen bonds whereas the nuclear configuration of the H20 molecule corresponds to single tetrahedral coordination. The basic reason of such structural partition is not clear until now. Here we show that it can be associated with the existence of two nuclear H2O spin-isomers which have different probability to be in one or another subphase. The para-molecule can transfer an excess of its rotational energy to the environment up to the complete stopping of rotation because its rotational quantum number J = 0 in the basic state. This property is favorable for the formation of clusters with closed H-bonds. Ortho-molecules with odd-numbered J states lack for this property and thus should be predominantly present in the surrounding with distorted bonds.

  19. Water Diffusion through a Titanium Dioxide/Poly(Carbonate Urethane) Nanocomposite for Protecting Cultural Heritage: Interactions and Viscoelastic Behavior

    PubMed Central

    Abbate, Mario; D’Orazio, Loredana

    2017-01-01

    Water diffusion through a TiO2/poly (carbonate urethane) nanocomposite designed for the eco-sustainable protection of outdoor cultural heritage stonework was investigated. Water is recognized as a threat to heritage, hence the aim was to gather information on the amount of water uptake, as well as of species of water molecules absorbed within the polymer matrix. Gravimetric and vibrational spectroscopy measurements demonstrated that diffusion behavior of the nanocomposite/water system is Fickian, i.e., diffusivity is independent of concentration. The addition of only 1% of TiO2 nanoparticles strongly betters PU barrier properties and water-repellency requirement is imparted. Defensive action against penetration of water free from, and bonded through, H-bonding association arises from balance among TiO2 hydrophilicity, tortuosity effects and quality of nanoparticle dispersion and interfacial interactions. Further beneficial to antisoiling/antigraffiti action is that water-free fraction was found to be desorbed at a constant rate. In environmental conditions, under which weathering processes are most likely to occur, nanocomposite Tg values remain suitable for heritage treatments. PMID:28902179

  20. Performance evaluation of CFRP-rubber shock absorbers

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

    Lamanna, Giuseppe, E-mail: giuseppe.lamanna@unina2.it; Sepe, Raffaele, E-mail: giuseppe.lamanna@unina2.it

    2014-05-15

    In the present work a numerical investigation on the energy absorbing capability of dedicated structural components made of a carbon fiber reinforced polymer and an emulsion polymerised styrene butadiene rubber is reported. The shock absorbers are devices designed to absorb large amounts of energy by sacrificing their own structural integrity. Their aim is to cushion the effects of an impact phenomenon with the intent to preserve other structures from global failure or local damaging. Another important role of shock absorbers is reducing the peak of the acceleration showed during an impact phenomenon. This effect is of considerable interest in themore » case of vehicles to preserve passengers’ safety. Static and dynamic numerical results are compared with experimental ones in terms of mean crushing forces, energy and peak crushing. The global performance of the absorbers has been evaluated by referencing to a proposed quality index.« less

  1. Investigation of tunable terahertz metamaterial perfect absorber with anisotropic dielectric liquid crystal

    NASA Astrophysics Data System (ADS)

    Hokmabadi, Mohammad P.; Tareki, Abubaker; Rivera, Elmer; Kung, Patrick; Lindquist, Robert G.; Kim, Seongsin M.

    2017-01-01

    In this letter, we report the unique design, simulation and experimental verification of an electrically tunable THz metamaterial perfect absorber consisting of complementary split ring resonator (CSRR) arrays integrated with liquid crystal as the subwavelength spacer in between. We observe a shift in resonance frequency of about 5.0 GHz at 0.567 THz with a 5 V bias voltage at 1KHz between the CSRR and the metal backplane, while the absorbance and full width at half maximum bandwidth are maintained at 90% and 0.025 THz, respectively. Simulated absorption spectrum by using a uniaxial model of LC matches perfectly the experiment data and demonstrates that the effective refractive index of LC changes between 1.5 and 1.7 by sweeping a 1 kHz bias voltage from 0 V to 5 V. By matching simulation and experiment for different bias voltages, we also estimate the angle of LC molecules versus the bias voltage. Additionally, we study the created THz fields inside the spacer to gain a better insight of the characteristics of tunable response of this device. This structure and associated study can support the design of liquid crystal based tunable terahertz detectors and sensors for various applications.

  2. Effect of low sea water temperature on water balance in the Atlantic salmon, (Salmo salar L.).

    PubMed

    Lega, Y V; Chernitsky, A G; Belkovsky, N M

    1992-08-01

    The water balance in Atlantic salmon (Salmo salar L.) overwintering in sea water (34 ‰) was investigated. With a decrease of temperature from 5.6 to 1.0°C the drinking rate decreased from 13.9 to 5.7 ml/kg/day, and the absolute amount of water absorbed decreased from 8.9 to 5.0 ml/kg/day. A decrease in temperature led, however, to an increase in the proportion of water absorbed in the intestines from 60 to 96%. Blood serum osmolarity increased from 320 to 440 mosm/1 with decreasing temperature and there was a reduction in tissue water content from 75 to 69% The disturbance of water balance at low temperature may be one of the factors responsible for mortality of salmon overwintering in sea water.

  3. A Flexible Metamaterial Terahertz Perfect Absorber

    NASA Astrophysics Data System (ADS)

    Chen, X. R.; Zheng, Y. W.; Qin, L. M.; Wei, G. C.; Qin, Z. P.; Zhang, N. G.; Liu, K.; Li, S. Z.; Wang, S. X.

    2017-12-01

    We designed a THz matematerial absorber using metallic wires (MWs) and split resonant rings (SRRs). This matematerial absorber exhibits perfect absorption which up to 96% at 4.03 THz and is capable of wrapped around objects because of flexible polyimide dielectric substrate.

  4. Determination of decay coefficients for combustors with acoustic absorbers

    NASA Technical Reports Server (NTRS)

    Mitchell, C. E.; Espander, W. R.; Baer, M. R.

    1972-01-01

    An analytical technique for the calculation of linear decay coefficients in combustors with acoustic absorbers is presented. Tuned circumferential slot acoustic absorbers were designed for the first three transverse modes of oscillation, and decay coefficients for these absorbers were found as a function of backing distance for seven different chamber configurations. The effectiveness of the absorbers for off-design values of the combustion response and acoustic mode is also investigated. Results indicate that for tuned absorbers the decay coefficient increases approximately as the cube of the backing distance. For most off-design situations the absorber still provides a damping effect. However, if an absorber designed for some higher mode of oscillation is used to damp lower mode oscillations, a driving effect is frequently found.

  5. Benchmark Evaluation of the HTR-PROTEUS Absorber Rod Worths (Core 4)

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

    John D. Bess; Leland M. Montierth

    2014-06-01

    PROTEUS was a zero-power research reactor at the Paul Scherrer Institute (PSI) in Switzerland. The critical assembly was constructed from a large graphite annulus surrounding a central cylindrical cavity. Various experimental programs were investigated in PROTEUS; during the years 1992 through 1996, it was configured as a pebble-bed reactor and designated HTR-PROTEUS. Various critical configurations were assembled with each accompanied by an assortment of reactor physics experiments including differential and integral absorber rod measurements, kinetics, reaction rate distributions, water ingress effects, and small sample reactivity effects [1]. Four benchmark reports were previously prepared and included in the March 2013 editionmore » of the International Handbook of Evaluated Reactor Physics Benchmark Experiments (IRPhEP Handbook) [2] evaluating eleven critical configurations. A summary of that effort was previously provided [3] and an analysis of absorber rod worth measurements for Cores 9 and 10 have been performed prior to this analysis and included in PROTEUS-GCR-EXP-004 [4]. In the current benchmark effort, absorber rod worths measured for Core Configuration 4, which was the only core with a randomly-packed pebble loading, have been evaluated for inclusion as a revision to the HTR-PROTEUS benchmark report PROTEUS-GCR-EXP-002.« less

  6. [Monitoring Water in Lubricating Oil with Min-Infrared LED].

    PubMed

    Yu, Liang-wu; Tian, Hong-xiang; Ming, Ting-feng; Yang, Kun

    2015-06-01

    A method that could be used to quantify the water concentration in ship machinery lubricating oil based on Mid-infrared LED is discussed. A Mid-infrared LED with peak emission wavelength of 2 840 nm and FWHM of 400 nm is used as the light source, the emitting light is partly absorbed by the oil sample, the remaining is received by the infrared detector. The percentage of water is determined according to the absorbance. In the experiment, a optical configuration including the transmission, absorbing and receiving of infrared light is designed, calcium fluoride wafer is used as the window, a hard metal coil with circular section is selected as the washer to get the fixed thickness of oil film accurately, a photoelectric diode with detection wavelength of 2 500-4 800 nm and response time of 10-20 ns is used as the detector of light intensity. Matching with this, a system of signal preamplifier, microcontroller-based data acquisition, storage and communication is developed. Absorbance data of six oil samples with different water mass concentration: 0, 0.062 5%, 0.125%, 0.25%, 0.375% and 0.5% is acquired through experiment. Fitting the data by the method of least squares, a linear equation in terms of absorbance and water concentration is obtained, and the determination coefficient is 0.996. Finally, in order to test the accuracy of this measurement method, using oil sample with water concentration of 0.317 5% to validate the equation, measuring the absorbance by the experimental device, the water content is calculated through the linear equation, the results show that the relative error is 2.7% between the percentage calculated and the real sample, indicating that this method can accurately measure the water concentration in the oil.

  7. Low temperature selective absorber research

    NASA Astrophysics Data System (ADS)

    Herzenberg, S. A.; Silberglitt, R.

    1982-04-01

    Research carried out since 1979 on selective absorbers is surveyed, with particular attention given to the low-temperature coatings seen as promising for flat plate and evacuated tube applications. The most thoroughly investigated absorber is black chrome, which is highly selective and is the most durable low-temperature absorber. It is believed that other materials, because of their low cost and lower content of strategic materials, may eventually supplant black chrome. Among these candidates are chemically converted black nickel; anodically oxidized nickel, zinc, and copper composites; and nickel or other low-cost multilayer coatings. In reviewing medium and high-temperature research, black chrome, multilayer coatings and black cobalt are seen as best medium-temperature candidates. For high temperatures, an Al2O3/Pt-Al203 multilayer composite or the zirconium diboride coating is preferred.

  8. Direct molecular diffusion and micro-mixing for rapid dewatering of LiBr solution

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

    Bigham, S; Isfahani, RN; Moghaddam, S

    2014-03-01

    A slow molecular diffusion rate often limits the desorption process of an absorbate molecule from a liquid absorbent. To enhance the desorption rate, the absorbent is often boiled to increase the liquid vapor interfacial area. However, the growth of bubbles generated during the nucleate boiling process still remains mass-diffusion limited. Here, it is shown that a desorption rate higher than that of boiling can be achieved, if the vapor absorbent interface is continuously replenished with the absorbate-rich solution to limit the concentration boundary layer growth. The study is conducted in a LiBr-water-solution, in which the water molecules' diffusion rate ismore » quite slow. The manipulation of the vapor solution interface concentration distribution is enabled by the mechanical confinement of the solution flow within microchannels, using a hydrophobic vapor-venting membrane and the implementation of microstructures on the flow channel's bottom wall. The microstructures stretch and fold the laminar streamlines within the solution film and produce vortices. The vortices continuously replace the concentrated solution at the vapor solution interface with the water-rich solution brought from the bottom and middle of the flow channel. The physics of the process is described using a combination of experimental and numerical studies. Published by Elsevier Ltd.« less

  9. Molecules for Fluorescence Detection of Specific Chemicals

    NASA Technical Reports Server (NTRS)

    Fedor, Steve

    2008-01-01

    A family of fluorescent dye molecules has been developed for use in on-off fluorescence detection of specific chemicals. By themselves, these molecules do not fluoresce. However, when exposed to certain chemical analytes in liquid or vapor forms, they do fluoresce (see figure). These compounds are amenable to fixation on or in a variety of substrates for use in fluorescence-based detection devices: they can be chemically modified to anchor them to porous or non-porous solid supports or can be incorporated into polymer films. Potential applications for these compounds include detection of chemical warfare agents, sensing of acidity or alkalinity, and fluorescent tagging of proteins in pharmaceutical research and development. These molecules could also be exploited for use as two-photon materials for photodynamic therapy in the treatment of certain cancers and other diseases. A molecule in this family consists of a fluorescent core (such as an anthracene or pyrene) attached to two end groups that, when the dye is excited by absorption of light, transfer an electron to the core, thereby quenching the fluorescence. The end groups can be engineered so that they react chemically with certain analytes. Upon reaction, electrons on the end groups are no longer available for transfer to the core and, consequently, the fluorescence from the core is no longer quenched. The chemoselectivity of these molecules can be changed by changing the end groups. For example, aniline end groups afford a capability for sensing acids or acid halides (including those contained in chemical warfare agents). Pyridine or bipyridyl end groups would enable sensing of metal ions. Other chemicals that can be selectively detected through suitable choice of end groups include glucose and proteins. Moreover, the fluorescent cores can be changed to alter light-absorption and -emission characteristics: anthracene cores fluoresce at wavelengths around 500 nm, whereas perylene cores absorb and emit at

  10. Ultra-thin, conformal, and hydratable color-absorbers using silk protein hydrogel

    NASA Astrophysics Data System (ADS)

    Umar, Muhammad; Min, Kyungtaek; Jo, Minsik; Kim, Sunghwan

    2018-06-01

    Planar and multilayered photonic devices offer unprecedented opportunities in biological and chemical sensing due to strong light-matter interactions. However, uses of rigid substances such as semiconductors and dielectrics confront photonic devices with issues of biocompatibility and a mechanical mismatch for their application on humid, uneven, and soft biological surfaces. Here, we report that favorable material traits of natural silk protein led to the fabrication of an ultra-thin, conformal, and water-permeable (hydratable) metal-insulator-metal (MIM) color absorber that was mapped on soft, curved, and hydrated biological interfaces. Strong absorption was induced in the MIM structure and could be tuned by hydration and tilting of the sample. The transferred MIM color absorbers reached the exhibition of a very strong resonant absorption in the visible and near infra-red ranges. In addition, we demonstrated that the conformal resonator could function as a refractometric glucose sensor applied on a contact lens.

  11. Synthesis and characterization of UV-absorbing fluorine-silicone acrylic resin polymer

    NASA Astrophysics Data System (ADS)

    Lei, Huibin; He, Deliang; Guo, Yanni; Tang, Yining; Huang, Houqiang

    2018-06-01

    A series of UV-absorbing fluorine-silicone acrylic resin polymers containing different amount of UV-absorbent were successfully prepared by solution polymerization, with 2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl] ethyl methacrylate (BHEM), vinyltrimethoxysilane (VTMS) and hexafluorobutyl methacrylate (HFMA) as modifying monomers. The acrylic polymers and the coatings thereof were characterized by Fourier transform infrared spectrum (FT-IR), X-ray photoelectron spectroscopy (XPS), Ultraviolet-visible (UV-vis) absorption spectrum, thermogravimetric analysis (TGA), water contact angle (CA) and Xenon lamp artificial accelerated aging tests. Results indicated that the resin exhibited high UV absorption performance as well as good thermal stability. The hydrophobicity of the coatings was of great improvement because of the bonded fluorine and silicone. Meanwhile, the weather-resistance was promoted through preferably colligating the protective effects of BHEM, organic fluorine and silicone. Also, a fitting formula about the weatherability with the BMHE content was tentatively proposed.

  12. Thermally Resilient, Broadband Optical Absorber from UV to IR Derived from Carbon Nanostructures

    NASA Technical Reports Server (NTRS)

    Kaul, Anupama B.; Coles, James B.

    2012-01-01

    Optical absorber coatings have been developed from carbon-based paints, metal blacks, or glassy carbon. However, such materials are not truly black and have poor absorption characteristics at longer wavelengths. The blackness of such coatings is important to increase the accuracy of calibration targets used in radiometric imaging spectrometers since blackbody cavities are prohibitively large in size. Such coatings are also useful potentially for thermal detectors, where a broadband absorber is desired. Au-black has been a commonly used broadband optical absorber, but it is very fragile and can easily be damaged by heat and mechanical vibration. An optically efficient, thermally rugged absorber could also be beneficial for thermal solar cell applications for energy harnessing, particularly in the 350-2,500 nm spectral window. It has been demonstrated that arrays of vertically oriented carbon nanotubes (CNTs), specifically multi-walled-carbon- nanotubes (MWCNTs), are an exceptional optical absorber over a broad range of wavelengths well into the infrared (IR). The reflectance of such arrays is 100x lower compared to conventional black materials, such as Au black in the spectral window of 350-2,500 nm. Total hemispherical measurements revealed a reflectance of approximately equal to 1.7% at lambda approximately equal to 1 micrometer, and at longer wavelengths into the infrared (IR), the specular reflectance was approximately equal to 2.4% at lambda approximately equal to 7 micrometers. The previously synthesized CNTs for optical absorber applications were formed using water-assisted thermal chemical vapor deposition (CVD), which yields CNT lengths in excess of 100's of microns. Vertical alignment, deemed to be a critical feature in enabling the high optical absorption from CNT arrays, occurs primarily via the crowding effect with thermal CVD synthesized CNTs, which is generally not effective in aligning CNTs with lengths less than 10 m. Here it has been shown that the

  13. Applicability of Fluorescence and Absorbance Spectroscopy to Estimate Organic Pollution in Rivers

    PubMed Central

    Knapik, Heloise Garcia; Fernandes, Cristovão Vicente Scapulatempo; de Azevedo, Júlio Cesar Rodrigues; do Amaral Porto, Monica Ferreira

    2014-01-01

    Abstract This article explores the applicability of fluorescence and absorbance spectroscopy for estimating organic pollution in polluted rivers. The relationship between absorbance, fluorescence intensity, dissolved organic carbon, biochemical oxygen demand (BOD), chemical oxygen demand (COD), and other water quality parameters were used to characterize and identify the origin and the spatial variability of the organic pollution in a highly polluted watershed. Analyses were performed for the Iguassu River, located in southern Brazil, with area about 2,700 km2 and ∼3 million inhabitants. Samples were collect at six monitoring sites covering 107 km of the main river. BOD, COD, nitrogen, and phosphorus concentration indicates a high input of sewage to the river. Specific absorbance at 254 and 285 nm (SUVA254 and A285/COD) did not show significant variation between sites monitored, indicating the presence of both dissolved compounds found in domestic effluents and humic and fulvic compounds derived from allochthonous organic matter. Correlations between BOD and tryptophan-like fluorescence peak (peak T2, r=0.7560, and peak T1, r=0.6949) and tyrosine-like fluorescence peak (peak B, r=0.7321) indicated the presence of labile organic matter and thus confirmed the presence of sewage in the river. Results showed that fluorescence and absorbance spectroscopy provide useful information on pollution in rivers from critical watersheds and together are a robust method that is simpler and more rapid than traditional methods employed by regulatory agencies. PMID:25469076

  14. Ultrasensitive sensing with three-dimensional terahertz metamaterial absorber

    NASA Astrophysics Data System (ADS)

    Tan, Siyu; Yan, Fengping; Wang, Wei; Zhou, Hong; Hou, Yafei

    2018-05-01

    Planar metasurfaces and metamaterial absorbers have shown great promise for label-free sensing applications at microwaves, optical and terahertz frequencies. The realization of high-quality-factor resonance in these structures is of significant interest to enhance the sensing sensitivities to detect minute frequency shifts. We propose and demonstrate in this manuscript an ultrasensitive terahertz metamaterial absorber sensor based on a three-dimensional split ring resonator absorber with a high quality factor of 60.09. The sensing performance of the proposed absorber sensor was systematically investigated through detailed numerical calculations and a maximum refractive index sensitivity of 34.40% RIU‑1 was obtained. Furthermore, the absorber sensor can maintain a high sensitivity for a wide range of incidence angles up to 60° under TM polarization incidence. These findings would improve the design flexibility of the absorber sensors and further open up new avenues to achieve ultrasensitive sensing in the terahertz regime.

  15. Synthetic fermentation of bioactive molecules.

    PubMed

    Stepek, Iain A; Bode, Jeffrey W

    2018-04-05

    The concept of synthetic fermentation is to 'grow' complex organic molecules in a controlled and predictable manner by combining small molecule building blocks in water-without the need for reagents, enzymes, or organisms. This approach mimics the production of small mixtures of structurally related natural products by living organisms, particularly microbes, under conditions compatible with direct screening of the cultures for biological activity. This review discusses the development and implementation of this concept, its use for the discovery of protease inhibitors, its basis as a chemistry outreach program allowing non-specialists to make and discover new antibiotics, and highlights of related approaches. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. Method of absorbance correction in a spectroscopic heating value sensor

    DOEpatents

    Saveliev, Alexei; Jangale, Vilas Vyankatrao; Zelepouga, Sergeui; Pratapas, John

    2013-09-17

    A method and apparatus for absorbance correction in a spectroscopic heating value sensor in which a reference light intensity measurement is made on a non-absorbing reference fluid, a light intensity measurement is made on a sample fluid, and a measured light absorbance of the sample fluid is determined. A corrective light intensity measurement at a non-absorbing wavelength of the sample fluid is made on the sample fluid from which an absorbance correction factor is determined. The absorbance correction factor is then applied to the measured light absorbance of the sample fluid to arrive at a true or accurate absorbance for the sample fluid.

  17. Non-absorbed Antibiotics for IBS

    DTIC Science & Technology

    2012-03-16

    absorbed antibiotic rifaximin for nonconstipated irritable bowel syndrome (IBS). This effort adds to the body of literature from other, smaller studies that...have demonstrated clinical efficacy for IBS with rifaximin . Non-absorbed antibiotics have been endorsed by the American College of Gastroenterology... rifaximin 400 mg three times daily for 10 days or placebo. During the initial 2 weeks of therapy and the subsequent 10 weeks of follow-up rifaximin

  18. A comparative computational study of Csbnd N and Csbnd C bonding visible to NIR absorbing croconines

    NASA Astrophysics Data System (ADS)

    Chetti, Prabhakar; Tripathi, Anuj

    2018-03-01

    The lowest electronic excitations and charge transfer properties in two series of croconine dyes; 1) molecules with Csbnd N bonding, having an absorption in the visible region (400-600 nm) and 2) molecules with Csbnd C bonding, showing absorption in visible to near infrared (NIR) region (600-1100 nm) are analyzed by quantum-chemical calculations. The absorption maxima in Csbnd C bonding croconines (CCR) are always having 200-300 nm red shifted than its corresponding Csbnd N bonding croconines (NCR). The reason for this drastic red shift in CCR series than its corresponding NCR has been systematically studied by DFT, TDDFT and SAC-CI methods. It is found that, CCR series are with less charge transfer in nature and are having larger diradical character, whereas NCR series molecules showing larger charge transfer with lower diradical character. The change in bonding mode of central five membered croconate ring, from Csbnd N to Csbnd C, destabilization and/stabilization of HOMO LUMO levels were observed. This study may helpful in the design and synthesis of new visible to NIR absorbing croconine dyes which are useful in materials applications.

  19. Water-induced ethanol dewetting transition.

    PubMed

    Ren, Xiuping; Zhou, Bo; Wang, Chunlei

    2012-07-14

    The dewetting transitions of two hydrophobic plates immersed in pure water, aqueous ethanol solutions with concentrations from 25% to 90%, and pure ethanol were investigated by molecular dynamics simulations, where the dewetting transition was analogous to a first-order phase transition from liquid to vapor. It was found that the dewetting transitions occurred except that in the pure ethanol system. Although the ethanol molecules prefer to locate in the vicinity of the two plates, the inter-plate region is unfavorable for water molecules, due to losing more than one hydrogen bond. Moreover, each inter-plate water molecule forms hydrogen bonds on average with about two ethanol molecules. These intermolecular hydrogen bonds cause water and ethanol to cooperatively fill or exit the inter-plate region. Thus, water molecules play a more important role in the inter-plate filling/empty process, and induce the ethanol dewetting transition. Our results provide insight into the effect of water on the ethanol dewetting phenomena.

  20. Adaptive inertial shock-absorber

    NASA Astrophysics Data System (ADS)

    Faraj, Rami; Holnicki-Szulc, Jan; Knap, Lech; Seńko, Jarosław

    2016-03-01

    This paper introduces and discusses a new concept of impact absorption by means of impact energy management and storage in dedicated rotating inertial discs. The effectiveness of the concept is demonstrated in a selected case-study involving spinning management, a recently developed novel impact-absorber. A specific control technique performed on this device is demonstrated to be the main source of significant improvement in the overall efficiency of impact damping process. The influence of various parameters on the performance of the shock-absorber is investigated. Design and manufacturing challenges and directions of further research are formulated.