Sample records for carbonyl fluoride cof2

  1. Retrievals of carbonyl fluoride (COF2) from ACE-FTS and MIPAS spectra and their comparison with SLIMCAT CTM calculations

    NASA Astrophysics Data System (ADS)

    Harrison, Jeremy; Cai, Shaomin; Dudhia, Anu; Chipperfield, Martyn; Boone, Chris; Bernath, Peter

    2014-05-01

    The majority of fluorine in the atmosphere has resulted from the anthropogenic emission of chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Most tropospheric fluorine is present in its emitted 'organic' form due to the molecules having long lifetimes. At the top of the stratosphere most of the fluorine is present as the 'inorganic' product HF, which, due to its extreme stability, is an almost permanent reservoir of stratospheric fluorine. The second most abundant stratospheric 'inorganic' fluorine reservoir is carbonyl fluoride (COF2). The major sources of COF2 are from the atmospheric degradation of CFC-12 (CCl2F2), which is now banned under the Montreal Protocol, and HCFC-22 (CHF2Cl), the most abundant HCFC and classed as a transitional substitute under the Montreal Protocol. Although the amount of CFC-12 in the atmosphere is slowly decreasing, HCFC-22 is still on the increase. The amounts of COF2, HF, and total fluorine in the atmosphere are all still increasing. Vertical profiles of COF2 in the atmosphere have previously been determined from measurements taken by the Atmospheric Trace MOlecule Spectrometry Experiment (ATMOS) instrument which flew four times on NASA space shuttles between 1985 and 1994. Additionally, there have been several studies into the seasonal variability of COF2 columns above Jungfraujoch using ground-based Fourier transform infrared (FTIR) solar observations. The concentration of COF2 in the atmosphere slowly increases with altitude up to the middle of the stratosphere, above which it decreases as photolysis becomes more efficient, leading to the production of HF. The use of satellite remote-sensing techniques allows the measurement of COF2 atmospheric abundances with impressive global coverage, and the investigation more fully of COF2 trends, and seasonal and latitudinal variability. This work presents global distributions of COF2 using data from two satellite limb instruments: the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS), onboard the SCISAT-1 satellite, which has been recording atmospheric spectra since 2004, and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument onboard the ENVIronmental SATellite (Envisat), which has recorded thermal emission atmospheric spectra between 2002 and 2012. The observations are compared with the output of SLIMCAT, a state-of-the-art three-dimensional chemical transport model (CTM). The model aids in the interpretation of the COF2 satellite observations, and the comparison provides a validation of emission inventories and the atmospheric degradation reaction schemes used in the model.

  2. Reaction of (carbonylimido)sulfur(IV) derivatives with TAS-fluoride, (Me2N)3S+Me3SiF2-.

    PubMed

    Lork, E; Viets, D; Mews, R; Oberhammer, H

    2000-10-16

    In the reaction of TAS-fluoride, (Me2N)3S+Me3SiF2-, with carbonyl sulfur difluoride imides RC(O)NSF2 (R = F, CF3), C-N bond, cleavage is observed, and TAS+RC(O)F2- and NSF are the final products. From TASF and RC(O)NS(CF3)F, the salts TAS+RC(O)NS(CF3)F2- (R = F (14), CF3 (15)), with psi-pentacoordinate sulfur centers in the anions, are formed. An X-ray structure investigation of 14 shows that the fluorine atoms occupy axial positions and CF3, NC(O)F, and the sulfur lone pair occupy equatorial positions of the trigonal bipyramid. The -C(O)F group lies in the equatorial plane with the CO bond synperiplanar to the SN bond. According to B3LYP calculations, this structure corresponds to a global minimum and the expected axial orientation of the -C(O)F group represents a transition state. Calculations for the unstable FC(O)NSF3- anion show a different geometry. The -C(O)F group deviates 40 degrees from axial orientation, and the equatorially bonded fluorine is, in contrast to the -CF3 group in 14, syn positioned.

  3. Ab initio study of the diatomic fluorides FeF, CoF, NiF, and CuF.

    PubMed

    Koukounas, Constantine; Mavridis, Aristides

    2008-11-06

    The late-3d transition-metal diatomic fluorides MF = FeF, CoF, NiF, and CuF have been studied using variational multireference (MRCI) and coupled-cluster [RCCSD(T)] methods, combined with large to very large basis sets. We examined a total of 35 (2S+1)|Lambda| states, constructing as well 29 full potential energy curves through the MRCI method. All examined states are ionic, diabatically correlating to M(+)+F(-)((1)S). Notwithstanding the "eccentric" character of the 3d transition metals and the difficulties to accurately be described with all-electron ab initio methods, our results are, in general, in very good agreement with available experimental numbers.

  4. Fluoride-Mediated Dephosphonylation of α-Diazo-β-carbonyl Phosphonates.

    PubMed

    Phatake, Ravindra S; Mullapudi, Venkannababu; Wakchaure, Vivek C; Ramana, Chepuri V

    2017-01-20

    The possibility of fluoride-mediated selective dephosphonylation of α-diazo-β-carbonyl phosphonates such as the Ohira-Bestmann reagent has been proposed and executed. The resulting α-diazocarbonyl intermediates undergo a (3 + 2)-cycloaddition at room temperature with conjugated olefins and benzynes. Interestingly, under the current conditions, the resulting cycloaddition products underwent either N-acylation (with excess α-diazo-β-carbonyl phosphonates) or Michael addition (with conjugated olefins).

  5. Capacitive behaviour of MnF2 and CoF2 submicro/nanoparticles synthesized via a mild ionic liquid-assisted route

    NASA Astrophysics Data System (ADS)

    Ma, Ruguang; Zhou, Yao; Yao, Lin; Liu, Guanghui; Zhou, Zhenzhen; Lee, Jong-Min; Wang, Jiacheng; Liu, Qian

    2016-01-01

    Submicro-/nano-sized MnF2 rods and hierarchical CoF2 cuboids are respectively synthesized via a facile precipitation method assisted by ionic liquid under a mild condition. The as-prepared MF2 (M = Mn, Co) submicro/nanoparticles exhibit impressive specific capacitance in 1.0 M KOH aqueous solution, especially at relatively high current densities, e.g. 91.2, 68.7 and 56.4 F g-1 for MnF2, and 81.7, 70.6 and 63.0 F g-1 for CoF2 at 5, 8 and 10 A g-1, respectively. The mechanism of striking capacitance of MF2 is clarified on the basis of analysing the cycled electrodes by different characterization techniques. Such remarkable capacitance is ascribed to the redox reactions between MF2 and MOOH in aqueous alkaline electrolytes, which can not be obtained in aqueous neutral electrolytes. This study for the first time provides direct evidences on the pseudocapacitance mechanism of MF2 in alkaline electrolytes and paves the way of application of transition metal fluorides as electrodes in supercapacitors.

  6. Magnetic properties of transition metal fluorides MF2 (M=Mn, Fe, Co, Ni) via high-energy photon diffraction

    NASA Astrophysics Data System (ADS)

    Strempfer, J.; Rütt, U.; Bayrakci, S.; Brückel, Th.; Jauch, W.

    2004-01-01

    We present an overview of recent results from nonresonant magnetic diffraction experiments on the antiferromagnetic compounds MnF2, FeF2, CoF2, and NiF2 using high-energy synchrotron radiation of photon energies above 100 keV. New results are presented on the determination of the spin and of the L/S ratio for CoF2 and NiF2. For CoF2, the saturation value of the long-range-ordered pure spin Sz component Sz=1.11(1) is considerably lower than the value Sz=3/2 for the free Co2+ ion. This is in contrast to our results for NiF2, where the full spin of the free transition-metal ion was found, Sz=0.98(1). The temperature dependence of the magnetization in the critical region as well as in the low-temperature region is also presented. For all compounds, Ising behavior is found in the critical regime, whereas the crossover to the low-temperature spin-wave behavior varies. We attribute this to different anisotropies in this series of compounds.

  7. XPS analysis of 440C steel surfaces lubricated with perfluoropolyethers under sliding conditions in high vacuum

    NASA Technical Reports Server (NTRS)

    Herrera-Fierro, Pilar; Masuko, Masabumi; Jones, William R., Jr.; Pepper, Stephen V.

    1994-01-01

    This work presents the results of the X-Ray Photoelectron Spectroscopy (XPS) analysis of AISI 440C ball surfaces lubricated with perfluoropolyether (PFPE) oils after friction experiments under sliding conditions at high load in air and vacuum environments. The PFPE lubricants tested were Demnum S100, Fomblin Z-25, and Krytox 143AB. It was found that all the PFPE lubricants were degraded by sliding contact causing the formation of inorganic fluorides on the metallic surfaces and a layer of organic decomposition products. KRYTOX 143AB was the least reactive of the three lubricants tested. It was also found that metal fluoride formed at off-scar areas. This suggests the formation of reactive species, such as COF2 or R(sub f)COF, during sliding experiments, which can diffuse through the lubricant film and react with the metallic surfaces away from the contact region. Comparison of reference specimens before sliding with those that had undergone the sliding tests showed that the amount of non-degraded PFPE remaining on the surface of the balls after the sliding experiments was greater than that of the balls without sliding.

  8. Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate.

    PubMed

    Schütte, Kai; Barthel, Juri; Endres, Manuel; Siebels, Marvin; Smarsly, Bernd M; Yue, Junpei; Janiak, Christoph

    2017-02-01

    Decomposition of transition-metal amidinates [M{MeC(N i Pr) 2 } n ] [M(AMD) n ; M=Mn II , Fe II , Co II , Ni II , n= 2; Cu I , n= 1) induced by microwave heating in the ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF 4 ]), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF 6 ]), 1-butyl-3-methylimidazolium trifluoromethanesulfonate (triflate) ([BMIm][TfO]), and 1-butyl-3-methylimidazolium tosylate ([BMIm][Tos]) or in propylene carbonate (PC) gives transition-metal nanoparticles (M-NPs) in non-fluorous media (e.g. [BMIm][Tos] and PC) or metal fluoride nanoparticles (MF 2 -NPs) for M=Mn, Fe, and Co in [BMIm][BF 4 ]. FeF 2 -NPs can be prepared upon Fe(AMD) 2 decomposition in [BMIm][BF 4 ], [BMIm][PF 6 ], and [BMIm][TfO]. The nanoparticles are stable in the absence of capping ligands (surfactants) for more than 6 weeks. The crystalline phases of the metal or metal fluoride synthesized in [BMIm][BF 4 ] were identified by powder X-ray diffraction (PXRD) to exclusively Ni- and Cu-NPs or to solely MF 2 -NPs for M=Mn, Fe, and Co. The size and size dispersion of the nanoparticles were determined by transmission electron microscopy (TEM) to an average diameter of 2(±2) to 14(±4) nm for the M-NPs, except for the Cu-NPs in PC, which were 51(±8) nm. The MF 2 -NPs from [BMIm][BF 4 ] were 15(±4) to 65(±18) nm. The average diameter from TEM is in fair agreement with the size evaluated from PXRD with the Scherrer equation. The characterization was complemented by energy-dispersive X-ray spectroscopy (EDX). Electrochemical investigations of the CoF 2 -NPs as cathode materials for lithium-ion batteries were simply evaluated by galvanostatic charge/discharge profiles, and the results indicated that the reversible capacity of the CoF 2 -NPs was much lower than the theoretical value, which may have originated from the complex conversion reaction mechanism and residue on the surface of the nanoparticles.

  9. Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1‐Butyl‐3‐Methylimidazolium Ionic Liquids and Propylene Carbonate

    PubMed Central

    Schütte, Kai; Barthel, Juri; Endres, Manuel; Siebels, Marvin; Smarsly, Bernd M.; Yue, Junpei

    2016-01-01

    Abstract Decomposition of transition‐metal amidinates [M{MeC(NiPr)2}n] [M(AMD)n; M=MnII, FeII, CoII, NiII, n=2; CuI, n=1) induced by microwave heating in the ionic liquids (ILs) 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIm][BF4]), 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIm][PF6]), 1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate (triflate) ([BMIm][TfO]), and 1‐butyl‐3‐methylimidazolium tosylate ([BMIm][Tos]) or in propylene carbonate (PC) gives transition‐metal nanoparticles (M‐NPs) in non‐fluorous media (e.g. [BMIm][Tos] and PC) or metal fluoride nanoparticles (MF2‐NPs) for M=Mn, Fe, and Co in [BMIm][BF4]. FeF2‐NPs can be prepared upon Fe(AMD)2 decomposition in [BMIm][BF4], [BMIm][PF6], and [BMIm][TfO]. The nanoparticles are stable in the absence of capping ligands (surfactants) for more than 6 weeks. The crystalline phases of the metal or metal fluoride synthesized in [BMIm][BF4] were identified by powder X‐ray diffraction (PXRD) to exclusively Ni‐ and Cu‐NPs or to solely MF2‐NPs for M=Mn, Fe, and Co. The size and size dispersion of the nanoparticles were determined by transmission electron microscopy (TEM) to an average diameter of 2(±2) to 14(±4) nm for the M‐NPs, except for the Cu‐NPs in PC, which were 51(±8) nm. The MF2‐NPs from [BMIm][BF4] were 15(±4) to 65(±18) nm. The average diameter from TEM is in fair agreement with the size evaluated from PXRD with the Scherrer equation. The characterization was complemented by energy‐dispersive X‐ray spectroscopy (EDX). Electrochemical investigations of the CoF2‐NPs as cathode materials for lithium‐ion batteries were simply evaluated by galvanostatic charge/discharge profiles, and the results indicated that the reversible capacity of the CoF2‐NPs was much lower than the theoretical value, which may have originated from the complex conversion reaction mechanism and residue on the surface of the nanoparticles. PMID:28168159

  10. A novel benzimidazole-functionalized 2-D COF material: synthesis and application as a selective solid-phase extractant for separation of uranium.

    PubMed

    Li, Juan; Yang, Xiaodan; Bai, Chiyao; Tian, Yin; Li, Bo; Zhang, Shuang; Yang, Xiaoyu; Ding, Songdong; Xia, Chuanqin; Tan, Xinyu; Ma, Lijian; Li, Shoujian

    2015-01-01

    A novel COF-based material (COF-COOH) containing large amounts of carboxylic groups was prepared for the first time by using a simple and effective one-step synthetic method, in which the cheap and commercially available raw materials, trimesoyl chloride and p-phenylenediamine, were used. The as-synthesized COF-COOH was modified with previously synthesized 2-(2,4-dihydroxyphenyl)-benzimidazole (HBI) by "grafting to" method, and a new solid-phase extractant (COF-HBI) with highly efficient sorption performance for uranium(VI) was consequently obtained. A series of characterizations demonstrated that COF-COOH and COF-HBI exhibited great thermostabilities and irradiation stabilities. Sorption behavior of the COF-based materials toward U(VI) was compared in simulated nuclear industrial effluent containing UO2(2+) and 11 undesired ions, and the UO2(2+) sorption amount of COF-HBI was 81 mg g(-1), accounting for approximately 58% of the total sorption amount, which was much higher than the sorption selectivity of COF-COOH to UO2(2+) (39%). Batch sorption experiment results indicated that the uranium(VI) sorption on COF-HBI was a pH dependent, rapid (sorption equilibrium was reached in 30 min), endothermic and spontaneous process. In the most favorable conditions, the equilibrium sorption capacity of the adsorbent for uranium could reach 211 mg g(-1). Copyright © 2014 Elsevier Inc. All rights reserved.

  11. Adsorption behavior of COF2 and CF4 gas on the MoS2 monolayer doped with Ni: A first-principles study

    NASA Astrophysics Data System (ADS)

    Li, Yi; Zhang, Xiaoxing; Chen, Dachang; Xiao, Song; Tang, Ju

    2018-06-01

    CF4 and COF2 are the two main decomposition products of fluorocarbon gas insulating medium. We explored the gas sensing properties of Ni-MoS2 to CF4 and COF2 based on the density functional theory calculations. The adsorption energy, charge transfer, density of states and electron density difference have been discussed. It was found that the interaction between COF2 molecule and Ni-MoS2 is strong, and the adsorption energy is 0.723 eV. Ni-MoS2 acts as the electron donor and transfers some electrons to COF2 molecule during the interaction. The adsorption energy of CF4 on Ni-MoS2 is lower than that of COF2, and the interaction between them belongs to physical adsorption. Ni-MoS2 has the potential to be used as a gas sensor for COF2 detection using in the field of gas insulated switchgear on-line monitoring.

  12. Lithium doping on covalent organic framework-320 for enhancing hydrogen storage at ambient temperature

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

    Xia, Liangzhi, E-mail: 15004110853@163.com; Liu, Qing

    2016-12-15

    Density Functional Theory (DFT) combines with grand canonical Monte Carlo (GCMC) simulations are performed to explore the effect of Li doping on the hydrogen storage capability of COF-320. The results show that the interaction energy between the H{sub 2} and the Li-doped COF-320 is about three times higher than that of pristine COF-320. GCMC simulations are employed to study the hydrogen uptake of Li-doped COF-320 at ambient temperature, further confirm that the lithium doping can improve the hydrogen uptake at ambient temperature. Our results demonstrate that Li-doped COFs have good potential in the field of hydrogen storage. - Graphical abstract:more » Fig. 1. The optimized cluster model used here to represent the COF-320 and possible adsorption sites (A, B, C) for adsorption of metals in the COF-320. The dangling bonds are terminated by H atoms. C, H, and N atoms are shown as gray, white, and blue colors, respectively. Fig. 2. The adsorption isotherm of H{sub 2} in the pristine and Li-doped COF-320 at 298 K. - Highlights: • The binding sites of single and two lithium atoms in COF-320 were studied. • The interaction energy between the H{sub 2} and the Li-doped COF-320 is about three times higher than that of pristine COF-320. • H{sub 2} uptakes on the Li-doped COFs obtain significant improvement at ambient temperature. • Lithium-doping is a successful strategy for improving hydrogen uptake.« less

  13. Doping of alkali, alkaline-earth, and transition metals in covalent-organic frameworks for enhancing CO2 capture by first-principles calculations and molecular simulations.

    PubMed

    Lan, Jianhui; Cao, Dapeng; Wang, Wenchuan; Smit, Berend

    2010-07-27

    We use the multiscale simulation approach, which combines the first-principles calculations and grand canonical Monte Carlo simulations, to comprehensively study the doping of a series of alkali (Li, Na, and K), alkaline-earth (Be, Mg, and Ca), and transition (Sc and Ti) metals in nanoporous covalent organic frameworks (COFs), and the effects of the doped metals on CO2 capture. The results indicate that, among all the metals studied, Li, Sc, and Ti can bind with COFs stably, while Be, Mg, and Ca cannot, because the binding of Be, Mg, and Ca with COFs is very weak. Furthermore, Li, Sc, and Ti can improve the uptakes of CO2 in COFs significantly. However, the binding energy of a CO2 molecule with Sc and Ti exceeds the lower limit of chemisorptions and, thus, suffers from the difficulty of desorption. By the comparative studies above, it is found that Li is the best surface modifier of COFs for CO2 capture among all the metals studied. Therefore, we further investigate the uptakes of CO2 in the Li-doped COFs. Our simulation results show that at 298 K and 1 bar, the excess CO2 uptakes of the Li-doped COF-102 and COF-105 reach 409 and 344 mg/g, which are about eight and four times those in the nondoped ones, respectively. As the pressure increases to 40 bar, the CO2 uptakes of the Li-doped COF-102 and COF-105 reach 1349 and 2266 mg/g at 298 K, respectively, which are among the reported highest scores to date. In summary, doping of metals in porous COFs provides an efficient approach for enhancing CO2 capture.

  14. Ammonium Fluoride Mediated Synthesis of Anhydrous Metal Fluoride-Mesoporous Carbon Nanocomposites for High-Performance Lithium Ion Battery Cathodes.

    PubMed

    Chun, Jinyoung; Jo, Changshin; Sahgong, Sunhye; Kim, Min Gyu; Lim, Eunho; Kim, Dong Hyeon; Hwang, Jongkook; Kang, Eunae; Ryu, Keun Ah; Jung, Yoon Seok; Kim, Youngsik; Lee, Jinwoo

    2016-12-28

    Metal fluorides (MF x ) are one of the most attractive cathode candidates for Li ion batteries (LIBs) due to their high conversion potentials with large capacities. However, only a limited number of synthetic methods, generally involving highly toxic or inaccessible reagents, currently exist, which has made it difficult to produce well-designed nanostructures suitable for cathodes; consequently, harnessing their potential cathodic properties has been a challenge. Herein, we report a new bottom-up synthetic method utilizing ammonium fluoride (NH 4 F) for the preparation of anhydrous MF x (CuF 2 , FeF 3 , and CoF 2 )/mesoporous carbon (MSU-F-C) nanocomposites, whereby a series of metal precursor nanoparticles preconfined in mesoporous carbon were readily converted to anhydrous MF x through simple heat treatment with NH 4 F under solventless conditions. We demonstrate the versatility, lower toxicity, and efficiency of this synthetic method and, using XRD analysis, propose a mechanism for the reaction. All MF x /MSU-F-C prepared in this study exhibited superior electrochemical performances, through conversion reactions, as the cathode for LIBs. In particular, FeF 3 /MSU-F-C maintained a capacity of 650 mAh g -1 FeF3 across 50 cycles, which is ∼90% of its initial capacity. We expect that this facile synthesis method will trigger further research into the development of various nanostructured MF x for use in energy storage and other applications.

  15. Identification of Two Metallothioneins as Novel Inhalative Coffee Allergens Cof a 2 and Cof a 3

    PubMed Central

    Peters, Ulrike; Frenzel, Karsten; Brettschneider, Reinhold; Oldenburg, Marcus; Bittner, Cordula

    2015-01-01

    Background Dust of green coffee beans is known to be a relevant cause for occupational allergic disorders in coffee industry workers. Recently, we described the first coffee allergen (Cof a 1) establishing an allergenic potential of green coffee dust. Objective Our aim was to identify allergenic components of green coffee in order to enhance inhalative coffee allergy diagnosis. Methods A Coffea arabica pJuFo cDNA phage display library was created and screened for IgE binding with sera from allergic coffee workers. Two further coffee allergens were identified by sequence analysis, expressed in E. coli, and evaluated by Western blots. The prevalence of sensitization to recombinant Cof a 1, Cof a 2, and Cof a 3 and to commercially available extract was investigated by ELISA (enzyme-linked immunosorbent assay) respectively CAP (capacity test) screening in 18 sera of symptomatic coffee workers. Results In addition to the previously described chitinase Cof a 1, two Coffea arabica cysteine-rich metallothioneins of 9 and 7 kDa were identified and included in the IUIS Allergen Nomenclature as Cof a 2 and Cof a 3. Serum IgE antibodies to at least one of the recombinant allergens were found in 8 out of 18 symptomatic coffee workers (44%). Only 2 of the analysed sera (11%) had reacted previously to the commercial allergy test. Conclusions In addition to the previously described Cof a 1 we have identified two further coffee proteins to be type I coffee allergens (Cof a 2 and Cof a 3) which may have a relevant potential for the specific diagnosis and/or therapy of coffee allergy. PMID:25962169

  16. Colloidal Covalent Organic Frameworks

    PubMed Central

    2017-01-01

    Covalent organic frameworks (COFs) are two- or three-dimensional (2D or 3D) polymer networks with designed topology and chemical functionality, permanent porosity, and high surface areas. These features are potentially useful for a broad range of applications, including catalysis, optoelectronics, and energy storage devices. But current COF syntheses offer poor control over the material’s morphology and final form, generally providing insoluble and unprocessable microcrystalline powder aggregates. COF polymerizations are often performed under conditions in which the monomers are only partially soluble in the reaction solvent, and this heterogeneity has hindered understanding of their polymerization or crystallization processes. Here we report homogeneous polymerization conditions for boronate ester-linked, 2D COFs that inhibit crystallite precipitation, resulting in stable colloidal suspensions of 2D COF nanoparticles. The hexagonal, layered structures of the colloids are confirmed by small-angle and wide-angle X-ray scattering, and kinetic characterization provides insight into the growth process. The colloid size is modulated by solvent conditions, and the technique is demonstrated for four 2D boronate ester-linked COFs. The diameter of individual COF nanoparticles in solution is monitored and quantified during COF growth and stabilization at elevated temperature using in situ variable-temperature liquid cell transmission electron microscopy imaging, a new characterization technique that complements conventional bulk scattering techniques. Solution casting of the colloids yields a free-standing transparent COF film with retained crystallinity and porosity, as well as preferential crystallite orientation. Collectively this structural control provides new opportunities for understanding COF formation and designing morphologies for device applications. PMID:28149954

  17. Fabrication of COF-MOF Composite Membranes and Their Highly Selective Separation of H2/CO2.

    PubMed

    Fu, Jingru; Das, Saikat; Xing, Guolong; Ben, Teng; Valtchev, Valentin; Qiu, Shilun

    2016-06-22

    The search for new types of membrane materials has been of continuous interest in both academia and industry, given their importance in a plethora of applications, particularly for energy-efficient separation technology. In this contribution, we demonstrate for the first time that a metal-organic framework (MOF) can be grown on the covalent-organic framework (COF) membrane to fabricate COF-MOF composite membranes. The resultant COF-MOF composite membranes demonstrate higher separation selectivity of H2/CO2 gas mixtures than the individual COF and MOF membranes. A sound proof for the synergy between two porous materials is the fact that the COF-MOF composite membranes surpass the Robeson upper bound of polymer membranes for mixture separation of a H2/CO2 gas pair and are among the best gas separation MOF membranes reported thus far.

  18. Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks

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

    Johnson, Justin C; Braunecker, Wade A; Hurst, Katherine E

    A two-dimensional imine-based covalent organic framework (COF) was designed and synthesized such that phenyl and perfluorophenyl structural units can seamlessly alternate between layers of the framework. X-ray diffraction of the COF powders reveals a striking increase in crystallinity for the COF with self-complementary phenyl/perfluorophenyl interactions (FASt-COF). Whereas measured values of the Brunauer-Emmet-Teller (BET) surface areas for the nonfluorinated Base-COF and the COF employing hydrogen bonding were ~37% and 59%, respectively, of their theoretical Connolly surface areas, the BET value for FASt-COF achieves >90% of its theoretical value (~1700 m2/g). Transmission electron microscopy images also revealed unique micron-sized rodlike features inmore » FASt-COF that were not present in the other materials. The results highlight a promising approach for improving surface areas and long-range order in two-dimensional COFs.« less

  19. The injury of fine particulate matter from cooking oil fumes on umbilical cord blood vessels in vitro.

    PubMed

    Hou, Lijuan; Zhang, Jian; Zhang, Chao; Xu, Yachun; Zhu, Xiaoxia; Yao, Cijiang; Liu, Ying; Li, Tao; Cao, Jiyu

    2017-01-01

    Cooking oil fumes (COFs) derived PM 2.5 is the major source of indoor air pollution in Asia. For this, a pregnant rat model within different doses of cooking oil fumes (COFs) derived PM 2.5 was established in pregnancy in our research. Our previous studies have showed that exposure to COFs-derived PM 2.5 was related to adverse pregnancy outcomes. However, the mechanisms of signaling pathways remain unknown. Therefore, this study aimed to investigate the underlying mechanisms induced by COFs-derived PM2.5 injury on umbilical cord blood vessels (UCs) in vitro. Exposure to COFs-derived PM 2.5 resulted in changing the expression of eNOS, ET-1, ETRA, and ETRB. In additions, western blot analysis indicated that the HIF-1α/iNOS/NO signaling pathway and VEGF/VEGFR1/iNOS signaling pathway were involved in UCs injury triggered by COFs-derived PM 2.5 . In conclusion, our data suggested that exposure to COFs-derived PM 2.5 resulted in increasing of oxidative stress and inflammation, as well as dysfunction of UCs. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Design of stereoelectronically promoted super lewis acids and unprecedented chemistry of their complexes.

    PubMed

    Foroutan-Nejad, Cina; Vicha, Jan; Marek, Radek

    2014-09-01

    A new family of stereoelectronically promoted aluminum and scandium super Lewis acids is introduced on the basis of state-of-the-art computations. Structures of these molecules are designed to minimize resonance electron donation to central metal atoms in the Lewis acids. Acidity of these species is evaluated on the basis of their fluoride-ion affinities relative to the antimony pentafluoride reference system. It is demonstrated that introduced changes in the stereochemistry of the designed ligands increase acidity considerably relative to Al and Sc complexes with analogous monodentate ligands. The high stability of fluoride complexes of these species makes them ideal candidates to be used as weakly coordinating anions in combination with highly reactive cations instead of conventional Lewis acid-fluoride complexes. Further, the interaction of all designed molecules with methane is investigated. All studied acids form stable pentavalent-carbon complexes with methane. In addition, interactions of the strongest acid of this family with very weak bases, namely, H2, N2, carbon oxides, and noble gases were investigated; it is demonstrated that this compound can form considerably stable complexes with the aforementioned molecules. To the best of our knowledge, carbonyl and nitrogen complexes of this species are the first hypothetical four-coordinated carbonyl and nitrogen complexes of aluminum. The nature of bonding in these systems is studied in detail by various bonding analysis approaches. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Fluoride decreased the sperm ATP of mice through inhabiting mitochondrial respiration.

    PubMed

    Sun, Zilong; Zhang, Wen; Xue, Xingchen; Zhang, Yuliang; Niu, Ruiyan; Li, Xuying; Li, Baojun; Wang, Xiaowen; Wang, Jundong

    2016-02-01

    Fluoride-induced low sperm motility was observed in accumulated investigations. However, the effect of fluoride exposure on ATP generation which is essential to sperm motility remains to be elucidated. In this study, 120 healthy male mice were orally administrated with 0, 25, 50, and 100 mg L(-1) NaF for 90 d. Results showed that compared with controls, fluoride ingestion significantly reduced sperm count, survival, as well as mobility and total ATP level in sperm untreated with carbonyl cyanide m-chlorophenylhydrazone (CCCP) or pyruvate, which was used to establish glycolysis or mitochondrial respiration model, respectively. Data further revealed that sperm mobility and ATP level under mitochondrial respiration condition were significantly suppressed, while no statistical difference occurred in the model of glycolysis, indicating ATP derived from mitochondria was affected. Moreover, mRNA expressions of mitochondrial cytochrome b (mt-Cytb) and cytochrome c oxidase subunit 2 (mt-COX2), two important molecules in mitochondrial electron transport chain (ETC), were down-regulated in all fluoride treatment groups. Mitochondria in sperm of mice exposed to 100 mg L(-1) NaF appeared to be irregular and vacuolated. These findings suggested that decreased sperm motility induced by fluoride may result from low ATP generation due to the disturbed ETC in sperm mitochondrial. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. First-Principles Prediction of Spin-Polarized Multiple Dirac Rings in Manganese Fluoride

    NASA Astrophysics Data System (ADS)

    Jiao, Yalong; Ma, Fengxian; Zhang, Chunmei; Bell, John; Sanvito, Stefano; Du, Aijun

    2017-07-01

    Spin-polarized materials with Dirac features have sparked great scientific interest due to their potential applications in spintronics. But such a type of structure is very rare and none has been fabricated. Here, we investigate the already experimentally synthesized manganese fluoride (MnF3 ) as a novel spin-polarized Dirac material by using first-principles calculations. MnF3 exhibits multiple Dirac cones in one spin orientation, while it behaves like a large gap semiconductor in the other spin channel. The estimated Fermi velocity for each cone is of the same order of magnitude as that in graphene. The 3D band structure further reveals that MnF3 possesses rings of Dirac nodes in the Brillouin zone. Such a spin-polarized multiple Dirac ring feature is reported for the first time in an experimentally realized material. Moreover, similar band dispersions can be also found in other transition metal fluorides (e.g., CoF3 , CrF3 , and FeF3 ). Our results highlight a new interesting single-spin Dirac material with promising applications in spintronics and information technologies.

  3. First-Principles Prediction of Spin-Polarized Multiple Dirac Rings in Manganese Fluoride.

    PubMed

    Jiao, Yalong; Ma, Fengxian; Zhang, Chunmei; Bell, John; Sanvito, Stefano; Du, Aijun

    2017-07-07

    Spin-polarized materials with Dirac features have sparked great scientific interest due to their potential applications in spintronics. But such a type of structure is very rare and none has been fabricated. Here, we investigate the already experimentally synthesized manganese fluoride (MnF_{3}) as a novel spin-polarized Dirac material by using first-principles calculations. MnF_{3} exhibits multiple Dirac cones in one spin orientation, while it behaves like a large gap semiconductor in the other spin channel. The estimated Fermi velocity for each cone is of the same order of magnitude as that in graphene. The 3D band structure further reveals that MnF_{3} possesses rings of Dirac nodes in the Brillouin zone. Such a spin-polarized multiple Dirac ring feature is reported for the first time in an experimentally realized material. Moreover, similar band dispersions can be also found in other transition metal fluorides (e.g., CoF_{3}, CrF_{3}, and FeF_{3}). Our results highlight a new interesting single-spin Dirac material with promising applications in spintronics and information technologies.

  4. Amine-Functionalized Covalent Organic Framework for Efficient SO2 Capture with High Reversibility.

    PubMed

    Lee, Gang-Young; Lee, Joohyeon; Vo, Huyen Thanh; Kim, Sangwon; Lee, Hyunjoo; Park, Taiho

    2017-04-03

    Removing sulfur dioxide (SO 2 ) from exhaust flue gases of fossil fuel power plants is an important issue given the toxicity of SO 2 and subsequent environmental problems. To address this issue, we successfully developed a new series of imide-linked covalent organic frameworks (COFs) that have high mesoporosity with large surface areas to support gas flowing through channels; furthermore, we incorporated 4-[(dimethylamino)methyl]aniline (DMMA) as the modulator to the imide-linked COF. We observed that the functionalized COFs serving as SO 2 adsorbents exhibit outstanding molar SO 2 sorption capacity, i.e., PI-COF-m10 record 6.30 mmol SO 2 g -1 (40 wt%). To our knowledge, it is firstly reported COF as SO 2 sorbent to date. We also observed that the adsorbed SO 2 is completely desorbed in a short time period with remarkable reversibility. These results suggest that channel-wall functional engineering could be a facile and powerful strategy for developing mesoporous COFs for high-performance reproducible gas storage and separation.

  5. Construction of hierarchically porous monoliths from covalent organic frameworks (COFs) and their application for bisphenol A removal.

    PubMed

    Liu, Zhongshan; Wang, Hongwei; Ou, Junjie; Chen, Lianfang; Ye, Mingliang

    2018-05-11

    Subject to synthetic conditions, covalent organic frameworks (COFs) are usually in powder form. Herein, taking an azine-linked COF as an example, detailed characterizations indicated that accessible aldehyde groups and hydrazine groups (CNNH 2 , 88 μmol g -1 ) concurrently existed on its surface. Intrigued by such feature, we have developed an approach based on ring-opening polymerization to shape COF powder into monoliths. The crystallinity and micropore of COF in monoliths were well remained, meanwhile, the ring-opening polymerization remarkably generated macropores ranging from 0.43 to 3.51 μm, indicating a hierarchically porous structure. The BET surface area of resultant monoliths with different COF mass fractions of 16%, 28% and 43% ranged from 105 to 281 m 2  g -1 . Due to the π-π interaction and hydrogen bond interaction, COF-based monoliths exhibited strong retention and rapid adsorption for bisphenol A (BPA) in aqueous medium. When 29 mL BPA solution (22.8 mg L -1 ) passed through COF-based monolith (28%), the adsorption capacity was up to 61.3 mg g -1 . Furthermore, the COF-based monolith demonstrated excellent cycle use for catalyzing Suzuki-Miyaura coupling reaction after being coordinated with palladium acetate. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Origin of the SN2 benzylic effect.

    PubMed

    Galabov, Boris; Nikolova, Valia; Wilke, Jeremiah J; Schaefer, Henry F; Allen, Wesley D

    2008-07-30

    The S N2 identity exchange reactions of the fluoride ion with benzyl fluoride and 10 para-substituted derivatives (RC6H 4CH 2F, R = CH3, OH, OCH 3, NH2, F, Cl, CCH, CN, COF, and NO2) have been investigated by both rigorous ab initio methods and carefully calibrated density functional theory. Groundbreaking focal-point computations were executed for the C6H5CH 2F + F (-) and C 6H 5CH2Cl + Cl (-) SN2 reactions at the highest possible levels of electronic structure theory, employing complete basis set (CBS) extrapolations of aug-cc-pV XZ (X = 2-5) Hartree-Fock and MP2 energies, and including higher-order electron correlation via CCSD/aug-cc-pVQZ and CCSD(T)/aug-cc-pVTZ coupled cluster wave functions. Strong linear dependences are found between the computed electrostatic potential at the reaction-center carbon atom and the effective SN2 activation energies within the series of para-substituted benzyl fluorides. An activation strain energy decomposition indicates that the SN2 reactivity of these benzylic compounds is governed by the intrinsic electrostatic interaction between the reacting fragments. The delocalization of nucleophilic charge into the aromatic ring in the SN2 transition states is quite limited and should not be considered the origin of benzylic acceleration of SN2 reactions. Our rigorous focal-point computations validate the benzylic effect by establishing SN2 barriers for (F (-), Cl (-)) identity exchange in (C6H5CH2F, C6H 5CH2Cl) that are lower than those of (CH3F, CH3Cl) by (3.8, 1.6) kcal mol (-1), in order.

  7. Thiophene-based covalent organic frameworks

    PubMed Central

    Bertrand, Guillaume H. V.; Michaelis, Vladimir K.; Ong, Ta-Chung; Griffin, Robert G.; Dincă, Mircea

    2013-01-01

    We report the synthesis and characterization of covalent organic frameworks (COFs) incorporating thiophene-based building blocks. We show that these are amenable to reticular synthesis, and that bent ditopic monomers, such as 2,5-thiophenediboronic acid, are defect-prone building blocks that are susceptible to synthetic variations during COF synthesis. The synthesis and characterization of an unusual charge transfer complex between thieno[3,2-b]thiophene-2,5-diboronic acid and tetracyanoquinodimethane enabled by the unique COF architecture is also presented. Together, these results delineate important synthetic advances toward the implementation of COFs in electronic devices. PMID:23479656

  8. Oriented Covalent Organic Framework Film on Graphene for Robust Ambipolar Vertical Organic Field-Effect Transistor

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

    Sun, Bing; Zhu, Chen-Hui; Liu, Yi

    Periodically eclipsed π-stacking columns in two-dimensional covalent organic frameworks (2D COFs) could function as direct channel paths for charge carrier transport. Incorporating a welldefined 2D COF into organic electronic devices, however, is still a challenge. Herein, we reported the solvothermal synthesis of a COF TFPy-PPDA film on single layer graphene (SLG), which was constructed via covalent imine-type linkage by employing 1,3,6,8-tetrakis(p-formylphenyl)pyrene (TFPy) and p-phenylenediamine (PPDA) as building blocks. A vertical field-effect transistor (VFET) based on the heterostructure of COF TFPy-PPDA film and SLG shows ambipolar charge carrier behavior under lower modulating voltages. Work-function-tunable contact between SLG and COFTFPy-PPDA film andmore » suitable injection barriers of charge carriers lead to the ambipolar transport with high current density on/off ratio (>10 5) and high on-current density (>4.1 Acm -2). Interfacing 2D COF with graphene for VFET could shed the promising application prospect of 2D COFs in organic electronics and optoelectronics.« less

  9. Oriented Covalent Organic Framework Film on Graphene for Robust Ambipolar Vertical Organic Field-Effect Transistor

    DOE PAGES

    Sun, Bing; Zhu, Chen-Hui; Liu, Yi; ...

    2017-04-13

    Periodically eclipsed π-stacking columns in two-dimensional covalent organic frameworks (2D COFs) could function as direct channel paths for charge carrier transport. Incorporating a welldefined 2D COF into organic electronic devices, however, is still a challenge. Herein, we reported the solvothermal synthesis of a COF TFPy-PPDA film on single layer graphene (SLG), which was constructed via covalent imine-type linkage by employing 1,3,6,8-tetrakis(p-formylphenyl)pyrene (TFPy) and p-phenylenediamine (PPDA) as building blocks. A vertical field-effect transistor (VFET) based on the heterostructure of COF TFPy-PPDA film and SLG shows ambipolar charge carrier behavior under lower modulating voltages. Work-function-tunable contact between SLG and COFTFPy-PPDA film andmore » suitable injection barriers of charge carriers lead to the ambipolar transport with high current density on/off ratio (>10 5) and high on-current density (>4.1 Acm -2). Interfacing 2D COF with graphene for VFET could shed the promising application prospect of 2D COFs in organic electronics and optoelectronics.« less

  10. Degradation and crosslinking of perfluoroalkyl polyethers under X-ray irradiation in ultrahigh vacuum

    NASA Technical Reports Server (NTRS)

    Mori, Shigeyuki; Morales, Wilfredo

    1989-01-01

    Degradation of three types of commercially available perfluoroalkyl polyethers (PFPE)-Demnum S200, Fomblin Z25, and Krytox 16256-by X-ray irradiation was studied by using X-ray photoemission spectroscopy (XPS) and a mass spectrometer under ultra-high-vacuum conditions. The carbons in the polymers were characterized by chemical shifts of Cls binding energies. Gaseous products containing COF2 and low-molecular-weight fluorocarbons were formed. From Fomblin Z25, which has acetal linkages (-OCF2O-), a large quantity of COF2 gas was evolved. Liquid products became tacky after a long irradiation time, and some did not dissolve in Freon. High-pressure liquid chromatography (HPLC) showed that molecular weight distribution became broader and that higher molecular weight polymers were formed from Demnum and Krytox. We concluded from these results that degradation and cross-linking took place simultaneously. Demnum crosslinked more easily than the other fluids. The time dependence of both XPS spectra of Cls and mass spectra showed that C-O-bonded carbons in PFPE'S were removed faster than other carbons. There was no substrate effect on the degradation reaction because the first-order rate constants calculated from the change of gaseous products were similar when stainless steel (440C) and gold-coated surfaces were used. Metal fluorides were formed on stainless steel during the reaction. A mechanism for the degradation of PFPE'S is discussed on the basis of their molecular structures.

  11. Effect of adding cofactors to exogenous fibrolytic enzymes on preingestive hydrolysis, in vitro digestibility, and fermentation of bermudagrass haylage.

    PubMed

    Romero, J J; Ma, Z X; Gonzalez, C F; Adesogan, A T

    2015-07-01

    Our objectives were to examine if adding metal ion cofactors (COF) to exogenous fibrolytic enzymes (EFE) would increase the beneficial effects of the EFE on the preingestive hydrolysis and in vitro digestibility and fermentation of bermudagrass haylage. In experiment 1, 5 COF (Mn(2+), Co(2+), Fe(2+), Ca(2+), and Mg(2+)) were screened to select the best candidates for synergistically enhancing release of water-soluble carbohydrates (WSC) from bermudagrass haylage by 5 EFE. The 5 EFE (1A, 2A, 11C, 13D, and 15D) were sourced from Trichoderma reesei and Aspergillus oryzae and they were the most effective of 12 EFE at increasing the neutral detergent fiber digestibility of bermudagrass haylage in a previous trial. Adding 1mM of each of the COF to EFE 2A or 11C synergistically increased release of WSC from bermudagrass haylage, as did adding (1mM) Fe(2+) to 1A, Mn(2+), Co(2+), or Fe(2+) to 13D, or Co(2+)or Fe(2+) to 15D. The greatest release of WSC responses were obtained by adding Mn(2+) to 11C (38%) or by adding Fe(2+) to 2A or 13D (10 and 21.9%, respectively). In experiment 2, the effect of increasing the COF dose on in vitro digestibility and fermentation of bermudagrass haylage was examined using the best EFE-COF combinations from experiment 1. Effects of adding increasing doses of these COF on EFE-mediated changes in vitro digestibility depended on the COF-EFE combination. Adding 10mM Mn(2+) alone to bermudagrass haylage increased DMD and NDFD by 2.7 and 6.3% and adding 11C alone increased these measures by 6.6 and 15.5%, respectively. However, adding 10mM Mn(2+) with 11C resulted in 3.5 and 8.1% increases in DMD and NDFD, respectively, beyond the increases caused by adding 11C alone. Adding Fe(2+) to 2A had no effects on EFE-mediated digestibility responses, but 2A prevented adverse effects of adding Fe(2+) alone on DMD and NDFD. In contrast, adding Fe(2+) to 13D reduced the increases in DMD and NDFD caused by adding the EFE alone. This study shows that adding COF to EFE can synergistically increase, decrease, or not affect the hydrolytic effects of EFE on bermudagrass haylage cell walls. The outcome depends on the specific EFE-COF combination and the COF dose. More research is required to understand the mechanisms resulting in these outcomes to exploit beneficial effects of COF on EFE. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  12. Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films

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

    DeBlase, Catherine R.; Hernández-Burgos, Kenneth; Silberstein, Katharine E.

    2015-03-24

    Two-dimensional covalent organic frameworks (2D COFs) are ideally suited for organizing redox-active subunits into periodic, permanently porous polymer networks of interest for pseudocapacitive energy storage. Here we describe a method for synthesizing crystalline, oriented thin films of a redox-active 2D COF on Au working electrodes. The thickness of the COF film was controlled by varying the initial monomer concentration. A large percentage (80–99%) of the anthraquinone groups are electrochemically accessible in films thinner than 200 nm, an order of magnitude improvement over the same COF prepared as a randomly oriented microcrystalline powder. As a result, electrodes functionalized with oriented COFmore » films exhibit a 400% increase in capacitance scaled to electrode area as compared to those functionalized with the randomly oriented COF powder. These results demonstrate the promise of redox-active COFs for electrical energy storage and highlight the importance of controlling morphology for optimal performance.« less

  13. Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films

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

    DeBlase, Catherine R.; Hernández-Burgos, Kenneth; Silberstein, Katharine E.

    2015-02-17

    Two-dimensional covalent organic frameworks (2D COFs) are ideally suited for organizing redox-active subunits into periodic, permanently porous polymer networks of interest for pseudocapacitive energy storage. Here we describe a method for synthesizing crystalline, oriented thin films of a redox-active 2D COF on Au working electrodes. The thickness of the COF film was controlled by varying the initial monomer concentration. A large percentage (80–99%) of the anthraquinone groups are electrochemically accessible in films thinner than 200 nm, an order of magnitude improvement over the same COF prepared as a randomly oriented microcrystalline powder. As a result, electrodes functionalized with oriented COFmore » films exhibit a 400% increase in capacitance scaled to electrode area as compared to those functionalized with the randomly oriented COF powder. These results demonstrate the promise of redox-active COFs for electrical energy storage and highlight the importance of controlling morphology for optimal performance.« less

  14. First-principles study of hydrogen adsorption in metal-doped COF-10

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

    Wu Miaomiao; Sun Qiang; Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284

    2010-10-21

    Covalent organic frameworks (COFs), due to their low-density, high-porosity, and high-stability, have promising applications in gas storage. In this study we have explored the potential of COFs doped with Li and Ca metal atoms for storing hydrogen under ambient thermodynamic conditions. Using density functional theory we have performed detailed calculations of the sites Li and Ca atoms occupy in COF-10 and their interaction with hydrogen molecules. The binding energy of Li atom on COF-10 substrate is found to be about 1.0 eV and each Li atom can adsorb up to three H{sub 2} molecules. However, at high concentration, Li atomsmore » cluster and, consequently, their hydrogen storage capacity is reduced due to steric hindrance between H{sub 2} molecules. On the other hand, due to charge transfer from Li to the substrate, O sites provide additional enhancement for hydrogen adsorption. With increasing concentration of doped metal atoms, the COF-10 substrate provides an additional platform for storing hydrogen. Similar conclusions are reached for Ca doped COF-10.« less

  15. Control Of Flexible Structures-2 (COFS-2) flight control, structure and gimbal system interaction study

    NASA Technical Reports Server (NTRS)

    Fay, Stanley; Gates, Stephen; Henderson, Timothy; Sackett, Lester; Kirchwey, Kim; Stoddard, Isaac; Storch, Joel

    1988-01-01

    The second Control Of Flexible Structures Flight Experiment (COFS-2) includes a long mast as in the first flight experiment, but with the Langley 15-m hoop column antenna attached via a gimbal system to the top of the mast. The mast is to be mounted in the Space Shuttle cargo bay. The servo-driven gimbal system could be used to point the antenna relative to the mast. The dynamic interaction of the Shuttle Orbiter/COFS-2 system with the Orbiter on-orbit Flight Control System (FCS) and the gimbal pointing control system has been studied using analysis and simulation. The Orbiter pointing requirements have been assessed for their impact on allowable free drift time for COFS experiments. Three fixed antenna configurations were investigated. Also simulated was Orbiter attitude control behavior with active vernier jets during antenna slewing. The effect of experiment mast dampers was included. Control system stability and performance and loads on various portions of the COFS-2 structure were investigated. The study indicates possible undesirable interaction between the Orbiter FCS and the flexible, articulated COFS-2 mast/antenna system, even when restricted to vernier reaction jets.

  16. Ionic Conductivity and Potential Application for Fuel Cell of a Modified Imine-Based Covalent Organic Framework.

    PubMed

    Montoro, Carmen; Rodríguez-San-Miguel, David; Polo, Eduardo; Escudero-Cid, Ricardo; Ruiz-González, Maria Luisa; Navarro, Jorge A R; Ocón, Pilar; Zamora, Félix

    2017-07-26

    We present the novel potential application of imine-based covalent organic frameworks (COFs), formed by the direct Schiff reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarbaldehyde building blocks in m-cresol or acetic acid, named RT-COF-1 or RT-COF-1Ac/RT-COF-1AcB. The post-synthetic treatment of RT-COF-1 with LiCl leads to the formation of LiCl@RT-COF-1. The ionic conductivity of this series of polyimine COFs has been characterized at variable temperature and humidity, using electrochemical impedance spectroscopy. LiCl@RT-COF-1 exhibits a conductivity value of 6.45 × 10 -3 S cm -1 (at 313 K and 100% relative humidity) which is among the highest values so far reported in proton conduction for COFs. The mechanism of conduction has been determined using 1 H and 7 Li solid-state nuclear magnetic resonance spectroscopy. Interestingly, these materials, in the presence of controlled amounts of acetic acid and under pressure, show a remarkable processability that gives rise to quasi-transparent and flexible films showing in-plane structural order as confirmed by X-ray crystallography. Finally, we prove that these films are useful for the construction of proton exchange membrane fuel cells (PEMFC) reaching values up to 12.95 mW cm -2 and 53.1 mA cm -2 for maximum power and current density at 323 K, respectively.

  17. Instantaneous Conversion of [11 C]CO2 to [11 C]CO via Fluoride-Activated Disilane Species.

    PubMed

    Taddei, Carlotta; Bongarzone, Salvatore; Gee, Antony D

    2017-06-07

    The development of a fast and novel methodology to generate carbon-11 carbon monoxide ([ 11 C]CO) from cyclotron-produced carbon-11 carbon dioxide ([ 11 C]CO 2 ) mediated by a fluoride-activated disilane species is described. This methodology allows up to 74 % conversion of [ 11 C]CO 2 to [ 11 C]CO using commercially available reagents, readily available laboratory equipment and mild reaction conditions (room temperature). As proof of utility, radiochemically pure [carbonyl- 11 C]N-benzylbenzamide was successfully synthesized from produced [ 11 C]CO in up to 74 % radiochemical yield (RCY) and >99 % radiochemical purity (RCP) in ≤10 min from end of [ 11 C]CO 2 delivery. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  18. Temperature Dependence of Gas Properties in Polynomial Form

    DTIC Science & Technology

    1981-01-01

    Carbonyl Sulfide Chlorine Chlorine (Monatomic) Chlorine Dioxide Chlorine Fluoride Chlorine Monoxide Chlorine Oxide Chlorine Trifluoride ...dis- cussed in Section 5 and the following eqn: 100-1500K~ Cp(T)= 515.3754 + 0.426933T -2.91036E-04T 2 -+ 6.836113E-08Ti CHLORINE TRIFLUORIDE C1F 3...3 Trimeric Boron Tribromide BBr3 250.538 33.186 A-3 Boron Trichloride BC1 3 117.170 70.959 A-4 Boron Trifluoride BF3 67.806 122.619 A-4 Bromine Br2

  19. Tunable electrical conductivity in oriented thin films of tetrathiafulvalene-based covalent organic framework

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

    Cai, SL; Zhang, YB; Pun, AB

    2014-09-16

    Despite the high charge-carrier mobility in covalent organic frameworks (COFs), the low intrinsic conductivity and poor solution processability still impose a great challenge for their applications in flexible electronics. We report the growth of oriented thin films of a tetrathiafulvalene-based COF (TTF-COF) and its tunable doping. The porous structure of the crystalline TTF-COF thin film allows the diffusion of dopants such as I-2 and tetracyanoquinodimethane (TCNQ) for redox reactions, while the closely packed 2D grid sheets facilitate the cross-layer delocalization of thus-formed TTF radical cations to generate more conductive mixed-valence TTF species, as is verified by UV-vis-NIR and electron paramagneticmore » resonance spectra. Conductivity as high as 0.28 S m(-1) is observed for the doped COF thin films, which is three orders of magnitude higher than that of the pristine film and is among the highest for COF materials.« less

  20. Ultrathin Two-Dimensional Covalent Organic Framework Nanosheets: Preparation and Application in Highly Sensitive and Selective DNA Detection.

    PubMed

    Peng, Yongwu; Huang, Ying; Zhu, Yihan; Chen, Bo; Wang, Liying; Lai, Zhuangchai; Zhang, Zhicheng; Zhao, Meiting; Tan, Chaoliang; Yang, Nailiang; Shao, Fangwei; Han, Yu; Zhang, Hua

    2017-06-28

    The ability to prepare ultrathin two-dimensional (2D) covalent organic framework (COF) nanosheets (NSs) in high yield is of great importance for the further exploration of their unique properties and potential applications. Herein, by elaborately designing and choosing two flexible molecules with C 3v molecular symmetry as building units, a novel imine-linked COF, namely, TPA-COF, with a hexagonal layered structure and sheet-like morphology, is synthesized. Since the flexible building units are integrated into the COF skeletons, the interlayer stacking becomes weak, resulting in the easy exfoliation of TPA-COF into ultrathin 2D NSs. Impressively, for the first time, the detailed structural information, i.e., the pore channels and individual building units in the NSs, is clearly visualized by using the recently developed low-dose imaging technique of transmission electron microscopy (TEM). As a proof-of-concept application, the obtained ultrathin COF NSs are used as a novel fluorescence sensing platform for the highly sensitive and selective detection of DNA.

  1. A Joint Theory and Experimental Project in the Synthesis and Testing of Porous COFs for On-Board Vehicular Hydrogen Storage

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

    Yaghi, Omar M.; Goddard, William A.

    2013-06-29

    Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g/L) densities to be achieved by 2015. From our continuous efforts on hydrogen storage, it is believed that metalation of highly porous solids with high-valence metals is promising and provides a rational direction to realize high volumetric hydrogen density near room temperature. This grant was focusedmore » on the study of high surface area covalent organic frameworks (COFs) with these specific objectives (1) to introduce potential metal binding sites through the COF synthesis and (2) to implement metalation experiments and evaluate their respective hydrogen adsorption properties. To maximize our efforts, simulation calculations were also performed (prior to experiments) for the prediction of binding enthalpy of hydrogen for molecular building units containing transition metals and promising COF structures to increase volumetric hydrogen uptake at room temperature. In this effort, first molecular building units with optimal binding energy for hydrogen storage (20 kJ/mol) were designed by quantum mechanical (QM) methods. Employing these results, it was revealed that one of metalated COFs takes up 60 g/L (total) of H2 at 100 bar and 298 K. To realize proposed COF structures, chemistry of COF synthesis has been developed; for instance, new air stable COFs were synthesized via hydrazone (COF-41 to 43) and imine condensation (COF-301, 320, 340, and 366) and some of them were tested the effect on metalation. Finally, a new triazine COF with high volumetric hydrogen uptake capacity was presented as a proposed future direction.« less

  2. Frequency of Intracranial Aneurysms Determined by Magnetic Resonance Angiography in Children (Mean Age 16) Having Operative or Endovascular Treatment of Coarctation of the Aorta (Mean Age 3).

    PubMed

    Donti, Andrea; Spinardi, Luca; Brighenti, Maurizio; Faccioli, Luca; Leoni, Chiara; Fabi, Marianna; Trossello, Marco P; Gargiulo, Gaetano D; Bonvicini, Marco

    2015-08-15

    Coarctation of the aorta (CofA) has been associated with an increased risk of intracranial aneurysm (IA). This magnetic resonance angiography (MRA) study investigates the prevalence of IAs in 80 children treated in early life for CofA. MRA was performed at mean age of 15.7 ± 7.1 years, and surgical or endovascular treatment for CofA occurred at a mean age of 2.6 ± 4.4 years. No IA was found. In contrast with earlier findings in adult patients with late treatment for CofA, this first systematic study of very early treated patients for CofA failed to confirm the association between CofA and IAs. Our results call the abnormal developmental relation between CofA and IAs into question and suggest that modifiable risk factors like hypertension may be responsible for IA development in patients with CofA with adult diagnosis and treatment. In conclusion, our data suggest that early treatment of CofA can reduce the formation of IAs in children so as to make MRA screening less valuable in this young population. Copyright © 2015 Elsevier Inc. All rights reserved.

  3. Does fluoride disrupt hydrogen bond network in cationic lipid bilayer? Time-dependent fluorescence shift of Laurdan and molecular dynamics simulations

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

    Pokorna, Sarka; Jurkiewicz, Piotr; Hof, Martin, E-mail: martin.hof@jh-inst.cas.cz

    2014-12-14

    Time-dependent fluorescence shift (TDFS) of Laurdan embedded in phospholipid bilayers reports on hydration and mobility of the phospholipid acylgroups. Exchange of H{sub 2}O with D{sub 2}O prolongs the lifetime of lipid-water and lipid-water-lipid interactions, which is reflected in a significantly slower TDFS kinetics. Combining TDFS measurements in H{sub 2}O and D{sub 2}O hydrated bilayers with atomistic molecular dynamics (MD) simulations provides a unique tool for characterization of the hydrogen bonding at the acylgroup level of lipid bilayers. In this work, we use this approach to study the influence of fluoride anions on the properties of cationic bilayers composed of trimethylammonium-propanemore » (DOTAP). The results obtained for DOTAP are confronted with those for neutral phosphatidylcholine (DOPC) bilayers. Both in DOTAP and DOPC H{sub 2}O/D{sub 2}O exchange prolongs hydrogen-bonding lifetime and does not disturb bilayer structure. These results are confirmed by MD simulations. TDFS experiments show, however, that for DOTAP this effect is cancelled in the presence of fluoride ions. We interpret these results as evidence that strongly hydrated fluoride is able to steal water molecules that bridge lipid carbonyls. Consequently, when attracted to DOTAP bilayer, fluoride disrupts the local hydrogen-bonding network, and the differences in TDFS kinetics between H{sub 2}O and D{sub 2}O hydrated bilayers are no longer observed. A distinct behavior of fluoride is also evidenced by MD simulations, which show different lipid-ion binding for Cl{sup −} and F{sup −}.« less

  4. Human 8-oxoguanine DNA glycosylase 1 mRNA expression as an oxidative stress exposure biomarker of cooking oil fumes.

    PubMed

    Cherng, Shur-Hueih; Huang, Kuo Hao; Yang, Sen-Chih; Wu, Tzu-Chin; Yang, Jia-Ling; Lee, Huei

    2002-02-01

    Epidemiological studies have indicated that the exposure to carcinogenic components formed during the cooking of food might be associated with lung cancer risk of Chinese women. Previous studies have confirmed that cooking oil fumes from frying fish (COF) contained relatively high amount of benzo[a]pyrene, 2-methyl-3,8-dimethylimidazo[4,5-f] qunoxaline, benzene, and 1,3-butadiene, reported in fumes from heated soybean oil. Thus, we consider that oxidative stress induced by COF may play a role in lung cancer development among Chinese women. To verify whether the oxidative DNA damage was induced by COF, high-performance liquid chromatography (HPLC) analysis data showed that the levels of 8-hydroxydeoxyguanine (8-OH dG) were increased in a dose-dependent manner when calf thymus DNA reacted with various concentrations of COF. Since human 8-oxoguanine DNA glycosylase 1 (hOGG1) was a repair enzyme for removing 8- OH dG from damaged DNA, we hypothesized that hOGG1 mRNA may be used to assess the risk of oxidative damage induced by the exposure of COF. The results from reverse-transcription polymerase chain reaction showed that the hOGG1 mRNA expression was induced by hydrogen peroxide (H2O2) and COF in human lung adenocarcinoma CL-3 cells. To elucidate whether hOGG1 mRNA expression was an exposure biomarker of COF, a cross-sectional study of 238 subjects including 94 professional cooks, 43 housewives, and 101 COF-nonexposed control subjects was conducted. The hOGG1 mRNA expression frequencies of COF-exposed cooks (27 of 94, 28.7%) and housewives (6 of 43, 14%) were significantly higher than those of control subjects (4 of 101, 4%). After adjusting for age, sex, and smoking and drinking status, the odds risks (ORs) of housewives versus control and cooks versus control were 3.94 (95% confidence interval [CI] = 0.95-16.62) and 10.12 (95% CI = 2.83-36.15), respectively. These results indicated that hOGG1 may be adequate to act as an exposure biomarker to assess the oxidative DNA damage induced by COF. This also suggests that oxidative stress induced by COF may play a role in lung cancer development among Chinese women.

  5. Passive smoking and cooking oil fumes (COF) may modify the association between tea consumption and oral cancer in Chinese women.

    PubMed

    Chen, Fa; He, Baochang; Hu, Zhijian; Huang, Jiangfeng; Liu, Fangping; Yan, Lingjun; Lin, Zheng; Zheng, Xiaoyan; Lin, Lisong; Zhang, Zuofeng; Cai, Lin

    2016-05-01

    To evaluate the confounding effects of passive smoking and COF exposure on association between tea and oral cancer in Chinese women. A case-control study including 207 female oral cancer cases and 480 age-matched controls was performed in Fujian, China. Data were collected with a structured questionnaire by face-to-face interviews. The effects of tea consumption on oral cancer were, respectively, adjusted for Model-1 and Model-2 using logistic regression analysis. Model-1 did not adjusted for passive smoking and COF; Model-2 included the variables in Model-1, passive smoking and COF. Tea consumption was associated with a decreased risk of oral cancer in females: The OR was 0.498 (95 % CI 0.312-0.795) for Model-1 and 0.565 (95 % CI 0.352-0.907) for Model-2. The ORs for all the categories of tea consumption estimated by Model-2 were slightly higher than Model-1. When stratified by passive smoking, the statistically significant association between tea drinking and oral cancer was only emerged in non-passive smoking women. Stratification by COF found tea drinking was still associated with a decreased risk of oral cancer for women who have light-COF exposure, but an increased risk for those who subjected to heavy exposure. A negative, multiplicative interaction was found between tea consumption and COF exposure for oral cancer, but not found between tea consumption and passive smoking. Tea consumption reduces the risk of oral cancer in Chinese women, but this effect is modified by the carcinogenic effects of passive smoking and COF exposure.

  6. Metabolic and exercise endurance effects of coffee and caffeine ingestion.

    PubMed

    Graham, T E; Hibbert, E; Sathasivam, P

    1998-09-01

    Caffeine (Caf) ingestion increases plasma epinephrine (Epi) and exercise endurance; these results are frequently transferred to coffee (Cof) consumption. We examined the impact of ingestion of the same dose of Caf in Cof or in water. Nine healthy, fit, young adults performed five trials after ingesting (double blind) either a capsule (Caf or placebo) with water or Cof (decaffeinated Cof, decaffeinated with Caf added, or regular Cof). In all three Caf trials, the Caf dose was 4.45 mg/kg body wt and the volume of liquid was 7.15 ml/kg. After 1 h of rest, the subject ran at 85% of maximal O2 consumption until voluntary exhaustion (approximately 32 min in the placebo and decaffeinated Cof tests). In the three Caf trials, the plasma Caf and paraxanthine concentrations were very similar. After 1 h of rest, the plasma Epi was increased (P < 0.05) by Caf ingestion, but the increase was greater (P < 0.05) with Caf capsules than with Cof. During the exercise there were no differences in Epi among the three Caf trials, and the Epi values were all greater (P < 0.05) than in the other tests. Endurance was only increased (P < 0. 05) in the Caf capsule trial; there were no differences among the other four tests. One cannot extrapolate the effects of Caf to Cof; there must be a component(s) of Cof that moderates the actions of Caf.

  7. Design Principles for Covalent Organic Frameworks as Efficient Electrocatalysts in Clean Energy Conversion and Green Oxidizer Production.

    PubMed

    Lin, Chun-Yu; Zhang, Lipeng; Zhao, Zhenghang; Xia, Zhenhai

    2017-05-01

    Covalent organic frameworks (COFs), an emerging class of framework materials linked by covalent bonds, hold potential for various applications such as efficient electrocatalysts, photovoltaics, and sensors. To rationally design COF-based electrocatalysts for oxygen reduction and evolution reactions in fuel cells and metal-air batteries, activity descriptors, derived from orbital energy and bonding structures, are identified with the first-principle calculations for the COFs, which correlate COF structures with their catalytic activities. The calculations also predict that alkaline-earth metal-porphyrin COFs could catalyze the direct production of H 2 O 2 , a green oxidizer and an energy carrier. These predictions are supported by experimental data, and the design principles derived from the descriptors provide an approach for rational design of new electrocatalysts for both clean energy conversion and green oxidizer production. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Central odontogenic fibroma: new findings and report of a multicentric collaborative study.

    PubMed

    Mosqueda-Taylor, Adalberto; Martínez-Mata, Guillermo; Carlos-Bregni, Roman; Vargas, Pablo Agustin; Toral-Rizo, Victor; Cano-Valdéz, Ana María; Palma-Guzmán, José Mario; Carrasco-Daza, Daniel; Luna-Ortiz, Kuauhyama; Ledesma-Montes, Constantino; de Almeida, Oslei Paes

    2011-09-01

    The aim of this study was to describe the clinicopathologic and immunohistochemical characteristics of 14 cases of central odontogenic fibroma (COF), and the ultrastructural features of 2 of them. Collaborative retrospective study based on the records of 4 oral pathology diagnostic services in Latin America based on the current World Health Organization classification. There were 7 male and 7 female patients (mean age 31.8 years). Eight tumors occurred in the maxilla and 6 in the mandible. Thirteen cases were epithelium-rich and 1 epithelium-poor COF. Three were classified as hybrid COF with giant cell lesion. Mean size of the hybrid lesions were larger than pure COF (3.8 vs. 2.4 cm). Odontogenic epithelial islands were immunoreactive for cytokeratin (CK) AE1/AE3, CK5, CK14, CK19, and 34BE12 and negative for CK1 and CK18. Langerhans cells positive for S-100 and CD1a were found within the epithelial islands in 6/6 tested cases. CD68 was expressed in the giant cells of the hybrid lesions and in a few mononuclear cells of 2 cases of COF. Ki-67 index was <1% in all cases. In 6 tumors (42.8%), there were small globular eosinophilic droplets within the epithelial islands, which were positive for collagen type IV, and 9/13 cases (69.2%) were focally positive for smooth muscle actin. In addition to fibroblasts, myofibroblastic differentiation was found in the 2 cases studied ultrastructurally. Immunohistochemistry was useful to confirm the presence of epithelium and to exclude other central fibrous tumors. COF also contains a variable number of mast cells, Langerhans cells, and myofibroblasts, and further studies are needed to better understand the participation of these cells in COF histogenesis. Copyright © 2011 Mosby, Inc. All rights reserved.

  9. Construction of a Hierarchical Architecture of Covalent Organic Frameworks via a Postsynthetic Approach.

    PubMed

    Zhang, Gen; Tsujimoto, Masahiko; Packwood, Daniel; Duong, Nghia Tuan; Nishiyama, Yusuke; Kadota, Kentaro; Kitagawa, Susumu; Horike, Satoshi

    2018-02-21

    Covalent organic frameworks (COFs) represent an emerging class of crystalline porous materials that are constructed by the assembly of organic building blocks linked via covalent bonds. Several strategies have been developed for the construction of new COF structures; however, a facile approach to fabricate hierarchical COF architectures with controlled domain structures remains a significant challenge, and has not yet been achieved. In this study, a dynamic covalent chemistry (DCC)-based postsynthetic approach was employed at the solid-liquid interface to construct such structures. Two-dimensional imine-bonded COFs having different aromatic groups were prepared, and a homogeneously mixed-linker structure and a heterogeneously core-shell hollow structure were fabricated by controlling the reactivity of the postsynthetic reactions. Solid-state nuclear magnetic resonance (NMR) spectroscopy and transmission electron microscopy (TEM) confirmed the structures. COFs prepared by a postsynthetic approach exhibit several functional advantages compared with their parent phases. Their Brunauer-Emmett-Teller (BET) surface areas are 2-fold greater than those of their parent phases because of the higher crystallinity. In addition, the hydrophilicity of the material and the stepwise adsorption isotherms of H 2 O vapor in the hierarchical frameworks were precisely controlled, which was feasible because of the distribution of various domains of the two COFs by controlling the postsynthetic reaction. The approach opens new routes for constructing COF architectures with functionalities that are not possible in a single phase.

  10. Fluorene-Based Two-Dimensional Covalent Organic Framework with Thermoelectric Properties through Doping.

    PubMed

    Wang, Liangying; Dong, Bin; Ge, Rile; Jiang, Fengxing; Xu, Jingkun

    2017-03-01

    Organic semiconductors have great potential as flexible thermoelectric materials. A fluorene-based covalent organic framework (FL-COF-1) was designed with the aim of creating an enhanced π-π interaction among the crystalline backbones. By the introduction of fluorene units into the frameworks, the FL-COF-1 had high thermal stability with a BET surface area over 1300 m 2 g -1 . The open frameworks were favorable for doping with iodine and followed with the improved charge carrier mobility. The compressed pellet of I 2 @FL-COF-1 exhibited a high Seebeck coefficient of 2450 μV K -1 and power factor of 0.063 μW m -1 K -2 at room temperature, giving the first example of COFs' potential application as thermoelectric materials.

  11. Two-Dimensional Covalent Organic Frameworks for Carbon Dioxide Capture through Channel-Wall Functionalization

    PubMed Central

    Huang, Ning; Chen, Xiong; Krishna, Rajamani; Jiang, Donglin

    2015-01-01

    Ordered open channels found in two-dimensional covalent organic frameworks (2D COFs) could enable them to adsorb carbon dioxide. However, the frameworks’ dense layer architecture results in low porosity that has thus far restricted their potential for carbon dioxide adsorption. Here we report a strategy for converting a conventional 2D COF into an outstanding platform for carbon dioxide capture through channel-wall functionalization. The dense layer structure enables the dense integration of functional groups on the channel walls, creating a new version of COFs with high capacity, reusability, selectivity, and separation productivity for flue gas. These results suggest that channel-wall functional engineering could be a facile and powerful strategy to develop 2D COFs for high-performance gas storage and separation. PMID:25613010

  12. Rationally Designed 2D Covalent Organic Framework with a Brick-Wall Topology

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

    Cai, Song-Liang; Zhang, Kai; Tan, Jing-Bo

    In this paper, we report the design and synthesis of an imine-based two-dimensional covalent organic framework (2D COF) with a novel brick-wall topology by judiciously choosing a tritopic T-shaped building block and a ditopic linear linker. Unlike the main body of COF frameworks reported to-date, which consists of higher-symmetry 2D topologies, the unconventional layered brick-wall topology have only been proposed but never been realized experimentally. The brick-wall structure was characterized by powder X-ray diffraction analysis, FT-IR, solid state 13C NMR spectroscopy, nitrogen, and carbon oxide adsorption-desorption measurements as well as theoretical simulations. Lastly, our present work opens the door tomore » the design of novel 2D COFs and will broaden the scope of emerging COF materials.« less

  13. Rationally Designed 2D Covalent Organic Framework with a Brick-Wall Topology

    DOE PAGES

    Cai, Song-Liang; Zhang, Kai; Tan, Jing-Bo; ...

    2016-11-23

    In this paper, we report the design and synthesis of an imine-based two-dimensional covalent organic framework (2D COF) with a novel brick-wall topology by judiciously choosing a tritopic T-shaped building block and a ditopic linear linker. Unlike the main body of COF frameworks reported to-date, which consists of higher-symmetry 2D topologies, the unconventional layered brick-wall topology have only been proposed but never been realized experimentally. The brick-wall structure was characterized by powder X-ray diffraction analysis, FT-IR, solid state 13C NMR spectroscopy, nitrogen, and carbon oxide adsorption-desorption measurements as well as theoretical simulations. Lastly, our present work opens the door tomore » the design of novel 2D COFs and will broaden the scope of emerging COF materials.« less

  14. Single-Crystal Structure of a Covalent Organic Framework

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

    Zhang, YB; Su, J; Furukawa, H

    2013-11-06

    The crystal structure of a new covalent organic framework, termed COF-320, is determined by single-crystal 3D electron diffraction using the rotation electron diffraction (RED) method for data collection. The COF crystals are prepared by an imine condensation of tetra-(4-anilyl)methane and 4,4'-biphenyldialdehyde in 1,4-dioxane at 120 degrees C to produce a highly porous 9-fold interwoven diamond net. COF-320 exhibits permanent porosity with a Langmuir surface area of 2400 m(2)/g and a methane total uptake of 15.0 wt % (176 cm(3)/cm(3)) at 25 degrees C and 80 bar. The successful determination of the structure of COF-320 directly from single-crystal samples is anmore » important advance in the development of COF chemistry.« less

  15. Independent and joint exposure to passive smoking and cooking oil fumes on oral cancer in Chinese women: a hospital-based case-control study.

    PubMed

    He, Baochang; Chen, Fa; Yan, Lingjun; Huang, Jiangfeng; Liu, Fangping; Qiu, Yu; Lin, Lisong; Zhang, Zuofeng; Cai, Lin

    2016-10-01

    Passive smoking and COF exposure are independent risk factors for oral cancer in Chinese women, with the multiplicative interactions from combined exposures. Avoiding exposure to environmental tobacco smoke and COF may contribute to the prevention of oral cancer in Chinese women. To evaluate the independent and joint effects of passive smoking and cooking oil fumes (COF) on oral cancer in Chinese women. A case-control study was performed including 238 female patients with pathologically confirmed oral cancer and 470 controls as age-matched controls. Face-to-face interviews were conducted based on a structured questionnaire. The effects of passive smoking and COF exposure were analyzed using non-conditional logistic regression models. Passive smoking significantly increased the risk of oral cancer in Chinese women: adjusted ORs were 2.12 (95% CI = 1.11-4.07) for those only exposed before age 18, 1.52 (95% CI = 1.01-2.31) for those only exposed after age 18, and 2.38 (95% CI = 1.47-3.85) for those both exposed before and after age 18. In addition, COF exposure was significantly associated with a risk of oral cancer (adjusted ORs were 1.69 (95% CI = 1.03-2.78) for light exposure and 2.06 (95% CI = 1.21-3.50) for heavy exposure). Furthermore, there was a significantly multiplicative interaction between passive smoking and COF for oral cancer.

  16. The Required Coefficient of Friction for evaluating gait alterations in people with Multiple Sclerosis during gait.

    PubMed

    Pacifici, Ilaria; Galli, Manuela; Kleiner, Ana Francisca Rozin; Corona, Federica; Coghe, Giancarlo; Marongiu, Elisabetta; Loi, Andrea; Crisafulli, Antonio; Cocco, Eleonora; Marrosu, Maria Giovanna; Pau, Massimiliano

    2016-11-01

    Required Coefficient of Friction (RCOF) is one of the most critical gait parameters associated to the occurrence of slipping in individuals affected by neurological disorders characterized by balance impairments. This study aims to calculate RCOF in people with Multiple Sclerosis (MS) on the basis of three-dimensional Gait Analysis (GA) data. This study enrolls 22 people with MS (pwMS) who were characterized by an Expanded Disability Status Score in the range 1.5-6 and 10 healthy controls (HC). All participants underwent to three-dimensional GA from which we extracted kinematic and kinetic data (i.e. the Ground Reaction Forces, GRF, and joint moments and powers in the sagittal plane). RCOF was calculated as the ratio of the shear to normal GRF components during the stance phase of gait cycle, and normalized by the walking velocity. Thus, the following variables were extracted: first peak (named P1COF), valley (named V1COF), and second peak (named P2COF) in RCOF curve; also computating the maximum ankle dorsi-plantarflexion moment (MOMmax) and the maximum ankle joint power (PWRmax). Our data revealed that P2COF results are significantly lower in pwMS when compared to HC (p=0.043; Z=-2.025). In pwMS, the study found a moderate, positive correlation between V1COF and MOMmax (r=0.558; p<0.001) and a moderate, positive correlation between EDSS score and MOMmax (rho=0.622; p=0.001). While, in HC group, the study detected a moderate positive correlation between P1COF and MOM max (r=0.636; p=0.008). Friction during mid stance and push off phases is critically important to determine whether the frictional capabilities of foot/floor interface are sufficient to prevent slips in pwMS. The impaired ankle moment in MS group causes increased P2COF in comparison to HC, increasing the risk of slipping in the critical phase of transmission of the developed forces to kinematic chain. Also, the correlation analysis among RCOF values and kinetic variables describe the interplay between V1COF and MOMmax: the higher V1COF is, the higher is MOMmax; and the different correlation the study found between COF and kinetic parameters in MS and HC group highlightes the different gait patterns of the two classes of subjects. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. 3D Graphene Functionalized by Covalent Organic Framework Thin Film as Capacitive Electrode in Alkaline Media.

    PubMed

    Zha, Zeqi; Xu, Lirong; Wang, Zhikui; Li, Xiaoguang; Pan, Qinmin; Hu, Pingan; Lei, Shengbin

    2015-08-19

    To harness the electroactivity of anthraquinone as an electrode material, a great recent effort have been invested to composite anthraquinone with carbon materials to improve the conductivity. Here we report on a noncovalent way to modify three-dimensional graphene with anthraquinone moieties through on-surface synthesis of two-dimensional covalent organic frameworks. We incorporate 2,6-diamino-anthraquinone moieties into COF through Schiff-base reaction with benzene-1,3,5-tricarbaldehyde. The synthesized COF -graphene composite exhibits large specific capacitance of 31.7 mF/cm(2). Long-term galvanostatic charge/discharge cycling experiments revealed a decrease of capacitance, which was attributed to the loss of COF materials and electrostatic repulsion accumulated during charge-discharge circles which result in the poor electrical conductivity between 2D COF layers.

  18. Construction of a hydrazone-linked chiral covalent organic framework-silica composite as the stationary phase for high performance liquid chromatography.

    PubMed

    Zhang, Kai; Cai, Song-Liang; Yan, Yi-Lun; He, Zi-Hao; Lin, Hui-Mei; Huang, Xiao-Ling; Zheng, Sheng-Run; Fan, Jun; Zhang, Wei-Guang

    2017-10-13

    Covalent organic frameworks (COFs), as an emerging class of crystalline porous organic polymers, have great potential for applications in chromatographic separation owning to their fascinating crystalline structures and outstanding properties. However, development of COF materials as novel stationary phases in high performance liquid chromatography (HPLC) is just in its infancy. Herein, we report the design and construction of a new hydrazone-linked chiral COF, termed BtaMth COF, from a chiral hydrazide building block (Mth) and present a one-pot synthetic method for the fabrication of BtaMth@SiO 2 composite for HPLC separation of isomers. The as-synthesized BtaMth chiral COF displays good crystallinity, high porosity, as well as excellent chemical stability. Meanwhile, the fabricated HPLC column by using BtaMth@SiO 2 composite as the new stationary phase exhibits high resolution performances for the separation of positional isomers including nitrotoluene and nitrochlorobenzene, as well as cis-trans isomers including beta-cypermethrin and metconazole. Additionally, some effects such as the composition of the mobile phase and column temperature for HPLC separations on the BtaMth@SiO 2 packed column also have been studied in detail. The successful applications indicate the great potentials of hydrazone-linked chiral COF-silica composite as novel stationary phase for the efficient HPLC separation. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Cloning, expression, purification, crystallization and X-ray crystallographic analysis of CofB, the minor pilin subunit of CFA/III from human enterotoxigenic Escherichia coli.

    PubMed

    Kawahara, Kazuki; Oki, Hiroya; Fukakusa, Shunsuke; Maruno, Takahiro; Kobayashi, Yuji; Motooka, Daisuke; Taniguchi, Tooru; Honda, Takeshi; Iida, Tetsuya; Nakamura, Shota; Ohkubo, Tadayasu

    2015-06-01

    Colonization factor antigen III (CFA/III) is one of the virulence factors of human enterotoxigenic Escherichia coli (ETEC) that forms the long, thin, proteinaceous fibres of type IV pili through assembly of its major and minor subunits CofA and CofB, respectively. The crystal structure of CofA has recently been reported; however, the lack of structural information for CofB, the largest among the known type IV pilin subunits, hampers a comprehensive understanding of CFA/III pili. In this study, constructs of wild-type CofB with an N-terminal truncation and the corresponding SeMet derivative were cloned, expressed, purified and crystallized. The crystals belonged to the rhombohedral space group R32, with unit-cell parameters a = b = 103.97, c = 364.57 Å for the wild-type construct and a = b = 103.47, c = 362.08 Å for the SeMet-derivatized form. Although the diffraction quality of these crystals was initially very poor, dehydration of the crystals substantially improved the resolution limit from ∼ 4.0 to ∼ 2.0 Å. The initial phase was solved by the single-wavelength anomalous dispersion (SAD) method using a dehydrated SeMet CofB crystal, which resulted in an interpretable electron-density map.

  20. Fretting Wear Damage Mechanism of Uranium under Various Atmosphere and Vacuum Conditions

    PubMed Central

    Li, Zhengyang; Wu, Yanping; Meng, Xiandong; Zhang, Dongxu

    2018-01-01

    A fretting wear experiment with uranium has been performed on a linear reciprocating tribometer with ball-on-disk contact. This study focused on the fretting behavior of the uranium under different atmospheres (Ar, Air (21% O2 + 78% N2), and O2) and vacuum conditions (1.05 and 1 × 10−4 Pa). Evolution of friction was assessed by coefficient of friction (COF) and friction-dissipated energy. The oxide of the wear surface was evaluated by Raman spectroscopy. The result shows that fretting wear behavior presents strong atmosphere and vacuum condition dependence. With increasing oxygen content, the COF decreases due to abrasive wear and formation of oxide film. The COF in the oxygen condition is at least 0.335, and it has a maximum wear volume of about 1.48 × 107 μm3. However, the COF in a high vacuum condition is maximum about 1.104, and the wear volume is 1.64 × 106 μm3. The COF in the low vacuum condition is very different: it firstly increased and then decreased rapidly to a steady value. It is caused by slight abrasive wear and the formation of tribofilm after thousands of cycles. PMID:29659484

  1. Nanocoating covalent organic frameworks on nickel nanowires for greatly enhanced-performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Han, Yang; Hu, Nantao; Liu, Shuai; Hou, Zhongyu; Liu, Jiaqiang; Hua, Xiaolin; Yang, Zhi; Wei, Liangming; Wang, Lin; Wei, Hao

    2017-08-01

    Nanocoatings of covalent organic frameworks (COFs) on nickel nanowires (NiNWs) have been designed and successfully fabricated for the first time, which showed greatly enhanced electrochemical performances for supercapacitors. The specific capacitance of electrodes based on as-fabricated COFs nanocoatings reached up to 314 F g-1 at 50 A g-1, which retained 74% of the specific capacitance under the current density of 2 A g-1. The ultrahigh current density makes the charge-discharge process extremely rapid. The outstanding electrochemical performances of COFs nanocoating on NiNWs make it an ideal candidate for supercapacitors. And the nanocoating-design can also give a guidance for application of COFs in high-performance energy storages.

  2. Facile synthesis of -C[double bond, length as m-dash]N- linked covalent organic frameworks under ambient conditions.

    PubMed

    Ding, San-Yuan; Cui, Xiao-Hui; Feng, Jie; Lu, Gongxuan; Wang, Wei

    2017-10-31

    We reported herein a facile approach for the synthesis of -C[double bond, length as m-dash]N- linked covalent organic frameworks under ambient conditions. Three known (COF-42, COF-43, and COF-LZU1) and one new (Pr-COF-42) COF materials were successfully synthesized using this method. Furthermore, this simple synthetic approach makes the large-scale synthesis of -C[double bond, length as m-dash]N- linked COFs feasible.

  3. Methacrylate-bonded covalent-organic framework monolithic columns for high performance liquid chromatography.

    PubMed

    Liu, Li-Hua; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2017-01-06

    Covalent-organic frameworks (COFs) are a newfangled class of intriguing microporous materials. Considering their unique properties, COFs should be promising as packing materials for high performance liquid chromatography (HPLC). However, the irregular shape and sub-micrometer size of COFs synthesized via the traditional methods render the main obstacles for the application of COFs in HPLC. Herein, we report the preparation of methacrylate-bonded COF monolithic columns for HPLC to overcome the above obstacles. The prepared COF bonded monolithic columns not only show good homogeneity and permeability, but also give high column efficiency, good resolution and precision for HPLC separation of small molecules including polycyclic aromatic hydrocarbons, phenols, anilines, nonsteroidal anti-inflammatory drugs and benzothiophenes. Compared with the bare polymer monolithic column, the COF bonded monolithic columns show enhanced hydrophobic, π-π and hydrogen bond interactions in reverse phase HPLC. The results reveal the great potential of COF bonded monoliths for HPLC and COFs in separation sciences. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Electronic structure and vibrational analysis of AHA⋯HX complexes

    NASA Astrophysics Data System (ADS)

    Joshi, Kaustubh A.; Gejji, Shridhar P.

    2005-10-01

    Electronic structures of the binary complexes of acetohydroxamic acid (AHA) and hydrogen halides, HX (X = F, Cl, Br) have been investigated using the second order perturbation theory. In the lowest energy structure of AHA⋯HF complex, hydrogen fluoride acts as a proton-donor with carbonyl oxygen and simultaneously as a proton-acceptor with the hydroxyl group. For chloro- and bromo-substituted derivatives, however, the lowest minimum possesses hydrogen-bonded interactions with the carbonyl oxygen in addition to those from the methyl proton of AHA. Frequency shifts of NH and CN stretching vibrations enable one to distinguish different conformers of AHA⋯HX complexes.

  5. Molecular mechanisms of fluoride toxicity.

    PubMed

    Barbier, Olivier; Arreola-Mendoza, Laura; Del Razo, Luz María

    2010-11-05

    Halfway through the twentieth century, fluoride piqued the interest of toxicologists due to its deleterious effects at high concentrations in human populations suffering from fluorosis and in in vivo experimental models. Until the 1990s, the toxicity of fluoride was largely ignored due to its "good reputation" for preventing caries via topical application and in dental toothpastes. However, in the last decade, interest in its undesirable effects has resurfaced due to the awareness that this element interacts with cellular systems even at low doses. In recent years, several investigations demonstrated that fluoride can induce oxidative stress and modulate intracellular redox homeostasis, lipid peroxidation and protein carbonyl content, as well as alter gene expression and cause apoptosis. Genes modulated by fluoride include those related to the stress response, metabolic enzymes, the cell cycle, cell-cell communications and signal transduction. The primary purpose of this review is to examine recent findings from our group and others that focus on the molecular mechanisms of the action of inorganic fluoride in several cellular processes with respect to potential physiological and toxicological implications. This review presents an overview of the current research on the molecular aspects of fluoride exposure with emphasis on biological targets and their possible mechanisms of involvement in fluoride cytotoxicity. The goal of this review is to enhance understanding of the mechanisms by which fluoride affects cells, with an emphasis on tissue-specific events in humans. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

  6. The effect of shoe soling tread groove width on the coefficient of friction with different sole materials, floors, and contaminants.

    PubMed

    Li, Kai Way; Chen, Chin Jung

    2004-11-01

    Tread groove design is very common in footwear. However, coefficient of friction (COF) measurements between the footwear material and floor using a slipmeter were commonly performed using flat footwear pads. Such measurements might underestimate the actual slip resistance of the footwear pad. This research investigates the effects of the tread groove width on the measured COF using four footwear materials, three floors, and four liquid-contamination conditions using a Brungraber Mark II slipmeter. The analysis of variance results indicated that the footwear material, floor, contamination conditions, and groove width were all significant (p < 0.0001) factors affecting the measured COF. The hypothesis that wider tread grooves result in higher COF values was true with some exceptions especially on oil contaminated floors. A regression model, with an R2 of 0.91, was established to describe and predict the relationship between the COF and the tread groove width under footwear material/floor/contamination conditions.

  7. A Combustion Products Analyzer for contingency use during thermodegradation events on spacecraft

    NASA Technical Reports Server (NTRS)

    Limero, Thomas; James, John T.; Beck, Steven; Cromer, Raymond

    1991-01-01

    This paper will describe the Combustion Products Analyzer (CPA), which is being developed under the direction of the Toxicology Laboratory at Johnson Space Center to provide necessary data on air quality in the Shuttle following a thermodegradation incident. Using separate electrochemical sensors, the CPA monitors four gases (hydrogen fluoride/carbonyl fluoride, hydrogen chloride, hydrogen cyanide, and carbon monoxide), which were selected as the most hazardous compounds likely to be released during thermodegradation of synthetic materials. Electrochemical sensors have been available for several years; the CPA sensors, which are unique because of their small size and zero-gravity compatibility, will be described in detail.

  8. Reproductive and developmental toxicity of degradation products of refrigerants in experimental animals.

    PubMed

    Ema, Makoto; Naya, Masato; Yoshida, Kikuo; Nagaosa, Ryuichi

    2010-01-01

    The present paper summarizes the results of animal studies on the reproductive and developmental toxicity of the degradation products of refrigerants, including trifluoroacetic acid (TFA), carbon dioxide (CO(2)), carbon monoxide (CO), carbonyl fluoride (CF), hydrogen fluoride (HF) and formic acid (FA). Excessive CO(2) in the atmosphere is testicular and reproductive toxic, embryolethal, developmentally neurotoxic and teratogenic in experimental animals. As for CO, maternal exposure causes prenatal and postnatal lethality and growth retardation, skeletal variations, cardiomegaly, blood biochemical, immunological and postnatal behavioral changes, and neurological impairment in offspring of several species. Very early studies of CO in rats and guinea pigs reported fetal malformations in exposed dams. The results of toxicological studies on sodium fluoride (NaF) were used to obtain insight into the toxicity of CF and HF, because CF is rapidly hydrolyzed in contact with water yielding CO(2) and HF, and NaF is similar in kinetics and dynamics to HF. Increased fetal skeletal variation, but not malformation, was noted after the maternal administration of NaF. Rat multiple-generation studies revealed that NaF caused retarded ossification and degenerative changes in the lung and kidney in offspring. There is a lack of information about the toxicity of TFA and FA. Copyright 2009 Elsevier Inc. All rights reserved.

  9. Pore surface engineering in covalent organic frameworks.

    PubMed

    Nagai, Atsushi; Guo, Zhaoqi; Feng, Xiao; Jin, Shangbin; Chen, Xiong; Ding, Xuesong; Jiang, Donglin

    2011-11-15

    Covalent organic frameworks (COFs) are a class of important porous materials that allow atomically precise integration of building blocks to achieve pre-designable pore size and geometry; however, pore surface engineering in COFs remains challenging. Here we introduce pore surface engineering to COF chemistry, which allows the controlled functionalization of COF pore walls with organic groups. This functionalization is made possible by the use of azide-appended building blocks for the synthesis of COFs with walls to which a designable content of azide units is anchored. The azide units can then undergo a quantitative click reaction with alkynes to produce pore surfaces with desired groups and preferred densities. The diversity of click reactions performed shows that the protocol is compatible with the development of various specific surfaces in COFs. Therefore, this methodology constitutes a step in the pore surface engineering of COFs to realize pre-designed compositions, components and functions.

  10. Highly crystalline covalent organic frameworks from flexible building blocks.

    PubMed

    Xu, Liqian; Ding, San-Yuan; Liu, Junmin; Sun, Junliang; Wang, Wei; Zheng, Qi-Yu

    2016-03-28

    Two novel 2D covalent organic frameworks (TPT-COF-1 and TPT-COF-2) were synthesized from the flexible 2,4,6-triaryloxy-1,3,5-triazine building blocks on a gram scale, which show high crystallinity and large surface area. The controllable formation of highly ordered frameworks is mainly attributed to the self-assembly Piedfort unit of 2,4,6-triaryloxy-1,3,5-triazine.

  11. Large mandibular central odontogenic fibroma documented over 20 years: A case report.

    PubMed

    Bandura, Patrick; Sutter, Walter; Meier, Marius; Berger, Sebastian; Turhani, Dritan

    2017-01-01

    Central odontogenic fibroma (COF) is a rare, benign, slow-growing intraosseous odontogenic tumor, and accounts for 0.1% of all odontogenic tumors. It is often confused with other entities, such as keratocysts, ameloblastomas, and odontogenic myxomas. Complete enucleation followed by curettage is the treatment of choice for COF to ensure the lowest possible chance of recurrence. We report the case of a young Caucasian woman with COF that went undiagnosed for several years despite repeated radiologic examinations. Finally, a massive tumor was surgically removed and the wound was curetted. The specimen was histologically confirmed to be a COF. The patient remains under regular follow-up, and thus far there have been no clinical or radiologic signs of recurrence. This rare case of COF, which was documented over a period of 20 years, has helped us to describe the features of this tumor. It also confirms that adequate surgical treatment can lead to impressive bone regeneration in healthy individuals, as evident from the radiologic findings acquired before, during, and after enucleation of the COF in our patient. Our findings also confirm the view that COF has a favorable prognosis regardless of its final size. Early diagnosis is key to successful treatment of COF. The slow but steady increase in the size of a COF with no accompanying symptoms has not been reported previously. To our knowledge, this is the only documented case of a COF that has been under continuous radiologic observation for over 20 years.

  12. Reaction of perfluoroalkylpolyethers (PFPE) with 440C steel in vacuum under sliding conditions at room temperature

    NASA Technical Reports Server (NTRS)

    Mori, Shigeyuki; Morales, Wilfredo

    1989-01-01

    Reactions of perfluoroalkylpolyethers (PFPE: Fomblin, Demnum and Krytox) were studied during the sliding contact of stainless steel specimens under ultrahigh vacuum conditions. All three fluids reacted with the steel specimens during sliding. Fomblin, which has acetal linkages, decomposed under the sliding conditions generating gaseous products, (COF2 and fluorinated carbons) which were detected by a quadrupole mass spectrometer. Gaseous products were not detected for the Demnum and Krytox fluids. The amount of gaseous products from Fomblin increased with increasing sliding speed. At the end of the sliding experiments, the wear scar and deposits on the specimens were examined by small spot size XPS. The oxide layer on the specimen surface was removed during sliding, and metal fluorides were formed on the worn surface. The surface of the wear scar and deposits were covered with adsorbed PFPE. Based on these results, it was concluded that the decomposition reaction on Fomblin was initiated by contacting the fluid with a fresh metal surface which was formed during sliding.

  13. Influence of sulfides on the tribological properties of composites produced by pulse electric current sintering

    NASA Astrophysics Data System (ADS)

    Kim, Seung Ho

    2014-01-01

    Self-lubricating Al2O3-15wt% ZrO2 composites with sulfides, such as molybdenum disulfide (MoS2) and tungsten disulfide (WS2) serving as solid lubricants, were fabricated by using the pulse electric current sintering (PECS) technique. The coefficient of friction (COF) of the Al2O3-15wt% ZrO2 composite without/with sulfides was in the range of 0.37-0.48 and 0.27-0.49, respectively. As the amount of sulfides increased, the COF and the wear rate decreased. The reduction in COF and wear rate of the sulfide-containing composite is caused by a reduction in shear stresses between the specimen and the tribological medium due to the formation of a lubricating film resulting from the lamellar structure of sulfides located on the worn surface.

  14. Exploring Applications of Covalent Organic Frameworks: Homogeneous Reticulation of Radicals for Dynamic Nuclear Polarization.

    PubMed

    Cao, Wei; Wang, Wei David; Xu, Hai-Sen; Sergeyev, Ivan V; Struppe, Jochem; Wang, Xiaoling; Mentink-Vigier, Frederic; Gan, Zhehong; Xiao, Ming-Xing; Wang, Lu-Yao; Chen, Guo-Peng; Ding, San-Yuan; Bai, Shi; Wang, Wei

    2018-06-06

    Rapid progress has been witnessed in the past decade in the fields of covalent organic frameworks (COFs) and dynamic nuclear polarization (DNP). In this contribution, we bridge these two fields by constructing radical-embedded COFs as promising DNP agents. Via polarization transfer from unpaired electrons to nuclei, DNP realizes significant enhancement of NMR signal intensities. One of the crucial issues in DNP is to screen for suitable radicals to act as efficient polarizing agents, the basic criteria for which are homogeneous distribution and fixed orientation of unpaired electrons. We therefore envisioned that the crystalline and porous structures of COFs, if evenly embedded with radicals, may work as a new "crystalline sponge" for DNP experiments. As a proof of concept, we constructed a series of proxyl-radical-embedded COFs (denoted as PR( x)-COFs) and successfully applied them to achieve substantial DNP enhancement. Benefiting from the bottom-up and multivariate synthetic strategies, proxyl radicals have been covalently reticulated, homogeneously distributed, and rigidly embedded into the crystalline and mesoporous frameworks with adjustable concentration ( x%). Excellent performance of PR( x)-COFs has been observed for DNP 1 H, 13 C, and 15 N solid-state NMR enhancements. This contribution not only realizes the direct construction of radical COFs from radical monomers, but also explores the new application of COFs as DNP polarizing agents. Given that many radical COFs can therefore be rationally designed and facilely constructed with well-defined composition, distribution, and pore size, we expect that our effort will pave the way for utilizing radical COFs as standard polarizing agents in DNP NMR experiments.

  15. Michael Additions of Highly Basic Enolates to ortho-Quinone Methides

    PubMed Central

    Lewis, Robert S.; Garza, Christopher J.; Dang, Ann T.; Pedro, Te Kie A.; Chain, William J.

    2015-01-01

    A protocol by which ketone or ester enolates and ortho-quinone methides (o-QMs) are generated in situ in a single reaction flask from silylated precursors under the action of anhydrous fluoride is reported. The reaction partners are joined to give a variety of β-(2-hydroxyphenyl)-carbonyl compounds in 32–94% yield in a single laboratory operation. The intermediacy of o-QMs is supported by control experiments utilizing enolate precursors and conventional alkyl halides as competitive alkylating agents and the isolation of 1,5-dicarbonyl products resulting from conjugate additions that do not restore the aromatic system. PMID:25906358

  16. Advances in covalent organic frameworks in separation science.

    PubMed

    Qian, Hai-Long; Yang, Cheng-Xiong; Wang, Wen-Long; Yang, Cheng; Yan, Xiu-Ping

    2018-03-23

    Covalent organic frameworks (COFs) are a new class of multifunctional crystalline organic polymer constructed with organic monomers via robust covalent bonds. The unique properties such as convenient modification, low densities, large specific surface areas, good stability and permanent porosity make COFs great potential in separation science. This review shows the state-of-the art for the application of COFs and their composites in analytical separation science. COFs and their composites have been explored as promising sorbents for solid phase extraction, potential coatings for solid phase microextraction, and novel stationary phases for gas chromatography, high-performance liquid chromatography and capillary electrochromatography. The prospects of COFs for separation science are also presented, which can offer an outlook and reference for further study on the applications of COFs. Copyright © 2018 Elsevier B.V. All rights reserved.

  17. Three-dimensional metal-intercalated covalent organic frameworks for near-ambient energy storage

    PubMed Central

    Gao, Fei; Ding, Zijing; Meng, Sheng

    2013-01-01

    A new form of nanoporous material, metal intercalated covalent organic framework (MCOF) is proposed and its energy storage property revealed. Employing density functional and thermodynamical analysis, we find that stable, chemically active, porous materials could form by stacking covalent organic framework (COF) layers with metals as a gluing agent. Metal acts as active sites, while its aggregation is suppressed by a binding energy significantly larger than the corresponding cohesive energy of bulk metals. Two important parameters, metal binding and metal-metal separation, are tuned by selecting suitable building blocks and linkers when constructing COF layers. Systematic searches among a variety of elements and organic molecules identify Ca-intercalated COF with diphenylethyne units as optimal material for H2 storage, reaching a striking gravimetric density ~ 5 wt% at near-ambient conditions (300 K, 20 bar), in comparison to < 0.1 wt% for bare COF-1 under the same condition. PMID:23698018

  18. The influence of heel height on utilized coefficient of friction during walking.

    PubMed

    Blanchette, Mark G; Brault, John R; Powers, Christopher M

    2011-05-01

    Wearing high heel shoes has been associated with an increased potential for slips and falls. The association between wearing high heels and the increased potential for slipping suggests that the friction demand while wearing high heels may be greater when compared to wearing low heel shoes. The purpose of this study was to determine if heel height affects utilized friction (uCOF) during walking. A secondary purpose of this study was to compare kinematics at the ankle, knee, and hip that may explain uCOF differences among shoes with varied heel heights. Fifteen healthy women (mean age 24.5±2.5yrs) participated. Subjects walked at self-selected velocity under 3 different shoe conditions that varied in heel height (low: 1.27cm, medium: 6.35cm, and high: 9.53cm). Ground reaction forces (GRFs) were recorded using a force platform (1560Hz). Kinematic data were obtained using an 8 camera motion analysis system (120Hz). Utilized friction was calculated as the ratio of resultant shear force to vertical force. One-way repeated measures ANOVAs were performed to test for differences in peak uCOF, GRFs at peak uCOF and lower extremity joint angles at peak uCOF. On average, peak uCOF was found to increase with heel height. The increased uCOF observed in high heel shoes was related to an increase in the resultant shear force and decrease in the vertical force. Our results signify the need for proper public education and increased footwear industry awareness of how high heel shoes affect slip risk. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Chemistry of Covalent Organic Frameworks.

    PubMed

    Waller, Peter J; Gándara, Felipe; Yaghi, Omar M

    2015-12-15

    Linking organic molecules by covalent bonds into extended solids typically generates amorphous, disordered materials. The ability to develop strategies for obtaining crystals of such solids is of interest because it opens the way for precise control of the geometry and functionality of the extended structure, and the stereochemical orientation of its constituents. Covalent organic frameworks (COFs) are a new class of porous covalent organic structures whose backbone is composed entirely of light elements (B, C, N, O, Si) that represent a successful demonstration of how crystalline materials of covalent solids can be achieved. COFs are made by combination of organic building units covalently linked into extended structures to make crystalline materials. The attainment of crystals is done by several techniques in which a balance is struck between the thermodynamic reversibility of the linking reactions and their kinetics. This success has led to the expansion of COF materials to include organic units linked by these strong covalent bonds: B-O, C-N, B-N, and B-O-Si. Since the organic constituents of COFs, when linked, do not undergo significant change in their overall geometry, it has been possible to predict the structures of the resulting COFs, and this advantage has facilitated their characterization using powder X-ray diffraction (PXRD) techniques. It has also allowed for the synthesis of COF structures by design and for their formation with the desired composition, pore size, and aperture. In practice, the modeled PXRD pattern for a given expected COF is compared with the experimental one, and depending on the quality of the match, this is used as a starting point for solving and then refining the crystal structure of the target COF. These characteristics make COFs an attractive class of new porous materials. Accordingly, they have been used as gas storage materials for energy applications, solid supports for catalysis, and optoelectronic devices. A large and growing library of linkers amenable to the synthesis of COFs is now available, and new COFs and topologies made by reticular synthesis are being reported. Much research is also directed toward the development of new methods of linking organic building units to generate other crystalline COFs. These efforts promise not only new COF chemistry and materials, but also the chance to extend the precision of molecular covalent chemistry to extended solids.

  20. Advanced zirconia-coated carbonyl-iron particles for acidic magnetorheological finishing of chemical-vapor-deposited ZnS and other IR materials

    NASA Astrophysics Data System (ADS)

    Salzman, S.; Giannechini, L. J.; Romanofsky, H. J.; Golini, N.; Taylor, B.; Jacobs, S. D.; Lambropoulos, J. C.

    2015-10-01

    We present a modified version of zirconia-coated carbonyl-iron (CI) particles that were invented at the University of Rochester in 2008. The amount of zirconia on the coating is increased to further protect the iron particles from corrosion when introduced to an acidic environment. Five low-pH, magnetorheological (MR) fluids were made with five acids: acetic, hydrochloric, nitric, phosphoric, and hydrofluoric. All fluids were based on the modified zirconia-coated CI particles. Off-line viscosity and pH stability were measured for all acidic MR fluids to determine the ideal fluid composition for acidic MR finishing of chemical-vapor-deposited (CVD) zinc sulfide (ZnS) and other infrared (IR) optical materials, such as hot-isostatic-pressed (HIP) ZnS, CVD zinc selenide (ZnSe), and magnesium fluoride (MgF2). Results show significant reduction in surface artifacts (millimeter-size, pebble-like structures on the finished surface) for several standard-grade CVD ZnS substrates and good surface roughness for the non-CVD MgF2 substrate when MR finished with our advanced acidic MR fluid.

  1. 30 CFR 253.42 - How can I amend my list of COFs?

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false How can I amend my list of COFs? 253.42 Section 253.42 Mineral Resources MINERALS MANAGEMENT SERVICE, DEPARTMENT OF THE INTERIOR OFFSHORE OIL SPILL FINANCIAL RESPONSIBILITY FOR OFFSHORE FACILITIES Requirements for Submitting OSFR Information § 253.42 How...

  2. 30 CFR 553.42 - How can I amend my list of COFs?

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 2 2012-07-01 2012-07-01 false How can I amend my list of COFs? 553.42 Section 553.42 Mineral Resources BUREAU OF OCEAN ENERGY MANAGEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL SPILL FINANCIAL RESPONSIBILITY FOR OFFSHORE FACILITIES Requirements for Submitting OSFR Information...

  3. 30 CFR 553.42 - How can I amend my list of COFs?

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 2 2014-07-01 2014-07-01 false How can I amend my list of COFs? 553.42 Section 553.42 Mineral Resources BUREAU OF OCEAN ENERGY MANAGEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL SPILL FINANCIAL RESPONSIBILITY FOR OFFSHORE FACILITIES Requirements for Submitting OSFR Information...

  4. 30 CFR 553.42 - How can I amend my list of COFs?

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 2 2013-07-01 2013-07-01 false How can I amend my list of COFs? 553.42 Section 553.42 Mineral Resources BUREAU OF OCEAN ENERGY MANAGEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL SPILL FINANCIAL RESPONSIBILITY FOR OFFSHORE FACILITIES Requirements for Submitting OSFR Information...

  5. Covalent Organic Frameworks: From Materials Design to Biomedical Application

    PubMed Central

    Zhao, Fuli; Liu, Huiming; Mathe, Salva D. R.; Dong, Anjie

    2017-01-01

    Covalent organic frameworks (COFs) are newly emerged crystalline porous polymers with well-defined skeletons and nanopores mainly consisted of light-weight elements (H, B, C, N and O) linked by dynamic covalent bonds. Compared with conventional materials, COFs possess some unique and attractive features, such as large surface area, pre-designable pore geometry, excellent crystallinity, inherent adaptability and high flexibility in structural and functional design, thus exhibiting great potential for various applications. Especially, their large surface area and tunable porosity and π conjugation with unique photoelectric properties will enable COFs to serve as a promising platform for drug delivery, bioimaging, biosensing and theranostic applications. In this review, we trace the evolution of COFs in terms of linkages and highlight the important issues on synthetic method, structural design, morphological control and functionalization. And then we summarize the recent advances of COFs in the biomedical and pharmaceutical sectors and conclude with a discussion of the challenges and opportunities of COFs for biomedical purposes. Although currently still at its infancy stage, COFs as an innovative source have paved a new way to meet future challenges in human healthcare and disease theranostic. PMID:29283423

  6. Acute lung injury following refrigeration coil deicing.

    PubMed

    McKeown, Nathanael J; Burton, Brent T

    2012-03-01

    We report a case of a worker who developed ALI requiring mechanical ventilatory support after attempting to melt ice condensate by applying the flame of an oxy-acetylene torch to refrigeration coils charged with a halocarbon refrigerant in a closed environment. A discussion of possible etiologies are discussed, including phosgene, carbonyl fluoride, and nitrogen oxides. Primary prevention with adequate respiratory protection is recommended whenever deicing is performed in a closed space environment.

  7. 30 CFR 253.13 - How much OSFR must I demonstrate?

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...: COF worst case oil-spill discharge volume Applicable amount of OSFR Over 1,000 bbls but not more than... must demonstrate OSFR in accordance with the following table: COF worst case oil-spill discharge volume... applicable table in paragraph (b)(1) or (b)(2) for a facility with a potential worst case oil-spill discharge...

  8. Does dual task training improve walking performance of older adults with concern of falling?

    PubMed

    Wollesen, B; Schulz, S; Seydell, L; Delbaere, K

    2017-09-11

    Older adults with concerns of falling show decrements of gait stability under single (ST) and dual task (DT) conditions. To compare the effects of a DT training integrating task managing strategies for independent living older adults with and without concern about falling (CoF) to a non-training control group on walking performance under ST and DT conditions. Single center parallel group single blind randomized controlled trial with group-based interventions (DT-managing balance training) compared to a control group (Ninety-five independent living older adults; 71.5 ± 5.2 years). A progressive DT training (12 sessions; 60 min each; 12 weeks) including task-managing strategies was compared to a non-training control group. group based intervention for independent living elderly in a gym. ST and DT walking (visual verbal Stroop task) were measured on a treadmill. Gait parameters (step length, step width, and gait line) and cognitive performance while walking were compared with a 2x2x2 Repeated Measures Analyses of Variance. Participants in the intervention group showed an increased step length under ST and DT conditions following the intervention, for both people with and without CoF compared to their respective control groups. Foot rolling movement and cognitive performance while walking however only improved in participants without CoF. The results showed that DT managing training can improve walking performance under ST and DT conditions in people with and without CoF. Additional treatment to directly address CoF, such as cognitive behavioural therapy, should be considered to further improve the cautious gait pattern (as evidenced by reduced foot rolling movements). The study was retrospectively registered in the German Clinical Trials Register (DRKS; Identification number DRKS00012382 , 11.05.2017).

  9. Seismic wave propagation in anisotropic ice - Part 2: Effects of crystal anisotropy in geophysical data

    NASA Astrophysics Data System (ADS)

    Diez, A.; Eisen, O.; Hofstede, C.; Lambrecht, A.; Mayer, C.; Miller, H.; Steinhage, D.; Binder, T.; Weikusat, I.

    2015-02-01

    We investigate the propagation of seismic waves in anisotropic ice. Two effects are important: (i) sudden changes in crystal orientation fabric (COF) lead to englacial reflections; (ii) the anisotropic fabric induces an angle dependency on the seismic velocities and, thus, recorded travel times. Velocities calculated from the polycrystal elasticity tensor derived for the anisotropic fabric from measured COF eigenvalues of the EDML ice core, Antarctica, show good agreement with the velocity trend determined from vertical seismic profiling. The agreement of the absolute velocity values, however, depends on the choice of the monocrystal elasticity tensor used for the calculation of the polycrystal properties. We make use of abrupt changes in COF as a common reflection mechanism for seismic and radar data below the firn-ice transition to determine COF-induced reflections in either data set by joint comparison with ice-core data. Our results highlight the possibility to complement regional radar surveys with local, surface-based seismic experiments to separate isochrones in radar data from other mechanisms. This is important for the reconnaissance of future ice-core drill sites, where accurate isochrone (i.e. non-COF) layer integrity allows for synchronization with other cores, as well as studies of ice dynamics considering non-homogeneous ice viscosity from preferred crystal orientations.

  10. Differences in Tribological Behaviors upon Switching Fixed and Moving Materials of Tribo-pairs including Metal and Polymer.

    PubMed

    Xu, Aijie; Tian, Pengyi; Wen, Shizhu; Guo, Fei; Hu, Yueqiang; Jia, Wenpeng; Dong, Conglin; Tian, Yu

    2017-10-12

    The coefficient of friction (COF) between two materials is usually believed to be an intrinsic property of the materials themselves. In this study, metals of stainless steel (304) and brass (H62), and polymers of polypropylene (PP) and polytetrafluoroethylene (PTFE) were tested on a standard ball-on-three-plates test machine. Significantly different tribological behaviors were observed when fixed and moving materials of tribo-pairs (metal/polymer) were switched. As an example, under the same applied load and rotating speed, the COF (0.49) between a rotating PP ball and three fixed H62 plates was approximately 2.3 times higher than that between switched materials of tribo-pairs. Meanwhile, the COF between H62 and PTFE was relatively stable. The unexpected tribological behaviors were ascribed to the thermal and mechanical properties of tribo-pairs. Theoretical analysis revealed that the differences in the maximum local temperature between switching the fixed and moving materials of tribo-pairs were consistent with the differences in the tested COF. This result indicated the precise prediction of the COF of two materials is complexcity, and that thermal and mechanical properties should be properly considered in designing tribo-pairs, because these properties may significantly affect tribological performance.

  11. Evaluation of sodium fluoride toxicity in Schistosoma infected snails: assessment of antioxidants, antiapoptotic, hypoprotein and hypocholesterol activities.

    PubMed

    Koriem, Khaled M M; Shamsuri, Radziyah B; Ubaidillah, Asliza M

    2016-12-01

    The snails' tissues represents an intermediate or secondary host for Schistosoma sporocysts where, germ cells within the secondary sporocyst begin to divide to produce thousands of cercariae capable of infecting humans. The aim of the study was to evaluate the toxicity of sodium fluoride in Schistosoma snails' tissue homogenates. A total number of 264 different Schistosoma snails were collected from eight drainage water resources and divided into control uninfected and infected snails; where infected snails divided into four group; the first group without any treatment while second, third and fourth groups immersed in 25, 50 and 100 mg sodium fluoride/L during the period of 4 weeks then the snails' hemolymph and tissue homogenates were prepared to evaluate the snail' tissue antioxidants, protein content, lipid profile and apoptosis. The results obtained revealed that superoxide dismutase, glutathione- S -transferase, glutathione peroxidase, catalase, reduced glutathione, glutathione reductase levels were decreased while malondialdehyde, protein carbonyl, total protein, albumin, globulin, cholesterol, low density lipoprotein and triglycerides levels were increased in Schistosoma infected snails' tissues. Schistosoma also induced apoptosis in snails' tissues homogenates. Sodium fluoride restores all the above parameters to approach the control uninfected snails levels. In conclusion, sodium fluoride inhibits oxidative stress and apoptosis produced in Schistosoma infected snails and consequently it is be useful to be used in Schistosoma infection inhibition where sodium fluoride at higher dose was more effective than the lower two doses.

  12. Lowering coefficient of friction in Cu alloys with stable gradient nanostructures

    PubMed Central

    Chen, Xiang; Han, Zhong; Li, Xiuyan; Lu, K.

    2016-01-01

    The coefficient of friction (COF) of metals is usually high, primarily because frictional contacts induce plastic deformation underneath the wear surface, resulting in surface roughening and formation of delaminating tribolayers. Lowering the COF of metals is crucial for improving the reliability and efficiency of metal contacts in engineering applications but is technically challenging. Refining the metals’ grains to nanoscale cannot reduce dry-sliding COFs, although their hardness may be elevated many times. We report that a submillimeter-thick stable gradient nanograined surface layer enables a significant reduction in the COF of a Cu alloy under high-load dry sliding, from 0.64 (coarse-grained samples) to 0.29, which is smaller than the COFs of many ceramics. The unprecedented stable low COF stems from effective suppression of sliding-induced surface roughening and formation of delaminating tribolayer, owing to the stable gradient nanostructures that can accommodate large plastic strains under repeated sliding for more than 30,000 cycles. PMID:27957545

  13. Maxillo-Mandibular Cemento-ossifying Fibroma: A Rare Case Report.

    PubMed

    Peravali, Ranjit Kumar; Bhat, H Hari Kishore; Reddy, Sreenatha

    2015-03-01

    Cemento-ossifying fibroma (COF) is a benign fibro osseous lesion of the jaws which has been described as a demarcated or rarely encapsulated neoplasm consisting of fibrous tissue and varying amounts of mineralized material resembling bone and/or cementum (Dinkar et al. in IJDA 2(4):45-47, 2010). Majority of lesions occur in the mandible and only few cases of COFs of the maxillary sinus and bilateral COFs of the mandible have been reported in literature (Dinkar et al. in IJDA 2(4):45-47, 2010; Tamiolakis et al. in Acta Stomatol Croat 39(3):319-321, 2005; Hamner et al. in Oral Surg Oral Med Oral Pathol 26(4):579-587, 1968; Gunaseelan et al. in Oral Med Oral Pathol Oral Radiol Endod 104:e21-e25, 2007). These lesions have a very low recurrence rate (Ertug et al. in Quintessence Int 35(10):808-810, 2004) and are generally treated by enucleation. In this paper we present a rare case of COF occurring in both the maxilla and mandible of the same patient. Only one such case (Takeda and Fujioka in Int J Oral Maxillofac Surg 16(3):368-371, 1987) has been reported in literature so far.

  14. Scratch Testing of Hot-Pressed Monolithic Chromium Diboride (CrB2) and CrB2 + MoSi2 Composite

    NASA Astrophysics Data System (ADS)

    Bhatt, B.; Murthy, T. S. R. Ch.; Singh, K.; Sashanka, A.; Vishwanadh, B.; Sonber, J. K.; Sairam, K.; Nageswara Rao, G. V. S.; Srinivasa Rao, T.; Kain, Vivekanand

    2017-10-01

    The tribological performance of hot-pressed monolithic CrB2 and a newly developed CrB2 + 20 vol.% MoSi2 composite was investigated by using scratch test. The test was carried out under progressive loading ranging from 0.9 to 30 N over a scratch distance of 3 mm. In situ values of coefficient of friction (COF), depth of penetration and acoustic emission were recorded. The wear volume and fracture toughness were also calculated. COF of both materials is increased with increasing the scratch length and progressive load. COF of the composite was observed to be slightly higher compared to the monolithic CrB2. The wear volume of the composite is 60% higher compared to monolithic CrB2. Fracture toughness values of 2.48 and 2.81 MPa m1/2 were calculated for monolithic CrB2 and CrB2 + 20 vol.% MoSi2 composite, respectively. Microstructural characterization indicates that the abrasive wear is the dominant wear mechanism in both the materials.

  15. Crystal Structure of the Minor Pilin CofB, the Initiator of CFA/III Pilus Assembly in Enterotoxigenic Escherichia coli*

    PubMed Central

    Kolappan, Subramania; Ng, Dixon; Yang, Guixiang; Harn, Tony; Craig, Lisa

    2015-01-01

    Type IV pili are extracellular polymers of the major pilin subunit. These subunits are held together in the pilus filament by hydrophobic interactions among their N-terminal α-helices, which also anchor the pilin subunits in the inner membrane prior to pilus assembly. Type IV pilus assembly involves a conserved group of proteins that span the envelope of Gram-negative bacteria. Among these is a set of minor pilins, so named because they share their hydrophobic N-terminal polymerization/membrane anchor segment with the major pilins but are much less abundant. Minor pilins influence pilus assembly and retraction, but their precise functions are not well defined. The Type IV pilus systems of enterotoxigenic Escherichia coli and Vibrio cholerae are among the simplest of Type IV pilus systems and possess only a single minor pilin. Here we show that the enterotoxigenic E. coli minor pilins CofB and LngB are required for assembly of their respective Type IV pili, CFA/III and Longus. Low levels of the minor pilins are optimal for pilus assembly, and CofB can be detected in the pilus fraction. We solved the 2.0 Å crystal structure of N-terminally truncated CofB, revealing a pilin-like protein with an extended C-terminal region composed of two discrete domains connected by flexible linkers. The C-terminal region is required for CofB to initiate pilus assembly. We propose a model for CofB-initiated pilus assembly with implications for understanding filament growth in more complex Type IV pilus systems as well as the related Type II secretion system. PMID:26324721

  16. Crystal Structure of the Minor Pilin CofB, the Initiator of CFA/III Pilus Assembly in Enterotoxigenic Escherichia coli.

    PubMed

    Kolappan, Subramania; Ng, Dixon; Yang, Guixiang; Harn, Tony; Craig, Lisa

    2015-10-23

    Type IV pili are extracellular polymers of the major pilin subunit. These subunits are held together in the pilus filament by hydrophobic interactions among their N-terminal α-helices, which also anchor the pilin subunits in the inner membrane prior to pilus assembly. Type IV pilus assembly involves a conserved group of proteins that span the envelope of Gram-negative bacteria. Among these is a set of minor pilins, so named because they share their hydrophobic N-terminal polymerization/membrane anchor segment with the major pilins but are much less abundant. Minor pilins influence pilus assembly and retraction, but their precise functions are not well defined. The Type IV pilus systems of enterotoxigenic Escherichia coli and Vibrio cholerae are among the simplest of Type IV pilus systems and possess only a single minor pilin. Here we show that the enterotoxigenic E. coli minor pilins CofB and LngB are required for assembly of their respective Type IV pili, CFA/III and Longus. Low levels of the minor pilins are optimal for pilus assembly, and CofB can be detected in the pilus fraction. We solved the 2.0 Å crystal structure of N-terminally truncated CofB, revealing a pilin-like protein with an extended C-terminal region composed of two discrete domains connected by flexible linkers. The C-terminal region is required for CofB to initiate pilus assembly. We propose a model for CofB-initiated pilus assembly with implications for understanding filament growth in more complex Type IV pilus systems as well as the related Type II secretion system. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  17. Structural characterization of CFA/III and Longus type IVb pili from enterotoxigenic Escherichia coli.

    PubMed

    Kolappan, Subramaniapillai; Roos, Justin; Yuen, Alex S W; Pierce, Owen M; Craig, Lisa

    2012-05-01

    The type IV pili are helical filaments found on many Gram-negative pathogenic bacteria, with multiple diverse roles in pathogenesis, including microcolony formation, adhesion, and twitching motility. Many pathogenic enterotoxigenic Escherichia coli (ETEC) isolates express one of two type IV pili belonging to the type IVb subclass: CFA/III or Longus. Here we show a direct correlation between CFA/III expression and ETEC aggregation, suggesting that these pili, like the Vibrio cholerae toxin-coregulated pili (TCP), mediate microcolony formation. We report a 1.26-Å resolution crystal structure of CofA, the major pilin subunit from CFA/III. CofA is very similar in structure to V. cholerae TcpA but possesses a 10-amino-acid insertion that replaces part of the α2-helix with an irregular loop containing a 3(10)-helix. Homology modeling suggests a very similar structure for the Longus LngA pilin. A model for the CFA/III pilus filament was generated using the TCP electron microscopy reconstruction as a template. The unique 3(10)-helix insert fits perfectly within the gap between CofA globular domains. This insert, together with differences in surface-exposed residues, produces a filament that is smoother and more negatively charged than TCP. To explore the specificity of the type IV pilus assembly apparatus, CofA was expressed heterologously in V. cholerae by replacing the tcpA gene with that of cofA within the tcp operon. Although CofA was synthesized and processed by V. cholerae, no CFA/III filaments were detected, suggesting that the components of the type IVb pilus assembly system are highly specific to their pilin substrates.

  18. Structure of the CFA/III major pilin subunit CofA from human enterotoxigenic Escherichia coli determined at 0.90 Å resolution by sulfur-SAD phasing.

    PubMed

    Fukakusa, Shunsuke; Kawahara, Kazuki; Nakamura, Shota; Iwashita, Takaki; Baba, Seiki; Nishimura, Mitsuhiro; Kobayashi, Yuji; Honda, Takeshi; Iida, Tetsuya; Taniguchi, Tooru; Ohkubo, Tadayasu

    2012-10-01

    CofA, a major pilin subunit of colonization factor antigen III (CFA/III), forms pili that mediate small-intestinal colonization by enterotoxigenic Escherichia coli (ETEC). In this study, the crystal structure of an N-terminally truncated version of CofA was determined by single-wavelength anomalous diffraction (SAD) phasing using five sulfurs in the protein. Given the counterbalance between anomalous signal strength and the undesired X-ray absorption of the solvent, diffraction data were collected at 1.5 Å resolution using synchrotron radiation. These data were sufficient to elucidate the sulfur substructure at 1.38 Å resolution. The low solvent content (29%) of the crystal necessitated that density modification be performed with an additional 0.9 Å resolution data set to reduce the phase error caused by the small sulfur anomalous signal. The CofA structure showed the αβ-fold typical of type IVb pilins and showed high structural homology to that of TcpA for toxin-coregulated pili of Vibrio cholerae, including spatial distribution of key residues critical for pilin self-assembly. A pilus-filament model of CofA was built by computational docking and molecular-dynamics simulation using the previously reported filament model of TcpA as a structural template. This model revealed that the CofA filament surface was highly negatively charged and that a 23-residue-long loop between the α1 and α2 helices filled the gap between the pilin subunits. These characteristics could provide a unique binding epitope for the CFA/III pili of ETEC compared with other type IVb pili.

  19. Effects of coffee and caffeine anhydrous on strength and sprint performance

    PubMed Central

    TREXLER, ERIC T.; SMITH-RYAN, ABBIE E.; ROELOFS, ERICA J.; HIRSCH, KATIE R.; MOCK, MEREDITH G.

    2015-01-01

    Caffeine and coffee are widely used among active individuals to enhance performance. The purpose of the current study was to compare the effects of acute coffee (COF) and caffeine anhydrous (CAF) intake on strength and sprint performance. Fifty-four resistance-trained males completed strength testing, consisting of one-rep max (1RM) and repetitions to fatigue (RTF) at 80% of 1RM for leg press (LP) and bench press (BP). Participants then completed five, ten-second cycle ergometer sprints separated by one minute of rest. Peak power (PP) and total work (TW) were recorded for each sprint. At least 48 hours later, participants returned and ingested a beverage containing CAF (300 mg flat dose; yielding 3–5 mg/kg bodyweight), COF (8.9 g; 303 mg caffeine), or placebo (PLA; 3.8 g noncaloric flavoring) 30 minutes before testing. LP 1RM was improved more by COF than CAF (p=0.04), but not PLA (p=0.99). Significant interactions were not observed for BP 1RM, BP RTF, or LP RTF (p>0.05). There were no sprint × treatment interactions for PP or TW (p>0.05). 95% confidence intervals revealed a significant improvement in sprint 1 TW for CAF, but not COF or PLA. For PLA, significant reductions were observed in sprint 4 PP, sprint 2 TW, sprint 4 TW, and average TW; significant reductions were not observed with CAF or COF. Neither COF nor CAF improved strength outcomes more than PLA, while both groups attenuated sprint power reductions to a similar degree. Coffee and caffeine anhydrous may be considered suitable pre-exercise caffeine sources for high-intensity exercise. PMID:26394649

  20. Effects of coffee and caffeine anhydrous on strength and sprint performance.

    PubMed

    Trexler, Eric T; Smith-Ryan, Abbie E; Roelofs, Erica J; Hirsch, Katie R; Mock, Meredith G

    2016-09-01

    Caffeine and coffee are widely used among active individuals to enhance performance. The purpose of the current study was to compare the effects of acute coffee (COF) and caffeine anhydrous (CAF) intake on strength and sprint performance. Fifty-four resistance-trained males completed strength testing, consisting of one-rep max (1RM) and repetitions to fatigue (RTF) at 80% of 1RM for leg press (LP) and bench press (BP). Participants then completed five, 10-second cycle ergometer sprints separated by one minute of rest. Peak power (PP) and total work (TW) were recorded for each sprint. At least 48 hours later, participants returned and ingested a beverage containing CAF (300 mg flat dose; yielding 3-5 mg/kg bodyweight), COF (8.9 g; 303 mg caffeine), or placebo (PLA; 3.8 g non-caloric flavouring) 30 minutes before testing. LP 1RM was improved more by COF than CAF (p = .04), but not PLA (p = .99). Significant interactions were not observed for BP 1RM, BP RTF, or LP RTF (p > .05). There were no sprint × treatment interactions for PP or TW (p > .05). 95% confidence intervals revealed a significant improvement in sprint 1 TW for CAF, but not COF or PLA. For PLA, significant reductions were observed in sprint 4 PP, sprint 2 TW, sprint 4 TW, and average TW; significant reductions were not observed with CAF or COF. Neither COF nor CAF improved strength outcomes more than PLA, while both groups attenuated sprint power reductions to a similar degree. Coffee and caffeine anhydrous may be considered suitable pre-exercise caffeine sources for high-intensity exercise.

  1. Aptamer-functionalized Magnetic Conjugated Organic Frameworks for Selective Extraction of Trace Hydroxylated Polychlorinated Biphenyls in Human Serum.

    PubMed

    Jiang, Dandan; Hu, Tingting; Zheng, Haijiao; Xu, Guoxing; Jia, Qiong

    2018-05-02

    Herein, a novel solid phase extraction adsorbent based on aptamer-functionalized magnetic conjugated organic frameworks (COFs) was developed for selective extraction of trace hydroxylated polychlorinated biphenyls (OH-PCBs). The material possessed advantages of superparamagnetism of magnetic core, high surface area and porous structure of COFs, and high specific affinity of aptamer. In combination with high-performance liquid chromatography/mass spectrometry, the aptamer-functionalized magnetic COFs was used for the capture of hydroxy-2',3',4',5,5'-pentachlorobiphenyl (2-OH-CB 124) in human serum. The method provided a linear range of 0.01-40 ng mL-1 with a good correlation coefficient (R2= 0.9973). The limit of detection was found to be as low as 2.1 pg mL-1. Furthermore, the material possessed good reusability and could be applied in replicate at least for 10 extraction cycles with recoveries over 90%. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. MicroRNA profiling reveals dysregulated microRNAs and their target gene regulatory networks in cemento-ossifying fibroma.

    PubMed

    Pereira, Thaís Dos Santos Fontes; Brito, João Artur Ricieri; Guimarães, André Luiz Sena; Gomes, Carolina Cavaliéri; de Lacerda, Júlio Cesar Tanos; de Castro, Wagner Henriques; Coimbra, Roney Santos; Diniz, Marina Gonçalves; Gomez, Ricardo Santiago

    2018-01-01

    Cemento-ossifying fibroma (COF) is a benign fibro-osseous neoplasm of uncertain pathogenesis, and its treatment results in morbidity. MicroRNAs (miRNA) are small non-coding RNAs that regulate gene expression and may represent therapeutic targets. The purpose of the study was to generate a comprehensive miRNA profile of COF compared to normal bone. Additionally, the most relevant pathways and target genes of differentially expressed miRNA were investigated by in silico analysis. Nine COF and ten normal bone samples were included in the study. miRNA profiling was carried out by using TaqMan® OpenArray® Human microRNA panel containing 754 validated human miRNAs. We identified the most relevant miRNAs target genes through the leader gene approach, using STRING and Cytoscape software. Pathways enrichment analysis was performed using DIANA-miRPath. Eleven miRNAs were downregulated (hsa-miR-95-3p, hsa-miR-141-3p, hsa-miR-205-5p, hsa-miR-223-3p, hsa-miR-31-5p, hsa-miR-944, hsa-miR-200b-3p, hsa-miR-135b-5p, hsa-miR-31-3p, hsa-miR-223-5p and hsa-miR-200c-3p), and five were upregulated (hsa-miR-181a-5p, hsa-miR-181c-5p, hsa-miR-149-5p, hsa-miR-138-5p and hsa-miR-199a-3p) in COF compared to normal bone. Eighteen common target genes were predicted, and the leader genes approach identified the following genes involved in human COF: EZH2, XIAP, MET and TGFBR1. According to the biology of bone and COF, the most relevant KEGG pathways revealed by enrichment analysis were proteoglycans in cancer, miRNAs in cancer, pathways in cancer, p53-, PI3K-Akt-, FoxO- and TGF-beta signalling pathways, which were previously found to be differentially regulated in bone neoplasms, odontogenic tumours and osteogenesis. miRNA dysregulation occurs in COF, and EZH2, XIAP, MET and TGFBR1 are potential targets for functional analysis validation. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  3. Pd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation

    PubMed Central

    Mullangi, Dinesh; Nandi, Shyamapada; Shalini, Sorout; Sreedhala, Sheshadri; Vinod, Chathakudath P.; Vaidhyanathan, Ramanathan

    2015-01-01

    COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd0 nanoparticles into it. An 18–20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) <0.05 mol%, average TON 1500) catalyzing simultaneous multiple site Heck couplings and C-C couplings using ‘non-boronic acid’ substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150 °C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable. PMID:26057044

  4. M4FT-15OR03100415 - Update on COF-based Adsorbent Survey

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

    Mayes, Richard T.; Dai, Sheng

    2015-02-01

    This letter report provides an update on activities focused on generating nanoporous adsorbents involving covalent organic frameworks (COF) and zeolitic imidazolium frameworks (ZIF). The adsorbents have been generated and screened in a uranyl-spiked brine (6 ppm U) to understand uranyl-binding behavior. Porous organic polymers (POP) also qualify under this title and are similar to the COF PPN-6 that is discussed herein. Seven COF/POP and one 1 ZIF were synthesized and screened for uranyl adsorption. Seawater screening is on-going via batch testing while flow screening systems are being developed at PNNL.

  5. Correlation of subjective slipperiness judgements with quantitative COF (Coefficient Of Friction) measurements for structural steel

    NASA Astrophysics Data System (ADS)

    Purswell, Jerry L.; Schlegel, Robert E.

    1988-06-01

    When there is no simple or accurate procedure for measuring the coefficient of friction (COF) at a job site, workers and/or supervisors involved must make subjective judgments about the slipperiness of the walking and climbing surfaces and in turn decide whether the surface presents a safe or an unsafe condition for work. This project was designed to determine whether these subjective judgment calls did in fact agree with the COF measurements obtained using a mechanical device. It was noted that the coatings chosen for study were subject to a polishing factor by the boot soles during the trials, causing the COF values to become lower as the trials continued. Poor correlation was obtained between subjective ratings of slipperiness and the COF values measured before the trials began. A relatively high correlation was obtained between subjective ratings and the COF values measured after the trials had been completed. A difference was noted in the subjective ratings for the effects of water on a coating for column climbing, but not for walking a beam, suggesting the effects of water on a coating are related to the type of task being performed in steel erection. An increase in the measured COF was noted for all of the coatings when they were wet as compared to the dry condition. The importance of clean shoe soles was clearly demonstrated.

  6. The Wnt/β-catenin pathway is deregulated in cemento-ossifying fibromas.

    PubMed

    Pereira, Thaís Dos Santos Fontes; Diniz, Marina Gonçalves; França, Josiane Alves; Moreira, Rennan Garcias; Menezes, Grazielle Helena Ferreira de; Sousa, Sílvia Ferreira de; Castro, Wagner Henriques de; Gomes, Carolina Cavaliéri; Gomez, Ricardo Santiago

    2018-02-01

    The molecular pathogenesis of cemento ossifying fibroma (COF) is unclear. The purpose of this study was to investigate mutations in 50 oncogenes and tumor suppressor genes, including APC and CTNNB1, in which mutations in COF have been previously reported. In addition, we assessed the transcriptional levels of the Wnt/β-catenin pathway genes in COF. We used a quantitative polymerase chain reaction array to evaluate the transcriptional levels of 44 Wnt/β-catenin pathway genes in 6 COF samples, in comparison with 6 samples of healthy jaws. By using next-generation sequencing (NGS) in 7 COF samples, we investigated approximately 2800 mutations in 50 genes. The expression assay revealed 12 differentially expressed Wnt/β-catenin pathway genes in COF, including the upregulation of CTNNB1, TCF7, NKD1, and WNT5 A, and downregulation of CTNNBIP1, FRZB, FZD6, RHOU, SFRP4, WNT10 A, WNT3 A, and WNT4, suggesting activation of the Wnt/β-catenin signaling pathway. NGS revealed 5 single nucleotide variants: TP53 (rs1042522), PIK3 CA (rs2230461), MET (rs33917957), KIT (rs3822214), and APC (rs33974176), but none of them was pathogenic. Although NGS detected no oncogenic mutation, deregulation of key Wnt/β-catenin signaling pathway genes appears to be relevant to the molecular pathogenesis of COF. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Development of Army Facility Functionality Assessment Criteria and Procedures

    DTIC Science & Technology

    2010-09-01

    critical facility types: the Tactical Equipment Main- tenance Facility (TEMF), the Company Operations Facility (COF), the Bat- talion Headquarters...Criteria for Company Operations Facilities (COF) ................ 56 Appendix G: Army Standard Design Criteria for Tactical Equipment Maintenance...1 mission-critical facility types: the Tactical Equipment Mainten- ance Facility (TEMF), the Company Operations Facility (COF), the Batta- lion

  8. Sensitivity enhancement of fluorescence detection in CE by coupling and conducting excitation light with tapered optical fiber.

    PubMed

    Yang, Xiupei; Huo, Feng; Yuan, Hongyan; Zhang, Bo; Xiao, Dan; Choi, Martin M F

    2011-01-01

    This paper reports the enhancement of sensitivity of detection for in-column fiber optic-induced fluorescence detection system in CE by tapered optical fiber (TOF). Two types of optical fiber, TOF and conventional cylindrical optical fiber (COF), were employed to construct the CE (TOF-CE and COF-CE) and were compared for sensitivity to riboflavin (RF). The fluorescence intensities from a RF sample with excitation light sources and fibers at various coupling angles were investigated. The fluorescence signal from TOF-CE was ca. ten times that of COF-CE. In addition, the detection performance of four excitation light source-fiber configurations including Laser-TOF, Laser-COF, LED-TOF, and LED-COF were compared. The LODs for RF were 0.21, 0.82, 0.80, and 7.5 nM, respectively, for the four excitation light source-fiber configurations. The results demonstrate that the sensitivity obtained by LED-TOF is close to that of Laser-COF. Both Laser-TOF and LED-TOF can greatly improve the sensitivity of detection in CE. TOF has the major attribute of collecting and focusing the excitation light intensity. Thus, the sensitivity obtained by LED-TOF without focusing lens is just same as that of LED-COF with a focusing lens. This demonstrates that the CE system can be further simplified by eliminating the focusing lens for excitation light. LED-TOF-CE and LED-COF-CE system were applied to the separation and determination of RF in real sample (green tea), respectively. The tapered fiber optic-induced fluorescence detection system in CE is an ideal tool for trace analysis. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Effects of humidity on skin friction against medical textiles as related to prevention of pressure injuries.

    PubMed

    Schwartz, Danit; Magen, Yana Katsman; Levy, Ayelet; Gefen, Amit

    2018-05-24

    Sustained pressure, shear forces, and friction, as well as elevated humidity/moisture, are decisive physical factors in the development of pressure injuries (PIs). To date, further research is needed in order to understand the influence of humidity and moisture on the coefficient of friction (COF) of skin against different types of medical textiles. The aim of this work was to investigate the effects of moisture caused by sweat, urine, or saline on the resulting COF of skin against different textiles used in the medical setting in the context of PI prevention. For that purpose, we performed physical measurements of static COFs of porcine skin followed by finite element (FE) computational modelling in order to illustrate the effect of increased COF at the skin on the resulting strains and stresses deep within the soft tissues of the buttocks. The COF of dry skin obtained for the 3 textiles varied between 0.59 (adult diaper) and 0.91 (polyurethane dressing). In addition, the COF increased with the added moisture in all of the tested cases. The results of the FE simulations further showed that increased COF results in elevated strain energy density and shear strain values in the skin and deeper tissues and, hence, in an increased risk for PI development. We conclude that moisture may accelerate PI formation by increasing the COF between the skin and the medical textile, regardless of the type of the liquid that is present. Hence, reduction of the wetness/moisture between the skin and fabrics in patients at a high risk of developing PIs is a key measure in PI prevention. © 2018 Medicalhelplines.com Inc and John Wiley & Sons Ltd.

  10. A coumarin-pyrazolone based fluorescent probe for selective colorimetric and fluorimetric fluoride detection: Synthesis, spectroscopic properties and DFT calculations

    NASA Astrophysics Data System (ADS)

    Babür, Banu; Seferoğlu, Nurgül; Seferoğlu, Zeynel

    2018-06-01

    A novel coumarin based fluorescence anion chemosensor (P-1) bearing pyrazolone as a receptoric part was synthesized and characterized by using FT-IR, 1H/13C NMR and HRMS for the purpose of recognition of anions in DMSO. P-1 has four tautomeric structures and the most stable tautomeric form of P-1 was determined experimentally and theoretically. The chemosensor P-1 consists two receptoric parts as free amide Nsbnd H and enamine Nsbnd H which is stabilized intramolecular H-bonding with coumarin carbonyl oxygen. P-1 interacts selectively with fluoride anion via amide Nsbnd H. The selectivity and sensitivity of probe to various anions were determined with spectrophotometric and 1H NMR titration techniques as experimentally and all results were also explained by theoretical calculations.

  11. Influence of Nitrogen Flow Rate on Friction Coefficient and Surface Roughness of TiN Coatings Deposited on Tool Steel Using Arc Method

    NASA Astrophysics Data System (ADS)

    Hamzah, Esah; Ourdjini, Ali; Ali, Mubarak; Akhter, Parvez; Hj. Mohd Toff, Mohd Radzi; Abdul Hamid, Mansor

    In the present study, the effect of various N2 gas flow rates on friction coefficient and surface roughness of TiN-coated D2 tool steel was examined by a commercially available cathodic arc physical vapor deposition (CAPVD) technique. A Pin-on-Disc test was carried out to study the Coefficient of friction (COF) versus sliding distance. A surface roughness tester measured the surface roughness parameters. The minimum values for the COF and surface roughness were recorded at a N2 gas flow rate of 200 sccm. The increase in the COF and surface roughness at a N2 gas flow rate of 100 sccm was mainly attributed to an increase in both size and number of titanium particles, whereas the increase at 300 sccm was attributed to a larger number of growth defects generated during the coating process. These ideas make it possible to optimize the coating properties as a function of N2 gas flow rate for specific applications, e.g. cutting tools for automobiles, aircraft, and various mechanical parts.

  12. Enamel Insulated Copper Wire in Electric Motors: Sliding Behavior and Possible Damage Mechanisms During Die Bending

    NASA Astrophysics Data System (ADS)

    Demiri, Albion

    This study investigates the sliding friction and the forming behaviour of enamel insulated copper wire during the die-forming process. It also aims to determine potential damage mechanisms to the wire during bending process for electric motor coils. In this investigation a wire-bending machine was designed and built in order to simulate the wire forming process in a laboratory scale. Bending angle of the wire and the bending radii were used to control the strain on the wire surface. The effect of speed on COF was investigated for different speeds of of 1, 5, 10, 15, and 20mm/s. A positive correlation was observed between the COF and the testing speed. Additionally, the effect of strain on COF was studied for 2% and 23% to determine its influence on the COF. A general trend was observed of decreased COF with increased strain in wires. Finally, the ability of the enamel coating to resist external damage and wire strain was investigated by tensile testing of pre-scratched magnet wire. The results showed that wire enamel can withstand significant surface damage prior to breach and failure. The insulating polymer coating failed under the scratch tests at 20N load using a Rockwell indenter and at 5N load using a 90° conical steel indenter. Additional tests, such as tensile testing, scratch testing and reciprocating friction testing, were used to characterize the mechanical and tribological properties of the enamel insulated copper wire.

  13. Ankle joint pressure changes in a pes cavovarus model: supramalleolar valgus osteotomy versus lateralizing calcaneal osteotomy.

    PubMed

    Schmid, Timo; Zurbriggen, Sebastian; Zderic, Ivan; Gueorguiev, Boyko; Weber, Martin; Krause, Fabian G

    2013-09-01

    A fixed cavovarus foot deformity can be associated with anteromedial ankle arthrosis due to elevated medial joint contact stresses. Supramalleolar valgus osteotomies (SMOT) and lateralizing calcaneal osteotomies (LCOT) are commonly used to treat symptoms by redistributing joint contact forces. In a cavovarus model, the effects of SMOT and LCOT on the lateralization of the center of force (COF) and reduction of the peak pressure in the ankle joint were compared. A previously published cavovarus model with fixed hindfoot varus was simulated in 10 cadaver specimens. Closing wedge supramalleolar valgus osteotomies 3 cm above the ankle joint level (6 and 11 degrees) and lateral sliding calcaneal osteotomies (5 and 10 mm displacement) were analyzed at 300 N axial static load (half body weight). The COF migration and peak pressure decrease in the ankle were recorded using high-resolution TekScan pressure sensors. A significant lateral COF shift was observed for each osteotomy: 2.1 mm for the 6 degrees (P = .014) and 2.3 mm for the 11 degrees SMOT (P = .010). The 5 mm LCOT led to a lateral shift of 2.0 mm (P = .042) and the 10 mm LCOT to a shift of 3.0 mm (P = .006). Comparing the different osteotomies among themselves no significant differences were recorded. No significant anteroposterior COF shift was seen. A significant peak pressure reduction was recorded for each osteotomy: The SMOT led to a reduction of 29% (P = .033) for the 6 degrees and 47% (P = .003) for the 11 degrees osteotomy, and the LCOT to a reduction of 41% (P = .003) for the 5 mm and 49% (P = .002) for the 10 mm osteotomy. Similar to the COF lateralization no significant differences between the osteotomies were seen. LCOT and SMOT significantly reduced anteromedial ankle joint contact stresses in this cavovarus model. The unloading effects of both osteotomies were equivalent. More correction did not lead to significantly more lateralization of the COF or more reduction of peak pressure but a trend was seen. In patients with fixed cavovarus feet, both SMOT and LCOT provided equally good redistribution of elevated ankle joint contact forces. Increasing the amount of displacement did not seem to equally improve the joint pressures. The site of osteotomy could therefore be chosen on the basis of surgeon's preference, simplicity, or local factors in case of more complex reconstructions.

  14. Molecular docking sites designed for the generation of highly crystalline covalent organic frameworks

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

    Ascherl, Laura; Sick, Torben; Margraf, Johannes

    Covalent organic frameworks (COFs) formed by connecting multidentate organic building blocks through covalent bonds provide a platform for designing multifunctional porous materials with atomic precision. As they are promising materials for applications in optoelectronics, they would benefit from a maximum degree of long-range order within the framework, which has remained a major challenge. We have developed a synthetic concept to allow consecutive COF sheets to lock in position during crystal growth, and thus minimize the occurrence of stacking faults and dislocations. Hereby, the three-dimensional conformation of propeller-shaped molecular building units was used to generate well-defined periodic docking sites, which guidedmore » the attachment of successive building blocks that, in turn, promoted long-range order during COF formation. This approach enables us to achieve a very high crystallinity for a series of COFs that comprise tri- and tetradentate central building blocks. We expect this strategy to be transferable to a broad range of customized COFs.« less

  15. Molecular docking sites designed for the generation of highly crystalline covalent organic frameworks

    NASA Astrophysics Data System (ADS)

    Ascherl, Laura; Sick, Torben; Margraf, Johannes T.; Lapidus, Saul H.; Calik, Mona; Hettstedt, Christina; Karaghiosoff, Konstantin; Döblinger, Markus; Clark, Timothy; Chapman, Karena W.; Auras, Florian; Bein, Thomas

    2016-04-01

    Covalent organic frameworks (COFs) formed by connecting multidentate organic building blocks through covalent bonds provide a platform for designing multifunctional porous materials with atomic precision. As they are promising materials for applications in optoelectronics, they would benefit from a maximum degree of long-range order within the framework, which has remained a major challenge. We have developed a synthetic concept to allow consecutive COF sheets to lock in position during crystal growth, and thus minimize the occurrence of stacking faults and dislocations. Hereby, the three-dimensional conformation of propeller-shaped molecular building units was used to generate well-defined periodic docking sites, which guided the attachment of successive building blocks that, in turn, promoted long-range order during COF formation. This approach enables us to achieve a very high crystallinity for a series of COFs that comprise tri- and tetradentate central building blocks. We expect this strategy to be transferable to a broad range of customized COFs.

  16. Covalent organic framework as efficient desorption/ionization matrix for direct detection of small molecules by laser desorption/ionization mass spectrometry.

    PubMed

    Feng, Dan; Xia, Yan

    2018-07-19

    Covalent organic framework (COF) was explored as a novel matrix with a high desorption/ionization efficiency for direct detection of small molecules by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS). By using COF as an LDI MS matrix, we could detect not only biological micro molecules such as amino acids and fatty acids, but also emerging environmental pollutants like bisphenol S (BPS) and pyrene. With COF as the matrix, higher desorption/ionization efficiency, and less background interference were achieved than the conventional organic matrices. Good salt tolerance (as high as 500 mM NaCl) and repeatability allowed the detection limit of amino acids was 90 fmol. In addition, COF matrix performed well for amino acids analysis in the honey sample. The ionization mechanism was also discussed. These results demonstrate that COF is a powerful matrix for small molecules analysis in real samples by MS. Copyright © 2018 Elsevier B.V. All rights reserved.

  17. Cationic Covalent Organic Frameworks: A Simple Platform of Anionic Exchange for Porosity Tuning and Proton Conduction.

    PubMed

    Ma, Heping; Liu, Bailing; Li, Bin; Zhang, Liming; Li, Yang-Guang; Tan, Hua-Qiao; Zang, Hong-Ying; Zhu, Guangshan

    2016-05-11

    Mimicking proton conduction mechanism of Nafion to construct novel proton-conducting materials with low cost and high proton conductivity is of wide interest. Herein, we have designed and synthesized a cationic covalent organic framework with high thermal and chemical stability by combining a cationic monomer, ethidium bromide (EB) (3,8-diamino-5-ethyl-6-phenylphenanthridinium bromide), with 1,3,5-triformylphloroglucinol (TFP) in Schiff base reactions. This is the first time that the stable cationic crystalline frameworks allowed for the fabrication of a series of charged COFs (EB-COF:X, X = F, Cl, Br, I) through ion exchange processes. Exchange of the extra framework ions can finely modulate the COFs' porosity and pore sizes at nanoscale. More importantly, by introducing PW12O40(3-) into this porous cationic framework, we can greatly enhance the proton conductivity of ionic COF-based material. To the best of our knowledge, EB-COF:PW12 shows the best proton conductivity at room temperature among ever reported porous organic materials.

  18. Designed synthesis of double-stage two-dimensional covalent organic frameworks

    PubMed Central

    Chen, Xiong; Addicoat, Matthew; Jin, Enquan; Xu, Hong; Hayashi, Taku; Xu, Fei; Huang, Ning; Irle, Stephan; Jiang, Donglin

    2015-01-01

    Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers in which organic building blocks are covalently and topologically linked to form extended crystalline polygon structures, constituting a new platform for designing π-electronic porous materials. However, COFs are currently synthesised by a few chemical reactions, limiting the access to and exploration of new structures and properties. The development of new reaction systems that avoid such limitations to expand structural diversity is highly desired. Here we report that COFs can be synthesised via a double-stage connection that polymerises various different building blocks into crystalline polygon architectures, leading to the development of a new type of COFs with enhanced structural complexity and diversity. We show that the double-stage approach not only controls the sequence of building blocks but also allows fine engineering of pore size and shape. This strategy is widely applicable to different polymerisation systems to yield hexagonal, tetragonal and rhombus COFs with predesigned pores and π-arrays. PMID:26456081

  19. Designed synthesis of double-stage two-dimensional covalent organic frameworks

    NASA Astrophysics Data System (ADS)

    Chen, Xiong; Addicoat, Matthew; Jin, Enquan; Xu, Hong; Hayashi, Taku; Xu, Fei; Huang, Ning; Irle, Stephan; Jiang, Donglin

    2015-10-01

    Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers in which organic building blocks are covalently and topologically linked to form extended crystalline polygon structures, constituting a new platform for designing π-electronic porous materials. However, COFs are currently synthesised by a few chemical reactions, limiting the access to and exploration of new structures and properties. The development of new reaction systems that avoid such limitations to expand structural diversity is highly desired. Here we report that COFs can be synthesised via a double-stage connection that polymerises various different building blocks into crystalline polygon architectures, leading to the development of a new type of COFs with enhanced structural complexity and diversity. We show that the double-stage approach not only controls the sequence of building blocks but also allows fine engineering of pore size and shape. This strategy is widely applicable to different polymerisation systems to yield hexagonal, tetragonal and rhombus COFs with predesigned pores and π-arrays.

  20. Covalent Organic Frameworks as a Decorating Platform for Utilization and Affinity Enhancement of Chelating Sites for Radionuclide Sequestration

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

    Sun, Qi; Aguila, Briana; Earl, Lyndsey D.

    The potential consequences of nuclear events and the complexity of nuclear waste management motivate the development of selective solid-phase sorbents to provide enhanced protection. In this paper, it is shown that 2D covalent organic frameworks (COFs) with unique structures possess all the traits to be well suited as a platform for the deployment of highly efficient sorbents such that they exhibit remarkable performance, as demonstrated by uranium capture. The chelating groups laced on the open 1D channels exhibit exceptional accessibility, allowing significantly higher utilization efficiency. In addition, the 2D extended polygons packed closely in an eclipsed fashion bring chelating groupsmore » in adjacent layers parallel to each other, which may facilitate their cooperation, thereby leading to high affinity toward specific ions. As a result, the amidoxime-functionalized COFs far outperform their corresponding amorphous analogs in terms of adsorption capacities, kinetics, and affinities. Specifically, COF-TpAb-AO is able to reduce various uranium contaminated water samples from 1 ppm to less than 0.1 ppb within several minutes, well below the drinking water limit (30 ppb), as well as mine uranium from spiked seawater with an exceptionally high uptake capacity of 127 mg g -1. Finally, these results delineate important synthetic advances toward the implementation of COFs in environmental remediation.« less

  1. Covalent Organic Frameworks as a Decorating Platform for Utilization and Affinity Enhancement of Chelating Sites for Radionuclide Sequestration

    DOE PAGES

    Sun, Qi; Aguila, Briana; Earl, Lyndsey D.; ...

    2018-03-27

    The potential consequences of nuclear events and the complexity of nuclear waste management motivate the development of selective solid-phase sorbents to provide enhanced protection. In this paper, it is shown that 2D covalent organic frameworks (COFs) with unique structures possess all the traits to be well suited as a platform for the deployment of highly efficient sorbents such that they exhibit remarkable performance, as demonstrated by uranium capture. The chelating groups laced on the open 1D channels exhibit exceptional accessibility, allowing significantly higher utilization efficiency. In addition, the 2D extended polygons packed closely in an eclipsed fashion bring chelating groupsmore » in adjacent layers parallel to each other, which may facilitate their cooperation, thereby leading to high affinity toward specific ions. As a result, the amidoxime-functionalized COFs far outperform their corresponding amorphous analogs in terms of adsorption capacities, kinetics, and affinities. Specifically, COF-TpAb-AO is able to reduce various uranium contaminated water samples from 1 ppm to less than 0.1 ppb within several minutes, well below the drinking water limit (30 ppb), as well as mine uranium from spiked seawater with an exceptionally high uptake capacity of 127 mg g -1. Finally, these results delineate important synthetic advances toward the implementation of COFs in environmental remediation.« less

  2. Lewis Acidity of Bis(perfluorocatecholato)silane: Aldehyde Hydrosilylation Catalyzed by a Neutral Silicon Compound

    DOE PAGES

    Liberman-Martin, Allegra L.; Bergman, Robert G.; Tilley, T. Don

    2015-04-16

    Bis(perfluorocatecholato)silane Si(cat( F) 2 was prepared, and stoichiometric binding to Lewis bases was demonstrated with fluoride, triethylphosphine oxide, and N,N'-diisopropylbenzamide. The potent Lewis acidity of Si(cat( F) 2 was suggested from catalytic hydrosilylation and silylcyanation reactions with aldehydes. Mechanistic studies of hydrosilylation using an optically active silane substrate, R-(+)-methyl-(1-naphthyl)phenylsilane, proceeded with predominant stereochemical retention at silicon, consistent with a carbonyl activation pathway. The enantiospecificity was dependent on solvent and salt effects, with increasing solvent polarity or addition of NBu 4BAr( F) 4 leading to a diminished enantiomeric ratio. The medium effects are consistent with an ionic mechanism, wherein hydride transfermore » occurs prior to silicon-oxygen bond formation.« less

  3. Using Radar and Seismic Methods for the Determination of Ice Column Properties and Basal Conditions at Jakobshavn Isbrae and the NEEM Drill Site

    NASA Astrophysics Data System (ADS)

    Velez Gonzalez, Jose A.

    The development of preferred crystal orientation fabrics (COF) within the ice column can have a strong influence on the flow behavior of an ice sheet or glacier. Typically, COF information comes from ice cores. Observations of anisotropic seismic wave propagation and backscatter variation as a function of antenna orientation in GPR measurements have been proposed as methods to detect COF. For this investigation I evaluate the effectiveness of the GPR and seismic methods to detect COF by conducting a seismic and GPR experiment at the North Greenland Eemian Ice Drilling facility (NEEM) ice core location, where COF data is available. The seismic experiment was conducted 6.5 km North West of the NEEM facility and consisted of three multi-offset seismic gathers. The results of the anisotropy analysis conducted at NEEM yielded mean c-axes distributed over a conical region of I angle of 30 to 32 degrees. No internal ice reflectors were imaged. Direct COF measurements collected in the ice core are in agreement with the results from the seismic anisotropy analysis. The GPR experiment covered an area of 100 km2 and consisted of parallel, perpendicular, oblique and circular (radius: 35 m) acquisition patterns. Results show evidence for COF for the entire 100 km2 area. Furthermore, for the first time it was possible to image three different COF (random, disk and single maxima) and their respective transition zones. The interpretation of the GPR experiment showed a strong correlation with the ice core measurements. Glacier basal drag is also an important, and difficult to predict, property that influences glacier flow. For this investigation I re-processed a 10 km-long high-resolution reflection seismic line at Jakobshavn Isbrae, Greenland, using an iterative velocity determination approach for optimizing sub-glacier imaging. The resultant line imaged a sub-glacier sediment layer ranging in thickness between 35 and 200 meters. I interpret three distinct seismic facies based on the geometry of the reflectors as a basal till layer, accreted sediments and re-worked till. The basal till and accreted sediments vary in thickness between 4 and 93 meters and are thought to be water-saturated actively-deforming sub-glacier sediments. A polarity reversal observed at one location along the ice-sediment interface suggests the presence of water saturated sediments or water ponding 2-4 m thick spanning approximately 240 m across. Using information from the seismic line (bed geometry, ice thickness, till thickness) as well as information available for the area of study (ice surface elevation and ice flow velocity) we evaluate the effect of sub-glacier sediment viscosity on the basal drag using a linearly viscous model and the assumption of a deforming bed. Basal drag values estimated for the study area fall within the range of physically acceptable values. However, the analysis revealed that the assumption of a deforming bed might not be compatible for the area of study given the presence of water at the ice/bed interface.

  4. Micro- and macroscale coefficients of friction of cementitious materials

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

    Lomboy, Gilson; Sundararajan, Sriram, E-mail: srirams@iastate.edu; Wang, Kejin

    2013-12-15

    Millions of metric tons of cementitious materials are produced, transported and used in construction each year. The ease or difficulty of handling cementitious materials is greatly influenced by the material friction properties. In the present study, the coefficients of friction of cementitious materials were measured at the microscale and macroscale. The materials tested were commercially-available Portland cement, Class C fly ash, and ground granulated blast furnace slag. At the microscale, the coefficient of friction was determined from the interaction forces between cementitious particles using an Atomic Force Microscope. At the macroscale, the coefficient of friction was determined from stresses onmore » bulk cementitious materials under direct shear. The study indicated that the microscale coefficient of friction ranged from 0.020 to 0.059, and the macroscale coefficient of friction ranged from 0.56 to 0.75. The fly ash studied had the highest microscale coefficient of friction and the lowest macroscale coefficient of friction. -- Highlights: •Microscale (interparticle) coefficient of friction (COF) was determined with AFM. •Macroscale (bulk) COF was measured under direct shear. •Fly ash had the highest microscale COF and the lowest macroscale COF. •Portland cement against GGBFS had the lowest microscale COF. •Portland cement against Portland cement had the highest macroscale COF.« less

  5. Using intranet-based order sets to standardize clinical care and prepare for computerized physician order entry.

    PubMed

    Heffner, John E; Brower, Kathleen; Ellis, Rosemary; Brown, Shirley

    2004-07-01

    The high cost of computerized physician order entry (CPOE) and physician resistance to standardized care have delayed implementation. An intranet-based order set system can provide some of CPOE's benefits and offer opportunities to acculturate physicians toward standardized care. INTRANET CLINICIAN ORDER FORMS (COF): The COF system at the Medical University of South Carolina (MUSC) allows caregivers to enter and print orders through the intranet at points of care and to access decision support resources. Work on COF began in March 2000 with transfer of 25 MUSC paper-based order set forms to an intranet site. Physician groups developed additional order sets, which number more than 200. Web traffic increased progressively during a 24-month period, peaking at more than 6,400 hits per month to COF. Decision support tools improved compliance with Centers for Medicare & Medicaid Services core indicators. Clinicians demonstrated a willingness to develop and use order sets and decision support tools posted on the COF site. COF provides a low-cost method for preparing caregivers and institutions to adopt CPOE and standardization of care. The educational resources, relevant links to external resources, and communication alerts will all link to CPOE, thereby providing a head start in CPOE implementation.

  6. Association between Chinese cooking oil fumes and sleep quality among a middle-aged Chinese population.

    PubMed

    Wei, Fu; Nie, Guanghui; Zhou, Bo; Wang, Liang; Ma, Yifei; Peng, Suwan; Ou, Songfeng; Qin, Jian; Zhang, Li'e; Li, Shu; Zou, Ruosi; Zeng, Xiaoyun; Zhang, Zhiyong; Zou, Yunfeng

    2017-08-01

    Poor sleep quality is an important symptom of many medical or psychiatric disorders. However, the impact of cooking oil fumes (COFs) on sleep quality has not been studied. This population-based cross-sectional study was conducted to examine the association between COFs of Chinese household cooking and sleep quality. Individual sleep quality assessment was completed in 2197 participants with an average age of 37.52 years, through Pittsburgh Sleep Quality Index (PSQI). Information about their cooking practice were also collected by self-reported questionnaire. As an internal biomarker of COFs, urinary 1-hydroxypyrene (1-HOP) (n = 562) was further measured using high-performance liquid chromatography. Binary logistic regression models were performed to evaluate the association between exposure to COFs and individual sleep quality. We found that, subjective poor kitchen ventilation, preheating oil to smoking, and cooking for over 30 minutes were positively associated with overall poor sleep quality (global PSQI score >5) [odds ratio (OR) = 1.75, 95% confidence interval (CI) = 1.43-2.16; 1.25, (1.03-1.52); 1.42, (1.15-1.76), respectively]. After adjusting for potential confounders, subjective poor kitchen ventilation still tend to increase the risk of long sleep latency, sleep disturbances, and daytime dysfunction [OR = 1.37, 95% CI = 1.09-1.73; 1.91, (1.39-2.61); 1.54, (1.23-1.93), respectively]. Similar results were observed in participants who preheated oil to smoking [OR = 1.36, 95% CI = 1.08-1.72; 1.55, (1.14-2.14); 1.25, (1.02-1.55), respectively] and cooked for over 30 minutes [OR = 1.34, 95% CI = 1.05-1.72; 1.46, (1.03-2.06); 1.36, (1.08-1.72), respectively]. Furthermore, high urinary 1-HOP level was also positively associated with overall poor sleep quality (OR = 2.30, 95% CI = 1.31-4.05). The results indicated that exposure to COFs from Chinese household cooking may be a risk factor for poor sleep quality among middle-aged Chinese population. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Wear Mechanism Maps for Magnesium Alloy AM60 and Composite AM60-9% (Al2O3)f

    NASA Astrophysics Data System (ADS)

    Ullah Khan, Muhammad Zafar

    The purpose of this work was to study the tribological behaviour of squeeze cast Mg alloy AM60 and its composite AM60-9% (Al2O3) f. Dry sliding wear tests were performed on specimens of these materials using a block-on-ring tribometer which was equipped with a COF and temperature measurement system. Wear, COF and temperature maps were constructed to illustrate the effect of temperature and COF on the wear behaviour of the Mg alloy and it's composite. Four wear regimes namely low, mild, transient and severe wear were identified. The transition from mild to severe wear regime was found to be dependent on the bulk temperature of the specimen. Oxidational wear prevailed in low and mild wear whereas plastic deformation induced wear and melt wear controlled the wear rates in transient and severe wear regimes, respectively. This study shows that the incorporation of Al2O3 fibres in AM60 alloy improved the wear resistance of the resulting composite by delaying the transition from mild to severe wear.

  8. Giant cemento-ossifying fibroma of the maxilla.

    PubMed

    Unal, Adnan; Yurtsever Kum, Nurcan; Kum, Rauf Oguzhan; Erdogan, Aysun; Ciliz, Deniz Sozmen; Guresci, Servet; Ozcan, Muge

    2015-11-14

    Fibro-osseous lesions of the skull and facial bones are benign tumors, but they can be mistaken for malignant tumors due to their clinically aggressive behavior. Cemento-ossifying fibroma (COF) is a benign fibro-osseous lesion characterized by slow growth and fibrous and calcified tissue content. COFs are locally destructive lesions causing deformities in the bones. The recurrence risk is high if they are not completely removed. In this case report we describe a giant COF mimicking chondrosarcoma in the oral cavity of a 55-year-old woman causing significant facial deformity and feeding problems. Giant COF occurs rarely in the jaws and given that this lesion has similar imaging and clinical features to several other tumors, the diagnosis is always a challenge for clinicians, radiologists and pathologists.

  9. A tunable azine covalent organic framework platform for visible light-induced hydrogen generation

    PubMed Central

    Vyas, Vijay S.; Haase, Frederik; Stegbauer, Linus; Savasci, Gökcen; Podjaski, Filip; Ochsenfeld, Christian; Lotsch, Bettina V.

    2015-01-01

    Hydrogen evolution from photocatalytic reduction of water holds promise as a sustainable source of carbon-free energy. Covalent organic frameworks (COFs) present an interesting new class of photoactive materials, which combine three key features relevant to the photocatalytic process, namely crystallinity, porosity and tunability. Here we synthesize a series of water- and photostable 2D azine-linked COFs from hydrazine and triphenylarene aldehydes with varying number of nitrogen atoms. The electronic and steric variations in the precursors are transferred to the resulting frameworks, thus leading to a progressively enhanced light-induced hydrogen evolution with increasing nitrogen content in the frameworks. Our results demonstrate that by the rational design of COFs on a molecular level, it is possible to precisely adjust their structural and optoelectronic properties, thus resulting in enhanced photocatalytic activities. This is expected to spur further interest in these photofunctional frameworks where rational supramolecular engineering may lead to new material applications. PMID:26419805

  10. Tribology study on TiB2+WSi2 composite against WC

    NASA Astrophysics Data System (ADS)

    Murthy, T. S. R. Ch.; Basha, M. M.; Sonber, J. K.; Singh, K.; Raju, K.; Sairam, K.; Nagaraj, A.; Majumdar, S.; Rao, G. V. S. Nageswara; Kain, Vivekanand

    2018-04-01

    Titanium diboride (TiB2) is one of the potential material for green energy applications such as neutron absorber in high temperature/advanced nuclear reactors, receiver materials for second generation concentrated solar power. We developed the process flow sheet for synthesis and consolidation of various series of TiB2 based materials in our laboratory. Amongst these, TiB2+WSi2 exhibited better sinterability and oxidation resistance properties. In the present work, tribology properties of TiB2+2.5%WSi2 composite was studied against WC-Co ball using different normal loads (5, 10 and 20 N) and frequencies (10, 15 Hz) under dry condition. Coefficient of friction (COF) and wear rate was measured at all test conditions. Wear mechanism was analyzed by microstructural characterization. It was found that COF is decreased from 0.46 to 0.36 with increasing load (5 to 20 N) at 15 Hz frequency; whereas at 10 Hz frequency COF is measured a constant average value of 0.49. The specific wear rate measured was minimum at 5 N load and 15 Hz frequency combination and was found to be 2.84×10-6 mm3/N m. The wear mechanisms identified during reciprocative sliding wear of composite were abrasion and surface tribo-oxidative reactions with delamination from tribo-zone.

  11. Comparison of the frictional characteristics of aesthetic orthodontic brackets measured using a modified in vitro technique

    PubMed Central

    Arici, Nursel

    2015-01-01

    Objective The coefficients of friction (COFs) of aesthetic ceramic and stainless steel brackets used in conjunction with stainless steel archwires were investigated using a modified linear tribometer and special computer software, and the effects of the bracket slot size (0.018 inches [in] or 0.022 in) and materials (ceramic or metal) on the COF were determined. Methods Four types of ceramic (one with a stainless steel slot) and one conventional stainless steel bracket were tested with two types of archwire sizes: a 0.017 × 0.025-in wire in the 0.018-in slots and a 0.019 × 0.025-in wire in the 0.022-in slot brackets. For pairwise comparisons between the 0.018-in and 0.022-in slot sizes in the same bracket, an independent sample t-test was used. One-way and two-way analysis of variance (ANOVA) and Tukey's post-hoc test at the 95% confidence level (α = 0.05) were also used for statistical analyses. Results There were significant differences between the 0.022-in and 0.018-in slot sizes for the same brand of bracket. ANOVA also showed that both slot size and bracket slot material had significant effects on COF values (p < 0.001). The ceramic bracket with a 0.022-in stainless steel slot showed the lowest mean COF (µ = 0.18), followed by the conventional stainless steel bracket with a 0.022-in slot (µ = 0.21). The monocrystalline alumina ceramic bracket with a 0.018-in slot had the highest COF (µ = 0.85). Conclusions Brackets with stainless steel slots exhibit lower COFs than ceramic slot brackets. All brackets show lower COFs as the slot size increases. PMID:25667915

  12. Effects of cooking method, cooking oil, and food type on aldehyde emissions in cooking oil fumes.

    PubMed

    Peng, Chiung-Yu; Lan, Cheng-Hang; Lin, Pei-Chen; Kuo, Yi-Chun

    2017-02-15

    Cooking oil fumes (COFs) contain a mixture of chemicals. Of all chemicals, aldehydes draw a great attention since several of them are considered carcinogenic and formation of long-chain aldehydes is related to fatty acids in cooking oils. The objectives of this research were to compare aldehyde compositions and concentrations in COFs produced by different cooking oils, cooking methods, and food types and to suggest better cooking practices. This study compared aldehydes in COFs produced using four cooking oils (palm oil, rapeseed oil, sunflower oil, and soybean oil), three cooking methods (stir frying, pan frying, and deep frying), and two foods (potato and pork loin) in a typical kitchen. Results showed the highest total aldehyde emissions in cooking methods were produced by deep frying, followed by pan frying then by stir frying. Sunflower oil had the highest emissions of total aldehydes, regardless of cooking method and food type whereas rapeseed oil and palm oil had relatively lower emissions. This study suggests that using gentle cooking methods (e.g., stir frying) and using oils low in unsaturated fatty acids (e.g., palm oil or rapeseed oil) can reduce the production of aldehydes in COFs, especially long-chain aldehydes such as hexanal and t,t-2,4-DDE. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Domain structure and reorientation in CoF e2O4

    NASA Astrophysics Data System (ADS)

    Abes, M.; Koops, C. T.; Hrkac, S. B.; McCord, J.; Urs, N. O.; Wolff, N.; Kienle, L.; Ren, W. J.; Bouchenoire, L.; Murphy, B. M.; Magnussen, O. M.

    2016-05-01

    The microscopic processes underlying magnetostriction in ferrites were studied for the case of CoF e2O4 single crystals by high-resolution in situ x-ray diffraction and complementary magnetic microscopy techniques. The data support the reports of Yang and Ren [Phys. Rev. B 77, 014407 (2008), 10.1103/PhysRevB.77.014407] that magnetostriction in these materials originates from the switching of crystallographic domains, similar to ferroelastic or ferroelectric domain switching, and reveals the presence of two coexisting tetragonal spinel structures, corresponding to domains of high and of low strain. The latter alternate in the crystal, separated by 90° domain boundaries, and can be explained by the effect of internal stress emerging during the transition into the ferrimagnetic phase. During magnetization of the sample two structural transitions are observed: a conversion of the transversal into axial domains at 1.95 kOe and a growth of the high-strain domains at the cost of the low-strain axial domains at 2.8 kOe. These microscopic changes are in good agreement with the macroscopic magnetization and magnetostriction behavior of CoF e2O4 .

  14. Chemical Makeup and Hydrophilic Behavior of Graphene Oxide Nanoribbons after Low-Temperature Fluorination.

    PubMed

    Romero Aburto, Rebeca; Alemany, Lawrence B; Weldeghiorghis, Thomas K; Ozden, Sehmus; Peng, Zhiwei; Lherbier, Aurélien; Botello Méndez, Andrés Rafael; Tiwary, Chandra Sekhar; Taha-Tijerina, Jaime; Yan, Zheng; Tabata, Mika; Charlier, Jean-Christophe; Tour, James M; Ajayan, Pulickel M

    2015-07-28

    Here we investigated the fluorination of graphene oxide nanoribbons (GONRs) using H2 and F2 gases at low temperature, below 200 °C, with the purpose of elucidating their structure and predicting a fluorination mechanism. The importance of this study is the understanding of how fluorine functional groups are incorporated in complex structures, such as GONRs, as a function of temperature. The insight provided herein can potentially help engineer application-oriented materials for several research and industrial sectors. Direct (13)C pulse magic angle spinning (MAS) nuclear magnetic resonance (NMR) confirmed the presence of epoxy, hydroxyl, ester and ketone carbonyl, tertiary alkyl fluorides, as well as graphitic sp(2)-hybridized carbon. Moreover, (19)F-(13)C cross-polarization MAS NMR with (1)H and (19)F decoupling confirmed the presence of secondary alkyl fluoride (CF2) groups in the fluorinated graphene oxide nanoribbon (FGONR) structures fluorinated above 50 °C. First-principles density functional theory calculations gained insight into the atomic arrangement of the most dominant chemical groups. The fluorinated GONRs present atomic fluorine percentages in the range of 6-35. Interestingly, the FGONRs synthesized up to 100 °C, with 6-19% of atomic fluorine, exhibit colloidal similar stability in aqueous environments when compared to GONRs. This colloidal stability is important because it is not common for materials with up to 19% fluorine to have a high degree of hydrophilicity.

  15. Friction Reduction in Powertrain Materials: Role of Tribolayers

    NASA Astrophysics Data System (ADS)

    Banerji, Anindya

    This study aims at understanding the micromechanisms responsible for reduction in friction and wear in the engine cylinder bore/liner materials when tested under lubricated and unlubricated conditions. The tribolayers formed in-situ during sliding contact are unique to each tribosystem and a detailed study of these tribolayers will shed light on the friction reduction mechanisms in powertrain materials. Boundary lubricated tribological performance of grey cast iron (CI) tested against non-hydrogenated diamond-like carbon coating (NH-DLC) resulted in 21% lower coefficient of friction (COF) and an order of magnitude lower volumetric wear compared to CI and steel counterfaces. Dilution of the engine oil by ethanol containing E85 biofuel, consisting of 85% ethanol and 15% gasoline, was beneficial as COF and volumetric wear losses were further reduced. TEM/EELS studies of the NH-DLC counterface provided evidence for OH adsorption of the dangling carbon bonds at the coating surface leading to low friction. Advantage of E85/engine oil blend was also evident during boundary lubricated sliding of eutectic Al-12.6% Si alloy against AISI 52100 steel. The oil residue layer (ORL) formed during boundary lubricated sliding incorporated nanocrystalline regions of Al, Si, ZnS, AlPO4 and ZnO surrounded by amorphous carbon regions. Higher proportions of Zn, S, and P antiwear compounds formed in the ORL when tested using the E85/oil (1:1) blend compared to the unmixed engine oil as the hydroxyl groups in ethanol molecules facilitated ZDDP degradation. Mico-Raman spectroscopy indicated two types of tribolayers formed during unlubricated sliding of thermally sprayed low carbon steel 1010 coating deposited on linerless Al 380 cylinder bore: i) Fe2O3 layer transformed from FeO during dry sliding and ii) Fe2O3 layer with a top amorphous carbon transfer layer when run against H-DLC coated TCR with COF of 0.18. The NH- and H-DLC coatings, that provide low friction under room temperature conditions, fail at temperatures > 200 °C. It was shown that W containing DLC (W-DLC) coatings offered low and stable COF of 0.07 at 400 °C while a Ti incorporated multilayer MoS2 (Ti-MoS2) coating maintained COF between 0.11 at 25 °C to 0.13 at 350 °C. The low friction provided by these coatings was attributed to formation of high temperature lubricious oxides: tungsten trioxide (WO3) in case of W-DLC and MoO3 in case of MoS2, as revealed by Raman analyses of the tribolayers formed on counterface surfaces. Tribolayer formation during sliding friction of multuilayered graphene (MLG), a potential lubricant, depended on the material transfer and relative humidity (RH). Sliding friction tests performed on MLG in air (10- 45% RH) and under a dry N2 atmosphere showed that progressively lower friction values were observed when the RH was increased, with maximum COF of 0.52 in dry N2 and lowest COF of about 0.10 at 45% RH. Microstructural studies including cross-sectional FIB/HR-TEM determined that sliding induced defects which comprised of edge fracture, fragmented/bent graphene stacks compared to pristine graphene and disordered regions between them. In summary, this work shows that delineating the micromechanisms responsible for reduction in friction and wear is critical for development of appropriate materials and coatings for powertrain components.

  16. The impact of surface and geometry on coefficient of friction of artificial hip joints.

    PubMed

    Choudhury, Dipankar; Vrbka, Martin; Mamat, Azuddin Bin; Stavness, Ian; Roy, Chanchal K; Mootanah, Rajshree; Krupka, Ivan

    2017-08-01

    Coefficient of friction (COF) tests were conducted on 28-mm and 36-mm-diameter hip joint prostheses for four different material combinations, with or without the presence of Ultra High Molecular Weight Polyethylene (UHMWPE) particles using a novel pendulum hip simulator. The effects of three micro dimpled arrays on femoral head against a polyethylene and a metallic cup were also investigated. Clearance played a vital role in the COF of ceramic on polyethylene and ceramic on ceramic artificial hip joints. Micro dimpled metallic femoral heads yielded higher COF against a polyethylene cup; however, with metal on metal prostheses the dimpled arrays significantly reduced the COF. In situ images revealed evidence that the dimple arrays enhanced film formation, which was the main mechanism that contributed to reduced friction. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Emergence of multi-acaricide resistant Rhipicephalus ticks and its implication on chemical tick control in Uganda.

    PubMed

    Vudriko, Patrick; Okwee-Acai, James; Tayebwa, Dickson Stuart; Byaruhanga, Joseph; Kakooza, Steven; Wampande, Edward; Omara, Robert; Muhindo, Jeanne Bukeka; Tweyongyere, Robert; Owiny, David Okello; Hatta, Takeshi; Tsuji, Naotoshi; Umemiya-Shirafuji, Rika; Xuan, Xuenan; Kanameda, Masaharu; Fujisaki, Kozo; Suzuki, Hiroshi

    2016-01-04

    Acaricide failure has been on the rise in the western and central cattle corridor of Uganda. In this study, we identified the tick species associated with acaricide failure and determined their susceptibility to various acaricide molecules used for tick control in Uganda. In this cross sectional study, tick samples were collected and identified to species level from 54 purposively selected farms (from 17 districts) that mostly had a history of acaricide failure. Larval packet test was used to screen 31 tick populations from 30 farms for susceptibility at discriminating dose (DD) and 2 × DD of five panels of commercial acaricide molecules belonging to the following classes; amidine, synthetic pyrethroid (SP), organophosphate (OP) and OP-SP co-formulations (COF). Resistance was assessed based on World Health Organization criteria for screening insecticide resistance. Of the 1357 ticks identified, Rhipicephalus (Rhipicephalus) appendiculatus and Rhipicephalus (Boophilus) decoloratus were the major (95.6%) tick species in farms sampled. Resistance against SP was detected in 90.0% (27/30) of the tick populations tested. Worryingly, 60.0% (18/30) and 63.0% (19/30) of the above ticks were super resistant (0% mortality) against 2 × DD cypermethrin and deltamethrin, respectively. Resistance was also detected against COF (43.3%), OP chlorfenvinphos (13.3%) and amitraz (12.9%). In two years, 74.1% (20/27) of the farms had used two to three acaricide molecules, and 55.6% (15/27) rotated the molecules wrongly. Multi-acaricide resistance (at least 2 molecules) was detected in 55.2% (16/29) of the resistant Rhipicephalus ticks and significantly associated with R. decoloratus (p = 0.0133), use of both SP and COF in the last 2 years (p < 0.001) and Kiruhura district (p = 0.0339). Despite emergence of amitraz resistance in the greater Bushenyi area, it was the most efficacious molecule against SP and COF resistant ticks. This study is the first to report emergence of super SP resistant and multi-acaricide resistant Rhipicephalus ticks in Uganda. Amitraz was the best acaricide against SP and COF resistant ticks. However, in the absence of technical interventions, farmer-led solutions aimed at troubleshooting for efficacy of multitude of acaricides at their disposal are expected to potentially cause negative collateral effects on future chemical tick control options, animal welfare and public health.

  18. Tribological evaluation of biomedical polycarbonate urethanes against articular cartilage.

    PubMed

    Kanca, Yusuf; Milner, Piers; Dini, Daniele; Amis, Andrew A

    2018-06-01

    This research investigated the in-vitro wear and friction performance of polycarbonate urethane (PCU) 80A as they interact with articular cartilage, using a customised multidirectional pin-on-plate tester. Condyles were articulated against PCU 80A discs (Bionate ® I and Bionate ® II) (configuration 1) and the results arising from these tests were compared to those recorded during the sliding of PCU pins against cartilage plates (configuration 2). Configuration 1 produced steadily increasing coefficient of friction (COF) (up to 0.64 ± 0.05) and had the same trend as the cartilage-on-stainless steel articulation (positive control). When synovial fluid rather than bovine calf serum was used as lubricant, average COF significantly decreased from 0.50 ± 0.02-0.38 ± 0.06 for condyle-on-Bionate ® I (80AI) and from 0.41 ± 0.02-0.24 ± 0.04 for condyle-on-Bionate ® II (80AII) test configurations (p < 0.05). After 15 h testing, the cartilage-on-cartilage articulation (negative control) tests showed no cartilage degeneration. However, different levels of cartilage volume loss were found on the condyles from the positive control (12.5 ± 4.2 mm 3 ) and the PCUs (20.1 ± 3.6 mm 3 for 80 AI and 19.0 ± 2.3 mm 3 for 80AII) (p > 0.05). A good correlation (R 2 =0.84) was found between the levels of average COF and the volume of cartilage lost during testing; increasing wear was found at higher levels of COF. Configuration 2 showed low and constant COF values (0.04 ± 0.01), which were closer to the negative control (0.03 ± 0.01) and significantly lower than configuration 1 (p < 0.05). The investigation showed that PCU is a good candidate for use in hemiarthroplasty components, where only one of the two articulating surfaces is replaced, as long as the synthetic material is implanted in a region where migrating cartilage contact is achieved. Bionate ® II showed better tribological performance, which suggests it is more favourable for use in hemiarthroplasty design. Copyright © 2018 Elsevier Ltd. All rights reserved.

  19. Integration of chemical scrubber with sodium hypochlorite and surfactant for removal of hydrocarbons in cooking oil fume.

    PubMed

    Cheng, Hsin-Han; Hsieh, Chu-Chin

    2010-10-15

    There are many types of technologies to control cooking oil fumes (COFs), but current typical technologies, such as electrostatic precipitator, conventional scrubber, catalyst, or condenser, are unable to efficiently remove the odorous materials present in COFs which are the primary cause of odor-complaint cases. There is also a lack of information about using sodium hypochlorite (NaOCl) and surfactants to remove contaminants in COFs, and previous studies lack on-site investigations in restaurants. This study presents a chemical scrubber integrated with an automatic control system (ACS) to treat hydrocarbons (HCs) in COFs, and to monitor non-methane HCs (NMHC) and odor as indicators for its efficiency evaluation. The chemical scrubber effectively treats hydrophobic substances in COFs by combining surfactant and NaOCl under optimal operational conditions with NHMC removal efficiency as high as 85%. The mass transfer coefficient (K(L)a) of NMHC was enhanced by 50% under the NaOCl and surfactant conditions, as compared to typical wet scrubber. Further, this study establishes the fuzzy equations of the ACS, including the relationship between the removal efficiency and K(L)a, liquid/gas ratio, pH and C(NaOCl). 2010 Elsevier B.V. All rights reserved.

  20. Extraction of Photogenerated Electrons and Holes from a Covalent Organic Framework Integrated Heterojunction

    PubMed Central

    2014-01-01

    Covalent organic frameworks (COFs) offer a strategy to position molecular semiconductors within a rigid network in a highly controlled and predictable manner. The π-stacked columns of layered two-dimensional COFs enable electronic interactions between the COF sheets, thereby providing a path for exciton and charge carrier migration. Frameworks comprising two electronically separated subunits can form highly defined interdigitated donor–acceptor heterojunctions, which can drive the photogeneration of free charge carriers. Here we report the first example of a photovoltaic device that utilizes exclusively a crystalline organic framework with an inherent type II heterojunction as the active layer. The newly developed triphenylene–porphyrin COF was grown as an oriented thin film with the donor and acceptor units forming one-dimensional stacks that extend along the substrate normal, thus providing an optimal geometry for charge carrier transport. As a result of the degree of morphological precision that can be achieved with COFs and the enormous diversity of functional molecular building blocks that can be used to construct the frameworks, these materials show great potential as model systems for organic heterojunctions and might ultimately provide an alternative to the current disordered bulk heterojunctions. PMID:25412210

  1. Selective chromo-fluorogenic detection of DFP (a Sarin and Soman mimic) and DCNP (a Tabun mimic) with a unique probe based on a boron dipyrromethene (BODIPY) dye.

    PubMed

    Barba-Bon, Andrea; Costero, Ana M; Gil, Salvador; Martínez-Máñez, Ramón; Sancenón, Félix

    2014-11-21

    A novel colorimetric probe (P4) for the selective differential detection of DFP (a Sarin and Soman mimic) and DCNP (a Tabun mimic) was prepared. Probe P4 contains three reactive sites; i.e. (i) a nucleophilic phenol group able to undergo phosphorylation with nerve gases, (ii) a carbonyl group as a reactive site for cyanide; and (iii) a triisopropylsilyl (TIPS) protecting group that is known to react with fluoride. The reaction of P4 with DCNP in acetonitrile resulted in both the phosphorylation of the phenoxy group and the release of cyanide, which was able to react with the carbonyl group of P4 to produce a colour modulation from pink to orange. In contrast, phosphorylation of P4 with DFP in acetonitrile released fluoride that hydrolysed the TIPS group in P4 to yield a colour change from pink to blue. Probe P4 was able to discriminate between DFP and DCNP with remarkable sensitivity; limits of detection of 0.36 and 0.40 ppm for DCNP and DFP, respectively, were calculated. Besides, no interference from other organophosphorous derivatives or with presence of acid was observed. The sensing behaviour of P4 was also retained when incorporated into silica gel plates or onto polyethylene oxide membranes, which allowed the development of simple test strips for the colorimetric detection of DCNP and DFP in the vapour phase. P4 is the first probe capable of colorimetrically differentiating between a Tabun mimic (DCNP) and a Sarin and Soman mimic (DFP).

  2. Electronic structure and magnetic anisotropies of antiferromagnetic transition-metal difluorides

    NASA Astrophysics Data System (ADS)

    Corrêa, Cinthia Antunes; Výborný, Karel

    2018-06-01

    We compare calculations based on density functional theory (DFT) with available experimental data and analyze the origin of magnetic anisotropies in MnF2, FeF2, CoF2, and NiF2. We confirm that the magnetic anisotropy of MnF2 stems almost completely from the dipolar interaction, while magnetocrystalline anisotropy energy (originating in spin-orbit interaction) plays a dominant role in the other three compounds, and discuss how it depends on the details of band structure. The latter is critically compared to available optical measurements. The case of CoF2, where magnetocrystalline anisotropy energy strongly depends on U (the Hubbard parameter in DFT +U ), is put into contrast with FeF2 where theoretical predictions of magnetic anisotropies are nearly quantitative.

  3. Covalent Organic Framework Functionalized with 8-Hydroxyquinoline as a Dual-Mode Fluorescent and Colorimetric pH Sensor.

    PubMed

    Chen, Long; He, Linwei; Ma, Fuyin; Liu, Wei; Wang, Yaxing; Silver, Mark A; Chen, Lanhua; Zhu, Lin; Gui, Daxiang; Diwu, Juan; Chai, Zhifang; Wang, Shuao

    2018-05-09

    Real-time and accurate detection of pH in aqueous solution is of great significance in chemical, environmental, and engineering-related fields. We report here the use of 8-hydroxyquinoline-functionalized covalent organic framework (COF-HQ) for dual-mode pH sensing. In the fluorescent mode, the emission intensity of COF-HQ weakened as the pH decreased, and also displayed a good linear relationship against pH in the range from 1 to 5. In addition, COF-HQ showed discernible color changes from yellow to black as the acidity increased and can be therefore used as a colorimetric pH sensor. All these changes are reversible and COF-HQ can be recycled for multiple detection runs owing to its high hydrolytical stability. It can be further assembled into a mixed matrix membrane for practical applications.

  4. Highly Microporous Nitrogen-doped Carbon Synthesized from Azine-linked Covalent Organic Framework and its Supercapacitor Function.

    PubMed

    Kim, Gayoung; Yang, Jun; Nakashima, Naotoshi; Shiraki, Tomohiro

    2017-12-11

    Porous carbons with nitrogen-doped (N-doped) structures are promising materials for advanced energy conversion and storage applications, including supercapacitors and fuel cell catalysts. In this study, microporous N-doped carbon was successfully fabricated through carbonization of covalent organic frameworks (COFs) with an azine-linked two-dimensional molecular network (ACOF1). In the carbonized ACOF1, micropores with diameters smaller than 1 nm are selectively formed, and a high specific surface area (1596 cm 2  g -1 ) is achieved. In addition, the highly porous structure with N-doped sites results in enhancement of the electrochemical capacitance. Detailed investigation for the micropore-forming process reveals that the formation of nitrogen gas during the thermal degradation of the azine bond contributes to the microporous structure formation. Therefore, the present direct carbonization approach using COFs allows the fabrication of microporous heteroatom-doped carbons, based on molecularly designed COFs, toward future electrochemical and energy applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Role of humidity in reducing the friction of graphene layers on textured surfaces

    NASA Astrophysics Data System (ADS)

    Li, Zheng-yang; Yang, Wen-jing; Wu, Yan-ping; Wu, Song-bo; Cai, Zhen-bing

    2017-05-01

    A multiple-layer graphene was prepared on steel surface to reduce friction and wear. A graphene-containing ethanol solution was dripped on the steel surface, and several layers of graphene flakes were deposited on the surface after ethanol evaporated. Tribological performance of graphene-contained surface (GCS) was induced by reciprocating ball against plate contact in different RH (0% (dry nitrogen), 30%, 60%, and 90%). Morphology and wear scar were analyzed by OM, 2D profile, SEM, Raman spectroscopy, and XPS. Results show that GCS can substantially reduce the wear and coefficient of friction (COF) in 60% relative humidity (RH). Low COF occurs due to graphene layer providing a small shear stress on the friction interface. Meanwhile, conditions of high RH and textured surface could make the low COF persist for a longer time. High moisture content can stabilize and protect the graphene C-network from damage due to water dissociative chemisorption with carbon dangling bonds, and the textured surface was attributed to release graphene layer stored in the dimple.

  6. An in vitro study of cartilage-meniscus tribology to understand the changes caused by a meniscus implant.

    PubMed

    Majd, Sara Ehsani; Rizqy, Aditya Iman; Kaper, Hans J; Schmidt, Tannin A; Kuijer, Roel; Sharma, Prashant K

    2017-07-01

    Active lifestyles increase the risk of meniscal injury. A permanent meniscus implant of polycarbonate urethane (PCU) is a promising treatment to postpone/prevent total knee arthroplasty. Study of the changes in articular cartilage tribology in the presence of PCU is essential in developing the optimum meniscus implant. Therefore, a cartilage-meniscus reciprocating, sliding model was developed in vitro, mimicking the stance and swing phases of the gait cycle. The meniscus was further replaced with PCU and surface-modified PCUs (with C18 chains, mono-functional polydimethylsiloxane groups and mono-functional polytetrafluoroethylene groups) to study the changes. The coefficient of friction (COF) was calculated, and cartilage wear was determined and quantified histologically. The cartilage-meniscus sliding resulted in low COF during both stance and swing (0.01< COF <0.12) and low wear of cartilage (scores <1). The cartilage-PCU sliding, during stance, revealed similar low COFs. But during swing, the COFs were high (average ∼1, maximum 1.6), indicating a breakdown in interstitial fluid pressurization lubrication and non-effective activation of the boundary lubrication. This may lead to wear of cartilage in long term. However, under the tested conditions the wear of cartilage against PCUs was not higher than its wear against meniscus, and the cartilage was occasionally damaged. The COF decreased with increasing the contact pressure (as-per a power equation) up to 1MPa. The changes in the surface modification of PCU did not affect PCU's tribological performance. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

  7. The effect of roughness, floor polish, water, oil and ice on underfoot friction: current safety footwear solings are less slip resistant than microcellular polyurethane.

    PubMed

    Manning, D P; Jones, C

    2001-04-01

    Research over a period of about 18 years has shown that a microcellular polyurethane known as AP66033 is the most slip-resistant safety footwear soling material on oily and wet surfaces. In recent years it has been replaced in commercially available footwear by a dual density polyurethane (DDP) which has a dense outer layer and a soft microcellular backing. This research programme has compared the slip resistance of AP66033 with DDP and some rubber solings. In addition, data were obtained on the effects of soling and floor roughness, and floor polish on slip resistance. Some data were also obtained for walking on ice. The coefficient of friction (CoF) of the solings was measured on 19 water wet surfaces in three conditions: (I) when the solings were new, (II) following abrasion to create maximum roughness and (III) after polishing. The CoF was measured on four oily surfaces after each of 11 abrasion or polishing treatments. The profound effects of the roughening of all soles and of floor roughness on the CoF were demonstrated for both wet and oily surfaces. The superior slip resistance of AP66033 was confirmed for oily and wet conditions; however, some rubbers not suitable for safety footwear achieved higher CoF values on wet floors. All of the floor polishes reduced the CoF of all floors when contaminated with water. The mean CoF of DDP solings was lower than the mean for AP66033 on wet and oily surfaces. No safety footwear soling provided adequate grip on dry ice and the CoF was reduced by water on the ice. A rubber used for rock climbing footwear was one of the most slip-resistant solings on wet surfaces in the laboratory but recorded the lowest CoF on ice. It is concluded that the incidence of occupational injuries caused by slipping could be reduced by the following: (A) returning to safety footwear soled with the microcellular polyurethane AP66033; (B) abrading all new and smooth footwear solings with a belt sanding machine coated with P100 grit; (C) avoiding the use of floor polish; (D) informing the general public about the poor slip resistance of ordinary footwear on ice and the lowering of slip resistance in cold weather.

  8. Microwave-assisted synthesis of highly fluorescent nanoparticles of a melamine-based porous covalent organic framework for trace-level detection of nitroaromatic explosives.

    PubMed

    Zhang, Wang; Qiu, Ling-Guang; Yuan, Yu-Peng; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

    2012-06-30

    Covalent organic frameworks (COFs) are a new generation of porous materials constructed from light elements linked by strong covalent bonds. Herein we present rapid preparation of highly fluorescent nanoparticles of a new type of COF, i.e. melamine-based porous polymeric network SNW-1, by a microwave-assisted synthesis route. Although the synthesis of SNW-1 has to be carried out at 180°C for 3d under conventional reflux conditions, SNW-1 nanoparticles could be obtained in 6h by using such a microwave-assisted method. The results obtained have clearly demonstrated that microwave-assisted synthesis is a simple yet highly efficient approach to nanoscale COFs or other porous polymeric materials. Remarkably, the as-synthesized SNW-1 nanoparticles exhibit extremely high sensitivity and selectivity, as well as fast response to nitroaromatic explosives such as 2,4,6-trinitrotoluene (TNT), 2,4,6-trinitrophenylmethylnitramine (Tetryl) and picric acid (PA) without interference by common organic solvents, which is due to the nanoscaled size and unique hierarchical porosity of such fluorescence-based sensing material. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Application of Cardio-O-Fix occluders for transcatheter closure of patent ductus arteriosus and interatrial communications: Preliminary experience.

    PubMed

    Białkowski, Jacek; Szkutnik, Małgorzata; Fiszer, Roland; Głowacki, Jan; Banaszak, Paweł; Zembala, Marian

    2010-01-01

    Transcatheter treatment has become the method of choice for treating many heart defects. Recently, Cardio-O-Fix occluder (COF) - a new, self-expandable nitinol wire-mesh device very similar to the Amplatzer device - has been introduced into clinical practice. To the best of our knowledge, this is the first publication related to its application. Five patients aged from six months to 69 years were included in the study: two with atrial septal defect (ASD), one with patent foramen ovale (PFO) after cryptogenic stroke, and two with patent ductus arteriosus (PDA). These latter two comprised one six month old infant with co-existent hypertrophied cardiomyopathy, and a 53 year-old woman with recanalized PDA after previous ligation. All were treated percutaneously with COF. There was no preliminary patient selection. The only limitation was the size of the devices in our possession (16 and 22 mm ASD COF, 25 PFO COF, 4/6 and 6/8 PDA COF). The implantation technique was the same as previously described for Amplatzer occluders. All procedures were finished successfully with complete closure of the shunt. No complications were observed during a six month follow-up. In the child with PDA, we observed decrease of gradient from 80 to 60 mm Hg in hypertrophied left ventricular outflow tract, although a small protrusion of PDA-COF device was noted in the descending aorta (8 mm Hg gradient in ECHO). In the patient with recanalized PDA, the procedure was performed after arterio-venous loop creation. Mean fluoroscopy time was 4.4 (range from 1.6 to 11) minutes. Our preliminary experience indicates that the application of Cardio-O-Fix devices is safe and effective.

  10. Preparation of new crosslinking agents and additives for use in polymer electrolyte membranes (PEMs) for fuel cell applications

    NASA Astrophysics Data System (ADS)

    Zhou, Yangliu

    The most commonly used proton conductive membrane in polymer electrolyte membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFC) studies to date is DuPont's NafionRTM, which is a perfluorinated copolymer of tetrafluoroethylene (TFE) and perfluorovinyl ether with a pendant sulfonic acid group. A focus of this work is to find ways to improve the performance of NafionRTM membranes. Crosslinking the TFE chains of fluorinated ionomeric copolymers to improve their thermal and mechanical stability is a proven route to this goal. A straightforward synthetic route to perfluorinated divinyl ethers of the formula CF2=CFO(CF 2)3[OCF(CF3)CF2]mOCF=CF 2 (m = 0-1) has been demonstrated. The compounds CF2=CFO(CF 2)3OCF=CF2 and CF2=CFO(CF2) 3OCF(CF3)CF2OCF=CF2 were prepared and characterized by GC-MS, 13C and 19F NMR, and gas-IR spectroscopy. Synthetic routes to fluorosulfato-tetrafluoropropionyl fluoride [FSO3CF2CF2C(O)F] and difluoromalonyl difluoride [F(O)CCF2C(O)F] with improved yields were found. The second focus of the dissertation was the development of fluorous triarylphosphines for use as new doping materials for the modification of NafionRTM membranes and for use as ligands in catalysts for biphasic catalysis. The synthesis and characterization of a series of new polyhexafluoropropylene oxide derivatives for preparation of fluorous triarylphosphines and phosphonium salts was studied, such as F[CF(CF3)CF2O] 4CF(CF3)CH2CH2I, F[CF(CF3)CF 2O]4CF(CF3)CH=CH2, F[CF(CF3)CF 2O]4CF(CF3) CH2CH2C6H5, and F[CF(CF 3)CF2O]4CF(CF3)CH2CH 2C6H4Br. In a separate study, the photochlorination of 2,2,3,3-tetrafluoro-1-propanol (HCF2CF2CH2OH) and 2,2,3,3-tetrafluoropropyl 2,2,3,3-tetrafluoropropionate [HCF2CF2C(O)OCH2 CF2CF2H] with super diazo blue light (lambda max = 420 nm) were investigated. The photochemical products are different from those obtained under mercury light (lambda = 253.7nm). A new compound ClCF2CF2C(O)OC(H)ClCF2CF2Cl was prepared and characterized by GC-MS, elemental analysis, 1H, 13C and 19F NMR, and gas-IR spectroscopy.

  11. Cocrystal Solubility Product Prediction Using an in combo Model and Simulations to Improve Design of Experiments.

    PubMed

    Avdeef, Alex

    2018-02-02

    To predict the aqueous solubility product (K sp ) and the solubility enhancement of cocrystals (CCs), using an approach based on measured drug and coformer intrinsic solubility (S 0 API , S 0 cof ), combined with in silico H-bond descriptors. A regression model was constructed, assuming that the concentration of the uncharged drug (API) can be nearly equated to drug intrinsic solubility (S 0 API ) and that the concentration of the uncharged coformer can be estimated from a linear combination of the log of the coformer intrinsic solubility, S 0 cof , plus in silico H-bond descriptors (Abraham acidities, α, and basicities, β). The optimal model found for n:1 CCs (-log 10 form) is pK sp  = 1.12 n pS 0 API  + 1.07 pS 0 cof  + 1.01 + 0.74 α API ·β cof  - 0.61 β API ; r 2  = 0.95, SD = 0.62, N = 38. In illustrative CC systems with unknown K sp , predicted K sp was used in simulation of speciation-pH profiles. The extent and pH dependence of solubility enhancement due to CC formation were examined. Suggestions to improve assay design were made. The predicted CC K sp can be used to simulate pH-dependent solution characteristics of saturated systems containing CCs, with the aim of ranking the selection of coformers, and of optimizing the design of experiments.

  12. Adsorption of marine phycotoxin okadaic acid on a covalent organic framework.

    PubMed

    Salonen, Laura M; Pinela, Sara R; Fernandes, Soraia P S; Louçano, João; Carbó-Argibay, Enrique; Sarriá, Marisa P; Rodríguez-Abreu, Carlos; Peixoto, João; Espiña, Begoña

    2017-11-24

    Phycotoxins, compounds produced by some marine microalgal species, can reach high concentrations in the sea when a massive proliferation occurs, the so-called harmful algal bloom. These compounds are especially dangerous to human health when concentrated in the digestive glands of seafood. In order to generate an early warning system to alert for approaching toxic outbreaks, it is very important to improve monitoring methods of phycotoxins in aquatic ecosystems. Solid-phase adsorption toxin tracking devices reported thus far based on polymeric resins have not been able to provide an efficient harmful algal bloom prediction system due to their low adsorption capabilities. In this work, a water-stable covalent organic framework (COF) was evaluated as adsorbent for the hydrophobic toxin okadaic acid, one of the most relevant marine toxins and the parental compound of the most common group of toxins responsible for the diarrhetic shellfish poisoning. Adsorption kinetics of okadaic acid onto the COF in seawater showed that equilibrium concentration was reached in only 60min, with a maximum experimental adsorption of 61mgg -1 . Desorption of okadaic acid from the COF was successful with both 70% ethanol and acetonitrile as solvent, and the COF material could be reused with minor losses in adsorption capacity for three cycles. The results demonstrate that COF materials are promising candidates for solid-phase adsorption in water monitoring devices. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Biosynthetic versatility and coordinated action of 5'-deoxyadenosyl radicals in deazaflavin biosynthesis.

    PubMed

    Philmus, Benjamin; Decamps, Laure; Berteau, Olivier; Begley, Tadhg P

    2015-04-29

    Coenzyme F420 is a redox cofactor found in methanogens and in various actinobacteria. Despite the major biological importance of this cofactor, the biosynthesis of its deazaflavin core (8-hydroxy-5-deazaflavin, F(o)) is still poorly understood. F(o) synthase, the enzyme involved, is an unusual multidomain radical SAM enzyme that uses two separate 5'-deoxyadenosyl radicals to catalyze F(o) formation. In this paper, we report a detailed mechanistic study on this complex enzyme that led us to identify (1) the hydrogen atoms abstracted from the substrate by the two radical SAM domains, (2) the second tyrosine-derived product, (3) the reaction product of the CofH-catalyzed reaction, (4) the demonstration that this product is a substrate for CofG, and (5) a stereochemical study that is consistent with the formation of a p-hydroxybenzyl radical at the CofH active site. These results enable us to propose a mechanism for F(o) synthase and uncover a new catalytic motif in radical SAM enzymology involving the use of two 5'-deoxyadenosyl radicals to mediate the formation of a complex heterocycle.

  14. Coefficient of Friction of Human Corneal Tissue.

    PubMed

    Wilson, Tawnya; Aeschlimann, Rudolf; Tosatti, Samuele; Toubouti, Youssef; Kakkassery, Joseph; Osborn Lorenz, Katherine

    2015-09-01

    A novel property evaluation methodology was used to determine the elusive value for the human corneal coefficient of friction (CoF). Using a microtribometer on 28 fresh human donor corneas with intact epithelia, the CoF was determined in 4 test solutions (≥5 corneas/solution): tear-mimicking solution (TMS) in borate-buffered saline (TMS-PS), TMS in phosphate-buffered saline (TMS-PBS), TMS with HEPES-buffered saline (TMS-HEPES), and tear-like fluid in PBS (TLF-PBS). Mean (SD) CoF values ranged from 0.006 to 0.015 and were 0.013 (0.010) in TMS-PS, 0.006 (0.003) in TMS-PBS, 0.014 (0.005) in TMS-HEPES, and 0.015 (0.009) in TLF-PBS. Statistically significant differences were shown for TMS-PBS versus TLF (P = 0.0424) and TMS-PBS versus TMS-HEPES (P = 0.0179), but not for TMS-PBS versus TMS-PS (P = 0.2389). Successful measurement of the fresh human corneal tissue CoF was demonstrated, with values differing in the evaluated buffer solutions, within this limited sample size.

  15. Reduction of cooking oil fume exposure following an engineering intervention in Chinese restaurants.

    PubMed

    Pan, Chih-Hong; Shih, Tung-Sheng; Chen, Chiou-Jong; Hsu, Jin-Huei; Wang, Shun-Chih; Huang, Chien-Ping; Kuo, Ching-Tang; Wu, Kuen-Yuh; Hu, Howard; Chan, Chang-Chuan

    2011-01-01

    A new engineering intervention measure, an embracing air curtain device (EACD), was used to increase the capture efficiency of cooker hoods and reduce cooking oil fume (COF) exposure in Chinese restaurants. An EACD was installed in six Chinese restaurants where the cooks complained of COF exposure. Before- and after-installation measurements were taken to compare changes in particulate matter (PM) and polycyclic aromatic hydrocarbons (PAHs) in kitchen air, and changes in levels of urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG) and malondialdehyde (MDA). The association between PM and PAHs in air and 8-OHdG and MDA in urine was evaluated by linear mixed-effects regression analysis. Results showed that geometric mean kitchen air levels of PM(10), PM(2.5), PM(1.0) and total particulate PAHs were significantly reduced after the EACDs were introduced. Urinary levels of 8-OHdG and MDA in cooks were also significantly lower after EACD instalment. PM(2.5), PM(1.0) and benzo(a)pyrene (BaP) levels were positively associated with urinary 8-OHdG levels after adjusting for key personal covariates. Urinary MDA levels in cooks were also positively associated with BaP levels after adjusting for key personal covariates. This study demonstrates that the EACD is effective for reducing COF and oxidative stress levels in cooks working in Chinese kitchens.

  16. Interaction of N-hydroxyurea with strong proton donors: HCl and HF

    NASA Astrophysics Data System (ADS)

    Sałdyka, Magdalena

    2014-11-01

    An infrared spectroscopic and MP2/6-311++G(2d,2p) study of strong hydrogen bonded complexes of N-hydroxyurea (NH2CONHOH) with hydrogen halides (HCl and HF) trapped in solid argon matrices is reported. 1:1 and 1:2 complexes between N-hydroxyurea and hydrogen chloride, hydrogen fluoride have been identified in the NH2CONHOH/HCl/Ar, NH2CONHOH/HF/Ar matrices, respectively; their structures were determined by comparison of the spectra with the results of calculations. In the 1:1 complexes, identified for both hydrogen halide molecules, the cyclic structure stabilized by the X-H⋯O and N-H⋯X bonds is present; for the NH2CONHOH⋯HF system another isomeric 1:1 complex is also observed. Two 1:2 complexes were identified for the N-hydroxyurea-hydrogen chloride system characterised by the Cl-H⋯O and N-H⋯Cl bonds. The results of the study evidence that N-hydroxyurea is an oxygen base in the gas-phase with the carbonyl group as the strongest proton acceptor centre in the molecule.

  17. Prolonged respiratory symptoms caused by thermal degradation products of freons.

    PubMed

    Piirilä, Päivi; Espo, Timo; Pfäffli, Pirkko; Riihimäki, Vesa; Wolff, Henrik; Nordman, Henrik

    2003-02-01

    The chlorofluorocarbons (CFC) used in refrigeration systems decompose on heating and produce substances that are highly irritating to the airways (eg, chlorine, carbonyl fluoride, and hydrogen fluoride). This study examined persistent respiratory symptoms among several workers exposed to thermal decomposition products of CFC. Seven patients with respiratory symptoms caused by inadvertent exposure to thermal decomposition products of CFC in a restaurant kitchen or during refrigerator repair were studied with the use of spirometry, peak flow follow-up, and histamine challenge tests. Three patients also underwent bronchoscopy and bronchoalveolar lavage. In five of the cases, cough or dyspnea lasted longer than 1 month; for three of the five, the symptoms lasted more than 4 years. Three cases showed increased bronchial hyperreactivity, and two of the three had increased diurnal peak flow variation. Three patients fulfilled the criteria for acute irritant-induced asthma or reactive airway dysfunction syndrome. One case exhibited bronchiolitis while, for the other six, the clinical picture was consistent with bronchitis. The studied cases indicate that the thermal decomposition products of CFC used in refrigerators may cause irritant-induced airway diseases of long duration.

  18. Trans, trans-2,4-decadienal induced cell proliferation via p27 pathway in human bronchial epithelial cells

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

    Chang, Y.-C.; Lin Pinpin

    2008-04-01

    Lung cancer is the leading cause of cancer deaths worldwide. Epidemiological studies have shown that exposure to cooking oil fumes (COF) is a risk factor for lung cancer. Trans, trans-2,4-decadienal (tt-DDE), a dienaldehyde, is abundant in heated oils and COF. Previously, we found that long-term exposure (45 days) to a sub-lethal dose (1 {mu}M) of tt-DDE significantly increased growth of human bronchial epithelial cells (BEAS-2B). Aims of this study are to understand the mechanism of tt-DDE-induced cell proliferation and possible protective effects of antioxidant, vitamin C and N-acetylcysteine (NAC) in BEAS-2B cells. Utilizing the real-time RT-PCR and Western immunoblotting, wemore » found that p27 mRNA and protein levels were significantly increased by 1 {mu}M tt-DDE treatment. Co-treatment with vitamin C or NAC partially prevented tt-DDE-induced cell proliferation. In addition, the downstream targets of p27, including CDK4, cyclin D{sub 1} and phosphorylated-Rb proteins, increased in 1 {mu}M tt-DDE-treated cells and these changes were prevented by NAC co-treatment. Therefore, these results suggest that tt-DDE increased cell proliferation via inhibition of p27 expression, increase in CDK4/cyclin D{sub 1} protein accumulation and enhancement of Rb phosphorylation. Increased cell proliferation is considered as the early stages of lung carcinogenesis. Administration of antioxidants may prevent COF-associated lung carcinogenesis.« less

  19. Iridium-catalyzed Arene ortho-Silylation by Formal Hydroxyl-directed C-H Activation

    PubMed Central

    Simmons, Eric M.; Hartwig, John F.

    2010-01-01

    A strategy for the ortho-silylation of aryl ketone, benzaldehyde and benzyl alcohol derivatives has been developed in which a hydroxyl group formally serves as the directing element for Ir-catalyzed arene C-H bond activation. One-pot generation of a (hydrido)silyl ether from the carbonyl compound or alcohol is followed by dehydrogenative cyclization at 80–100 °C in the presence of norbornene as hydrogen acceptor and the combination of 1 mol % [Ir(cod)OMe]2 and 1,10-phenanthroline as catalyst to form benzoxasiloles. The synthetic utility of the benzoxasilole products is demonstrated by conversion to phenol or biaryl derivatives by Tamao-Fleming oxidation or Hiyama cross-coupling. Both of these transformations of the C-H silylation products exploit the Si-O bond in the system and proceed by activation of the silyl moiety with hydroxide, rather than fluoride. PMID:21077625

  20. Dermatologic findings in 16 patients with Cockayne syndrome and cerebro-oculo-facial-skeletal syndrome.

    PubMed

    Frouin, Eric; Laugel, Vincent; Durand, Myriam; Dollfus, Hélène; Lipsker, Dan

    2013-12-01

    Cockayne syndrome (CS) and cerebro-oculo-facial-skeletal (COFS) syndrome are autosomal recessive diseases that belong to the family of nucleotide excision repair disorders. Our aim was to describe the cutaneous phenotype of patients with these rare diseases. A systematic dermatologic examination of 16 patients included in a European study of CS was performed. The patients were aged 1 to 28 years. Six patients (38%) had mutations in the Cockayne syndrome A (CSA) gene, and the remaining had Cockayne syndrome B (CSB) gene mutations. Fourteen patients were classified clinically as having CS and 2 as having COFS syndrome. Photosensitivity was present in 75% of the patients and was characterized by sunburn after brief sun exposure. Six patients developed symptoms after short sun exposure through a windshield. Six patients had pigmented macules on sun-exposed skin, but none developed a skin neoplasm. Twelve patients (75%) displayed cyanotic acral edema of the extremities. Eight patients had nail dystrophies and 7 had hair anomalies. The dermatologic findings of 16 cases of CS and COFS syndrome highlight the high prevalence of photosensitivity and hair and nail disorders. Cyanotic acral edema was present in 75% of our patients, a finding not previously reported in CS.

  1. Carbon dioxide capture using covalent organic frameworks (COFs) type material-a theoretical investigation.

    PubMed

    Dash, Bibek

    2018-04-26

    The present work deals with a density functional theory (DFT) study of porous organic framework materials containing - groups for CO 2 capture. In this study, first principle calculations were performed for CO 2 adsorption using N-containing covalent organic framework (COFs) models. Ab initio and DFT-based methods were used to characterize the N-containing porous model system based on their interaction energies upon complexing with CO 2 and nitrogen gas. Binding energies (BEs) of CO 2 and N 2 molecules with the polymer framework were calculated with DFT methods. Hybrid B3LYP and second order MP2 methods combined with of Pople 6-31G(d,p) and correlation consistent basis sets cc-pVDZ, cc-pVTZ and aug-ccVDZ were used to calculate BEs. The effect of linker groups in the designed covalent organic framework model system on the CO 2 and N 2 interactions was studied using quantum calculations.

  2. Multi-scale theoretical investigation of hydrogen storage in covalent organic frameworks.

    PubMed

    Tylianakis, Emmanuel; Klontzas, Emmanouel; Froudakis, George E

    2011-03-01

    The quest for efficient hydrogen storage materials has been the limiting step towards the commercialization of hydrogen as an energy carrier and has attracted a lot of attention from the scientific community. Sophisticated multi-scale theoretical techniques have been considered as a valuable tool for the prediction of materials storage properties. Such techniques have also been used for the investigation of hydrogen storage in a novel category of porous materials known as Covalent Organic Frameworks (COFs). These framework materials are consisted of light elements and are characterized by exceptional physicochemical properties such as large surface areas and pore volumes. Combinations of ab initio, Molecular Dynamics (MD) and Grand Canonical Monte-Carlo (GCMC) calculations have been performed to investigate the hydrogen adsorption in these ultra-light materials. The purpose of the present review is to summarize the theoretical hydrogen storage studies that have been published after the discovery of COFs. Experimental and theoretical studies have proven that COFs have comparable or better hydrogen storage abilities than other competitive materials such as MOF. The key factors that can lead to the improvement of the hydrogen storage properties of COFs are highlighted, accompanied with some recently presented theoretical multi-scale studies concerning these factors.

  3. Effects of Coffee and Caffeine Anhydrous Intake During Creatine Loading.

    PubMed

    Trexler, Eric T; Smith-Ryan, Abbie E; Roelofs, Erica J; Hirsch, Katie R; Persky, Adam M; Mock, Meredith G

    2016-05-01

    The purpose of this study was to determine the effect of 5 days of creatine (CRE) loading alone or in combination with caffeine anhydrous (CAF) or coffee (COF) on upper-body and lower-body strength and sprint performance. Physically active males (n = 54; mean ± SD; age = 20.1 ± 2.1 years; weight = 78.8 ± 8.8 kg) completed baseline testing, consisting of 1 repetition maximum (1RM) and repetitions to fatigue with 80% 1RM for bench press and leg press, followed by a repeated sprint test of five, 10-second sprints separated by 60-second rest on a cycle ergometer to determine peak power (PP) and total power (TP). At least 72 hours later, subjects were randomly assigned to supplement with CRE (5 g of CRE monohydrate, 4 times per day; n = 14), CRE + CAF (CRE +300 mg·d of CAF; n = 13), CRE + COF (CRE +8.9 g of COF, yielding 303 mg of CAF; n = 13), or placebo (PLA; n = 14) for 5 days. Serum creatinine (CRN) was measured before and after supplementation, and on day 6, participants repeated pretesting procedures. Strength measures were improved in all groups (p ≤ 0.05), with no significant time × treatment interactions. No significant interaction or main effects were observed for PP. For TP, a time × sprint interaction was observed (p ≤ 0.05), with no significant interactions among treatment groups. A time × treatment interaction was observed for serum CRN values (p ≤ 0.05) that showed increases in all groups except PLA. Four subjects reported mild gastrointestinal discomfort with CRE + CAF, with no side effects reported in other groups. These findings suggest that neither CRE alone nor in combination with CAF or COF significantly affected performance compared with PLA.

  4. Effects of coffee and caffeine anhydrous intake during creatine loading

    PubMed Central

    Trexler, Eric T.; Smith-Ryan, Abbie E.; Roelofs, Erica J.; Hirsch, Katie R.; Persky, Adam M.; Mock, Meredith G.

    2015-01-01

    The purpose of this study was to determine the effect of 5 d of creatine (CRE) loading alone or in combination with caffeine anhydrous (CAF) or coffee (COF) on upper and lower body strength and sprint performance. Physically active males (n=54; Mean ± SD; Age = 20.1 ± 2.1 yrs; Weight = 78.8 ± 8.8 kg) completed baseline testing, consisting of one-repetition maximum (1RM) and repetitions to fatigue (RTF) with 80% 1RM for bench press (BP) and leg press (LP), followed by a repeated sprint test of five, 10 s sprints separated by 60 s rest on a cycle ergometer to determine peak power (PP) and total power (TP). At least 72 hr later, subjects were randomly assigned to supplement with CRE (5 g creatine monohydrate, 4 times*d−1; n=14), CRE+CAF (CRE + 300 mg*d−1 of CAF; n=13), CRE+COF (CRE + 8.9 g COF, yielding 303 mg caffeine; n=13), or placebo (PLA; n=14) for 5 d. Serum creatinine (CRN) was measured prior to and following supplementation and on day six, participants repeated pre-testing procedures. Strength measures were improved in all groups (p<0.05), with no significant time × treatment interactions. No significant interaction or main effects were observed for PP. For TP, a time × sprint interaction was observed (p<0.05), with no significant interactions between treatment groups. A time × treatment interaction was observed for serum CRN values (p<0.05) that showed increases in all groups except PLA. Four subjects reported mild gastrointestinal discomfort with CRE+CAF, with no side effects reported in other groups. These findings suggest that neither CRE alone, nor in combination with CAF or COF, significantly affected performance compared to PLA. PMID:26439785

  5. Tribological properties of PVA/PVP blend hydrogels against articular cartilage.

    PubMed

    Kanca, Yusuf; Milner, Piers; Dini, Daniele; Amis, Andrew A

    2018-02-01

    This research investigated in-vitro tribological performance of the articulation of cartilage-on- polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) blend hydrogels using a custom-designed multi-directional wear rig. The hydrogels were prepared by repeated freezing-thawing cycles at different concentrations and PVA to PVP fractions at a given concentration. PVA/PVP blend hydrogels showed low coefficient of friction (COF) values (between 0.12 ± 0.01 and 0.14 ± 0.02) which were closer to the cartilage-on-cartilage articulation (0.03 ± 0.01) compared to the cartilage-on-stainless steel articulation (0.46 ± 0.06). The COF increased with increasing hydrogel concentration (p = 0.03) and decreasing PVP content at a given concentration (p < 0.05). The cartilage-on-hydrogel tests showed only the surface layers of the cartilage being removed (average volume loss of the condyles was 12.5 ± 4.2mm 3 ). However, the hydrogels were found to be worn/deformed. The hydrogels prepared at a higher concentration showed lower apparent volume loss. A strong correlation (R 2 = 0.94) was found between the COF and compressive moduli of the hydrogel groups, resulting from decreasing contact congruency. It was concluded that the hydrogels were promising as hemiarthroplasty materials, but that improved mechanical behaviour was required for clinical use. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Covalent Organic Frameworks as a Platform for Multidimensional Polymerization.

    PubMed

    Bisbey, Ryan P; Dichtel, William R

    2017-06-28

    The simultaneous polymerization and crystallization of monomers featuring directional bonding designs provides covalent organic frameworks (COFs), which are periodic polymer networks with robust covalent bonds arranged in two- or three-dimensional topologies. The range of properties characterized in COFs has rapidly expanded to include those of interest for heterogeneous catalysis, energy storage and photovoltaic devices, and proton-conducting membranes. Yet many of these applications will require materials quality, morphological control, and synthetic efficiency exceeding the capabilities of contemporary synthetic methods. This level of control will emerge from an improved fundamental understanding of COF nucleation and growth processes. More powerful characterization of structure and defects, improved syntheses guided by mechanistic understanding, and accessing diverse isolated forms, ranging from single crystals to thin films to colloidal suspensions, remain important frontier problems.

  7. Covalent Organic Frameworks as a Platform for Multidimensional Polymerization

    PubMed Central

    2017-01-01

    The simultaneous polymerization and crystallization of monomers featuring directional bonding designs provides covalent organic frameworks (COFs), which are periodic polymer networks with robust covalent bonds arranged in two- or three-dimensional topologies. The range of properties characterized in COFs has rapidly expanded to include those of interest for heterogeneous catalysis, energy storage and photovoltaic devices, and proton-conducting membranes. Yet many of these applications will require materials quality, morphological control, and synthetic efficiency exceeding the capabilities of contemporary synthetic methods. This level of control will emerge from an improved fundamental understanding of COF nucleation and growth processes. More powerful characterization of structure and defects, improved syntheses guided by mechanistic understanding, and accessing diverse isolated forms, ranging from single crystals to thin films to colloidal suspensions, remain important frontier problems. PMID:28691064

  8. Pericoronal occurrence of cemento-ossifying fibroma: an unexemplified and unusual case report with review of literature.

    PubMed

    K L, Kumaraswamy; R S, Arvind Babu; P, Sheshadri; Kumaran, Santhosh

    2014-03-01

    The Cemento-ossifying fibroma (COF) is an odontogenic neoplasm that is predominantly considered as a fibro osseous lesion of the jaw bone. The histogenetic origin of COF was thought to be derived from the periodontal cells, which have the ability to form fibrous, cementum and osseous tissue. Due to the periodontal cellular origin, the lesion often occurs in the radicular portion of the bicuspid and molar tooth region of the lower jaw. We present a case of Cemento-ossifying fibroma in a 43-year-old female in the pericoronal aspect of an impacted third molar mimicking an odontogenic lesion. The occurrence of COF in pericoronal region is an unusual site. This article also discusses about the various hamartomatous lesions occurring in the pericoronal region of the teeth.

  9. Covalent organic framework-derived microporous carbon nanoparticles coated with conducting polypyrrole as an electrochemical capacitor

    NASA Astrophysics Data System (ADS)

    Kim, Dong Jun; Yoon, Jung Woon; Lee, Chang Soo; Bae, Youn-Sang; Kim, Jong Hak

    2018-05-01

    We report a high-performance electrochemical capacitor based on covalent organic framework (COF)-derived microporous carbon (MPC) nanoparticles and electrochemically polymerized polypyrrole (Ppy) as a pseudocapacitive material. The COF, Schiff-based network-1 (SNW-1) nanoparticles are prepared via a condensation reaction between melamine and terephthalaldehyde, and the resultant MPC film is prepared via a screen-printing method. The MPC film exhibits a bimodal porous structure with micropores and macropores, resulting in both a large surface area and good electrolyte infiltration. Ppy is synthesized potentio-statically (0.8 V vs. Ag/AgCl) by varying the reaction time, and successful synthesis of Ppy is confirmed via Raman spectroscopy. The specific capacitance with the Ppy coating is enhanced by up to 2.55 F cm-2 due to the synergetic effect of pseudocapacitance and reduced resistance.

  10. A Hydrazone-Based Covalent Organic Framework as an Efficient and Reusable Photocatalyst for the Cross-Dehydrogenative Coupling Reaction of N-Aryltetrahydroisoquinolines.

    PubMed

    Liu, Wanting; Su, Qing; Ju, Pengyao; Guo, Bixuan; Zhou, Hui; Li, Guanghua; Wu, Qiaolin

    2017-02-22

    A hydrazone-based covalent organic framework (COF) was synthesized by condensation of 2,5-dimethoxyterephthalohydrazide with 1,3,5-triformylbenzene under solvothermal conditions. The COF material exhibits excellent porosity with a BET surface area of up to 1501 m 2  g -1 , high crystallinity, and good thermal and chemical stability. Moreover, it showed efficient photocatalytic activity towards cross-dehydrogenative coupling (CDC) reactions between tetrahydroisoquinolines and nucleophiles such as nitromethane, acetone, and phenylethyl ketone. The metal-free catalytic system also offers attractive advantages including simplicity of operation, wide substrate adaptability, ambient reaction conditions, and robust recycling capability of the catalyst, thus providing a promising platform for highly efficient and reusable photocatalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Long-Term Trends in the Concentrations of SF6, CHClF2, and COF2 in the Lower Stratosphere from Analysis of High-Resolution Infrared Solar Occultation Spectra

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Goldman, A.; Murcray, F. J.; Blatherwick, R. D.; Kosters, J. J.; Murcray, D. G.; Sze, N. D.; Massie, S. T.

    1990-01-01

    Long-term trends in the concentrations of SF6, CHClF2 (CFC-22), and COF2 in the lower stratosphere have been derived from analysis of ca. 1980 and more recent infrared solar occultation spectra recorded near 32 deg N latitude at approx. 0.02/ cm resolution. Consistent sets of line parameters and spectral calibration methods have been used in the retrievals to minimize systematic error effects. Quoted error limits are 1 sigma estimated precisions. The SF6 and CHClF2 results are based on spectra recorded by balloon-borne interferometers in March 1981 and June 1988 and a comparison of these results with the Atmospheric Trace Molecule Spectroscopy (ATMOS) Experiment/Spacelab 3 measurements obtained in May 1985 near 30 deg N latitude. In the 13-18 km altitude range the mean measured SF6 mixing ratio in parts per trillion by volume (pptv) increased from 1.17 +/- 0.21 in March 1981 to 2.02 +/- 0.20 pptv in June 1988, and the CHClF2 mixing ratio below 15 km altitude increased from 51 +/- 8 pptv in March 1981 to 102 +/- 10 pptv in June 1988. The CHClF2 retrievals used new empirical CHClF2 line parameters derived from 0.03/cm resolution laboratory spectra recorded at six temperatures between 203 and 293 K; the derived mixing ratios are approx. 30% higher than obtained with earlier sets of line parameters, thereby removing a large discrepancy noted previously between IR and in situ measurements of CHClF2. Assuming an exponential growth model for fitting the trends, SF6 and CHClF2 mean increase rates of 7.4% +/- 1.9% and 9.4% +/- 1.3% /year, are obtained, respectively, which correspond to cumulative increases by factors of approx. 1.7 and -2.0 in the concentrations of these gases over the 7.2-year measurement period. Analysis of spectra recorded in October 1979 and April 1989 yields COF2 volume mixing ratios that are respectively 0.44 +/- 0.17 and 1.21 +/- 0.24 times the ATMOS/Spacelab 3 values, from which an average COF2 increase rate of 10.3 +/- 1.8%/ year over this time period has been estimated. The present results are compared with previously reported observations and trends and with one-dimensional model calculations. The model calculated trends are in reasonably good agreement with the observations.

  12. Differential Solutions Using Long-Range Dual-Frequency GPS Correction Data

    DTIC Science & Technology

    2002-09-01

    coordinates the network of CORS sites to provide range measurement data to users in the United States. The data is available, via the Internet , to...of 3-dimensional positioning activities throughout the United States (NGS, 2002). CORS data is posted daily on the Internet from which the user may...KING AZ Scottsdale COSA 1998/258 -------- 5 sec H CofS AZ Tolleson

  13. Determination of carbonyl pollutants adsorbed on ambient particulate matter of type PM2.5 by using magnetic molecularly imprinted microspheres for sample pretreatment and capillary electrophoresis for separation and quantitation.

    PubMed

    Li, Yunling; Sun, Hui; Lai, Jiaping; Chang, Xiangyang; Zhang, Ping; Chen, Shili

    2018-01-19

    The authors describe a method for the determination of carbonyl pollutants adsorbed on ambient particulate matter (diameter < 2.5 μm; PM2.5). 2,4-Dinitrophenylhydrazine (DNPH) was used to derivatize carbonyl compounds. Magnetic molecularly imprinted polymers (MMIPs) selective for 2,4-DNPH were synthesized to remove excess of the derivatization reagent 2,4-DNPH. Micellar electrokinetic chromatography (MEKC) was then applied to the separation of DNPH-derivatized carbonyl compounds. The increased sensitivity of MEKC with UV detection and the sample cleanup resulted in drastically reduced sampling times (15 min) with detection limits ranging from 0.005-0.068 μg·m -3 for different carbonyls. The method was applied to continuous monitoring of carbonyl compounds on ambient PM 2.5 for two consecutive months. The concentrations and gas-to-particle ratios of carbonyls were determined, and a statistical method was used to evaluate the correlation among different carbonyls. It was observed that the total concentration of carbonyls, especially of multi-carbon carbonyls, increases with the level of air pollution. The level of isovaleraldehyde rises sharply and accounts for 37% of total carbonyls on days with extremely humid haze. The ratio of acetaldehyde to propionaldehyde (C2/C3) decreases with the duration and heaviness of haze conditions. Results indicate that anthropogenic emissions and the characteristics of the atmosphere (e.g. temperature, sunlight, and relative humidity) are the main factors that lead to abnormally high levels of isovaleraldehyde and other carbonyls in ambient PM 2.5. Graphical abstract Schematic of a method for the determination of carbonyl pollutants adsorbed on ambient fine particle of type PM2.5. Magnetic molecularly imprinted polymers (MMIPs) were synthesized to remove the excess derivatization reagent (2,4-DNPH) in air sample prior to CE separation.

  14. A numerical investigation of factors affecting cervical spine injuries during rollover crashes.

    PubMed

    Hu, Jingwen; Yang, King H; Chou, Clifford C; King, Albert I

    2008-11-01

    Factors affecting the risk of cervical spine injury in rollover crashes were investigated using a detailed finite element human head-neck model. Analyze systematically neck responses and associated injury predictors under complex loading conditions similar to real-world rollover scenarios and use the findings to identify potential design improvements. Although many previous experimental and numerical studies have focused on cervical spine injury mechanisms and tolerance, none of them have investigated the risk of cervical spine injuries under loading condition similar to that in rollovers. The effects of changing the coefficient of friction (COF), impact velocity, padding material thickness and stiffness, and muscle force on the risk of neck injuries were analyzed in 16 different impact orientations based on a Taguchi array of design of experiments. Impact velocity is the most important factor in determining the risk of cervical spine fracture (P = 0.000). Decreases in the COF between the head and impact surface can effectively reduce the risk of cervical spine fracture (P = 0.038). If the COF is not 0, an impact with lateral force component could sometimes increase the risk of cervical spine fracture; and the larger the oriented angle of the impact surface, the more important it becomes to reduce the COF to protect the neck. Soft (P = 0.033) and thick (P = 0.137) padding can actually decrease the neck fracture risk, which is in contrast to previous experimental data. A careful selection of proper padding stiffness and thickness, along with a minimized COF between the head and impact surface or between the padding and its supporting structure, may simultaneously decrease the risk of head and neck injuries during rollover crashes. A seatbelt design to effectively reduce/eliminate the head-to-roof impact velocity is also very crucial to enhance the neck protection in rollovers.

  15. Developing an interdisciplinary and cross-sectoral community of practice in the domain of forests and livelihoods.

    PubMed

    Watkins, Cristy; Zavaleta, Jennifer; Wilson, Sarah; Francisco, Scott

    2018-02-01

    Although significant resources are being spent researching and fostering the relationship between forests and livelihoods to promote mutually beneficial outcomes, critical gaps in understanding persist. A core reason for such gaps is that researchers, practitioners, and policy makers lack the structured space to interact and collaborate, which is essential for effective, interdisciplinary research, practice, and evaluation. Thus, scientific findings, policy recommendations, and measured outcomes have not always been synthesized into deep, systemic understanding; learning from practice and implementation does not easily find its way into scientific analyses, and science often fails to influence policy. Communities of practice (CofPs) are dynamic sociocultural systems that bring people together to share and create knowledge around a common topic of interest. They offer participants a space and structure within which to develop new, systemic approaches to multidimensional problems on a common theme. Uniquely informed by a systems-thinking perspective and drawing from the scientific and gray literatures and in-depth interviews with representatives of established CofPs in the natural resource management and development domain, we argue that a well-designed and adequately funded CofP can facilitate interdisciplinary and cross-sectoral relationships and knowledge exchange. Well-designed CofPs integrate a set of core features and processes to enhance individual, collective, and domain outcomes; they set out an initial but evolving purpose, encourage diverse leadership, and promote collective-identity development. Funding facilitates effective communication strategies (e.g., in person meetings). We urge our colleagues across sectors and disciplines to take advantage of CofPs to advance the domain of forests and livelihoods. © 2017 Society for Conservation Biology.

  16. Radical covalent organic frameworks: a general strategy to immobilize open-accessible polyradicals for high-performance capacitive energy storage.

    PubMed

    Xu, Fei; Xu, Hong; Chen, Xiong; Wu, Dingcai; Wu, Yang; Liu, Hao; Gu, Cheng; Fu, Ruowen; Jiang, Donglin

    2015-06-01

    Ordered π-columns and open nanochannels found in covalent organic frameworks (COFs) could render them able to store electric energy. However, the synthetic difficulty in achieving redox-active skeletons has thus far restricted their potential for energy storage. A general strategy is presented for converting a conventional COF into an outstanding platform for energy storage through post-synthetic functionalization with organic radicals. The radical frameworks with openly accessible polyradicals immobilized on the pore walls undergo rapid and reversible redox reactions, leading to capacitive energy storage with high capacitance, high-rate kinetics, and robust cycle stability. The results suggest that channel-wall functional engineering with redox-active species will be a facile and versatile strategy to explore COFs for energy storage. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Pericoronal Occurrence of Cemento-Ossifying Fibroma: An Unexemplified and Unusual Case Report with Review of Literature

    PubMed Central

    K.L, Kumaraswamy; R.S, Arvind Babu; P, Sheshadri; Kumaran, Santhosh

    2014-01-01

    The Cemento-ossifying fibroma (COF) is an odontogenic neoplasm that is predominantly considered as a fibro osseous lesion of the jaw bone. The histogenetic origin of COF was thought to be derived from the periodontal cells, which have the ability to form fibrous, cementum and osseous tissue. Due to the periodontal cellular origin, the lesion often occurs in the radicular portion of the bicuspid and molar tooth region of the lower jaw. We present a case of Cemento-ossifying fibroma in a 43-year-old female in the pericoronal aspect of an impacted third molar mimicking an odontogenic lesion. The occurrence of COF in pericoronal region is an unusual site. This article also discusses about the various hamartomatous lesions occurring in the pericoronal region of the teeth. PMID:24783159

  18. Carbonylated plasma proteins as potential biomarkers of obesity induced type 2 diabetes mellitus.

    PubMed

    Bollineni, Ravi Chand; Fedorova, Maria; Blüher, Matthias; Hoffmann, Ralf

    2014-11-07

    Protein carbonylation is a common nonenzymatic oxidative post-translational modification, which is often considered as biomarker of oxidative stress. Recent evidence links protein carbonylation also to obesity and type 2 diabetes mellitus (T2DM), though the protein targets of carbonylation in human plasma have not been identified. In this study, we profiled carbonylated proteins in plasma samples obtained from lean individuals and obese patients with or without T2DM. The plasma samples were digested with trypsin, carbonyl groups were derivatized with O-(biotinylcarbazoylmethyl)hydroxylamine, enriched by avidin affinity chromatography, and analyzed by RPC-MS/MS. Signals of potentially modified peptides were targeted in a second LC-MS/MS analysis to retrieve the peptide sequence and the modified residues. A total of 158 unique carbonylated proteins were identified, of which 52 were detected in plasma samples of all three groups. Interestingly, 36 carbonylated proteins were detected only in obese patients with T2DM, whereas 18 were detected in both nondiabetic groups. The carbonylated proteins originated mostly from liver, plasma, platelet, and endothelium. Functionally, they were mainly involved in cell adhesion, signaling, angiogenesis, and cytoskeletal remodeling. Among the identified carbonylated proteins were several candidates, such as VEGFR-2, MMP-1, argin, MKK4, and compliment C5, already connected before to diabetes, obesity and metabolic diseases.

  19. Structure, tribological and electrochemical properties of low friction TiAlSiCN/MoSeC coatings

    NASA Astrophysics Data System (ADS)

    Bondarev, A. V.; Kiryukhantsev-Korneev, Ph. V.; Sheveyko, A. N.; Shtansky, D. V.

    2015-02-01

    The present paper is focused on the development of hard tribological coatings with low friction coefficient (CoF) in different environments (humid air, distilled water) and at elevated temperatures. TiAlSiCN/MoSeC coatings were deposited by magnetron sputtering of four-segment targets consisting of quarter circle TiAlSiCN segments, obtained by self-propagating high-temperature synthesis, and one or two cold pressed segments made of MoSe2 and C powders in a ratio 1:1 wt%. The structure and phase composition of coatings were investigated by means of X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. The coatings were characterized in terms of their hardness, elastic modulus, and elastic recovery. The tribological properties of coatings were investigated first at room temperature against Al2O3 and WC-Co balls, after which studied in distilled water and during continuous heating in air in the temperature range of 25-400 °C against Al2O3 counterpart material. To evaluate their electrochemical characteristics, the coatings were tested in 1 N H2SO4 solution. The obtained results show that the coating hardness depends on the amount of MoSeC additives and decreased from 40 to 28 (one MoSeC segment) and 12 GPa (two MoSeC segments). Doping with MoSeC resulted in a significant reduction of CoF values measured in humid air (RH 60 ± 5%) from 0.8-0.9 to 0.05 and an increase of wear resistance by one or two orders of magnitude depending on counterpart material. This was attributed to the presence of MoSe2 and free carbon-based phases in the tribological contact. The TiAlSiCN/MoSeC coating with a maximal amount of MoSeC also demonstrated superior tribological characteristics in distilled water (CoF ∼ 0.1) and at moderate temperatures up to 300 °C (CoF < 0.1). The electrochemical tests showed that, in general, doping with MoSeC did not negatively affect the coating electrochemical behavior. On the contrary, the MoSeC phase demonstrated small positive effect on the anti-corrosive properties of TiAlSiCN coatings under small polarizations.

  20. The excimer lamp induces cutaneous nerve degeneration and reduces scratching in a dry-skin mouse model.

    PubMed

    Kamo, Atsuko; Tominaga, Mitsutoshi; Kamata, Yayoi; Kaneda, Kazuyuki; Ko, Kyi C; Matsuda, Hironori; Kimura, Utako; Ogawa, Hideoki; Takamori, Kenji

    2014-12-01

    Epidermal hyperinnervation, which is thought to underlie intractable pruritus, has been observed in patients with atopic dermatitis (AD). The epidermal expression of axonal guidance molecules has been reported to regulate epidermal hyperinnervation. Previously, we showed that the excimer lamp has antihyperinnervative effects in nonpruritic dry-skin model mice, although epidermal expression of axonal guidance molecules was unchanged. Therefore, we investigated the antipruritic effects of excimer lamp irradiation and its mechanism of action. A single irradiation of AD model mice significantly inhibited itch-related behavior 1 day later, following improvement in the dermatitis score. In addition, irradiation of nerve fibers formed by cultured dorsal root ganglion neurons increased bleb formation and decreased nerve fiber expression of nicotinamide mononucleotide adenylyl transferase 2, suggesting degenerative changes in these fibers. We also analyzed whether attaching a cutoff excimer filter (COF) to the lamp, thus decreasing cytotoxic wavelengths, altered hyperinnervation and the production of cyclobutane pyrimidine dimer (CPD), a DNA damage marker, in dry-skin model mice. Irradiation with COF decreased CPD production in keratinocytes, as well as having an antihyperinnervative effect, indicating that the antipruritic effects of excimer lamp irradiation with COF are due to induction of epidermal nerve degeneration and reduced DNA damage.

  1. COFS 1 Guest Investigator Program

    NASA Technical Reports Server (NTRS)

    Fontana, Anthony; Wright, Robert L.

    1986-01-01

    The process for selecting guest investigators for participation in the Control of Flexible Structures (COFS)-1 program is described. Contracts and grants will be awarded in late CY87. A straw-man list of types of experiments and a distribution of the experiments has been defined to initiate definition of an experiments package which supports development and validation of control structures interaction technology. A schedule of guest investigator participation has been developed.

  2. Combined Effect of Textured Patterns and Graphene Flake Additives on Tribological Behavior under Boundary Lubrication

    PubMed Central

    Cai, Zhen-bing; Zhao, Lei; Zhang, Xu; Yue, Wen; Zhu, Min-hao

    2016-01-01

    A ball-on-plate wear test was employed to investigate the effectiveness of graphene (GP) nanoparticles dispersed in a synthetic-oil-based lubricant in reducing wear. The effect by area ratio of elliptically shaped dimple textures and elevated temperatures were also explored. Pure PAO4 based oil and a mixture of this oil with 0.01 wt% GP were compared as lubricants. At pit area ratio of 5%, GP-base oil effectively reduced friction and wear, especially at 60 and 100°C. Under pure PAO4 oil lubrication, the untextured surfaces gained low friction coefficients (COFs) and wear rates under 60 and 100°C. With increasing laser—texture area ratio, the COF and wear rate decreased at 25 and 150°C but increased at 60 and 100°C. Under the GP-based oil lubrication, the textured surface with 5% area ratio achieved the lowest COF among those of the area ratios tested at all test temperatures. Meanwhile, the textured surface with 20% area ratio obtained the highest COF among those of the area ratios. With the joint action of GP and texture, the textured surface with 10% area ratio exhibited the best anti-wear performance among all of the textured surfaces at all test temperatures. PMID:27054762

  3. Hepatocyte or serum albumin protein carbonylation by oxidized fructose metabolites: Glyceraldehyde or glycolaldehyde as endogenous toxins?

    PubMed

    Dong, Qiang; Yang, Kai; Wong, Stephanie M; O'Brien, Peter J

    2010-10-06

    Excessive sugar intake in animal models may cause tissue damage associated with oxidative and carbonyl stress cytotoxicity as well as inflammation. Fructose became a 100-fold more cytotoxic if hepatocytes were exposed to a non-toxic infusion of H(2)O(2) so as to simulate H(2)O(2) released by Kupffer cells or infiltrating immune cells. In order to determine the molecular mechanisms involved, protein carbonylation of fructose and its metabolites were determined using the 2,4-dinitrophenylhydrazine method. In a cell-free system, fructose was found to carbonylate bovine serum albumin (BSA) only if low concentrations of FeII/H(2)O(2) were added. Protein carbonylation by the fructose metabolites glyceraldehyde or glycolaldehyde was also markedly increased by FeII/H(2)O(2). The protein carbonylation may be attributed to glyoxal formation by hydroxyl radicals as the glyoxal trapping agent aminoguanidine or hydroxyl radical scavengers prevented protein carbonylation. Glyoxal was also much more effective than other carbonyls at causing protein carbonylation. When BSA was replaced by isolated rat hepatocytes, fructose metabolite glyceraldehyde in the presence of non-toxic 2 microM FeII:8-hydroxyquinoline (HQ) and a H(2)O(2) generating system (glucose/glucose oxidase) markedly increased cytotoxicity, protein carbonylation and reactive oxygen species (ROS)/H(2)O(2) formation. Furthermore this was prevented by hydroxyl radical scavengers or aminoguanidine, a glyoxal scavenger. CuII: 8-hydroxyquinoline increased H(2)O(2) induced hepatocyte protein carbonylation less but was prevented by aminoguanidine. However, cytotoxicity and protein carbonylation induced by glyceraldehyde/CuII:HQ/H(2)O(2) were not affected by hydroxyl radical scavengers. Although fatty liver induced by an excessive sugar diet in animal models has been proposed as the first hit for non-alcoholic steatohepatitis (NASH) we propose that oxidative stress induced by the oxidation of fructose or fructose metabolites catalysed by Fenton FeII/H(2)O(2) could be a 'second hit'. A perpetual cycle of oxidative stress in hepatocytes could lead to cytotoxicity and contribute to NASH development. Copyright 2010 Elsevier Ireland Ltd. All rights reserved.

  4. Urinary 1-hydroxypyrene and malondialdehyde in male workers in Chinese restaurants

    PubMed Central

    Pan, C-H; Chan, C-C; Huang, Y-L; Wu, K-Y

    2008-01-01

    Objectives: To assess internal dose and oxidative stress in male restaurant workers exposed to polycyclic aromatic hydrocarbons (PAHs) from cooking oil fumes (COFs) in Chinese restaurants. Methods: The study participants included 288 male restaurant workers (171 kitchen and 117 service staff) in Chinese restaurants in Taiwan. Airborne particulate PAHs were measured over 12 h on each of two consecutive work days and then identified using high performance liquid chromatography. Urinary 1-hydroxypyrene (1-OHP) measurements were used to indicate COF exposure, and urinary malondialdehyde (MDA) was adopted as an oxidative stress marker. Multiple regression models were used to assess the relationship between MDA and 1-OHP levels after adjusting for key personal covariates. Results: Summed particulate PAH levels in kitchens (median 23.9 ng/m3) were significantly higher than those in dining areas (median 4.9 ng/m3). For non-smoking kitchen staff, mean MDA and 1-OHP levels were 344.2 (SD 243.7) and 6.0 (SD 8.0) μmol/mol creatinine, respectively. These levels were significantly higher than those for non-smoking service staff, which were 244.2 (SD 164.4) and 2.4 (SD 4.3) μmol/mol creatinine, respectively. Urinary 1-OHP levels were significantly associated with work in kitchens (p<0.05). Furthermore, urinary MDA levels were significantly associated with urinary 1-OHP levels (p<0.001) and working hours per day (p<0.05). Conclusions: These findings indicate that urinary 1-OHP and MDA levels reflect occupational exposure to PAHs from COFs and oxidative stress in workers in Chinese restaurants. PMID:18940956

  5. Urinary 1-hydroxypyrene and malondialdehyde in male workers in Chinese restaurants.

    PubMed

    Pan, C-H; Chan, C-C; Huang, Y-L; Wu, K-Y

    2008-11-01

    To assess internal dose and oxidative stress in male restaurant workers exposed to polycyclic aromatic hydrocarbons (PAHs) from cooking oil fumes (COFs) in Chinese restaurants. The study participants included 288 male restaurant workers (171 kitchen and 117 service staff) in Chinese restaurants in Taiwan. Airborne particulate PAHs were measured over 12 h on each of two consecutive work days and then identified using high performance liquid chromatography. Urinary 1-hydroxypyrene (1-OHP) measurements were used to indicate COF exposure, and urinary malondialdehyde (MDA) was adopted as an oxidative stress marker. Multiple regression models were used to assess the relationship between MDA and 1-OHP levels after adjusting for key personal covariates. Summed particulate PAH levels in kitchens (median 23.9 ng/m(3)) were significantly higher than those in dining areas (median 4.9 ng/m(3)). For non-smoking kitchen staff, mean MDA and 1-OHP levels were 344.2 (SD 243.7) and 6.0 (SD 8.0) mumol/mol creatinine, respectively. These levels were significantly higher than those for non-smoking service staff, which were 244.2 (SD 164.4) and 2.4 (SD 4.3) mumol/mol creatinine, respectively. Urinary 1-OHP levels were significantly associated with work in kitchens (p<0.05). Furthermore, urinary MDA levels were significantly associated with urinary 1-OHP levels (p<0.001) and working hours per day (p<0.05). These findings indicate that urinary 1-OHP and MDA levels reflect occupational exposure to PAHs from COFs and oxidative stress in workers in Chinese restaurants.

  6. Spacecraft on-board propulsion

    NASA Technical Reports Server (NTRS)

    Byers, D.

    1991-01-01

    The topics presented are covered in viewgraph form and include the following: (1) planetary dual mode; and (2) space station H/O and H2O/gas resistojet. The major benefits identified by users are: (1) 280 kG payload for MMII CRAF class mission; and (2) eliminate orbiter/year and N2H4 COF.

  7. Hyaluronic acid-fabricated nanogold delivery of the inhibitor of apoptosis protein-2 siRNAs inhibits benzo[a]pyrene-induced oncogenic properties of lung cancer A549 cells

    NASA Astrophysics Data System (ADS)

    Lin, Chung-Ming; Kao, Wei-Chien; Yeh, Chun-An; Chen, Hui-Jye; Lin, Shinn-Zong; Hsieh, Hsien-Hsu; Sun, Wei-Shen; Chang, Chih-Hsuan; Hung, Huey-Shan

    2015-03-01

    Benzo[a]pyrene (BaP), a component of cooking oil fumes (COF), promotes lung cancer cell proliferation and survival via the induction of inhibitor of apoptosis protein-2 (IAP-2) proteins. Thus knockdown of IAP-2 would be a promising way to battle against lung cancer caused by COF. Functionalized gold nanoparticle (AuNP) is an effective delivery system for bio-active materials. Here, biocompatible hyaluronic acid (HA) was fabricated into nanoparticles to increase the target specificity by binding to CD44-over-expressed cancer cells. IAP-2-specific small-interfering RNA (siRNAs) or fluorescein isothiocyanate (FITC) were then incorporated into AuNP-HA. Conjugation of IAP-2 siRNA into AuNPs-HA was verified by the UV-vis spectrometer and Fourier transform infrared spectrometer. Further studies showed that AuNP-HA/FITC were effectively taken up by A549 cells through CD44-mediated endocytosis. Incubation of BaP-challenged cells with AuNP-HA-IAP-2 siRNAs silenced the expression of IAP-2, decreased cell proliferation and triggered pronounced cell apoptosis by the decrease in Bcl-2 protein and the increase in Bax protein as well as the active form of caspases-3. The BaP-elicited cell migration and enzymatic activity of the secreted matrix metalloproteinase-2 were also substantially suppressed by treatment with AuNP-HA-IAP-2 siRNAs. These results indicated that IAP-2 siRNAs can be efficiently delivered into A549 cells by functionalized AuNP-HA to repress the IAP-2 expression and BaP-induced oncogenic events, suggesting the potential therapeutic application of IAP-2 siRNA or other siRNA-conjugated AuNP-HA composites to COF-induced lung cancer and other gene-caused diseases in the future.

  8. Effectiveness of Two Forecast Models for Stratiform Precipitation

    DTIC Science & Technology

    2004-04-01

    an enhanced release of precipitation in clouds containing a mixture of droplets and ice crystals (Bergeron- Findeisen mechanism), he adds another...Fcrc c COF H w gg r ρρ (16) where COF = Parameter to include Bergeron- Findeisen mechanism for precipitation formation ρw = density of water The...subscript F in the term Q(c,cr)F indicates that the additional parameter for the coalescence and Bergeron- Findeisen mechanism are included. The final

  9. Room-temperature synthesis of core-shell structured magnetic covalent organic frameworks for efficient enrichment of peptides and simultaneous exclusion of proteins.

    PubMed

    Lin, Guo; Gao, Chaohong; Zheng, Qiong; Lei, Zhixian; Geng, Huijuan; Lin, Zian; Yang, Huanghao; Cai, Zongwei

    2017-03-28

    Core-shell structured magnetic covalent organic frameworks (Fe 3 O 4 @COFs) were synthesized via a facile approach at room temperature. Combining the advantages of high porosity, magnetic responsiveness, chemical stability and selectivity, Fe 3 O 4 @COFs can serve as an ideal absorbent for the highly efficient enrichment of peptides and the simultaneous exclusion of proteins from complex biological samples.

  10. Quantitative scale for the extent of conjugation of carbonyl groups: "carbonylicity" percentage as a chemical driving force.

    PubMed

    Mucsi, Zoltán; Chass, Gregory A; Viskolcz, Béla; Csizmadia, Imre G

    2008-09-25

    Despite the carbonyl group being one of the most pervasive chemical building blocks in natural, synthetic, and industrial processes, its exact description in terms of precise quantification of the degree of carbonyl conjugation has yet to be determined. The present work suggests a novel yet simple method for quantifying the conjugation in general carbonyl groups (such as ketones, aldehydes, carboxylic acids and their respective halogenides, amides, etc.) on a linear scale, defined as the "carbonylicity scale". This was achieved by use of the computed enthalpy of hydrogenation (DeltaH(H2)) of the > C=O group in the compounds examined. In the present conceptual work, the DeltaH(H2) value for formate ion is used to define complete conjugated character (carbonylicity = +100%), while formaldehyde represents complete absence of conjugation (carbonylicity = 0%). The component DeltaH(H2) values were computed at differing levels of theory, providing a nearly "method-independent" measure of carbonylicity computationally. A total of 49 common carbonyl compounds were used as accuracy scoring criteria of the methodology. For the compounds examined, correlations have been made between the computed carbonylicity percentage and the > C=O proton affinities, IR frequencies, and their reactivity values in a nucleophilic addition reaction. Selected chemical reactions were also studied to illustrate the utility of carbonylicity scale. Examples herein include demonstrating that change in the carbonylicity value represents a thermodynamic driving force in acylation reactions. The definition was extended to substituted thiocarbonyl and imino compounds.

  11. Protein carbonylation: avoiding pitfalls in the 2,4-dinitrophenylhydrazine assay.

    PubMed

    Luo, Shen; Wehr, Nancy B

    2009-01-01

    Protein carbonyl content is widely used as both a marker for oxidative stress and a measure of oxidative damage. Widely used methods for determination of protein carbonylation utilize the reaction of carbonyl groups with 2,4-dinitrophenylhydrazine (DNPH) to form protein-bound 2,4-dinitrophenylhydrazones. Hydrazones can be quantitated spectrophotometrically or, for greater sensitivity, detected immunochemically with anti-dinitrophenyl antibodies. Attention to methodology is important to avoid artifactual elevation in protein carbonyl measurements. We studied extracts of Escherichia coli to identify and eliminate such effects. Nucleic acid contamination caused serious artifactual increases in the protein carbonyl content determined by spectrophotometric techniques. Both in vitro synthesized DNA oligonucleotides and purified chromosomal DNA reacted strongly with 2,4-DNPH. Treatment of cell extracts with DNase+RNase or with streptomycin sulfate to precipitate nucleic acids dramatically reduced the apparent carbonyl, while exposure to proteinase K did not. The commercial kit for immunochemical detection of protein carbonylation (OxyBlot from Chemicon/Millipore) recommends a high concentration of thiol in the homogenizing buffer. We found this recommendation leads to an artifactual doubling of the protein carbonyl, perhaps due to a thiol-stimulated Fenton reaction. Avoiding oxidizing conditions, removal of nucleic acids, and prompt assay of samples can prevent artifactual effects on protein carbonyl measurements.

  12. Effects of rare earth oxide additive on surface and tribological properties of polyimide composites

    NASA Astrophysics Data System (ADS)

    Pan, Zihe; Wang, Tianchang; Chen, Li; Idziak, Stefan; Huang, Zhaohui; Zhao, Boxin

    2017-09-01

    Rare earth oxide La2O3 microparticles-reinforced polyimide (PI) composites (La-PI-Cs) were fabricated, aiming to improve the tribological property of PI. Surface roughness, surface composition, bulk structure, friction force (Ff) and coefficient of friction (COF) at macro/micro preload, and anti-wear performances of La-PI-Cs were studied and compared with neat PI. With La2O3 microparticles, La-PI-Cs showed larger surface roughness, lower surface energy, and higher hydrophobicity than neat PI, and displayed beneficial layered structure different from the compact structure of PI. Owing to these advantages, La-PI-Cs were found to show a 70% reduction in Ff and COF, and a 30% reduction in wear rate, indicating significantly lowered friction and enhanced anti-wear properties after adding La2O3 microparticles. Our research findings demonstrated an easy and low cost method to fabricate polymer composites with low friction and high wear resistance, and help meet the demanding of polymer composites with high tribological performances in broaden applications.

  13. Quantitation of Protein Carbonylation by Dot Blot

    PubMed Central

    Wehr, Nancy B.; Levine, Rodney L.

    2012-01-01

    Protein carbonylation is the most commonly used measure of oxidative modification of proteins. It is frequently measured spectrophotometrically or immunochemically by derivatizing proteins with the classical carbonyl reagent, 2,4-dinitrophenylhydrazine. We developed an immunochemical dot blot method for quantitation of protein carbonylation in homogenates or purified proteins. Dimethyl sulfoxide was employed as the solvent because it very efficiently extracts proteins from tissues and keeps them soluble. It also readily dissolves 2,4-dinitrophenylhydrazine and wets PVDF membranes. The detection limit is 0.19 ± 0.04 pmol carbonyl. Sixty ng protein is sufficient to measure protein carbonyl content. This level of sensitivity allowed measurement of protein carbonylation in individual Drosophila. PMID:22326366

  14. Experimental analysis of tablet properties for discrete element modeling of an active coating process.

    PubMed

    Just, Sarah; Toschkoff, Gregor; Funke, Adrian; Djuric, Dejan; Scharrer, Georg; Khinast, Johannes; Knop, Klaus; Kleinebudde, Peter

    2013-03-01

    Coating of solid dosage forms is an important unit operation in the pharmaceutical industry. In recent years, numerical simulations of drug manufacturing processes have been gaining interest as process analytical technology tools. The discrete element method (DEM) in particular is suitable to model tablet-coating processes. For the development of accurate simulations, information on the material properties of the tablets is required. In this study, the mechanical parameters Young's modulus, coefficient of restitution (CoR), and coefficients of friction (CoF) of gastrointestinal therapeutic systems (GITS) and of active-coated GITS were measured experimentally. The dynamic angle of repose of these tablets in a drum coater was investigated to revise the CoF. The resulting values were used as input data in DEM simulations to compare simulation and experiment. A mean value of Young's modulus of 31.9 MPa was determined by the uniaxial compression test. The CoR was found to be 0.78. For both tablet-steel and tablet-tablet friction, active-coated GITS showed a higher CoF compared with GITS. According to the values of the dynamic angle of repose, the CoF was adjusted to obtain consistent tablet motion in the simulation and in the experiment. On the basis of this experimental characterization, mechanical parameters are integrated into DEM simulation programs to perform numerical analysis of coating processes.

  15. Characterization of PM 2.5 and selected gas-phase compounds at multiple indoor and outdoor sites in Mira Loma, California

    NASA Astrophysics Data System (ADS)

    Sawant, Aniket A.; Na, Kwangsam; Zhu, Xiaona; Cocker, Kathalena; Butt, Sheraz; Song, Chen; Cocker, David R.

    Fine particulate matter (PM 2.5) and gas-phase carbonyls are categories of atmospheric pollutants that have components known to adversely affect human health. This work describes the chemical characterization of PM 2.5 and 13 carbonyl compounds measured inside 20 residences and 7 schoolrooms in Mira Loma, western Riverside County, California. Median PM 2.5 concentrations were 32.2 and 13.2 μg m -3, while median total carbonyl concentrations were 50.8 and 62.9 μg m -3 inside the residences and schoolrooms, respectively. Organic carbon was typically the largest contributor to indoor PM 2.5 concentrations, while formaldehyde, acetaldehyde and acetone were the largest contributors to gas-phase carbonyl concentrations. Indoor/outdoor ratios for PM 2.5 were greater for residences than for schoolrooms, while the reverse was true for these ratios for gas-phase carbonyls. These results are likely due to effective PM 2.5 removal by filtration on the HVAC and the presence of more significant indoor carbonyl sources within the schoolrooms. Regression analysis of indoor and outdoor pollutant concentrations showed that for PM 2.5, sulfate and nitrate were the best- and worst-correlated species, respectively. This suggests that nitrate is a poor tracer for outdoor-to-indoor PM 2.5 transfer. In addition, no significant correlations were observed for any of the carbonyl compounds measured. This further suggests the presence of indoor carbonyl sources inside the schoolrooms, and that indoor air quality especially in terms of carbonyl concentrations may be substantially poorer than outdoor air quality.

  16. Effective Enrichment and Detection of Trace Polycyclic Aromatic Hydrocarbons in Food Samples based on Magnetic Covalent Organic Framework Hybrid Microspheres.

    PubMed

    Li, Ning; Wu, Di; Hu, Na; Fan, Guangsen; Li, Xiuting; Sun, Jing; Chen, Xuefeng; Suo, Yourui; Li, Guoliang; Wu, Yongning

    2018-04-04

    The present study reported a facile, sensitive, and efficient method for enrichment and determination of trace polycyclic aromatic hydrocarbons (PAHs) in food samples by employing new core-shell nanostructure magnetic covalent organic framework hybrid microspheres (Fe 3 O 4 @COF-(TpBD)) as the sorbent followed by HPLC-DAD. Under mild synthetic conditions, the Fe 3 O 4 @COF-(TpBD) were prepared with the retention of colloidal nanosize, larger specific surface area, higher porosity, uniform morphology, and supermagnetism. The as-prepared materials showed an excellent adsorption ability for PAHs, and the enrichment efficiency of the Fe 3 O 4 @COF-(TpBD) could reach 99.95%. The obtained materials also had fast adsorption kinetics and realized adsorption equilibrium within 12 min. The eluent was further analyzed by HPLC-DAD, and good linearity was observed in the range of 1-100 ng/mL with the linear correlation being above 0.9990. The limits of detection (S/N = 3) and limits of quantitation (S/N = 10) for 15 PAHs were in the range of 0.83-11.7 ng/L and 2.76-39.0 ng/L, respectively. For the application, the obtained materials were employed for the enrichment of trace PAHs in food samples and exhibited superior enrichment capacity and excellent applicability.

  17. Enhanced proton conductivity of Nafion composite membrane by incorporating phosphoric acid-loaded covalent organic framework

    NASA Astrophysics Data System (ADS)

    Yin, Yongheng; Li, Zhen; Yang, Xin; Cao, Li; Wang, Chongbin; Zhang, Bei; Wu, Hong; Jiang, Zhongyi

    2016-11-01

    Design and fabrication of efficient proton transport channels within solid electrolytes is crucial and challenging to new energy-relevant devices such as proton exchange membrane fuel cells (PEMFCs). In this study, the phosphoric acid (H3PO4) molecules are impregnated into SNW-1-type covalent organic frameworks (COFs) via vacuum assisted method. High loading of H3PO4 in SNW-1 and low guest leaching rate are achieved due to the similar diameter between H3PO4 and micropores in SNW-1. Then the COF-based composite membranes are fabricated for the first time with impregnated COFs (H3PO4@SNW-1) and Nafion matrix. For the composite membranes, the acid-base pairs formed between H3PO4@SNW-1 networks and Nafion optimize the interfacial interactions and hydrophilic domains. The acidic -PO3H2 groups in pores of H3PO4@SNW-1 provide abundant proton transfer sites. As a result, the continuous proton transfer channels with low energy barrier are created. At the filler content of 15 wt%, the composite membrane exhibits a superior proton conductivity of 0.0604 S cm-1 at 51% relative humidity and 80 °C. At the same time, the maximum power density of single fuel cell is 60.3% higher than that of the recast Nafion membrane.

  18. Application of Carbon Based Nano-Materials to Aeronautics and Space Lubrication

    NASA Technical Reports Server (NTRS)

    Street, Kenneth W., Jr.; Miyoshi, Kazuhisa; Wal, Randy L. Vander

    2007-01-01

    The tribology program at NASA Glenn Research Center in Cleveland, Ohio, is investigating carbon based nano-particles for their potential in advanced concept lubrication products. Service conditions range from high temperature atmospheric to low temperature vacuum. Some of the lubricants and surface coatings of tribological significance that we have evaluated include neat nano-particles, both grown in-situ and as bulk material deposited on the substrate, and nano-particles dispersed in oils which are all highly substrate interactive. We discuss results of testing these systems in a spiral orbit tribometer (SOT) and a unidirectional pin-on-disc (PoD) tribometer. A nano-onions/Krytox mixture evaluated as a lubricant for angular contact bearings in air caused a marked lowering of the coefficient of friction (CoF) (0.04 to 0.05) for the mixture with an eight-fold improvement in lifetime over that of the Krytox alone. In vacuum, no effect was observed from the nano-onions. Multi-walled nanotubes (MWNT) and graphitized MWNT were tested under sliding friction in both air and vacuum. The MWNT which were grown in-situ oriented normal to the sliding surface exhibited low CoF (0.04) and long wear lives. Bulk MWNT also generate low CoF (0.01 to 0.04, vacuum; and 0.06, air) and long wear life (>1 million orbits, vacuum; and >3.5 million, air). Dispersed graphitized MWNT were superior to MWNT and both were superior to aligned MWNT indicating that orientation is not an issue for solid lubrication. Single-walled nanotubes (SWNT) were modified by cutting into shorter segments and by fluorination. All SWNTs exhibited low CoF in air, with good wear lives. The SWNT with slight fluorination yielded an ultra-low CoF of 0.002 although the best wear life was attributed to the nascent SWNT.

  19. Quantitation of protein carbonylation by dot blot.

    PubMed

    Wehr, Nancy B; Levine, Rodney L

    2012-04-15

    Protein carbonylation is the most commonly used measure of oxidative modification of proteins. It is frequently measured spectrophotometrically or immunochemically by derivatizing proteins with the classical carbonyl reagent, 2,4-dinitrophenylhydrazine. We developed an immunochemical dot blot method for quantitation of protein carbonylation in homogenates or purified proteins. Dimethyl sulfoxide was employed as the solvent because it very efficiently extracts proteins from tissues and keeps them soluble. It also readily dissolves 2,4-dinitrophenylhydrazine and wets polyvinylidene difluoride (PVDF) membranes. The detection limit is 0.19 ± 0.04 pmol of carbonyl, and 60 ng of protein is sufficient to measure protein carbonyl content. This level of sensitivity allowed measurement of protein carbonylation in individual Drosophila. Copyright © 2012 Elsevier Inc. All rights reserved.

  20. Perception of slipperiness and prospective risk of slipping at work

    PubMed Central

    Courtney, Theodore K; Verma, Santosh K; Chang, Wen-Ruey; Huang, Yueng-Hsiang; Lombardi, David A; Brennan, Melanye J; Perry, Melissa J

    2013-01-01

    Objectives Falls are a leading cause of injury at work, and slipping is the predominant cause of falling. Prior research has suggested a modest correlation between objective measures (such as coefficient of friction, COF) and subjective measures of slipperiness (such as worker perceptions) in the workplace. However, the degree of association between subjective measures and the actual risk of slipping at the workplace is unknown. This study examined the association between perception of slipperiness and the risk of slipping. Methods 475 workers from 36 limited-service restaurants participated in a 12-week prospective cohort study. At baseline, demographic information was collected, participants rated floor slipperiness in eight areas of the restaurant, and work environment factors, such as COF, were measured. Restaurant-level and area-level mean perceptions of slipperiness were calculated. Participants then reported their slip experience at work on a weekly basis for the next 12 weeks. The associations between perception of slipperiness and the rate of slipping were assessed. Results Adjusting for age, gender, body mass index, education, primary language, mean COF, use of slip-resistant shoes, and restaurant chain, each 1-point increase in mean restaurant-level perception of slipperiness (4-point scale) was associated with a 2.71 times increase in the rate of slipping (95% CI 1.25 to 5.87). Results were similar for area-level perception within the restaurant (rate ratios (RR) 2.92, 95% CI 2.41 to 3.54). Conclusions Perceptions of slipperiness and the subsequent rate of slipping were strongly associated. These findings suggest that safety professionals, risk managers and employers could use aggregated worker perceptions of slipperiness to identify slipping hazards and, potentially, to assess intervention effectiveness. PMID:22935953

  1. Perception of slipperiness and prospective risk of slipping at work.

    PubMed

    Courtney, Theodore K; Verma, Santosh K; Chang, Wen-Ruey; Huang, Yueng-Hsiang; Lombardi, David A; Brennan, Melanye J; Perry, Melissa J

    2013-01-01

    Falls are a leading cause of injury at work, and slipping is the predominant cause of falling. Prior research has suggested a modest correlation between objective measures (such as coefficient of friction, COF) and subjective measures of slipperiness (such as worker perceptions) in the workplace. However, the degree of association between subjective measures and the actual risk of slipping at the workplace is unknown. This study examined the association between perception of slipperiness and the risk of slipping. 475 workers from 36 limited-service restaurants participated in a 12-week prospective cohort study. At baseline, demographic information was collected, participants rated floor slipperiness in eight areas of the restaurant, and work environment factors, such as COF, were measured. Restaurant-level and area-level mean perceptions of slipperiness were calculated. Participants then reported their slip experience at work on a weekly basis for the next 12 weeks. The associations between perception of slipperiness and the rate of slipping were assessed. Adjusting for age, gender, body mass index, education, primary language, mean COF, use of slip-resistant shoes, and restaurant chain, each 1-point increase in mean restaurant-level perception of slipperiness (4-point scale) was associated with a 2.71 times increase in the rate of slipping (95% CI 1.25 to 5.87). Results were similar for area-level perception within the restaurant (rate ratios (RR) 2.92, 95% CI 2.41 to 3.54). Perceptions of slipperiness and the subsequent rate of slipping were strongly associated. These findings suggest that safety professionals, risk managers and employers could use aggregated worker perceptions of slipperiness to identify slipping hazards and, potentially, to assess intervention effectiveness.

  2. [Association of cooking oil fumes exposure and oxidative DNA damage among occupational exposed populations].

    PubMed

    Ke, Yue-bin; Xu, Xin-yun; Yuan, Jian-hui; Fang, Shi-song; Liu, Yi-min; Wu, Tang-chun

    2010-08-01

    Previous investigations indicate that cooks are exposed to polycyclic aromatic hydrocarbons (PAH) from cooking oil fumes (COF). However, Emission of PAH and their carcinogenic potencies from cooking oil fumes sources have not been investigated among cooks. To investigate the urinary excretion of a marker for oxidative DNA damage, 8-hydroxydeoxyguanosine (8-OHdG), in different groups of cooks and different exposure groups, and to study the association between 8-OHdG and 1-hydroxypyrene (1-OHP), a biological marker for PAH exposure. Urine samples were collected from different groups of cooks (n = 86) and from unexposed controls (n = 36), all are male with similar age and smoking habits. The health status, occupational history, smoking, and alcohol consumption 24 hours prior to sampling was estimated from questionnaires. The urinary samples were frozen for later analyses of 8-OHdG and 1-OHP by high performance liquid chromatography. Excretion in urine of 8-OHdG were similar for controls (mean 1.2 µmol/mol creatinine, n = 36), and for those who had been in the kitchen room with exhaust hood operation (mean 1.5 µmol/mol creatinine, n = 45). COF exposed cooks without exhaust hood operation had increased excretion of 8-OHdG (mean 2.3 µmol/mol creatinine, n = 18). The difference between this group and the unexposed controls was significant. The urinary levels of ln 1-OHP and ln 8-OHdG were still significantly correlated in a multiple regression analysis. Results indicate that exposure to PAH or possibly other compounds in COF may cause oxidative DNA damage.

  3. The relationship of lung cancer with menstrual and reproductive factors may be influenced by passive smoking, cooking oil fumes, and tea intake

    PubMed Central

    He, Fei; Xie, Jing-xian; Liu, Chun-lan; Xiong, Wei-min; Xu, Qiu-ping; Liu, Zhi-qiang; Lin, Tao; Xiao, Ren-dong; Li, Xu; Cai, Lin

    2017-01-01

    Abstract The aim of this study was to investigate the association of menstrual and reproductive factors with risk of lung cancer in women. Potential etiological clues related to lung cancer in women are identified to inform preventive strategies. Case–control study of 477 newly diagnosed women with lung cancer and 479 age-matched (±2 years) controls. Data on menstrual and reproductive factors and history of oral contraceptive use were obtained on personal interviews using a structured questionnaire. Risk factors were analyzed by unconditional logistic regression analysis. Maternal age ≥25 years at first birth appeared to protect against female lung cancer [odds ratios (ORs): 0.511, 95% confidence interval (CI), 0.376–0.693]. Age at menopause > 50 years and use of contraceptives was associated with an increased risk of lung cancer in women (OR: 1.471, 95% CI, 1.021–2.119 and OR: 1.844, 95% CI: 1.111–3.061, respectively). Age ≥13 years at menarche was associated with a decreased risk of lung adenocarcinoma (OR: 0.563, 95% CI, 0.317–0.997). There was significant heterogeneity in the levels of cooking oil fume (COF) exposure (Pheterogeneity = .015). Higher levels of exposure to passive smoking, COF, and lack of tea intake were associated with an increased risk of lung cancer. Menstrual and reproductive factors are considered to play a role in the development of lung cancer in women. Exposure to passive smoking, COF, and lack of tea intake appeared to significantly modify the relationship. PMID:29145344

  4. The relationship of lung cancer with menstrual and reproductive factors may be influenced by passive smoking, cooking oil fumes, and tea intake: A case-control study in Chinese women.

    PubMed

    He, Fei; Xie, Jing-Xian; Liu, Chun-Lan; Xiong, Wei-Min; Xu, Qiu-Ping; Liu, Zhi-Qiang; Lin, Tao; Xiao, Ren-Dong; Li, Xu; Cai, Lin

    2017-11-01

    The aim of this study was to investigate the association of menstrual and reproductive factors with risk of lung cancer in women. Potential etiological clues related to lung cancer in women are identified to inform preventive strategies.Case-control study of 477 newly diagnosed women with lung cancer and 479 age-matched (±2 years) controls. Data on menstrual and reproductive factors and history of oral contraceptive use were obtained on personal interviews using a structured questionnaire. Risk factors were analyzed by unconditional logistic regression analysis.Maternal age ≥25 years at first birth appeared to protect against female lung cancer [odds ratios (ORs): 0.511, 95% confidence interval (CI), 0.376-0.693]. Age at menopause > 50 years and use of contraceptives was associated with an increased risk of lung cancer in women (OR: 1.471, 95% CI, 1.021-2.119 and OR: 1.844, 95% CI: 1.111-3.061, respectively). Age ≥13 years at menarche was associated with a decreased risk of lung adenocarcinoma (OR: 0.563, 95% CI, 0.317-0.997). There was significant heterogeneity in the levels of cooking oil fume (COF) exposure (Pheterogeneity = .015). Higher levels of exposure to passive smoking, COF, and lack of tea intake were associated with an increased risk of lung cancer.Menstrual and reproductive factors are considered to play a role in the development of lung cancer in women. Exposure to passive smoking, COF, and lack of tea intake appeared to significantly modify the relationship.

  5. Electron collisions with F2CO molecules

    NASA Astrophysics Data System (ADS)

    Freitas, Thiago Corrêa; Barbosa, Alessandra Souza; Bettega, Márcio Henrique Franco

    2017-07-01

    In this paper we present elastic differential, integral, and momentum-transfer cross sections for electron collisions with carbonyl fluoride (F2CO ) molecules for the incident electron's energy from 0.5 eV to 20 eV. The Schwinger multichannel method with pseudopotentials was employed to obtain the cross sections in the static-exchange and static-exchange plus polarization approximations. The present results were compared with the available data in the literature, in particular, with the results of Kaur, Mason, and Antony [Phys. Rev. A 92, 052702 (2015), 10.1103/PhysRevA.92.052702] for the differential, total, and momentum-transfer cross sections. We have found a π* shape resonance centered at 2.6 eV in the B1 symmetry and other resonance, in the B2 symmetry, located at around 9.7 eV. A systematic study of the inclusion of polarization effects was performed in order to have a well balanced description of this negative-ion transient state. The effects of the long-range electric dipole potential were included by the Born closure scheme. Electronic structure calculations were also performed to help in the interpretation of the scattering results, and associate the transient states to the unoccupied orbitals.

  6. Virtual screening and biological evaluation of piperazine derivatives as human acetylcholinesterase inhibitors.

    PubMed

    Varadaraju, Kavitha Raj; Kumar, Jajur Ramanna; Mallesha, Lingappa; Muruli, Archana; Mohana, Kikkeri Narasimha Shetty; Mukunda, Chethan Kumar; Sharanaiah, Umesha

    2013-01-01

    The piperazine derivatives have been shown to inhibit human acetylcholinesterase. Virtual screening by molecular docking of piperazine derivatives 1-(1,4-benzodioxane-2-carbonyl) piperazine (K), 4-(4-methyl)-benzenesulfonyl-1-(1,4-benzodioxane-2-carbonyl) piperazine (S1), and 4-(4-chloro)-benzenesulfonyl-1-(1,4-benzodioxane-2-carbonyl) piperazine (S3) has been shown to bind at peripheral anionic site and catalytic sites, whereas 4-benzenesulfonyl-1-(1,4-benzodioxane-2-carbonyl) piperazine (S4) and 4-(2,5-dichloro)-benzenesulfonyl-1-(1,4-benzodioxane-2-carbonyl) piperazine (S7) do not bind either to peripheral anionic site or catalytic site with hydrogen bond. All the derivatives have differed in number of H-bonds and hydrophobic interactions. The peripheral anionic site interacting molecules have proven to be potential therapeutics in inhibiting amyloid peptides aggregation in Alzheimer's disease. All the piperazine derivatives follow Lipinski's rule of five. Among all the derivatives 1-(1,4-benzodioxane-2-carbonyl) piperazine (K) was found to have the lowest TPSA value.

  7. Virtual Screening and Biological Evaluation of Piperazine Derivatives as Human Acetylcholinesterase Inhibitors

    PubMed Central

    Varadaraju, Kavitha Raj; Kumar, Jajur Ramanna; Mallesha, Lingappa; Muruli, Archana; Mohana, Kikkeri Narasimha Shetty; Mukunda, Chethan Kumar; Sharanaiah, Umesha

    2013-01-01

    The piperazine derivatives have been shown to inhibit human acetylcholinesterase. Virtual screening by molecular docking of piperazine derivatives 1-(1,4-benzodioxane-2-carbonyl) piperazine (K), 4-(4-methyl)-benzenesulfonyl-1-(1,4-benzodioxane-2-carbonyl) piperazine (S1), and 4-(4-chloro)-benzenesulfonyl-1-(1,4-benzodioxane-2-carbonyl) piperazine (S3) has been shown to bind at peripheral anionic site and catalytic sites, whereas 4-benzenesulfonyl-1-(1,4-benzodioxane-2-carbonyl) piperazine (S4) and 4-(2,5-dichloro)-benzenesulfonyl-1-(1,4-benzodioxane-2-carbonyl) piperazine (S7) do not bind either to peripheral anionic site or catalytic site with hydrogen bond. All the derivatives have differed in number of H-bonds and hydrophobic interactions. The peripheral anionic site interacting molecules have proven to be potential therapeutics in inhibiting amyloid peptides aggregation in Alzheimer's disease. All the piperazine derivatives follow Lipinski's rule of five. Among all the derivatives 1-(1,4-benzodioxane-2-carbonyl) piperazine (K) was found to have the lowest TPSA value. PMID:24288651

  8. Atmospheric Chemistry of (CF3)2CHOCH3, (CF3)2CHOCHO, and CF3C(O)OCH3.

    PubMed

    Østerstrøm, Freja From; Wallington, Timothy J; Sulbaek Andersen, Mads P; Nielsen, Ole John

    2015-10-22

    Smog chambers with in situ FTIR detection were used to measure rate coefficients in 700 Torr of air and 296 ± 2 K of: k(Cl+(CF3)2CHOCH3) = (5.41 ± 1.63) × 10(-12), k(Cl+(CF3)2CHOCHO) = (9.44 ± 1.81) × 10(-15), k(Cl+CF3C(O)OCH3) = (6.28 ± 0.98) × 10(-14), k(OH+(CF3)2CHOCH3) = (1.86 ± 0.41) × 10(-13), and k(OH+(CF3)2CHOCHO) = (2.08 ± 0.63) × 10(-14) cm(3) molecule(-1) s(-1). The Cl atom initiated oxidation of (CF3)2CHOCH3 gives (CF3)2CHOCHO in a yield indistinguishable from 100%. The OH radical initiated oxidation of (CF3)2CHOCH3 gives the following products (molar yields): (CF3)2CHOCHO (76 ± 8)%, CF3C(O)OCH3 (16 ± 2)%, CF3C(O)CF3 (4 ± 1)%, and C(O)F2 (45 ± 5)%. The primary oxidation product (CF3)2CHOCHO reacts with Cl atoms to give secondary products (molar yields): CF3C(O)CF3 (67 ± 7)%, CF3C(O)OCHO (28 ± 3)%, and C(O)F2 (118 ± 12)%. CF3C(O)OCH3 reacts with Cl atoms to give: CF3C(O)OCHO (80 ± 8)% and C(O)F2 (6 ± 1)%. Atmospheric lifetimes of (CF3)2CHOCH3, (CF3)2CHOCHO, and CF3C(O)OCH3 were estimated to be 62 days, 1.5 years, and 220 days, respectively. The 100-year global warming potentials (GWPs) for (CF3)2CHOCH3, (CF3)2CHOCHO, and CF3C(O)OCH3 are estimated to be 6, 121, and 46, respectively. A comprehensive description of the atmospheric fate of (CF3)2CHOCH3 is presented.

  9. Nanocomposite tribological coatings with "chameleon" surface adaptation

    NASA Astrophysics Data System (ADS)

    Voevodin, A. A.; Fitz, T. A.; Hu, J. J.; Zabinski, J. S.

    2002-07-01

    Nanocomposite tribological coatings were designed to respond to changing environmental conditions by self-adjustment of their surface properties to maintain good tribological performance in any environment. These smart coatings have been dubbed "chameleon" because, analogous to a chameleon changing its skin color to avoid predators, the coating changes its "skin" chemistry and structure to avoid wear. The concept was originally developed using WC, diamondlike carbon, and WS2 material combination for adaptation to a humid/dry environment cycling. In order to address temperature variation, nanocomposite coatings made of yttria-stabilized zirconia (YSZ) in a gold matrix were developed with encapsulated nanosized reservoirs of MoS2 and diamondlike carbon (DLC). Coatings were produced using a combination of laser ablation and magnetron sputtering. They were characterized by x-ray photoelectron spectroscopy, x-ray diffraction, transmission electron microscopy, x-ray energy dispersive spectroscopy, and micro-Raman spectroscopy. Results were correlated with mechanical and tribological characterization. Coating hardness was evaluated using nanoindentation, while coating adhesion and toughness were estimated using scratch and Vickers indentation tests. Friction and wear endurance measurements of YSZ/Au/MoS2/DLC coatings against steel and Si3N4 balls were performed at room temperature in controlled humidity air, dry nitrogen, and vacuum environments, as well as at 500 degC in air. Depending on the environment, coating friction surface changed its chemistry and structure between (i) graphitic carbon for sliding in humid air [coating friction coefficients (c.o.f. 0.10-0.15)], (ii) hexagonal MoS2 for sliding in dry N2 and vacuum (c.o.f. 0.02-0.05), and (iii) metallic Au for sliding in air at 500 degC (c.o.f. 0.10-0.20). The unique coating skin adaptation realized with YSZ/Au/MoS2/DLC and WC/DLC/WS composites proves a universal applicability of the chameleon design concept. copyright 2002 American Vacuum Society.

  10. Synthesis of methyl 2-O-alpha-D-mannopyranosyl-alpha-D-talopyranoside and methyl 2-O-alpha-D-talopyranosyl-alpha-D-talopyranoside.

    PubMed

    Jain, R K; Dubey, R; Abbas, S A; Matta, K L

    1987-03-15

    Treatment of methyl 3-O-benzyl-2-O-(2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl)-alpha-D- mannopyranoside (1) with tert-butyldiphenylsilyl chloride in N,N-dimethylformamide afforded methyl 3-O-benzyl-6-O-tert-butyldiphenylsilyl-2-O-(2,3,4,6-tetra-O-acetyl -alpha-D- mannopyranosyl)-alpha-D-mannopyranoside (2). Oxidation of 2 with pyridinium chlorochromate, followed by reduction of the carbonyl group, and subsequent O-deacetylation afforded methyl 3-O-benzyl-6-O-tert-butyldiphenylsilyl-2-O-alpha-D-mannopyranosyl- alpha-D- talopyranoside (5). Cleavage of the tert-butyldiphenylsilyl group of 5 with tetrabutylammonium fluoride in oxolane, followed by hydrogenolysis, gave methyl 2-O-alpha-D-mannopyranosyl-alpha-D-talopyranoside (7). O-Deacetylation of 1 gave methyl 3-O-benzyl-2-O-alpha-D-mannopyranosyl-alpha-D-mannopyranoside (8). Treatment of 8 with tert-butyldiphenylsilyl chloride afforded a 6,6'-disilyl derivative, which was converted into a 2',3'-O-isopropylidene derivative, and then further oxidized with pyridinium chlorochromate. The resulting diketone was reduced and removal of the protecting groups gave methyl 2-O-alpha-D-talopyranosyl-alpha-D-talopyranoside (15). The structures of both 7 and 15 were established by 13C-n.m.r. spectroscopy.

  11. Effect of fluoride exposure on mRNA expression of cav1.2 and calcium signal pathway apoptosis regulators in PC12 cells.

    PubMed

    Liao, Qiuxia; Zhang, Rui; Wang, Xiaoyu; Nian, Weiwei; Ke, Lulu; Ouyang, Wei; Zhang, Zigui

    2017-09-01

    This study investigated the effects of fluoride exposure on the mRNA expression of Cav1.2 calcium signaling pathway and apoptosis regulatory molecules in PC12 cells. The viability of PC12 cell receiving high fluoride (5.0mM) and low fluoride (0.5mM) alone or fluoride combined with L-type calcium channel (LTCC) agonist/inhibitor (5umol/L FPL6417/2umol/L nifedipine) was detected using cell counting kit-8 at different time points (2, 4, 6, 8, 12, 10, and 24h). Changes in the cell configuration were observed after exposing the cells to fluoride for 24h. The expression levels of molecules related to the LTCC were examined, particularly, Cav1.2, c-fos, CAMK II, Bax, and Bcl-2. Fluoride poisoning induced severe cell injuries, such as decreased PC12 cell activity, enhanced cell apoptosis, high c-fos, CAMKII, and Bax mRNA expression levels. Bcl-2 expression level was also reduced. Meanwhile, high fluoride, high fluoride with FPL64176, and low fluoride with FPL64176 enhanced the Cav1.2 expression level. In contrast, low fluoride, high fluoride with nifedipine, and low fluoride with nifedipine reduced the Cav1.2 expression level. Thus, Cav1.2 may be an important molecular target for the fluorosis treatment, and the LTCC inhibitor nifedipine may be an effective drug for fluorosis. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Electrochemical degradation of 5-FU using a flow reactor with BDD electrode: Comparison of two electrochemical systems.

    PubMed

    Ochoa-Chavez, A S; Pieczyńska, A; Fiszka Borzyszkowska, A; Espinoza-Montero, P J; Siedlecka, E M

    2018-06-01

    In this study, the electrochemical degradation process of 5-fluorouracil (5-FU) in aqueous media was performed using a continuous flow reactor in an undivided cell (system I), and in a divided cell with a cationic membrane (Nafion ® 424) (system II). In system I, 75% of 5-FU degradation was achieved (50 mg L -1 ) with a applied current density j app  = 150 A m -2 , volumetric flow rate qv = 13 L h -1 , after 6 h of electrolysis (k app  = 0.004 min -1 ). The removal efficiency of 5-FU was higher (95%) when the concentration was 5 mg L -1 under the same conditions. Nitrates (22% of initial amount of N), fluorides (27%) and ammonium (10%) were quantified after 6 h of electrolysis. System II, 77% of 5-FU degradation was achieved (50 mg L -1 ) after 6 h of electrolysis (k app  = 0.004 min -1 ). The degradation rate of 5-FU was complete when the concentration was 5 mg L -1 under the same conditions. Nitrates (29% of initial amount of N), fluorides (25%) and ammonium (5%) were quantified after 6 h of electrolysis. In addition, the main organic byproducts identified by mass spectroscopy were aliphatic compound with carbonyl and carboxyl functionalities. Due to, the mineralization of 5-FU with acceptable efficiency of 88% found in system II (j app of 200 A m -2 ), this system seems to be more promising in the cytostatic drug removal. Moreover the efficiency of 5-FU removal in diluted solutions is better in system II than in system I. Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Determination of carbonyl compounds generated from the E-cigarette using coupled silica cartridges impregnated with hydroquinone and 2,4-dinitrophenylhydrazine, followed by high-performance liquid chromatography.

    PubMed

    Uchiyama, Shigehisa; Ohta, Kazushi; Inaba, Yohei; Kunugita, Naoki

    2013-01-01

    Carbonyl compounds in E-cigarette smoke mist were measured using coupled silica cartridges impregnated with hydroquinone and 2,4-dinitrophenylhydrazine, followed by high-performance liquid chromatography. A total of 363 E-cigarettes (13 brands) were examined. Four of the 13 E-cigarette brands did not generate any carbonyl compounds, while the other nine E-cigarette brands generated various carbonyl compounds. However, the carbonyl concentrations of the E-cigarette products did not show typical distributions, and the mean values were largely different from the median values. It was elucidated that E-cigarettes incidentally generate high concentrations of carbonyl compounds.

  14. Effect of Al2O3sf addition on the friction and wear properties of (SiCp+Al2O3sf)/Al2024 composites fabricated by pressure infiltration

    NASA Astrophysics Data System (ADS)

    Xu, Hui; Zhang, Gong-zhen; Cui, Wei; Ren, Shu-bin; Wang, Qian-jin; Qu, Xuan-hui

    2018-03-01

    Aluminum (Al) 2024 matrix composites reinforced with alumina short fibers (Al2O3sf) and silicon carbide particles (SiCp) as wear-resistant materials were prepared by pressure infiltration in this study. Further, the effect of Al2O3sf on the friction and wear properties of the as-synthesized composites was systematically investigated, and the relationship between volume fraction and wear mechanism was discussed. The results showed that the addition of Al2O3sf, characterized by the ratio of Al2O3sf to SiCp, significantly affected the properties of the composites and resulted in changes in wear mechanisms. When the volume ratio of Al2O3sf to SiCp was increased from 0 to 1, the rate of wear mass loss ( K m) and coefficients of friction (COFs) of the composites decreased, and the wear mechanisms were abrasive wear and furrow wear. When the volume ratio was increased from 1 to 3, the COF decreased continuously; however, the K m increased rapidly and the wear mechanism became adhesive wear.

  15. Study on the friction of κ-carrageenan hydrogels in air and aqueous environments.

    PubMed

    Kozbial, Andrew; Li, Lei

    2014-03-01

    Understanding the friction mechanism of polysaccharide hydrogels, which is the key component of human cartilage that has very low friction coefficient, is critical to develop next generation artificial joint replacement materials. In this study, the friction of the polysaccharide κ-carrageenan hydrogel was investigated to elucidate the effect of external load, cross-linking density, velocity, and environment on friction. Our experimental results show that (1) coefficient of friction (COF) decreases with normal load in air and remains constant in water, (2) increasing cross-linking density concurrently increases friction and is proportional to Young's modulus, (3) COF increases with testing velocity in both air and water, and (4) friction is reduced in aqueous environment due to the lubricating effect of water. The underlying frictional mechanism is discussed on the basis of water transport from bulk to surface and a previously proposed "repulsion-adsorption" model. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Chemical probes for analysis of carbonylated proteins: a review

    PubMed Central

    Yan, Liang-Jun; Forster, Michael J.

    2010-01-01

    Protein carbonylation is a major form of protein oxidation and is widely used as an indicator of oxidative stress. Carbonyl groups do not have distinguishing UV or visible, spectrophotometric absorbance/fluorescence characteristics and thus their detection and quantification can only be achieved using specific chemical probes. In this paper, we review the advantages and disadvantages of several chemical probes that have been and are still being used for protein carbonyl analysis. These probes include 2, 4-dinitrophenylhydazine (DNPH), tritiated sodium borohydride ([3H]NaBH4), biotin-containing probes, and fluorescence probes. As our discussions lean toward gel-based approaches, utilizations of these probes in 2D gel-based proteomic analysis of carbonylated proteins are illustrated where applicable. Analysis of carbonylated proteins by ELISA, immunofluorescent imaging, near infrared fluorescence detection, and gel-free proteomic approaches are also discussed where appropriate. Additionally, potential applications of blue native gel electrophoresis as a tool for first dimensional separation in 2D gel-based analysis of carbonylated proteins are discussed as well. PMID:20732835

  17. No calcium-fluoride-like deposits detected in plaque shortly after a sodium fluoride mouthrinse.

    PubMed

    Vogel, G L; Tenuta, L M A; Schumacher, G E; Chow, L C

    2010-01-01

    Plaque 'calcium-fluoride-like' (CaF(2)-like) and fluoride deposits held by biological/bacterial calcium fluoride (Ca-F) bonds appear to be the source of cariostatic concentrations of fluoride in plaque fluid. The aim of this study was to quantify the amounts of plaque fluoride held in these reservoirs after a sodium fluoride rinse. 30 and 60 min after a 228 microg/g fluoride rinse, plaque samples were collected from 11 volunteers. Each sample was homogenized, split into 2 aliquots (aliquots 1 and 2), centrifuged, and the recovered plaque fluid combined and analyzed using microelectrodes. The plaque mass from aliquot 1 was retained. The plaque mass from aliquot 2 was extracted several times with a solution having the same fluoride, calcium and pH as the plaque fluid in order to extract the plaque CaF(2)-like deposits. The total fluoride in both aliquots was then determined. In a second experiment, the extraction completeness was examined by applying the above procedure to in vitro precipitates containing known amounts of CaF(2)-like deposits. Nearly identical fluoride concentrations were found in both plaque aliquots. The extraction of the CaF(2)-like precipitates formed in vitro removed more than 80% of these deposits. The results suggest that either CaF(2)-like deposits were not formed in plaque or, if these deposits had been formed, they were rapidly lost. The inability to form persistent amounts of CaF(2)-like deposits in plaque may account for the relatively rapid loss of plaque fluid fluoride after the use of conventional fluoride dentifrices or rinses. (c) 2010 S. Karger AG, Basel.

  18. No Calcium-Fluoride-Like Deposits Detected in Plaque Shortly after a Sodium Fluoride Mouthrinse

    PubMed Central

    Vogel, G.L.; Tenuta, L.M.A.; Schumacher, G.E.; Chow, L.C.

    2010-01-01

    Plaque ‘calcium-fluoride-like’ (CaF2-like) and fluoride deposits held by biological/bacterial calcium fluoride (Ca-F) bonds appear to be the source of cariostatic concentrations of fluoride in plaque fluid. The aim of this study was to quantify the amounts of plaque fluoride held in these reservoirs after a sodium fluoride rinse. 30 and 60 min after a 228 μg/g fluoride rinse, plaque samples were collected from 11 volunteers. Each sample was homogenized, split into 2 aliquots (aliquots 1 and 2), centrifuged, and the recovered plaque fluid combined and analyzed using microelectrodes. The plaque mass from aliquot 1 was retained. The plaque mass from aliquot 2 was extracted several times with a solution having the same fluoride, calcium and pH as the plaque fluid in order to extract the plaque CaF2-like deposits. The total fluoride in both aliquots was then determined. In a second experiment, the extraction completeness was examined by applying the above procedure to in vitro precipitates containing known amounts of CaF2-like deposits. Nearly identical fluoride concentrations were found in both plaque aliquots. The extraction of the CaF2-like precipitates formed in vitro removed more than 80% of these deposits. The results suggest that either CaF2-like deposits were not formed in plaque or, if these deposits had been formed, they were rapidly lost. The inability to form persistent amounts of CaF2-like deposits in plaque may account for the relatively rapid loss of plaque fluid fluoride after the use of conventional fluoride dentifrices or rinses. PMID:20185917

  19. Structures and Fragmentation Mechanisms of the Ions of Ethanol by Triple Quadrupole Mass Spectrometry.

    DTIC Science & Technology

    1982-07-15

    structural information contained in deuterated sp ies is readily obtainable. Eth 1 ions ty stdied tnc) Vde (CH3CHOH?’., [CH CHOHJ. (CH2COH]r-% [CH 2COF...high and low energy systems involves electronic 18 and vibrational 19 excitation respectively, the amount of energy thus deposited must be approximately

  20. Decentralized control of the COFS-I Mast using linear dc motors

    NASA Technical Reports Server (NTRS)

    Lindner, Douglas K.; Celano, Tom; Ide, Eric

    1989-01-01

    Consideration is given to a decentralized control design for vibration suppression in the COFS-I Mast using linear dc motors for actuators. The decentralized control design is based results from power systems using root locus techniques that are not well known. The approach is effective because the loop gain is low due to low actuator authority. The frequency-dependent nonlinearities of the actuator are taken into account. Because of the tendency of the transients to saturate the the stroke length of the actuator, its effectiveness is limited.

  1. Oxidative versus Non-oxidative Decarboxylation of Amino Acids: Conditions for the Preferential Formation of Either Strecker Aldehydes or Amines in Amino Acid/Lipid-Derived Reactive Carbonyl Model Systems.

    PubMed

    Zamora, Rosario; León, M Mercedes; Hidalgo, Francisco J

    2015-09-16

    Comparative formation of both 2-phenylethylamine and phenylacetaldehyde as a consequence of phenylalanine degradation by carbonyl compounds was studied in an attempt to understand if the amine/aldehyde ratio can be changed as a function of reaction conditions. The assayed carbonyl compounds were selected because of the presence in the chain of both electron-donating and electron-withdrawing groups and included alkenals, alkadienals, epoxyalkenals, oxoalkenals, and hydroxyalkenals as well as lipid hydroperoxides. The obtained results showed that the 2-phenylethylamine/phenylacetaldehyde ratio depended upon both the carbonyls and the reaction conditions. Thus, it can be increased using electron-donating groups in the chain of the carbonyl compound, small amounts of carbonyl compound, low oxygen content, increasing the pH, or increasing the temperature at pH 6. Opposed conditions (use of electron-withdrawing groups in the chain of the carbonyl compound, large amounts of carbonyl compound, high oxygen contents, low pH values, and increasing temperatures at low pH values) would decrease the 2-phenylethylamine/phenylacetaldehyde ratio, and the formation of aldehydes over amines in amino acid degradations would be favored.

  2. Synthesis and investigation of Pd(I) carbonyl complexes with heteroorganic ligands

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

    Lamberov, A.A.; Polovnyak, V.K.; Akhmetov, N.S.

    1987-09-10

    Pd(I) carbonyl complexes are attracting attention because they have been shown to have catalytic properties in a series of organic syntheses. The stability and catalytic properties of these compounds are determined by the nature of the phosphine ligand and the bridge coordination of the carbonylgroup. Through the partial replacement of carbonyl and acido ligands by heteroorganic ligands in carbonyl halogenide and carbonyl acetate Pd(I) complexes, new stable Pd(I) complexes were obtained: (PdLX)/sub 2/CO, where L = PPh/sub 3/, X = OAc; L = AsPh/sub 3/, X = Cl, Br, OAc; L = SbPh/sub 3/, X = Cl Br, OAc; Lmore » = Ph/sub 2/PCH/sub 2/PPh/sub 2/, Ph/sub 2/AsCH/sub 2/AsPh/sub 2/, X = OAc. Atoms of the heteroorganic and acido ligands are equivalently coordinated to the palladium atoms. The carbonyl group in the complexes has bridge coordination to palladium atoms in the Pd(CO)Pd fragment; in complexes with bidentate heteroorganic ligands the covalent bond between palladium atoms is absent.« less

  3. Fluoride Binding to Dental Biofilm Bacteria: Synergistic Effect with Calcium Questioned.

    PubMed

    Nóbrega, Diego Figueiredo; Leitão, Tarcísio Jorge; Cury, Jaime Aparecido; Tenuta, Livia Maria Andaló

    2018-06-06

    It has been suggested that fluoride binding to dental biofilm is enhanced when more bacterial calcium binding sites are available. However, this was only observed at high calcium and fluoride concentrations (i.e., when CaF2 precipitation may have occurred). We assessed fluoride binding to Streptococcus mutans pellets treated with calcium and fluoride at concentrations allowing CaF2 precipitation or not. Increasing calcium concentration resulted in a linear increase (p < 0.01) in fluoride concentration only in the pellets in which CaF2 precipitated. The results suggest that CaF2 precipitation, rather than bacterially bound fluoride, is responsible for the increase in fluoride binding to dental biofilm with the increase in calcium availability. © 2018 S. Karger AG, Basel.

  4. Comparison of carbonyl compounds emissions from diesel engine fueled with biodiesel and diesel

    NASA Astrophysics Data System (ADS)

    He, Chao; Ge, Yunshan; Tan, Jianwei; You, Kewei; Han, Xunkun; Wang, Junfang; You, Qiuwen; Shah, Asad Naeem

    The characteristics of carbonyl compounds emissions were investigated on a direct injection, turbocharged diesel engine fueled with pure biodiesel derived from soybean oil. The gas-phase carbonyls were collected by 2,4-dinitrophenylhydrazine (DNPH)-coated silica cartridges from diluted exhaust and analyzed by HPLC with UV detector. A commercial standard mixture including 14 carbonyl compounds was used for quantitative analysis. The experimental results indicate that biodiesel-fueled engine almost has triple carbonyls emissions of diesel-fueled engine. The weighted carbonyls emission of 8-mode test cycle of biodiesel is 90.8 mg (kW h) -1 and that of diesel is 30.7 mg (kW h) -1. The formaldehyde is the most abundant compound of carbonyls for both biodiesel and diesel, taking part for 46.2% and 62.7% respectively. The next most significant compounds are acetaldehyde, acrolein and acetone for both fuels. The engine fueled with biodiesel emits a comparatively high content of propionaldehyde and methacrolein. Biodiesel, as an alternative fuel, has lower specific reactivity (SR) caused by carbonyls compared with diesel. When fueled with biodiesel, carbonyl compounds make more contribution to total hydrocarbon emission.

  5. Gas chromatography-mass spectrometry of carbonyl compounds in cigarette mainstream smoke after derivatization with 2,4-dinitrophenylhydrazine.

    PubMed

    Dong, Ji-Zhou; Moldoveanu, Serban C

    2004-02-20

    An improved gas chromatography-mass spectrometry (GC-MS) method was described for the analysis of carbonyl compounds in cigarette mainstream smoke (CMS) after 2,4-dinitrophenylhydrazine (DNPH) derivatization. Besides formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, methyl ethyl ketone, butyraldehyde, and crotonaldehyde that are routinely analyzed in cigarette smoke, this technique separates and allows the analysis of several C4, C5 and C6 isomeric carbonyl compounds. Differentiation could be made between the linear and branched carbon chain components. In cigarette smoke, the branched chain carbonyls are found at higher level than the linear chain carbonyls. Also, several trace carbonyl compounds such as methoxyacetaldehyde were found for the first time in cigarette smoke. For the analysis, cigarette smoke was collected using DNPH-treated pads, which is a simpler procedure compared to conventional impinger collection. Thermal decomposition of DNPH-carbonyl compounds was minimized by the optimization of the GC conditions. The linear range of the method was significantly improved by using a standard mixture of DNPH-carbonyl compounds instead of individual compounds for calibration. The minimum detectable quantity for the carbonyls ranged from 1.4 to 5.6 microg/cigarette.

  6. [Chronic combined effects of fluoride and arsenite on the Runx2 and downstream related factors of bone metabolism in rats].

    PubMed

    Hong, Feng; Zheng, Chong; Xu, De-gan; Qian, Ya-li

    2013-09-01

    To observe the chronic combined effects of sodium fluoride and sodium arsenite on the Runx2 and downstream related factors of bone metabolism in SD rats. SD rats were divided randomly into nine groups of 6 each by factorial experimental design (half female and half male) , and supplied with the different doses of fluoride, arsenite and fluoride plus arsenite containing in deionized water (untreated control containing 0 mg/kg fluoride and 0 mg/kg arsenite, and low-fluoride and high supplemented with 5 and 20 mg/kg fluoride, and low-arsenite and high supplemented with 2.5 and 10 mg/kg arsenite, and low-fluoride plus low-arsenite, and low-fluoride plus high-arsenite, and high-fluoride plus low-arsenite, and high-fluoride plus high-arsenite, respectively) . After 6 months exposure, the concentration of Runx2, matrix metallopeptidase 9 (MMP-9) ,Osterix, Receptor activator for nuclear factor-κ β ligand (RANKL) were detected by enzyme-linked immunosorbent assay method, respectively. There were no dental fluorosis found in the control group, low-arsenic group and high-arsenic group. There were significant differences in the constituent ratio of dental fluorosis among the rats from low-fluoride and high-fluoride (that is 5 rats out of 6 and 6 rats out of 6) compared with the control group (0 rat out of 6) (χ(2) = 8.57, 12.00, P < 0.05). The bone fluorine level increased with the increase of fluoride dose, the groups without fluoride supply (control group, low-arsenite and high-arsenite group's geometric mean (minimum-maximum) were 0.005 (0.003-0.009), 0.006 (0.003-0.021), 0.003 (0.002-0.100) mg/g, respectively), low-fluorine groups (low-fluoride group, low-fluoride plus low-arsenite, and low-fluoride plus high-arsenite group were 3.395 (2.416-5.871), 3.809 (1.471-7.799), 1.471 (1.473-6.732)mg/g, respectively) , the high-fluorine groups (high-fluoride, high-fluoride plus low-arsenite, and high-fluoride plus high-arsenite group were 70.086 (46.183-131.927), 69.925 (40.503-96.183), 40.503 (52.622-89.487) mg/g, respectively) and the differences between groups was significant (P < 0.05). The bone arsenic level increased with the increase of arsenite dose. The low-arsenic groups (low-arsenite group, low-arsenite plus low-fluoride, and low-arsenite plus high-fluoride group were 7.195 (5.060-9.860), 6.518 (2.960-12.130), 6.970 (3.400-9.730) µg/g, respectively), the high-arsenic groups (high-arsenite, high-arsenite plus low-fluoride, and high-fluoride plus high-arsenite group's geometric mean(minimum-maximum) were 8.823 (5.760-10.840), 9.470 (7.230-12.860), 8.321 (2.420-17.540) µg/g, respectively) were significantly higher than that in the groups without arsenic supply (control group, low-fluoride and high-fluoride group were 1.785 (0.300-3.750), 2.226 (1.410-3.980), 2.030 (1.040-3.850)µg/g, respectively) (P < 0.05). There was no significant difference of the bone arsenic concentration between low-arsenic and high arsenic group. There was significant positive correlation between fluoride concentration and Runx2, MMP-9, Osterix, RANKL level (the correlation coefficient was 0.647, 0.354, 0.582, 0.613 between fluorine gavage concentration and protein level, the correlation coefficient was 0.559,0.387, 0.487, 0.525 between bone fluorine concentration and protein level, respectively, P < 0.01). There was negative correlation between arsenite gavage concentration with Runx2 level (r = -0.527, P < 0.05) and was no correlation between arsenite gavage concentration with MMP-9, RANKL,Osterix level (P > 0.05). There was interaction between fluoride and arsenite to Runx2, MMP-9, RANKL,Osterix (F = 3.88, 15.66, 2.92, 6.42, respectively, P = 0.01, <0.01, 0.031, <0.01, respectively). The combined effects of fluoride and arsenic on the Runx2, MMP-9, RANKL, Osterix of bone metabolism showed antagonistic effects.

  7. Analysis of biogenic carbonyl compounds in rainwater by stir bar sorptive extraction technique with chemical derivatization and gas chromatography‐mass spectrometry

    PubMed Central

    Lewis, Alastair C.; Shaw, Marvin D.

    2016-01-01

    Stir bar sorptive extraction is a powerful technique for the extraction and analysis of organic compounds in aqueous matrices. Carbonyl compounds are ubiquitous components in rainwater, however, it is a major challenge to accurately identify and sensitively quantify carbonyls from rainwater due to the complex matrix. A stir bar sorptive extraction technique was developed to efficiently extract carbonyls from aqueous samples following chemical derivatization by O‐(2,3,4,5,6‐pentafluorobenzyl) hydroxylamine hydrochloride. Several commercial stir bars in two sizes were used to simultaneously measure 29 carbonyls in aqueous samples with detection by gas chromatography with mass spectrometry. A 100 mL aqueous sample was extracted by stir bars and the analytes on stir bars were desorbed into a 2 mL solvent solution in an ultrasonic bath. The preconcentration Coefficient for different carbonyls varied between 30 and 45 times. The limits of detection of stir bar sorptive extraction with gas chromatography mass spectrometry for carbonyls (10–30 ng/L) were improved by ten times compared with other methods such as gas chromatography with electron capture detection and stir bar sorptive extraction with high‐performance liquid chromatography and mass spectrometry. The technique was used to determine carbonyls in rainwater samples collected in York, UK, and 20 carbonyl species were quantified including glyoxal, methylglyoxal, isobutenal, 2‐hydroxy ethanal. PMID:27928898

  8. In situ study of the anticariogenic potential of fluoride varnish combined with CO2 laser on enamel.

    PubMed

    Souza-Gabriel, Aline Evangelista; Turssi, Cecília Pedroso; Colucci, Vivian; Tenuta, Lívia Maria Andaló; Serra, Mônica Campos; Corona, Silmara Aparecida Milori

    2015-06-01

    This in situ study evaluated the effect of fluoride varnish combined with CO2 laser in controlling enamel demineralization caused by cariogenic challenges. In a crossover study conducted in 2 phases of 14 days each, 14 volunteers (n = 14) wore palatal appliances with bovine enamel slabs treated with fluoride varnish + CO2 laser (FV + CO2), fluoride varnish (FV), nonfluoride placebo varnish (PV) and nonfluoride placebo varnish + CO2 laser (PV + CO2). Drops of sucrose solution were dripped onto enamel slabs allowing the accumulation of biofilm. At the first phase, half of the volunteers received 4 enamel slabs treated with FV while the remainders received slabs exposed to the PV with and without CO2 laser. In the second phase, the vonlunteers were reversed treatments. The slabs were evaluated for cross-sectional microhardness (CSMH) and the concentration of loosely bound fluoride (CaF2) and firmly bound fluoride (FAp). The concentration of fluoride in biofilm were also determined. Two-way ANOVA showed that the CSMH values were higher in laser-irradiated enamel, regardless of the fluoride varnish. Friedman test showed that FV group presented significantly larger amount of fluoride in biofilm (P < 0.05). In the enamel, the largest amount of fluoride was found in the groups FV + CO2, which was not different from FV (P > 0.05). The synergistic effect of fluoride varnish and CO2 laser on enamel demineralization was not observed, however, CO2 laser reduces enamel demineralization. CO2 laser might reduce the demineralization of subsurface enamel, although its association with a high concentrated fluoride therapy may not result in a positive synergistic interaction. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Factors associated with worker slipping in limited-service restaurants.

    PubMed

    Courtney, Theodore K; Verma, Santosh K; Huang, Yueng-Hsiang; Chang, Wen-Ruey; Li, Kai Way; Filiaggi, Alfred J

    2010-02-01

    Slips, trips and falls (STF) are responsible for a substantial injury burden in the global workplace. Restaurant environments are challenged by STF. This study assessed individual and work environment factors related to slipping in US limited-service restaurant workers. Workers in 10 limited-service restaurants in Massachusetts were recruited to participate. Workers' occupational slip and/or fall history within the past 4 weeks was collected by multilingual written questionnaires. Age, gender, job tenure, work hours per week and work shift were also collected. Shoe type, condition and gross shoe contamination were visually assessed. Floor friction was measured and each restaurant's overall mean coefficient of friction (COF) was calculated. The logistic generalised estimating equations model was used to compute adjusted odds ratios (OR). Of 125 workers, 42 reported one or more slips in the past 4 weeks with two reporting a resultant fall. Results from multivariable regression showed that higher restaurant mean COF was significantly associated with a decreased risk of self-reported slipping (OR 0.59, 95% CI 0.42 to 0.82). From the highest to the lowest COF restaurant, the odds of a positive slip history increased by a factor of more than seven. Younger age, male gender, lower weekly work hours and the presence of gross contamination on worker's shoe sole were also associated with increased odds of slip history. Published findings of an association between friction and slipping and falling in actual work environments are rare. The findings suggest that effective intervention strategies to reduce the risk of slips and falls in restaurant workers could include increasing COF and improving housekeeping practices.

  10. Cognitive and emotional functioning in binge-eating disorder: A systematic review.

    PubMed

    Kittel, Rebekka; Brauhardt, Anne; Hilbert, Anja

    2015-09-01

    Binge-eating disorder (BED) is characterized by recurrent episodes of binge eating and is associated with eating disorder and general psychopathology and overweight/obesity. Deficits in cognitive and emotional functioning for eating disorders or obesity have been reported. However, a systematic review on cognitive and emotional functioning for individuals with BED is lacking. A systematic literature search was conducted across three databases (Medline, PubMed, and PsycINFO). Overall, n = 57 studies were included in the present review. Regarding cognitive functioning (CoF), individuals with BED consistently demonstrated higher information processing biases compared to obese and normal-weight controls in the context of disorder-related stimuli (i.e., food and body cues), whereas CoF in the context of neutral stimuli appeared to be less affected. Thus, results suggest disorder-related rather than general difficulties in CoF in BED. With respect to emotional functioning (EmF), individuals with BED reported difficulties similar to individuals with other eating disorders, with a tendency to show less severe difficulties in some domains. In addition, individuals with BED reported greater emotional deficits when compared to obese and normal-weight controls. Findings suggest general difficulties in EmF in BED. Thus far, however, investigations of EmF in disorder-relevant situations are lacking. Overall, the cross-sectional findings indicate BED to be associated with difficulties in CoF and EmF. Future research should determine the nature of these difficulties, in regards to general and disorder-related stimuli, and consider interactions of both domains to foster the development and improvement of appropriate interventions in BED. © 2015 Wiley Periodicals, Inc.

  11. Coffee Ingestion Enhances One-Mile Running Race Performance.

    PubMed

    Clarke, Neil D; Richardson, Darren L; Thie, James; Taylor, Richard

    2017-11-15

    Caffeine, often in the form of coffee, is frequently supplemented by athletes in an attempt to facilitate improved performance during exercise. The aim of the present study was to investigate the effectiveness of coffee ingestion as an ergogenic aid prior to a one-mile (1609 m) race. In a double-blind, randomised, crossover, placebo-controlled design 13 trained male runners completed a one-mile race 60 minutes following the ingestion of 0.09 g·kg -1 coffee (COF), 0.09 g·kg -1 decaffeinated coffee (DEC), or a placebo (PLA). All trials were dissolved in 300 ml of hot water. The race completion time was 1.3% faster following the ingestion of COF (04:35:37 ± 00:10:51 mm·ss) compared with DEC (04:39:14 ± 00:11:21 mm·ss; P=0.018; 95%CI: -0.11, -0.01; d=0.32) and 1.9% faster compared with PLA (04:41:00 ± 00:09:57 mm:ss; P=0.006; 95%CI: -0.15, -0.03; d=0.51). A large trial and time interaction for salivary caffeine concentration was observed (P<0.001; η 2 P =0.69) with a very large increase (6.40 ± 1.57 μg·ml -1 , 95%CI: 5.5, 7.3; d=3.86) following the ingestion of COF. However, only a trivial difference between DEC and PLA was observed (P=0.602; 95%CI: -0.09, 0.03; d=0.17). Furthermore, only trivial differences for blood glucose (P=0.839; η 2 P =0.02) and lactate (P=0.096; η 2 P =0.18), and maximal heart rate (P=0.286; η 2 P =0.13) were observed between trials. The results of the present study show that 60 minutes after ingesting 0.09 g·kg -1 of caffeinated coffee one-mile race performance was enhanced by 1.9% and 1.3% compared with placebo and decaffeinated coffee respectively, in trained male runners.

  12. Quantification of protein carbonylation.

    PubMed

    Wehr, Nancy B; Levine, Rodney L

    2013-01-01

    Protein carbonylation is the most commonly used measure of oxidative modification of proteins. It is most often measured spectrophotometrically or immunochemically by derivatizing proteins with the classical carbonyl reagent 2,4 dinitrophenylhydrazine (DNPH). We present protocols for the derivatization and quantification of protein carbonylation with these two methods, including a newly described dot blot with greatly increased sensitivity.

  13. Active control of methanol carbonylation selectivity over Au/carbon anode by electrochemical potential.

    PubMed

    Funakawa, Akiyasu; Yamanaka, Ichiro; Otsuka, Kiyoshi

    2005-05-12

    Electrochemical oxidative carbonylation of methanol was studied over Au supported carbon anode in CO. The major carbonylation products were dimethyl oxalate (DMO) and dimethyl carbonate (DMC). The minor oxidation products were dimethoxy methane (DMM) and methyl formate (MF) from methanol and CO(2). Influences of various reaction conditions were studied on carbonylation activities and selectivities. The selectivities to DMO and DMC can be controlled by the electrochemical potential. Electrocatalysis of Au/carbon anode was studied by cyclic voltammetry (CV), stoichiometric reactions among Au(3+), methanol, and CO, and UV-vis spectra. The Au/carbon anode was characterized by XRD, SEM, and BE images before and after the carbonylation. These experimental facts strongly suggest that transition of oxidation states of Au affects changing of the carbonylation selectivities to DMO and DMC. Au(0) is the active species for the selective DMO formation by direct electrochemical carbonylation at low potentials (<+1.2 V (Ag/AgCl)). On the other hand, Au(3+) is the active spices for the selective DMC formation by indirect electrochemical carbonylation through Au(3+)/Au(+) redox at high potentials (>+1.3 V).

  14. FLUORIDATION CHEMISTRY: EQUILIBRIA AND KINETICS OF FLUORIDE AND FLUORO-COMPLEXES

    EPA Science Inventory

    The most common fluoridating agents used by major American waterworks are hexafluorosilicic acid (H2SiF6) and sodium hexxafluorosilicate (Na2SiF6). According to the 1992 Water Fluoridation Census where 10,002 utilities responded affirmatively to fluoridating their water, 59
    % ...

  15. Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms for organometallic complexes

    NASA Astrophysics Data System (ADS)

    Our studies of reactions of metal carbonyl cations and anions have shown that metal carbonyl cations can catalyze CO exchange reactions on metal carbonyl anions. This result provides further evidence for a mechanism involving attack of the metal carbonyl anion on a carbon of the metal carbonyl cation in CO(exp 2+) transfer reactions. Reaction of metal carbonyl anions with metal carbonyl halides is a common approach to formation of metal-metal bonds. We have begun to use kinetic data and product analysis to understand the formation of homobimetallic versus heterobimetallic products in such reactions. Initial data indicate a nucleophilic attack, possibly through a ring-slippage mechanism.

  16. Hazardous airborne carbonyls emissions in industrial workplaces in China.

    PubMed

    Ho, Steven Sai Hang; Ip, Ho Sai Simon; Ho, Kin Fai; Ng, Louisa Pan Ting; Chan, Chi Sing; Dai, Wen Ting; Cao, Jun Ji

    2013-07-01

    A pilot hazardous airborne carbonyls study was carried out in Hong Kong and the Mainland of China. Workplace air samples in 14 factories of various types of manufacturing and industrial operations were collected and analyzed for a panel of 21 carbonyl compounds. The factories can be classified into five general categories, including food processing, electroplating, textile dyeing, chemical manufacturer, and petroleum refinery. Formaldehyde was invariably the most abundant carbonyl compound among all the workplace air samples, accounting for 22.0-44.0% of the total measured amount of carbonyls on a molar basis. Acetone was also found to be an abundant carbonyl in workplace settings; among the selected industrial sectors, chemical manufacturers' workplaces had the highest percentage (an average of 42.6%) of acetone in the total amount of carbonyls measured in air. Benzaldehyde accounted for an average of 20.5% of the total amount of detected carbonyls in electroplating factories, but its contribution was minor in other industrial workplaces. Long-chain aliphatic carbonyls (C6-C10) accounted for a large portion (37.2%) of the total carbonyls in food-processing factories. Glyoxal and methylglyoxal existed at variable levels in the selected workplaces, ranging from 0.2% to 5.5%. The mixing ratio of formaldehyde ranged from 8.6 to 101.2 ppbv in the sampled workplaces. The observed amount of formaldehyde in two paint and wax manufacturers and food-processing factories exceeded the World Health Organization (WHO) air quality guideline of 81.8 ppbv. Carcinogenic risks of chronic exposure to formaldehyde and acetaldehyde by the workers were evaluated. The lifetime cancer hazard risks associated with formaldehyde exposure to male and female workers ranged from 2.01 x 10(-5) to 2.37 x 10(-4) and 2.68 x 10(-5) to 3.16 x 10(-4), respectively. Such elevated risk values suggest that the negative health impact of formaldehyde exposure represents a valid concern, and proper actions should be taken to protect workers from such risks. Many carbonyl species (e.g., formaldehyde, acetaldehyde, and acrolein) are air toxins and they pose public healt risks. The scope of this investigation covers 21 types of carbonyls based on samples collected from 14 different workplaces. Findings of the study will not only provide a comprehensive assessment of indoor air quality with regard to workers' healthy and safety, but also establish a theoretical foundation for future formulation of intervention strategies to reduce occupational carbonyl exposures. No similar study has been carried out either in Hong Kong or the Mainland of China.

  17. Rh(I) -Catalyzed Intramolecular Carbonylative C-H/C-I Coupling of 2-Iodobiphenyls Using Furfural as a Carbonyl Source.

    PubMed

    Furusawa, Takuma; Morimoto, Tsumoru; Nishiyama, Yasuhiro; Tanimoto, Hiroki; Kakiuchi, Kiyomi

    2016-08-19

    Synthesis of fluoren-9-ones by a Rh-catalyzed intramolecular C-H/C-I carbonylative coupling of 2-iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate-determining step is not a C-H bond cleavage but, rather, the oxidative addition of the C-I bond to a Rh(I) center. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Enhanced antioxidation and microwave absorbing properties of SiO2-coated flaky carbonyl iron particles

    NASA Astrophysics Data System (ADS)

    Zhou, Yingying; Xie, Hui; Zhou, Wancheng; Ren, Zhaowen

    2018-01-01

    SiO2 was successfully coated on the surface of flaky carbonyl iron particles using a chemical bath deposition method in the presence of 3-aminopropyl triethoxysilane (APTES). The morphologies, composition, valence states of elements, as well as antioxidation and electromagnetic properties of the samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG) and microwave network analyzer. TG curve shows the obvious weight gain of carbonyl iron was deferred to 360 °C after SiO2-coated, which can be ascribed to the exits of SiO2 overlayer. Compared with the raw carbonyl iron, SiO2-coated sample shows good wave absorption performance due to its impedance matching. The electromagnetic properties of raw and SiO2-coated carbonyl iron particles were characterized in X band before and after heat treatment at 250 °C for 10 h. It was established that SiO2-coated carbonyl iron demonstrate good thermal stability, indicating SiO2-coating is useful in the usage of microwave absorbers operating at temperature up to 250 °C.

  19. Fluoridation and Defluoridation. Training Module 2.230.2.77.

    ERIC Educational Resources Information Center

    McMullen, L. D.

    This document is an instructional module package prepared in objective form for use by an instructor familiar with fluoridation and fluoride feeding equipment. Enclosed are objectives, an instructor guide, student handouts and transparency masters. The module considers the principles and purposes of fluoridation, methods of feeding fluoride,…

  20. Exchange bias in bulk layered hydroxylammonium fluorocobaltate (NH₃OH)₂CoF₄.

    PubMed

    Jagličić, Z; Zentková, M; Mihalik, M; Arnold, Z; Drofenik, M; Kristl, M; Dojer, B; Kasunič, M; Golobič, A; Jagodič, M

    2012-02-08

    The magnetic properties of layered hydroxylammonium fluorocobaltate (NH(3)OH)(2)CoF(4) were investigated by measuring its dc magnetic susceptibility in zero-field-cooled (ZFC) and field-cooled (FC) regimes, its frequency dependent ac susceptibility, its isothermal magnetization curves after ZFC and FC regimes, and its heat capacity. Effects of pressure and magnetic field on magnetic phase transitions were studied by susceptibility and heat capacity measurements, respectively. The system undergoes a magnetic phase transition from a paramagnetic state to a canted antiferromagnetic state exhibiting a weak ferromagnetic behavior at T(C) = 46.5 K and an antiferromagnetic transition at T(N) = 2.9 K. The most spectacular manifestation of the complex magnetic behavior in this system is a shift of the isothermal magnetization hysteresis loop in a temperature range below 20 K after the FC regime-an exchange bias phenomenon. We investigated the exchange bias as a function of the magnetic field during cooling and as a function of temperature. The observed exchange bias was attributed to the large exchange anisotropy which exists due to the quasi-2D structure of the layered (NH(3)OH)(2)CoF(4) material.

  1. Reactive Landing of Gramicidin S and Ubiquitin Ions onto Activated Self-Assembled Monolayer Surfaces

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

    Laskin, Julia; Hu, Qichi

    2017-03-13

    Using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS), we examined the reactive landing of gramicidin S and ubiquitin ions onto activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester (NHS-SAM) and acyl fluoride (COF-SAM) groups. Doubly protonated gramicidin S, [GS+2H]2+, and two charge states of ubiquitin, [U+5H]5+ and [U+13H]13+, were used as model systems, allowing us to explore the effect of the number of free amino groups and the secondary structure on the efficiency of covalent bond formation between the projectile ion and the surface. For all projectile ions, ion deposition resulted in the depletionmore » of IRRAS bands corresponding to the terminal groups on the SAM and the appearance of several new bands not associated with the deposited species. These new bands were assigned to the C=O stretching vibrations of COOH and COO- groups formed on the surface as a result of ion deposition. The presence of these bands was attributed to an alternative reactive landing pathway that competes with covalent bond formation. This pathway with similar yields for both gramicidin S and ubiquitin ions is analogous to the hydrolysis of the NHS ester bond in solution. The covalent bond formation efficiency increased linearly with the number of free amino groups and was found to be lower for the more compact conformation of ubiquitin compared with the fully unfolded conformation. This observation was attributed to the limited availability of amino groups on the surface of the folded conformation. Our results have provided new insights on the efficiency and mechanism of reactive landing of peptides and proteins onto activated SAMs« less

  2. Reactive Landing of Gramicidin S and Ubiquitin Ions onto Activated Self-Assembled Monolayer Surfaces

    NASA Astrophysics Data System (ADS)

    Laskin, Julia; Hu, Qichi

    2017-07-01

    Using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS), we examined the reactive landing of gramicidin S and ubiquitin ions onto activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester (NHS-SAM) and acyl fluoride (COF-SAM) groups. Doubly protonated gramicidin S, [GS + 2H]2+, and two charge states of ubiquitin, [U + 5H]5+ and [U + 13H]13+, were used as model systems, allowing us to explore the effect of the number of free amino groups and the secondary structure on the efficiency of covalent bond formation between the projectile ion and the surface. For all projectile ions, ion deposition resulted in the depletion of IRRAS bands corresponding to the terminal groups on the SAM and the appearance of several new bands not associated with the deposited species. These new bands were assigned to the C=O stretching vibrations of COOH and COO- groups formed on the surface as a result of ion deposition. The presence of these bands was attributed to an alternative reactive landing pathway that competes with covalent bond formation. This pathway with similar yields for both gramicidin S and ubiquitin ions is analogous to the hydrolysis of the NHS ester bond in solution. The covalent bond formation efficiency increased linearly with the number of free amino groups and was found to be lower for the more compact conformation of ubiquitin compared with the fully unfolded conformation. This observation was attributed to the limited availability of amino groups on the surface of the folded conformation. Our results have provided new insights on the efficiency and mechanism of reactive landing of peptides and proteins onto activated SAMs.

  3. Fluoride gastrointestinal absorption from Na2FPO3/CaCO3- and NaF/SiO2-based toothpastes.

    PubMed

    Falcão, A; Tenuta, L M A; Cury, J A

    2013-01-01

    Depending on toothpaste formulation, part of the fluoride is insoluble and would not be totally absorbable in the gastrointestinal tract, thus changing dental fluorosis risk estimation. This hypothesis was tested with formulations with either all fluoride in a soluble form (NaF/SiO2-based toothpaste, 1,100 µg F/g as labeled, 1,129.7 ± 49.4 µg F/g soluble fluoride as analyzed) or with around 20% of insoluble fluoride (Na2FPO3/CaCO3-based toothpaste, 1,450 µg F/g as labeled, 1,122.4 ± 76.4 µg F/g soluble fluoride as analyzed). Toothpastes were evaluated either fresh or after accelerated aging, which increased insoluble fluoride to 40% in the Na2FPO3/CaCO3-based toothpaste. In a blind, crossover clinical trial conducted in five legs, 20 adult volunteers ingested 49.5 µg of total fluoride/kg body weight from each formulation or purified water (control). Whole saliva and urine were collected as bioavailability indicators, and pharmacokinetics parameters calculated showed significantly (p < 0.05) lower fluoride bioavailability for Na2FPO3/CaCO3 toothpaste, which was reduced further after aging. A significant correlation between the amount of soluble fluoride ingested, but not total fluoride, and fluoride bioavailability was found (r = 0.57, p < 0.0001). The findings suggest that the estimated fluorosis risk as a result of ingestion of Na2FPO3/CaCO3-based toothpastes should be calculated based on the toothpaste's soluble rather than total fluoride concentration. Copyright © 2012 S. Karger AG, Basel.

  4. Giant cemento-ossifying fibroma of the mandible

    PubMed Central

    Naik, Raghavendra Mahadev; Guruprasad, Yadavalli; Sujatha, D; Gurudath, Shubha; Pai, Anuradha; Suresh, KV

    2014-01-01

    Cemento-ossifying fibroma (COF) is classified as a fibro-osseous neoplasm and included among the non-odontogenic tumors derived from the mesenchymal blast cells of the periodontal ligament, with a potential for forming fibrous tissue, cementum and bone, or a combination of such elements. These are slow-growing lesions, and are more frequent in women between the third and fourth decades of life. Case reports of massive expansile COF, measuring more than 10 cm are rarely reported in the literature. We report a case of giant cemento-ossifying fibroma of the mandible in a 34 year old female patient. PMID:24678226

  5. Giant cemento-ossifying fibroma of the mandible.

    PubMed

    Naik, Raghavendra Mahadev; Guruprasad, Yadavalli; Sujatha, D; Gurudath, Shubha; Pai, Anuradha; Suresh, Kv

    2014-01-01

    Cemento-ossifying fibroma (COF) is classified as a fibro-osseous neoplasm and included among the non-odontogenic tumors derived from the mesenchymal blast cells of the periodontal ligament, with a potential for forming fibrous tissue, cementum and bone, or a combination of such elements. These are slow-growing lesions, and are more frequent in women between the third and fourth decades of life. Case reports of massive expansile COF, measuring more than 10 cm are rarely reported in the literature. We report a case of giant cemento-ossifying fibroma of the mandible in a 34 year old female patient.

  6. [Spectroscopic study of photocatalytic mechanism of methanol and CO2].

    PubMed

    Hai, Feng; Zhang, Qian-cheng; Bai, Feng-rong; Wang, A-nan; Wang, Zhi-wei; Jian, Li

    2011-12-01

    Ni-Ti-O/SiO2 catalyst was prepared by impregnation method, and its photocatalytic performance for carbonylation of methanol with CO2 was investigated under UV light. The in-situ IR, XPS and MS were carried out to analyze the possible photocatalytic reaction mechanism. Results indicated that the Ni-Ti-O/SiO2 exhibited good photocatalytic performance for carbonylation of methanol with CO2, the methanol conversion reached up to 24.9%, and the selectivity for the carbonylated products was more than 60% within 180 min reaction time. The catalyst characterization results showed that the O==C .--O- and CH3OC(O)* might be important intermediate in the carbonylation of methanol with CO2.

  7. The effects of sodium fluoride and stannous fluoride on the surface roughness of intraoral magnet systems.

    PubMed

    Obatake, R M; Collard, S M; Martin, J; Ladd, G D

    1991-10-01

    Four types of intraoral magnets used for retention of overdentures and maxillofacial prostheses were exposed in vitro to SnF2 and NaF to determine the effects of fluoride rinses on surface roughness. The surface roughness (Ra) was measured, after simulated 1, 2, and 5 years' clinical exposure to fluoride (31, 62, and 155 hours). The mean change in Ra was calculated for each period of simulated exposure to fluoride for each magnet type. Two-way ANOVA was used to compare mean change in Ra between magnets within fluorides, and between fluorides within magnets. Paired t tests were used to compare mean change in Ra within fluorides within magnets. The mean change in Ra increased for all magnets after simulated 1, 2, and 5 years of exposure to SnF2 and NaF (p less than 0.03). Using the change in Ra as an indicator for corrosion, PdCo encapsulated SmCo5 magnets and their keepers demonstrated the least corrosion with either fluoride.

  8. Fluoride varnishes containing calcium glycerophosphate: fluoride uptake and the effect on in vitro enamel erosion.

    PubMed

    Carvalho, Thiago S; Bönecker, Marcelo; Altenburger, Markus J; Buzalaf, Marília A R; Sampaio, Fabio C; Lussi, Adrian

    2015-07-01

    Calcium glycerophosphate (CaGP) was added to fluoride varnishes to analyze their preventive effect on initial enamel erosion and fluoride uptake: potassium hydroxide (KOH)-soluble and KOH-insoluble fluoride bound to enamel. This study was carried out in two parts. Part 1: 108 enamel samples were randomly distributed into six varnish groups: base varnish (no active ingredients); Duraphat® (2.26%NaF); Duofluorid® (5.63%NaF/CaF2); experimental varnish 1 (1%CaGP/5.63 NaF/CaF2); experimental varnish 2 (5%CaGP/5.63%NaF/CaF2); and no varnish. Cyclic demineralization (90 s; citric acid, pH = 3.6) and remineralization (4 h) was made once a day, for 3 days. Change in surface microhardness (SMH) was measured. Part 2: 60 enamel samples were cut in half and received no varnish (control) or a layer of varnish: Duraphat®, Duofluorid®, experimental varnishes 1 and 2. Then, KOH-soluble and KOH-insoluble fluoride were analyzed using an electrode. After cyclic demineralization, SMH decreased in all samples, but Duraphat® caused less hardness loss. No difference was observed between varnishes containing CaGP and the other varnishes. Similar amounts of KOH-soluble and insoluble fluoride was found in experimental varnish 1 and Duofluorid®, while lower values were found for experimental varnish 2 and Duraphat®. The addition of CaGP to fluoride varnishes did not increase fluoride bound to enamel and did not enhance their protection against initial enamel erosion. We observe that the fluoride varnishes containing CaGP do not promote greater amounts of fluoride bound to enamel and that fluoride bound to enamel may not be closely related to erosion prevention.

  9. Oral fluoride retention after use of fluoride dentifrices.

    PubMed

    Duckworth, R M; Morgan, S N

    1991-01-01

    Fluoride is the only extensively clinically proven means of reducing dental caries. Despite a large body of epidemiological data on the effectiveness of fluoride, delivered in the form of dentifrices, mouthrinses, drinking water, etc., the precise mode of action of fluoride is not completely understood. The purpose of this paper is to report an investigation of the link between oral fluoride levels and applied fluoride dose from dentifrices. Human salivary fluoride clearance studies and equilibrium baseline studies of fluoride in saliva and plaque have been carried out with dentifrices which contained 1,000, 1,500 and 2,500 micrograms fluoride per gram as sodium monofluorophosphate. After a single brushing with a fluoride dentifrice, salivary fluoride decreased in two distinct phases: an initial rapid phase which lasted for 40-80 min, depending on the individual, and a second slow phase lasting for several hours. The latter phase is believed to be due to fluoride released from an oral fluoride reservoir. During regular repeated use of the test dentifrices, the equilibrium baseline fluoride concentration, attained in both saliva and plaque between one application and the next, increased significantly compared with placebo values. Such elevated baseline fluoride concentrations also increased with increasing Na2FPO3 content of the dentifrices. The present work supports the concept that labile fluoride, stored in an oral fluoride reservoir at the time of treatment application, may maintain a prolonged protective effect against dental caries.

  10. Fluoride-dependent formation of mineralized layers in bovine dentin during demineralization in vitro.

    PubMed

    Damen, J J; Buijs, M J; ten Cate, J M

    1998-01-01

    Demineralization of dentin in the presence of fluoride produces lesions with a mineralized surface layer which becomes thicker and more mineralized with higher fluoride concentrations whereas the lesion depth is hardly affected. The aim of this study was to investigate the effects of the time of fluoride treatment and the amount of fluoride taken up on the properties of the mineralized layer. Discs of bovine dentin embedded in methylmethacrylate with one surface exposed were demineralized in 50 mM acetic acid, 2.2 mM CaCl2, 2.2 mM KH2PO4, pH 5.0. At the start and/or later during the demineralization period, the specimens were incubated individually for 1 or 2 days in 10 ml of the same demineralization solution supplemented with 0.5, 2.0 or 5.0 ppm fluoride, which was then assessed for changes in calcium and fluoride concentrations. After 2, 5 and 8 days, specimens were sectioned for microradiographic analysis so as to follow development of the lesions and the mineralized layers. The results were the following: While demineralization with fluoride present at the first day led to the formation of a surface layer, fluoride present only at a later day produced a subsurface layer, not at the lesion front but closer to the surface. This layer resulted from (re)precipitation and not from preservation of the original mineral. The 'integrated mineral content' of the surface layer increased linearly with the uptake of fluoride, which resulted in an apparent fluorapatite content of about 20 vol%. The profiles of the surface layers remained unchanged during continued demineralization in the absence of fluoride. It was concluded that in the presence of fluoride mineral loss is reduced as a result of the reprecipitation of dissolved mineral ions as a layer of fluoride-enriched apatite. This layer does not offer protection of underlying dentin against continued demineralization.

  11. Patterns of dental caries following the cessation of water fluoridation.

    PubMed

    Maupomé, G; Clark, D C; Levy, S M; Berkowitz, J

    2001-02-01

    To compare prevalence and incidence of caries between fluoridation-ended and still-fluoridated communities in British Columbia, Canada, from a baseline survey and after three years. At the baseline (1993/4 academic year) and follow-up (1996/7) surveys, children were examined at their schools. Data were collected on snacking, oral hygiene, exposure to fluoride technologies, and socio-economic level. These variables were used together with D1D2MFS indices in multiple regression models. The prevalence of caries (assessed in 5,927 children, grades 2, 3, 8, 9) decreased over time in the fluoridation-ended community while remaining unchanged in the fluoridated community. While numbers of filled surfaces did not vary between surveys, sealed surfaces increased at both study sites. Caries incidence (assessed in 2,994 life-long residents, grades 5, 6, 11, 12) expressed in terms of D1D2MFS was not different between the still-fluoridating and fluoridation-ended communities. There were, however, differences in caries experienced when D1D2MFS components and surfaces at risk were investigated in detail. Regression models did not identify specific variables markedly affecting changes in the incidence of dental decay. Our results suggest a complicated pattern of disease following cessation of fluoridation. Multiple sources of fluoride besides water fluoridation have made it more difficult to detect changes in the epidemiological profile of a population with generally low caries experience, and living in an affluent setting with widely accessible dental services. There are, however, subtle differences in caries and caries treatment experience between children living in fluoridated and fluoridation-ended areas.

  12. Molecular Engineering with Organic Carbonyl Electrode Materials for Advanced Stationary and Redox Flow Rechargeable Batteries.

    PubMed

    Zhao, Qing; Zhu, Zhiqiang; Chen, Jun

    2017-12-01

    Organic carbonyl electrode materials that have the advantages of high capacity, low cost and being environmentally friendly, are regarded as powerful candidates for next-generation stationary and redox flow rechargeable batteries (RFBs). However, low carbonyl utilization, poor electronic conductivity and undesired dissolution in electrolyte are urgent issues to be solved. Here, we summarize a molecular engineering approach for tuning the capacity, working potential, concentration of active species, kinetics, and stability of stationary and redox flow batteries, which well resolves the problems of organic carbonyl electrode materials. As an example, in stationary batteries, 9,10-anthraquinone (AQ) with two carbonyls delivers a capacity of 257 mAh g -1 (2.27 V vs Li + /Li), while increasing the number of carbonyls to four with the formation of 5,7,12,14-pentacenetetrone results in a higher capacity of 317 mAh g -1 (2.60 V vs Li + /Li). In RFBs, AQ, which is less soluble in aqueous electrolyte, reaches 1 M by grafting -SO 3 H with the formation of 9,10-anthraquinone-2,7-disulphonic acid, resulting in a power density exceeding 0.6 W cm -2 with long cycling life. Therefore, through regulating substituent groups, conjugated structures, Coulomb interactions, and the molecular weight, the electrochemical performance of carbonyl electrode materials can be rationally optimized. This review offers fundamental principles and insight into designing advanced carbonyl materials for the electrodes of next-generation rechargeable batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Concerns regarding 24-h sampling for formaldehyde, acetaldehyde, and acrolein using 2,4-dinitrophenylhydrazine (DNPH)-coated solid sorbents

    NASA Astrophysics Data System (ADS)

    Herrington, Jason S.; Hays, Michael D.

    2012-08-01

    There is high demand for accurate and reliable airborne carbonyl measurement methods due to the human and environmental health impacts of carbonyls and their effects on atmospheric chemistry. Standardized 2,4-dinitrophenylhydrazine (DNPH)-based sampling methods are frequently applied for measuring gaseous carbonyls in the atmospheric environment. However, there are multiple short-comings associated with these methods that detract from an accurate understanding of carbonyl-related exposure, health effects, and atmospheric chemistry. The purpose of this brief technical communication is to highlight these method challenges and their influence on national ambient monitoring networks, and to provide a logical path forward for accurate carbonyl measurement. This manuscript focuses on three specific carbonyl compounds of high toxicological interest—formaldehyde, acetaldehyde, and acrolein. Further method testing and development, the revision of standardized methods, and the plausibility of introducing novel technology for these carbonyls are considered elements of the path forward. The consolidation of this information is important because it seems clear that carbonyl data produced utilizing DNPH-based methods are being reported without acknowledgment of the method short-comings or how to best address them.

  14. Kinetics of fluoride bioavailability in supernatant saliva and salivary sediment.

    PubMed

    Naumova, E A; Sandulescu, T; Bochnig, C; Gaengler, P; Zimmer, S; Arnold, W H

    2012-07-01

    The assessment of the fluoride kinetics in whole saliva as well as in the different salivary phases (supernatant saliva and sediment) is essential for the understanding of fluoride bioavailability. To assess the fluoride content, provided by sodium fluoride and amine fluoride, in the supernatant saliva and in salivary sediment. Seven trained volunteers were randomly attributed to 2 groups in a cross-over design and brushed their teeth in the morning for 3 min with a product containing either sodium fluoride or amine fluoride. Saliva was collected before, immediately after tooth brushing and 30, 120, and 360 min later and measured. The samples were centrifuged 10 min at 3024 × g. Fluoride content of the supernatant saliva and of the sediment was analysed using a fluoride sensitive electrode. All subjects repeated the study cycles 2 times, and statistical analyses were made using the nonparametric sign test for related samples, the Wilcoxon-Mann-Whitney-test for independent samples. There was a significant increase in fluoride immediately after tooth brushing in both groups in saliva and sediment. The distribution of fluoride between salivary sediment and supernatant saliva (ratio) varied considerably at the different collection times: decreased from 17.87 in baseline samples of saliva to 0.07 immediately and to 0.86 half an hour after tooth brushing in the sodium fluoride group and from 14.33 to 2.85 and to 3.09 in the amine fluoride group. Furthermore after 120 min and after 360 min after tooth brushing the ratio increased from 17.6 to 31.6 in the sodium fluoride group and from 20.5 to 25.76 in the amine fluoride group. No difference was found in the sediment-supernatant saliva ratio between the sodium fluoride and the amine fluoride groups 360 min after tooth brushing. For the assessment of fluoride kinetics in whole saliva it is necessary to pay attention to at least four factors: fluoride formulation, time after fluoride application, fluoride concentration in supernatant saliva and fluoride concentration in salivary sediment. This study was approved by the Ethical Committee of the University of Witten/Herdecke permission 21/2008. Copyright © 2012 Elsevier Ltd. All rights reserved.

  15. Chemical and biological techniques for identifying irradiated foods and food constituents-carbonyls and 2-deoxygluconic acid

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

    Schubert, J.; Esterbauer, H.

    1973-01-01

    From international colloquium: the identification of irradiated foodstuffs; Karlsruhe, Germany (24 Oct 1973). New microbiological and chemical procedures are described for the detection, concentration, and identification of compounds produced in irradiated foods. The microbiological method employs an equation, by which inhibition of cell growth is expressed in a simple, economic, and consistent manner for identification of different classes of growth inhibitors using a single growth index, namely, concentration of substance at which time needed for log phase cells to double is ten times the controls. The chemical procedure permits carbonyl compounds to be spectrophotometrically determined in the presence of carbohydratesmore » without prior separation. The G(carbonyl) yields have been measured in irradiated hexoses and disaccharide solutions in the presence and absence of OH scavengers (KI and formate) and e/sub aq/ scavengers (N/sub 2/O). It has been demonstrated that the cytotoxic carbonyls produced upon carbohydrate irradiation are dicarbonyl sugars which convert to alpha , BETA -unsaturated carbonyl sugars by enolization or dehydration upon heating. Carbonyl yields in various irradiated foods are reported (e.g., strawberries: G = 2.2 and beef, G = 0.8). Both the carbonyl and microbiological techniques are uniquely applicable to the identification of non- volative compounds produced in irradiated foods. By anion exchange, we can rapidly separate enolizable carbonyls and 2-deoxygluconic acid from neutrnl sugars and obtain concentration factors of 50-fold and greater, thus enabling us to differentiate irradiated from nonirradiated foods at low radiation doses (approximately 1 Krad). (GE)« less

  16. Observations and Explicit Modeling of Summertime Carbonyl Formation in Beijing: Identification of Key Precursor Species and Their Impact on Atmospheric Oxidation Chemistry

    NASA Astrophysics Data System (ADS)

    Yang, Xue; Xue, Likun; Wang, Tao; Wang, Xinfeng; Gao, Jian; Lee, Shuncheng; Blake, Donald R.; Chai, Fahe; Wang, Wenxing

    2018-01-01

    Carbonyls are an important group of volatile organic compounds (VOCs) that play critical roles in tropospheric chemistry. To better understand the formation mechanisms of carbonyl compounds, extensive measurements of carbonyls and related parameters were conducted in Beijing in summer 2008. Formaldehyde (11.17 ± 5.32 ppbv), acetone (6.98 ± 3.01 ppbv), and acetaldehyde (5.27 ± 2.24 ppbv) were the most abundant carbonyl species. Two dicarbonyls, glyoxal (0.68 ± 0.26 ppbv) and methylglyoxal (MGLY; 1.10 ± 0.44 ppbv), were also present in relatively high concentrations. An observation-based chemical box model was used to simulate the in situ production of formaldehyde, acetaldehyde, glyoxal, and MGLY and quantify their contributions to ozone formation and ROx budget. All four carbonyls showed similar formation mechanisms but exhibited different precursor distributions. Alkenes (mainly isoprene and ethene) were the dominant precursors of formaldehyde, while both alkenes (e.g., propene, i-butene, and cis-2-pentene) and alkanes (mainly i-pentane) were major precursors of acetaldehyde. For dicarbonyls, both isoprene and aromatic VOCs were the dominant parent hydrocarbons of glyoxal and MGLY. Photolysis of oxygenated VOCs was the dominant source of ROx radicals (approximately >80% for HO2 and approximately >70% for RO2) in Beijing. Ozone production occurred under a mixed-control regime with carbonyls being the key VOC species. Overall, this study provides some new insights into the formation mechanisms of carbonyls, especially their parent hydrocarbon species, and underlines the important role of carbonyls in radical chemistry and ozone pollution in Beijing. Reducing the emissions of alkenes and aromatics would be an effective way to mitigate photochemical pollution in Beijing.

  17. Diurnal and seasonal variations of carbonyls and their effect on ozone concentrations in the atmosphere of Monterrey, Mexico.

    PubMed

    Menchaca-Torre, H Lizette; Mercado-Hernández, Roberto; Rodríguez-Rodríguez, José; Mendoza-Domínguez, Alberto

    2015-04-01

    Few studies have been made regarding carbonyl concentrations in Monterrey, México. The Monterrey Metropolitan Area (MMA) has the third largest population in the country and has increasing pollution issues. The concentrations of 10 aldehydes and two ketones were measured in the MMA, in the spring and fall of 2011 and 2012. Formaldehyde (16-42 ppbv) was the most abundant carbonyl, followed by acetaldehyde (5-15 ppbv) and acetone (7-15 ppbv). The concentrations showed marked diurnal trends with maximum values between 10:00 a.m. and 2:00 p.m., when photochemical activity is intense. Thus, secondary production of carbonyls is statistically significant in the city. Biogenic production of several carbonyls, such as 2-butanone, was supported by their mid correlation with solar radiation and low correlation with propionaldehyde, which is mainly emitted by anthropogenic sources. The seasonal variability of the concentrations was observed in the first three samplings, with the highest levels reached in the fall. The rainy conditions during the fourth sampling did not allow comparison. Carbonyl-NOx-O3 analysis was made. Results indicated a carbonyl-sensitive atmosphere, especially during the midday samplings of 10:00 a. m. to 2:00 p.m. and 2:00 p.m. and 6:00 p.m. because of the intense solar radiation during these periods. Monitoring of carbonyls in Monterrey, Mexico, was performed to quantify the pollutant concentration in the city's atmosphere. Although primary emission is significantly important, the secondary production of the pollutants, along with ozone production being carbonyl sensitive, indicates that air pollution controls must address the direct sources and the precursors of the pollutants to achieve air quality.

  18. [The dose-effect relationship of water fluoride levels and renal damage in children].

    PubMed

    Liu, Jun-Ling; Xia, Tao; Yu, Yao-Yong; Sun, Xian-Zhong; Zhu, Qilong; He, Weihong; Zhang, Ming; Wang, Aiguo

    2005-05-01

    To explore the dose-effect relationship of water fluoride levels and renal damage in children and observe the difference of renal function between high-loaded fluoride people and dental fluorosis people in the same water fluoride level region. 210 children were divided into seven groups in term of drinking water fluoride levels and whether they suffered from dental fluorosis. Fluoride concentrations in urine and serum and activities of urine NAG and gamma-GT were determined. The urine and serum fluoride of high-loaded fluoride people and dental fluorosis people increased compared with control, moreover fluoride contents in urine and serum increased gradually with the increase of fluoride level in drinking water. Urine NAG and gamma-GT activities significantly increased in dental fluorosis people from area of 2.58 mg/L fluoride in drinking water and in those two groups from area of 4.51 mg/L fluoride in drinking water. Moreover, there existed an obvious dose-effect relationship between the drinking water fluoride concentration and NAG and gamma-GT activity. Over 2.0 mg/L fluoride in drinking water can cause renal damage in children, and the damage degree increases with the drinking water fluoride content. Renal damage degree is not related to whether the children suffered from dental fluorosis and mainly due to water fluoride concentration.

  19. Chemical Ignition of Flame Throwers

    DTIC Science & Technology

    1944-04-20

    fluorinating agents such as fluorine, antimony penta- fluoride, oxygen fluoride or bromine and chlorine trifluoride mixtures be evaluated. The use...0F2), and bromine and chlorine trifluoride mixtures (BrF3-ClF3). Oxygen fluoride, a gas boiling at -l67°C., has the interesting property of being...ShFc), oxygen fluoride (0F2), and bromine and chlorine fluoride mixtures (BrF3-ClFsJ. Oxygen fluoride Is stable In the presence of moisture. 4

  20. Trace analysis of carbonyl compounds by liquid chromatography-mass spectrometry after collection as 2,4-dinitrophenylhydrazine derivatives.

    PubMed

    Sakuragawa, A; Yoneno, T; Inoue, K; Okutani, T

    1999-06-04

    This study describes the utilization of carbonyl- 2,4-dinitrophenylhydrazine (DNPH) derivatives for the determination of a micro amount of carbonyl compounds in air by liquid chromatography-mass spectrometry (LC-MS). After the carbonyl compounds are collected using a Waters Sep-Pak C18 cartridge column with-impregnated DNPH on octadecylsilica, they are eluted by acetonitrile as carbonyl-DNPH derivatives. A 20-mm3 aliquot of eluent is injected into the LC-MS system. The four derivatives (formaldehyde-, acetaldehyde-, acrolein- and acetone-DNPH) were eluted within 7 min with acetonitrile-water (60:40, v/v) as the mobile phase. The proposed method offers sub-ppb sensitivity and good reproducibility and was applied to the determination of these carbonyl compounds in actual air samples from store rooms, laboratories and offices. The relative standard deviations for these samples (n = 6) were 1 to 3%.

  1. Measurement of sub-parts-per-billion levels of carbonyl compounds in marine air by a simple cartridge trapping procedure followed by liquid chromatography

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

    Xianliang, Zhou; Mopper, K.

    1990-10-01

    Carbonyl compounds in clean marine air were trapped onto 2,4-dinitrophenylhydrazine- (DNPH-) coated cartridges, and their hydrazone derivatives were separated by HPLC and detected by UV absorbance. More than 20 carbonyl compounds were isolated from marine air with >92% collection efficiency. The technique employs a highly effective reagent purification procedure, which results in much lower blanks compared to previously reported trapping techniques for carbonyl compounds. Blanks were routinely <0.07 ppb for formaldehyde and acetone and <0.02 ppb for the others. Humidity and reactive gases have no detectable effect on collection efficiencies. Carbonyl-DNPH derivatives eluted from the cartridges are stable in acetonitrilemore » for at least 2 weeks, which facilitates field studies. Several previously undetected unknown carbonyl compounds were found in marine air by this technique. Typical results for open ocean and coastal marine air are shown.« less

  2. 40 CFR 721.9517 - Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Siloxanes and silicones, de-Me, 3-[4... Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1-pyrrolidinyl... substance identified as siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethylamino) propyl]amino] carbonyl]-2...

  3. 40 CFR 721.9517 - Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and silicones, de-Me, 3-[4... Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1-pyrrolidinyl... substance identified as siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethylamino) propyl]amino] carbonyl]-2...

  4. 40 CFR 721.9517 - Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Siloxanes and silicones, de-Me, 3-[4... Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1-pyrrolidinyl... substance identified as siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethylamino) propyl]amino] carbonyl]-2...

  5. 40 CFR 721.9517 - Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Siloxanes and silicones, de-Me, 3-[4... Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1-pyrrolidinyl... substance identified as siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethylamino) propyl]amino] carbonyl]-2...

  6. 40 CFR 721.9517 - Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and silicones, de-Me, 3-[4... Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1-pyrrolidinyl... substance identified as siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethylamino) propyl]amino] carbonyl]-2...

  7. The Hyphen as a Syllabification Cue in Reading Bisyllabic and Multisyllabic Words among Finnish 1st and 2nd Graders

    ERIC Educational Resources Information Center

    Häikiö, Tuomo; Bertram, Raymond; Hyönä, Jukka

    2016-01-01

    Finnish ABC books present words with hyphens inserted at syllable boundaries. Syllabification by hyphens is abandoned in the 2nd grade for bisyllabic words, but continues for words with three or more syllables. The current eye movement study investigated how and to what extent syllable hyphens in bisyllabic ("kah-vi" "cof-fee")…

  8. Quantification of airborne fossil and biomass carbonylic carbon by combined radiocarbon and liquid chromatography mass spectrometry

    NASA Astrophysics Data System (ADS)

    Larsen, B. R.; Tudos, A.; Slanina, J.; Van der Borg, K.; Kotzias, D.

    Airborne carbonyl compounds have been sampled at three European semi-remote to semi-urban test sites for radiocarbon ( 14C) analysis. The used methodology included collection on 2,4-dinitrophenylhydrazine coated silica gel cartridges, chromatographic isolation of the formed hydrazones, combustion into CO 2, reduction into graphite followed by accelerator mass spectrometry. In combination with this, liquid chromatography coupled to atmospheric pressure chemical ionisation mass spectrometry was used for chemical speciation of the collected carbonyls. At all sites the carbonyls were found to be of a mixed biogenic/anthropogenic origin. The determining factor for the proportion of fossil (anthropogenic) carbon in the samples was the vicinity of urban sources for carbonyls and their photochemical precursors. At meteorological conditions, which gave the test sites semi-rural/semi-remote characteristics the samples contained an average of 24% (range: 10-34%) of fossil carbonylic carbon. When air masses were transported from urban areas to the test-sites significantly higher proportions of fossil carbonylic carbon were determined with a maximum of 61%. Principal component analysis on this limited data set indicated that a low fossil proportion of carbonylic carbon is associated with high proportions of acetaldehyde, acetone, pentanone and acrolein. Until further radicarbon studies are carried out the conclusion remains that for the carbonyl compounds measured European background levels are of a predominant biogenic origin.

  9. No effect of cigarette smoking dose on oxidized plasma proteins

    PubMed Central

    Yeh, Chih-Ching; Barr, R. Graham; Powell, Charles A.; Mesia-Vela, Sonia; Wang, Yuanjia; Hamade, Nada K.; Austin, John H.M.; Santella, Regina M.

    2008-01-01

    Cigarette smoking is a major source of oxidative stress. Protein carbonyls have been used as a biomarker of oxidative stress because of the relative stability of carbonylated proteins and the high protein concentration in blood. Increased levels of carbonyl groups have been found in serum proteins of smokers compared to nonsmokers. However, neither the dose effect of current cigarette smoke nor other predictors of oxidative stress have been studied. Hence, we used an ELISA (Enzyme-Linked Immunosorbent Assay) to evaluate plasma protein carbonyls in smokers recruited in the Early Lung Cancer Action Project (ELCAP) program. The lung cancer screening program enrolled current and former smokers age 60 years and over without a prior cancer diagnosis. A total of 542 participants (282 men and 260 women) completed a baseline questionnaire and provided blood samples for the biomarker study. Protein oxidation was measured by derivatization of the carbonyl groups with 2,4-dinitrophenylhydrazine (DNPH) and ELISA quantitation of the DNPH group. Current smoking status was confirmed with urinary cotinine. The mean (± SD) protein carbonyl level was 17.9 ± 2.9 nmol carbonyls/ml plasma. Protein carbonyls did not differ significantly by gender. Carbonyl levels were higher among current than former smokers, but these differences did not attain statistical significance, nor did differences by urine cotinine levels, pack-years, pack/day among current smokers, and smoking duration. In a multiple regression analysis, higher protein carbonyl levels were independently associated with increasing age (0.59 nmol/ml increase per 10 years, 95% CI 0.14, 1.05, p = 0.01), African-American vs. white race/ethnicity, (1.30 nmol/ml, 95% CI 0.4, 2.19, p =0.008), and lower educational attainment (0.75 nmol/ml, 95% CI 0.12, 1.38, p = 0.02). Although we found no significant difference between current versus past cigarette smoking and protein carbonyls in this older group of smokers, associations were found for age, ethnicity and educational attainment. Our results indicate that the measurement of plasma carbonyls by this ELISA technique is still an easy and suitable method for studies of diseases related to oxidative stress. PMID:17996865

  10. Hospitalizations for dental infections: optimally versus nonoptimally fluoridated areas in Israel.

    PubMed

    Klivitsky, Amir; Tasher, Diana; Stein, Michal; Gavron, Etan; Somekh, Eli

    2015-03-01

    Odontogenic infections may result in local, systemic, and even potentially life-threatening complications. The authors investigated whether water fluoridation was associated with reduction in rates of hospitalizations due to odontogenic infections. The authors included cities in Israel that had fluoride concentrations of either 0.7 milligrams per liter or more (optimally fluoridated) or 0.5 mg/L or less (nonoptimally fluoridated) and that had a public water fluoride concentration consistent for the last decade. The authors compared hospitalization rates (per 10,000 children) for odontogenic infections in children younger than 18 years in each socioeconomic group between optimally and nonoptimally fluoridated cities. The authors included 1,413 hospitalizations between January 2005 and December 2011 of children residing in the 38 studied municipalities. The cities with the higher fluoride concentration reported a lower hospitalization rate (2.0 versus 4.3 for cities with a lower fluoride concentration; relative risk [RR]: 2.16; P < .001). When the authors divided cities into 3 socioeconomic groups, a large difference in hospitalization rates was seen in the lowest socioeconomic group (10.1 versus 2.6; RR: 3.79; P < .001) and the middle socioeconomic group (3.6 versus 1.9; RR: 2.35; P < .001) in optimally and nonoptimally fluoridated cities, respectively. No significant difference in hospitalization rates was apparent between the 2 fluoridation groups in the higher socioeconomic level. These results clearly indicate that there is an association between adequacy of water fluoridation and hospitalization due to dental infections among children and adolescents. This effect is more prominent in populations of lower socioeconomic status. Water fluoridation is associated with reduction in dental health disparity. Copyright © 2015 American Dental Association. Published by Elsevier Inc. All rights reserved.

  11. Fluoride in drinking water and human urine in Southern Haryana, India.

    PubMed

    Singh, Bhupinder; Gaur, Shalini; Garg, V K

    2007-06-01

    The objective of this study was to determine the fluoride content in drinking water and urine samples of adolescent males aged 11-16 years living in Southern Haryana, India. A total of 30 drinking water sources in the studied habitations were assessed for fluoride contamination. Fluoride was estimated in the urine of 400 male children randomly selected from these habitations. The fluoride concentration in drinking water and urine samples was determined using USEPA fluoride ion selective electrode method. The mean fluoride concentration in drinking water samples of Pataudi, Haily Mandi and Harsaru villages was 1.68+/-0.35, 3.22+/-1.18 and 1.78+/-0.12 mg/l, respectively. The mean urinary fluoride concentration was 2.26+/-0.024 mg/l at Pataudi, 2.48+/-0.77 mg/l at Haily Mandi and 2.43+/-0.84 mg/l at Harsaru village. The higher fluoride levels in the urine of children may be associated to higher fluoride levels in drinking water. The accuracy of measurements was assessed with known addition method in water and urine. Mean fluoride recovery was 98.0 and 99.1% in water and urine. The levels obtained were reproducible with in +/-3% error limit.

  12. 1-Bromoethene-1-sulfonyl fluoride (BESF) is another good connective hub for SuFEx click chemistry.

    PubMed

    Smedley, Christopher J; Giel, Marie-Claire; Molino, Andrew; Barrow, Andrew S; Wilson, David J D; Moses, John E

    2018-05-25

    We demonstrate 1,2-dibromoethane-1-sulfonyl fluoride (DESF) as a bench-stable and readily accessible precursor to the robust SuFEx connector, 1-bromoethene-1-sulfonyl fluoride (BESF). The in situ generation of BESF from DESF opens up several new reaction profiles, including application in the syntheses of unprecedented 3-substituted isoxazole-5-sulfonyl fluorides, 1-substituted-1H-1,2,3-triazole-4-sulfonyl fluorides, 2-amino-1-bromoethane-1-sulfonyl fluorides and 4-bromo-β-sultams in good to excellent yields. These new modules comprise a pendant sulfonyl fluoride handle, which further undergoes facile and selective SuFEx reactions with a selection of aryl silyl ethers to generate stable and useful sulfonate connections.

  13. Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation

    USGS Publications Warehouse

    Deng, Y.; Nordstrom, D. Kirk; McCleskey, R. Blaine

    2011-01-01

    Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1–10), temperature, and high concentrations of fluoride (up to 50 mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50 °C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006–2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H+ and Al3+ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3–30% for more than 90% of samples at or above 10−6 molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F−, and major complexes (HF(aq)0">HF(aq)0, AlF2+, AlF2+">AlF2+and AlF30">AlF30) account for more than 95% of total fluoride. Occasionally, some complex species like AlF4-">AlF4-, FeF2+, FeF2+">FeF2+, MgF+ and BF2(OH)2-">BF2(OH)2- may comprise 1–10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al.

  14. Tribological Properties of Water-lubricated Rubber Materials after Modification by MoS2 Nanoparticles

    PubMed Central

    Dong, Conglin; Yuan, Chengqing; Wang, Lei; Liu, Wei; Bai, Xiuqin; Yan, Xinping

    2016-01-01

    Frictional vibration and noise caused by water-lubricated rubber stern tube bearings, which are generated under extreme conditions, severely threaten underwater vehicles’ survivability and concealment performance. This study investigates the effect of flaky and spherical MoS2 nanoparticles on tribological properties and damping capacity of water-lubricated rubber materials, with the aim of decreasing frictional noise. A CBZ-1 tribo-tester was used to conduct the sliding tests between rubber ring-discs and ZCuSn10Zn2 ring-discs with water lubrication. These materials’ typical mechanical properties were analysed and compared. Coefficients of friction (COFs), wear rates, and surface morphologies were evaluated. Frictional noise and critical velocities of generating friction vibration were examined to corroborate above analysis. Results showed that spherical MoS2 nanoparticles enhanced rubber material’s mechanical and tribological properties and, in turn, reduced the friction noise and critical velocity. Flaky MoS2 nanoparticles reduced COF but did not enhance their mechanical properties, i.e., the damping capacity, wear resistance property; thus, these nanoparticles did not reduce the critical velocity obviously, even though increased the frictional noise at high load. The knowledge gained in the present work will be useful for optimizing friction pairs under extreme conditions to decrease frictional noise of water-lubricated rubber stern tube bearings. PMID:27713573

  15. The Impact of Selected Fluoridated Toothpastes on Dental Erosion in Profilometric Measurement.

    PubMed

    Fita, Katarzyna; Kaczmarek, Urszula

    2016-01-01

    Some fluoridated toothpastes, available commercially, are described to have a protective effect against dental erosion. To evaluate the influence of the selected marketed toothpastes on the human enamel exposed to acid beverages. Enamel specimens from extracted human teeth were prepared (n = 40). Specimens were randomly divided into 10 experimental groups, 4 specimens each, which were subjected to acid challenge for 10 min using orange juice (pH 3.79) or Pepsi Cola (pH 2.58) and then immersed for 2 min into a slurry of five marketed toothpastes with distilled water (1 : 3 w/w). The tested toothpastes contained 1450 or 5000 ppm fluoride, CPP-ACP with 900 ppm fluoride, 1450 ppm fluoride with potassium nitrate 5%, all of them as sodium fluoride, and 700 ppm fluoride as amine and sodium fluoride with 3500 ppm SnCl2. Enamel roughness (Ra parameter) by contact profilometer at baseline and after exposure onto soft drinks and slurry was measured. Exposure to both beverages caused a similar increase of enamel surface roughness. After the specimens immersion into slurries of toothpastes with 1450 or 5000 ppm fluoride, 1450 ppm fluoride with potassium nitrate 5% and CPP-ACP with 900 ppm fluoride the significant decrease of Ra values were found, reaching the baseline values. However, toothpaste with 700 ppm fluoride and 3500 ppm SnCl2 did not cause any fall in Ra value, probably due to other mechanism of action. Within the limitation of the study we can conclude that the sodium fluoride toothpastes are able to restore the surface profile of enamel exposed shortly to acidic soft drinks.

  16. Chronologic Trends in Studies on Fluoride Mechanisms of Action.

    PubMed

    Oh, H J; Oh, H W; Lee, D W; Kim, C H; Ahn, J Y; Kim, Y; Shin, H B; Kim, C Y; Park, S H; Jeon, J G

    2017-11-01

    Fluoride has been widely used for the prevention of dental caries since the mid-20th century. The aim of this study was to investigate the chronologic trends in studies on fluoride mechanisms of action against dental caries during the years 1950 to 2015. To this aim, queries such as "fluoride," "fluoride and demineralization," "fluoride and remineralization," "fluoride and (plaque or biofilms)," and "fluoride and (bacteria or microbials)" were submitted to PubMed to collect research article information, including titles, abstracts, publication dates, author affiliations, and publication journals. The article information that PubMed produced was then collected by an automatic web crawler and examined through informetrics and linguistic analyses. We found that the number of articles concerned with fluoride mechanisms of action against dental caries was 6,903 and gradually increased over time during the years 1950 to 2015. They were published by 1,136 journals-most notably, Caries Research and Journal of Dental Research. Of the articles published, those related to bacteria/microbials had a higher percentage (44%) than those dealing with plaque/biofilms, demineralization, and remineralization. With regard to the geographic distribution of authors, Europe and North America accounted for 65% of the articles during the years 1987 to 2015, although the number of authors in Asia sharply increased in recent years. Among the fluoride compounds, NaF was mentioned more frequently than SnF 2 , Na 2 PO 3 F, amine fluoride, and acidulated phosphate fluoride during the years 1986 to 2015. Water fluoridation received the most attention among the various fluoride application methods (toothpastes, mouthwashes, fluoride varnishes, and fluoride gels) during the same period. These results, obtained from employing informetrics and linguistic analyses, suggest that in studies on fluoride mechanisms of action, 1) the unbalanced geographic distribution of articles and 2) the heavy concentration of articles on particular fluoride compounds and application methods should be overcome in future research.

  17. Characterisation and optimisation of a method for the detection and quantification of atmospherically relevant carbonyl compounds in aqueous medium

    NASA Astrophysics Data System (ADS)

    Rodigast, M.; Mutzel, A.; Iinuma, Y.; Haferkorn, S.; Herrmann, H.

    2015-01-01

    Carbonyl compounds are ubiquitous in the atmosphere and either emitted primarily from anthropogenic and biogenic sources or they are produced secondarily from the oxidation of volatile organic compounds (VOC). Despite a number of studies about the quantification of carbonyl compounds a comprehensive description of optimised methods is scarce for the quantification of atmospherically relevant carbonyl compounds. Thus a method was systematically characterised and improved to quantify carbonyl compounds. Quantification with the present method can be carried out for each carbonyl compound sampled in the aqueous phase regardless of their source. The method optimisation was conducted for seven atmospherically relevant carbonyl compounds including acrolein, benzaldehyde, glyoxal, methyl glyoxal, methacrolein, methyl vinyl ketone and 2,3-butanedione. O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was used as derivatisation reagent and the formed oximes were detected by gas chromatography/mass spectrometry (GC/MS). The main advantage of the improved method presented in this study is the low detection limit in the range of 0.01 and 0.17 μmol L-1 depending on carbonyl compounds. Furthermore best results were found for extraction with dichloromethane for 30 min followed by derivatisation with PFBHA for 24 h with 0.43 mg mL-1 PFBHA at a pH value of 3. The optimised method was evaluated in the present study by the OH radical initiated oxidation of 3-methylbutanone in the aqueous phase. Methyl glyoxal and 2,3-butanedione were found to be oxidation products in the samples with a yield of 2% for methyl glyoxal and 14% for 2,3-butanedione.

  18. Preload, Coefficient of Friction, and Thread Friction in an Implant-Abutment-Screw Complex.

    PubMed

    Wentaschek, Stefan; Tomalla, Sven; Schmidtmann, Irene; Lehmann, Karl Martin

    To examine the screw preload, coefficient of friction (COF), and tightening torque needed to overcome the thread friction of an implant-abutment-screw complex. In a customized load frame, 25 new implant-abutment-screw complexes including uncoated titanium alloy screws were torqued and untorqued 10 times each, applying 25 Ncm. Mean preload values decreased significantly from 209.8 N to 129.5 N according to the number of repetitions. The overall COF increased correspondingly. There was no comparable trend for the thread friction component. These results suggest that the application of a used implant-abutment-screw complex may be unfavorable for obtaining optimal screw preload.

  19. Investigating Alkylsilane Monolayer Tribology at a Single-Asperity Contact with Molecular Dynamics Simulation.

    PubMed

    Summers, Andrew Z; Iacovella, Christopher R; Cummings, Peter T; McCabe, Clare

    2017-10-24

    Chemisorbed monolayer films are known to possess favorable characteristics for nanoscale lubrication of micro- and nanoelectromechanical systems (MEMS/NEMS). Prior studies have shown that the friction observed for monolayer-coated surfaces features a strong dependence on the geometry of contact. Specifically, tip-like geometries have been shown to penetrate into monolayer films, inducing defects in the monolayer chains and leading to plowing mechanisms during shear, which result in higher coefficients of friction (COF) than those observed for planar geometries. In this work, we use molecular dynamics simulations to examine the tribology of model silica single-asperity contacts under shear with monolayer-coated substrates featuring various film densities. It is observed that lower monolayer densities lead to reduced COFs, in contrast to results for planar systems where COF is found to be nearly independent of monolayer density. This is attributed to a liquid-like response to shear, whereby fewer defects are imparted in monolayer chains from the asperity, and chains are easily displaced by the tip as a result of the higher free volume. This transition in the mechanism of molecular plowing suggests that liquid-like films should provide favorable lubrication at single-asperity contacts.

  20. A chromatographic objective function to characterise chromatograms with unknown compounds or without standards available.

    PubMed

    Alvarez-Segura, T; Gómez-Díaz, A; Ortiz-Bolsico, C; Torres-Lapasió, J R; García-Alvarez-Coque, M C

    2015-08-28

    Getting useful chemical information from samples containing many compounds is still a challenge to analysts in liquid chromatography. The highest complexity corresponds to samples for which there is no prior knowledge about their chemical composition. Computer-based methodologies are currently considered as the most efficient tools to optimise the chromatographic resolution, and further finding the optimal separation conditions. However, most chromatographic objective functions (COFs) described in the literature to measure the resolution are based on mathematical models fitted with the information obtained from standards, and cannot be applied to samples with unknown compounds. In this work, a new COF based on the automatic measurement of the protruding part of the chromatographic peaks (or peak prominences) that indicates the number of perceptible peaks and global resolution, without the need of standards, is developed. The proposed COF was found satisfactory with regard to the peak purity criterion when applied to artificial peaks and simulated chromatograms of mixtures built using the information of standards. The approach was applied to mixtures of drugs containing unknown impurities and degradation products and to extracts of medicinal herbs, eluted with acetonitrile-water mixtures using isocratic and gradient elution. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Comparison of the toxicity of fluoridation compounds in the nematode Caenorhabditis elegans.

    PubMed

    Rice, Julie R; Boyd, Windy A; Chandra, Dave; Smith, Marjolein V; Den Besten, Pamela K; Freedman, Jonathan H

    2014-01-01

    Fluorides are commonly added to drinking water in the United States to decrease the incidence of dental caries. Silicofluorides, such as sodium hexafluorosilicate (Na2 SiF6 ) and fluorosilicic acid (H2 SiF6 ), are mainly used for fluoridation, although fluoride salts such as sodium fluoride (NaF) are also used. Interestingly, only the toxicity of NaF has been examined and not that of the more often used silicofluorides. In the present study, the toxicities of NaF, Na2 SiF6 , and H2 SiF6 were compared. The toxicity of these fluorides on the growth, feeding, and reproduction in the alternative toxicological testing organism Caenorhabditis elegans was examined. Exposure to these compounds produced classic concentration-response toxicity profiles. Although the effects of the fluoride compounds varied among the 3 biological endpoints, no differences were found between the 3 compounds, relative to the fluoride ion concentration, in any of the assays. This suggests that silicofluorides have similar toxicity to NaF. © 2013 SETAC.

  2. Influence of the Ionic Liquid Type on the Gel Polymer Electrolytes Properties

    PubMed Central

    Tafur, Juan P.; Santos, Florencio; Fernández Romero, Antonio J.

    2015-01-01

    Gel Polymer Electrolytes (GPEs) composed by ZnTf2 salt, poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), and different ionic liquids are synthesized using n-methyl-2-pyrrolidone (NMP) as solvent. Three different imidazolium-based ionic liquids containing diverse cations and anions have been explored. Structural and electrical properties of the GPEs varying the ZnTf2 concentration are analyzed by ATR-FTIR, DSC, TG, and cyclic voltammetry. Free salt IL-GPEs present distinct behavior because they are influenced by the different IL cations and anions composition. However, inclusion of ZnTf2 salt inside the polymers provide GPEs with very similar characteristics, pointing out that ionic transport properties are principally caused by Zn2+ and triflate movement. Whatever the IL used, the presence of NMP solvent inside the polymer’s matrix turns out to be a key factor for improving the Zn2+ transport inside the GPE due to the interaction between Zn2+ cations and carbonyl groups of the NMP. High values of ionic conductivity, low activation energy values, and good voltammetric reversibility obtained regardless of the ionic liquid used enable these GPEs to be applied in Zn batteries. Capacities of 110–120 mAh·g−1 have been obtained for Zn/IL-GPE/MnO2 batteries discharged at −1 mA·cm−2. PMID:26610580

  3. JNK and NADPH Oxidase Involved in Fluoride-Induced Oxidative Stress in BV-2 Microglia Cells

    PubMed Central

    Yan, Ling; Liu, Shengnan; Wang, Chen; Wang, Fei; Song, Yingli; Yan, Nan; Xi, Shuhua; Liu, Ziyou; Sun, Guifan

    2013-01-01

    Excessive fluoride may cause central nervous system (CNS) dysfunction, and oxidative stress is a recognized mode of action of fluoride toxicity. In CNS, activated microglial cells can release more reactive oxygen species (ROS), and NADPH oxidase (NOX) is the major enzyme for the production of extracellular superoxide in microglia. ROS have been characterized as an important secondary messenger and modulator for various mammalian intracellular signaling pathways, including the MAPK pathways. In this study we examined ROS production and TNF-α, IL-1β inflammatory cytokines releasing, and the expression of MAPKs in BV-2 microglia cells treated with fluoride. We found that fluoride increased JNK phosphorylation level of BV-2 cells and pretreatment with JNK inhibitor SP600125 markedly reduced the levels of intracellular O2 ·− and NO. NOX inhibitor apocynin and iNOS inhibitor SMT dramatically decreased NaF-induced ROS and NO generations, respectively. Antioxidant melatonin (MEL) resulted in a reduction in JNK phosphorylation in fluoride-stimulated BV-2 microglia. The results confirmed that NOX and iNOS played an important role in fluoride inducing oxidative stress and NO production and JNK took part in the oxidative stress induced by fluoride and meanwhile also could be activated by ROS in fluoride-treated BV-2 cells. PMID:24072958

  4. Functionalization of 6-nitrobenzo[1,3]dioxole with carbonyl compounds via TDAE methodology.

    PubMed

    Amiri-Attou, Ouassila; Terme, Thierry; Vanelle, Patrice

    2005-05-13

    We report herein the synthesis of substituted 2-(6-nitrobenzo[1,3]dioxol-5-yl)-1- aryl ethanols and 2-(6-nitrobenzo[1,3]dioxol-5-yl)-propionic acid ethyl esters from the reaction of 5-chloromethyl-6-nitrobenzo[1,3]dioxole with various aromatic carbonyl and alpha- carbonyl ester derivatives using the tetrakis(dimethylamino)ethylene (TDAE) methodology.

  5. The cariostatic mechanisms of fluoride.

    PubMed

    Rošin-Grget, Kata; Peroš, Kristina; Sutej, Ivana; Bašić, Krešimir

    2013-11-01

    This article discusses the possible cariostatic mechanisms of the action of fluoride. In the past, fluoride inhibition of caries was ascribed to reduced solubility of enamel due to incorporation of fluoride (F-) into the enamel minerals. The present evidence from clinical and laboratory studies suggests that the caries-preventive mode of action of fluoride is mainly topical. There is convincing evidence that fluoride has a major effect on demineralisation and remineralisation of dental hard tissue. The source of this fluoride could either be fluorapatite (formed due to the incorporation of fluoride into enamel) or calcium fluoride (CaF2)-like precipitates, which are formed on the enamel and in the plaque after application of topical fluoride. Calcium fluoride deposits are protected from rapid dissolution by a phosphate -protein coating of salivary origin. At lower pH, the coating is lost and an increased dissolution rate of calcium fluoride occurs. The CaF2, therefore, act as an efficient source of free fluoride ions during the cariogenic challenge. The current evidence indicates that fluoride has a direct and indirect effect on bacterial cells, although the in vivo implications of this are still not clear. A better understanding of the mechanisms of the action of fluoride is very important for caries prevention and control. The effectiveness of fluoride as a cariostatic agent depends on the availability of free fluoride in plaque during cariogenic challenge, i.e. during acid production. Thus, a constant supply of low levels of fluoride in biofilm/saliva/dental interference is considered the most beneficial in preventing dental caries. Copyright © 2013 by Academy of Sciences and Arts of Bosnia and Herzegovina.

  6. Effect of CO2 Laser and Fluoride Varnish Application on Microhardness of Enamel Surface Around Orthodontic Brackets

    PubMed Central

    Mahmoudzadeh, Majid; Rezaei-Soufi, Loghman; Farhadian, Nasrin; Jamalian, Seyed Farzad; Akbarzadeh, Mahdi; Momeni, Mohammadali; Basamtabar, Masome

    2018-01-01

    Introduction: Orthodontic treatment has many advantages such as esthetic improvement and self-esteem enhancement; yet it has some disadvantages such as increasing the risk of formation of white spot lesions, because it makes oral hygiene more difficult. It is rational to implement procedures to prevent these lesions. The present study was aimed to assess the effect of CO2 laser and fluoride varnish on the surface of the enamel surface microhardness around the orthodontic braces. Methods: Eighty extracted premolar teeth were selected, scaled, polished with nonfluoridated pumic and metal brackets were bonded to them. Then, they were randomly allocated to 5 groups: control (neither fluoride nor laser is used on enamel surfaces), fluoride (4 minutes fluoride varnish treatment of the enamel surfaces), CO2 laser (10.6 µm CO2 laser irradiation of the teeth), laserfluoride (fluoride application after laser irradiation) and fluoride-laser (fluoride was applied and then teeth were irradiated with laser). After surface treatment around brackets on enamel, the samples were stored in 0.1% thymol for less than 5 days and then they were exposed to a 10-day microbiological caries model. Microhardness values of enamel were evaluated with Vickers test. One sample of each group (5 teeth from 80 samples) was prepared for SEM (scanning electron microscopy) and the data from 75 remaining teeth were analyzed with analysis of variance (ANOVA) and chi-square tests (α =0.05). Results: Microhardness mean values from high to low were as follow: fluoride-laser, laser-fluoride, laser, fluoride and control. Microhardness in fluoride-laser group was significantly higher compared with that of the control group. Distribution adhesive remnant index (ARI) scores were significantly different between groups and most of bond failures occurred at the enamel-adhesive interface in groups 2 to 5 and at the adhesive-bracket interface in the control group. Conclusion: Combination of fluoride varnish and CO2 laser irradiation can reduce enamel demineralization around orthodontic brackets. PMID:29399311

  7. Effect of CO2 Laser and Fluoride Varnish Application on Microhardness of Enamel Surface Around Orthodontic Brackets.

    PubMed

    Mahmoudzadeh, Majid; Rezaei-Soufi, Loghman; Farhadian, Nasrin; Jamalian, Seyed Farzad; Akbarzadeh, Mahdi; Momeni, Mohammadali; Basamtabar, Masome

    2018-01-01

    Introduction: Orthodontic treatment has many advantages such as esthetic improvement and self-esteem enhancement; yet it has some disadvantages such as increasing the risk of formation of white spot lesions, because it makes oral hygiene more difficult. It is rational to implement procedures to prevent these lesions. The present study was aimed to assess the effect of CO 2 laser and fluoride varnish on the surface of the enamel surface microhardness around the orthodontic braces. Methods: Eighty extracted premolar teeth were selected, scaled, polished with nonfluoridated pumic and metal brackets were bonded to them. Then, they were randomly allocated to 5 groups: control (neither fluoride nor laser is used on enamel surfaces), fluoride (4 minutes fluoride varnish treatment of the enamel surfaces), CO 2 laser (10.6 µm CO 2 laser irradiation of the teeth), laserfluoride (fluoride application after laser irradiation) and fluoride-laser (fluoride was applied and then teeth were irradiated with laser). After surface treatment around brackets on enamel, the samples were stored in 0.1% thymol for less than 5 days and then they were exposed to a 10-day microbiological caries model. Microhardness values of enamel were evaluated with Vickers test. One sample of each group (5 teeth from 80 samples) was prepared for SEM (scanning electron microscopy) and the data from 75 remaining teeth were analyzed with analysis of variance (ANOVA) and chi-square tests (α =0.05). Results: Microhardness mean values from high to low were as follow: fluoride-laser, laser-fluoride, laser, fluoride and control. Microhardness in fluoride-laser group was significantly higher compared with that of the control group. Distribution adhesive remnant index (ARI) scores were significantly different between groups and most of bond failures occurred at the enamel-adhesive interface in groups 2 to 5 and at the adhesive-bracket interface in the control group. Conclusion: Combination of fluoride varnish and CO2 laser irradiation can reduce enamel demineralization around orthodontic brackets.

  8. Determination of airborne carbonyls: comparison of a thermal desorption/GC method with the standard DNPH/HPLC method.

    PubMed

    Ho, Steven Sai Hang; Yu, Jian Zhen

    2004-02-01

    The standard method for the determination of gaseous carbonyls is to collect carbonyls onto 2,4-dinitrophenyl hydrazine (DNPH) coated solid sorbent followed by solvent extraction of the solid sorbent and analysis of the derivatives using high-pressure liquid chromatography (HPLC). This paper describes a newly developed approach that involves collection of the carbonyls onto pentafluorophenyl hydrazine (PFPH) coated solid sorbents followed by thermal desorption and gas chromatographic (GC) analysis of the PFPH derivatives with mass spectrometric (MS) detection. Sampling tubes loaded with 510 nmol of PFPH on Tenax sorbent effectively collect gaseous carbonyls, including formaldehyde, acetaldehyde, propanal, butanal, heptanal, octanal, acrolein, 2-furfural, benzaldehyde, p-tolualdehyde, glyoxal, and methylglyoxal, at a flow rate of at least up to 100 mL/min. All of the tested carbonyls are shown to have method detection limits (MDLs) of subnanomoles per sampling tube, corresponding to air concentrations of <0.3 ppbv for a sampled volume of 24 L. These limits are 2-12 times lower than those that can be obtained using the DNPH/HPLC method. The improvement of MDLs is especially pronounced for carbonyls larger than formaldehyde and acetaldehyde. The PFPH/GC method also offers better peak separation and more sensitive and specific detection through the use of MS detection. Comparison studies on ambient samples and kitchen exhaust samples have demonstrated that the two methods do not yield systematic differences in concentrations of the carbonyls that are above their respective MDLs in both methods, including formaldehyde, acetaldehyde, acrolein, and butanal. The lower MDLs afforded by the PFPH/ GC method also enable the determination of a few more carbonyls in both applications.

  9. Water fluoridation and dental caries in 5- and 12-year-old children from Canterbury and Wellington.

    PubMed

    Lee, Martin; Dennison, Peter J

    2004-03-01

    Claims have been made that the effectiveness of water fluoridation has reduced due to the widespread availability of other sources of fluoride. This study examines the differences in the oral health of children living in fluoridated and non-fluoridated areas of Canterbury and Wellington, New Zealand. The data used in this cross-sectional study had been routinely collected into a computerized data-collection system by the School Dental Services in the two study areas. Records of dental status (dmfs/DMFS), fluoridation status, ethnicity, and socio-economic status for 8030 5-year-olds, and 6916 12-year-olds in 1996 were analysed. Caries prevalence and severity was consistently lower for children in the fluoridated area for both age groups, and within all subgroups. Five-year-olds in the fluoridated area had 2.63 dmfs (sd, 5.88), and those in the non-fluoridated area 3.80 dmfs (sd, 6.79). For 12-year-olds the respective figures were 1.39 DMFS (sd, 2.30) and 2.37 DMFS (sd, 3.46). Multivariable analysis confirmed the independent association between water fluoridation and better dental health. This results of this study show children living in a fluoridated area to have significantly better oral health compared to those not in a fluoridated area. These differences are greater for Maori and Pacific children and children of low socio-economic status.

  10. Dental caries and dental fluorosis at varying water fluoride concentrations.

    PubMed

    Heller, K E; Eklund, S A; Burt, B A

    1997-01-01

    The purpose of this study was to investigate the relationships between caries experience and dental fluorosis at different fluoride concentrations in drinking water. The impact of other fluoride products also was assessed. This study used data from the 1986-87 National Survey of US School-children. Fluoride levels of school water were used as an indicator of the children's water fluoride exposure. The use of fluoride drops, tablets, professional fluoride treatments, and school fluoride rinses were ascertained from caregiver questionnaires. Only children with a single continuous residence (n = 18,755) were included in this analysis. The sharpest declines in dfs and DMFS were associated with increases in water fluoride levels between 0 and 0.7 ppm F, with little additional decline between 0.7 and 1.2 ppm F. Fluorosis prevalence was 13.5 percent, 21.7 percent, 29.9 percent, and 41.4 percent for children who consumed < 0.3, 0.3 to < 0.7, 0.7 to 1.2, and > 1.2 ppm F water. In addition to fluoridated water, the use of fluoride supplements was associated with both lower caries and increased fluorosis. A suitable trade-off between caries and fluorosis appears to occur around 0.7 ppm F. Data from this study suggest that a reconsideration of the policies concerning the most appropriate concentrations for water fluoridation might be appropriate for the United States.

  11. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    NASA Astrophysics Data System (ADS)

    Schindler, Matthias; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-01

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO2 and reduced to graphite to determine 14C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  12. In Vitro Comparison of the Effects of Diode Laser and CO2 Laser on Topical Fluoride Uptake in Primary Teeth

    PubMed Central

    Bahrololoomi, Zahra; Sorouri, Milad

    2015-01-01

    Objectives: Fluoride therapy is important for control and prevention of dental caries. Laser irradiation can increase fluoride uptake especially when combined with topical fluoride application. The objective of this study was to compare the effects of CO2 and diode lasers on enamel fluoride uptake in primary teeth. Materials and Methods: Forty human primary molars were randomly assigned to four groups (n=10). The roots were removed and the crowns were sectioned mesiodistally into buccal and lingual halves as the experimental and control groups. All samples were treated with 5% sodium fluoride (NaF) varnish. The experimental samples in the four groups were irradiated with 5 or 7W diode or 1 or 2W CO2 laser for 15 seconds and were compared with the controls in terms of fluoride uptake, which was determined using an ion selective electrode after acid dissolution of the specimens. Data were analyzed by SPSS version 16 using ANOVA treating the control measurements as covariates. Results: The estimated amount of fluoride uptake was 59.5± 16.31 ppm, 66.5± 14.9 ppm, 78.6± 12.43 ppm and 90.4± 11.51 ppm for 5W and 7 W diode and 1W and 2 W CO2 lasers, respectively, which were significantly greater than the values in the conventional topical fluoridation group (P<0.005). There were no significant differences between 7W diode laser and 1W CO2 laser, 5W and 7W diode laser, or 1W and 2W CO2 laser in this regard. Conclusion: The results showed that enamel surface irradiation by CO2 and diode lasers increases the fluoride uptake. PMID:27123018

  13. In Vitro Comparison of the Effects of Diode Laser and CO2 Laser on Topical Fluoride Uptake in Primary Teeth.

    PubMed

    Bahrololoomi, Zahra; Fotuhi Ardakani, Faezeh; Sorouri, Milad

    2015-08-01

    Fluoride therapy is important for control and prevention of dental caries. Laser irradiation can increase fluoride uptake especially when combined with topical fluoride application. The objective of this study was to compare the effects of CO2 and diode lasers on enamel fluoride uptake in primary teeth. Forty human primary molars were randomly assigned to four groups (n=10). The roots were removed and the crowns were sectioned mesiodistally into buccal and lingual halves as the experimental and control groups. All samples were treated with 5% sodium fluoride (NaF) varnish. The experimental samples in the four groups were irradiated with 5 or 7W diode or 1 or 2W CO2 laser for 15 seconds and were compared with the controls in terms of fluoride uptake, which was determined using an ion selective electrode after acid dissolution of the specimens. Data were analyzed by SPSS version 16 using ANOVA treating the control measurements as covariates. The estimated amount of fluoride uptake was 59.5± 16.31 ppm, 66.5± 14.9 ppm, 78.6± 12.43 ppm and 90.4± 11.51 ppm for 5W and 7 W diode and 1W and 2 W CO2 lasers, respectively, which were significantly greater than the values in the conventional topical fluoridation group (P<0.005). There were no significant differences between 7W diode laser and 1W CO2 laser, 5W and 7W diode laser, or 1W and 2W CO2 laser in this regard. The results showed that enamel surface irradiation by CO2 and diode lasers increases the fluoride uptake.

  14. Seasonal, diurnal and nocturnal behaviors of lower carbonyl compounds in the urban environment of Beirut, Lebanon

    NASA Astrophysics Data System (ADS)

    Moussa, Samar G.; El-Fadel, Mutassem; Saliba, Najat A.

    Lower carbonyl concentrations were measured for the first time in two different sampling sites (American University of Beirut (AUB) and Abdel-Aziz (AA)) in Beirut, Lebanon. Formaldehyde (C1) and acetaldehyde (C2) were the most abundant carbonyls with respective maximum concentrations of 12.2 and 5.2 ppbv at AUB and 8.6 and 5.1 ppbv at AA. Diurnal variations of carbonyls exhibited similar behaviors, suggesting related formation and decomposition routes. Morning levels of carbonyls were either equal or higher than the ones in the afternoon at the coastal site (AUB) due to atmospheric dilution. However, morning levels were mostly lower than noon levels at a three-busy street intersection (AA) due to the enhancement of photochemical activities. Vehicle emissions constituted the dominant source of carbonyls measured as confirmed by the good correlation between C1, C2 and propanal (C3) and the C1/CO and C2/CO ratios in the mornings. Seasonal variation showed the predominance of summertime photolysis and photo-oxidation reactions of aldehydes. Based on the measured formaldehyde levels, ozone and nitrous acid concentrations, morning and afternoon OH radical fluxes are computed and consequently their contribution to photochemical smog processes are assessed.

  15. Carbonyl atmospheric reaction products of aromatic hydrocarbons in ambient air

    NASA Astrophysics Data System (ADS)

    Obermeyer, Genevieve; Aschmann, Sara M.; Atkinson, Roger; Arey, Janet

    To convert gaseous carbonyls to oximes during sampling, an XAD-4 resin denuder system pre-coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine and followed by analysis with methane positive chemical ionization gas chromatography/mass spectrometry was used to measure carbonyls in ambient air samples in Riverside, CA. In conjunction with similar analyses of environmental chamber OH radical-initiated reactions of o- and p-xylene, 1,2,4-trimethylbenzene, ethylbenzene, 4-hydroxy-2-butanone and 1,4-butanediol, we identified benzaldehyde, o-, m- and p-tolualdehyde and acetophenone and the dicarbonyls glyoxal, methylglyoxal, biacetyl, ethylglyoxal, 1,4-butenedial, 3-hexene-2,5-dione, 3-oxo-butanal, 1,4-butanedial and malonaldehyde in the ambient air samples. As discussed, these carbonyls and dicarbonyls can be formed from the OH radical-initiated reactions of aromatic hydrocarbons and other volatile organic compounds emitted into the atmosphere, and we conclude that in situ atmospheric formation is a major source of these carbonyls in our Riverside, CA, ambient air samples.

  16. Novel DNPH-based method for determination of protein carbonylation in muscle and meat.

    PubMed

    Soglia, Francesca; Petracci, Massimiliano; Ertbjerg, Per

    2016-04-15

    Protein oxidation is considered an ongoing deteriorative process during storage of fresh and processed meat. Carbonyl compounds have traditionally been detected spectrophotometrically after derivatization with 2,4-dinitrophenylhydrazine (DNPH) to form protein-bound hydrazones with absorbance at 370 nm. Here we describe a novel DNPH-based method to quantify protein carbonylation in muscle and meat. The additional steps of the novel method aimed at increasing the protein solubility and inducing protein unfolding before labeling with DNPH. Compared to the traditional method, the new procedure reflected an increased protein carbonylation level measuring overall two to fourfold more carbonyls in muscles from different species as well as in soluble, salt-soluble and insoluble protein fractions. The study suggested that protein unfolding is a more important phenomenon than solubilization for increased DNPH labeling. The novel method resulted in three to fourfold larger carbonyl content determined in chicken, pork and beef (2.8, 3.6 and 3.1 nmol/mg of protein, respectively). Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Rapid method for determination of carbonyl groups in lignin compounds by headspace gas chromatography.

    PubMed

    Li, Jing; Hu, Hui-Chao; Chai, Xin-Sheng

    2015-07-24

    The paper reports on a novel method for rapid determination of carbonyl in lignins by headspace gas chromatography (HS-GC). The method involves the quantitative carbonyl reduction for aldehydes in 2min at room temperature or for acetones in 30min at 80°C by sodium borohydride solution in a closed headspace sample vial. After the reaction, the solution was acidified by injecting sulfuric acid solution and the hydrogen released to the headspace was determined by GC using thermal-conductivity detector. The results showed that with the addition of SiO2 powder, the reduction reaction of carbonyl groups can be greatly facilitated. The method has a good measurement precision (RSD<7.74%) and accuracy (relative error <10% compared with a reference method) in the carbonyl quantification. It is suitable to be used for rapid determination of carbonyl content in lignin and related materials. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. [Influence of different concentrations of fluoride in the water on epidemiologic indicators of oral health/disease].

    PubMed

    de Carvalho, Raquel Baroni; Medeiros, Urubatan Vieira de; dos Santos, Karina Tonini; Pacheco Filho, Antônio Carlos

    2011-08-01

    The scope of this study was to evaluate access to fluoride sources and oral health hygiene of 237 schoolchildren aged nine to sixteen, from three locations with different fluoride concentrations in the water. The fluoride level in the water of each area was analyzed by the selective electrode technique for the fluoride ion and the prevalence of dental caries and fluorosis were evaluated, respectively, by the DMFT and TSIF index, revealing a statistically significant difference (ANOVA; p <0,05) in the three locations: area without artificial fluoridation (DMTF 5.32 ± 3.49) and 16% of dental fluorosis; area with artificial fluoridation of 0.8 ppmF (DMTF 1.88 ± 2.22) and 94% of dental fluorosis; area with natural fluoridation of 2.54 ppmF (DMTF 3.96 ± 2.38) and 100% of dental fluorosis. The findings suggest that the epidemiologic indicators of oral health/disease are influenced by the presence of fluoride in the water supply and that supervision and orientation are fundamental in the correct use of fluoridated compositions, taking advantage of the maximum benefit in the control of dental caries with minimum risk of the occurrence of dental fluorosis.

  19. Communication network for decentralized remote tele-science during the Spacelab mission IML-2

    NASA Technical Reports Server (NTRS)

    Christ, Uwe; Schulz, Klaus-Juergen; Incollingo, Marco

    1994-01-01

    The ESA communication network for decentralized remote telescience during the Spacelab mission IML-2, called Interconnection Ground Subnetwork (IGS), provided data, voice conferencing, video distribution/conferencing and high rate data services to 5 remote user centers in Europe. The combination of services allowed the experimenters to interact with their experiments as they would normally do from the Payload Operations Control Center (POCC) at MSFC. In addition, to enhance their science results, they were able to make use of reference facilities and computing resources in their home laboratory, which typically are not available in the POCC. Characteristics of the IML-2 communications implementation were the adaptation to the different user needs based on modular service capabilities of IGS and the cost optimization for the connectivity. This was achieved by using a combination of traditional leased lines, satellite based VSAT connectivity and N-ISDN according to the simulation and mission schedule for each remote site. The central management system of IGS allows minimization of staffing and the involvement of communications personnel at the remote sites. The successful operation of IGS for IML-2 as a precursor network for the Columbus Orbital Facility (COF) has proven the concept for communications to support the operation of the COF decentralized scenario.

  20. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    PubMed Central

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-01-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N∙ (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C∙, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C∙, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals. PMID:26960916

  1. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    NASA Astrophysics Data System (ADS)

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  2. Metal-Diazo Radicals of α-Carbonyl Diazomethanes.

    PubMed

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-10

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [Rh(I)Cl(cod)]2, [Co(II)(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [Rh(I)Cl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N∙ (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C∙, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C∙, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  3. 49 CFR 173.163 - Hydrogen fluoride.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Hydrogen fluoride. 173.163 Section 173.163... Hydrogen fluoride. (a) Hydrogen fluoride (hydrofluoric acid, anhydrous) must be packaged as follows: (1) In... filling ratio of 0.84. (b) A cylinder removed from hydrogen fluoride service must be condemned in...

  4. 49 CFR 173.163 - Hydrogen fluoride.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Hydrogen fluoride. 173.163 Section 173.163... Hydrogen fluoride. (a) Hydrogen fluoride (hydrofluoric acid, anhydrous) must be packaged as follows: (1) In... filling ratio of 0.84. (b) A cylinder removed from hydrogen fluoride service must be condemned in...

  5. 49 CFR 173.163 - Hydrogen fluoride.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Hydrogen fluoride. 173.163 Section 173.163... Hydrogen fluoride. (a) Hydrogen fluoride (hydrofluoric acid, anhydrous) must be packaged as follows: (1) In... filling ratio of 0.84. (b) A cylinder removed from hydrogen fluoride service must be condemned in...

  6. 49 CFR 173.163 - Hydrogen fluoride.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Hydrogen fluoride. 173.163 Section 173.163... Hydrogen fluoride. (a) Hydrogen fluoride (hydrofluoric acid, anhydrous) must be packaged as follows: (1) In... filling ratio of 0.84. (b) A cylinder removed from hydrogen fluoride service must be condemned in...

  7. 49 CFR 173.163 - Hydrogen fluoride.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Hydrogen fluoride. 173.163 Section 173.163... Hydrogen fluoride. (a) Hydrogen fluoride (hydrofluoric acid, anhydrous) must be packaged as follows: (1) In... filling ratio of 0.84. (b) A cylinder removed from hydrogen fluoride service must be condemned in...

  8. Determination of Carbonyl Groups in Pyrolysis Bio-oils Using Potentiometric Titration: Review and Comparison of Methods

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

    Black, Stuart; Ferrell, Jack R.

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here in this study, we present a modification of the traditional carbonyl oximation procedures that results inmore » less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. Some compounds such as carbohydrates are not measured by the traditional method (modified Nicolaides method), resulting in low estimations of the carbonyl content. Furthermore, we have shown that reaction completion for the traditional method can take up to 300 hours. The new method presented here (the modified Faix method) reduces the reaction time to 2 hours, uses triethanolamine (TEA) in the place of pyridine, and requires a smaller sample size for the analysis. Carbonyl contents determined using this new method are consistently higher than when using the traditional titration methods.« less

  9. Determination of Carbonyl Groups in Pyrolysis Bio-oils Using Potentiometric Titration: Review and Comparison of Methods

    DOE PAGES

    Black, Stuart; Ferrell, Jack R.

    2016-01-06

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here in this study, we present a modification of the traditional carbonyl oximation procedures that results inmore » less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. Some compounds such as carbohydrates are not measured by the traditional method (modified Nicolaides method), resulting in low estimations of the carbonyl content. Furthermore, we have shown that reaction completion for the traditional method can take up to 300 hours. The new method presented here (the modified Faix method) reduces the reaction time to 2 hours, uses triethanolamine (TEA) in the place of pyridine, and requires a smaller sample size for the analysis. Carbonyl contents determined using this new method are consistently higher than when using the traditional titration methods.« less

  10. A reactive and sensitive diffusion sampler for the determination of aldehydes and ketones in ambient air

    NASA Astrophysics Data System (ADS)

    Uchiyama, Shigehisa; Hasegawa, Shuji

    We developed a diffusive sampling device (DSD-carbonyl) for organic carbonyl compounds (aldehydes and ketones) which is suitable for collection and analysis of low concentration levels. This sampling device is composed of three parts, an exposure part made of a porous polytetrafluoroethylene (PPTFE) tube, an analysis part made of polypropylene (PP) tubing and an absorbent part made of 2,4-dinitrophenylhydrazine (DNPH) coated silica gel (DNPH-silica). Aldehydes and ketones diffuse to the DSD-carbonyl through PPTFE-tube by the mechanism of molecular diffusion and react specifically with DNPH to form a stable DNPH-derivatives. Collection is controlled by moving the absorbent from the exposure part to the analysis part by changing the posture of the DSD-carbonyl. DNPH-derivatives were eluted from an analysis part of DSD-carbonyl with acetonitrile directly and analyzed by high performance liquid chromatography (HPLC). The advantages of the DSD-carbonyl are the following: (1) The DSD-carbonyl can be used in a wide range of concentration of aldehydes and ketones in atmosphere, as the DSD-carbonyl exposure part has a variable diffusion area, (2) DNPH-derivatives are eluted from DNPH-silica without contamination of air. (3) The sampler can be applied to active sampling by connecting it with a pump. The limit of detection (LOD) for concentrations of major aldehydes and ketones ranged from 0.072 to 0.13 ppb, and the limit of quantitation (LOQ) ranged from 0.24 to 0.42 ppb. The coefficient variation (CV) for concentrations of major aldehydes and ketones ranged from 2.5 to 3.0% in laboratory air. The DSD-carbonyl method and active sampling method (US EPA method IP-6A) showed a good correlation (formaldehyde, r2=0.995). The uptake rates for formaldehyde, acetaldehyde, and acetone were estimated as 0.078, 0.062 and 0.079 nmol ppb -1 h -1, respectively. It is possible to estimate atmospheric aldehydes and ketones at parts per billion (ppb), with high sensitivity and precision, by using DSD-carbonyl.

  11. Protein oxidation and aging. I. Difficulties in measuring reactive protein carbonyls in tissues using 2,4-dinitrophenylhydrazine.

    PubMed

    Cao, G; Cutler, R G

    1995-06-20

    A current hypothesis explaining the aging process implicates the accumulation of oxidized protein in animal tissues. This hypothesis is based on a series of reports showing an age-dependent increase in protein carbonyl content and an age-dependent loss of enzyme function. This hypothesis is also supported by the report of a novel effect of N-tert-butyl-alpha-phenylnitrone (PBN) in reversing these age-dependent changes. Here we specifically study the method that was used to measure reactive protein carbonyls in tissues. This method uses 2,4-dinitrophenylhydrazine (DNPH) and includes a washing procedure. Our results indicate that reactive protein carbonyls in normal crude tissue extracts cannot be reliably measured by this method, although it does reliably measure reactive carbonyls in purified proteins which have been oxidatively modified in vitro. The nucleic acids in tissues could be a major problem encountered in the assay. Using the streptomycin sulfate treatment combined with a dialysis step, we were successful in removing most nucleic acids from a crude tissue extract, but then the reactive carbonyl level in the crude tissue extract was too low to be reliably measured. This streptomycin sulfate treatment procedure, however, had no effect on the reactive carbonyl measurement of an oxidized protein sample. The unwashed free DNPH was another major problem in the assay because of its very strong absorption around 370 nm, where reactive carbonyls were quantitated. Nevertheless, on using the procedure described in the literature to measure total "reactive carbonyls" in rat liver and gerbil brain cortex, no change with age or PBN treatment was found. Then, we investigated a HPLC procedure which uses sodium dodecyl sulfate in the mobile phase but this was also found to be unsuitable for the reactive protein carbonyl assay in tissues.

  12. Does fluoride in the water close the dental caries gap between Indigenous and non-Indigenous children?

    PubMed

    Lalloo, R; Jamieson, L M; Ha, D; Ellershaw, A; Luzzi, L

    2015-09-01

    Indigenous children experience significantly more dental caries than non-Indigenous children. This study assessed if access to fluoride in the water closed the gap in dental caries between Indigenous and non-Indigenous children. Data from four states and two territories were sourced from the Child Dental Health Survey (CDHS) conducted in 2010. The outcomes were dental caries in the deciduous and permanent dentitions, and the explanatory variables were Indigenous status and access to fluoridated water (≥0.5 mg/L) prior to 2008. Dental caries prevalence and severity for Indigenous and non-Indigenous children, in both dentitions, was lower in fluoridated areas compared to non-fluoridated areas. Among non-Indigenous children, there was a 50.9% difference in mean dmft scores in fluoridated (1.70) compared to non-fluoridated (2.86) areas. The difference between Indigenous children in fluoridated (3.29) compared to non-fluoridated (4.16) areas was 23.4%. Among non-Indigenous children there was a 79.7% difference in the mean DMFT scores in fluoridated (0.68) compared to non-fluoridated (1.58) areas. The difference between Indigenous children in fluoridated (1.59) and non-fluoridated (2.23) areas was 33.5%. Water fluoridation is effective in reducing dental caries, but does not appear to close the gap between non-Indigenous children and Indigenous children. © 2015 Australian Dental Association.

  13. Influence of the Relative Enamel Abrasivity (REA) of Toothpastes on the Uptake of KOH-soluble and Structurally Bound Fluoride.

    PubMed

    Elmazi, Valbona; Sener, Beatrice; Attin, Thomas; Imfeld, Thomas; Wegehaupt, Florian J

    2015-01-01

    To determine the influence of the relative enamel abrasivity (REA) of fluoridated toothpaste on the uptake of KOH-soluble and structurally bound fluoride into enamel. Bovine enamel samples were randomly allocated to 6 groups (n=36 per group). Groups A to C were treated with sodium fluoride (NaF) toothpastes and groups D to F with amine fluoride (AmF) toothpastes (1500 ppm F each). The REA in groups A and D was 2, in groups B and E it was 6 and in groups C and F it was 9. Twice a day, 18 samples of each group were immersed for 2 min in a slurry (toothpaste:artificial saliva=1:3), while the remaining samples were brushed with the respective slurry (2.5 N force; 60 strokes/min; 2 min). All samples were stored at 37°C and 100% humidity. After five days, the amount of KOH-soluble and structurally bound fluoride was determined and statistically compared by Scheffe's post-hoc tests. REA value and mode of application (immersion or brushing) had no significant influence on the amount of either kind of fluoride from NaF toothpastes. Only for the NaF toothpaste with REA 6 was the amount of KOH-soluble fluoride significantly higher after brushing. With AmF toothpastes, KOH-soluble and structurally bound fluoride concentrations were significantly higher when the samples were brushed. Furthermore, in the REA-2 group, the amounts of KOH-soluble fluoride (brushed or immersed) and structurally bound fluoride (brushed) were significantly higher than in the other groups. The REA dependency of KOH-soluble and structurally bound fluoride was found only for the AmF toothpastes. Using AmF toothpaste, the mode of application influenced the uptake of KOH-soluble and structurally bound fluoride into enamel.

  14. Simultaneous determination of ozone and carbonyls using trans-1,2-bis(4-pyridyl)ethylene as an ozone scrubber for 2,4-dinitrophenylhydrazine-impregnated silica cartridge.

    PubMed

    Uchiyama, Shigehisa; Otsubo, Yasufumi

    2008-05-01

    A new method for the simultaneous determination of ozone and carbonyls in air using a two-bed cartridge system has been developed. Each bed consists of reagent-impregnated silica particles. The first contains trans-1,2-bis-(4-pyridyl) ethylene (BPE) while the second contains 2,4-dinitrophenylhydrazine (DNPH). Air samples are drawn through the cartridge first through the BPE and then through the DNPH. Ozone in the air sample is trapped in the first bed by the BPE-coated silica particles and produce pyridine-4-aldehyde. Airborne carbonyls pass unimpeded thorough the BPE and are trapped in the second bed by the DNPH-coated silica particles. They produce carbonyl 2,4-DNPhydrazones. DNPH and carbonyl 2,4-DNPhydrazones are not influenced by ozone because of effective trapping by the BPE. Extraction is performed in the direction reverse to air sampling. When solvent is eluted through the BEP/DNPH cartridge, excess DNPH is washed into the BPE bed where it reacted with pyridine-4-aldehyde and forms the corresponding hydrazone derivative. All of the hydrazones derived from airborne carbonyls and pyridine-4-aldehyde (derived from ozone) are completely separated and measured using high-performance liquid chromatography. An Ascentis RP-Amide column is used, and the mobile phase is 40% aqueous acetonitrile containing 2 mmol/L ammonium acetate. The use of a BPE/DNPH cartridge has made possible the simultaneous determination of ozone and carbonyls. A separate ozone scrubber is not necessary with the BPE/DNPH cartridge because the BPE portion of the sampler serves this function.

  15. Fluoride in groundwater: toxicological exposure and remedies.

    PubMed

    Jha, S K; Singh, R K; Damodaran, T; Mishra, V K; Sharma, D K; Rai, Deepak

    2013-01-01

    Fluoride is a chemical element that is found most frequently in groundwater and has become one of the most important toxicological environmental hazards globally. The occurrence of fluoride in groundwater is due to weathering and leaching of fluoride-bearing minerals from rocks and sediments. Fluoride when ingested in small quantities (<0.5 mg/L) is beneficial in promoting dental health by reducing dental caries, whereas higher concentrations (>1.5 mg/L) may cause fluorosis. It is estimated that about 200 million people, from among 25 nations the world over, may suffer from fluorosis and the causes have been ascribed to fluoride contamination in groundwater including India. High fluoride occurrence in groundwaters is expected from sodium bicarbonate-type water, which is calcium deficient. The alkalinity of water also helps in mobilizing fluoride from fluorite (CaF2). Fluoride exposure in humans is related to (1) fluoride concentration in drinking water, (2) duration of consumption, and (3) climate of the area. In hotter climates where water consumption is greater, exposure doses of fluoride need to be modified based on mean fluoride intake. Various cost-effective and simple procedures for water defluoridation techniques are already known, but the benefits of such techniques have not reached the rural affected population due to limitations. Therefore, there is a need to develop workable strategies to provide fluoride-safe drinking water to rural communities. The study investigated the geochemistry and occurrence of fluoride and its contamination in groundwater, human exposure, various adverse health effects, and possible remedial measures from fluoride toxicity effects.

  16. Analysis of Phone Calls Regarding Fluoride Exposure made to New Jersey Poison Control Center from 2010 to 2012.

    PubMed

    Shah, Sneha; Quek, Samuel; Ruck, Bruce

    2016-02-01

    The American Association of Poison Control Center's annual reports demonstrate that acute fluoride exposure is not an uncommon occurrence. Despite its prevalence, there has been little published research on the topic in the last 10 years. The purpose of this study was to calculate the incidence of acute fluoride toxicity and lethality as it occurs in New Jersey and provide a descriptive epidemiology of acute fluoride exposures. The study design was retrospective in nature. Records of phone calls made by individuals reporting excessive fluoride exposure (in an amount greater than directed/prescribed) to New Jersey's poison control center, known as Poison Information and Education System from the years 2010 through 2012, were extracted from Toxicall® (Computer Automatic Systems, Inc.) database. A total of 2,476 human-only exposure records met the inclusion criteria and were analyzed. Incidence rates were calculated, and population characteristics, circumstances and medical outcomes of acute fluoride exposure cases were assessed and categorized. A total of 2,476 phone call records met the inclusion criteria. The fluoride exposures reported were from toothpaste with fluoride (49%, n=1,214), mouth rinse with fluoride (21.6%, n=536), multivitamin with fluoride (21.4%, n=530) and pure fluoride (0.08%, n=199). Medically speaking, 94.75% of calls were asymptomatic cases (n=2,346), 4.24% were symptomatic (n=105) and 1.01% were informational inquiries (n=25). Adverse symptoms reported were mostly minor (83.9% of symptomatic cases, n=88) and moderate (16.1% of symptomatic cases, n=17). The age group 18 months to 3 years of age showed the highest incidence of acute fluoride exposure (53.2%, n=1,317). There was a slightly higher incidence of acute fluoride exposures among males (n=1,317) vs. females (n=1,159). Most incidences occurred in the home (93.1% of records, n=2,305) and occurred unintentionally (96.7%, n=2,394). Calls were mainly made by the subject's mother (67.5%, n=1,671). Based on the data, there were no reports of lethality or toxicity due to acute fluoride exposure in New Jersey from 2010 through 2012. Symptomatic reports and informational inquiries were few. All adverse outcomes due to excessive fluoride intake were remedied with calcium as the antidote. Dental hygienists should educate patients on safety measures of fluoride-containing products and evaluate overall fluoride exposure prior to making recommendations. However, findings in this study suggest that levels of fluoride in available commercial products will not produce life-threatening events, even if taken in doses higher than recommended. Copyright © 2016 The American Dental Hygienists’ Association.

  17. Evaluation of the head-helmet sliding properties in an impact test.

    PubMed

    Trotta, Antonia; Ní Annaidh, Aisling; Burek, Roy Owen; Pelgrims, Bart; Ivens, Jan

    2018-05-18

    The scalp plays a crucial role in head impact biomechanics, being the first tissue involved in the impact and providing a sliding interface between the impactor and/or helmet and the skull. It is important to understand both the scalp-skull and the scalp-helmet sliding in order to determine the head response due to an impact. However, experimental data on the sliding properties of the scalp is lacking. The aim of this work was to identify the sliding properties of the scalp using cadaver heads, in terms of scalp-skull and scalp-liner (internal liner of the helmet) friction and to compare these values with that of widely used artificial headforms (HIII and magnesium EN960). The effect of the hair, the direction of sliding, the speed of the test and the normal load were considered. The experiments revealed that the sliding behaviour of the scalp under impact loading is characterised by three main phases: (1) the low friction sliding of the scalp over the skull (scalp-skull friction), (2) the tensioning effect of the scalp and (3) the sliding of the liner fabric over the scalp (scalp-liner friction). Results showed that the scalp-skull coefficient of friction (COF) is very low (0.06 ± 0.048), whereas the scalp-liner COF is 0.29 ± 0.07. The scalp-liner COF is statistically different from the value of the HIII-liner (0.75 ± 0.06) and the magnesium EN960-liner (0.16 ± 0.026). These data will lead to the improvement of current headforms for head impact standard tests, ultimately leading to more realistic head impact simulations and the optimization of helmet designs. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Consumption of high ω-3 fatty acid diet suppressed prostate tumorigenesis in C3(1) Tag mice.

    PubMed

    Akinsete, Juliana A; Ion, Gabriela; Witte, Theodore R; Hardman, W Elaine

    2012-01-01

    Prostate cancer incidence and mortality are high in the Western world and high ω-6/ω-3 PUFA in the Western diet may be a contributing factor. We investigated whether changing from a diet that approximates ω-6 fat content of the Western diet to a high ω-3 fat diet at adulthood might reduce prostate cancer risk. Female SV 129 mice that had consumed a high ω-6 diet containing corn oil for 2 weeks were bred with homozygous C3(1)Tag transgenic male mice. All male offspring were weaned to the corn oil diet (CO) until postpuberty when half of the male offspring were transferred to a high ω-3 diet containing canola oil and fish oil concentrate (FS). High ω-3 diet increased ω-3 and decreased ω-6 fat content of mice tissues. Average weights of prostate and genitourinary bloc were significantly lower in mice consuming high ω-3 diet at adulthood (CO-FS) than mice fed a lifetime high ω-6 diet (CO-CO). There was slower progression of tumorigenesis in dorsalateral prostate of CO-FS than in CO-CO mice. CO-FS mice had slightly lower plasma testosterone level at 24 and 40 weeks, significantly lower estradiol level at 40 weeks and significantly less expressed androgen receptor (AR) in the dorsalateral prostate at 40 weeks than CO-CO mice. Consumption of high ω-3 diet lowered the expression of genes expected to increase proliferation and decrease apoptosis in dorsalateral prostate. Our results suggest that consumption of high ω-3 diet slows down prostate tumorigenesis by lowering estradiol, testosterone and AR levels, promoting apoptosis and suppressing cell proliferation in C3(1)Tag mice.

  19. Consumption of high ω-3 fatty acid diet suppressed prostate tumorigenesis in C3(1) Tag mice

    PubMed Central

    Ion, Gabriela; Witte, Theodore R.; Hardman, W.Elaine

    2012-01-01

    Prostate cancer incidence and mortality are high in the Western world and high ω-6/ω-3 PUFA in the Western diet may be a contributing factor. We investigated whether changing from a diet that approximates ω-6 fat content of the Western diet to a high ω-3 fat diet at adulthood might reduce prostate cancer risk. Female SV 129 mice that had consumed a high ω-6 diet containing corn oil for 2 weeks were bred with homozygous C3(1)Tag transgenic male mice. All male offspring were weaned to the corn oil diet (CO) until postpuberty when half of the male offspring were transferred to a high ω-3 diet containing canola oil and fish oil concentrate (FS). High ω-3 diet increased ω-3 and decreased ω-6 fat content of mice tissues. Average weights of prostate and genitourinary bloc were significantly lower in mice consuming high ω-3 diet at adulthood (CO-FS) than mice fed a lifetime high ω-6 diet (CO–CO). There was slower progression of tumorigenesis in dorsalateral prostate of CO-FS than in CO–CO mice. CO-FS mice had slightly lower plasma testosterone level at 24 and 40 weeks, significantly lower estradiol level at 40 weeks and significantly less expressed androgen receptor (AR) in the dorsalateral prostate at 40 weeks than CO–CO mice. Consumption of high ω-3 diet lowered the expression of genes expected to increase proliferation and decrease apoptosis in dorsalateral prostate. Our results suggest that consumption of high ω-3 diet slows down prostate tumorigenesis by lowering estradiol, testosterone and AR levels, promoting apoptosis and suppressing cell proliferation in C3(1)Tag mice. PMID:22045025

  20. Ten new predicted covalent organic frameworks with strong optical response in the visible and near infrared

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

    Yang, Li-Ming, E-mail: lmyang.uio@gmail.com, E-mail: ganzx001@umn.edu; Frauenheim, Thomas; Dornfeld, Matthew

    2015-06-28

    We use density functional theory to predict and evaluate 10 novel covalent organic frameworks (COFs), labeled (X{sub 4}Y)(BDC){sub 3}, (X = C/Si; Y = C, Si, Ge, Sn, and Pb), with topology based on metal organic framework isoreticular metal-organic framework (IRMOF-1), but with new elements substituted for the corner atoms. We show that these new materials are stable structures using frequency calculations. For two structures, (C{sub 4}C and Si{sub 4}C) molecular dynamics simulations were performed to demonstrate stability of the systems up to 600 K for 10 ps. This demonstrates the remarkable stability of these systems, some of which maymore » be experimentally accessible. For the C{sub 4}C material, we also explored the stability of isolated corners and linkers and vacuum and started to build the structure from these pieces. We discuss the equilibrium lattice parameters, formation enthalpies, electronic structures, chemical bonding, and mechanical and optical properties. The predicted bulk moduli of these COFs range from 18.9 to 23.9 GPa, larger than that of IRMOF-1 (ca. 15.4 GPa), and larger than many existing 3D COF materials. The band gaps range from 1.5 to 2.1 eV, corresponding to 600–830 nm wavelength (orange through near infrared). The negative values of the formation enthalpy suggest that they are stable and should be experimentally accessible under suitable conditions. Seven materials distort the crystal structure to a lower space group symmetry Fm-3, while three materials maintain the original Fm-3m space group symmetry. All of the new materials are highly luminescent. We hope that this work will inspire efforts for experimental synthesis of these new materials.« less

  1. A 4-year assessment of a new water-fluoridation scheme in New South Wales, Australia.

    PubMed

    Blinkhorn, Anthony S; Byun, Roy; Mehta, Pathik; Kay, Meredith

    2015-06-01

    To monitor the changes in dental caries prevalence of 5- to 7-year-old children living in a fluoridated area, a newly fluoridated area and in an area without water fluoridation, in NSW, Australia. Dental caries prevalence was recorded for 5- to 7-year-old children, living in the three study locations, by six trained and calibrated examiners in 2008, 2010 and 2012. A questionnaire recorded demographic data, toothbrushing behaviour and sugary drink consumption. Caries experience was measured using the decayed, missing, and filled teeth (dmft) index for primary teeth, the percentage of children who were caries free and the significant caries index. Univariate analysis was undertaken to determine independent predictors of caries. The caries prevalence changed over time. In 2008, the mean dmft index was 1.40 for the fluoridated area, 2.02 for the area about to fluoridate and 2.09 for the unfluoridated control. By 2012, these mean dmft scores were 0.69, 0.72 and 1.21, respectively. In the two areas where children received fluoridated water, the significant caries index was 2.30 for the fluoridated area and 2.40 for the newly fluoridated area. The significant caries score for children in the unfluoridated location was 3.93. Multivariate analysis showed that over time the differences in dental caries prevalence between the established fluoride area and the newly fluoridated area diminished. However, children in the unfluoridated control area continued to demonstrate significant differences in the mean number of decayed teeth compared with children in the fluoridated comparator sites, and the proportions of children free from decay were significantly higher in the fluoridated areas than in the unfluoridated area. Fluoridation of public water supplies in Gosford and Wyong offers young children better dental health than those children who do not have access to this public health measure. © 2015 FDI World Dental Federation.

  2. Fluoride concentration in urine after silver diamine fluoride application on tooth enamel

    NASA Astrophysics Data System (ADS)

    Sari, D. L.; Bahar, A.; Gunawan, H. A.; Adiatman, M.; Rahardjo, A.; Maharani, D. A.; Toptanci, I. R.; Yavuz, I.

    2017-08-01

    Silver Diammine Fluoride (SDF), which contains fluoride, is known to inhibit tooth enamel demineralization and increase fluoride concentrations in saliva and urine. The aim of this study is to analyze the fluoride concentration in urine after application of SDF on tooth enamel. Urine from four subjects was collected prior to, 30 minutes after, and two and three hours after the application of SDF, and an ion-selective electrode was used to measure the fluoride concentrations. There was no significant difference between time 1 and time 2, time 1 and time 3, time 1 and time 4, time 2 and 3 (p > 0.05), and there was a significant difference between time 2 and time 4 as well as time 3 and time 4 (p < 0.05). There was a decrease in the concentration of fluoride ions in urine from the baseline to 30 minutes after application, and an increase from baseline to two and three hours after the application of SDF.

  3. Relationship between water, urine and serum fluoride and fluorosis in school children of Jhajjar District, Haryana, India

    NASA Astrophysics Data System (ADS)

    Kumar, Sunil; Lata, Suman; Yadav, Jyoti; Yadav, J. P.

    2017-10-01

    The present study was undertaken to determine the relationship between fluoride in water, urine and serum and dental fluorosis. The fluoride level in water and urine were measured spectrophotometrically by using acid zirconyl and SPADNS reagents, while the fluoride level in serum was determined by ion selective electrode meter. Dental fluorosis survey was conducted with the help of Performa prescribed by Rajiv Gandhi Drinking Water Mission and the use of Tooth Surface Index for Fluorosis. Mean fluoride values in water samples of Jhajjar City and Dadanpur and Dariyapur villages of Jhajjar District were measured to be 2.17 (range from 1.92 to 2.60 mg/L), 2.81 (range from 2.53 to 3.14 mg/L) and 2.22 mg/L (range from 1.63 to 3.33 mg/L), respectively. The mean fluoride values in the urine samples of children were found to be 1.51 (range from 0.05 to 2.64 mg/L), 1.71 (range from 0.69 to 2.80 mg/L) and 1.45 mg/L (range from 0.31 to 2.50 mg/L) at Jhajjar City and Dadanpur and Dariyapur sites, respectively. Serum fluoride was detected in the blood samples of children, who have high urinary fluoride at these three sites. The mean serum fluoride level was reported to be 0.15, 0.34 and 0.17 mg/L, respectively. A total of 842 children were also analyzed for dental fluorosis. The mean values of fluorosis-affected children in Jhajjar, Dadanpur and Dariyapur were 51.90, 94.63 and 36.84 %, respectively. A significantly positive correlation between water, urine, serum fluoride concentration and fluorosis was seen.

  4. Use of 2,4-dinitrophenylhydrazine for the purification of technical isoprene from carbonyl compounds

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

    Kuznetsova, Y.V.; Taranenko, S.A.; Mil'kina, T.N.

    1983-01-01

    Technical isoprene can be freed from carbonyl compounds by conversion into non-volatile derivatives - hydrazones, with subsequent liberation of the purified isoprene during re-evaporation. The reaction takes place at room temperature with a molar ratio of 2,4-dinitrophenylhydrazine/carbonyl compounds in the range 2-10 to 1. This method of purification may also be used in other situations where a hydrocarbon flow freed from aldehydes and ketones is required.

  5. Assessment of fluoride-induced changes on physicochemical and structural properties of bone and the impact of calcium on its control in rabbits.

    PubMed

    Gopalakrishnan, Subarayan Bothi; Viswanathan, Gopalan

    2012-03-01

    Bone deformities caused by the chronic intake of large quantities of fluoride and the beneficial effect of calcium on its control have been studied for many years, but only limited data are available on the quantitative effect of fluoride intake and the beneficial impact of calcium on fluoride-induced changes in bone at the molecular level. It is necessary to determine the degree of fluoride-induced changes in bone at different levels of fluoride intake to evaluate the optimum safe intake level of fluoride for maintaining bone health and quality. The ameliorative effect of calcium at different dose levels on minimizing fluoride-induced changes in bone is important to quantify the amount of calcium intake necessary for reducing fluoride toxicity. Thirty rabbits, 2 months old, were divided into five groups. Group I animals received 1 mg/l fluoride and 0.11% calcium diet; groups II and III received 10 mg/l fluoride and diet with 0.11% or 2.11% calcium, respectively; and groups IV and V received 150 mg/l fluoride and diet with 2.11% or 0.11% calcium, respectively. Analysis of bone density, ash content, fluoride, calcium, phosphorus, and Ca:P molar ratio levels after 6 months of treatment indicated that animals that received high fluoride with low-calcium diet showed significant detrimental changes in physicochemical properties of bone. Animals that received fluoride with high calcium intake showed notable amelioration of the impact of calcium on fluoride-induced changes in bone. The degree of fluoride-induced characteristic changes in structural properties such as crystalline size, crystallinity, and crystallographic "c"-axis length of bone apatite cells was also assessed by X-ray diffraction and Fourier transform infrared studies. X-ray images showed bone deformity changes such as transverse stress growth lines, soft tissue ossification, and calcification in different parts of bones as a result of high fluoride accumulation and the beneficial role of calcium intake on its control.

  6. Characterisation and optimisation of a sample preparation method for the detection and quantification of atmospherically relevant carbonyl compounds in aqueous medium

    NASA Astrophysics Data System (ADS)

    Rodigast, M.; Mutzel, A.; Iinuma, Y.; Haferkorn, S.; Herrmann, H.

    2015-06-01

    Carbonyl compounds are ubiquitous in the atmosphere and either emitted primarily from anthropogenic and biogenic sources or they are produced secondarily from the oxidation of volatile organic compounds. Despite a number of studies about the quantification of carbonyl compounds a comprehensive description of optimised methods is scarce for the quantification of atmospherically relevant carbonyl compounds. The method optimisation was conducted for seven atmospherically relevant carbonyl compounds including acrolein, benzaldehyde, glyoxal, methyl glyoxal, methacrolein, methyl vinyl ketone and 2,3-butanedione. O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was used as derivatisation reagent and the formed oximes were detected by gas chromatography/mass spectrometry (GC/MS). With the present method quantification can be carried out for each carbonyl compound originating from fog, cloud and rain or sampled from the gas- and particle phase in water. Detection limits between 0.01 and 0.17 μmol L-1 were found, depending on carbonyl compounds. Furthermore, best results were found for the derivatisation with a PFBHA concentration of 0.43 mg mL-1 for 24 h followed by a subsequent extraction with dichloromethane for 30 min at pH = 1. The optimised method was evaluated in the present study by the OH radical initiated oxidation of 3-methylbutanone in the aqueous phase. Methyl glyoxal and 2,3-butanedione were found to be oxidation products in the samples with a yield of 2% for methyl glyoxal and 14% for 2,3-butanedione after a reaction time of 5 h.

  7. Brand variation in oxidant production in mainstream cigarette smoke: Carbonyls and free radicals.

    PubMed

    Reilly, Samantha M; Goel, Reema; Trushin, Neil; Elias, Ryan J; Foulds, Jonathan; Muscat, Joshua; Liao, Jason; Richie, John P

    2017-08-01

    Oxidative stress/damage resulting from exposure to cigarette smoke plays a critical role in the development of tobacco-caused diseases. Carbonyls and free radicals are two major classes of oxidants in tobacco smoke. There is little information on the combined delivery of these oxidants across different cigarette brands; thus, we set out to measure and compare their levels in mainstream smoke from popular US cigarettes. Mainstream smoke from 28 different cigarette brands produced by smoking (FTC protocol) was analyzed for five important, abundant carbonyls, and levels were compared to previously determined free radical for the same brands. Overall, there were large variations (3- to 6-fold) in carbonyl levels across brands with total carbonyl levels ranging from 275 to 804 μg/cigarette, which persisted even after adjusting for ventilation. Individual carbonyl levels were highly correlated with each other (r 2 : 0.40-0.95, P < 0.003) except for formaldehyde. Both gas-phase (r 2 : 0.37, P = 0.006) and particulate-phase (r 2 : 0.27, P = 0.005) free radicals were correlated to total carbonyl content; however, this correlation disappeared after adjusting for ventilation. These data show that overall oxidant production varies widely by cigarette brand and the resulting difference in oxidant burden could potentially lead to differences in disease risk. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Group transfer and electron transfer reactions of organometallic complexes

    NASA Astrophysics Data System (ADS)

    Atwood, Jim D.

    During 1994, despite the disruptions, the authors have made progress in several aspects of their research on electron transfer reactions between organometallic complexes. This summary covers three areas that are relatively complete: (1) reactions between metal carbonyl anions and metal carbonyl halides, (2) reactions of hydrido- and alkyl-containing anions (RFe(CO)4(-) and RW(CO)5(-) with metal carbonyl cations; and (3) reactions of a seventeen-electron complex (Cp* Cr(CO)3*) with metal carbonyl derivatives. Two areas of examination that have just begun (possible carbene transfer and the possible role of metal carbonyl anions in carbon-hydrogen bond activation) will also be described.

  9. Aldehyde dehydrogenase 2 activation in aged heart improves the autophagy by reducing the carbonyl modification on SIRT1.

    PubMed

    Wu, Bing; Yu, Lu; Wang, Yishi; Wang, Hongtao; Li, Chen; Yin, Yue; Yang, Jingrun; Wang, Zhifa; Zheng, Qiangsun; Ma, Heng

    2016-01-19

    Cardiac aging is characterized by accumulation of damaged proteins and decline of autophagic efficiency. Here, by forestalling SIRT1 carbonylated inactivation in aged heart, we determined the benefits of activation of aldehyde dehydrogenase 2 (ALDH2) on the autophagy. In this study, the ALDH2 KO mice progressively developed age-related heart dysfunction and showed reduction in the life span, which strongly suggests that ALDH2 ablation leads to cardiac aging. What's more, aged hearts displayed a significant decrease ALDH2 activity, resulting in accumulation of 4-HNE-protein adducts and protein carbonyls, impairment in the autophagy flux, and, consequently, deteriorated cardiac function after starvation. Sustained Alda-1 (selective ALDH2 activator) treatment increased cardiac ALDH2 activity and abrogated these effects. Using SIRT1 deficient heterozygous (Sirt1+/-) mice, we found that SIRT1 was necessary for ALDH2 activation-induced autophagy. We further demonstrated that ALDH2 activation attenuated SIRT1 carbonylation and improved SIRT1 activity, thereby increasing the deacetylation of nuclear LC3 and FoxO1. Sequentially, ALDH2 enhanced SIRT1 regulates LC3-Atg7 interaction and FoxO1 increased Rab7 expression, which were both necessary and sufficient for restoring autophagy flux. These results highlight that both accumulation of proteotoxic carbonyl stress linkage with autophagy decline contribute to heart senescence. ALDH2 activation is adequate to improve the autophagy flux by reducing the carbonyl modification on SIRT1, which in turn plays an important role in maintaining cardiac health during aging.

  10. Reconstruction of maxillary cemento-ossifying fibroma defect with buccal pad of fat.

    PubMed

    Sivaraj, Subramonian; Jeevadhas, Pratheep

    2013-07-01

    A cemento-ossifying fibroma (COF) is a rare benign neoplasm of maxilla when compared with mandible (World Health Organization, 1992). COF of maxilla may be quite large and locally very aggressive lesion. These tumor mass was peeled out by en-bloc excision using gentle blunt dissection. This paper presents 35-year-old male patient who had a gradually expanding lobular mass in the left maxillary posterior region for past 1 year. He has been treated successfully by surgical en-bloc resection. Various techniques were used to reconstruction the defect. Buccal pad of fat is a simple technique having advantages like good vascularity, adaptability, good closure of the defect with favorable prognosis.

  11. Cemento-ossifying fibroma of mandible: An unusual case report and review of literature.

    PubMed

    Mohapatra, Mounabati; Banushree, C S; Nagarajan, K; Pati, Debashish

    2015-01-01

    The term ossifying fibroma (OF) has recently been included under fibro-osseous lesions. Cemento-OF (COF) is a benign neoplasm that arises from the periodontal membrane which contains multipotential cells that are capable of forming cementum, lamellar bone and fibrous tissue. These tumors occur in the third and fourth decades of life with a predilection for women. The mandible is more commonly involved than the maxilla. This lesion has caused considerable controversy regarding the use of terminology, origin and diagnostic criteria. This article describes an unusual case of COF presenting as unilocular lytic lesion of mandible in a 38-year-old male patient with review of literature.

  12. Cemento-ossifying fibroma of mandible: An unusual case report and review of literature

    PubMed Central

    Mohapatra, Mounabati; Banushree, CS; Nagarajan, K; Pati, Debashish

    2015-01-01

    The term ossifying fibroma (OF) has recently been included under fibro-osseous lesions. Cemento-OF (COF) is a benign neoplasm that arises from the periodontal membrane which contains multipotential cells that are capable of forming cementum, lamellar bone and fibrous tissue. These tumors occur in the third and fourth decades of life with a predilection for women. The mandible is more commonly involved than the maxilla. This lesion has caused considerable controversy regarding the use of terminology, origin and diagnostic criteria. This article describes an unusual case of COF presenting as unilocular lytic lesion of mandible in a 38-year-old male patient with review of literature. PMID:26980975

  13. Adsorption of fluoride to UiO-66-NH2 in water: Stability, kinetic, isotherm and thermodynamic studies.

    PubMed

    Lin, Kun-Yi Andrew; Liu, Yu-Ting; Chen, Shen-Yi

    2016-01-01

    To provide safe drinking water, fluoride in water must be removed and adsorption processes appear to be the most widely used method. Metal organic frameworks (MOFs) represent a new class of adsorbents that have been used in various adsorption applications. To study the adsorption mechanism of fluoride to MOFs in water and obtain related adsorption parameters, we synthesized a zirconium-based MOF with a primary amine group on its ligand, named UiO-66-NH2. The kinetics, adsorption isotherm and thermodynamics of fluoride adsorption to UiO-66-NH2 were investigated. The crystalline structure of UiO-66-NH2 remained intact and the local structure of zirconium in UiO-66-NH2 did not change significantly after being exposed to fluoride. The kinetics of the fluoride adsorption in UiO-66-NH2 could be well represented by the pseudo second order rate law. The enthalpy of the adsorption indicates that the F(-) adsorption to UiO-66-NH2 was classified as a physical adsorption. However, the comparison between the adsorption capacities of UiO-66-NH2 and UiO-66 suggests that the fluoride adsorption to UiO-66-NH2 might primarily involve a strong interaction between F(-) and the metal site. The fluoride adsorption capacity of UiO-66-NH2 was found to decrease when pH>7. While the presence of chloride/bromide ions did not noticeably change the adsorption capacity of UiO-66-NH2, the ionic surfactants slightly affected the adsorption capacity of UiO-66-NH2. These findings provide insights to further optimize the adsorption process for removal of fluoride using zirconium-based MOFs. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Qualitative and quantitative evaluation of derivatization reagents for different types of protein-bound carbonyl groups.

    PubMed

    Bollineni, Ravi Chand; Fedorova, Maria; Hoffmann, Ralf

    2013-09-07

    Mass spectrometry (MS) of 'carbonylated proteins' often involves derivatization of reactive carbonyl groups to facilitate their enrichment, identification and quantification. Among the many reported reagents, 2,4-dinitrophenylhydrazine (DNPH), biotin hydrazide (BHZ) and O-(biotinylcarbazoylmethyl) hydroxylamine (ARP) are the most frequently used. Despite their common use in carbonylation research, their reactivity towards protein-bound carbonyls has not been quantitatively evaluated in detail, to the best of our knowledge. Thus we studied the reactivity and specificity of these reagents towards different classes of reactive carbonyl groups (e.g. aldehydes, ketones and lactams), each being represented by a synthetic peptide carrying an accordingly modified residue. All three tagging reagents were selective for aliphatic aldehydes and ketones. Lactams and carbonyl-containing tryptophan oxidation products, however, were labelled only at low levels or not at all. Whereas DNPH derivatization was efficient under the published standard conditions, the derivatization conditions for BHZ and ARP had to be altered. Acidic conditions provided quantitative labelling yields for ARP. Peptides derivatized with DNPH, BHZ and ARP fragmented efficiently in tandem mass spectrometry, when the experimental conditions were chosen carefully for each reagent. Importantly, the tested carbonylated peptides did not cross-react with amino groups in other proteins present during sample preparations or enzymatic digestion. Thus, it appears favourable to digest proteins first and then derivatise the reactive carbonyl groups more efficiently at the peptide level under acidic conditions. The carbonylated model peptides used in this study might be valid internal standards for carbonylation proteomics.

  15. Fluoride bioaccumulation by hydroponic cultures of camellia (Camellia japonica spp.) and sugar cane (Saccharum officinarum spp.).

    PubMed

    Camarena-Rangel, Nancy; Rojas Velázquez, Angel Natanael; Santos-Díaz, María del Socorro

    2015-10-01

    The ability of hydroponic cultures of camellia and sugar cane adult plants to remove fluoride was investigated. Plants were grown in a 50% Steiner nutrient solution. After an adaptation period to hydroponic conditions, plants were exposed to different fluoride concentrations (0, 2.5, 5 and 10 mg L(-1)). Fluoride concentration in the culture medium and in tissues was measured. In sugar cane, fluoride was mainly located in roots, with 86% of it absorbed and 14% adsorbed. Sugar cane plants removed 1000-1200 mg fluoride kg(-1) dry weight. In camellia plants the highest fluoride concentration was found in leaf. Roots accumulated fluoride mainly through absorption, which was 2-5 times higher than adsorption. At the end of the experiment, fluoride accumulation in camellia plants was 1000-1400 mgk g(-1) dry weight. Estimated concentration factors revealed that fluoride bioaccumulation is 74-221-fold in camellia plants and 100-500-fold in sugar cane plants. Thus, the latter appear as a suitable candidate for removing fluoride from water due to their bioaccumulation capacity and vigorous growth rate; therefore, sugar cane might be used for phytoremediation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Distribution of fluoride in ground water of West Virginia

    USGS Publications Warehouse

    Mathes, M.V.; Waldron, M.C.

    1993-01-01

    This report describes the results of a study by the U.S. Geological Survey, in cooperation with the West Virginia Geological and Economic Survey, to evaluate the distribution of fluoride in ground water of West Virginia. Fluoride is a natural chemical constituent in domestic and public water supplies in West Virginia. Fluoride concentrations of about 1.0 milligram per liter in drinking water are beneficial to dental health. Concentrations greater than 2.0 milligrams per liter, however, could harm teeth and bones. Fluoride concentra- tions in ground water of West Virginia range from less than 0.1 to 12 milligrams per liter. Fluoride concentrations that exceed 2.0 milligrams per liter are found in wells drilled to all depths, wells drilled in all topographic settings, and wells drilled into most geologic units. Most fluoride concentrations that exceed 2.0 milligrams per liter are located at sites clustered in the northwestern part of the State.

  17. Fluoride adsorption properties of three modified forms of activated alumina in drinking water.

    PubMed

    Duan, Ying; Wang, Chenchen; Li, Xuede; Xu, Wei

    2014-12-01

    The study describes the removal of fluoride from drinking water using activated alumina (AA). AA was modified with H2SO4, FeCl3 and a combination of the two to enhance fluoride adsorption. The AA adsorbents were characterized using Brunauer-Emmett-Teller surface area analysis and X-ray fluorescence. The maximum adsorption capacity of H2SO4- and FeCl3-modified AA adsorbents was 4.98 mg/g, which is 3.4 times higher compared with that of normal AA. The results showed that the surface area of AA increased when modified with H2SO4. AA modified with FeCl3 enhanced fluoride adsorption ability through ion-exchange between chlorine ions and fluoride ions. The fluoride adsorption properties of AA modified with both H2SO4 and FeCl3 were consistent with the Langmuir model. The fluoride adsorption kinetics of the adsorbents were well described by the pseudo-second-order kinetic model.

  18. 10 CFR Appendix A to Part 835 - Derived Air Concentrations (DAC) for Controlling Radiation Exposure to Workers at DOE Facilities

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ...+05 2 E+05 /ET/ET Ni-56 (Inorg) 4 E−07 4 E−07 - 1 E+04 1 E+04 - ET/ET/ Ni-56 (Carbonyl) - 4 E−07 - - 1 E+04 - /St/ Ni-57 (Inorg) 5 E−07 5 E−07 - 2 E+04 2 E+04 - ET/ET/ Ni-57 (Carbonyl) - 7 E−07 - - 2 E+04 - /ET/ Ni-59 (Inorg) 2 E−06 5 E−06 - 9 E+04 2 E+05 - St/St/ Ni-59 (Carbonyl) - 6 E−07 - - 2 E+04...

  19. 10 CFR Appendix A to Part 835 - Derived Air Concentrations (DAC) for Controlling Radiation Exposure to Workers at DOE Facilities

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ...+05 2 E+05 /ET/ET Ni-56 (Inorg) 4 E−07 4 E−07 - 1 E+04 1 E+04 - ET/ET/ Ni-56 (Carbonyl) - 4 E−07 - - 1 E+04 - /St/ Ni-57 (Inorg) 5 E−07 5 E−07 - 2 E+04 2 E+04 - ET/ET/ Ni-57 (Carbonyl) - 7 E−07 - - 2 E+04 - /ET/ Ni-59 (Inorg) 2 E−06 5 E−06 - 9 E+04 2 E+05 - St/St/ Ni-59 (Carbonyl) - 6 E−07 - - 2 E+04...

  20. Fluoride Increases Superoxide Production and Impairs the Respiratory Chain in ROS 17/2.8 Osteoblastic Cells

    PubMed Central

    Fina, Brenda Lorena; Lombarte, Mercedes; Rigalli, Juan Pablo; Rigalli, Alfredo

    2014-01-01

    It is known that fluoride produces oxidative stress. Inflammation in bone tissue and an impairment of the respiratory chain of liver have been described in treatments with fluoride. Whether the impairment of the respiratory chain and oxidative stress are related is not known. The aim of this work was to study the effects of fluoride on the production of superoxide radical, the function of the respiratory chain and the increase in oxidative stress in ROS 17/2.8 osteoblastic cells. We measured the effect of fluoride (100 µM) on superoxide production, oxygen consumption, lipid peroxidation and antioxidant enzymes activities of cultured cells following the treatment with fluoride. Fluoride decreased oxygen consumption and increased superoxide production immediately after its addition. Furthermore, chronic treatment with fluoride increased oxidative stress status in osteoblastic cells. These results indicate that fluoride could damage bone tissue by inhibiting the respiratory chain, increasing the production of superoxide radicals and thus of the others reactive oxygen species. PMID:24964137

  1. Testing the nature of reaction coordinate describing interaction of H2 with carbonyl carbon, activated by Lewis acid complexation, and the Lewis basic solvent: A Born-Oppenheimer molecular dynamics study with explicit solvent

    NASA Astrophysics Data System (ADS)

    Heshmat, Mojgan; Privalov, Timofei

    2017-09-01

    Using Born-Oppenheimer molecular dynamics (BOMD), we explore the nature of interactions between H2 and the activated carbonyl carbon, C(carbonyl), of the acetone-B(C6F5)3 adduct surrounded by an explicit solvent (1,4-dioxane). BOMD simulations at finite (non-zero) temperature with an explicit solvent produced long-lasting instances of significant vibrational perturbation of the H—H bond and H2-polarization at C(carbonyl). As far as the characteristics of H2 are concerned, the dynamical transient state approximates the transition-state of the heterolytic H2-cleavage. The culprit is the concerted interactions of H2 with C(carbonyl) and a number of Lewis basic solvent molecules—i.e., the concerted C(carbonyl)⋯H2⋯solvent interactions. On one hand, the results presented herein complement the mechanistic insight gained from our recent transition-state calculations, reported separately from this article. But on the other hand, we now indicate that an idea of the sufficiency of just one simple reaction coordinate in solution-phase reactions can be too simplistic and misleading. This article goes in the footsteps of the rapidly strengthening approach of investigating molecular interactions in large molecular systems via "computational experimentation" employing, primarily, ab initio molecular dynamics describing reactants-interaction without constraints of the preordained reaction coordinate and/or foreknowledge of the sampling order parameters.

  2. Ion release from, and fluoride recharge of a composite with a fluoride-containing bioactive glass.

    PubMed

    Davis, Harry B; Gwinner, Fernanda; Mitchell, John C; Ferracane, Jack L

    2014-10-01

    Materials that are capable of releasing ions such as calcium and fluoride, that are necessary for remineralization of dentin and enamel, have been the topic of intensive research for many years. The source of calcium has most often been some form of calcium phosphate, and that for fluoride has been one of several metal fluoride or hexafluorophosphate salts. Fluoride-containing bioactive glass (BAG) prepared by the sol-gel method acts as a single source of both calcium and fluoride ions in aqueous solutions. The objective of this investigation was to determine if BAG, when added to a composite formulation, can be used as a single source for calcium and fluoride ion release over an extended time period, and to determine if the BAG-containing composite can be recharged upon exposure to a solution of 5000ppm fluoride. BAG 61 (61% Si; 31% Ca; 4% P; 3% F; 1% B) and BAG 81 (81% Si; 11% Ca; 4% P; 3% F; 1% B) were synthesized by the sol-gel method. The composite used was composed of 50/50 Bis-GMA/TEGDMA, 0.8% EDMAB, 0.4% CQ, and 0.05% BHT, combined with a mixture of BAG (15%) and strontium glass (85%) to a total filler load of 72% by weight. Disks were prepared, allowed to age for 24h, abraded, then placed into DI water. Calcium and fluoride release was measured by atomic absorption spectroscopy and fluoride ion selective electrode methods, respectively, after 2, 22, and 222h. The composite samples were then soaked for 5min in an aqueous 5000ppm fluoride solution, after which calcium and fluoride release was again measured at 2, 22, and 222h time points. Prior to fluoride recharge, release of fluoride ions was similar for the BAG 61 and BAG 81 composites after 2h, and also similar after 22h. At the four subsequent time points, one prior to, and three following fluoride recharge, the BAG 81 composite released significantly more fluoride ions (p<0.05). Both composites were recharged by exposure to 5000ppm fluoride, although the BAG 81 composite was recharged more than the BAG 61 composite. The BAG 61 composite released substantially more calcium ions prior to fluoride recharge during each of the 2 and 22h time periods. Thereafter, the release of calcium at the four subsequent time points was not significantly different (p>0.05) for the two composites. These results show that, when added to a composite formulation, fluoride-containing bioactive glass made by the sol-gel route can function as a single source for both calcium and fluoride ions, and that the composite can be readily recharged with fluoride. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  3. Fluoride enrichment in groundwater of semi-arid urban area: Khan Younis City, southern Gaza Strip (Palestine)

    NASA Astrophysics Data System (ADS)

    Abu Jabal, Mohamed Shaban; Abustan, Ismail; Rozaimy, Mohd Remy; Al-Najar, Hussam

    2014-12-01

    The aim of this study is to determine fluoride enhancement in the groundwater of semi-arid urban area of Khan Younis City, southern Gaza Strip. Physicochemical data for a total of 200 groundwater samples were analyzed. The fluoride concentrations were varied from 0.3 to 6.45 mg/L with average value of 2.87 mg/L. Correlations between fluorides with other measured ions were relatively observed, negative correlation with calcium and the positive correlation with pH, bicarbonate and sodium increase the dissolution/solubility of fluoride bearing minerals, leading to fluoride leaching into the groundwater. Fluoride enrichment in the groundwater of the area is due to water hydrochemistry, mineral-water interaction (mainly calcite and fluorite), fluorite resulted from fluorapatite dissolution. The saturation indexes evaluation indicated that 42% of the samples are over saturated with respect to calcite and 35.5% under saturated with respect to fluorite, while 40.5% approached equilibrium with respect to both calcite and fluorite. At fluoride concentrations of less than 2.2 mg/L fluorite saturation indexes show under-saturation condition for fluorite and at higher fluoride concentrations show near saturation condition.

  4. Fluoride induces oxidative damage and SIRT1/autophagy through ROS-mediated JNK signaling.

    PubMed

    Suzuki, Maiko; Bandoski, Cheryl; Bartlett, John D

    2015-12-01

    Fluoride is an effective caries prophylactic, but at high doses can also be an environmental health hazard. Acute or chronic exposure to high fluoride doses can result in dental enamel and skeletal and soft tissue fluorosis. Dental fluorosis is manifested as mottled, discolored, porous enamel that is susceptible to dental caries. Fluoride induces cell stress, including endoplasmic reticulum stress and oxidative stress, which leads to impairment of ameloblasts responsible for dental enamel formation. Recently we reported that fluoride activates SIRT1 and autophagy as an adaptive response to protect cells from stress. However, it still remains unclear how SIRT1/autophagy is regulated in dental fluorosis. In this study, we demonstrate that fluoride exposure generates reactive oxygen species (ROS) and the resulting oxidative damage is counteracted by SIRT1/autophagy induction through c-Jun N-terminal kinase (JNK) signaling in ameloblasts. In the mouse-ameloblast-derived cell line LS8, fluoride induced ROS, mitochondrial damage including cytochrome-c release, up-regulation of UCP2, attenuation of ATP synthesis, and H2AX phosphorylation (γH2AX), which is a marker of DNA damage. We evaluated the effects of the ROS inhibitor N-acetylcysteine (NAC) and the JNK inhibitor SP600125 on fluoride-induced SIRT1/autophagy activation. NAC decreased fluoride-induced ROS generation and attenuated JNK and c-Jun phosphorylation. NAC decreased SIRT1 phosphorylation and formation of the autophagy marker LC3II, which resulted in an increase in the apoptosis mediators γH2AX and cleaved/activated caspase-3. SP600125 attenuated fluoride-induced SIRT1 phosphorylation, indicating that fluoride activates SIRT1/autophagy via the ROS-mediated JNK pathway. In enamel organs from rats or mice treated with 50, 100, or 125 ppm fluoride for 6 weeks, cytochrome-c release and the DNA damage markers 8-oxoguanine, p-ATM, and γH2AX were increased compared to those in controls (0 ppm fluoride). These results suggest that fluoride-induced ROS generation causes mitochondrial damage and DNA damage, which may lead to impairment of ameloblast function. To counteract this impairment, SIRT1/autophagy is induced via JNK signaling to protect cells/ameloblasts from fluoride-induced oxidative damage that may cause dental fluorosis. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Fluoride induces oxidative damage and SIRT1/autophagy through ROS-mediated JNK signaling

    PubMed Central

    Suzuki, Maiko; Bandoski, Cheryl; Bartlett, John D.

    2015-01-01

    Fluoride is an effective caries prophylactic, but at high doses can also be an environmental health hazard. Acute or chronic exposure to high fluoride doses can result in dental enamel and skeletal and soft tissue fluorosis. Dental fluorosis is manifested as mottled, discolored, porous enamel that is susceptible to dental caries. Fluoride induces cell stress, including endoplasmic reticulum stress and oxidative stress, which leads to impairment of ameloblasts responsible for dental enamel formation. Recently we reported that fluoride activates SIRT1 and autophagy as an adaptive response to protect cells from stress. However, it still remains unclear how SIRT1/autophagy is regulated in dental fluorosis. In this study, we demonstrate that fluoride exposure generates reactive oxygen species (ROS) and the resulting oxidative damage is counteracted by SIRT1/autophagy induction through c-Jun N-terminal kinase (JNK) signaling in ameloblasts. In the mouse-ameloblast-derived cell line LS8, fluoride induced ROS, mitochondrial damage including cytochrome-c release, up-regulation of UCP2, attenuation of ATP synthesis, and H2AX phosphorylation (γH2AX), which is a marker of DNA damage. We evaluated the effects of the ROS inhibitor N-acetylcysteine (NAC) and the JNK inhibitor SP600125 on fluoride-induced SIRT1/autophagy activation. NAC decreased fluoride-induced ROS generation and attenuated JNK and c-Jun phosphorylation. NAC decreased SIRT1 phosphorylation and formation of the autophagy marker LC3II, which resulted in an increase in the apoptosis mediators γH2AX and cleaved/activated caspase-3. SP600125 attenuated fluoride-induced SIRT1 phosphorylation, indicating that fluoride activates SIRT1/autophagy via the ROS-mediated JNK pathway. In enamel organs from rats or mice treated with 50, 100, or 125 ppm fluoride for 6 weeks, cytochrome-c release and the DNA damage markers 8-oxoguanine, p-ATM, and γH2AX were increased compared to those in controls (0 ppm fluoride). These results suggest that fluoride-induced ROS generation causes mitochondrial damage and DNA damage, which may lead to impairment of ameloblast function. To counteract this impairment, SIRT1/autophagy is induced via JNK signaling to protect cells/ameloblasts from fluoride-induced oxidative damage that may cause dental fluorosis. PMID:26431905

  6. Concentration of Fluoride in Cow's and Buffalo's Milk in Relation to Varying Levels of Fluoride Concentration in Drinking Water of Mathura City in India- A Pilot Study.

    PubMed

    Gupta, Prahlad; Gupta, Nidhi; Meena, Komal; Moon, Ninad Joshirao; Kumar, Puneet; Kaur, Ravneet

    2015-05-01

    To estimate fluoride concentration in drinking water, cow's milk and buffalo's milk and to correlate the concentration of fluoride in cow's milk and buffalo's milk with varying levels of fluoride concentration in drinking water. Ten households having both cows and buffalo's were selected by convenience in each of the 3 zones (below optimum fluoride <0.7 ppm (parts per million), optimum fluoride 0.7-1.2 ppm and above optimum fluoride areas > 1.2 ppm). From these selected households, 200 ml of fresh milk of both cows and buffaloes was collected along with 200 ml of drinking water for estimation of fluoride concentration by using a fluoride ion selective electrode method. The data was analysed using SPSS, version 11.5 for windows. The mean fluoride concentration of drinking water, cow's milk and buffalo's milk in three different fluoride zones was 0.89±0.39, 0.09±0.07, 0.09±0.08 respectively. Pearson's correlation found a statistically significant correlation between fluoride concentrations in cow's and buffalo's milk with varying levels of fluoride concentration in drinking water in zone B and zone C. However, this correlation was not statistically significant in zone A. With an increase in fluoride concentration in drinking water there was an increase in concentration of fluoride in cow's and buffalo's milk. We conclude that this association is seen in conjunction to not only a single factor but rather due to culmination of several other aspects. So, there is a need to elucidate the other factors that might be contributing to this increase and dental fluorosis.

  7. Development of resistance of mutans streptococci and Porphyromonas gingivalis to chlorhexidine digluconate and amine fluoride/stannous fluoride-containing mouthrinses, in vitro.

    PubMed

    Kulik, Eva M; Waltimo, Tuomas; Weiger, Roland; Schweizer, Irene; Lenkeit, Krystyna; Filipuzzi-Jenny, Elisabeth; Walter, Clemens

    2015-07-01

    The aim if this study was to determine the minimal inhibitory concentrations of chlorhexidine digluconate and an amine fluoride/stannous fluoride-containing mouthrinse against Porphyromonas gingivalis and mutans streptococci during an experimental long-term subinhibitory exposition. Five P. gingivalis strains and four mutans streptococci were subcultivated for 20-30 passages in subinhibitory concentrations of chlorhexidine digluconate or an amine fluoride/stannous fluoride-containing mouthrinse. Pre-passaging minimal inhibitory concentrations for chlorhexidine ranged from 0.5 to 2 mg/l for mutans streptococci and from 2 to 4 mg/l for the P. gingivalis isolates. For the amine fluoride/stannous fluoride-containing mouthrinse minimal inhibitory values from 0.125 to 0.25% for the mutans streptococci and from 0.063 to 0.125% for the P. gingivalis isolates were determined. Two- to fourfold increased minimal inhibitory concentrations against chlorhexidine were detected for two of the five P. gingivalis isolates, whereas no increase in minimal inhibitory concentrations was found for the mutans streptococci after repeated passaging through subinhibitory concentrations. Repeated exposure to subinhibitory concentrations of the amine fluoride/stannous fluoride-containing mouthrinse did not alter the minimally inhibitory concentrations of the bacterial isolates tested. Chlorhexidine and the amine fluoride/stannous fluoride-containing mouthrinse are effective inhibitory agents against the oral bacterial isolates tested. No general development of resistance against chlorhexidine or the amine fluoride/stannous fluoride-containing mouthrinse was detected. However, some strains showed potential to develop resistance against chlorhexidine after prolonged exposure. The use of chlorhexidine should be limited to short periods of time. The amine fluoride/stannous fluoride-containing mouthrinse appears to have the potential to be used on a long-term basis.

  8. Dose-effect relationship between drinking water fluoride levels and damage to liver and kidney functions in children.

    PubMed

    Xiong, Xianzhi; Liu, Junling; He, Weihong; Xia, Tao; He, Ping; Chen, Xuemin; Yang, Kedi; Wang, Aiguo

    2007-01-01

    Although a dose-effect relationship between water fluoride levels and damage to liver and kidney functions in animals has been reported, it was not demonstrated in humans. To evaluate the effects of drinking water fluoride levels on the liver and kidney functions in children with and without dental fluorosis, we identified 210 children who were divided into seven groups with 30 each based on different drinking water fluoride levels in the same residential area. We found that the fluoride levels in serum and urine of these children increased as the levels of drinking water fluoride increased. There were no significant differences in the levels of total protein (TP), albumin (ALB), aspartate transamine (AST), and alanine transamine (ALT) in serum among these groups. However, the activities of serum lactic dehydrogenase (LDH), urine N-acetyl-beta-glucosaminidase (NAG), and urine gamma-glutamyl transpeptidase (gamma-GT) in children with dental fluorosis and having water fluoride of 2.15-2.96 mg/L and in children having water fluoride of 3.15-5.69 mg/L regardless of dental fluorosis were significantly higher than children exposed to water fluoride of 0.61-0.87 mg/L in a dose-response manner. In contrast to children with dental fluorosis and having water fluoride of 2.15-2.96 and 3.10-5.69 mg/L, serum LDH activity of children without dental fluorosis but exposed to the same levels of water fluoride as those with dental fluorosis were also markedly lower, but the activities of NAG and gamma-GT in their urine were not. Therefore, our results suggest that drinking water fluoride levels over 2.0mg/L can cause damage to liver and kidney functions in children and that the dental fluorosis was independent of damage to the liver but not the kidney. Further studies on the mechanisms and significance underlying damage to the liver without dental fluorosis in the exposed children are warranted.

  9. Sulfate-doped Fe3O4/Al2O3 nanoparticles as a novel adsorbent for fluoride removal from drinking water.

    PubMed

    Chai, Liyuan; Wang, Yunyan; Zhao, Na; Yang, Weichun; You, Xiangyu

    2013-08-01

    A novel adsorbent of sulfate-doped Fe3O4/Al2O3 nanoparticles with magnetic separability was developed for fluoride removal from drinking water. The nanosized adsorbent was characterized and its performance in fluoride removal was evaluated. Kinetic data reveal that the fluoride adsorption was rapid in the beginning followed by a slower adsorption process, nearly 90% adsorption can be achieved within 20 min and only 10-15% additional removal occurred in the following 8 h. The fluoride adsorption isotherm was well described by Elovich model. The calculated adsorption capacity of this nanoadsorbent for fluoride by two-site Langmuir model was 70.4 mg/g at pH 7.0. Moreover, this nanoadsorbent performed well over a considerable wide pH range of 4-10, and the fluoride removal efficiencies reached up to 90% and 70% throughout the pH range of 4-10 with initial fluoride concentrations of 10 mg/L and 50 mg/L, respectively. The observed sulfate-fluoride displacement and decreased sulfur content on the adsorbent surface reveal that anion exchange process was an important mechanism for fluoride adsorption by the sulfate-doped Fe3O4/Al2O3 nanoparticles. Moreover, a shift of the pH of zero point charge (pHPZC) of the nanoparticles and surface analysis based on X-ray photoelectron spectroscopy (XPS) suggest the formation of inner-sphere fluoride complex at the aluminum center as another adsorption mechanism. With the exception of PO4(3-), other co-existing anions (NO3(-), Cl(-) and SO4(2-)) did not evidently inhibit fluoride removal by the nanoparticles. Findings of this study demonstrate the potential utility of the nanoparticles as an effective adsorbent for fluoride removal from drinking water. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. Fluoride exposure abates pro-inflammatory response and induces in vivo apoptosis rendering zebrafish (Danio rerio) susceptible to bacterial infections.

    PubMed

    Singh, Rashmi; Khatri, Preeti; Srivastava, Nidhi; Jain, Shruti; Brahmachari, Vani; Mukhopadhyay, Asish; Mazumder, Shibnath

    2017-04-01

    The present study describes the immunotoxic effect of chronic fluoride exposure on adult zebrafish (Danio rerio). Zebrafish were exposed to fluoride (71.12 mg/L; 1/10 LC 50 ) for 30 d and the expression of selected genes studied. We observed significant elevation in the detoxification pathway gene cyp1a suggesting chronic exposure to non-lethal concentration of fluoride is indeed toxic to fish. Fluoride mediated pro-oxidative stress is implicated with the downregulation in superoxide dismutase 1 and 2 (sod1/2) genes. Fluoride affected DNA repair machinery by abrogating the expression of the DNA repair gene rad51 and growth arrest and DNA damage inducible beta a gene gadd45ba. The upregulated expression of casp3a coupled with altered Bcl-2 associated X protein/B-cell lymphoma 2 ratio (baxa/bcl2a) clearly suggested chronic fluoride exposure induced the apoptotic cascade in zebrafish. Fluoride-exposed zebrafish when challenged with non-lethal dose of fish pathogen A. hydrophila revealed gross histopathology in spleen, bacterial persistence and significant mortality. We report that fluoride interferes with system-level output of pro-inflammatory cytokines tumour necrosis factor-α, interleukin-1β and interferon-γ, as a consequence, bacteria replicate efficiently causing significant fish mortality. We conclude, chronic fluoride exposure impairs the redox balance, affects DNA repair machinery with pro-apoptotic implications and suppresses pro-inflammatory cytokines expression abrogating host immunity to bacterial infections. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Two classes of capillary optical fibers: refractive and photonic

    NASA Astrophysics Data System (ADS)

    Romaniuk, Ryszard S.

    2008-11-01

    This paper is a digest tutorial on some properties of capillary optical fibers (COF). Two basic types of capillary optical fibers are clearly distinguished. The classification is based on propagation mechanism of optical wave. The refractive, singlemode COF guides a dark hollow beam of light (DHB) with zero intensity on fiber axis. The photonic, singlemode COF carries nearly a perfect axial Gaussian beam with maximum intensity on fiber axis. A subject of the paper are these two basic kinds of capillary optical fibers of pure refractive and pure photonic mechanism of guided wave transmission. In a real capillary the wave may be transmitted by a mixed mechanism, refractive and photonic, with strong interaction of photonic and refractive guided wave modes. Refractive capillary optical fibers are used widely for photonic instrumentation applications, while photonic capillary optical fibers are considered for trunk optical communications. Replacement of classical, single mode, dispersion shifted, 1550nm optimized optical fibers for communications with photonic capillaries would potentially cause a next serious revolution in optical communications. The predictions say that such a revolution may happen within this decade. This dream is however not fulfilled yet. The paper compares guided modes in both kinds of optical fiber capillaries: refractive and photonic. The differences are emphasized indicating prospective application areas of these fibers.

  12. Carbonyl species characteristics during the evaporation of essential oils

    NASA Astrophysics Data System (ADS)

    Chiang, Hsiu-Mei; Chiu, Hua-Hsien; Lai, Yen-Ming; Chen, Ching-Yen; Chiang, Hung-Lung

    2010-06-01

    Carbonyls emitted from essential oils can affect the air quality when they are used in indoors, especially under poor ventilation conditions. Lavender, lemon, rose, rosemary, and tea tree oils were selected as typical and popular essential oils to investigate in terms of composition, thermal characteristics and fifteen carbonyl constituents. Based on thermogravimetric (TG) analysis, the activation energy was 7.6-8.3 kcal mol -1, the reaction order was in the range of 0.6-0.7 and the frequency factor was 360-2838 min -1. Formaldehyde, acetaldehyde, acetone, and propionaldehyde were the dominant carbonyl compounds, and their concentrations were 0.034-0.170 ppm. The emission factors of carbonyl compounds were 2.10-3.70 mg g -1, and acetone, propionaldehyde, acetaldehyde, and formaldehyde accounted for a high portion of the emission factor of carbonyl compounds in essential oil exhaust. Some unhealthy carbonyl species such as formaldehyde and valeraldehyde, were measured at low-temperature during the vaporization of essential oils, indicating a potential effect on indoor air quality and human health.

  13. Fluoride therapy for osteoporosis: characterization of the skeletal response by serial measurements of serum alkaline phosphatase activity.

    PubMed

    Farley, S M; Wergedal, J E; Smith, L C; Lundy, M W; Farley, J R; Baylink, D J

    1987-03-01

    Optimum use of fluoride therapy for osteoporosis requires a sensitive and convenient index of the skeletal response to fluoride. Since previous studies had shown that serum alkaline phosphatase activity (SALP) was increased in response to fluoride therapy, we examined serial measurements of SALP in 53 osteoporotics treated with 66 to 110 mg of sodium fluoride (NaF) for 12 to 91 months. SALP was increased in 87% of the subjects during therapy with fluoride. The increase in SALP was thought to reflect the osteogenic action of fluoride based on the findings that SALP correlated with both trabecular bone area (r = .81, P less than .001) and osteoid length (r = .67, P less than .01) in iliac crest biopsies, predicted increased bone density on spinal radiographs in response to fluoride therapy with an 87% accuracy, and predicted decreased back pain in response to fluoride with a 91% accuracy. In addition, the SALP response to fluoride was seen earlier than other therapeutic responses as indicated by the findings that the tau 1/2 for the SALP response (ie, time for 1/2 of the patients to show a significant response) was significantly less (1.2 +/- 0.3 yr) than that for the pain response (1.6 +/- 0.3 yr, P less than .05) or that for the radiographic response (3.7 +/- 0.5 yr, P less than .001). Although most patients responded to fluoride with an increase in SALP, evaluation of the kinetics of the SALP response to fluoride revealed marked interpatient variation.(ABSTRACT TRUNCATED AT 250 WORDS)

  14. Derivatization of carbonyl compounds with 2,4-dinitrophenylhydrazine and their subsequent determination by high-performance liquid chromatography.

    PubMed

    Uchiyama, Shigehisa; Inaba, Yohei; Kunugita, Naoki

    2011-05-15

    Derivatization of carbonyl compounds with 2,4-dinitrophenylhydrazine (DNPH) is one of the most widely used analytical methods. In this article, we highlight recent advances using DNPH provided by our studies over past seven years. DNPH reacts with carbonyls to form corresponding stable 2,4-DNPhydrazone derivatives (DNPhydrazones). This method may result in analytical error because DNPhydrazones have both E- and Z-stereoisomers caused by the CN double bond. Purified aldehyde-2,4-DNPhydrazone demonstrated only the E-isomer, but under UV irradiation and the addition of acid, both E- and Z-isomers were seen. In order to resolve the isometric problem, a method for transforming the CN double bond of carbonyl-2,4-DNPhydrazone into a C-N single bond, by reductive amination using 2-picoline borane, has been developed. The amination reactions of C1-C10 aldehyde DNPhydrazones are completely converted into the reduced forms and can be analyzed with high-performance liquid chromatography. As a new application using DNPH derivatization, the simultaneous measurement of carbonyls with carboxylic acids or ozone is described in this review. Copyright © 2010 Elsevier B.V. All rights reserved.

  15. Propheromones that release pheromonal carbonyl compounds in light.

    PubMed

    Liu, X; Macaulay, E D; Pickett, J A

    1984-05-01

    Pheromonal carbonyl compounds; (Z)-11-hexadecanal, (E)-citral, and 2-heptanone were treated with six alcohols to give acetals or ketals, some of which acted as propheromones by releasing the pheromonal carbonyl compounds in ultraviolet or simulated sunlight. Highest yields of pheromone were obtained from adducts prepared witho-nitrobenzyl alcohol ando-nitrophenylethane-1,2-diol. Adducts from (Z)-11-hexadecenal and these two alcohols were employed in lures to catch diamondback moths,Plutella xylostella (L.).

  16. Mechanism of protein decarbonylation.

    PubMed

    Wong, Chi-Ming; Marcocci, Lucia; Das, Dividutta; Wang, Xinhong; Luo, Haibei; Zungu-Edmondson, Makhosazane; Suzuki, Yuichiro J

    2013-12-01

    Ligand/receptor stimulation of cells promotes protein carbonylation that is followed by the decarbonylation process, which might involve thiol-dependent reduction (C.M. Wong et al., Circ. Res. 102:301-318; 2008). This study further investigated the properties of this protein decarbonylation mechanism. We found that the thiol-mediated reduction of protein carbonyls is dependent on heat-labile biologic components. Cysteine and glutathione were efficient substrates for decarbonylation. Thiols decreased the protein carbonyl content, as detected by 2,4-dinitrophenylhydrazine, but not the levels of malondialdehyde or 4-hydroxynonenal protein adducts. Mass spectrometry identified proteins that undergo thiol-dependent decarbonylation, which include peroxiredoxins. Peroxiredoxin-2 and -6 were carbonylated and subsequently decarbonylated in response to the ligand/receptor stimulation of cells. siRNA knockdown of glutaredoxin inhibited the decarbonylation of peroxiredoxin. These results strengthen the concept that thiol-dependent decarbonylation defines the kinetics of protein carbonylation signaling. © 2013 Elsevier Inc. All rights reserved.

  17. Mechanism of protein decarbonylation

    PubMed Central

    Wong, Chi-Ming; Marcocci, Lucia; Das, Dividutta; Wang, Xinhong; Luo, Haibei; Zungu-Edmondson, Makhosazane; Suzuki, Yuichiro J.

    2013-01-01

    Ligand/receptor-stimulation of cells promotes protein carbonylation that is followed by the decarbonylation process, which might involve thiol-dependent reduction (Wong et al., Circ. Res. 102 301-318, 2008). The present study further investigated the properties of this protein decarbonylation mechanism. We found that the thiol-mediated reduction of protein carbonyls is dependent on heat-labile biologic components. Cysteine and glutathione were found to be efficient substrates for decarbonylation. Thiols decreased the protein carbonyl content, as detected by 2,4-dinitrophenylhydrazine, but not the levels of malondialdehyde or 4-hydroxynonenal protein adducts. Mass spectrometry identified proteins that undergo thiol-dependent decarbonylation, which include peroxiredoxins. Peroxiredoxins-2 and -6 were found to be carbonylated and subsequent decarbonylated in response to the ligand/receptor-stimulation of cells. siRNA knockdown of glutaredoxin inhibited the decarbonylation of peroxiredoxin. These results strengthen the concept that thiol-dependent decarbonylation defines the kinetics of protein carbonylation signaling. PMID:24044890

  18. 2,4-dinitrophenylhydrazine carbonyl assay in metal-catalysed protein glycoxidation.

    PubMed

    Stefek, M; Trnkova, Z; Krizanova, L

    1999-01-01

    Using an experimental in vitro glycation model, long-term incubations of bovine serum albumin with glucose (fructose) resulted in a significant increase in protein content of 2,4-dinitrophenylhydrazine (DNPH)-reactive carbonyl groups, which could be strongly inhibited by anaerobiosis and metal chelation. The pattern of yields of the protein-bound DNPH was not in accordance with that of the sugar-derived carbonyls determined as the ketoamine Amadori product. In spite of the fact that the contribution of the final advanced glycation end-products to the total DNPH-reactivity of glycation-altered protein remains unclear, the present results stress the need of oxidative steps in formation of most of the DNPH-reactive carbonyl compounds generated by glycation. The results provide evidence that, in protein glycoxidation, the DNPH assay is selective enough to discriminate between protein-bound carbonyls produced by metal-catalysed oxidations and those formed in the early glycation steps.

  19. Determination of carbonyls and their sources in three sites of the metropolitan area of Costa Rica, Central America.

    PubMed

    Murillo, Jorge Herrera; Marín, José Félix Rojas; Román, Susana Rodríguez

    2012-01-01

    Ambient levels of carbonyl compounds and their possible sources were studied at three places in the metropolitan area of Costa Rica, including a residential, an industrial, and a commercial downtown area with high vehicular flow, during the periods of April-May and September-December 2009. Fifteen carbonyl compounds were identified in the ambient air, of which acetone was the most abundant carbonyl, followed by formaldehyde and acetaldehyde. Concentrations were highest in rainy season at all sites and lower in dry season. These decreases in concentration are explained by the influences of both photochemical reactions and local meteorological conditions. The strong correlation between C1-C2 and C3 indicated a common origin for these carbonyls. The C1/C2 ratios varied between 0.49 to 1.05, values which can be considered typical of an urban area.

  20. Multi-step oxidations catalyzed by cytochrome P450 enzymes: Processive vs. distributive kinetics and the issue of carbonyl oxidation in chemical mechanisms

    PubMed Central

    Guengerich, F. Peter; Sohl, Christal D.; Chowdhury, Goutam

    2010-01-01

    Catalysis of sequential oxidation reactions is not unusual in cytochrome P450 (P450) reactions, not only in steroid metabolism but also with many xenobiotics. One issue is how processive/distributive these reactions are, i.e. how much do the “intermediate” products dissociate. Our work with human P450s 2E1, 2A6, and 19A1 on this subject has revealed a mixture of systems, surprisingly with a more distributive mechanism with an endogenous substrate (P450 19A1) than for some xenobiotics (P450s 2E1, 2A6). One aspect of this research involves carbonyl intermediates, and the choice of catalytic mechanism is linked to the hydration state of the aldehyde. The non-enzymatic rates of hydration and dehydration of carbonyls are not rapid and whether P450s catalyze the reversible hydration is unknown. If carbonyl hydration and dehydration are slow, the mechanism may be set by the carbonyl hydration status. PMID:20804723

  1. Anion Photoelectron Spectroscopic Studies of NbCr(CO)_n- (n = 2,3) Heterobimetallic Carbonyl Complexes

    NASA Astrophysics Data System (ADS)

    Baudhuin, Melissa A.; Boopalachandran, Praveenkumar; Leopold, Doreen

    2015-06-01

    Anion photoelectron spectra and density functional calculations are reported for NbCr(CO)2- and NbCr(CO)3- complexes prepared by addition of Cr(CO)6 vapor to a flow tube equipped with a niobium cathode discharge source. Electron affinities (± 0.007 eV) are measured to be 1.668 eV for NbCr(CO)2 and 1.162 eV for NbCr(CO)3, values which exceed the 0.793 eV electron affinity previously measured for ligand-free NbCr. The vibrationally-resolved 488 nm photoelectron spectra are compared with Franck-Condon spectra predicted for various possible isomers and spin states of the anionic and neutral metal carbonyl complexes. Results are also compared with photoelectron spectra of the corresponding chromium carbonyl complexes and of NbCr and NbCr-, which have formal bond orders of 5.5 (2Δ) and 6 (1σ+), respectively. These comparisons help to elucidate the effects of sequential carbonylation on this multiple metal-metal bond, and of the formation of this bond on the chromium-carbonyl interactions.

  2. Fluoride-Containing Metabolites after Methoxyflurane Anesthesia,

    DTIC Science & Technology

    Methoxyflurane (2,2-dichloro-1,1-difluoroethyl methyl ether) has been used for about 12 years for analgesia and anesthesia in surgery and obstetrics...Interest in methoxyflurane fluorometabolites arose when markedly elevated serum fluoride concentrations in a nephrotoxic patient were traced to the...use of methoxyflurane anesthesia for surgery. These high fluoride levels were peculiar in that the ionselective fluoride electrode did not detect a

  3. Effects of fluoride tablets on caries and fluorosis occurrence among 6- to 9-year olds using fluoridated salt.

    PubMed

    Meyer-Lueckel, H; Grundmann, E; Stang, A

    2010-08-01

    The aim of this retrospective cohort study was to investigate the association between the use of fluoride tablets among users of fluoridated salt and the occurrence of caries and fluorosis. We examined 583 school children aged 6-9 years in Berlin, Germany for caries-status (modified defs > or = 1; d(3)-level) and fluorosis occurrence on central incisors (TSIF > or = 1). Parents completed questionnaires about several sociodemographic and oral health related factors of the previous years. To adjust for confounding, we used log-risk regression and estimated relative risks (RR) and 95% confidence intervals. The mean modified defs was 3.2 (SD = 5.9) and 58% children were caries-free. Twenty-two per cent of the children revealed mild fluorosis (TSIF 1 and 2). Length of fluoride tablet use was inversely associated (adjusted for age and SES) with caries-status: 2-4 years: RR = 0.8, 95%CI: 0.7-1.0, > or =5 years: RR = 0.5, 95%CI 0.3-0.7 (reference: 0-1 year use). This inverse association could mainly be observed in children who consumed fluoridated salt as well. Relative risks for mild fluorosis were 1.8 (95%CI: 1.1-2.9) and 2.7 (95%CI: 1.6-4.5) for fluoride tablet use of 2-4 years and > or =5 years, respectively compared with 0-1 year use. Fluoride tablets seem to be effective in reducing the occurrence of caries in children with low caries levels in particular among those using fluoridated salt as well. However, fluoride tablets increase the occurrence of mild fluorosis in permanent incisors.

  4. A FLUORIMETRIC SEMI-MICROPLATE FORMAT ASSAY OF PROTEIN CARBONYLS IN BLOOD PLASMA

    PubMed Central

    Mohanty, Joy G.; Bhamidipaty, Surya; Evans, Michele K.; Rifkind, Joseph M.

    2010-01-01

    Oxidative stress, originating from reactive oxygen species (ROS), has been implicated in aging and various human diseases. The ROS generated can oxidize proteins producing protein carbonyl derivatives. The level of protein carbonyls in blood plasma has been used as a measure of overall oxidative stress in the body. Classically, protein carbonyls have been quantitated spectrophotometrically by directly reacting them with 2,4, dinitrophenylhydrazine (DNPH). However, the applicability of this method to biological samples is limited by its low inherent sensitivity. This limitation has been overcome by the development of sensitive ELISA methods to measure protein carbonyls. As part of the Healthy Aging in Neighborhoods of Diversity across the Lifespan study, oxidative stress in humans were quantified by measuring blood plasma protein carbonyls using the two commercially available ELISA kits and the spectrophotometric DNPH assay. Surprisingly, two ELISA methods gave very different values for protein carbonyls that were both different from the spectrophotometric method. We have developed a fluorescent semi-microplate format assay of protein carbonyls involving direct reaction of protein carbonyls with fluorescein thiosemicarbazide that correlates (R=0.992) with the direct spectrophotometric method. It has a coefficient of variation of 4.99% and is at least 100 times more sensitive than the spectrophotometric method. PMID:20122892

  5. Tribological Behavior of Aluminum Alloy AlSi10Mg-TiB2 Composites Produced by Direct Metal Laser Sintering (DMLS)

    NASA Astrophysics Data System (ADS)

    Lorusso, Massimo; Aversa, Alberta; Manfredi, Diego; Calignano, Flaviana; Ambrosio, Elisa Paola; Ugues, Daniele; Pavese, Matteo

    2016-08-01

    Direct metal laser sintering (DMLS) is an additive manufacturing technique for the production of parts with complex geometry and it is especially appropriate for structural applications in aircraft and automotive industries. Aluminum-based metal matrix composites (MMCs) are promising materials for these applications because they are lightweight, ductile, and have a good strength-to-weight ratio This paper presents an investigation of microstructure, hardness, and tribological properties of AlSi10Mg alloy and AlSi10Mg alloy/TiB2 composites prepared by DMLS. MMCs were realized with two different compositions: 10% wt. of microsize TiB2, 1% wt. of nanosize TiB2. Wear tests were performed using a pin-on-disk apparatus on the prepared samples. Performances of AlSi10Mg samples manufactured by DMLS were also compared with the results obtained on AlSi10Mg alloy samples made by casting. It was found that the composites displayed a lower coefficient of friction (COF), but in the case of microsize TiB2 reinforcement the wear rate was higher than with nanosize reinforcements and aluminum alloy without reinforcement. AlSi10Mg obtained by DMLS showed a higher COF than AlSi10Mg obtained by casting, but the wear rate was higher in the latter case.

  6. A step-by-step protocol for assaying protein carbonylation in biological samples.

    PubMed

    Colombo, Graziano; Clerici, Marco; Garavaglia, Maria Elisa; Giustarini, Daniela; Rossi, Ranieri; Milzani, Aldo; Dalle-Donne, Isabella

    2016-04-15

    Protein carbonylation represents the most frequent and usually irreversible oxidative modification affecting proteins. This modification is chemically stable and this feature is particularly important for storage and detection of carbonylated proteins. Many biochemical and analytical methods have been developed during the last thirty years to assay protein carbonylation. The most successful method consists on protein carbonyl (PCO) derivatization with 2,4-dinitrophenylhydrazine (DNPH) and consequent spectrophotometric assay. This assay allows a global quantification of PCO content due to the ability of DNPH to react with carbonyl giving rise to an adduct able to absorb at 366 nm. Similar approaches were also developed employing chromatographic separation, in particular HPLC, and parallel detection of absorbing adducts. Subsequently, immunological techniques, such as Western immunoblot or ELISA, have been developed leading to an increase of sensitivity in protein carbonylation detection. Currently, they are widely employed to evaluate change in total protein carbonylation and eventually to highlight the specific proteins undergoing selective oxidation. In the last decade, many mass spectrometry (MS) approaches have been developed for the identification of the carbonylated proteins and the relative amino acid residues modified to carbonyl derivatives. Although these MS methods are much more focused and detailed due to their ability to identify the amino acid residues undergoing carbonylation, they still require too expensive equipments and, therefore, are limited in distribution. In this protocol paper, we summarise and comment on the most diffuse protocols that a standard laboratory can employ to assess protein carbonylation; in particular, we describe step-by-step the different protocols, adding suggestions coming from our on-bench experience. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Fluoride content of tank water in Australia.

    PubMed

    Cochrane, N J; Hopcraft, M S; Tong, A C; Thean, H l; Thum, Y S; Tong, D E; Wen, J; Zhao, S C; Stanton, D P; Yuan, Y; Shen, P; Reynolds, E C

    2014-06-01

    The aims of this study were to: (1) analyse the fluoride content of tank water; (2) determine whether the method of water collection or storage influenced fluoride content; and (3) survey participant attitudes towards water fluoridation. Plastic tubes and a questionnaire were distributed through dentists to households with water tanks in Victoria. A midstream tank water sample was collected and fluoride analysed in triplicate using ion chromatography All samples (n = 123) contained negligible amounts of fluoride, with a mean fluoride concentration of <0.01 ppm (range: <0.01-0.18 ppm). No statistically significant association was found between fluoride content and variables investigated such as tank material, tank age, roof material and gutter material. Most people did not know whether their tank water contained fluoride and 40.8% preferred to have access to fluoridated water. The majority thought fluoride was safe and more than half of the respondents supported fluoridation. Fluoride content of tank water was well below the optimal levels for caries prevention. People who rely solely on tank water for drinking may require additional exposure to fluoride for optimal caries prevention. © 2014 Australian Dental Association.

  8. Influence of Fluoride Ion on the Performance of Pb-Ag Anode During Long-Term Galvanostatic Electrolysis

    NASA Astrophysics Data System (ADS)

    Zhong, Xiaocong; Yu, Xiaoying; Jiang, Liangxing; Lv, Xiaojun; Liu, Fangyang; Lai, Yanqing; Li, Jie

    2015-09-01

    Anodic potential, morphology and phase composition of the anodic layer, corrosion morphology of the metallic substrate, and oxygen evolution behavior of Pb-Ag anode in H2SO4 solution without/with fluoride ion were investigated and compared. The results showed that the presence of fluoride ions contributed to a smoother anodic layer with lower PbO2 concentration, which resulted in lower double layer capacity and higher charge transfer resistance for the oxygen evolution reaction. Consequently, the Pb-Ag anode showed a higher anodic potential (about 35 mV) in the fluoride-containing electrolyte. In addition, the fluoride ions accelerated the detachment of loose flakes on the anodic layer. It was demonstrated that the anodic layer formed in the fluoride-containing H2SO4 solution was thinner. Furthermore, fluoride ions aggravated the corrosion of the metallic substrate at interdendritic boundary regions. Hence, the presence of fluoride ions is detrimental to oxygen evolution reactivity and increases the corrosion of the Pb-Ag anode, which may further increase the energy consumption and capital cost of zinc plants.

  9. Calibration of equipment for analysis of drinking water fluoride: a comparison study.

    PubMed

    Quock, Ryan L; Chan, Jarvis T

    2012-03-01

    Current American Dental Association evidence-based recommendations for prescription of dietary fluoride supplements are based in part on the fluoride concentration of a pediatric patient's drinking water. With these recommendations in mind, this study compared the relative accuracy of fluoride concentration analysis when a common apparatus is calibrated with different combinations of standard values. Fluoride solutions in increments of 0.1 ppm, from a range of 0.1 to 1.0 ppm fluoride, as well as 2.0 and 4.0 ppm, were gravimetrically prepared and fluoride concentration measured in pentad, using a fluoride ion-specific electrode and millivolt meter. Fluoride concentrations of these solutions were recorded after calibration with the following 3 different combinations of standard fluoride solutions: 0.1 ppm and 0.5 ppm, 0.1 ppm and 1.0 ppm, 0.5 ppm and 1.0 ppm. Statistical analysis showed significant differences in the fluoride content of water samples obtained with different two-standard fluoride solutions. Among the two-standard fluoride solutions tested, using 0.5 ppm and 1.0 ppm as two-standard fluoride solutions provided the most accurate fluoride measurement of water samples containing fluoride in the range of 0.1 ppm to 4.0 ppm. This information should be valuable to dental clinics or laboratories in fluoride analysis of drinking water samples.

  10. Protein carbonylation: 2,4-dinitrophenylhydrazine reacts with both aldehydes/ketones and sulfenic acids.

    PubMed

    Dalle-Donne, Isabella; Carini, Marina; Orioli, Marica; Vistoli, Giulio; Regazzoni, Luca; Colombo, Graziano; Rossi, Ranieri; Milzani, Aldo; Aldini, Giancarlo

    2009-05-15

    Most of the assays for detection of carbonylated proteins, the most general and widely used marker of severe protein oxidation, involve derivatization of the carbonyl group with 2,4-dinitrophenylhydrazine (DNPH), which leads to formation of a stable dinitrophenyl hydrazone product. Here, by using a Cys-containing model peptide and high-resolution mass spectrometry, we demonstrate that DNPH is not exclusively selective for carbonyl groups, because it also reacts with sulfenic acids, forming a DNPH adduct, through the acid-catalyzed formation of a thioaldehyde intermediate that is further converted to an aldehyde. beta-Mercaptoethanol prevents the formation of the DNPH derivative because it reacts with the oxidized Cys residue, forming the corresponding disulfide.

  11. Effects of fluoride emissions on enzyme activity in metabolism of agricultural plants

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

    Moeri, P.B.

    1980-01-01

    The effects of fluoride on the activity of malatedehydrogenase (MDH) in rape seed and rye grass have been investigated. Fluoride, which has been absorbed from the air, seems to act differently from fluoride added to the soil. The action of airborne fluoride compounds resorbed by the plant on the activity of MDH significantly correlated with the distance from an aluminum plant, crop yield, and fluoride content. 5 references, 5 figures, 2 tables.

  12. Study on fluoride emission from soils at high temperature related to brick-making process.

    PubMed

    Xie, Z M; Wu, W H; Xu, J M

    2003-02-01

    Characteristics of fluoride emission from 12 soils at temperatures of 400-1,100 degrees C related to the brick-making process were studied. The results obtained in this study indicate that fluoride emission as gaseous HF and SiF4 was related to the firing temperature, soil total fluoride content, soil composition and calcium compounds added to soils. Soils began to release fluoride at temperatures between 500 and 700 degrees C. Marked increases of the average fluoride mission rate from 57.2% to 85.4% of soil total fluoride were noticed as the heating temperature was increased from 700 to 1,100 degrees C. It was found that the major proportion (over 50%) of the soil total fluoride was emitted from soils at approximate 800 degrees C. The amount of fluoride released into the atmosphere when heated depended on the total fluoride contents in the soils. Correlation analysis showed that the soil composition, such as cation exchange capacity, exchangeable calcium and CaCO3, had some influence on fluoride emission below 900 degrees C, but had no influence at temperatures above 900 degrees C. Addition of four calcium compounds (CaO, CaCO3, Ca(OH)2, and CaSO4) at 1.5% by weight raised the temperature at which fluoride began to be released to 700 degrees C. The greatest decrease in fluoride emission among the four calcium compound treatments was found with CaCO3.

  13. Fluoride exposure and indicators of thyroid functioning in the Canadian population: implications for community water fluoridation

    PubMed Central

    Barberio, Amanda M; Hosein, F Shaun; Quiñonez, Carlos; McLaren, Lindsay

    2017-01-01

    Background There are concerns that altered thyroid functioning could be the result of ingesting too much fluoride. Community water fluoridation (CWF) is an important source of fluoride exposure. Our objectives were to examine the association between fluoride exposure and (1) diagnosis of a thyroid condition and (2) indicators of thyroid functioning among a national population-based sample of Canadians. Methods We analysed data from Cycles 2 and 3 of the Canadian Health Measures Survey (CHMS). Logistic regression was used to assess associations between fluoride from urine and tap water samples and the diagnosis of a thyroid condition. Multinomial logistic regression was used to examine the relationship between fluoride exposure and thyroid-stimulating hormone (TSH) level (low/normal/high). Other available variables permitted additional exploratory analyses among the subset of participants for whom we could discern some fluoride exposure from drinking water and/or dental products. Results There was no evidence of a relationship between fluoride exposure (from urine and tap water) and the diagnosis of a thyroid condition. There was no statistically significant association between fluoride exposure and abnormal (low or high) TSH levels relative to normal TSH levels. Rerunning the models with the sample constrained to the subset of participants for whom we could discern some source(s) of fluoride exposure from drinking water and/or dental products revealed no significant associations. Conclusion These analyses suggest that, at the population level, fluoride exposure is not associated with impaired thyroid functioning in a time and place where multiple sources of fluoride exposure, including CWF, exist. PMID:28839078

  14. Carbonyl compounds in electronic cigarette vapors: effects of nicotine solvent and battery output voltage.

    PubMed

    Kosmider, Leon; Sobczak, Andrzej; Fik, Maciej; Knysak, Jakub; Zaciera, Marzena; Kurek, Jolanta; Goniewicz, Maciej Lukasz

    2014-10-01

    Glycerin (VG) and propylene glycol (PG) are the most common nicotine solvents used in e-cigarettes (ECs). It has been shown that at high temperatures both VG and PG undergo decomposition to low molecular carbonyl compounds, including the carcinogens formaldehyde and acetaldehyde. The aim of this study was to evaluate how various product characteristics, including nicotine solvent and battery output voltage, affect the levels of carbonyls in EC vapor. Twelve carbonyl compounds were measured in vapors from 10 commercially available nicotine solutions and from 3 control solutions composed of pure glycerin, pure propylene glycol, or a mixture of both solvents (50:50). EC battery output voltage was gradually modified from 3.2 to 4.8V. Carbonyl compounds were determined using the HPLC/DAD method. Formaldehyde and acetaldehyde were found in 8 of 13 samples. The amounts of formaldehyde and acetaldehyde in vapors from lower voltage EC were on average 13- and 807-fold lower than in tobacco smoke, respectively. The highest levels of carbonyls were observed in vapors generated from PG-based solutions. Increasing voltage from 3.2 to 4.8V resulted in a 4 to more than 200 times increase in formaldehyde, acetaldehyde, and acetone levels. The levels of formaldehyde in vapors from high-voltage device were in the range of levels reported in tobacco smoke. Vapors from EC contain toxic and carcinogenic carbonyl compounds. Both solvent and battery output voltage significantly affect levels of carbonyl compounds in EC vapors. High-voltage EC may expose users to high levels of carbonyl compounds. © The Author 2014. Published by Oxford University Press on behalf of the Society for Research on Nicotine and Tobacco. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  15. Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

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

    Kagan, Benjamin D.; Lichtscheidl, Alejandro G.; Erickson, Karla A.

    Trimethyltin fluoride (Me₃SnF) is a mild and selective reagent for the installation of actinide fluoride bonds as demonstrated by the room temperature synthesis of a variety of organometallic and inorganic thorium(IV), uranium(IV), and uranium(V) fluoride complexes ((1,2,4-tBu₃C₅H₂)₂ThF₂, (C₅Me₅)₂U(F)(O-2,6-iPr₂C₆H₃), U(F)(O-2,6-tBu₂C₆H₃)₃, U(F)[N(SiMe₃)₂]₃ (C₅Me₅)₂UF₂(L) (L = O=PMe₃, O=PPh₃, O=PCy₃), and (C₅Me₅)₂U(F)(=N-2,6-iPr₂C₆H₃)) from their corresponding chloride, bromide, and iodide analogues. From these reactions, the new (C₅Me₅)₂UF₂(L) (L = O=PPh₃, O=PCy₃) uranium fluoride complexes were isolated and characterized by NMR spectroscopy and X-ray crystallography.

  16. Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

    DOE PAGES

    Kagan, Benjamin D.; Lichtscheidl, Alejandro G.; Erickson, Karla A.; ...

    2017-11-07

    Trimethyltin fluoride (Me₃SnF) is a mild and selective reagent for the installation of actinide fluoride bonds as demonstrated by the room temperature synthesis of a variety of organometallic and inorganic thorium(IV), uranium(IV), and uranium(V) fluoride complexes ((1,2,4-tBu₃C₅H₂)₂ThF₂, (C₅Me₅)₂U(F)(O-2,6-iPr₂C₆H₃), U(F)(O-2,6-tBu₂C₆H₃)₃, U(F)[N(SiMe₃)₂]₃ (C₅Me₅)₂UF₂(L) (L = O=PMe₃, O=PPh₃, O=PCy₃), and (C₅Me₅)₂U(F)(=N-2,6-iPr₂C₆H₃)) from their corresponding chloride, bromide, and iodide analogues. From these reactions, the new (C₅Me₅)₂UF₂(L) (L = O=PPh₃, O=PCy₃) uranium fluoride complexes were isolated and characterized by NMR spectroscopy and X-ray crystallography.

  17. Effects of fluoridated milk on root dentin remineralization.

    PubMed

    Arnold, Wolfgang H; Heidt, Bastian A; Kuntz, Sebastian; Naumova, Ella A

    2014-01-01

    The prevalence of root caries is increasing with greater life expectancy and number of retained teeth. Therefore, new preventive strategies should be developed to reduce the prevalence of root caries. The aim of this study was to investigate the effects of fluoridated milk on the remineralization of root dentin and to compare these effects to those of sodium fluoride (NaF) application without milk. Thirty extracted human molars were divided into 6 groups, and the root cementum was removed from each tooth. The dentin surface was demineralized and then incubated with one of the following six solutions: Sodium chloride NaCl, artificial saliva, milk, milk+2.5 ppm fluoride, milk+10 ppm fluoride and artificial saliva+10 ppm fluoride. Serial sections were cut through the lesions and investigated with polarized light microscopy and quantitative morphometry, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). The data were statistically evaluated using a one-way ANOVA for multiple comparisons. The depth of the lesion decreased with increasing fluoride concentration and was the smallest after incubation with artificial saliva+10 ppm fluoride. SEM analysis revealed a clearly demarcated superficial remineralized zone after incubation with milk+2.5 ppm fluoride, milk+10 ppm fluoride and artificial saliva+10 ppm fluoride. Ca content in this zone increased with increasing fluoride content and was highest after artificial saliva+10 ppm fluoride incubation. In the artificial saliva+10 ppm fluoride group, an additional crystalline layer was present on top of the lesion that contained elevated levels of F and Ca. Incubation of root dentin with fluoridated milk showed a clear effect on root dentin remineralization, and incubation with NaF dissolved in artificial saliva demonstrated a stronger effect.

  18. Fluoride Increase in Saliva and Dental Biofilm due to a Meal Prepared with Fluoridated Water or Salt: A Crossover Clinical Study.

    PubMed

    Lima, Carolina V; Tenuta, Livia M A; Cury, Jaime A

    2018-06-07

    Knowledge about fluoride delivery to oral fluids from foods cooked with fluoridated water and salt is scarce, and no study has evaluated fluoride concentrations in saliva or biofilm during meal consumption. In this randomized double-blind crossover study, 12 volunteers ingested meals (rice, beans, meat, and legumes) prepared with nonfluoridated water and salt (control group), fluoridated water (0.70 mg F/L; water group), and fluoridated salt (183.7 mg F/kg; salt group). Whole saliva was collected before meal ingestion, during mastication, and up to 2 h after meal ingestion. Dental biofilm was collected before and immediately after meal ingestion. Fluoride concentrations in saliva and dental biofilm were determined by an ion-specific electrode. The mean (±standard deviation; n = 4) fluoride concentrations in meals prepared for the control, water, and salt groups were 0.039 ± 0.01, 0.43 ± 0.04, and 1.71 ± 0.32 μg F/g, respectively. The three groups had significantly different fluoride concentrations in saliva collected during mastication (p < 0.0001) and after meal ingestion (p < 0.04; salt > water > control). The fluoride concentration in saliva returned to baseline 30 min after meal ingestion in the water group but remained high for up to 2 h in the salt group (p = 0.002). The fluoride concentration in biofilm fluid differed only between the salt and control groups (p = 0.008). The mastication of foods cooked with fluoridated water and salt increases fluoride concentrations in oral fluids and may contribute to the local effect of these community-based fluoride interventions on caries control. © 2018 S. Karger AG, Basel.

  19. [Spectralsignatures of nickel and vanadium supported photocatalysts and their photocatalytic properties].

    PubMed

    Hai, Feng; Zhang, Qian-Cheng; Wang, Zhi-Wei; Jian, Li

    2011-04-01

    Using SiO2, activated carbon (AC) and Al2O3 as supports, the supported photocatalysts Ni-V-O/SiO2, Ni-V-O/AC and Ni-V-O/Al2O3 were prepared by impregnation method, and their spectralsignatures were investigated. The carbonylation of methanol with CO2 under UV irradiation was used as a probe reaction to compare the photocatalytic performance of the prepared catalysts. Integrated with the testing results of carbonylation, the effects of different supports on selectivity for the carbonylation products of methyl formate (MF) and dimethyl carbonate (DMC) were discussed by pyridine-IR and UV-Vis techniques. XRD results showed that the particles of nickel and vanadium supported on SiO2 had the highest degree of dispersion. Results of pyridine-IR indicated that all catalysts retained Lewis acid sites. The acid strength was different from catalyst samples with different supports but with the same active components. The acid strengths could be arranged as follows: Ni-V-O/SiO2 > Ni-V-O/Al2 O3 > Ni-V-O/AC. Different acid strengths exhibited different influence on the selectivity of products MF and DMC of carbonylation. The surface acid strengths of catalysts were the major factor influencing the selectivity of carbonylation products.

  20. Photocatalytic degradation of mixed gaseous carbonyl compounds at low level on adsorptive TiO2/SiO2 photocatalyst using a fluidized bed reactor.

    PubMed

    Zhang, Maolin; An, Taicheng; Fu, Jiamo; Sheng, Guoying; Wang, Xinming; Hu, Xiaohong; Ding, Xuejun

    2006-06-01

    An adsorptive silica-supported titania photocatalyst TiO(2)/SiO(2) was prepared by using nanosized titania (anatase) immobilized on silica gel by the sol-gel technique with the titanium tetra isopropoxide as the main raw material and acetic acid as the acid catalyst. Meanwhile the structure and properties of the TiO(2)/SiO(2) photocatalyst were studied by means of many modern analysis techniques such as TEM, XRD, and BET. Gas-solid heterogeneous photocatalytic decomposition of four carbonyl compounds mixture at low concentration levels over ultraviolet irradiated TiO(2)/SiO(2) photocatalyst were carried out with high degradation efficiencies in a coaxial triple-cylinder-type fluidized bed photocatalytic reactor, which provided efficient continuous contact of ultraviolet photons, silica-supported titania photocatalyst, and gaseous reactants. Experimental results showed that the photocatalyst had a high adsorption performance and a good photocatalytic activity for four carbonyl compounds mixture. Some factors influencing the photocatalytic decomposition of the mixed carbonyl compounds, i.e. the gas flowrate, relative humidity, concentration of oxygen, and illumination time, were discussed in detail. It is found that the photocatalytic reaction rate of four carbonyl compounds decreased in this order: propionaldehyde, acetone, acetaldehyde and formaldehyde.

  1. Hydrogeochemical characterization of fluoride rich groundwater of Wailpalli watershed, Nalgonda District, Andhra Pradesh, India.

    PubMed

    Reddy, A G S; Reddy, D V; Rao, P N; Prasad, K Maruthy

    2010-12-01

    The groundwater of Nalgonda district is well known for its very high fluoride content for the past five decades. Many researchers have contributed their scientific knowledge to unravel causes for fluoride enrichment of groundwater. In the present paper, an attempt has been made to relate the high fluoride content in the groundwater to hydrogeochemical characterization of the water in a fracture hard rock terrain--the Wailpally watershed. Groundwater samples collected from all the major geomorphic units in pre- and post-monsoon seasons were analyzed for its major ion constituents such as Ca(2+), Mg(2+), Na(+), K(+), CO3-, HCO3-, Cl(-), SO4(-2), NO3-, and F(-). The groundwaters in the watershed have the average fluoride content of 2.79 mg/l in pre-monsoon and 2.83 mg/l in post-monsoon. Fluoride concentration in groundwater does not show perceptible change neither with time nor in space. The ionic dominance pattern is in the order of Na(+) > Ca(2+) > Mg(2+) > K(-) among cations and HCO3- Cl(-) > SO4(-2) NO3- F(-) among anions in pre-monsoon. In post-monsoon, Mg replaces Ca(2+) and NO3- takes the place of SO4(-2). The Modified Piper diagram reflect that the water belong to Ca(+2)-Mg(+2)-HCO3- to Na(+)-HCO3- facies. Negative chloralkali indices in both the seasons prove that ion exchange between Na(+) and K(+) in aquatic solution took place with Ca(+2) and Mg(+2) of host rock. The interpretation of plots for different major ions and molar ratios suggest that weathering of silicate rocks and water-rock interaction is responsible for major ion chemistry of groundwater in Wailpally watershed. Chemical characteristics and evolution of this fluoride-contaminated groundwater is akin to normal waters of other hard rock terrain; hence, it can be concluded that aquifer material play an important role in the contribution of fluoride in to the accompanying water. High fluoride content in groundwater can be attributed to the continuous water-rock interaction during the process of percolation with fluoride-bearing country rocks under arid, low precipitation, and high evapotranspiration conditions.

  2. Efficient adsorption and photocatalytic degradation of organic pollutants diluted in water using fluoride-modified hydrophobic mesoporous silica

    NASA Astrophysics Data System (ADS)

    Yamashita, Hiromi; Maekawa, Kazuhiro; Nakao, Hidetoshi; Anpo, Masakazu

    2004-10-01

    Using a mixture of tetraethylammonium fluoride and dodecylamine as templates, hydrophobic mesoporous silica supports were prepared. The fine anatase TiO 2 photocatalysts were prepared on the fluoride-modified hydrophobic mesoporous silica and the adsorption properties and the photocatalytic degradation of an aqueous 2-propanol or 2-hexanol solution into CO 2 and H 2O have been studied. The amount of adsorption and the photocatalytic reactivities increased with increasing the content of fluoride ions on these photocatalysts. 2-Hexanol diluted in water was adsorbed on the hydrophobic catalysts more efficiently than 2-propanol.

  3. Hydrocodone Combination Products

    MedlinePlus

    Codiclear DH® (as a combination product containing Guaifenesin, Hydrocodone) ... EndaCof XP® (as a combination product containing Guaifenesin, Hydrocodone) ... Entuss® (as a combination product containing Guaifenesin, Hydrocodone)

  4. Funding Public Higher Education in Colorado: How Has the College Opportunity Funding Model Impacted Educational Funding and Performance?

    ERIC Educational Resources Information Center

    Middlemist, George Edward

    2017-01-01

    During the 2004 legislative session, the Colorado General Assembly enacted Senate Bill 189 (SB189), which established the first system of college vouchers in the United States. The supporters of SB189 hoped that the voucher system, called the College Opportunity Fund (COF), would: 1) stabilize the flow of state funding to higher education; 2)…

  5. Hybridizing CNT/PMMA/PVDF towards high-performance piezoelectric nanofibers

    NASA Astrophysics Data System (ADS)

    Fang, K. Y.; Fang, F.; Wang, S. W.; Yang, W.; Sun, W.; Li, J. F.

    2018-07-01

    Piezoelectric nanofibers are of great importance in their potential applications as smart fibers and textiles to bring changes to daily lives. By employing the technique of electrospinning, polyvinylidene fluoride (PVDF) nanofibers modified with polymethyl methacrylate (PMMA) and single-wall carbon nanotubes (CNTs) (referred to as CNT/PMMA/PVDF) are prepared. The electric field induced displacement of the as-prepared nanofibers is characterized by piezoresponse force microscopy. Compared with the pure PVDF nanofibers, the CNT/PMMA/PVDF nanofibers exhibit a great enhancement of about 196% for the electric field induced displacement, while increments of about 104% and 78% are obtained for the PMMA/PVDF and CNT/PVDF nanofibers, respectively. A structural analysis indicates that the hydrogen bonding between the O atom in the carbonyl group of PMMA and the hydrogen atom in the CH2 groups of PVDF, the promotion of the nucleation of crystallites by CNTs, work synergistically to produce the high electroactive response of the CNT/PMMA/PVDF nanofibers. Based on the high-performance nanofibers, a prototype of a flexible nanofiber generator is fabricated, which exhibits a typical electrical output of 3.11 V upon a repeated impact-release loading at a frequency of 50 Hz.

  6. Extraction and Quantitation of Ketones and Aldehydes from Mammalian Cells Using Fluorous Tagging and Capillary LC-MS.

    PubMed

    Yuan, Wei; Li, Shuwei; Edwards, James L

    2015-08-04

    The extraction and quantitation of carbonyl metabolites from cell lysate was accomplished using a carbonyl-reactive fluorous tag and capillary liquid chromatography coupled to mass spectrometry (capLC-MS). Selective fluorous tagging for ketones and aldehydes provided a 30-fold increase in sensitivity using electrospray ionization MS. Separation of fluorous tagged carbonyl resulted in good separation of all components, and tandem MS was able to differentiate structural carbonyl isomers. The average limit of detection for carbonyl standards was 37 nM (range 1.5-250 nM), with linearity of R(2) > 0.99. Reproducibility for metabolites in cell lysate averaged 9% RSD. Human aortic endothelial cells (HAECs) were exposed to varying levels of glucose, and their carbonyl metabolite levels were quantified. Significant metabolite changes were seen in glycolysis and the propanoate pathway from a glucose challenge. Using an untargeted approach, 120 carbonyl metabolites were found to change in hyperglycemic HAECs. From this list of compounds, multiple metabolites from the pentose phosphate and tryptophan metabolic pathways were discovered. This system provides excellent sensitivity and quantitation of carbonyl metabolites without the need for isotope standards or labels.

  7. A randomised clinical evaluation of a fluoride mouthrinse and dentifrice in an in situ caries model.

    PubMed

    Parkinson, Charles R; Hara, Anderson T; Nehme, Marc; Lippert, Frank; Zero, Domenick T

    2018-03-01

    Fluoride mouthrinses provide advantages for fluoride delivery by maintaining elevated intra-oral fluoride concentrations following fluoride dentifrice use. This in situ caries study investigated potential anti-caries efficacy of a 220 ppm fluoride mouthrinse. This was an analyst-blinded, four-treatment, randomised, crossover study using partially demineralised, gauze-wrapped, human enamel samples mounted in a mandibular partial denture. Participants brushed twice daily for 14 days with either a 1150 ppm fluoride or a fluoride-free placebo dentifrice and either rinsed once daily with the 220 ppm fluoride mouthrinse or not. Following each treatment period, percent surface microhardness recovery (%SMHR) and enamel fluoride uptake (EFU) were assessed. Fifty three participants completed the study. Compared with the placebo dentifrice/no rinse treatment, the fluoride-containing regimens demonstrated greater enamel remineralisation (%SMHR) and fluoridation (EFU): fluoride dentifrice/fluoride rinse (%SMHR difference: 21.55 [95% CI: 15.78,27.32]; EFU difference 8.35 [7.21,9.29]); fluoride dentifrice/no rinse: 19.48 [13.81,25.15]; 6.47 [5.35,7.60]; placebo dentifrice/fluoride rinse: 16.76 [11.06,22.45]; 5.87 [4.72,7.00] (all P < .0001). There were no significant differences in%SMHR between fluoride regimens. The fluoride dentifrice/fluoride rinse regimen was associated with higher EFU than the fluoride dentifrice/no rinse (1.88 [0.75,3.01], P = .0013) and placebo dentifrice/fluoride rinse regimens (2.48 [1.34,3.62], P < .0001). Treatments were generally well-tolerated. The in situ caries model demonstrated that the fluoride mouthrinse is effective in promoting enamel caries lesion remineralisation and fluoridation whether used following a fluoride or non-fluoride dentifrice. Additive (potential) anti-caries benefits of a fluoride rinse after a fluoride dentifrice were confined to enhancements in lesion fluoridation (EFU). In conjunction with a fluoride dentifrice, fluoride mouthrinses enhance enamel fluoridation, which may be useful in caries prevention. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

  8. An assessment of the relationship between excess fluoride intake from drinking water and essential hypertension in adults residing in fluoride endemic areas.

    PubMed

    Sun, Liyan; Gao, Yanhui; Liu, Hui; Zhang, Wei; Ding, Yunpeng; Li, Bingyun; Li, Mang; Sun, Dianjun

    2013-01-15

    In this study, the relationships between high water fluoride exposure and essential hypertension as well as plasma ET-1 levels were investigated. A total of 487 residents aged 40 to 75 were randomly recruited from eight villages in Zhaozhou County from Heilongjiang Province in China and were divided into 4 groups according to the concentrations of fluoride in their water. Consumption levels of drinking water fluoride for normal, mild, moderate, and high exposure groups were 0.84±0.26 mg/L, 1.55±0.22 mg/L, 2.49±0.30 mg/L, and 4.06±1.15 mg/L, respectively. The prevalence of hypertension in each group was 20.16%, 24.54%, 32.30%, and 49.23%, respectively. There were significant differences between all the groups; namely, with the increase in water fluoride concentrations, the risk of essential hypertension in adults grows in a concentration-dependent manner. Significant differences were observed in the plasma ET-1 levels between the different groups (P<0.0001). In the multivariable logistic regression model, high water fluoride concentrations (F(-)≥3.01 mg/L, OR(4/1)=2.84), age (OR(3/1)=2.63), and BMI (OR(2/1)=2.40, OR(3/1)=6.03) were closely associated with essential hypertension. In other words, the study not only confirmed the relationship between excess fluoride intake and essential hypertension in adults, but it also demonstrated that high levels of fluoride exposure in drinking water could increase plasma ET-1 levels in subjects living in fluoride endemic areas. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Fluoride in the diet of 2-years-old children.

    PubMed

    Martinez-Mier, E A; Spencer, Kathryn L; Sanders, Brian J; Jones, James E; Soto-Rojas, Armando E; Tomlin, Angela M; Vinson, LaQuia A; Weddell, James A; Eckert, George J

    2017-06-01

    This study aimed to calculate the fluoride concentrations of commonly consumed foods and beverages for 2-years-old children utilizing market basket information for the US Midwest region. Total Diet Study food lists were cross-referenced with National Health and Nutrition Examination Survey-What We Eat in America data to determine the foods and beverages to be included. Fluoride concentrations were determined using a modification of the hexamethyldisiloxane microdiffusion technique. Fluoride concentrations were summarized for each of the food categories. Daily dietary fluoride intake was estimated using a simulation analysis. Food and beverage fluoride concentrations varied widely, ranging from nondetectable for some oils and dairy products to more than 3.0 μgF/g food for some processed meats, fish and fruits. The estimated mean (±SD) daily dietary fluoride intake, excluding dentifrice and supplements, was 412±114 μgF/d. The estimated average ingestion for a 2-years-old weighing 12.24 kg was 0.034±0.009 mg/kg/d. A diet based on foods and beverages in the fifth percentile of fluoride intake distribution for an average child would result in 247 μgF/d or 0.020 mg/kg/d, while a diet with foods and beverages in the 95th percentile would result in a total intake of 622 μgF/d or 0.051 mg/kg/d. The fluoride concentrations of foods and beverages vary widely, and, if items in the 95th percentile of fluoride intake distribution are ingested, children could consume more fluoride than the recommended 0.05 mg/kg/d. Fluoride intake calculated in this study was higher than historically reported dietary levels. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  10. On the Reaction of Carbonyl Diphosphonic Acid with Hydroxylamine and O-alkylhydroxylamines: Unexpected Degradation of P-C-P Bridge.

    PubMed

    Khomich, Olga A; Yanvarev, Dmitry V; Novikov, Roman A; Kornev, Alexey B; Puljulla, Elina; Vepsäläinen, Jouko; Khomutov, Alex R; Kochetkov, Sergey N

    2017-06-23

    Derivatives of methylenediphosphonic acid possess wide spectra of biological activities and are used in enzymology as research tools as well as in practical medicine. Carbonyl diphosphonic acid is a promising starting building block for synthesis of functionally substituted methylenediphosphonates. Investigation of the interaction of carbonyl diphosphonic acid with hydroxylamine clearly demonstrates that it is impossible to isolate oxime within the pH range 2-12, while only cyanophosphonic and phosphoric acids are the products of the fast proceeding Beckmann-like fragmentation. In the case of O -alkylhydroxylamines, corresponding alcohols are found in the reaction mixtures in addition to cyanophosphonic and phosphoric acids. Therefore, two residues of phosphonic acid being attached to a carbonyl group provide new properties to this carbonyl group, making its oximes very unstable. This principally differs carbonyl diphosphonic acid from structurally related phosphonoglyoxalic acid and other α-ketophosphonates.

  11. Infrared spectroscopy of extreme coordination: the carbonyls of U(+) and UO(2)(+).

    PubMed

    Ricks, Allen M; Gagliardi, Laura; Duncan, Michael A

    2010-11-17

    Uranium and uranium dioxide carbonyl cations produced by laser vaporization are studied with mass-selected ion infrared spectroscopy in the C-O stretching region. Dissociation patterns, spectra, and quantum chemical calculations establish that the fully coordinated ions are U(CO)(8)(+) and UO(2)(CO)(5)(+), with D(4d) square antiprism and D(5h) pentagonal bipyramid structures. Back-bonding in U(CO)(8)(+) causes a red-shifted CO stretch, but back-donation is inefficient for UO(2)(CO)(5)(+), producing a blue-shifted CO stretch characteristic of nonclassical carbonyls.

  12. Fluoride-associated ultrastructural changes and apoptosis in human renal tubule: a pilot study.

    PubMed

    Quadri, J A; Sarwar, S; Sinha, A; Kalaivani, M; Dinda, A K; Bagga, A; Roy, T S; Das, T K; Shariff, A

    2018-01-01

    The susceptibility of the kidneys to fluoride toxicity can largely be attributed to its anatomy and function. As the filtrate moves along the complex tubular structure of each nephron, it is concentrated in the proximal and distal tubules and collecting duct. It has been frequently observed that the children suffering from renal impairments also have some symptoms of dental and skeletal fluorosis. The findings suggest that fluoride somehow interferes with renal anatomy and physiology, which may lead to renal pathogenesis. The aim of this study was to evaluate the fluoride-associated nephrotoxicity. A total of 156 patients with childhood nephrotic syndrome were screened and it was observed that 32 of them had significantly high levels ( p ≤ 0.05) of fluoride in urine (4.01 ± 1.83 ppm) and serum (0.1 ± 0.013 ppm). On the basis of urinary fluoride concentration, patients were divided into two groups, namely group 1 (G-1) ( n = 32) containing normal urine fluoride (0.61 ± 0.17 ppm) and group 2 (G-2) ( n = 32) having high urine fluoride concentration (4.01 ± 1.83 ppm). Age-matched healthy subjects ( n = 33) having normal levels of urinary fluoride (0.56 ± 0.15 ppm) were included in the study as control (group 0 (G-0)). Kidney biopsies were taken from G-1 and G-2 only, who were subjected to ultrastructural (transmission electron microscopy) and apoptotic (terminal deoxynucleotidyl transferase deoxyuridine triphosphate nick end labeling) analysis. Various subcellular ultrastructural changes including nuclear disintegration, chromosome condensation, cytoplasmic ground substance lysis, and endoplasmic reticulum blebbing were observed. Increased levels of apoptosis were observed in high fluoride group (G-2) compared to normal fluoride group (G-1). Various degrees of fluoride-associated damages to the architecture of tubular epithelia, such as cell swelling and lysis, cytoplasmic vacuolation, nuclear condensation, apoptosis, and necrosis, were observed.

  13. Protein carbonylation, protein aggregation and neuronal cell death in a murine model of multiple sclerosis

    NASA Astrophysics Data System (ADS)

    Dasgupta, Anushka

    Many studies have suggested that oxidative stress plays an important role in the pathophysiology of both multiple sclerosis (MS) and its animal model experimental autoimmune encephalomyelitis (EAE). Yet, the mechanism by which oxidative stress leads to tissue damage in these disorders is unclear. Recent work from our laboratory has revealed that protein carbonylation, a major oxidative modification caused by severe and/or chronic oxidative stress conditions, is elevated in MS and EAE. Furthermore, protein carbonylation has been shown to alter protein structure leading to misfolding/aggregation. These findings prompted me to hypothesize that carbonylated proteins, formed as a consequence of oxidative stress and/or decreased proteasomal activity, promote protein aggregation to mediate neuronal apoptosis in vitro and in EAE. To test this novel hypothesis, I first characterized protein carbonylation, protein aggregation and apoptosis along the spinal cord during the course of myelin-oligodendrocyte glycoprotein (MOG)35-55 peptide-induced EAE in C57BL/6 mice [Chapter 2]. The results show that carbonylated proteins accumulate throughout the course of the disease, albeit by different mechanisms: increased oxidative stress in acute EAE and decreased proteasomal activity in chronic EAE. I discovered not only that there is a temporal correlation between protein carbonylation and apoptosis but also that carbonyl levels are significantly higher in apoptotic cells. A high number of juxta-nuclear and cytoplasmic protein aggregates containing the majority of the oxidized proteins are also present during the course of EAE, which seems to be due to reduced autophagy. In chapter 3, I show that when gluthathione levels are reduced to those in EAE spinal cord, both neuron-like PC12 (nPC12) cells and primary neuronal cultures accumulate carbonylated proteins and undergo cell death (both by necrosis and apoptosis). Immunocytochemical and biochemical studies also revealed a temporal/spatial relationship between carbonylation, protein aggregation and cellular apoptosis. Furthermore, the effectiveness of the carbonyl scavenger hydralazine, histidine hydrazide and methoxylamine at preventing cell death identifies protein carbonyls as the toxic species. Experiments using well-characterized apoptosis inhibitors place protein carbonylation downstream of the mitochondrial transition pore opening and upstream of caspase activation. These in vitro studies demonstrate for the first time a causal relationship between carbonylation, protein aggregation and apoptosis of neurons undergoing oxidative damage. This relationship was further strengthened with the experiments carried out in chapter 4, which show that inhibition of protein aggregation with congo red (CR) or 2-hydroxypropyl beta-cyclodextrin (HPCD) significantly reduced neuronal cell death without affecting the levels of oxidized proteins. Interestingly, large, juxta-nuclear aggregates are not formed upon GSH depletion, suggesting that the small protein aggregates are the cytotoxic species. Together, our data suggest that protein carbonylation causes protein aggregation to mediate neuronal apoptosis in vitro and that a similar mechanism might be contributing to neuronal/glial apoptosis in EAE. These studies provide the basis for testing protein carbonylation scavengers and protein aggregation inhibitors for the treatment of inflammatory demyelinating disorders.

  14. Giant cemento-ossifying fibroma of the mandible: a rare case.

    PubMed

    Sujatha, D; Shubha, Gurudath; Anuradha, Pai; Ragavendra, Mahadev Naik

    2013-01-01

    The World Health Organization classifies cemento-ossifying fibroma (COF) as a fibro-osseous neoplasm included among the nonodontogenic tumors derived from the mesenchymal blast cells of the periodontal ligament, with a potential for forming fibrous tissue, cementum and bone, or a combination of such elements. These are slow-growing lesions, and are more frequent in women, between the third and fourth decades of life. Case reports of massive expansile COFs (measuring more than 10 cm) are rarely reported in the literature. This article aims to describe a case of giant cemento-ossifying fibroma with radiographic and 3D CT features in a 34 year old female patient, who came with the complaint of progressive swelling of the face which had started 6 years earlier.

  15. Cluster-randomized xylitol toothpaste trial for early childhood caries prevention

    PubMed Central

    Chi, Donald L.; Tut, Ohnmar K.; Milgrom, Peter

    2013-01-01

    Purpose We assessed the efficacy of supervised toothbrushing with xylitol toothpaste to prevent early childhood caries (ECC) and to reduce mutans streptococci (MS). Methods In this cluster-randomized efficacy trial, 4 Head Start classrooms in the Marshall Islands were randomly assigned to supervised toothbrushing with 1,400ppm/31% fluoride-xylitol (Epic Dental, Provo, UT) or 1,450ppm fluoride-sorbitol toothpaste (Colgate-Palmolive, New York, NY) (N=196 children, ages 4–5 yrs). We hypothesized no difference in efficacy between the two types of toothpaste. The primary outcome was primary molar d2-3mfs increment after 6 mos. A single examiner was blinded to classroom assignments. Two classrooms were assigned to the fluoride-xylitol group (85 children) and 2 classrooms to the fluoride-sorbitol group (83 children). The child-level analyses accounted for clustering. Results There was no difference between the two groups in baseline or end-of-trial mean d2-3mfs. The mean d2-3mfs increment was greater in the fluoride-xylitol group compared to the fluoride-sorbitol group (2.5 and 1.4 d2-3mfs, respectively), but the difference was not significant (95% CI:−0.17, 2.37;P=0.07). No adverse effects were reported. Conclusion After 6 mos, brushing with a low strength xylitol/fluoride toothpaste is no more efficacious in reducing ECC than a fluoride only toothpaste in a high caries risk child population. PMID:24709430

  16. Graphite fluoride as a solid lubricant in a polyimide binder

    NASA Technical Reports Server (NTRS)

    Fusaro, R. L.; Sliney, H. E.

    1972-01-01

    Polyimide resin (PI) was shown to be a suitable binder material for the solid lubricant graphite fluoride, (CF(1.1))n. Comparisons were made to similar tests using PI-bonded MOS2 films, graphite fluoride rubbed films, and MOS2 rubbed films. The results showed that, at any one specific temperature between 25 and 400 C, the wear life of PI-bonded graphite fluoride films exceeded those of the other three films by at least a factor of 2 and by as much as a factor of 60. Minimum friction coefficients for the PI-bonded films were 0.08 for graphite fluoride and 0.04 for MOS2. The rider wear rates for the two PI-bonded films at 25 C were nearly equal.

  17. Fluoride rinse effect on retention of CaF2 formed on enamel/dentine by fluoride application.

    PubMed

    Falcão, Amanda; Masson, Nadia; Leitão, Tarcísio Jorge; Botelho, Juliana Nunes; Ferreira-Nóbilo, Naiara de Paula; Tabchoury, Cínthia Pereira Machado; Tenuta, Livia Maria Andaló; Cury, Jaime Aparecido

    2016-01-01

    Calcium fluoride-like materials ("CaF2") formed on dental surfaces after professional fluoride application are unstable in the oral environment but can be retained longer with a daily NaF mouthrinse. We tested the effect of twice daily 0.05% NaF rinses on the retention of "CaF2" formed on enamel and dentine after applying acidulated phosphate fluoride (APF). "CaF2" formed on enamel/dentine by APF application significantly decreased after exposure to artificial saliva and the 0.05% NaF rinse was ineffective to avoid this reduction. These findings suggest that the combination of APF and 0.05% NaF is not clinically relevant, either for caries or dental hypersensitivity.

  18. Comparison of effects of diode laser and CO2 laser on human teeth and their usefulness in topical fluoridation.

    PubMed

    González-Rodríguez, Alberto; de Dios López-González, Juan; del Castillo, Juan de Dios Luna; Villalba-Moreno, Juan

    2011-05-01

    Various authors have reported more effective fluoridation from the use of lasers combined with topical fluoride than from conventional topical fluoridation. Besides the beneficial effect of lasers in reducing the acid solubility of an enamel surface, they can also increase the uptake of fluoride. The study objectives were to compare the action of CO(2) and GaAlAs diode lasers on dental enamel and their effects on pulp temperature and enamel fluoride uptake. Different groups of selected enamel surfaces were treated with amine fluoride and irradiated with CO(2) laser at an energy power of 1 or 2 W or with diode laser at 5 or 7 W for 15 s each and compared to enamel surfaces without treatment or topical fluoridated. Samples were examined by means of environmental scanning electron microscopy (ESEM). Surfaces of all enamel samples were then acid-etched, measuring the amount of fluoride deposited on the enamel by using a selective ion electrode. Other enamel surfaces selected under the same conditions were irradiated as described above, measuring the increase in pulp temperature with a thermocouple wire. Fluorination with CO(2) laser at 1 W and diode laser at 7 W produced a significantly greater fluoride uptake on enamel (89 ± 18 mg/l) and (77 ± 17 mg/l) versus topical fluoridation alone (58 ± 7 mg/l) and no treatment (20 ± 1 mg/l). Diode laser at 5 W produced a lesser alteration of the enamel surface compared to CO(2) laser at 1 W, but greater pulp safety was provided by CO(2) laser (ΔT° 1.60° ± 0.5) than by diode laser (ΔT° 3.16° ± 0.6). Diode laser at 7 W and CO(2) laser at 2 W both caused alterations on enamel surfaces, but great pulp safety was again obtained with CO(2) (ΔT° 4.44° ± 0.60) than with diode (ΔT° 5.25° ± 0.55). Our study demonstrates that CO(2) and diode laser irradiation of the enamel surface can both increase fluoride uptake; however, laser energy parameters must be carefully controlled in order to limit increases in pulpal temperature and alterations to the enamel surface.

  19. Gas-phase ozonolysis of ethene in the presence of carbonyl-oxide scavengers

    NASA Astrophysics Data System (ADS)

    Wolff, Silke; Boddenberg, Axel; Thamm, Jürgen; Turner, Walter V.; Gäb, Siegmar

    Potential carbonyl-oxide scavengers are included in gas-phase ozonolysis experiments in an attempt to determine the extent to which the Criegee mechanism is involved. The scavengers selected are those whose reaction mechanism in the liquid phase is understood; water, hydrogen peroxide, alcohols and carboxylic acids have thus far been examined. The products of the ozonolysis of ethene in the gas phase depend on whether carbonyl-oxide scavengers are present. In the absence of scavengers, formaldehyde and formic acid are the major products, and only minor amounts of H 2O 2 and hydroxymethyl hydroperoxide are found. In the presence of a scavenger, certain products observed in addition to these can be regarded as arising from addition of the scavenger to the carbonyl oxide. Thus, H 2O 2 leads to the formation of hydroperoxymethyl hydroperoxide, while alcohols and formic acid give alkoxymethyl hydroperoxides and hydroperoxymethyl formate, respectively.

  20. Selective separation of phosphate and fluoride from semiconductor wastewater.

    PubMed

    Warmadewanthi, B; Liu, J C

    2009-01-01

    Hydrofluoric acid (HF) and phosphoric acid (H(3)PO(4)) are widely used in semiconductor industry for etching and rinsing purposes. Consequently, significant amount of wastewater containing phosphate and fluoride is generated. Selective separation of phosphate and fluoride from the semiconductor wastewater, containing 936 mg/L of fluoride, 118 mg/L of phosphate, 640 mg/L of sulfate, and 26.7 mg/L of ammonia, was studied. Chemical precipitation and flotation reactions were utilized in the two-stage treatment processes. The first-stage reaction involved the addition of magnesium chloride (MgCl(2)) to induce selective precipitation of magnesium phosphate. The optimal condition was pH 10 and molar ratio, [Mg(2 + )]/[(PO(4) (3-))], of 3:1, and 66.2% of phosphate was removed and recovered as bobierrite (Mg(3)(PO(4))(2).8H(2)O). No reaction was found between MgCl(2) and fluoride. Calcium chloride (CaCl(2)) was used in the second-stage reaction to induce precipitation of calcium fluoride and calcium phosphate. The optimum molar ratio, [Ca(2 + )]/[F(-)], was 0.7 at pH 10, and residual fluoride concentration of 10.7 mg/L and phosphate concentration of lower than 0.5 mg/L was obtained. Thermodynamic equilibrium was modeled with PHREEQC and compared with experimental results. Sodium dodecylsulfate (SDS) was an effective collector for subsequent solid-liquid removal via dispersed air flotation (DiAF). The study demonstrated that phosphate can be selectively recovered from the wastewater. Potential benefits include recovery of phosphate for reuse, lower required dosage of calcium for fluoride removal, and less amount of CaF(2) sludge.

  1. Early events in copper-ion catalyzed oxidation of α-synuclein.

    PubMed

    Tiwari, Manish K; Leinisch, Fabian; Sahin, Cagla; Møller, Ian Max; Otzen, Daniel E; Davies, Michael J; Bjerrum, Morten J

    2018-04-22

    Previous studies on metal-ion catalyzed oxidation of α-synuclein oxidation have mostly used conditions that result in extensive modification precluding an understanding of the early events in this process. In this study, we have examined time-dependent oxidative events related to α-synuclein modification using six different molar ratios of Cu 2+ /H 2 O 2 /protein and Cu 2+ /H 2 O 2 /ascorbate/protein resulting in mild to moderate extents of oxidation. For a Cu 2+ /H 2 O 2 /protein molar ratio of 2.3:7.8:1 only low levels of carbonyls were detected (0.078 carbonyls per protein), whereas a molar ratio of 4.7:15.6:1 gave 0.22 carbonyls per α-synuclein within 15 min. With the latter conditions, rapid conversion of 3 out of 4 methionines (Met) to methionine sulfoxide, and 2 out of 4 tyrosines (Tyr) were converted to products including inter- and intra-molecular dityrosine cross-links and protein oligomers, as determined by SDS-PAGE and Western blot analysis. Limited histidine (His) modification was observed. The rapid formation of dityrosine cross-links was confirmed by fluorescence and mass-spectrometry. These data indicate that Met and Tyr oxidation are early events in Cu 2+ /H 2 O 2 -mediated damage, with carbonyl formation being a minor process. With the Cu 2+ /H 2 O 2 /ascorbate system, rapid protein carbonyl formation was detected with the first 5 min, but after this time point, little additional carbonyl formation was detected. With this system, lower levels of Met and Tyr oxidation were detected (2 Met and 1 Tyr modified with a Cu 2+ /H 2 O 2 /ascorbate/protein ratio of 2.3:7.8:7.8:1), but greater His oxidation. Only low levels of intra- dityrosine cross-links and no inter- dityrosine oligomers were detected under these conditions, suggesting that ascorbate limits Cu 2+ /H 2 O 2 -induced α-synuclein modification. Copyright © 2018. Published by Elsevier Inc.

  2. Exposure to fluoride in smelter workers in a primary aluminum industry in India.

    PubMed

    Susheela, A K; Mondal, N K; Singh, A

    2013-04-01

    Fluoride is used increasingly in a variety of industries in India. Emission of fluoride dust and fumes from the smelters of primary aluminum producing industries is dissipated in the work environment and poses occupational health hazards. To study the prevalence of health complaints and its association with fluoride level in body fluids of smelter workers in a primary aluminum producing industry. In an aluminum industry, health status of 462 smelter workers, 60 supervisors working in the smelter unit, 62 non-smelter workers (control group 1) and 30 administration staff (control group 2) were assessed between 2007 and 2009. Their health complaints were recorded and categorized into 4 groups: 1) gastro-intestinal complaints; 2) non-skeletal manifestations; 3) skeletal symptoms; and (4) respiratory problems. Fluoride level in body fluids, nails, and drinking water was tested by an ion selective electrode; hemoglobin level was tested using HemoCue. The total complaints reported by study groups were significantly higher than the control groups. Smelter workers had a significantly (p<0.001) higher urinary and serum fluoride level than non-smelter workers; the nail fluoride content was also higher in smelter workers than non-smelter workers (p<0.001). The smelter workers with higher hemoglobin level had a significantly (p<0.001) lower urinary fluoride concentration and complained less frequently of health problems. Only 1.4% of the smelter workers were consuming water with high fluoride concentrations. A high percentage of participants was using substances with high fluoride contents. Industrial emission of fluoride is not the only important sources of fluoride exposure--consumption of substance with high levels of fluoride is another important route of entry of fluoride into the body. Measurement of hemoglobin provides a reliable indicator for monitoring the health status of employees at risk of fluorosis.

  3. Effect of water fluoridation on the development of medial vascular calcification in uremic rats.

    PubMed

    Martín-Pardillos, Ana; Sosa, Cecilia; Millán, Ángel; Sorribas, Víctor

    2014-04-06

    Public water fluoridation is a common policy for improving dental health. Fluoride replaces the hydroxyls of hydroxyapatite, thereby improving the strength of tooth enamel, but this process can also occur in other active calcifications. This paper studies the effects of water fluoridation during the course of vascular calcification in renal disease. The effect of fluoride was studied in vitro and in vivo. Rat aortic smooth muscle cells were calcified with 2mM Pi for 5 days. Fluoride concentrations of 5-10 μM--similar to those found in people who drink fluoridated water--partially prevented calcification, death, and osteogene expression in vitro. The anticalcifying mechanism was independent of cell activity, matrix Gla protein, and fetuin A expressions, and it exhibited an IC50 of 8.7 μM fluoride. In vivo, however, fluoridation of drinking water at 1.5mg/L (concentration recommended by the WHO) and 15 mg/L dramatically increased the incipient aortic calcification observed in rats with experimental chronic kidney disease (CKD, 5/6-nephrectomy), fed a Pi-rich fodder (1.2% Pi). Fluoride further declined the remaining renal function of the CKD animals, an effect that most likely overwhelmed the positive effect of fluoride on calcification in vitro. Ultrastructural analysis revealed that fluoride did not modify the Ca/P atomic ratio, but it was incorporated into the lattice of in vivo deposits. Fluoride also converted the crystallization pattern from plate to rode-like structures. In conclusion, while fluoride prevents calcification in vitro, the WHO's recommended concentrations in drinking water become nephrotoxic to CKD rats, thereby aggravating renal disease and making media vascular calcification significant. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  4. Fluoride exposure and indicators of thyroid functioning in the Canadian population: implications for community water fluoridation.

    PubMed

    Barberio, Amanda M; Hosein, F Shaun; Quiñonez, Carlos; McLaren, Lindsay

    2017-10-01

    There are concerns that altered thyroid functioning could be the result of ingesting too much fluoride. Community water fluoridation (CWF) is an important source of fluoride exposure. Our objectives were to examine the association between fluoride exposure and (1) diagnosis of a thyroid condition and (2) indicators of thyroid functioning among a national population-based sample of Canadians. We analysed data from Cycles 2 and 3 of the Canadian Health Measures Survey (CHMS). Logistic regression was used to assess associations between fluoride from urine and tap water samples and the diagnosis of a thyroid condition. Multinomial logistic regression was used to examine the relationship between fluoride exposure and thyroid-stimulating hormone (TSH) level (low/normal/high). Other available variables permitted additional exploratory analyses among the subset of participants for whom we could discern some fluoride exposure from drinking water and/or dental products. There was no evidence of a relationship between fluoride exposure (from urine and tap water) and the diagnosis of a thyroid condition. There was no statistically significant association between fluoride exposure and abnormal (low or high) TSH levels relative to normal TSH levels. Rerunning the models with the sample constrained to the subset of participants for whom we could discern some source(s) of fluoride exposure from drinking water and/or dental products revealed no significant associations. These analyses suggest that, at the population level, fluoride exposure is not associated with impaired thyroid functioning in a time and place where multiple sources of fluoride exposure, including CWF, exist. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  5. Validation of a Cariogenic Biofilm Model to Evaluate the Effect of Fluoride on Enamel and Root Dentine Demineralization.

    PubMed

    Fernández, Constanza E; Tenuta, Livia M A; Cury, Jaime A

    2016-01-01

    Due to gingival recession both enamel and root dentine are at risk of developing caries. Both tissues are exposed to a similar environment, however there is not a validated model to evaluate the effect of fluoride on these dental substrates simultaneously. Hence, this study aimed to validate a caries model to evaluate the effect of fluoride to prevent demineralization on enamel and root-dentine. Streptococcus mutans UA159 biofilms were formed on saliva-coated bovine enamel and root dentine slabs (n = 12 per group) mounted in the same well of culture plates. The biofilms were exposed 8×/day to 10% sucrose and treated 2×/day with fluoridated solutions containing 0, 150, 450, or 1,350 ppm F; thus, simulating the use of low to high fluoride concentration toothpastes. The pH values of the culture medium was monitored 2×/day as a biofilm acidogenicity indicator. After 96 h, biofilms were collected for fluoride concentration analysis. The percentage of surface hardness loss (%SHL) was calculated for slabs. The fluoride uptake by the enamel and dentine was also determined. The model showed a dose-response because the biofilm and fluoride uptake increased and %SHL decreased at increasing fluoride concentrations (p < 0.05). Fluoride in the biofilm formed on dentine and fluoride uptake by dentine were higher than those for enamel. With the same fluoride concentration treatment, the percentage of reduction of demineralization was lower for dentine than for enamel. In conclusion, the model was validated in terms of a dose-response effect of fluoride on enamel and root dentine. Furthermore, the findings support the clinical data, suggesting that higher fluoride concentrations are necessary to control caries of root dentine than of enamel.

  6. Synthesis, spectroscopic characterizations, crystal structures and DFT studies of nalidixic acid carbonyl hydrazones derivatives

    NASA Astrophysics Data System (ADS)

    Bergamini, F. R. G.; Ribeiro, M. A.; Lancellotti, M.; Machado, D.; Miranda, P. C. M. L.; Cuin, A.; Formiga, A. L. B.; Corbi, P. P.

    2016-09-01

    This article describes the synthesis and characterization of the 1-ethyl-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazide (hzd) and six carbonyl hydrazones derivatives of the nalidixic with 1H-pyrrol-2-ylmethylidene (hpyrr), 1H-imidazol-2-ylmethylidene (h2imi), pyridin-2-ylmethylidene (h2py), pyridin-3-ylmethylidene (h3py), pyridin-4-ylmethylidene(h4py) and (2-hydroxyphenyl)methylidene (hsali). The carbonyl hydrazones were characterized by elemental and ESI-QTOF-MS analyses, IR and detailed NMR spectroscopic measurements. The 2D NMR experiments allowed the unambiguous assignment of the hydrogen, carbon and nitrogen atoms, which have not been reported for nalidixic acid carbonyl hydrazone derivatives so far. Crystal structures of hzd and the new carbonyl hydrazones h2imi, hpyrr and h3py were determined by X-ray diffraction studies. Although the synthesis of hzd was reported decades ago, the hzd crystal structure have not been reported yet. Geometric optimizations of all the characterized structures were performed with the aid of DFT studies. Despite the fact that the hydrazones with 2-pyridine carboxylic acid (h2py) and salicyl aldehyde (hsali) were already reported by literature, a detailed spectroscopic study followed by DFT studies are also reported for such compounds in this manuscript. Antimicrobial studies of the compounds are also presented.

  7. [Effect of fluoride on human hypothalamus-hypophysis-testis axis hormones].

    PubMed

    Hao, Pengfei; Ma, Xiaoying; Cheng, Xuemin; Ba, Yue; Zhu, Jingyuan; Cui, Liuxin

    2010-01-01

    To study of endocrine disturbing effect of fluoride on human hypothalamus-hypophysis-testis axis hormones. Sunying County, Kaifeng City was selected as polluted district which the fluoride in drinking water was 3.89 mg/L, and Shenlilou county was selected as control district which the fluoride was less than 1.0 mg/L. 150 individual lived there more than 5 years were srlected randomly. And investigated by medical examination, then blood and urine sample were collected, and the serum level of gonadotropin-releasing hormone (GnRH), luteinizing hormone (LH), testosterone (T) and estradiol (E2) were measured by RIA method, and the urine level of fluoride were measured. Other than that, the concentration of fluoride in the water, food, soil and air were detected by the standard methods. The concentrations of fluoride in the water, food and soil of the fluoride polluted district were significantly higher than those of control district (P < 0.05), and the concentration fluoride in the air of two district were not found. There was no significant difference of serum level of GnRH between fluoride polluted district and control district (P > 0.05). The serum level of LH in men of fluoride polluted district was significantly higher than that of control group (P < 0.05), and the serum level of T in men of fluoride polluted district was significantly less than that of control group (P < 0.05). There was no significant difference of serum level of LH between fluoride polluted district and control district (P > 0.05), and the serum level of T in women of fluoride polluted district was significantly higher than that of control group (P < 0.05). There was no significant difference of serum level of E2 between fluoride polluted district and control district (P > 0.05). Fluoride could effect hormone levels of each layer of the hypothalamus-hypophysis-testis axis, and show the reproductive endocrine disturbing effects. The reproductive endocrine disturbing effects of male maybe more severe than those of female.

  8. Carbonyl reduction of mequindox by chicken and porcine cytosol and cloned carbonyl reductase 1.

    PubMed

    Tang, Xianqing; Mu, Peiqiang; Wu, Jun; Jiang, Jun; Zhang, Caihui; Zheng, Ming; Deng, Yiqun

    2012-04-01

    Mequindox (MEQ) is a novel synthetic quinoxaline 1,4-dioxides derivative, which is widely used as a veterinary drug and animal feed additive. However, the metabolic mechanism of MEQ is rarely reported. The N-oxide reduction mechanism of MEQ was reported in our previous work. In this article, the toxicity and the reduction of the carbonyl of MEQ were studied. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium assays demonstrated that the carbonyl-reduced MEQ, 2-isoethanol MEQ was much less toxic than MEQ. High-performance liquid chromatography analysis showed that the cytosol extracts of chicken and pig livers were able to reduce MEQ to 2-isoethanol MEQ and the reaction was NADPH-dependent. Further study via enzyme-inhibitory experiment revealed that carbonyl reductase 1 (CBR1) participated in this metabolism. The enzyme activity analysis showed that both chicken CBR1 (cCBR1) and porcine CBR1 (pCBR1) were capable of catalyzing the carbonyl reduction of MEQ and its N-oxide reductive metabolite, 1-deoxymequindox. By comparison of the kinetic constants, we observed that the activity of cCBR1 was higher than pCBR1 to MEQ and the standard substrate of CBR1, menadione. On the other hand, both CBR1s exhibited higher activity to 1-deoxymequindox than MEQ. Mutation analysis suggested that the difference of amino acid at position 141/142 may be one possible reason that caused the activity difference between cCBR1 and pCBR1. Thus far, CBR1 was first reported to participate in the carbonyl reduction of MEQ. Our results will be helpful to recognize the metabolic pathways of quinoxaline drugs deeply and to provide a theoretical basis for controlling the negative effects of these drugs.

  9. COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

    DOEpatents

    Seaborg, G.T.

    1960-08-01

    A method is given for precipitating alkali metal plutonium fluorides. such as KPuF/sub 5/, KPu/sub 2/F/sub 9/, NaPuF/sub 5/, and RbPuF/sub 5/, from an aqueous plutonium(IV) solution by adding hydrogen fluoride and alkali-metal- fluoride.

  10. The fractional urinary fluoride excretion of adults consuming naturally and artificially fluoridated water and the influence of water hardness: a randomized trial.

    PubMed

    Villa, A; Cabezas, L; Anabalón, M; Rugg-Gunn, A

    2009-09-01

    To assess whether there was any significant difference in the average fractional urinary fluoride excretion (FUFE) values among adults consuming (NaF) fluoridated Ca-free water (reference water), naturally fluoridated hard water and an artificially (H2SiF6) fluoridated soft water. Sixty adult females (N=20 for each treatment) participated in this randomized, double-blind trial. The experimental design of this study provided an indirect estimation of the fluoride absorption in different types of water through the assessment of the fractional urinary fluoride excretion of volunteers. Average daily FUFE values (daily amount of fluoride excreted in urine/daily total fluoride intake) were not significantly different between the three treatments (Kruskal-Wallis; p = 0.62). The average 24-hour FUFE value (n=60) was 0.69; 95% C.I. 0.65-0.73. The results of this study suggest that the absorption of fluoride is not affected by water hardness.

  11. Corrosion behavior and cytocompatibility of fluoride-incorporated plasma electrolytic oxidation coating on biodegradable AZ31 alloy

    PubMed Central

    Tian, Peng; Peng, Feng; Wang, Donghui; Liu, Xuanyong

    2017-01-01

    Fluoride-incorporated plasma electrolytic oxidation (PEO) coating was fabricated on biodegradable AZ31 alloy. The surface morphologies and phases were investigated by scanning electron microscopy and X-ray diffraction. The effect of fluoride incorporation in coatings on corrosion behaviour was investigated in simulated body fluid and in vitro cytocompatibility of the coatings was also studied by evaluating cytotoxicity, adhesion, proliferation and live–dead stain of osteoblast cells (MC3T3-E1). Furthermore, the corrosion morphologies in vivo were examined. The results showed that the fluoride could be incorporated into the coating to form MgF2 phase. In vitro and in vivo degradation tests revealed that the corrosion resistance of the coating could be improved by the incorporation of fluoride, which may attribute to the chemical stability of MgF2 phase. Moreover, good cytocompatibility of fluoride-incorporated coating was confirmed with no obvious cytotoxicity, enhanced cell adhesion and proliferation. However, when the fluoride content was high, a slight inhibition of cell growth was observed. The results indicate that although fluoride incorporation can enhance the corrosion resistance of the coatings, thus resulting a more suitable environment for cells, the high content of fluoride in the coating also kill cells ascribed to the high released of fluorine. If the content of fluoride is well controlled, the PEO coating with MgF2 phase is a promising surface modification of Mg alloys. PMID:28149524

  12. Corrosion behavior and cytocompatibility of fluoride-incorporated plasma electrolytic oxidation coating on biodegradable AZ31 alloy.

    PubMed

    Tian, Peng; Peng, Feng; Wang, Donghui; Liu, Xuanyong

    2017-02-01

    Fluoride-incorporated plasma electrolytic oxidation (PEO) coating was fabricated on biodegradable AZ31 alloy. The surface morphologies and phases were investigated by scanning electron microscopy and X-ray diffraction. The effect of fluoride incorporation in coatings on corrosion behaviour was investigated in simulated body fluid and in vitro cytocompatibility of the coatings was also studied by evaluating cytotoxicity, adhesion, proliferation and live-dead stain of osteoblast cells (MC3T3-E1). Furthermore, the corrosion morphologies in vivo were examined. The results showed that the fluoride could be incorporated into the coating to form MgF 2 phase. In vitro and in vivo degradation tests revealed that the corrosion resistance of the coating could be improved by the incorporation of fluoride, which may attribute to the chemical stability of MgF 2 phase. Moreover, good cytocompatibility of fluoride-incorporated coating was confirmed with no obvious cytotoxicity, enhanced cell adhesion and proliferation. However, when the fluoride content was high, a slight inhibition of cell growth was observed. The results indicate that although fluoride incorporation can enhance the corrosion resistance of the coatings, thus resulting a more suitable environment for cells, the high content of fluoride in the coating also kill cells ascribed to the high released of fluorine. If the content of fluoride is well controlled, the PEO coating with MgF 2 phase is a promising surface modification of Mg alloys.

  13. REACTIVE CARBONYL SPECIES AND THEIR ROLES IN SARCOPLASMIC RETICULUM Ca2+ CYCLING DEFECT IN THE DIABETIC HEART

    PubMed Central

    Tian, Chengju; Alomar, Fadhel; Moore, Caronda J; Shao, Chun Hong; Kutty, Shelby; Singh, Jaipaul; Bidasee, Keshore R.

    2016-01-01

    Efficient and rhythmic cardiac contractions depend critically on the adequate and synchronized release of Ca2+ from the sarcoplasmic reticulum (SR) via ryanodine receptor Ca2+ release channels (RyR2) and its reuptake via sarco(endo)plasmic reticulum Ca2+-ATPase (SERCA2a). It is well established that this orchestrated process becomes compromised in diabetes. What remain incompletely defined are the molecular mechanisms responsible for the dysregulation of RyR2 and SERCA2a in diabetes. Earlier, found elevated levels of carbonyl adducts on RyR2 and SERCA2a isolated from hearts of type 1 diabetic rats and showed the presence of these post-translational modifications compromised their functions. We also showed that these mono- and di-carbonyl reactive carbonyl species (RCS) do not indiscriminately react with all basic amino acid residues on RyR2 and SERCA2a; some residues are more susceptible to carbonylation (modification by RCS) than others. A key unresolved question in the field is which of the many RCS that are upregulated in the heart in diabetes chemically react with RyR2 and SERCA2a? This brief review introduces readers to the field of RCS and their roles in perturbing SR Ca2+ cycling in diabetes. It also provides new experimental evidence that not all RCS that are upregulated in the heart in diabetes chemically react with RyR2 and SERCA2a, methylglyoxal and glyoxal preferentially do. PMID:23430128

  14. Cluster-randomized xylitol toothpaste trial for early childhood caries prevention.

    PubMed

    Chi, Donald L; Tut, Ohnmar; Milgrom, Peter

    2014-01-01

    The purpose of this study was to assess the efficacy of supervised tooth-brushing with xylitol toothpaste to prevent early childhood caries (ECC) and reduce mutans streptococci. In this cluster-randomized efficacy trial, 196 four- to five-year-old children in four Head Start classrooms in the Marshall Islands were randomly assigned to supervised toothbrushing with 1,400 ppm/31 percent fluoride xylitol or 1,450 ppm fluoride sorbitol toothpaste. We hypothesized that there would be no difference in efficacy between the two types of toothpaste. The primary outcome was the surface-level primary molar caries increment (d(2-3)mfs) after six months. A single examiner was blinded to classroom assignments. Two classrooms were assigned to the fluoride-xylitol group (85 children), and two classrooms were assigned to the fluoride-sorbitol group (83 children). The child-level analyses accounted for clustering. There was no difference between the two groups in baseline or end-of-trial mean d(2-3)mfs. The mean d(2-3)mfs increment was greater in the fluoride-xylitol group compared to the fluoride-sorbitol group (2.5 and 1.4 d(2-3)mfs, respectively), but the difference was not significant (95% confidence interval: -0.17, 2.37; P=.07). No adverse effects were reported. After six months, brushing with a low-strength xylitol/fluoride tooth-paste is no more efficacious in reducing ECC than a fluoride-only toothpaste in a high caries-risk child population.

  15. Identification of Anion Channels Responsible for Fluoride Resistance in Oral Streptococci

    PubMed Central

    Takeshita, Toru; Yamashita, Yoshihisa

    2016-01-01

    Recently, it has been reported that eriC and crcB are involved in bacterial fluoride resistance. However, the fluoride-resistance mechanism in oral streptococci remains unclear. BLAST studies showed that two types of eriCs (eriC1 and eriC2) and two types of crcBs (crcB1 and crcB2) are present across 18 oral streptococci, which were identified in ≥ 10% of 166 orally healthy subjects with ≥ 0.01% of the mean relative abundance. They were divided into three groups based on the distribution of these four genes: group I, only eriC1; group II, eriC1 and eriC2; and group III, eriC2, crcB1, and crcB2. Group I consisted of Streptococcus mutans, in which one of the two eriC1s predominantly affected fluoride resistance. Group II consisted of eight species, and eriC1 was responsible for fluoride resistance, but eriC2 was not, in Streptococcus anginosus as a representative species. Group III consisted of nine species, and both crcB1 and crcB2 were crucial for fluoride resistance, but eriC2 was not, in Streptococcus sanguinis as a representative species. Based on these results, either EriC1 or CrcBs play a role in fluoride resistance in oral streptococci. Complementation between S. mutans EriC1 and S. sanguinis CrcB1/CrcB2 was confirmed in both S. mutans and S. sanguinis. However, neither transfer of S. sanguinis CrcB1/CrcB2 into wild-type S. mutans nor S. mutans EriC1 into wild-type S. sanguinis increased the fluoride resistance of the wild-type strain. Co-existence of different F− channels (EriC and CrcB) did not cause the additive effect on fluoride resistance in oral Streptococcus species. PMID:27824896

  16. Carbonyls emission from ethanol-blended gasoline and biodiesel-ethanol-diesel used in engines

    NASA Astrophysics Data System (ADS)

    Pang, Xiaobing; Mu, Yujing; Yuan, Juan; He, Hong

    Detailed carbonyls emissions from ethanol-blended gasoline (containing 10% v/v, ethanol, E-10) and biodiesel-ethanol-diesel (BE-diesel) were carefully investigated on an EQ491i gasoline engine equipped with a three-way-catalyst (TWC) and a Commins-4B diesel engine. In engine-out emissions for the gasoline engine, total carbonyls from E-10 varied in the range of 66.7-99.4 mg kW -1 h -1, which was 3.1-8.2% less than those from fossil gasoline (E-0). In tailpipe emissions, total carbonyls from E-10 varied in the range of 9.2-20.7 mg kW -1 h -1, which were 3.0-61.7% higher than those from E-0. The total carbonyls emissions from BE-diesel were 1-22% higher than those from diesel at different engine operating conditions. Compared with fossil fuels, E-10 can slightly reduce CO emission, and BE-diesel can substantially decrease PM emission, while both alternative fuels increased slightly NO x emission.

  17. Unsuitability of using the DNPH-coated solid sorbent cartridge for determination of airborne unsaturated carbonyls

    NASA Astrophysics Data System (ADS)

    Ho, Steven Sai Hang; Ho, K. F.; Liu, W. D.; Lee, S. C.; Dai, W. T.; Cao, J. J.; Ip, H. S. S.

    2011-01-01

    Measurements of aldehydes and ketones are typically conducted by derivatization using sorbent cartridges coated with 2,4-dinitrophenylhydrazine (DNPH). The collected samples are eluted with acetonitrile and analyzed by high-pressure liquid chromatography coupled with an ultra-violet detector (HPLC/UV). This paper intends to examine artifacts about its suitability in identification of unsaturated carbonyls. Kinetic tests for acrolein, crotonaldehyde, methacrolein and methyl vinyl ketone (MVK) showed formations of carbonyl-DNP-hydrazone during sampling, which could further react with DNPH, resulting in undesired UV absorption products [e.g., carbonyl-DNP-hydrazone-DNPH (dimer) and 2(carbonyl-DNP-hydrazone)-DNPH (trimer)]. The dimerization and trimerization occurred for acrolein and MVK whereas only dimerization for crotonaldehyde and methacrolein. The polymerization products undoubtedly affect the integrity of the chromatogram, leading to misidentification and inaccurate quantification. Whether precautions taken during sampling and/or sample treatment could avoid or minimize this artifact has not been thoughtfully investigated. More often, such artifacts are usually overlooked by scientists when the data are reported.

  18. Development of a test method for carbonyl compounds from stationary source emissions

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

    Zhihua Fan; Peterson, M.R.; Jayanty, R.K.M.

    1997-12-31

    Carbonyl compounds have received increasing attention because of their important role in ground-level ozone formation. The common method used for the measurement of aldehydes and ketones is 2,4-dinitrophenylhydrazine (DNPH) derivatization followed by high performance liquid chromatography and ultra violet (HPLC-UV) analysis. One of the problems associated with this method is the low recovery for certain compounds such as acrolein. This paper presents a study in the development of a test method for the collection and measurement of carbonyl compounds from stationary source emissions. This method involves collection of carbonyl compounds in impingers, conversion of carbonyl compounds to a stable derivativemore » with O-2,3,4,5,6-pentafluorobenzyl hydroxylamine hydrochloride (PFBHA), and separation and measurement by electron capture gas chromatography (GC-ECD). Eight compounds were selected for the evaluation of this method: formaldehyde, acetaldehyde, acrolein, acetone, butanal, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and hexanal.« less

  19. Peroxidative oxidation of halides catalysed by myeloperoxidase. Effect of fluoride on halide oxidation.

    PubMed

    Zgliczyński, J M; Stelmaszyńska, T; Olszowska, E; Krawczyk, A; Kwasnowska, E; Wróbel, J T

    1983-01-01

    It was found that all halides can compete with cyanide for binding with myeloperoxidase. The lower is the pH, the higher is the affinity of halides. The apparent dissociation constants (Kd) of myeloperoxidase-cyanide complex were determined in the presence of F-, Cl-, Br- and I- in the pH range of 4 to 7. In slightly acidic pH (4 - 6) fluoride and chloride exhibit a higher affinity towards the enzyme than bromide and iodide. Taking into account competition between cyanide and halides for binding with myeloperoxidase the dissociation constants of halide-myeloperoxidase complexes were calculated. All halides except fluoride can be oxidized by H2O2 in the presence of myeloperoxidase. However, since fluoride can bind with myeloperoxidase, it can competitively inhibit the oxidation of other halides. Fluoride was a competitive inhibitor with respect to other halides as well as to H2O2. Inhibition constants (Ki) for fluoride as a competitive inhibitor with respect to H2O2 increased from iodide oxidation through bromide to chloride oxidation.

  20. Preparation of high density heavy metal fluoride glasses with extended ultraviolet and infra red ranges, and such high density heavy metal fluoride glasses

    NASA Technical Reports Server (NTRS)

    Martin, Steven W. (Inventor); Huebsch, Jesse (Inventor)

    2001-01-01

    A heavy metal fluoride glass composition range (in mol percent) consisting essentially of: (16-30)BaF.sub.2.(8-26)HfF.sub.4.(6-24)InF.sub.3 or GaF.sub.3.(4-16)CdF.sub.2.(6-24)YbF.sub.3.(4-22)ZnF.sub.2. In an alternative embodiment, a heavy metal fluoride glass composition range (in mol percent) comprises (16-30)BaF.sub.2.(8-26)HfF.sub.4.(6-24) of (0-24)InF.sub.3, (0-24)GaF.sub.3 and (0-19)AlF.sub.3.(1-16)CdF.sub.2.(6-24)YbF.sub.3.(4-26)ZnF.sub.2. A preferred heavy metal fluoride glass produced in accordance with the present invention comprises a composition (in mol %) and comprises about 26BaF.sub.2.18HfF.sub.4.7InF.sub.3.5GaF.sub.3.10CdF.sub.2.18YbF.sub.3. 16ZnF.sub.2. A preferred heavy metal fluoride glass has maximum thickness of most preferably about 3 mm. Another preferred heavy metal fluoride glass comprises a composition (in mol %) and comprises about 26BaF.sub.2.18HfF.sub.4.12AlF.sub.3.10CdF.sub.2.18YbF.sub.3.16ZnF.sub.2.

  1. Risk Assessment Study of Fluoride Salts: Probability-Impact Matrix of Renal and Hepatic Toxicity Markers.

    PubMed

    Usuda, Kan; Ueno, Takaaki; Ito, Yuichi; Dote, Tomotaro; Yokoyama, Hirotaka; Kono, Koichi; Tamaki, Junko

    2016-09-01

    The present risk assessment study of fluoride salts was conducted by oral administration of three different doses of sodium and potassium fluorides (NaF, KF) and zinc fluoride tetrahydrate (ZnF2 •4H2O) to male Wistar rats. The rats were divided into control and nine experimental groups, to which oral injections of 0.5 mL distilled water and 0.5 mL of fluoride solutions, respectively, were given. The dosage of fluoride compounds was adjusted to contain 2.1 mg (low-dose group, LG), 4.3 mg (mid-dose group, MG), and 5.4 mg fluoride per 200 g rat body weight (high-dose group, HG) corresponding to 5, 10, and 12.5 % of LD50 values for NaF. The 24-h urine volume, N-acetyl-β-D-glucosaminidase (NAG) and creatinine clearance (Ccr) were measured as markers of possible acute renal impact. The levels of alanine aminotransferase (ALT) and aspartate aminotransferase (AST) were determined in serum samples as markers of acute hepatic impact. The levels of serum and urinary fluoride were determined to evaluate fluoride bioavailability. The results reveal that higher doses of NaF, KF, and ZnF2 induced renal damage as indicated by higher urinary NAG (p < 0.05 with ≥90th percentile of control). High doses of ZnF2 also induced a significant Ccr decrease (p < 0.05 with ≤10th percentile of control). Low doses of NaF and mid-doses of ZnF2 induced polyuria (p < 0.05 with ≥90th percentile of control) while medium doses of NaF and low doses of KF also induced liver damage, as indicated by a high level of AST (p < 0.05 with ≥90th percentile of control). These findings suggest that oral administration of fluoride is a potential, dose-dependent risk factor of renal tubular damage.

  2. Improving Dental Health of DOD Related Persons Assigned to Okinawa by Using Fluoridated Salt in Lieu of Water Fluoridation: A Comparative Analysis

    DTIC Science & Technology

    1999-04-01

    1994-1997). During this time, the 18th Medical Group (MDG) set fluoridating the base water supply as a goal to prevent dental caries – a noble and...related personnel. Supplemental fluoride may be an effective method of improving oral health by reducing dental caries . Water and salt fluoridation ...372-5,381. 9 Colonel Canning and Mr. Noorda, “Talking Paper on Fluoridation of Kadena AB Drinking Water ,” 26 Apr 1995. 5 Chapter 2 Dental Caries The

  3. Urinary fluoride excretion in preschool children after intake of fluoridated milk and use of fluoride-containing toothpaste.

    PubMed

    Norman, M; Twetman, S; Hultgren Talvilahti, A; Granström, E; Stecksén-Blicks, C

    2017-03-01

    To assess the urinary fluoride excretion in preschool children after drinking fluoridated milk with 0.185 mg F and 0.375 mg F and to study the impact of use of fluoride toothpaste. Double-blind cross-over study. Nine healthy children, 2.5-4.5 years of age. In a randomized order, participants drank 1.5 dl milk once daily for 7 days with no fluoride added (control), 0.185 mg fluoride added and 0.375 mg fluoride added. The experiment was performed twice with (Part I) and without (Part II) parental tooth brushing with 1,000 ppm fluoride toothpaste. The fluoride content in the piped drinking water was 0.5 mg F/L. Urinary fluoride excretion. The 24-hour urinary fl uoride excretion/kg body weight varied from 0.014 mg F for the placebo intervention and non-fluoride toothpaste to 0.027 mg F for the 0.375 mg intervention with use of 1,000 ppm fluoride toothpaste. The difference compared with the placebo intervention was not statistically significant for any of the interventions when fluoride toothpaste was used (p⟩0.05) while it was statistically significantly different when non-fluoride toothpaste was used (p⟨0.05). All sources of fluoride must be considered when designing community programs. With 0.5 mg F/L in the drinking water and daily use of fluoride toothpaste, most children had a fluoride intake optimal for dental health. In this setting, additional intake of fluoride milk was within safe limits up to 0.185 mg/day while conclusions about the safety of 0.375 mg/day were uncertain. Copyright© 2017 Dennis Barber Ltd

  4. Determining the optimal fluoride concentration in drinking water for fluoride endemic regions in South India.

    PubMed

    Viswanathan, Gopalan; Jaswanth, A; Gopalakrishnan, S; Siva Ilango, S; Aditya, G

    2009-10-01

    Fluoride ion in drinking water is known for both beneficial and detrimental effects on health. The prevalence of fluorosis is mainly due to the intake of large quantities of fluoride through drinking water owing to more than 90% bioavailability. The objective of this study is to predict optimal fluoride level in drinking water for fluoride endemic regions by comprising the levels of fluoride and other water quality parameters in drinking water, prevalence of fluorosis, fluoride intake through water, food and beverages such as tea and coffee and also considering the progressive accumulation of fluoride in animal bones, by comparing with non fluoride endemic areas comprise of the same geological features with the aid of regression analysis. Result of this study shows that increase of fluoride level above 1.33 mg/l in drinking water increases the community fluorosis index (CFI) value more than 0.6, an optimum index value above which fluorosis is considered to be a public health problem. Regression plot between water fluoride and bone fluoride levels indicates that, every increase of 0.5mg/l unit of water fluoride level increases the bone fluoride level of 52 mg/kg unit within 2 to 3 years. Furthermore, the consumption of drinking water containing more than 0.65 mg/l of fluoride can raise the total fluoride intake per day more than 4 mg, which is the optimum fluoride dose level recommended for adults by the Agency for Toxic Substances and Disease Registry. From the result, the people in fluoride endemic areas in South India are advised to consume drinking water with fluoride level within the limit of 0.5 to 0.65 mg/l to avoid further fluorosis risk.

  5. Ion release and in vitro enamel fluoride uptake associated with pit and fissure sealants containing microencapsulated remineralizing agents.

    PubMed

    Burbank, Brant D; Cooper, Ryan L; Kava, Alyssa; Hartjes, Jennifer M; McHale, William A; Latta, Mark A; Gross, Stephen M

    2017-04-01

    To determine if pit-and-fissure sealants with microencapsulated remineralizing agents with sustained release of fluoride, calcium and phosphate ions could promote enamel fluoride uptake by demineralized tooth structure. Sealants that contained 5 w/w% microcapsules with aqueous solutions of 5M Ca(NO3)2 or 0.8M NaF or 6.0M K2HPO4 or a mixture of all three were prepared. Ion release profiles were measured as a function of time. Enamel fluoride uptake by demineralized tooth structure was determined. Sustained release of fluoride, calcium and phosphate ions from a sealant was demonstrated. Fluoride uptake by demineralized enamel was significantly increased compared to a control sealant manufactured without microcapsules (P< 0.01). Bovine enamel that contained 2.2±2.1 µg F/g of enamel prior to exposure to a sealant without microcapsules had 2.3±0.5 after 90 days. Enamel exposed to sealant with 5w/% NaF microcapsules went from 3.5±3.5 µg F/g of enamel prior to exposure to 148±76 after 90 days. Enamel exposed to sealant with 2 w/w% NaF, 2 w/w% Ca(NO3)2 and 1 w/w% K2HPO4 microcapsules went from 1.7±0.7 µg F/g of enamel prior to exposure to 190±137 after 90 days. Sealants with encapsulated remineralizing agents were capable of releasing biologically available fluoride, calcium, and phosphate ions. Incorporation of these microcapsules in pit and fissure sealants is a promising method for remineralization determined by enamel fluoride uptake measurements.

  6. Efficacy of calcium- and fluoride-containing materials for the remineralization of primary teeth with early enamel lesion.

    PubMed

    Memarpour, Mahtab; Soltanimehr, Elham; Sattarahmady, Naghmeh

    2015-09-01

    The aim of the study was to determine the efficacy of different products containing fluoride, calcium and phosphate for enamel remineralization in eroded primary teeth. A total of 90 sound primary canine teeth were randomly divided into 5 groups of 18 teeth each: 1) control (polished enamel), 2) 5% DuraShield sodium fluoride varnish, 3) 500 ppm fluoridated toothpaste, 4) casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) cream, and 5) Clinpro White varnish containing functionalized tri-calcium phosphate (fTCP). Enamel microhardness (EMH) was measured in all samples before and after demineralization and after 28 days of remineralization. Also 8 samples in groups 2 to 5 and four samples of sound and demineralized enamel were examined with atomic force microscopy (AFM). All data were analyzed with one-way ANOVA (p<0.05). Mean microhardness of demineralized enamel was significantly lower than in enamel at baseline (p<0.001). Remineralization significantly increased microharness in groups 2 to 5 compared to the control group (p<0.001). Percent EMH after remineralization with CPP-ACP was significantly higher than after fTCP (p=0.029), toothpaste (p< 0.001) or fluoride varnish (p<0.001); however, there was no significant difference between toothpaste and fluoride varnish (p=0.062). Microhardness increased more after fTCP treatment than after treatment with sodium fluoride varnish (p<0.001) or fluoridated toothpaste (p=0.045). AFM images showed that enamel roughness decreased most after treatment with fTCP, followed by CPP-ACP, toothpaste and fluoride varnish. The efficacy of CPP-ACP cream for remineralizing eroded enamel was greater than fluoride toothpaste, fluoride varnish or fTCP varnish. © 2015 Wiley Periodicals, Inc.

  7. Energy dispersive X-ray spectrometry study of the protective effects of fluoride varnish and gel on enamel erosion.

    PubMed

    De Carvalho Filho, Antonio Carlos Belfort; Sanches, Roberto Pizarro; Martin, Airton Abrahão; Do Espírito Santo, Ana Maria; Soares, Luís Eduardo Silva

    2011-09-01

    Dental erosion is a risk factor for dental health, introduced by today's lifestyle. Topical fluoride applications in the form of varnishes and gel may lead to deposition of fluoride on enamel. This in vitro study aimed to evaluate the effect of two fluoride varnishes and one fluoride gel on the dissolution of bovine enamel by acids. Enamel samples (72) were divided (n = 8): artificial saliva (control-G1), Pepsi Twist® (G2), orange juice (G3), Duraphat® + Pepsi Twist® (G4), Duraphat® + orange juice (G5), Duofluorid® + Pepsi Twist® (G6), Duofluorid® + orange juice (G7), fluoride gel + Pepsi Twist® (G8), and fluoride gel + orange juice (G9). Fluoride gel was applied for 4 min and the varnishes were applied and removed after 6 h. The samples were submitted to six cycles (demineralization: Pepsi Twist® or orange juice, 10 min; remineralization: saliva, 1 h). Samples were analyzed by energy-dispersive X-ray fluorescence (144 line-scanning). The amount of Ca and P decreased significantly in the samples of G2 and G3, and the Ca/P ratio decreased in G3. Mineral gain (Ca) was greater in G9 samples than in G4 > G3 > G5 > G1, and (P) greater in G7 samples than in G9 > G4-6 > G2-3. The protective effect of Duofluorid® was significantly lower than fluoride gel against orange juice. The fluoride varnishes can interfere positively with the dissolution of dental enamel in the presence of acidic beverages. Fluoride gel showed the best protection level to extrinsic erosion with low costs. Copyright © 2010 Wiley-Liss, Inc.

  8. Health effects of groundwater fluoride contamination.

    PubMed

    Nayak, Bishwajit; Roy, Madan Mohan; Das, Bhaskar; Pal, Arup; Sengupta, Mrinal Kumar; De, Shankar Prasad; Chakraborti, Dipankar

    2009-04-01

    The people in Berhait block, Sahibganj district, Jharkhand state, India, have been exposed chronically to fluoridecontaminated groundwater. Hereby, we report the clinical effects of chronic exposure to fluoride. The study population was a convenience sample of 342 adults and 258 children living in the affected area. All volunteers filled out questionnaires and were examined. Well water from the six affected villages and urine samples were analyzed for fluoride using an ion-sensitive electrode. Twenty nine percent of 89 well water samples had fluoride concentrations above the Indian permissible limit of fluoride in drinking water. Eighty-five children and 72 adults had clinical fluorosis. Urine fluoride concentrations in children were 0.758-2.88 mg/L whereas in adults they were 0.331-10.36 mg/L. Clinical effects of fluoride included abnormal tooth enamel in children; adults had joint pain and deformity of the limbs and spine, along with ligamentous calcifications and exostosis formations in seven patients. Elevated urine fluoride concentrations supported the clinical diagnosis of fluorosis. Owing to insufficient fluoride-safe wells and lack of awareness of the danger of fluoride toxicity, villagers often drink fluoride-contaminated water. Villagers of Berhait block, including children, are at risk from chronic fluoride toxicity. To combat the situation, villagers need fluoride-safe water, education, and awareness of the danger about fluoride toxicity.

  9. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation.

    PubMed

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter; Fehrmann, Rasmus

    2006-03-07

    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)2I2]-[BMIM]I-SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.

  10. 4-phenylbutyrate Mitigates Fluoride-Induced Cytotoxicity in ALC Cells

    PubMed Central

    Suzuki, Maiko; Everett, Eric T.; Whitford, Gary M.; Bartlett, John D.

    2017-01-01

    Chronic fluoride over-exposure during pre-eruptive enamel development can cause dental fluorosis. Severe dental fluorosis is characterized by porous, soft enamel that is vulnerable to erosion and decay. The prevalence of dental fluorosis among the population in the USA, India and China is increasing. Other than avoiding excessive intake, treatments to prevent dental fluorosis remain unknown. We previously reported that high-dose fluoride induces endoplasmic reticulum (ER) stress and oxidative stress in ameloblasts. Cell stress induces gene repression, mitochondrial damage and apoptosis. An aromatic fatty acid, 4-phenylbutyrate (4PBA) is a chemical chaperone that interacts with misfolded proteins to prevent ER stress. We hypothesized that 4PBA ameliorates fluoride-induced ER stress in ameloblasts. To determine whether 4PBA protects ameloblasts from fluoride toxicity, we analyzed gene expression of Tgf-β1, Bcl2/Bax ratio and cytochrome-c release in vitro. In vivo, we measured fluorosis levels, enamel hardness and fluoride concentration. Fluoride treated Ameloblast-lineage cells (ALC) had decreased Tgf-β1 expression and this was reversed by 4PBA treatment. The anti-apoptotic Blc2/Bax ratio was significantly increased in ALC cells treated with fluoride/4PBA compared to fluoride treatment alone. Fluoride treatment induced cytochrome-c release from mitochondria into the cytosol and this was inhibited by 4PBA treatment. These results suggest that 4PBA mitigates fluoride-induced gene suppression, apoptosis and mitochondrial damage in vitro. In vivo, C57BL/6J mice were provided fluoridated water for six weeks with either fluoride free control-chow or 4PBA-containing chow (7 g/kg 4PBA). With few exceptions, enamel microhardness, fluorosis levels, and fluoride concentrations of bone and urine did not differ significantly between fluoride treated animals fed with control-chow or 4PBA-chow. Although 4PBA mitigated high-dose fluoride toxicity in vitro, a diet rich in 4PBA did not attenuate dental fluorosis in rodents. Perhaps, not enough intact 4PBA reaches the rodent ameloblasts necessary to reverse the effects of fluoride toxicity. Further studies will be required to optimize protocols for 4PBA administration in vivo in order to evaluate the effect of 4PBA on dental fluorosis. PMID:28553235

  11. 4-phenylbutyrate Mitigates Fluoride-Induced Cytotoxicity in ALC Cells.

    PubMed

    Suzuki, Maiko; Everett, Eric T; Whitford, Gary M; Bartlett, John D

    2017-01-01

    Chronic fluoride over-exposure during pre-eruptive enamel development can cause dental fluorosis. Severe dental fluorosis is characterized by porous, soft enamel that is vulnerable to erosion and decay. The prevalence of dental fluorosis among the population in the USA, India and China is increasing. Other than avoiding excessive intake, treatments to prevent dental fluorosis remain unknown. We previously reported that high-dose fluoride induces endoplasmic reticulum (ER) stress and oxidative stress in ameloblasts. Cell stress induces gene repression, mitochondrial damage and apoptosis. An aromatic fatty acid, 4-phenylbutyrate (4PBA) is a chemical chaperone that interacts with misfolded proteins to prevent ER stress. We hypothesized that 4PBA ameliorates fluoride-induced ER stress in ameloblasts. To determine whether 4PBA protects ameloblasts from fluoride toxicity, we analyzed gene expression of Tgf -β 1, Bcl2 / Bax ratio and cytochrome-c release in vitro . In vivo , we measured fluorosis levels, enamel hardness and fluoride concentration. Fluoride treated Ameloblast-lineage cells (ALC) had decreased Tgf -β 1 expression and this was reversed by 4PBA treatment. The anti-apoptotic Blc2 / Bax ratio was significantly increased in ALC cells treated with fluoride/4PBA compared to fluoride treatment alone. Fluoride treatment induced cytochrome-c release from mitochondria into the cytosol and this was inhibited by 4PBA treatment. These results suggest that 4PBA mitigates fluoride-induced gene suppression, apoptosis and mitochondrial damage in vitro . In vivo , C57BL/6J mice were provided fluoridated water for six weeks with either fluoride free control-chow or 4PBA-containing chow (7 g/kg 4PBA). With few exceptions, enamel microhardness, fluorosis levels, and fluoride concentrations of bone and urine did not differ significantly between fluoride treated animals fed with control-chow or 4PBA-chow. Although 4PBA mitigated high-dose fluoride toxicity in vitro , a diet rich in 4PBA did not attenuate dental fluorosis in rodents. Perhaps, not enough intact 4PBA reaches the rodent ameloblasts necessary to reverse the effects of fluoride toxicity. Further studies will be required to optimize protocols for 4PBA administration in vivo in order to evaluate the effect of 4PBA on dental fluorosis.

  12. Urinary fluoride levels and prevalence of dental fluorosis in three Brazilian cities with different fluoride concentrations in the drinking water.

    PubMed

    Heintze, S D; Bastos, J R; Bastos, R

    1998-10-01

    Urine samples from three daytime periods were collected from 545 5-50-year-old residents of three different Brazilian cities: Garça had fluoridated drinking water since 1973, Bauru since 1975 and Itápolis was not fluoridated. Dental fluorosis was examined in 985 5-24-year-olds using the Thylstrup-Fejerskov index (TF). The subjects were asked to estimate their daily intake of liquids and frequency of beverage consumption. The analysis of 94 water samples showed high variations in the fluoride content of the drinking water. The mean fluoride concentration of the water samples in Garça was 0.9 mg/L (range 0.75-1.2), in Bauru 0.64 mg/L (range 0.01-1.3), and in Itápolis 0.02 mg/L. Mean urinary fluoride concentration was 1.31 mg/L (s 0.61) in Garça, 0.88 mg/L (s 0.49) in Bauru, and 0.39 mg/L (s 0.21) in Itápolis. Self-reported daily liquid intake was not related to urinary fluoride concentration. The mean prevalence of fluorosis was 13.3% in Garça, 6.8% in Bauru, and 1.7% in Itápolis, with mainly categories TF 1 and TF 2 being recorded. Subjects with dental fluorosis tended to show a higher mean urinary fluoride concentration but the difference was not statistically significant. The study showed that fluoride exposure measured by urinary fluoride excretion was within the range expected for the level of fluoride concentration in the drinking water. However, enamel fluorosis tended to be markedly lower than expected. This study revealed that fluoride levels in the two cities with fluoridated drinking water were variable. To optimise anticaries benefits and minimise the risk of fluorosis greater control of the fluoride dosing of the drinking water is required.

  13. An in vitro evaluation of a novel high fluoride daily mouthrinse using a combination of microindentation, 3D profilometry and DSIMS.

    PubMed

    Gracia, Louise H; Rees, Gareth D; Brown, Alan; Fowler, Christabel E

    2010-11-01

    Firstly, to evaluate the in vitro anti-erosion efficacy of a new mouthrinse formulation containing 450 ppm fluoride using profilometry and microindentation. Secondly, to compare fluoride uptake by erosive lesions from two mouthrinses containing different fluoride sources using dynamic secondary ion mass spectrometry (DSIMS). Sound human enamel was treated (60s) with mouthrinses containing different fluoride concentrations, then immersed in 1.0% citric acid pH 3.8 for either 300 s or 30 min (Studies 1 & 2 respectively). Surface roughness and erosion depth were determined profilometrically in Study 1, and surface microhardness monitored as a function of time in Study 2. Lesion rehardening was monitored following a 60 s rinse and immersion in artificial saliva for 48 h (Study 3), whilst Study 4 employed DSIMS to quantify fluoride uptake by lesions treated (60s) with rinses containing either sodium fluoride (NaF) or a NaF/Olaflur/stannous chloride combination. The test rinse (450 ppm fluoride) suppressed surface roughening and bulk tissue loss versus all comparators (p< 0.0001), except in the latter measure for the rinse containing 112 ppm fluoride. The test rinse significantly inhibited enamel surface softening versus the three rinses containing ≤112 ppm fluoride (as NaF) at 30 min (p<0.05), but was not statistically significantly different from the 225 ppm fluoride rinse. The test rinse conferred statistically superior lesion rehardening versus all comparators at both 24 and 48 h (p< 0.0001). DSIMS demonstrated statistically significantly higher fluoride uptake by incipient erosive lesions treated with the test rinse versus the NaF/Olaflur/stannous rinse. Anti-erosion efficacy was positively correlated with fluoride concentration. DSIMS showed significantly higher levels of fluoride uptake by incipient erosive lesions treated with the 450 ppm fluoride rinse versus the NaF/Olaflur/stannous rinse. Copyright © 2010 Elsevier Ltd. All rights reserved.

  14. A Decolorization Technique with Spent “Greek Coffee” Grounds as Zero-Cost Adsorbents for Industrial Textile Wastewaters

    PubMed Central

    Kyzas, George Z.

    2012-01-01

    In this study, the decolorization of industrial textile wastewaters was studied in batch mode using spent “Greek coffee” grounds (COF) as low-cost adsorbents. In this attempt, there is a cost-saving potential given that there was no further modification of COF (just washed with distilled water to remove dirt and color, then dried in an oven). Furthermore, tests were realized both in synthetic and real textile wastewaters for comparative reasons. The optimum pH of adsorption was acidic (pH = 2) for synthetic effluents, while experiments in free pH (non-adjusted) were carried out for real effluents. Equilibrium data were fitted to the Langmuir, Freundlich and Langmuir-Freundlich (L-F) models. The calculated maximum adsorption capacities (Qmax) for total dye (reactive) removal at 25 °C was 241 mg/g (pH = 2) and 179 mg/g (pH = 10). Thermodynamic parameters were also calculated (ΔH0, ΔG0, ΔS0). Kinetic data were fitted to the pseudo-first, -second and -third order model. The optimum pH for desorption was determined, in line with desorption and reuse analysis. Experiments dealing the increase of mass of adsorbent showed a strong increase in total dye removal.

  15. Effect of Coating Thickness on the Properties of TiN Coatings Deposited on Tool Steels Using Cathodic Arc Pvd Technique

    NASA Astrophysics Data System (ADS)

    Mubarak, A.; Akhter, Parvez; Hamzah, Esah; Mohd Toff, Mohd Radzi Hj.; Qazi, Ishtiaq A.

    Titanium nitride (TiN) widely used as hard coating material, was coated on tool steels, namely on high-speed steel (HSS) and D2 tool steel by physical vapor deposition method. The study concentrated on cathodic arc physical vapor deposition (CAPVD), a technique used for the deposition of hard coatings for tooling applications, and which has many advantages. The main drawback of this technique, however, is the formation of macrodroplets (MDs) during deposition, resulting in films with rougher morphology. Various standard characterization techniques and equipment, such as electron microscopy, atomic force microscopy, hardness testing machine, scratch tester, and pin-on-disc machine, were used to analyze and quantify the following properties and parameters: surface morphology, thickness, hardness, adhesion, and coefficient of friction (COF) of the deposited coatings. Surface morphology revealed that the MDs produced during the etching stage, protruded through the TiN film, resulting in film with deteriorated surface features. Both coating thickness and indentation loads influenced the hardness of the deposited coatings. The coatings deposited on HSS exhibit better adhesion compared to those on D2 tool steel. Standard deviation indicates that the coating deposited with thickness around 6.7 μm showed the most stable trend of COF versus sliding distance.

  16. A rapid, one step preparation for measuring selected free plus SO2-bound wine carbonyls by HPLC-DAD/MS.

    PubMed

    Han, Guomin; Wang, Hua; Webb, Michael R; Waterhouse, Andrew L

    2015-03-01

    Carbonyl compounds are produced during fermentation and chemical oxidation during wine making and aging, and they are important to wine flavor and color stability. Since wine also contains these compounds as α-hydroxysulfonates as a result of their reaction with sulfur dioxide, an alkaline pre-treatment requiring oxygen exclusion has been used to release these bound carbonyls for analysis. By modifying the method to hydrolyze the hydroxysulfonates with heating and acid in the presence of 2,4-dinitrophenylhydrazine (DNPH), the carbonyl compounds are simultaneously and quickly released and derivatized, resulting in a simpler and more rapid method. In addition, the method avoids air exclusion complications during hydrolysis by the addition of sulfur dioxide. The method was optimized for temperature, reaction time, and the concentrations of DNPH, sulfur dioxide and acid. The hydrazones were shown to be stable for 10 h, adequate time for chromatographic analysis by HPLC-DAD/MS. This method is demonstrated for 2-ketoglutaric acid, pyruvic acid, acetoin and acetaldehyde, wine carbonyls of very different reactivities, and it offers good specificity, high recovery and low limits of detection. This new rapid, simple method is demonstrated for the measurement of carbonyl compounds in a range of wines of different ages and grape varieties. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Design of Tribologically Enhanced Polymeric Materials for Biomedical Applications

    NASA Astrophysics Data System (ADS)

    Osaheni, Allen O.

    Anytime two surfaces are in normal contact, accompanied by tangential motion, there is potential for deterioration of one or both surfaces. Gradual wear, or the removal of surface material, is typically an undesirable event. Therefore, the need for lubrication arises to minimize the amount of shear stress that develops between opposing surfaces. This reduction in shear stress is characterized by the coefficient of friction (COF). Friction is one of the primary subjects of interest in tribology, the science of the friction and wear of articulating surfaces. A number of fascinating tribological systems can be found in nature. One example which has drawn a considerable interest is articular cartilage. This smooth white tissue lines the articulating surfaces of our joints and sustains a tremendous amount of stress while maintaining smooth joint motion and low COF. The low COF exhibited by articular cartilage is unmatched by any man-made material. The phenomenal tribological properties of this biphasic material are attributed to a combination of a unique boundary lubrication mechanism and its ability to support interstitial fluid pressurization. This dissertation details the synthesis and characterization of novel tribologically enhanced polymeric materials which show great potential for several biomedical applications. Design of these material relied on the use of biomimetic tribological mechanisms. The overarching characterization described in this investigation provides valuable insight into the physical and mechanical characteristics of these unique materials.

  18. Enhanced dynamic wedge and independent monitor unit verification.

    PubMed

    Howlett, S J

    2005-03-01

    Some serious radiation accidents have occurred around the world during the delivery of radiotherapy treatment. The regrettable incident in Panama clearly indicated the need for independent monitor unit (MU) verification. Indeed the International Atomic Energy Agency (IAEA), after investigating the incident, made specific recommendations for radiotherapy centres which included an independent monitor unit check for all treatments. Independent monitor unit verification is practiced in many radiotherapy centres in developed countries around the world. It is mandatory in USA but not yet in Australia. This paper describes development of an independent MU program, concentrating on the implementation of the Enhanced Dynamic Wedge (EDW) component. The difficult case of non centre of field (COF) calculation points under the EDW was studied in some detail. Results of a survey of Australasian centres regarding the use of independent MU check systems is also presented. The system was developed with reference to MU calculations made by Pinnacle 3D Radiotherapy Treatment Planning (RTP) system (ADAC - Philips) for 4MV, 6MV and 18MV X-ray beams used at the Newcastle Mater Misericordiae Hospital (NMMH) in the clinical environment. A small systematic error was detected in the equation used for the EDW calculations. Results indicate that COF equations may be used in the non COF situation with similar accuracy to that achieved with profile corrected methods. Further collaborative work with other centres is planned to extend these findings.

  19. Exposure to cooking oil fumes and oxidative damages: a longitudinal study in Chinese military cooks.

    PubMed

    Lai, Ching-Huang; Jaakkola, Jouni J K; Chuang, Chien-Yi; Liou, Saou-Hsing; Lung, Shih-Chun; Loh, Ching-Hui; Yu, Dah-Shyong; Strickland, Paul T

    2013-01-01

    Cooking oil fumes (COF) contain polycyclic aromatic hydrocarbons (PAHs), heterocyclic aromatic amines, benzene, and formaldehyde, which may cause oxidative damages to DNA and lipids. We assessed the relations between exposure to COF and subsequent oxidative DNA damage and lipid peroxidation among military cooks and office-based soldiers. The study population, including 61 Taiwanese male military cooks and a reference group of 37 office soldiers, collected urine samples pre-shift of the first weekday and post-shift of the fifth workday. We measured airborne particulate PAHs in military kitchens and offices and concentrations of urinary 1-OHP, a biomarker of PAH exposure, urinary 8-hydroxydeoxyguanosine (8-OHdG), a biomarkers of oxidative DNA damage, and urinary isoprostane (Isop). Airborne particulate PAHs levels in kitchens significantly exceeded those in office areas. The concentrations of urinary 1-OHP among military cooks increased significantly after 5 days of exposure to COF. Using generalized estimating equation analysis adjusting for confounding, a change in log(8-OHdG) and log(Isop) were statistically significantly related to a unit change in log(1-OHP) (regression coefficient (β), β=0.06, 95% CI 0.001-0.12) and (β=0.07, 95% CI 0.001-0.13), respectively. Exposure to PAHs, or other compounds in cooking oil fumes, may cause both oxidative DNA damage and lipid peroxidation.

  20. Combined electrocoagulation and electroflotation for removal of fluoride from drinking water.

    PubMed

    Zuo, Qianhai; Chen, Xueming; Li, Wei; Chen, Guohua

    2008-11-30

    A combined electrocoagulation (EC) and electroflotation (EF) process was proposed to remove fluoride from drinking water. Its efficacy was investigated under different conditions. Experimental results showed that the combined process could remove fluoride effectively. The total hydraulic retention time required was only 30 min. After treatment, the fluoride concentration was reduced from initial 4.0-6.0mg/L to lower than 1.0mg/L. The influent pH value was found to be a very important variable that affected fluoride removal significantly. The optimal influent pH range is 6.0-7.0 at which not only can effective defluoridation be achieved, but also no pH readjustment is needed after treatment. In addition, it was found that SO(4)(2-) had negative effect; Ca(2+) had positive effect; while Cl(-) had little effect on the fluoride removal. The EC charge loading, EF charge loading and energy consumption were 3.0 Faradays/m(3), 1.5 Faradays/m(3), and 1.2 kWh/m(3), respectively, under typical conditions where fluoride was reduced from initial 4.0 to 0.87 mg/L.

  1. Hepatocyte Growth Factor Inhibits Apoptosis by the Profibrotic Factor Angiotensin II via Extracellular Signal-regulated Kinase 1/2 in Endothelial Cells and Tissue Explants

    DTIC Science & Technology

    2010-12-01

    were subjected to SDS- polyacryl - amide gel electrophoresis and electroblotted onto nitrocellulose membrane. Membranes were blocked with 5% bovine...1 mM sodium fluoride, 0.1 mM sodium orthovanadate, 1 mM tetrasodium pyrophosphate, 2 mM phenylmethylsulfonyl fluoride, 10 g/ml leupeptin, and 10 g...buffer [50 mM Tris-HCl, 1 mM EGTA, 1% (wt/vol) CHAPS, 10% glycerol, 50 mM sodium fluoride, 1 mM sodium orthovanadate, 2 mM phenylmethylsulfonyl fluoride

  2. Spectrophotometric determination of boric acid in boron powder with curcumin

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

    Grotheer, E.W.

    1979-12-01

    A rapid and accurate method was needed to determine trace amounts of boric acid for quality control and specification testing of elemental boron. The reaction between boric acid and curcumin occurs at a measurable rate only when the curcumin molecule is protonated. Protonation takes place at the carbonyl groups in the presence of a strong acid and occurs completely and rapidly when sulfuric acid is added to a solution of curcumin in acetic acid. Spectrophotometric measurements were made. The extraction of boric acid from boron powder was found to be complete within 2h when either water or the diol solutionmore » was used. Whatman No. 40 cr 42 filter paper was used to obtain diol samples free of boron particles. The extraction efficiency of 2-ethyl-1,3-hexanediol was evaluated by adding 1 ml of 500 ppM aqueous boric acid and 1 drop of 10% NaOH to accurately weighed samples of boron powder. The water then was evaporated at room temperature and the samples were extracted with diol solution. The data obtained are included. The extraction efficiency also was evaluated by determining the boric acid content of boron which had been recovered from a previous extraction and boric acid determination. The determination of boric acid using curcumin is unaffected by the presence of other compounds, except for fluoride and nitrate ions. 2 tables. (DP)« less

  3. Specific reaction of alpha,beta-unsaturated carbonyl compounds such as 6-shogaol with sulfhydryl groups in tubulin leading to microtubule damage.

    PubMed

    Ishiguro, Kazuhiro; Ando, Takafumi; Watanabe, Osamu; Goto, Hidemi

    2008-10-15

    6-Shogaol and 6-gingerol are ginger components with similar chemical structures. However, while 6-shogaol damages microtubules, 6-gingerol does not. We have investigated the molecular mechanism of 6-shogaol-induced microtubule damage and found that the action of 6-shogaol results from the structure of alpha,beta-unsaturated carbonyl compounds. alpha,beta-Unsaturated carbonyl compounds such as 6-shogaol react with sulfhydryl groups of cysteine residues in tubulin, and impair tubulin polymerization. The reaction with sulfhydryl groups depends on the chain length of alpha,beta-unsaturated carbonyl compounds. In addition, alpha,beta-unsaturated carbonyl compounds are more reactive with sulfhydryl groups in tubulin than in 2-mercaptoethanol, dithiothreitol, glutathione and papain, a cysteine protease.

  4. Fluoride contamination and fluorosis in rural community in the vicinity of a phosphate fertilizer factory in India.

    PubMed

    Pandey, J; Pandey, U

    2011-09-01

    We studied chronic fluoride intoxication in 10 villages of Udaipur receiving F emissions from phosphate fertilizer factories. Although fluoride remained below permissible limit in most of the drinking water samples, the incidence of fluorosis in adults as well as in children was surprisingly high. Khemli appeared to be the most affected village (with >48% cases) where, about 93% of 2 h air samples contained fluoride above 2.0 μg m(-3) and crops and vegetable F ranged from 27.5 to 143.4 μg g(-1). Concentrations of fluoride and inorganic P in urine showed asynchrony and were well linked with prevalence of fluorosis. The study indicated that air-borne fluoride was the major factor for higher prevalence of fluorosis in these rural areas.

  5. Fluoride sensing by catechol-based π-electron systems.

    PubMed

    An, Byeong-Kwan; Wang, Xin; Burn, Paul L; Meredith, Paul

    2010-11-15

    We have developed new catechol-based sensors that can detect fluoride via fluorescence or optical absorption even in the presence of other halides. The level and sensitivity of detection of the sensing molecules is dependent on the chromophore length, which is controlled by the number of thiophene units (one to three) within the chromophore. The sensor with three thiophene units, (E)-2-(2,2'-terthiophen-5-yl)-3-(3,4-dihydroxyphenyl)acrylonitrile, gives the best response to fluoride. By using fluorescence measurements fluoride is detectable over the concentration range 1.7 μM to 200 μM. Importantly, when adsorbed onto a solid support the fluorescent catechol dye can be used to detect the presence of fluoride in aqueous solution.

  6. 40 CFR 141.208 - Special notice for exceedance of the SMCL for fluoride.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Drinking Water Violations § 141.208 Special notice for exceedance of the SMCL for fluoride. (a) When is the special notice to be given? Community water systems that exceed the fluoride secondary maximum contaminant..., fluoride can help prevent cavities, but children drinking water containing more than 2 milligrams per liter...

  7. 40 CFR 141.208 - Special notice for exceedance of the SMCL for fluoride.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Drinking Water Violations § 141.208 Special notice for exceedance of the SMCL for fluoride. (a) When is the special notice to be given? Community water systems that exceed the fluoride secondary maximum contaminant..., fluoride can help prevent cavities, but children drinking water containing more than 2 milligrams per liter...

  8. 40 CFR 141.208 - Special notice for exceedance of the SMCL for fluoride.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Drinking Water Violations § 141.208 Special notice for exceedance of the SMCL for fluoride. (a) When is the special notice to be given? Community water systems that exceed the fluoride secondary maximum contaminant..., fluoride can help prevent cavities, but children drinking water containing more than 2 milligrams per liter...

  9. Improved Energetic-Behaviors of Spontaneously Surface-Mediated Al Particles.

    PubMed

    Kim, Dong Won; Kim, Kyung Tae; Min, Tae Sik; Kim, Kyung Ju; Kim, Soo Hyung

    2017-07-05

    Surface-mediated Al particles are synthesized by incorporating the stable fluoride reaction of Al-F on a pure Al surface in place of natural oxides. Al particles with fluoro-polymer directly adsorbed on the surface show a considerable capability to overcome limitations caused by the surface oxide. Here, we report that Al fluoride when spontaneously formed at the poly(vinylidene fluoride)/Al interface serves as an oxidation-protecting layer while also providing an efficient combustion path along which the internal Al rapidly reacts with external oxygen atoms. Both thermal oxidation and explosion tests of the poly(vinylidene fluoride)/Al particles show superior exothermic enthalpy energy and simultaneously rapid oxidation reactivity compared to those of Al 2 O 3 passivated Al particles. It is clearly elucidated that the enhanced energetic properties of Al particles mediated by poly(vinylidene fluoride) originate from the extraordinary pyrolytic process of Al fluoride occurring at a low temperature compared to Al 2 O 3 passivated Al. Hence, these results clarify that the surface mediation of Al particles can be significantly considered as advanced technology for many energetic applications.

  10. Possibility to realize spin-orbit-induced correlated physics in iridium fluorides

    NASA Astrophysics Data System (ADS)

    Rossi, M.; Retegan, M.; Giacobbe, C.; Fumagalli, R.; Efimenko, A.; Kulka, T.; Wohlfeld, K.; Gubanov, A. I.; Moretti Sala, M.

    2017-06-01

    Recent theoretical predictions of "unprecedented proximity" of the electronic ground state of iridium fluorides to the SU(2) symmetric jeff=1 /2 limit, relevant for superconductivity in iridates, motivated us to investigate their crystal and electronic structure. To this aim, we performed high-resolution x-ray powder diffraction, Ir L3-edge resonant inelastic x-ray scattering, and quantum chemical calculations on Rb2[IrF6] and other iridium fluorides. Our results are consistent with the Mott insulating scenario predicted by Birol and Haule [Phys. Rev. Lett. 114, 096403 (2015), 10.1103/PhysRevLett.114.096403], but we observe a sizable deviation of the jeff=1 /2 state from the SU(2) symmetric limit. Interactions beyond the first coordination shell of iridium are negligible, hence the iridium fluorides do not show any magnetic ordering down to at least 20 K. A larger spin-orbit coupling in iridium fluorides compared to oxides is ascribed to a reduction of the degree of covalency, with consequences on the possibility to realize spin-orbit-induced strongly correlated physics in iridium fluorides.

  11. Severity of dental caries among 12-year-old Sudanese children with different fluoride exposure.

    PubMed

    Birkeland, J M; Ibrahim, Y E; Ghandour, I A; Haugejorden, O

    2005-03-01

    The aim of this study was to assess the effect of fluoride on the severity of caries among children exposed to different concentrations of fluoride in the drinking water and living in rural areas in the Sudan. Permanently resident schoolchildren (n = 299) aged 11-13 years from three villages were clinically examined under field conditions. The caries criterion was teeth in need of extraction or extracted; only molars were recorded. Dental fluorosis was scored on all buccal tooth surfaces by the Thylstrup and Fejerskov index. The fluoride concentrations of the drinking water were assessed in samples (n = 25) collected from wells and households. Predictors of caries were assessed by logistic regression analyses. There was no significant difference regarding age and gender distribution between the areas (P > 0.05, df = 2, Kruskal-Wallis test). The socio-economic conditions in these villages were presumed to be equal. Significantly different fluoride concentrations in the drinking water were verified by the severity of dental fluorosis. Children in Abu Delaig, drinking water with 1.0-2.0 mg fluoride/L (median = 1.8), had significantly higher caries prevalence (21% versus 8%) than in a 0.4 mg fluoride area. Area was the only significant predictor for caries; odds ratio 3.7 for children in Abu Delaig compared with the low fluoride area. There was no difference in caries prevalence between the lowest and the highest fluoride (2.9 mg) area. This study failed to demonstrate an effect of fluoride in drinking water on caries experience when the end point was molars indicated for extraction or missing because of caries.

  12. Simultaneous determination of gaseous and particulate carbonyls in air by coupling micellar electrokinetic capillary chromatography with molecular imprinting solid-phase extraction.

    PubMed

    Sun, Hui; Lai, Jia-Ping; Fung, Ying Sing

    2014-09-05

    A novel method coupling molecular imprinting solid-phase extraction (MISPE) and micellar electrokinetic capillary chromatography (MEKC) was developed to enable the hourly determination of low level of ambient carbonyls, and study their partition between gaseous phase and particulate phase. With 2,4-dinitroaniline (DNAN) as dummy imprinting template, the unreacted 2,4-Dinitrophenylhydrazine (DNPH) in sampling solution could be removed effectively using MISPE, and an average recovery of 97±5.3% (n=5) for the carbonyl-DNPH derivatives was achieved. Owing to the high enrichment due to sample clean-up, and the improvement of MEKC separation efficiency, many low abundant carbonyls could be detected by hourly in the field study. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Topical fluoride for caries prevention

    PubMed Central

    Weyant, Robert J.; Tracy, Sharon L.; Anselmo, Theresa (Tracy); Beltrán-Aguilar, Eugenio D.; Donly, Kevin J.; Frese, William A.; Hujoel, Philippe P.; Iafolla, Timothy; Kohn, William; Kumar, Jayanth; Levy, Steven M.; Tinanoff, Norman; Wright, J. Timothy; Zero, Domenick; Aravamudhan, Krishna; Frantsve-Hawley, Julie; Meyer, Daniel M.

    2015-01-01

    Background A panel of experts convened by the American Dental Association (ADA) Council on Scientific Affairs presents evidence-based clinical recommendations regarding professionally applied and prescription-strength, home-use topical fluoride agents for caries prevention. These recommendations are an update of the 2006 ADA recommendations regarding professionally applied topical fluoride and were developed by using a new process that includes conducting a systematic review of primary studies. Types of Studies Reviewed The authors conducted a search of MEDLINE and the Cochrane Library for clinical trials of professionally applied and prescription-strength topical fluoride agents—including mouthrinses, varnishes, gels, foams and pastes—with caries increment outcomes published in English through October 2012. Results The panel included 71 trials from 82 articles in its review and assessed the efficacy of various topical fluoride caries-preventive agents. The panel makes recommendations for further research. Practical Implications The panel recommends the following for people at risk of developing dental caries: 2.26 percent fluoride varnish or 1.23 percent fluoride (acidulated phosphate fluoride) gel, or a prescription-strength, home-use 0.5 percent fluoride gel or paste or 0.09 percent fluoride mouthrinse for patients 6 years or older. Only 2.26 percent fluoride varnish is recommended for children younger than 6 years. The strengths of the recommendations for the recommended products varied from “in favor” to “expert opinion for.” As part of the evidence-based approach to care, these clinical recommendations should be integrated with the practitioner's professional judgment and the patient's needs and preferences. PMID:24177407

  14. Evaluation of C4 diphosphine ligands in rhodium catalysed methanol carbonylation under a syngas atmosphere: synthesis, structure, stability and reactivity of rhodium(I) carbonyl and rhodium(III) acetyl intermediates.

    PubMed

    Lamb, Gareth; Clarke, Matthew; Slawin, Alexandra M Z; Williams, Bruce; Key, Lesley

    2007-12-21

    The carbonylation of methanol to acetic acid is a hugely important catalytic process, and there are considerable cost and environmental advantages if a process could be designed that was tolerant of hydrogen impurities in the CO feed gas, while eliminating by-products such as propionic acid and acetaldehyde altogether. This paper reports on an investigation into the application of rhodium complexes of several C(4) bridged diphosphines, namely BINAP, 1,4-bis(diphenylphosphino)butane (dppb), bis(diphenylphosphino)xylene (dppx) and 1,4-bis(dicyclohexylphosphino)butane (dcpb) as catalysts for hydrogen tolerant methanol carbonylation. An investigation into the structure, reactivity and stability of pre-catalysts and catalyst resting states of these complexes has also been carried out in order to understand the observations in catalysis. Rh(I) carbonyl halide complexes of each of the ligands have been prepared from both [Rh(2)(CO)(4)Cl(2)] and dimeric mu-Cl-[Rh(L)Cl](2) complexes. These Rh(I) carbonyl complexes are either dimeric with bridging phosphine ligands (dppb, dcpb, dppx) or monomeric chelate complexes. The reaction of the complexes with methyl iodide at 140 degrees C has been studied, which has revealed clear differences in the stability of the corresponding Rh(III) complexes. Surprisingly, the dimeric Rh(I) carbonyls react cleanly with MeI with rearrangement of the diphosphine to a chelate co-ordination mode to give stable Rh(III) acetyl complexes. The Rh acetyls for L=dppb and dppx have been fully characterised by X-ray crystallography. During the catalytic studies, the more rigid dppx and BINAP ligands were found to be nearly 5 times more hydrogen tolerant than [Rh(CO)(2)I(2)](-), as revealed by by-product analysis. The origin of this hydrogen tolerance is explained based on the differing reactivities of the Rh acetyls with hydrogen gas, and by considering the structure of the complexes.

  15. Kinetics and Mechanism of the Gas-Phase Reaction of Selected Carbonyls with Cl Atoms between 250 and 340 K

    NASA Astrophysics Data System (ADS)

    Hasson, A. S.; Algrim, L.; Abdelhamid, A.; Tyndall, G. S.; Orlando, J. J.

    2013-12-01

    Carbonyls are important products from the gas phase degradation of most volatile organic compounds. Their atmospheric reactions therefore have a significant impact on atmospheric composition, particularly in aged air masses. While the reactions of short-chain linear carbonyls are well understood, the chemistry of larger (> C6) and branched carbonyl is more uncertain. To provide insight into these reactions, the reactions of three carbonyls (methyl isopropyl ketone, MIK; di-isopropyl ketone, DIK; and diethyl ketone, DEK) with chlorine atoms were investigated between 250 and 340 K and 1 atm in the presence and absence of NOx and an HO2 source (methanol). Experiments were performed in a photochemical reactor using a combination of long-path Fourier transform infra-red spectroscopy, proton transfer reaction mass spectrometry and gas chromatography with flame ionization detection. The kinetics were studied using the relative rate technique with butanone and isopropanol as the reference compounds. The Arrhenius expression for the three rate coefficients was determined to be k(DEK+Cl) = 3.87 x 10-11e(2 × 7 kJ/mol)/RT cm3 molecules-1 s-1 , k(MIPK+Cl) = 7.20 x 10-11e(0.2× 8 kJ/mol)/RT cm3 molecules-1 s-1 , and k(DIPK+Cl) = 3.33 x 10-10e(-3× 8 kJ/mol)/RT cm3 molecules-1 s-1 . Measured reaction products accounted for 38-72 % of the reacted carbon and were consistent with strong deactivation of the carbon atom adjacent to the carbonyl group with respect to H-atom abstraction by Cl atoms. The product distributions also provide insight into radical recycling from the organic peroxy + HO2 reaction, and the relative rates of isomerization, fragmentation and reaction with O2 for carbonyl-containing alkoxy radicals. Implications of these results will be discussed.

  16. Efficacy of silver diamine fluoride as an antibacterial as well as antiplaque agent compared to fluoride varnish and acidulated phosphate fluoride gel: an in vivo study.

    PubMed

    Shah, Shalin; Bhaskar, Vijay; Venkataraghavan, Karthik; Choudhary, Prashant; Ganesh, M; Trivedi, Krishna

    2013-01-01

    Silver diamine fluoride (SDF) is already proven as an antibacterial agent in vitro. Present study was formulated to compare the efficacy of SDF as an antibacterial as well as antiplaque agent in vivo with fluoride varnish and acidulated phosphate fluoride (APF) gel. Total 123 children (male = 82, female = 41) were included in the study for a period of 18 months. Children were divided into three different groups-Group 1: SDF; Group 2: fluoride varnish; and Group 3: APF gel. All subjects were evaluated via plaque score at 6 th, 12 th, and 18 th months as well as Streptococcus mutans counts in saliva at 72 h, 6 th, 12 th, and 18 th months of follow-up. Significant reduction was found in plaque score as well as S. mutans counts irrespective of group division. On intergroup comparison, no statistically significant difference was found in plaque score, but significant reduction in S. mutans counts was found in Group 1 as compared with Groups 2 and 3, while no significant difference was found between Groups 2 and 3. In vivo application of SDF on enamel significantly decreases S. mutans counts as compared to fluoride varnish and APF gel.

  17. Surface Modification by Friction Stir Processing of Low-Carbon Steel: Microstructure Investigation and Wear Performance

    NASA Astrophysics Data System (ADS)

    Sattari, Behnoosh; Shamanian, Morteza; Salimijazi, Farshid; Salehi, Mehdi

    2018-02-01

    A low-carbon steel sheet with a thickness of 5 mm was subjected to friction stir processing (FSP) by one to four different passes. The microstructures of different regions were characterized using the optical microscopy and electron backscatter diffraction. The Vickers micro-harness was measured at the distance of 200 μm below the processed surfaces. The influence of pass numbers (PNs) on wear resistance was studied in terms of coefficients of friction (CoFs), weight losses and wear rates. SEM topographies of the worn surfaces were also studied to evaluate the wear mechanisms. Microstructure observations showed that Widmänstatten ferrite plates were formed in stir zones (SZs) and heat affected zones. As PN increased, these grains were widened due to the increment of the carbon diffusivity and lengthened because of the high heat input and microstructure anisotropy. Besides, increasing the PN causes increasing of the hardness and wear resistance, simultaneously. Specifically, the wear rate in the SZ was reduced from 2.8 × 10-2 mm3 m-1 in base metal to 0.3 × 10-2 mm3 m-1 in sample which was subjected to 4 FSP passes. However, variation in PN had no considerable effect on CoFs. Oxidative wear mechanism was observed on the worn surface of the steel and the FSPed samples while more debris was formed by increasing the PNs.

  18. A clinical investigation of the efficacy of three commercially available dentifrices for controlling established gingivitis and supragingival plaque.

    PubMed

    Singh, Surrendra; Chaknis, Patricia; DeVizio, William; Petrone, Margaret; Panagakos, Fotinos S; Proskin, Howard M

    2010-01-01

    To assess the efficacy ofa dentifrice containing 0.3% triclosan/2.0% PVM/MA copolymer/0.243% sodium fluoride for controlling established gingivitis and supragingival plaque relative to that of a dentifrice containing 0.454% stannous fluoride, sodium hexametaphosphate, and zinc lactate, and a dentifrice containing 0.243% sodium fluoride as a negative control. Following a baseline examination for gingivitis and supragingival plaque, qualifying adult male and female subjects from the Piscataway, NJ, USA area were randomized into three dentifrice groups. Subjects were instructed to brush their teeth twice daily (morning and evening) for one minute with their assigned dentifrice and a soft-bristled toothbrush. Examinations for gingivitis and supragingival plaque were repeated after six weeks of product use. One-hundred and seventy-one (171) subjects complied with the protocol and completed the study. Relative to the group using the dentifrice with 0.243% sodium fluoride alone, the 0.3% triclosan/2.0% PVM/MA copolymer/0.243% sodium fluoride group exhibited statistically significant reductions in gingival index and supragingival plaque index scores of 25.3% and 33.0%, respectively, after six weeks of product use. Similarly, relative to the group using the 0.243% sodium fluoride dentifrice, the 0.454% stannous fluoride, sodium hexametaphosphate, and zinc lactate dentifrice group exhibited statistically significant reductions in gingival index and plaque index scores of 8.1% and 14.1% after six weeks of product use. Further, relative to the 0.454% stannous fluoride, sodium hexametaphosphate, and zinc lactate dentifrice group, the 0.3% triclosan/2.0% PVM/MA copolymer/0.243% sodium fluoride dentifrice group exhibited statistically significant reductions in gingival index and plaque index scores of 18.7% and 22%, respectively. The overall results of this double-blind clinical study support the conclusion that a dentifrice containing 0.3% triclosan/2.0% PVM/MA copolymer/0.243% sodium fluoride is efficacious for the control of established gingivitis and supragingival plaque as compared to a regular fluoride dentifrice, and that it provides a greater level of efficacy for the control of gingivitis and supragingival plaque than does a dentifrice containing 0.454% stannous fluoride, sodium hexametaphosphate, and zinc lactate.

  19. Exposure to water fluoridation and caries increment.

    PubMed

    Spencer, A J; Armfield, J M; Slade, G D

    2008-03-01

    The objective of this cohort study was to examine the association between exposure to water fluoridation and the increment of dental caries in two Australian states: Queensland (Qld)--5 per cent fluoridation coverage; and South Australia (SA)--70 per cent fluoridation coverage. Stratified random samples were drawn from fluoridated Adelaide and the largely non-fluoridated rest-of-state in SA, and fluoridated Townsville and non-fluoridated Brisbane in Qld. Children were enrolled between 1991 and 1992 (SA: 5-15 yrs old, n = 9,980; Qld: 5-12 yrs old, n = 10,695). Follow-up caries status data for 3 years (+/- 1/2 year) were available on 8,183 children in SA and 6,711 children in Qld. Baseline data on lifetime exposure to fluoridated water, use of other fluorides and socio-economic status (SES) were collected by questionnaire, and tooth surface caries status by dental examinations in school dental service clinics. Higher per cent lifetime exposure to fluoridated water (6 categories: 0;1-24; 25-49; 50-74; 75-99; 100 per cent) was a significant predictor (ANOVA, p < 0.01) of lower annualised Net Caries Increment (NCI) for the deciduous dentition in SA and Qld, but only for Qld in the permanent dentition. These associations persisted in multiple linear regression analyses controlling for age, gender, exposure to other fluorides and SES (p < 0.05). Water fluoridation was effective in reducing caries increment, even in the presence of a dilution effect from other fluorides. The effect of fluoridated water consumption was strongest in the deciduous dentition and where diffusion of food and beverages from fluoridated to non-fluoridated areas was less likely.

  20. Moving Beyond Boron: The Emergence of New Linkage Chemistries in Covalent Organic Frameworks

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

    DeBlase, Catherine R.; Dichtel, William R.

    Since their discovery in 2005, covalent organic frameworks (COFs) have attracted interest as potential materials for gas storage, catalysis, energy storage, and other applications because of their ability to periodically and reliably organize designed functionality into high surface area materials. Most of the first examples relied on boron-containing linkages, which suffer from hydrolytic and oxidative instability that limit their utility. In this Perspective, we describe the trend toward more robust linkages by highlighting the design, synthesis, and properties of several recent examples. Finally, the continued development of new COF chemistries, along with improved understanding of their formation and control ofmore » their final form, will provide a means to harness their molecularly precise solidstate structures for useful purposes.« less

  1. Moving Beyond Boron: The Emergence of New Linkage Chemistries in Covalent Organic Frameworks

    DOE PAGES

    DeBlase, Catherine R.; Dichtel, William R.

    2016-06-21

    Since their discovery in 2005, covalent organic frameworks (COFs) have attracted interest as potential materials for gas storage, catalysis, energy storage, and other applications because of their ability to periodically and reliably organize designed functionality into high surface area materials. Most of the first examples relied on boron-containing linkages, which suffer from hydrolytic and oxidative instability that limit their utility. In this Perspective, we describe the trend toward more robust linkages by highlighting the design, synthesis, and properties of several recent examples. Finally, the continued development of new COF chemistries, along with improved understanding of their formation and control ofmore » their final form, will provide a means to harness their molecularly precise solidstate structures for useful purposes.« less

  2. Synthesis of 2‐Alkynoates by Palladium(II)‐Catalyzed Oxidative Carbonylation of Terminal Alkynes and Alcohols

    PubMed Central

    Cao, Qun; Hughes, N. Louise

    2016-01-01

    Abstract A homogeneous PdII catalyst, utilizing a simple and inexpensive amine ligand (TMEDA), allows 2‐alkynoates to be prepared in high yields by an oxidative carbonylation of terminal alkynes and alcohols. The catalyst system overcomes many of the limitations of previous palladium carbonylation catalysts. It has an increased substrate scope, avoids large excesses of alcohol substrate and uses a desirable solvent. The catalyst employs oxygen as the terminal oxidant and can be operated under safer gas mixtures. PMID:27305489

  3. Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

    PubMed

    Heshmat, Mojgan; Privalov, Timofei

    2017-07-06

    By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H 2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C 6 F 5 ) 3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H 2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H 2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H 2 splitting at the carbonyl carbon atom of (C 6 F 5 ) 3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C 6 F 5 ) 3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C 6 F 5 ) 3 B, as a catalyst, namely, 1) the step of H 2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C 6 F 5 ) 3 B-ketone adducts in which (C 6 F 5 ) 3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C 6 F 5 ) 3 B-alkoxide intermediate giving the (C 6 F 5 ) 3 B-alcohol adduct, and 3) the S N 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Absence of Fluoride Varnish–Related Adverse Events in Caries Prevention Trials in Young Children, United States

    PubMed Central

    Gregorich, Steven E.; Ramos-Gomez, Francisco; Braun, Patricia A.; Wilson, Anne; Albino, Judith; Tiwari, Tamanna; Harper, Maya; Batliner, Terrence S.; Rasmussen, Margaret; Cheng, Nancy F.; Santo, William; Geltman, Paul L.; Henshaw, Michelle; Gansky, Stuart A.

    2017-01-01

    Introduction Fluoride varnish is an effective prevention intervention for caries in young children. Its routine use in clinical care is supported by meta-analyses and recommended by clinical guidelines, including the US Preventive Services Task Force (B rating). This report is the first prospective systematic assessment of adverse events related to fluoride varnish treatment in young children. Methods We determined the incidence of adverse events related to fluoride varnish treatment in 3 clinical trials on the prevention of early childhood caries, conducted under the auspices of the Early Childhood Caries Collaborating Centers, an initiative sponsored by the National Institute of Dental and Craniofacial Research. Each trial incorporated use of fluoride varnish in its protocol and systematically queried all children’s parents or legal guardians about the occurrence of acute adverse events after each fluoride varnish treatment. Results A total of 2,424 community-dwelling, dentate children aged 0 to 5 years were enrolled and followed for up to 3 years. These children received a cumulative total of 10,249 fluoride varnish treatments. On average, each child received 4.2 fluoride varnish treatments. We found zero fluoride varnish–related adverse events. Conclusion Fluoride varnish was not associated with treatment-related adverse events in young children. Our findings support its safety as an effective prevention intervention for caries in young children. PMID:28207379

  5. The interaction of zinc oxide-based dental cements with aqueous solutions of potassium fluoride.

    PubMed

    Pawluk, K; Booth, S E; Coleman, N J; Nicholson, J W

    2008-09-01

    The ability of zinc oxide-based dental cements (zinc phosphate and zinc polycarboxylate) to take up fluoride from aqueous solution has been studied. Only zinc phosphate cement was found to take up any measurable fluoride after 5 h exposure to the solutions. The zinc oxide filler of the zinc phosphate also failed to take up fluoride from solution. The key interaction for this uptake was thus shown to involve the phosphate groups of the set cement. However, whether this took the form of phosphate/fluoride exchange, or the formation of oxyfluoro-phosphate groups was not clear. Fluoride uptake followed radicaltime kinetics for about 2 h in some cases, but was generally better modelled by the Elovich equation, dq(t)/dt = alpha exp(-betaq(t)). Values for alpha varied from 3.80 to 2.48 x 10(4), and for beta from 7.19 x 10(-3) to 0.1946, though only beta showed any sort of trend, becoming smaller with increasing fluoride concentration. Fluoride was released from the zinc phosphate cements in processes that were diffusion based up to M(t)/M(infinity) of about 0.4. No further release occurred when specimens were placed in fresh volumes of deionised water. Only a fraction of the fluoride taken up was re-released, demonstrating that most of the fluoride taken up becomes irreversibly bound within the cement.

  6. Spatial and temporal patterns in the fluoride content of vegetation around two aluminium smelters in the Hunter Valley, New South Wales.

    PubMed

    Bowen, S E

    1988-01-01

    Spatial and temporal patterns in the fluoride content of native vegetation around two aluminium smelters in the Hunter Valley were studied between 1982 and 1985. Foliage samples were collected every month from dominant tree, shrub and herb species located up to 15 km from each smelter and, after washing, were analysed for their fluoride concentrations. At Kurri Kurri, an established smelter, fluoride emissions varied between 10 and 15 tonnes per month, or 1.8 and 2 kg [corrected] per tonne Al produced. At Tomago, they increased rapidly during start-up, peaked at 15.2 tonnes per month (0.7 kg per tonne Al), and then fell to around 10 tonnes per month. Fluoride isopleths for Angophora bakeri and a histogram for A. costata, revealed that the main areas of impact were to the immediate north and north-east of Kurri Kurri and immediate north and south-east of Tomago. Although foliar fluoride concentrations greater than background levels extended 3 km from Kurri Kurri and 1 km from Tomago, fluoride-induced, visible injury was more limited in extent. Close to the smelters tree species accumulated more foliar fluoride than shrub species, which in turn accumulated more foliar fluoride than herb species. Foliar fluoride concentrations in tree and herb species were lowest in summer; spring peaks were also apparent at Tomago.

  7. Fluoride release from fluoride varnishes under acidic conditions.

    PubMed

    Lippert, F

    2014-01-01

    The aim was to investigate the in vitro fluoride release from fluoride varnishes under acidic conditions. Poly(methyl methacrylate) blocks (Perspex, n=3 per group) were painted with 80 ± 5 mg fluoride varnish (n=10) and placed into artificial saliva for 30 min. Then, blocks were placed into either 1% citric acid (pH 2.27) or 0.3% citric acid (pH 3.75) solutions (n=3 per solution and varnish) for 30 min with the solutions being replaced every 5 min. Saliva and acid solutions were analyzed for fluoride content. Data were analyzed using three-way ANOVA (varnish, solution, time). The three-way interaction was significant (p>0.0001). Fluoride release and release patterns varied considerably between varnishes. Fluoride release in saliva varied by a factor of more than 10 between varnishes. Some varnishes (CavityShield, Nupro, ProFluorid, Vanish) showed higher fluoride release in saliva than during the first 5 min of acid exposure, whereas other varnishes (Acclean, Enamel-Pro, MI Varnish, Vella) showed the opposite behavior. There was little difference between acidic solutions. Fluoride release from fluoride varnishes varies considerably and also depends on the dissolution medium. Bearing in mind the limitations of laboratory research, the consumption of acidic drinks after fluoride varnish application should be avoided to optimize the benefit/risk ratio.

  8. Fluoride glass compositions

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

    El-Bayoumi, O.

    1983-08-09

    This invention relates to Fluoride-based glasses that exhibit a high degree of transparency throughout the near ultraviolet visible and mid infrared portions of the spectrum. The glasses are composed of MgF2 and ZnF2 as essential compositional ingredients together with at least two other metallic fluorides from the group of YbF3, ThF4, PbF2, A1F3 and MnF2.

  9. Antibacterial effects of fluoride varnish compared with chlorhexidine plus fluoride in disabled children.

    PubMed

    Baygin, Ozgul; Tuzuner, Tamer; Kusgoz, Adem; Senel, Ahmet Can; Tanriver, Mehmet; Arslan, Ipek

    2014-01-01

    To evaluate the effects of fluoride varnish vs a combination of chlorhexidine-thymol varnish plus a gel containing chlorhexidine and fluoride on oral hygiene and caries prevention in disabled children. Ninety patients aged 3-17 years who were treated under general anaesthesia were randomly assigned into three groups as follows: group 1: Fluor Protector (0.1% fluoride varnish); group 2: Cervitec Plus (1% chlorhexidine- 1% thymol varnish) + Cervitec Gel (0.2% chlorhexidine-0.2% sodium fluoride); group 3: control (toothbrushing only). Mutans streptococci (MS) and lactobacilli (LB) levels, visible plaque index (VPI) and gingival bleeding index (GBI) were evaluated at four stages: T0, before general anaesthesia; T1, one month after treatment; T2, six months after treatment; T3, twelve months after treatment. The data were evaluated using Kruskal-Wallis and Mann-Whitney U-tests (P < 0.05). Groups 1 and 2 showed significantly lower scores than group 3 for all parameters at T1 and T2. No statistically significant difference was detected among any of the the groups at T3 (P > 0.05). The use of materials that include both fluoride and chlorhexidine as routine treatment of children with disability may increase the success of restorations by improving oral hygiene, reduce the need for future restorative treatments and thus the need for general anaesthesia.

  10. Cryopreservation of bull semen is associated with carbonylation of sperm proteins.

    PubMed

    Mostek, Agnieszka; Dietrich, Mariola Aleksandra; Słowińska, Mariola; Ciereszko, Andrzej

    2017-04-01

    Artificial insemination with cryopreserved semen enables affordable, large-scale dissemination of gametes with superior genetics. However, cryopreservation can cause functional and structural damage to spermatozoa that is associated with reactive oxygen species (ROS) production, impairment of sperm motility and decreased fertilizing potential, but little attention has been paid to protein changes. The goal of this study was to investigate the oxidative modifications (measured as carbonylation level changes) of bull spermatozoa proteins triggered by the cryopreservation process. Flow cytometry and computer-assisted sperm analysis were used to evaluate changes in viability, ROS level and motility of spermatozoa. Western blotting, in conjunction with two-dimensional electrophoresis (2D-oxyblot) and matrix-assisted laser desorption/ionization time-of-flight/time-of-flight spectrometry, was employed to identify and quantify the specifically carbonylated spermatozoa proteins. Cryopreservation decreased motility and viability but increased the number of ROS-positive cells. We identified 11 proteins (ropporin-1, outer dense fiber protein 2, glutathione S-transferase, triosephosphate isomerase, capping protein beta 3 isoform, actin-related protein M1, actin-related protein T2, NADH dehydrogenase, isocitrate dehydrogenase, cilia- and flagella-associated protein 161, phosphatidylethanolamine-binding protein 4) showing differences in protein carbonylation in response to cryopreservation. The identified proteins are associated with cytoskeleton and flagella organization, detoxification and energy metabolism. Moreover, almost all of the identified carbonylated proteins are involved in capacitation. Our results indicate for the first time that cryopreservation induces oxidation of selected sperm proteins via carbonylation. We suggest that carbonylation of sperm proteins could be a direct result of oxidative stress and potentially lead to disturbances of capacitation-involved proteins or could indicate cryopreservation-induced premature capacitation. Copyright © 2017. Published by Elsevier Inc.

  11. Determination of gaseous and particulate carbonyls (glycolaldehyde, hydroxyacetone, glyoxal, methylglyoxal, nonanal and decanal) in the atmosphere at Mt. Tai

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Okuzawa, K.; Aggarwal, S. G.; Irie, H.; Kanaya, Y.; Wang, Z.

    2013-01-01

    Gaseous and particulate semi-volatile carbonyl compounds were determined every three hours in the atmosphere of Mount Tai (elevation, 1534 m) in the North China Plain during 2-5, 23-24 and 25 June, 2006 under a clear sky condition. Using two-step filter cartridge in a series, particulate carbonyls were first collected on a quartz filter and then gaseous carbonyls were collected on a quartz filter impregnated with O-benzylhydroxylamine (BHA). After the two-step derivatization with BHA and N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), carbonyl derivatives were measured using a gas chromatography. The gaseous concentrations were obtained as follow: glycolaldehyde (range 0-1271 ng m-3, average 555 ng m-3), hydroxyacetone (0-707 ng m-3, 163 ng m-3), glyoxal (198-1396 ng m-3, 720 ng m-3), methylglyoxal (410-3170 ng m-3, 1376 ng m-3), n-nonanal (0-236 ng m-3, 71 ng m-3), and n-decanal (0-159 ng m-3, 31 ng m-3). These concentrations are among the highest ever reported in the urban and forest atmosphere. We found that gaseous carbonyls are more than 10 times more abundant than particulate carbonyls. Time-resolved variations of carbonyls did not show any a clear diurnal pattern, except for hydroxyacetone. We found that glyoxal, methylglyoxal and glycolaldehyde positively correlated with levoglucosan (a tracer of biomass burning), suggesting that a contribution from field burning of agricultural wastes (wheat crops) is significant for the bifunctional carbonyls in the atmosphere of Mt. Tai. Upward transport of the pollutants to the mountaintop from the low lands in the North China Plain is a major process to control the distributions of carbonyls in the upper atmosphere over Mt. Tai.

  12. Contrasting influence of NADPH and a NADPH-regenerating system on the metabolism of carbonyl-containing compounds in hepatic microsomes.

    PubMed

    Mazur, Christopher S; Kenneke, John F; Goldsmith, Michael-Rock; Brown, Cather

    2009-09-01

    Carbonyl containing xenobiotics may be susceptible to NADPH-dependent cytochrome P450 (P450) and carbonyl-reduction reactions. In vitro hepatic microsome assays are routinely supplied NADPH either by direct addition of NADPH or via an NADPH-regenerating system (NRS). In contrast to oxidative P450 transformations, which occur on the periphery of a microsome vesicle, intraluminal carbonyl reduction depends on transport of cofactors across the endoplasmic reticulum (ER) membrane into the lumen. Glucose 6-phosphate, a natural cofactor and component of the NRS matrix, is readily transported across the ER membrane and facilitates intraluminal NADPH production, whereas direct addition of NADPH has limited access to the lumen. In this study, we compared the effects of direct addition of NADPH and use of an NRS on the P450-mediated transformation of propiconazole and 11 beta-hydroxysteroid dehydrogenase type 1 (HSD1) carbonyl reduction of cortisone and the xenobiotic triadimefon in hepatic microsomes. Our results demonstrate that the use of NADPH rather than NRS can underestimate the kinetic rates of intraluminal carbonyl reduction, whereas P450-mediated transformations were unaffected. Therefore, in vitro depletion rates measured for a carbonyl-containing xenobiotic susceptible to both intraluminal carbonyl reduction and P450 processes may not be properly assessed with direct addition of NADPH. In addition, we used in silico predictions as follows: 1) to show that 11 beta-HSD1 carbonyl reduction was energetically more favorable than oxidative P450 transformation; and 2) to calculate chemical binding score and the distance between the carbonyl group and the hydride to be transferred by NADPH to identify other 11 beta-HSD1 substrates for which reaction kinetics may be underestimated by direct addition of NADPH.

  13. Successful fluoride plebiscite in the township of Deniliquin, New South Wales, Australia.

    PubMed

    Sivaneswaran, Shanti; Chong, Gabriel T F; Blinkhorn, Anthony S

    2010-01-01

    This article describes the strategies adopted to influence the outcome of a plebiscite held in March 2004 in favor of water fluoridation in Deniliquin, a rural town in New South Wales, Australia. The health promotion strategies undertaken included the following: a) the skillful use of media to educate the community on the benefits of water fluoridation; b) disseminating contemporary local data to demonstrate oral health disparities with neighboring fluoridated townships; and c) a well-established lobbying machine to mobilize the community. Out of a total population of 5,280 on the electoral roll, 4,539 residents voted, giving a response rate of 86 percent. The wording of the plebiscite was "Do you support the addition of fluoride to Deniliquin town water supply?" There were 2,533 "yes" votes (55.8 percent), 1,879 "no" votes (41.4 percent), and 127 spoiled votes (2.8 percent). The council resolved to implement water fluoridation and the residents received fluoridated water in January 2005.

  14. Fluoride ion encapsulation by Mg2+ and phosphates in a fluoride riboswitch

    PubMed Central

    Ren, Aiming; Rajashankar, Kanagalaghatta R.; Patel, Dinshaw J.

    2012-01-01

    Significant advances in our understanding of RNA architecture, folding and recognition have emerged from structure-function studies on riboswicthes, non-coding RNAs whose sensing domains bind small ligands and whose adjacent expression platforms contain RNA elements involved in the control of gene regulation. We now report on the ligand-bound structure of the Thermotoga petrophila fluoride riboswitch, which adopts a higher-order RNA architecture stabilized by pseudoknot and long-range reversed Watson-Crick and Hoogsteen A•U pair formation. The bound fluoride ion is encapsulated within the junctional architecture, anchored in place through direct coordination to three Mg2+ ions, which in turn are octahedrally coordinated to waters and five inwardly-pointing backbone phosphates. Our structure of the fluoride riboswitch in the bound state defines how RNA can form a binding pocket selective for fluoride, while discriminating against larger halide ions. The T. petrophila fluoride riboswitch most likely functions in gene regulation through a transcription termination mechanism. PMID:22678284

  15. Sub-ablative Er,Cr:YSGG laser irradiation under all-ceramic restorations: effects on demineralization and shear bond strength.

    PubMed

    Bağlar, Serdar

    2018-01-01

    This study evaluated the caries resistant effects of sub-ablative Er,Cr:YSGG laser irradiation alone and combined with fluoride in comparison with fluoride application alone on enamel prepared for veneer restorations. And also, evaluated these treatments' effects on the shear bond strength of all-ceramic veneer restorations. One hundred and thirty-five human maxillary central teeth were assigned to groups of 1a-control, 1b-laser treated, 1c-fluoride treated, 1d-laser + fluoride treated for shear bond testing and to groups of 2a-positive control(non-demineralised), 2b-laser treated, 2c-fluoride treated, 2d-laser + fluoride treated, 2e-negative control (demineralised) for microhardness testing (n = 15, N = 135). Demineralisation solutions of microhardness measurements were used for the ICP-OES elemental analysis. The parameters for laser irradiation were as follows: power output, 0.25 W; total energy density, 62.5 J/cm 2 and energy density per pulse, 4.48 J/cm 2 with an irradiation time of 20 s and with no water cooling. Five percent NaF varnish was used as fluoride preparate. ANOVA and Tukey HSD tests were performed (α = 5%). Surface treatments showed no significant effects on shear bond strength values (p = 0.579). However, significant differences were found in microhardness measurements and in elemental analysis of Ca and P amounts (p < 0.01). Surface-treated groups showed significantly high VNH values and significantly low ICP-OES values when compared with non-treated (-control) group while there were no significance among surface-treated groups regarding VHN and ICP-OES values. Sub-ablative Er,Cr:YSGG treatment alone or combined with fluoride is as an effective method as at least fluoride alone for preventing the prepared enamel to demineralization with no negative effect on shear bond strength.

  16. Influences of sampling volume and sample concentration on the analysis of atmospheric carbonyls by 2,4-dinitrophenylhydrazine cartridge.

    PubMed

    Pal, Raktim; Kim, Ki-Hyun

    2008-03-10

    In this study, the analytical bias involved in the application of the 2,4-dinitrophenylhydrazine (2,4-DNPH)-coated cartridge sampling method was investigated for the analysis of five atmospheric carbonyl species (i.e., acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde). In order to evaluate the potential bias of the sampling technique, a series of the laboratory experiments were conducted to cover a wide range of volumes (1-20 L) and concentration levels (approximately 100-2000 ppb in case of acetaldehyde). The results of these experiments were then evaluated in terms of the recovery rate (RR) for each carbonyl species. The detection properties of these carbonyls were clearly distinguished between light and heavy species in terms of RR and its relative standard error (R.S.E.). It also indicates that the studied analytical approach can yield the most reliable pattern for light carbonyls, especially acetaldehyde. When these experimental results were tested further by a two-factor analysis of variance (ANOVA), the analysis based on the cartridge sampling method is affected more sensitively by the concentration levels of samples rather than the sampling volume.

  17. Contrasting recovery patterns of 2, 4-dinitrophenylhydrazones (DNPH) derivative of carbonyls between liquid and gas phase standards using HPLC-based analysis

    NASA Astrophysics Data System (ADS)

    Saha, Subbroto Kumar; Jo, Sang-Hee; Song, Hee-Nam; Brown, Richard J. C.; Kim, Ki-Hyun

    2012-12-01

    This study evaluates the relative recovery (RR) of five different carbonyls (CCs) (i.e., acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde) following their reaction as 2, 4-dinitrophenylhydrazine (DNPH) derivatives when using gas phase and liquid phase standards. To this end, relative efficiency of CC-DNPH derivatization is compared between two liquid-phase standards (commercially available vs. lab made mixture) and between liquid and gas-phase standard. If the results are compared in terms of response factors (RF) derived for five carbonyls from all different standard phases, the recovery of gaseous CC standard was distinguished from that of liquid counterparts. The RR of the heavier carbonyls (propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde) was approximately 60% low relative to their liquid counterparts; however, it was not the case for the lighter carbonyls (acetaldehyde) with the RR of ˜92%. This study thus suggests that the quantification of heavy carbonyls in ambient air, unless made by standards of the same matrix (i.e., gas phase) or compensated by the proper correction factor, may be subject to a large bias due to difference in derivatization reaction efficiency between matrix types. Hence, consideration of the matrix effect at the calibration stage is of particular importance to measure CC quantitatively.

  18. Determination of acrolein and other carbonyls in cigarette smoke using coupled silica cartridges impregnated with hydroquinone and 2,4-dinitrophenylhydrazine.

    PubMed

    Uchiyama, Shigehisa; Inaba, Yohei; Kunugita, Naoki

    2010-06-25

    A new method for the determination of acrolein and other carbonyls in cigarette smoke using a dual cartridge system has been developed. Each cartridge consists of reagent-impregnated silica particles. The first contains hydroquinone (HQ) for the inhibition of acrolein polymerization, while the second contains 2,4-dinitrophenylhydrazine (DNPH) for the derivatization of carbonyls. Smoke samples were firstly drawn through the cartridge containing HQ-impregnated silica (HQ-silica) and then through the DNPH-impregnated silica (DNPH-silica). Acrolein in the sample was completely trapped in the first HQ-silica cartridge. Some other airborne carbonyls were also trapped by the HQ-silica, and those that pass through were trapped in the second DNPH-silica cartridge. Extraction was performed in the reverse direction to air sampling. When solvent was eluted through the dual-cartridges, excess DNPH was washed into the HQ bed where it reacted with acrolein and other trapped carbonyls to form the corresponding hydrazone derivatives. All of the hydrazones derived from airborne carbonyls were completely separated and measured using high-performance liquid chromatography. This HQ-DNPH-method can be applied for the determination of acrolein and other alpha,beta-unsaturated aldehydes, such as crotonaldehyde, in cigarette smoke. Copyright 2010 Elsevier B.V. All rights reserved.

  19. Cytochemical demonstration of oxidative damage in Alzheimer disease by immunochemical enhancement of the carbonyl reaction with 2,4-dinitrophenylhydrazine.

    PubMed

    Smith, M A; Sayre, L M; Anderson, V E; Harris, P L; Beal, M F; Kowall, N; Perry, G

    1998-06-01

    Formation of carbonyls derived from lipids, proteins, carbohydrates, and nucleic acids is common during oxidative stress. For example, metal-catalyzed, "site-specific" oxidation of several amino acid side-chains produces aldehydes or ketones, and peroxidation of lipids generates reactive aldehydes such as malondialdehyde and hydroxynonenal. Here, using in situ 2,4-dinitrophenylhydrazine labeling linked to an antibody system, we describe a highly sensitive and specific cytochemical technique to specifically localize biomacromolecule-bound carbonyl reactivity. When this technique was applied to tissues from cases of Alzheimer disease, in which oxidative events including lipoperoxidative, glycoxidative, and other oxidative protein modifications have been reported, we detected free carbonyls not only in the disease-related intraneuronal lesions but also in other neurons. In marked contrast, free carbonyls were not found in neurons or glia in age-matched control cases. Importantly, this assay was highly specific for detecting disease-related oxidative damage because the site of oxidative damage can be assessed in the midst of concurrent age-related increases in free carbonyls in vascular basement membrane that would contaminate biochemical samples subjected to bulk analysis. These findings demonstrate that oxidative imbalance and stress are key elements in the pathogenesis of Alzheimer disease.

  20. Observation of Intermolecular Hydrogen Bonding Interactions in Biosynthesized and Biodegradable Poly [(R)-3-hydroxybutyrate- co-(R)-3-hydroxyhexanoate] in Chloroform and 1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP).

    PubMed

    Sobieski, Brian J; Noda, Isao; Rabolt, John F; Chase, D Bruce

    2017-10-01

    In this work, we describe polymer-solvent interactions in biosynthesized and biodegradable poly[(R)-3-hydroxybutyrate- co-(R)-3-hydroxyhexanoate] (PHBHx) and the atactic homopolymer, poly(3-hydroxybutyrate) (a-PHB), which were studied both as neat polymers and in solutions of chloroform and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). Specifically, infrared frequency shifts of the carbonyl band were observed in semi-crystalline PHBHx, but not in a-PHB, because it cannot form the helical conformation required for crystallization. The carbonyl band of PHBHx exhibited the high frequency associated with amorphous structure in chloroform and the lower frequency traditionally attributed to the helical crystalline structure in HFIP. The same results were obtained for a-PHB, demonstrating that the helical structure is not required for a lower frequency carbonyl-stretching mode. It is proposed that the band shift is due to hydrogen bonding between the carbonyl and hydroxyl hydrogen in HFIP. Therefore, the carbonyl frequency observed upon crystallization is most likely due to hydrogen bonding between the carbonyl and methyl hydrogen of the neighboring polymer chain in the crystal lattice as previously suggested.

  1. 40 CFR 60.192 - Standard for fluorides.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standard for fluorides. 60.192 Section... Plants § 60.192 Standard for fluorides. (a) On and after the date on which the initial performance test... total fluorides, as measured according to § 60.195, in excess of: (1) 1.0 kg/Mg (2.0 lb/ton) of aluminum...

  2. 40 CFR 60.232 - Standard for fluorides.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standard for fluorides. 60.232 Section... Industry: Triple Superphosphate Plants § 60.232 Standard for fluorides. On and after the date on which the... gases which contain total fluorides in excess of 100 g/megagram (Mg) of equivalent P2O5 feed (0.20 lb...

  3. 40 CFR 60.192 - Standard for fluorides.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 6 2011-07-01 2011-07-01 false Standard for fluorides. 60.192 Section... Plants § 60.192 Standard for fluorides. (a) On and after the date on which the initial performance test... total fluorides, as measured according to § 60.195, in excess of: (1) 1.0 kg/Mg (2.0 lb/ton) of aluminum...

  4. 40 CFR 60.232 - Standard for fluorides.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 6 2011-07-01 2011-07-01 false Standard for fluorides. 60.232 Section... Industry: Triple Superphosphate Plants § 60.232 Standard for fluorides. On and after the date on which the... gases which contain total fluorides in excess of 100 g/megagram (Mg) of equivalent P2O5 feed (0.20 lb...

  5. 40 CFR 60.222 - Standard for fluorides.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 6 2011-07-01 2011-07-01 false Standard for fluorides. 60.222 Section... Industry: Diammonium Phosphate Plants § 60.222 Standard for fluorides. (a) On and after the date on which... facility any gases which contain total fluorides in excess of 30 g/megagram (Mg) of equivalent P2O5 feed (0...

  6. 40 CFR 60.212 - Standard for fluorides.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 6 2011-07-01 2011-07-01 false Standard for fluorides. 60.212 Section... Industry: Superphosphoric Acid Plants § 60.212 Standard for fluorides. (a) On and after the date on which... facility any gases which contain total fluorides in excess of 5.0 g/megagram (Mg) of equivalent P2O5 feed...

  7. 40 CFR 60.222 - Standard for fluorides.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standard for fluorides. 60.222 Section... Industry: Diammonium Phosphate Plants § 60.222 Standard for fluorides. (a) On and after the date on which... facility any gases which contain total fluorides in excess of 30 g/megagram (Mg) of equivalent P2O5 feed (0...

  8. 40 CFR 60.212 - Standard for fluorides.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standard for fluorides. 60.212 Section... Industry: Superphosphoric Acid Plants § 60.212 Standard for fluorides. (a) On and after the date on which... facility any gases which contain total fluorides in excess of 5.0 g/megagram (Mg) of equivalent P2O5 feed...

  9. Fluoride and sulfur dioxide indoor pollution situation and control in coal-burning endemic area in Zhaotong, Yunnan, China

    NASA Astrophysics Data System (ADS)

    Liu, Yonglin; Luo, Kunli; Li, Ling; Shahid, Muhammad Zeeshaan

    2013-10-01

    The presented study aims to investigate the gaseous fluoride and sulfur dioxide (SO2) pollution level in the kitchen, traditional flue-curing barn and outdoor environment and to find economically feasible method to reduce fluorine and sulfur release. The gaseous fluoride and SO2 concentrations in air of outdoor environment, kitchen and traditional flue-curing barn were determined in 56 households in coal-burning endemic fluorosis areas of Zhaotong. Among these, 21 households in Yujiawan Village, Zhenxiong County, Zhaotong City were chosen for this experiment to reduce gaseous fluoride and SO2 concentration in traditional flue-curing barn air by using calcined dolomitic siliceous limestone (CDSL) instead of clay mixed with coal. The result showed that: (1) gaseous fluoride and SO2 concentration in the outdoor air in Mangbu Township area was 0.51 μg dm-2ṡday and <0.05 mg m-3, respectively and in Xiaolongdong Township was 2.7 μg dm-2 day and <0.05 mg m-3, respectively while in Zhaotong City these concentration were lower than the ambient air standard (3 μg dm-2ṡday and 0.5 mg m-3, respectively). (2) The indoor gaseous fluoride concentration (3.7 μg m-3) in air of kitchen with the improved coal stove was within the reference value (10 μg m-3); SO2 concentration (0.94 mg m-3) in kitchen air had decline, but its concentration was still higher than indoor air quality standard (0.5 mg m-3). (3) Average concentration of gaseous fluoride and SO2 in air of traditional flue-curing barn of Xiaolongdong Township was 7.2 μg m-3 and 6.8 mg m-3 respectively, and in Yujiawan village were 10.1 μg m-3 and 14.4 mg m-3, respectively. (4) After using the calcined dolomitic siliceous limestone instead of clay mixed with coal, gaseous fluoride and SO2 concentration in the traditional flue-curing barn air decreased of 45% and 91%, respectively. The gaseous fluoride and SO2 pollution in the traditional flue-curing barn is very serious. The corn and chili baked by open stoves in traditional flue-curing barn (baking room) was also seriously polluted by fluoride and sulfur. After using the calcined dolomitic siliceous limestone instead of clay mixed with coal, gaseous fluoride and SO2 concentration in the traditional flue-curing barn air have declined markedly. The way of adding calcined dolomitic siliceous limestone instead of clay as a binder for briquette-making is an economically feasible way to control the indoor pollution of fluorine and sulfur in coal-burning endemic in Zhaotong, Yunnan.

  10. 14 CFR 1216.301 - Applicability.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... fall within any of the four NASA budget categories: Research and Development (R&D), Construction of Facilities (CoF), Research and Program Management (R&PM), and Space Flight Control and Data Communications...

  11. Enamel-Caries Prevention Using Two Applications of Fluoride-Laser Sequence.

    PubMed

    Noureldin, Amal; Quintanilla, Ines; Kontogiorgos, Elias; Jones, Daniel

    2016-03-01

    Studies demonstrated a significant synergism between fluoride and laser in reduction of enamel solubility. However, minimal research has focused on testing the sequence of their application and no other research investigated the preventive effect of repeated applications of a combined treatment. This study investigated the effect of two applications of fluoride-laser sequence on the resistance of sound enamel to cariogenic challenge compared to one-time application. Sixty enamel slabs were cut from 10 human incisors, ground flat, polished and coated with nail varnish except a 2 x 2 mm window. Specimens were randomly assigned into five groups of 12 specimens; (CON-) negative-control received no treatment, (CON+) positive-control received pH challenge, (FV) treated with M fluoride varnish, (F-L1) one-application fluoride-varnish followed by CO2 laser-treatment (short-pulsed 10.6 µm, 2.4J/ cm2, 10HZ, 10sec), and (F-L2) two-applications of fluoride varnish-laser treatment. Specimens were left in distilled water for one day between applications. Except CON-, all groups were submitted to pH cycling for 9-days (8 demin/ remin + 1 day remineralisation bath) at 37°C. Enamel demineralization was quantitatively evaluated by measurement of Knoop surface-microhardness (SM H) (50-grams/10 seconds). Data were analyzed using one-way ANOVA (p ≤ 0.05) followed by Duncan's Multiple Range Test. Within the limitations of this study, it was found that one or two applications of fluoride-laser sequence significantly improved resistance of the sound enamel surface to acid attack compared to FV-treated group. Although the two applications of fluoride-laser sequence (F-L1 and F-L2) showed higher SMH values, significant resistance to demineralization was only obtained with repeated applications.

  12. The effect of CO2 laser irradiation plus fluoride dentifrice on the inhibition of secondary caries on root surfaces adjacent to glass ionomer cement or composite resin restorations

    NASA Astrophysics Data System (ADS)

    Rodrigues, S. R.; Moraes, M.; Hanashiro, F. S.; Youssef, M. N.; Brugnera Junior, A.; Nobre-dos-Santos, M.; de Souza-Zaroni, W. C.

    2016-02-01

    Although the cariostatic effects of CO2 laser on the root surface have been shown, there is scarce information regarding its effects on root secondary caries. The objective of this research was to investigate the effect of the association of CO2 laser and a fluoride dentifrice on the inhibition of secondary caries on root surfaces adjacent to composite-resin or glass-ionomer-cement restorations. Dental blocks of human roots were divided into two groups: composite resin (CR) or glass ionomer cement (GIC). Subsequently, the blocks were divided into four subgroups (n  =  10): C, non-fluoride dentifrice; FD, fluoride dentifrice; L, CO2 laser with an energy density of 6.0 J cm-2  +  non-fluoride dentifrice; and L  +  FD, CO2 laser  +  fluoride dentifrice. The blocks were subjected to pH cycling to simulate a high cariogenic challenge. Dental demineralization around the restorations was quantified by microhardness analysis. The results were subjected to analysis of variance (ANOVA) and the Tukey-Kramer test (p  ⩽  0.05). As for mineral loss, it can be observed that all the groups that were treated with a fluoride dentifrice and laser, used alone or not, were statistically similar and superior to the RC-C group. It was concluded that CO2 laser irradiation and a fluoride dentifrice used alone or combined with each other are efficient surface treatments for preventing secondary root caries, regardless of the restorative material used.

  13. Preparation of Ti3C2 and Ti2C MXenes by fluoride salts etching and methane adsorptive properties

    NASA Astrophysics Data System (ADS)

    Liu, Fanfan; Zhou, Aiguo; Chen, Jinfeng; Jia, Jin; Zhou, Weijia; Wang, Libo; Hu, Qianku

    2017-09-01

    Here we reported the preparation of Ti3C2 MXene and Ti2C MXene by etching Ti3AlC2 and Ti2AlC with various fluoride salts in hydrochloric acid (HCl), including lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), and ammonium fluoride (NH4F). As-prepared Ti2C was further delaminated by urea, dimethylsulfoxide or ammonium hydroxide. Based on theoretical calculation and XPS results, the type of positive ions (Li+, Na+, K+, or NH4+) in etchant solution affect the surface structure of prepared MXene, which, in turn, affects the methane adsorption properties of MXene. The highest methane adsorption capacity is 8.5 cm3/g for Ti3C2 and 11.6 cm3/g for Ti2C. MXenes made from LiF and NH4F can absorb methane under high pressure and can keep methane under normal pressure, these MXenes may have important application on capturing methane or other hazardous gas molecules. MXenes made from NaF and KF can absorb methane under high pressure and release methane under low pressure. They can have important application in the adsorb storage of nature gas.

  14. A prospective study of floor surface, shoes, floor cleaning and slipping in US limited-service restaurant workers.

    PubMed

    Verma, Santosh K; Chang, Wen Ruey; Courtney, Theodore K; Lombardi, David A; Huang, Yueng-Hsiang; Brennan, Melanye J; Mittleman, Murray A; Ware, James H; Perry, Melissa J

    2011-04-01

    Slips and falls are a leading cause of injury at work. Few studies, however, have systematically examined risk factors of slipping outside the laboratory environment. This study examined the association between floor surface characteristics, slip-resistant shoes, floor cleaning frequency and the risk of slipping in limited-service restaurant workers. 475 workers from 36 limited-service restaurants from three major chains in six states in the USA were recruited to participate in a prospective cohort study of workplace slipping. Kitchen floor surface roughness and coefficient of friction (COF) were measured in eight working areas and then averaged within each restaurant. The use of slip-resistant shoes was determined by examining the participant's shoes and noting the presence of a 'slip-resistant' marking on the sole. Restaurant managers reported the frequency of daily kitchen floor cleaning. Participants reported their slip experience and work hours weekly for up to 12 weeks. The survey materials were made available in three languages: English, Spanish and Portuguese. The associations between rate of slipping and risk factors were assessed using a multivariable negative binomial generalised estimating equation model. The mean of individual slipping rate varied among the restaurants from 0.02 to 2.49 slips per 40 work hours. After adjusting for age, gender, BMI, education, primary language, job tenure and restaurant chain, the use of slip-resistant shoes was associated with a 54% reduction in the reported rate of slipping (95% CI 37% to 64%), and the rate of slipping decreased by 21% (95% CI 5% to 34%) for each 0.1 increase in the mean kitchen COF. Increasing floor cleaning frequency was significantly associated with a decreasing rate of slipping when considered in isolation but not after statistical adjustment for other factors. These results provide support for the use of slip-resistant shoes and measures to increase COF as preventive interventions to reduce slips, falls and injuries.

  15. Periodontal health status among permanent residents of low, optimum and high fluoride areas in Kolar District, India.

    PubMed

    Megalamanegowdru, Jayachandra; Ankola, Anil V; Vathar, Jagadishchandra; Vishwakarma, Prashanthkumar; Dhanappa, Kirankumar B; Balappanavar, Aswini Y

    2012-01-01

    To assess and compare the periodontal health status among permanent residents of low, optimum and high fluoride areas in Kolar District, India. A house-to-house survey was conducted in a population consisting of 925 permanent residents aged 35 to 44 years in three villages having different levels of fluoride concentrations in the drinking water. The fluoride concentrations in selected villages were 0.48 ppm (low), 1.03 ppm (optimum) and 3.21 ppm (high). The ion selective electrode method was used to estimate the fluoride concentration in the drinking water. Periodontal status was assessed using the Community Periodontal Index (CPI) and loss of attachment (LOA). Results were analysed using the chi-square test and logistic regression. The chi-square test was used to find the group differences and logistic regression to find association between the variables. The overall prevalence of periodontitis was 72.9%; specifically, prevalences were 95.4%, 76.3% and 45.7% in low, optimum and high fluoride areas, respectively. The number of sextants with shallow or deep pockets decreased (shallow pockets: 525, 438, 217; deep pockets: 183, 81, 34) from low to high fluoride areas (odds ratio: 71.3). The low fluoride area had a 7.9-fold higher risk of periodontitis than the optimum fluoride area and a 30-fold higher risk than the high fluoride area, which was highly significant (χ2 = 53.5, P < 0.0001 and χ2 = 192.8, P < 0.001, respectively). The severity of periodontal disease is inversely associated with the fluoride concentrations in drinking water. This relation can provide an approach to fluoride treatments to reduce the prevalence or incidence of this disease.

  16. Spatial and temporal variability of fluoride concentrations in groundwater resources of Larestan and Gerash regions in Iran from 2003 to 2010.

    PubMed

    Amini, Hassan; Haghighat, Gholam Ali; Yunesian, Masud; Nabizadeh, Ramin; Mahvi, Amir Hossein; Dehghani, Mohammad Hadi; Davani, Rahim; Aminian, Abd-Rasool; Shamsipour, Mansour; Hassanzadeh, Naser; Faramarzi, Hossein; Mesdaghinia, Alireza

    2016-02-01

    There is discrepancy about intervals of fluoride monitoring in groundwater resources by Iranian authorities. Spatial and temporal variability of fluoride in groundwater resources of Larestan and Gerash regions in Iran were analyzed from 2003 to 2010 using a geospatial information system and the Mann-Kendall trend test. The mean concentrations of fluoride for the 8-year period in the eight cities and 31 villages were 1.6 and 2.0 mg/l, respectively; the maximum values were 2.4 and 3.8 mg/l, respectively. Spatial, temporal, and spatiotemporal variability of fluoride in overall groundwater resources were relatively constant over the years. However, results of the Mann-Kendall trend test revealed a monotonic trend in the time series of one city and 11 villages for the 8-year period. Specifically, one city and three villages showed positive significant Kendall's Tau values, suggesting an upward trend in fluoride concentrations over the 8-year period. In contrast, seven villages displayed negative significant Kendall's Tau values, arguing for a downward trend in fluoride concentrations over the years. From 2003 to 2010, approximately 52 % of the Larestan and Gerash areas have had fluoride concentrations above the maximum permissible Iranian drinking water standard fluoride level (1.4 mg/l), and about 116,000 people were exposed to such excess amounts. Therefore, our study supports for a close monitoring of fluoride concentrations from health authorities in monthly intervals, especially in villages and cities that showed positive trend in fluoride concentrations. Moreover, we recommend simultaneous implementation of cost-effective protective measures or interventions until a standard fluoride level is achieved.

  17. Effect of eliminating the residual fluoride gel on titanium bracket corrosion.

    PubMed

    Khoury, Elie S; Abboud, Maher; Bassil-Nassif, Nayla; Bouserhal, Joseph

    2011-09-01

    Fluoride ions, in long-term applications on titanium brackets, cause their corrosion. Fluoride gel used for caries prevention during orthodontic treatment has a very high concentration in fluoride ions, and therefore has the potential for causing bracket corrosion. The main aim of this study was to determine the effect of eliminating the residual fluoride gel, by rinsing it, on the corrosion of titanium brackets. The secondary aim was to evaluate the corrosion of titanium brackets in the presence of fluoride gel. One hundred titanium brackets were divided into five groups of 20 brackets each. Group 1 being the control group, the rest of the groups were immersed in fluoride gel: Group 2 for 4 minutes and kept for 30 minutes with the residual fluoride gel on; Group 3 for 4 minutes followed by immediate water rinsing; Group 4 for 12 minutes and kept for 90 minutes with the residual fluoride gel on and Group 5 for 12 minutes followed by immediate water rinsing. All groups were rinsed then dried, for 20 hours, using Silica gel in a desiccator maintained at 37°C before testing. Gravimetrical results and SEM analysis showed no significant difference between Groups 2, 3 and 5 compared to each other and to the control group. Only Group 4 showed significant weight loss and pitting corrosion in four of the 20 brackets. In sliding resistance, no significant difference was detected between any of the groups. Short time applications of fluoride gel do not affect sliding resistance of titanium brackets. No titanium corrosion was detected for one application of concentrated fluoride gel and some brackets showed pitting corrosion for three applications. The rinsing of residual fluoride gel eliminates completely the risk of bracket corrosion. Copyright © 2011 CEO. Published by Elsevier Masson SAS. All rights reserved.

  18. Method for the Determination of Carbonyl Compounds in E-Cigarette Aerosols

    PubMed Central

    Flora, Jason W.; Wilkinson, Celeste T.; Wilkinson, James W.; Lipowicz, Peter J.; Skapars, James A.; Anderson, Adam; Miller, John H.

    2017-01-01

    Low levels of thermal degradation products such as carbonyls (formaldehyde, acetaldehyde, acrolein, crotonaldehyde) have been reported in e-cigarette aerosols. The collection and analysis of e-cigarette aerosol carbonyls are often adapted from methods developed for tobacco cigarette smoke. These methodologies are often not sensitive enough to detect low carbonyl levels in e-cigarette aerosols. One objective of this work was to develop and validate a rapid, selective and sensitive ultra-performance liquid chromatography with mass spectrometry method optimized for analysis of carbonyls in e-cigarette aerosols. Aerosols were trapped in 20-puff collections, 4-s durations, 55-mL volumes, 30-s intervals, square wave puff profiles. Collection apparatus involved a linear smoking machine with Cambridge filter pad followed by a glass impinger containing acidified 2,4-dinitrophenylhydrazine. This method showed limits of quantitation and detection of 0.016 and 0.003 µg puff−1, respectively, and run time of 4 min. Six e-cigarettes were evaluated (five devices each). All contained measurable levels of carbonyls. Levels were mostly well below those in conventional cigarettes. However, for some e-cigarettes, formaldehyde levels were above those for tobacco cigarettes (highest at 14.1 µg puff−1). Temperatures related to carbonyl yields in e-cigarette aerosols were explored to better understand carbonyl formation: formation of formaldehyde is low at temperatures below 350°C. PMID:28087758

  19. Semi-automated image analysis: detecting carbonylation in subcellular regions of skeletal muscle

    PubMed Central

    Kostal, Vratislav; Levar, Kiara; Swift, Mark; Skillrud, Erik; Chapman, Mark; Thompson, LaDora V.

    2011-01-01

    The level of carbonylation in skeletal muscle is a marker of oxidative damage associated with disease and aging. While immunofluorescence microscopy is an elegant method to identify carbonylation sites in muscle cross-sections, imaging analysis is manual, tedious, and time consuming, especially when the goal is to characterize carbonyl contents in subcellular regions. In this paper, we present a semi-automated method for the analysis of carbonylation in subcellular regions of skeletal muscle cross-sections visualized with dual fluorescent immunohistochemistry. Carbonyls were visualized by their reaction with 2,4-dinitrophenylhydrazine (DNPH) followed by immunolabeling with an Alexa488-tagged anti-DNP antibody. Mitochondria were probed with an anti-COXI primary antibody followed by the labeling with an Alexa568-tagged secondary antibody. After imaging, muscle fibers were individually analyzed using a custom-designed, lab-written, computer-aided procedure to measure carbonylation levels in subsarcolemmal and interfibrillar mitochondrial regions, and in the cytoplasmic and extracellular regions. Using this procedure, we were able to decrease the time necessary for the analysis of a single muscle fiber from 45 min to about 1 min. The procedure was tested by four independent analysts and found to be independent on inter-person and intra-person variations. This procedure will help increase highly needed throughput in muscle studies related to ageing, disease, physical performance, and inactivity that use carbonyl levels as markers of oxidative damage. PMID:21327623

  20. Cationic boranes for the complexation of fluoride ions in water below the 4 ppm maximum contaminant level.

    PubMed

    Kim, Youngmin; Gabbaï, François P

    2009-03-11

    In search of a molecular receptor that could bind fluoride ions in water below the maximum contaminant level of 4 ppm set by the Environmental Protection Agency (EPA), we have investigated the water stability and fluoride binding properties of a series of phosphonium boranes of general formula [p-(Mes(2)B)C(6)H(4)(PPh(2)R)](+) with R = Me ([1](+)), Et ([2](+)), n-Pr ([3](+)), and Ph ([4](+)). These phosphonium boranes are water stable and react reversibly with water to form the corresponding zwitterionic hydroxide complexes of general formula p-(Mes(2)(HO)B)C(6)H(4)(PPh(2)R). They also react with fluoride ions to form the corresponding zwitterionic fluoride complexes of general formula p-(Mes(2)(F)B)C(6)H(4)(PPh(2)R). Spectrophotometric acid-base titrations carried out in H(2)O/MeOH (9:1 vol.) afford pK(R+) values of 7.3(+/-0.07) for [1](+), 6.92(+/-0.1) for [2](+), 6.59(+/-0.08) for [3](+), and 6.08(+/-0.09) for [4](+), thereby indicating that the Lewis acidity of the cationic boranes increases in following order: [1](+) < [2](+) < [3](+) < [4](+). In agreement with this observation, fluoride titration experiments in H(2)O/MeOH (9:1 vol.) show that the fluoride binding constants (K = 840(+/-50) M(-1) for [1](+), 2500(+/-200) M(-1) for [2](+), 4000(+/-300) M(-1) for [3](+), and 10 500(+/-1000) M(-1) for [4](+)) increase in the same order. These results show that the Lewis acidity of the cationic boranes increases with their hydrophobicity. The resulting Lewis acidity increase is substantial and exceeds 1 order of magnitude on going from [1](+) to [4](+). In turn, [4](+) is sufficiently fluorophilic to bind fluoride ions below the EPA contaminant level in pure water. These results indicate that phosphonium boranes related to [4](+) could be used as molecular recognition units in chemosensors for drinking water analysis.

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