Fluoroalkyl containing salts combined with fluorinated solvents for electrolytes

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

Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan

Provided are electrochemical cells and electrolytes used to build such cells. An electrolyte may include a fluoroalkyl-substituted LiPF.sub.6 salt or a fluoroalkyl-substituted LiBF.sub.4 salt. In some embodiments, at least one fluorinated alkyl of the salt has a chain length of from 1 to 8 or, more specifically, between about 2 and 8. These fluorinated alkyl groups, in particular, relatively large fluorinated alkyl groups improve solubility of these salts in fluorinated solvents that are less flammable than, for example, conventional carbonate solvents. At the same time, the size of fluoroalkyl-substituted salts should be limited to ensure adequate concentration of the saltmore » in an electrolyte and low viscosity of the electrolyte. In some embodiments, the concentration of a fluoroalkyl-substituted salt is at least about 0.5M. Examples of fluorinated solvents include various fluorinated esters, fluorinated ethers, and fluorinated carbonates, such a 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane.« less

Evaluation of Efficient and Practical Methods for the Preparation of Functionalized Aliphatic Trifluoromethyl Ethers.

PubMed

Sokolenko, Taras M; Dronkina, Maya I; Magnier, Emmanuel; Yagupolskii, Lev M; Yagupolskii, Yurii L

2017-05-14

The "chlorination/fluorination" technique for aliphatic trifluoromethyl ether synthesis was investigated and a range of products with various functional groups was prepared. The results were compared with oxidative desulfurization-fluorination of xanthates with the same structure.

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

DTIC Science & Technology

1990-08-22

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

Partially Fluorinated Solvent as a co-solvent for the Non-aqueous Electrolyte of Li/air Battery

DTIC Science & Technology

2010-11-11

ether ( MFE ) and tris(2,2,2-trifluoroethyl) phosphite (TTFP), respectively, as a co-solvent for the non-aqueous electrolyte of Li–air battery. Results...fluorinated solvents on the discharge performance of Li–air bat- tery. For this purpose, we here selectmethyl nonafluorobutyl ether ( MFE ) and tris...196, (2011) pgs. 2867-2870 14. ABSTRACT In this workwestudy methyl nonafluorobutyl ether ( MFE ) and tris(2,2,2-trifluoroethyl) phosphite (TTFP

Fluorinated diglucose detergents for membrane-protein extraction.

PubMed

Boussambe, Gildas Nyame Mendendy; Guillet, Pierre; Mahler, Florian; Marconnet, Anaïs; Vargas, Carolyn; Cornut, Damien; Soulié, Marine; Ebel, Christine; Le Roy, Aline; Jawhari, Anass; Bonneté, Françoise; Keller, Sandro; Durand, Grégory

2018-05-29

Fluorinated surfactants have scarcely been explored for the direct extraction of proteins from membranes because fluorination is believed to abrogate detergency. However, we have recently shown that a commercially available fluorinated surfactant readily solubilizes lipid membranes, thereby suggesting that fluorination per se does not interfere with detergent activity. In this work, we developed new fluorinated surfactants that exhibit detergency in terms of both lipid-vesicle solubilization and membrane-protein extraction. The compounds made and tested contain two glucose moieties as polar headgroup, a hydrogenated thioether linker, and a perfluorinated alkyl tail with either 4, 6, or 8 carbon atoms. The physicochemical properties of the micelles formed by the three fluorinated surfactants were evaluated by NMR spectroscopy, surface tensiometry, isothermal titration calorimetry, dynamic light scattering, small-angle X-ray scattering, and analytical ultracentrifugation. At 25°C, micellization was mainly entropy-driven, and the CMC values were found to decrease with chain length of the fluorinated tail, whereas the aggregation number increased with chain length. Remarkably, all three surfactants were found to solubilize lipid vesicles and extract a broad range of proteins from Escherichiacoli membranes. These findings demonstrate, for the first time, that nonionic fluorinated surfactants could be further exploited for the direct extraction and solubilization of membrane proteins. Copyright © 2018. Published by Elsevier Inc.

Hydrofluorination of Alkynes Catalysed by Gold Bifluorides.

PubMed

Nahra, Fady; Patrick, Scott R; Bello, Davide; Brill, Marcel; Obled, Alan; Cordes, David B; Slawin, Alexandra M Z; O'Hagan, David; Nolan, Steven P

2015-01-01

We report the synthesis of nine new N -heterocyclic carbene gold bifluoride complexes starting from the corresponding N -heterocyclic carbene gold hydroxides. A new methodology to access N,N' -bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) fluoride starting from N,N' -bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) hydroxide and readily available potassium bifluoride is also reported. These gold bifluorides were shown to be efficient catalysts in the hydrofluorination of symmetrical and unsymmetrical alkynes, thus affording fluorinated stilbene analogues and fluorovinyl thioethers in good to excellent yields with high stereo- and regioselectivity. The method is exploited further to access a fluorinated combretastatin analogue selectively in two steps starting from commercially available reagents.

Fluorinated Electrolytes for Li-S Battery: Suppressing the Self-Discharge with an Electrolyte Containing Fluoroether Solvent

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

Azimi, N.; Xue, Z.; Rago, N. D.

The fluorinated electrolyte containing a fluoroether 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) was investigated as a new electrolyte for lithium-sulfur (Li-S) batteries. The low solubility of lithium polysulfides (LiPS) in the fluorinated electrolyte reduced the parasitic reactions with Li anode and mitigated the self-discharge by limiting their diffusion from the cathode to the anode. The use of fluorinated ether as a co-solvent and LiNO3 as an additive in the electrolyte shows synergetic effect in suppressing the self-discharge of Li-S battery due to the formation of the solid electrolyte interphase (SEI) on both sulfur cathode and the lithium anode. The Li-S cell with themore » fluorinated electrolyte showed prolonged shelf life at fully charged state.« less

A Facile and Efficient Synthesis of Diaryl Amines or Ethers under Microwave Irradiation at Presence of KF/Al2O3 without Solvent and Their Anti-Fungal Biological Activities against Six Phytopathogens

PubMed Central

Huang, Liang-Zhu; Han, Pan; Li, You-Qiang; Xu, Ying-Meng; Zhang, Tao; Du, Zhen-Ting

2013-01-01

A series of diaryl amines, ethers and thioethers were synthesized under microwave irradiation efficiently at presence of KF/Al2O3 in 83%–96% yields without any solvent. The salient characters of this method lie in short reaction time, high yields, general applicability to substrates and simple workup procedure. At the same time, their antifungal biological activities against six phytopathogen were evaluated. Most of the compounds (3b, 3c, 3g–o) are more potent than thiophannate-methyl against to Magnaporthe oryzae. This implies that diaryl amine or ether moiety may be helpful in finding a fungicide against Magnaporthe oryzae. PMID:24036444

PHYSICAL PROPERTIES OF FLUORINATED PROPANE AND BUTANE DERIVATIVES AS ALTERNATIVE REFRIGERANTS

EPA Science Inventory

Physical property measurements are presented for 24 fluorinated propane and butane derivatives and one fluorinated ether. These measurements include melting point, boiling point, vapor pressure below the boiling point, heat of vaporization at the boiling point, critical propertie...

Environmental Compliance Assessment and Management Program

DTIC Science & Technology

1994-04-01

following classes: 1. cyclic, branched, or linear, completely fluorinated alkanes 2. cyclic, branched, or linear, completely fluorinated ethers with no...unsaturations 3. cyclic, branched, or linear, completely fluorinated tertiary amines with no unsaturations 4. sulfur containing perfluorocarbons with no...unsaturations and with sulfur bonds only to carbon and fluorine . 2.58. VOC Water Separator - a tank, box, or other container which is primarily

Platinum(0)-mediated C-O bond activation of ethers via an SN2 mechanism.

PubMed

Ortuño, Manuel A; Jasim, Nasarella A; Whitwood, Adrian C; Lledós, Agustí; Perutz, Robin N

2016-11-29

A computational study of the C(methyl)-O bond activation of fluorinated aryl methyl ethers by a platinum(0) complex Pt(PCyp 3 ) 2 (Cyp = cyclopentyl) (N. A. Jasim, R. N. Perutz, B. Procacci and A. C. Whitwood, Chem. Commun., 2014, 50, 3914) demonstrates that the reaction proceeds via an S N 2 mechanism. Nucleophilic attack of Pt(0) generates an ion pair consisting of a T-shaped platinum cation with an agostic interaction with a cyclopentyl group and a fluoroaryloxy anion. This ion-pair is converted to a 4-coordinate Pt(ii) product trans-[PtMe(OAr F )(PCyp 3 ) 2 ]. Structure-reactivity correlations are fully consistent with this mechanism. The Gibbs energy of activation is calculated to be substantially higher for aryl methyl ethers without fluorine substituents and higher still for alkyl methyl ethers. These conclusions are in accord with the experimental results. Further support was obtained in an experimental study of the reaction of Pt(PCy 3 ) 2 with 2,3,5,6-tetrafluoro-4-allyloxypyridine yielding the salt of the Pt(η 3 -allyl) cation and the tetrafluoropyridinolate anion [Pt(PCy 3 ) 2 (η 3 -allyl)][OC 5 NF 4 ]. The calculated activation energy for this reaction is significantly lower than that for fluorinated aryl methyl ethers.

A beta-keto ester as a novel, efficient, and versatile ligand for copper(I)-catalyzed C-N, C-O, and C-S coupling reactions.

PubMed

Lv, Xin; Bao, Weiliang

2007-05-11

Employing ethyl 2-oxocyclohexanecarboxylate as a novel, efficient, and versatile ligand, the copper-catalyzed coupling reactions of various N/O/S nucleophilic reagents with aryl halides could be successfully carried out under mild conditions. A variety of products including N-arylamides, N-arylimidazoles, aryl ethers, and aryl thioethers were synthesized in good to excellent yields.

Electrophilic fluorinating reagent mediated synthesis of fluorinated alpha-keto Ethers, benzil, and 6,6'-dialkoxy-2,2'-bipyridines.

PubMed

Manandhar, Sudha; Singh, Rajendra P; Eggers, Gary V; Shreeve, Jean'ne M

2002-09-06

Interactions of various fluorinated and nonfluorinated alcohols with trans-stilbene in the presence of electrophilic reagents were studied. Under neat conditions, reactions of trans-stilbene (1) with fluorinated alcohols, R(f)OH (R(f) = CF3CH2-, CFH2CH2-, CF3CF2CH2-, CF2H(CF2)3CH2-, (CF3)2CH-, (CF3)3C- (2a-f) in the presence of an electrophilic reagent, 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) or N,N-difluoro-2,2'-bipyridinium bis(tetrafluoroborate) (MEC-31), gave alpha-keto ethers (3a-f) and benzil (4) in good to moderate yields. alpha-Keto ether and benzil formation was very much dependent on the reaction time, the degree of fluorination of the alcohols, and whether a solvent such as CH3CN, DMF or DMA was utilized. In solution, alpha-keto ethers and benzil did not form. Interestingly, under neat conditions, nonfluorinated alcohols, ROH (R = CH3-, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-, CH3CH2CH2CH2CH2CH2-) (5g-k) did not react with trans-stilbene in the presence of MEC-31 but gave 6,6'-dialkoxy-2,2'-bipyridines (6g-k), regioselectively, in excellent isolated yields. On the other hand, fluorinated alcohols did not react with MEC-31. Reaction of MEC-31 with an excess of diethylene glycol (7) gave the bipyridine derivative (8) in 88% isolated yield. Reaction of 8 either with diethylaminosulfur trifluoride (DAST) or bis(2-methoxyethyl)aminosulfur trifluoride (Deoxofluor) readily produced the corresponding difluoro derivative (9) in 85% isolated yield. All new compounds have been characterized by spectroscopic and elemental analysis.

THE HEAT CAPACITY OF FLUORINATED PROPANE AND BUTANE DERIVATIVES BY DIFFERENTIAL SCANNING CALORIMETRY

EPA Science Inventory

The paper gives results of the measurement (to 3% accuracy) of the constant-pressure liquid-phase heat capacities of 21 hydrogen-containing fluorinated propane and butane derivatives and one fluorinated ether (CF3OCF2H) with boiling points ranging from -34.6 to 76.7 C, using diff...

Fluorinated Alkyl Ether Epoxy Resin Compositions and Applications Thereof

NASA Technical Reports Server (NTRS)

Connell, John W. (Inventor); Wohl, Christopher J. (Inventor); Siochi, Emilie J. (Inventor); Gardner, John M. (Inventor); Smith, Joseph G. (Inventor); Palmieri, Frank M. (Inventor)

2017-01-01

Epoxy resin compositions prepared using amino terminated fluoro alkyl ethers. The epoxy resin compositions exhibit low surface adhesion properties making them useful as coatings, paints, moldings, adhesives, and fiber reinforced composites.

Effect of viscosity on rolling-element fatigue life at cryogenic temperature with fluorinated ether lubricants

NASA Technical Reports Server (NTRS)

Dietrich, M. W.; Zaretsky, E. V.

1975-01-01

Rolling-element fatigue tests were conducted with 12.7-mm-(1/2-in.-) diameter AISI 52100 steel balls in the NASA five-ball fatigue tester, with a maximum hertz stress of 5500 mN/m2 (800 000 psi), a shaft speed of 4750 rpm, lubricant temperature of 200 K (360 R), a contact angle of 20 deg, using four fluorinated ether lubricants of varying viscosities. No statistically significant differences in rolling-element fatigue life occurred using the four viscosity levels. Elastohydrodynamic calculations indicate that values of the lubricant film parameter were approximately 2 or greater.

Oxidative desulfurization-fluorination of thioethers. Application for the synthesis of fluorinated nitrogen containing building blocks.

PubMed

Hugenberg, Verena; Fröhlich, Roland; Haufe, Günter

2010-12-21

An oxidative desulfurization-fluorination protocol has been used to synthesize (2S)-2-(difluoromethyl)-N-tosylpyrrolidine (6a) and (2S)-2-(trifluoromethyl)-N-tosylpyrrolidine (7a) from the (2S)-prolinol-derived (2S)-2-(4-chlorophenylthiomethyl)-N-tosylpyrrolidine (9) or (2S)-2-(dithian-2-yl)-N-tosylpyrrolidine (5). Efforts to prepare 3,3-difluoroalanine similarly from an N-protected S-aryl-cysteine ester 17 gave only traces of the target compound 18. Instead, an unique N-(α,α-difluorobenzyl)-N-α',α'-dibromoglycine ester 19 was formed by an unprecedented sequence of reaction steps. A plausible mechanism is suggested involving a sulfur-assisted deoxygenation-difluorination of an imino oxygen and a haloform reaction like carbon-carbon bond fission as key-steps. Efforts to prepare (2S)-2-(fluoromethyl)-N-tosylpyrrolidine (12) from (2S)-N-tosylprolinol (3) by treatment with Fluolead™ (1-tert-butyl-4-trifluorosulfanyl-3,5-dimethylbenzene) gave only 5% of the target compound, but 95% of (3R)-3-fluoro-N-tosylpiperidine (11a) by ring enlargement.

Study of sulfonated polyether ether ketone with pendant lithiated fluorinated sulfonic groups as ion conductive binder in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wei, Zengbin; Xue, Lixin; Nie, Feng; Sheng, Jianfang; Shi, Qianru; Zhao, Xiulan

2014-06-01

In an attempt to reduce the Li+ concentration polarization and electrolyte depletion from the electrode porous space, sulfonated polyether ether ketone with pendant lithiated fluorinated sulfonic groups (SPEEK-FSA-Li) is prepared and attempted as ionic conductivity binder. Sulfonated aromatic poly(ether ether ketone) exhibits strong adhesion and chemical stability, and lithiated fluorinated sulfonic side chains help to enhance the ionic conductivity and Li+ ion diffusion due to the charge delocalization over the sulfonic chain. The performances are evaluated by cyclic voltammetry, electrochemical impedance spectroscopy, charge-discharge cycle testing, 180° peel testing, and compared with the cathode prepared with polyvinylidene fluoride binder. The electrode prepared with SPEEK-FSA-Li binder forms the relatively smaller resistances of both the SEI and the charge transfer of lithium ion transport. This is beneficial to lithium ion intercalation and de-intercalation of the cathode during discharging-charging, therefore the cell prepared with SPEEK-FSA-Li shows lower charge plateau potential and higher discharge plateau potential. Compared with PVDF, the electrode with ionic binder shows smaller decrease in capacity with the increasing of cycle rate. Meanwhile, adhesion strength of electrode prepared with SPEEK-FSA-Li is more than five times greater than that with PVDF.

Improved performance of lithium–sulfur battery with fluorinated electrolyte

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

Azimi, Nasim; Weng, Wei; Takoudis, Christos

An organo-fluorine compound, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), was investigated for the first time as the electrolyte solvent in the lithium–sulfur battery. The new fluorinated electrolyte suppressed the deleterious shuttling effect and improved the capacity retention and coulombic efficiency in cell tests. In addition, it was found to eliminate the self-discharge of the lithium–sulfur battery.

Trifluoromethyl ethers – synthesis and properties of an unusual substituent

PubMed Central

Manteau, Baptiste; Vors, Jean-Pierre; Pazenok, Sergiy

2008-01-01

Summary After nitrogen, fluorine is probably the next most favorite hetero-atom for incorporation into small molecules in life science-oriented research. This review focuses on a particular fluorinated substituent, the trifluoromethoxy group, which is finding increased utility as a substituent in bioactives, but it is still perhaps the least well understood fluorine substituent in currency. The present review will give an overview of the synthesis, properties and reactivity of this important substituent. PMID:18941485

VAPOR PRESSURES, LIQUID MOLAR VOLUMES, VAPOR NON- IDEALITIES, AND CRITICAL PROPERTIES OF SOME FLUORINATED ETHERS: CF3OCF2OCF3, CF3OCF2 CF2H, c-CF2CF2CF2O, CF3OCF2H, AND CF3OCH3; AND OF CCl3F AND CF2ClH

EPA Science Inventory

Vapor pressures, compressibilities, expansivities, and molar volumes of the liquid phase have been measured between room temperature and the critical temperature for a series of fluorinated ethers: CF3OCF2OCF3, CF3OCF2CF2H, c-CF2CF2CF2O, CF3OCF2H, and CF3OCH3. Vapor-phase non-ide...

A review of liquid lubricant thermal/oxidative degradation

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.

1983-01-01

The fundamental processes occurring during the thermal and oxidative degradation of hydrocarbons are reviewed. Particular emphasis is given to various classes of liquid lubricants such as mineral oils, esters, polyphenyl ethers, C-ethers, and fluorinated polyethers. Experimental techniques for determining thermal and oxidative stabilities of lubricants are discussed. The role of inhibitors and catalysis is also covered.

Effect of phenytoin (DPH) treatment on methoxyflurane metabolism in rats.

PubMed

Caughey, G H; Rice, S A; Kosek, J C; Mazze, R I

1979-08-01

The toxicity and metabolism of the fluorinated anesthetic methoxyflurane were compared in Fischer 344 rats pretreated with phenytoin or phenobarbital. Treatment with either drug potentiated the polyuric effects of methoxyflurane by more than 100%. Also, serum inorganic fluoride (F-) levels and urinary F- excretions after methoxyflurane exposure were comparable in phenytoin- and phenobarbital-treated rats, a 26 to 49% increase as compared to rats treated with methoxyflurane alone. In vitro, 10-fold increases in the rate of hepatic microsomal methoxyflurane defluorination were observed after treatment of rats with either phenytoin or phenobarbital. Kinetic studies with microsomes demonstrated inhibition of methoxyflurane defluorination in the presence of phenytoin. Defluorination of three additional fluorinated ether anesthetics, enflurane, isoflurane and sevoflurane, also was examined in vitro. Phenytoin and phenobarbital treatment resulted in similar enhancement of defluorination of the latter two anesthetics, but not enflurane. Phenytoin and phenobarbital treatment increase defluorination of fluorinated ether anesthetics to approximately the same extent in vitro and in vivo in Fischer 344 rats.

A New Approach to Highly Fluorinated Lubricants.

DTIC Science & Technology

1987-10-30

demonstrated the value of perfluoroalkyl groups being present. 7 In this way, xrious perfluoroethers were characterised, thus demonstrating the...mixture, containing four components (g.l.c. col. A 450C), was separated using preparative scale g.l.c. techniques to give:- perfluoropentane (4%); perfluoro ...CHRFOCHRFCH2 OCHRFCH 3 ) (where RF - CF 2CFHCF3 ) 2. These adducts were then fluorinated by cobalt trifluoride to give corresponding perfluoro -ethers

A Fluorinated Ether Electrolyte Enabled High Performance Prelithiated Graphite/Sulfur Batteries

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

Chen, Shuru; Yu, Zhaoxin; Gordin, Mikhail L.

Lithium/sulfur (Li/S) batteries have attracted great attention as a promising energy storage technology, but so far their practical applications are greatly hindered by issues of polysulfide shuttling and unstable lithium/electrolyte interface. To address these issues, a feasible strategy is to construct a rechargeable prelithiated graphite/sulfur batteries. In this study, a fluorinated ether of bis(2,2,2-trifluoroethyl) ether (BTFE) was reported to blend with 1,3-dioxolane (DOL) for making a multifunctional electrolyte of 1.0 M LiTFSI DOL/BTFE (1:1, v/v) to enable high performance prelithiated graphite/S batteries. First, the electrolyte significantly reduces polysulfide solubility to suppress the deleterious polysulfide shuttling and thus improves capacity retentionmore » of sulfur cathodes. Second, thanks to the low viscosity and good wettability, the fluorinated electrolyte dramatically enhances the reaction kinetics and sulfur utilization of high-areal-loading sulfur cathodes. More importantly, this electrolyte forms a stable solid-electrolyte interphase (SEI) layer on graphite surface and thus enables remarkable cyclability of graphite anodes. Lastly, by coupling prelithiated graphite anodes with sulfur cathodes with high areal capacity of ~3 mAh cm -2, we demonstrate prelithiated graphite/sulfur batteries that show high sulfur-specific capacity of ~1000 mAh g -1 and an excellent capacity retention of >65% after 450 cycles at C/10.« less

A Fluorinated Ether Electrolyte Enabled High Performance Prelithiated Graphite/Sulfur Batteries

DOE PAGES

Chen, Shuru; Yu, Zhaoxin; Gordin, Mikhail L.; ...

2017-02-03

Lithium/sulfur (Li/S) batteries have attracted great attention as a promising energy storage technology, but so far their practical applications are greatly hindered by issues of polysulfide shuttling and unstable lithium/electrolyte interface. To address these issues, a feasible strategy is to construct a rechargeable prelithiated graphite/sulfur batteries. In this study, a fluorinated ether of bis(2,2,2-trifluoroethyl) ether (BTFE) was reported to blend with 1,3-dioxolane (DOL) for making a multifunctional electrolyte of 1.0 M LiTFSI DOL/BTFE (1:1, v/v) to enable high performance prelithiated graphite/S batteries. First, the electrolyte significantly reduces polysulfide solubility to suppress the deleterious polysulfide shuttling and thus improves capacity retentionmore » of sulfur cathodes. Second, thanks to the low viscosity and good wettability, the fluorinated electrolyte dramatically enhances the reaction kinetics and sulfur utilization of high-areal-loading sulfur cathodes. More importantly, this electrolyte forms a stable solid-electrolyte interphase (SEI) layer on graphite surface and thus enables remarkable cyclability of graphite anodes. Lastly, by coupling prelithiated graphite anodes with sulfur cathodes with high areal capacity of ~3 mAh cm -2, we demonstrate prelithiated graphite/sulfur batteries that show high sulfur-specific capacity of ~1000 mAh g -1 and an excellent capacity retention of >65% after 450 cycles at C/10.« less

Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

DOE PAGES

Horowitz, Yonatan; Han, Hui-Ling; Ralston, Walter T.; ...

2017-05-12

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by summore » frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.« less

Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

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

Horowitz, Yonatan; Han, Hui-Ling; Ralston, Walter T.

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by summore » frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.« less

Experimental and Calculational Studies of the Interactions of BF3 with Fluoroethers

NASA Technical Reports Server (NTRS)

Zehe, Michael J.; Morales, Wilfredo; Ball, David W.

1998-01-01

BF3 was co-condensed with (C2H5)2O, (CF3CH2)2O and (C2F5)2O in excess argon at 15 K. Infrared spectra of the matrices showed a definite Lewis acid-base interaction between BF3 and diethyl ether; a weak but definite interaction with bis(2,2,2,-trifluorodiethyl)ether, and no observable interaction with perfluorodiethyl ether. Molecular orbital (MO) calculations complemented the experimental observations by revealing that fluorine atoms on the ethers decreased electron localization about the oxygen atom. Thus, the experimental data and MO calculations indicated a clear trend between strength of interaction with BF3 and the degree of ether F substitution. The implications of the results for commercial perfluoro ether lubricant/metal oxide surface interactions are discussed.

Degradation of Perfluorinated Ether Lubricants on Pure Aluminum Surfaces: Semiempirical Quantum Chemical Modeling

NASA Technical Reports Server (NTRS)

Slaby, Scott M.; Ewing, David W.; Zehe, Michael J.

1997-01-01

The AM1 semiempirical quantum chemical method was used to model the interaction of perfluoroethers with aluminum surfaces. Perfluorodimethoxymethane and perfluorodimethyl ether were studied interacting with aluminum surfaces, which were modeled by a five-atom cluster and a nine-atom cluster. Interactions were studied for edge (high index) sites and top (low index) sites of the clusters. Both dissociative binding and nondissociative binding were found, with dissociative binding being stronger. The two different ethers bound and dissociated on the clusters in different ways: perfluorodimethoxymethane through its oxygen atoms, but perfluorodimethyl ether through its fluorine atoms. The acetal linkage of perfluorodimeth-oxymethane was the key structural feature of this molecule in its binding and dissociation on the aluminum surface models. The high-index sites of the clusters caused the dissociation of both ethers. These results are consistent with the experimental observation that perfluorinated ethers decompose in contact with sputtered aluminum surfaces.

Fluorinated Graphene Prepared by Direct Fluorination of N, O-Doped Graphene Aerogel at Different Temperatures for Lithium Primary Batteries.

PubMed

Bi, Xu; Li, Yanyan; Qiu, Zhipeng; Liu, Chao; Zhou, Tong; Zhuo, Shuping; Zhou, Jin

2018-06-25

Fluorinated graphene (FG) has been a star material as a new derivative of graphene. In this paper, a series of fluorinated graphene materials are prepared by using N, O-doped graphene aerogel as precursor via a direct fluorination method, and the effect of fluorination temperature on the FG structure is investigated. The prepared FG samples are systematically characterized by scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. It is found that the structure of FG, including features such as layer size, chemical composition, chemical bond state of the component elements, etc., is significantly related to the fluorination temperature. With the change of the fluorination temperature, fluorine atoms enter the graphene framework by a substitution process of the N, O-containing groups, including residual phenol, ether, carbonyl groups, or C⁻N groups, and the addition to CC bonds, subsequently forming a fluoride with different fluorine contents. The fluorine content increases as the fluorination temperature increases from 200 °C to 300 °C, but decreases at a fluorination temperature of 350 °C due to the decomposition of the fluorinated graphene. The prepared FG samples are used as cathode material for lithium primary batteries. The FG sample prepared at 300 °C gives a high specific capacity of 632 mAh g −1 and a discharge plateau of 2.35 V at a current density of 10 mA g −1 , corresponding to a high energy density of 1485 Wh kg −1 .

1H, 13C and 19F NMR studies on fluorinated ethers

NASA Astrophysics Data System (ADS)

Balonga, P. E.; Kowalewski, V. J.; Contreras, R. H.

The enflurane and ethoxyflurane 1H, 13C and 19F NMR spectra are examined—including sign determination of FF and FH couplings—and considered in the light of previously reported results for methoxyflurane. Conformational differences between methoxyflurane and the former two molecules are indicated by through space FH coupling constants and by the nonequivalence of geminal fluorine nuclei. Populations of conformers about the CC bond are estimated.

Heme-Coordinating Inhibitors of Neuronal Nitric Oxide Synthase. Iron-Thioether Coordination is Stabilized by Hydrophobic Contacts Without Increased Inhibitor Potency

PubMed Central

Martell, Jeffrey D.; Li, Huiying; Doukov, Tzanko; Martásek, Pavel; Roman, Linda J.; Soltis, Michael; Poulos, Thomas L.; Silverman, Richard B.

2010-01-01

The heme-thioether ligand interaction often occurs between heme iron and native methionine ligands, but thioether-based heme-coordinating (type II) inhibitors are uncommon due to the difficulty in stabilizing the Fe-S bond. Here, a thioether-based inhibitor (3) of neuronal nitric oxide synthase (nNOS) was designed, and its binding was characterized by spectrophotometry and crystallography. A crystal structure of inhibitor 3 coordinated to heme iron was obtained, representing, to our knowledge, the first crystal structure of a thioether inhibitor complexed to any heme enzyme. A series of related potential inhibitors (4-8) also were evaluated. Compounds 4-8 were all found to be type I (non-heme-coordinating) inhibitors of ferric nNOS, but 4 and 6-8 were found to switch to type II upon heme reduction to the ferrous state, reflecting the higher affinity of thioethers for ferrous heme than for ferric heme. Contrary to what has been widely thought, thioether-heme ligation was found not to increase inhibitor potency, illustrating the intrinsic weakness of the thioether-ferric heme linkage. Subtle changes in the alkyl groups attached to the thioether sulfur caused drastic changes in binding conformation, indicating that hydrophobic contacts play a crucial role in stabilizing the thioether-heme coordination. PMID:20014790

Exchange Reactions of Organotin and Organosilicon Compounds with Mild Fluorinating Agents

DTIC Science & Technology

1992-03-01

methylphosphonic difluoride, boron trifluoride etherate, and perfluoroisobutene all react with both organosilicon and organotin. alkoxides to give...inlet tube, was charged with tributyltin cyanide (53.30 gm, 0.1686 mol) in a dry glove bag under an inert atmosphere and 500 ml of dry xylene was then...Chem. Vol. 29, p 471 (1985). 6. Tyuleneva, V.V., Rozov, L.A., Zeifman, Yu.V. and I. L. Knuny- ants,"Exchange of Fluorine by Chlorine in Perfluoro-isobutene," Tzv.Akad.Nauk. SSSR. Ser. Khim No. 5, p 1136 (1975). 17

Sealed Gravitational Capillary Viscometry of Dimethyl Ether and Two Next-Generation Alternative Refrigerants

PubMed Central

Cousins, Dylan S.; Laesecke, Arno

2012-01-01

The viscosities of dimethyl ether (DME, C2H6O) and of the fluorinated propene isomers 2,3,3,3-tetrafluoroprop-1-ene (R1234yf, C3H2F4) and trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) were measured in a combined temperature range from 242 K to 350 K at saturated liquid conditions. The instrument was a sealed gravitational capillary viscometer developed at NIST for volatile liquids. Calibration and adjustment of the instrument constant were conducted with n-pentane. The repeatability of the measurements was found to be approximately 1.5 %, leading to a temperature-dependent estimated combined standard uncertainty of the experimental data between 5.7 % at 242 K for dimethyl ether and 2.6 % at 340 K for R1234yf. The measurements were supplemented by ab initio calculations of the molecular size, shape, and charge distributions of the measured compounds. The viscosity results for dimethyl ether were compared with literature data. One other data set measured with a sealed capillary viscometer and exceeding the present results by up to 7 % could be reconciled by applying the vapor buoyancy correction. Then, all data agreed within the estimated uncertainty of the present results. Viscosities for the fluorinated propene isomers deviate up to 4 % from values predicted with the NIST extended corresponding-states model. The viscosities of the two isomers do not scale with their dipole moments. While the measured viscosity of R1234ze(E) with the lower dipole moment is close to that of R134a, the refrigerant to be replaced, that of R1234yf with the higher dipole moment is up to 25 % lower. The viscosity of dimethyl ether is compared with those of water and methanol. PMID:26900526

Syntheses and degradations of fluorinated heterocyclics

NASA Technical Reports Server (NTRS)

Paciorek, K. L.; Kratzer, R. H.; Kaufman, J.; Rosser, R. W.

1975-01-01

The relative stability of two ring systems, the triazine rings and 1,2,4-oxadiazoles, which offer potential crosslinks useful for curing perfluoroalkyl ether elastomers, has been investigated. Tris (perfluoro-n-heptyl)-s-triazine, the perfluoroether substituted-s-triazine, 1,4-bis/(5-perfluoro-n-heptyl)-1,2,4-oxadiazolyl/benzene, its perfluoroalkyl ether substituted analog, and 3,5-bis-(perfluoro-n-heptyl)-1,2,4-oxadiazole were synthesized and subjected to thermal and oxidative degradation at 235 and 325 C and to hydrolytic degradation at 235 C. The perfluoroalkyl ether substituted triazine and 3,5-bis(perfluoro-n-heptyl)-1,2,4-oxadiazole were found to be stable under all conditions investigated.

FTIR cryospectroscopic and ab initio studies of desflurane-dimethyl ether H-bonded complexes.

PubMed

Melikova, S M; Rutkowski, K S; Rospenk, M

2017-09-05

The IR spectra of mixtures of desflurane and dimethyl ether are studied with the help of FTIR cryospectroscopy in liquefied Kr at T~118-158K. Comparative analysis of the experimental data and results of ab initio calculations show that either of the two C-H groups of desflurane is involved in heterodimer formation of comparable strengths. The blue frequency shift is found for stretching vibrations of those C-H donors which directly participate in H-bond formation. Additionally the complexes are stabilized by weaker contacts between hydrogen atoms of dimethyl ether and fluorine atoms of desflurane. Copyright © 2017 Elsevier B.V. All rights reserved.

Urinary thioether of employees of a chemical plant.

PubMed

Vainio, H; Savolainen, H; Kilpikari, I

1978-08-01

The thiols in the morning urine of 224 employees of a chemical plant were determined after alkaline hydrolysis of all urinary thioethers. The highest thioether excretion was found in rubber workers and radial tyre builders in comparison with clerks, plastic monomer mixers and footwear preparers. Smoking and medication tended to increase thioether excretion. Urinary thioether determination may prove to be a valuable tool in assessing exposure to mixtures of chemicals regardless of the route of absorption.

Urinary thioether of employees of a chemical plant.

PubMed Central

Vainio, H; Savolainen, H; Kilpikari, I

1978-01-01

The thiols in the morning urine of 224 employees of a chemical plant were determined after alkaline hydrolysis of all urinary thioethers. The highest thioether excretion was found in rubber workers and radial tyre builders in comparison with clerks, plastic monomer mixers and footwear preparers. Smoking and medication tended to increase thioether excretion. Urinary thioether determination may prove to be a valuable tool in assessing exposure to mixtures of chemicals regardless of the route of absorption. PMID:698138

40 CFR 721.10113 - Thioether epoxy (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Thioether epoxy (generic). 721.10113... Substances § 721.10113 Thioether epoxy (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as thioether epoxy (PMN P-04-547) is subject to...

40 CFR 721.10113 - Thioether epoxy (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Thioether epoxy (generic). 721.10113... Substances § 721.10113 Thioether epoxy (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as thioether epoxy (PMN P-04-547) is subject to...

40 CFR 721.10113 - Thioether epoxy (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Thioether epoxy (generic). 721.10113... Substances § 721.10113 Thioether epoxy (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as thioether epoxy (PMN P-04-547) is subject to...

40 CFR 721.10113 - Thioether epoxy (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Thioether epoxy (generic). 721.10113... Substances § 721.10113 Thioether epoxy (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as thioether epoxy (PMN P-04-547) is subject to...

40 CFR 721.10113 - Thioether epoxy (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Thioether epoxy (generic). 721.10113... Substances § 721.10113 Thioether epoxy (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as thioether epoxy (PMN P-04-547) is subject to...

Nucleophile Assisting Leaving Groups: A Strategy for Aliphatic 18F-Fluorination

PubMed Central

Lu, Shuiyu; Lepore, Salvatore D.; Li, Song Ye; Mondal, Deboprosad; Cohn, Pamela C.; Bhunia, Anjan K.; Pike, Victor W.

2009-01-01

A series of arylsulfonate nucleophile assisting leaving groups (NALGs) were prepared in which the metal chelating unit is attached to the aryl ring via an ether linker. These NALGs exhibited significant rate enhancements in halogenation reactions using metal halides. Studies with a NALG containing a macrocyclic ether unit suggest that rate enhancements of these nucleophilic halogenation reactions are facilitated by stabilization of charge in the transition state rather than through strong pre-complexation with metal cation. In several cases, a primary substrate containing one of the new leaving groups rivaled or surpassed the reactivity of triflates when exposed to nucleophile but was otherwise highly stable and isolable. These and previously disclosed chelating leaving groups were used in 18F-fluorination reactions using no-carrier-added [18F]fluoride ion (t1/2 = 109.7 min, β+ = 97%) in CH3CN. Under microwave irradiation and without the assistance of a cryptand, such as K2.2.2, primary substrates with select NALGs led to a substantial improvement (2 to 3 fold) in radiofluorination yields over traditional leaving groups. PMID:19572583

Simulation of lubricating behavior of a thioether liquid lubricant by an electrochemical method

NASA Technical Reports Server (NTRS)

Morales, W.

1984-01-01

An electrochemical cell was constructed to explore the possible radical anion forming behavior of a thioether liquid lubricant. The electrochemical behavior of the thioether was compared with the electrochemical behavior of biphenyl, which is known to form radical anions. Under controlled conditions biphenyl undergoes a reversible reaction to a radical anion, whereas the thioether undergoes an irreversible reduction yielding several products. These results are discussed in relation to boundary lubrication.

Supercritical fluid extraction

DOEpatents

Wai, Chien M.; Laintz, Kenneth

1994-01-01

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated or lipophilic crown ether or fluorinated dithiocarbamate. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

Sulfur Donor Atom Effects on Copper(I)/O2 Chemistry with Thioanisole Containing Tetradentate N3S Ligand Leading to μ-1,2-Peroxo-Dicopper(II) species

PubMed Central

Lee, Yunho; Lee, Dong-Heon; Park, Ga Young; Lucas, Heather R.; Sarjeant, Amy A. Narducci; Kieber-Emmons, Matthew T.; Vance, Michael A.; Milligan, Ashley E.; Solomon, Edward I.; Karlin, Kenneth D.

2010-01-01

To better understand the effect of thioether coordination in copper-O2 chemistry, the tetradentate N3S ligand LASM (2-(methylthio)-N,N-bis((pyridin-2-yl)methyl)benzenamine) and related alkylether ligand LEOE (2-ethoxy-N,N-bis((pyridin-2-yl)methyl)ethanamine) have been studied. The corresponding copper(I) complexes, [(LASM)CuI]+ (1a) and [(LEOE)CuI]+ (3a) were studies as were the related compound [(LESE)CuI]+ (2a, LESE = (2-ethylthio-N,N-bis((pyridin-2-yl)methyl)ethanamine). The X-ray structure of 1a and its solution conductivity reveal a monomeric molecular structure possessing thioether coordination which persists in solution. In contrast, the C-O stretching frequencies of the derivative Cu(I)-CO complexes reveal that for these complexes, the modulated ligand arms, whether arylthioether, alkylthioether or ether, are not coordinated to the cuprous ion. Electrochemical data for 1a and 2a in CH3CN and DMF show the thioanisole moiety to be a poor electron donor compared to alkylthioether (1a is ~ 200 mV more positive than 2a). The structures of [(LASM)CuII(CH3OH)]2+ (1c) and [(LESE)CuII(CH3OH)]2+ (2c) have also been obtained and indicate nearly identical copper coordination environments. Oxygenation of 1a at reduced temperature gives a characteristic deep blue colored intermediate [{(LASM)CuII}2(O22−)]2+ (1bP) with absorption features at 442 (1,500 M−1cm−1), 530 (8,600 M−1cm−1) and 605 nm (10,400 M−1cm−1); these values compare well to the LMCT transitions previously reported for [{(LESE)CuII}2(O22−)]2+ (2bP). Resonance Raman data for [{(LASM)CuII}2(O22−)]2+ (1bP) support the formation of μ-1,2-peroxo species (ν(O-O) = 828 cm−1 (Δ(18O2) = 48), νsym(Cu-O) = 547 cm−1 (Δ(18O2) = 23) and νasym(Cu-O) = 497 cm−1 (Δ(18O2) = 22) and suggest the LASM ligand is a poorer electron donor to copper than is LESE. In contrast, the oxygenation of [(LEOE)CuI]+ (3a), possessing an ether donor as an analogue of the thioether in LESE, led to the formation of a bis(μ-oxo) species [{(LEOE)CuIII}2(O2−)2]2+ (3bO; 380 nm, ε ~ 10,000 M−1cm−1). This result provides further support for the sulfur influence in 1bP and 2bP, in particular coordination of the sulfur to the Cu. Thermal decomposition of 1bP is accompanied by ligand sulfoxidation. The structure of [{(LEOE)CuII(Cl)}2]+ (3c) generated from the reductive dehalogenation of organic chlorides suggests that the ether moiety is weakly bound to the cupric ion. A detailed discussion of the spectroscopic and structural characteristics of 1bP, 2bP and 3bO is presented. PMID:20822156

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

NASA Technical Reports Server (NTRS)

Napier, Mary E.; Stair, Peter C.

1992-01-01

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

The preparation of new perfluoro ether fluids exhibiting excellent thermal-oxidative stabilities

NASA Technical Reports Server (NTRS)

Jones, William R., Jr.; Bierschenk, Thomas R.; Juhlke, Timothy J.; Kawa, Hajima; Lagow, Richard J.

1988-01-01

A series of low molecular weight perfluoroalkyl ethers (PFAEs) were synthesized by direct fluorination. Viscosity-temperature properties and oxidation stabilities were determined. Viscosity-temperature correlations indicated that increases in branching and increases in the size of the branching substituent caused a deterioration in viscometric properties (i.e., an increase in ASTM slope). In addition, increasing the ratio of carbon to oxygen in these compounds also increased the ASTM slope. Preliminary oxidation stability measurements indicated that highly branched PFAE fluids (i.e., those containing quaternary carbons) may be less stable than either those containing a single trifluoromethyl pendant group or those containing no branching at all.

Legacy and Emerging Perfluoroalkyl Substances Are Important Drinking Water Contaminants in the Cape Fear River Watershed of North Carolina

EPA Science Inventory

Long-chain per- and polyfluoroalkyl substances (PFASs) are being replaced by short-chain PFASs and fluorinated alternatives. For ten legacy PFASs and seven recently discovered perfluoroalkyl ether carboxylic acids (PFECAs), we report (1) their occurrence in the Cape Fear River (C...

Functional Modification of Thioether Groups in Peptides, Polypeptides, and Proteins.

PubMed

Deming, Timothy J

2017-03-15

Recent developments in the modification of methionine and other thioether-containing residues in peptides, polypeptides, and proteins are reviewed. Properties and potential applications of the resulting functionalized products are also discussed. While much of this work is focused on natural Met residues, modifications at other side-chain residues have also emerged as new thioether-containing amino acids have been incorporated into peptidic materials. Functional modification of thioether-containing amino acids has many advantages and is a complementary methodology to the widely utilized methods for modification at cysteine residues.

Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; DeMore, W. B.

1995-01-01

Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

Controlled disulfonated poly(arylene ether sulfone) multiblock copolymers for direct methanol fuel cells.

PubMed

Li, Qing; Chen, Yu; Rowlett, Jarrett R; McGrath, James E; Mack, Nathan H; Kim, Yu Seung

2014-04-23

Structure-property-performance relationships of disulfonated poly(arylene ether sulfone) multiblock copolymer membranes were investigated for their use in direct methanol fuel cell (DMFC) applications. Multiple series of reactive polysulfone, polyketone, and polynitrile hydrophobic block segments having different block lengths and molecular composition were synthesized and reacted with a disulfonated poly(arylene ether sulfone) hydrophilic block segment by a coupling reaction. Large-scale morphological order of the multiblock copolymers evolved with the increase of block size that gave notable influence on mechanical toughness, water uptake, and proton/methanol transport. Chemical structural changes of the hydrophobic blocks through polar group, fluorination, and bisphenol type allowed further control of the specific properties. DMFC performance was analyzed to elicit the impact of structural variations of the multiblock copolymers. Finally, DMFC performances of selected multiblock copolymers were compared against that of the industrial standard Nafion in the DMFC system.

Theory versus Practice in the Twentieth-Century Search for the Ideal Anaesthetic Gas.

PubMed

Rae, Ian D

2016-02-01

At the beginning of the twentieth century, an anaesthetist could choose between nitrous oxide, chloroform, and ether (diethyl ether) for the induction of painrelieving unconsciousness. By the end of century, the choice was between a small number of fluorinated aliphatic ethers such as Enflurane, Desflurane, and Sevoflurane, and (in some jurisdictions) the rare gas, xenon. Between these endpoints researchers had identified a surprisingly broad range of hydrocarbons, noble gases, organohalogens, and aliphatic ethers that possessed anaesthetic properties. None was entirely satisfactory, but clinicians at various times and in various places employed substances in each of these categories. Behind the search for new anaesthetic gases was a theory of action (Meyer- Overton theory) that was known to be inadequate, but as no alternative was strong enough to displace it the search continued on purely empirical grounds, while lip-service was paid to the theory. By the time a theory couched in more modern terms was proposed, a suite of modern anaesthetic gases was in place, and there have been no attempts to use that theory to drive a new search.

Increased urinary excretion of thioether in new rubber workers

PubMed Central

Kilpikari, I; Savolainen, H

1982-01-01

ABSTRACT Urinary excretion of thioether before starting work and in the early work period in a rubber factory was measured in urine samples collected after one, two to four, and five or more months of starting work. The study population consisted of 84 new workers. The urinary excretion of thioether decreased after one month's exposure and increased thereafter up to five months. Measurement of urinary thioethers in groups of new workers is therefore informative of exposure to alkylating agents only after several months from starting work. This effect may be mediated by the induction of the pertinent metabolic pathway. PMID:7138800

Fluorinated poly(ether sulfone) ionomers with disulfonated naphthyl pendants for proton exchange membrane applications

NASA Astrophysics Data System (ADS)

Hu, Zhaoxia; Lu, Yao; Zhang, Xulve; Yan, Xiaobo; Li, Na; Chen, Shouwen

2018-06-01

Proton exchange membranes based on fluorinated poly(ether sulfone)s with disulfonated naphthyl pendants (sSPFES) have been successfully prepared by post functionalization through polymeric SNAr reaction. Copolymer structure was confirmed by H-nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy, the physico-chemical properties of the sSPFES membranes were evaluated by thermogravimetric analysis, gel permeation chromatography, electro-chemical impedance spectroscopy, atomic force microscopy, Fenton, water-swelling and fuel cell test. The pendant grafting degree was controlled by varying the feeding amount of the disulfonaphthols, resulting in the ion exchange capacity about 1.28-1.73 mmol/g. The obtained sSPFES membranes were thermal stable, mechanical ductile, and exhibited dimensional change less than 17%, water uptake below 70%, and proton conductivity as high as 0.17-0.28 S/cm at 90°C in water. In a single H2/O2 fuel cell test at 80°C, the sSPFES-B-3.2 membrane (1.61 mmol/g) showed the maximum power output of 593-658 mW/cm2 at 60%-80% relative humidity, indicating their rather promising potential for fuel cell applications.

Fluorinated poly(ether sulfone) ionomers with disulfonated naphthyl pendants for proton exchange membrane applications

NASA Astrophysics Data System (ADS)

Hu, Zhaoxia; Lu, Yao; Zhang, Xulve; Yan, Xiaobo; Li, Na; Chen, Shouwen

2018-05-01

Proton exchange membranes based on fluorinated poly(ether sulfone)s with disulfonated naphthyl pendants (sSPFES) have been successfully prepared by post functionalization through polymeric SNAr reaction. Copolymer structure was confirmed by H-nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy, the physico-chemical properties of the sSPFES membranes were evaluated by thermogravimetric analysis, gel permeation chromatography, electro-chemical impedance spectroscopy, atomic force microscopy, Fenton, water-swelling and fuel cell test. The pendant grafting degree was controlled by varying the feeding amount of the disulfonaphthols, resulting in the ion exchange capacity about 1.28-1.73 mmol/g. The obtained sSPFES membranes were thermal stable, mechanical ductile, and exhibited dimensional change less than 17%, water uptake below 70%, and proton conductivity as high as 0.17-0.28 S/cm at 90°C in water. In a single H2/O2 fuel cell test at 80°C, the sSPFES-B-3.2 membrane (1.61 mmol/g) showed the maximum power output of 593-658 mW/cm2 at 60%-80% relative humidity, indicating their rather promising potential for fuel cell applications.

Novel fluorinated surfactants tentatively identified in firefighters using liquid chromatography quadrupole time-of-flight tandem mass spectrometry and a case-control approach.

PubMed

Rotander, Anna; Kärrman, Anna; Toms, Leisa-Maree L; Kay, Margaret; Mueller, Jochen F; Gómez Ramos, María José

2015-02-17

Fluorinated surfactant-based aqueous film-forming foams (AFFFs) are made up of per- and polyfluorinated alkyl substances (PFAS) and are used to extinguish fires involving highly flammable liquids. The use of perfluorooctanesulfonic acid (PFOS) and other perfluoroalkyl acids (PFAAs) in some AFFF formulations has been linked to substantial environmental contamination. Recent studies have identified a large number of novel and infrequently reported fluorinated surfactants in different AFFF formulations. In this study, a strategy based on a case-control approach using quadrupole time-of-flight tandem mass spectrometry (QTOF-MS/MS) and advanced statistical methods has been used to extract and identify known and unknown PFAS in human serum associated with AFFF-exposed firefighters. Two target sulfonic acids [PFOS and perfluorohexanesulfonic acid (PFHxS)], three non-target acids [perfluoropentanesulfonic acid (PFPeS), perfluoroheptanesulfonic acid (PFHpS), and perfluorononanesulfonic acid (PFNS)], and four unknown sulfonic acids (Cl-PFOS, ketone-PFOS, ether-PFHxS, and Cl-PFHxS) were exclusively or significantly more frequently detected at higher levels in firefighters compared to controls. The application of this strategy has allowed for identification of previously unreported fluorinated chemicals in a timely and cost-efficient way.

Design, Synthesis and Evaluation of Novel 2,5,6-Trisubstituted Benzimidazoles Targeting FtsZ as Antitubercular Agents

PubMed Central

Park, Bora; Awasthi, Divya; Chowdhury, Soumya R.; Melief, Eduard H.; Kumar, Kunal; Knudson, Susan E.; Slayden, Richard A.; Ojima, Iwao

2014-01-01

Filamenting temperature-sensitive protein Z (FtsZ), an essential cell division protein, is a promising target for the drug discovery of new-generation antibacterial agents against various bacterial pathogens. As a part of SAR studies on benzimidazoles, we have synthesized a library of 376 novel 2,5,6-trisubstituted benzimidazoles, bearing ether or thioether linkage at the 6-position. In a preliminary HTP screening against Mtb H37Rv, 108 compounds were identified as hits at a cut off concentration of 5 μg/mL. Among those hits, 10 compounds exhibited MIC values in the range of 0.63–12.5 μg/mL. Light scattering assay and TEM analysis with the most potent compound 5a clearly indicate that its molecular target is Mtb-FtsZ. Also, the Kd of 5a with Mtb-FtsZ was determined to be 1.32 μM. PMID:24726304

Preliminary results of the comparison of the electrochemical behavior of a thioether and biphenyl

NASA Technical Reports Server (NTRS)

Morales, W.; Jones, W. R.

1983-01-01

An electrochemical cell was constructed to explore the feasibility of using electrochemical techniques to simulate the tribochemistry of various substances. The electrochemical cell was used to study and compare the behavior of a thioether 1,3-bis(phenylthio) benzene and biphenyl. It is found that under controlled conditions biphenyl undergoes a reversible reduction to a radical anion whereas the thioether undergoes an irreversible reduction yielding several products. The results are discussed in relationship to boundary lubrication.

Synthesis of 2-aryl and 3-aryl benzo[b]furan thioethers using aryl sulfonyl hydrazides as sulfenylation reagents.

PubMed

Zhao, Xia; Zhang, Lipeng; Lu, Xiaoyu; Li, Tianjiao; Lu, Kui

2015-03-06

An efficient, metal-free protocol used to synthesize aryl benzo[b]furan thioethers based on the I2-catalyzed cross-coupling of benzo[b]furans as well as the electrophilic cyclization of 2-alkynylphenol derivatives with aryl sulfonyl hydrazides was developed. Various 2-aryl and 3-aryl benzo[b]furan thioethers were obtained in moderate to good yields.

A High-Performance Recycling Solution for Polystyrene Achieved by the Synthesis of Renewable Poly(thioether) Networks Derived from d-Limonene

PubMed Central

Nash, Landon D.; Rodriguez, Jennifer N.; Lonnecker, Alexander T.; Raymond, Jeffery E.; Wilson, Thomas S.; Wooley, Karen L.; Maitland, Duncan J.

2014-01-01

Nanocomposite polymers have been prepared using a new sustainable materials synthesis process in which d-Limonene functions simultaneously both as a solvent for recycling polystyrene (PS) waste and as a monomer that undergoes UV-catalyzed thiol-ene polymerization reactions with polythiol co-monomers to afford polymeric products comprised of precipitated PS phases dispersed throughout elastomeric poly(thioether) networks. These blended networks exhibit mechanical properties that greatly exceed those of either polystyrene or the poly(thioether) network homopolymers alone. PMID:24249666

Use of Lantibiotic Synthetases for the Preparation of Bioactive Constrained Peptides

PubMed Central

Levengood, Matthew R.

2008-01-01

Stabilization of biologically active peptides is a major goal in peptide-based drug design. Cyclization is an often-used strategy to enhance resistance of peptides towards protease degradation and simultaneously improve their affinity for targets by restricting their conformational flexibility. Amongst the various cyclization strategies, the use of thioether crosslinks has been successful for various peptides including enkephalin. The synthesis of these thioethers can be arduous, especially for longer peptides. Described herein is an enzymatic strategy taking advantage of the lantibiotic synthetase LctM that dehydrates Ser and Thr residues to the corresponding dehydroalanine and dehydrobutyrine residues and catalyzes the Michael-type addition of Cys residues to form thioether crosslinks. The use of LctM to prepare thioether containing analogs of enkephalin, contryphan, and inhibitors of human tripeptidyl peptidase II and spider venom epimerase is demonstrated. PMID:18294843

Oxidation of dimethyl-ether and ethylene in the atmosphere and combustion environment and thermodynamic studies on hydrofluorocarbons usingab initio calculation methods

NASA Astrophysics Data System (ADS)

Yamada, Takahiro

1999-08-01

Reaction pathways and kinetics are analyzed on CH3OC.H2 unimolecular decay and on the complete CH3OC.H2 + O2 reaction system using thermodynamic properties DHdegf 298,Sdeg 298, and Cp(T) 300 <= T/K <= 1500) derived by two ab initio calculation methods, CBS-q and G2. These are used to determine thermodynamic properties of reactants, intermediate radicals and transition state (TS) compounds. Quantum Rice-Ramsperger-Kassel (QRRK) analysis is used to calculate energy dependent rate constants, k(E), and master equation is used to account for collisional stabilization. Comparison of calculated fall-off with experiment indicates that the CBS-q and G2 calculated Ea,rxn for the rate controlling transition state (β-scission reaction to CH 2O + C.H2OOH) needs to be lowered by factor of 3.3 kcal/mol and 4.0 kcal/mol respectively in order to match the data of Sehested et al. Experimental results on dimethyl-ether pyrolysis and oxidation reaction systems are compared with a detailed reaction mechanism model. The computer code CHEMKIN II is used for numerical integration. Overall agreement of the model data with experimental data is very good. Reaction pathways are analyzed and kinetics are determined on formation and reactions of the adduct resulting from OH addition to ethylene using the above ab initio methods. Hydrogen atom tunneling is included by use of Eckart formalism. Rate constants are compared with experimentally determined product branching ratios (C.H2CH 2OH stabilization: CH2O + CH3: CH3CHO + H). ab initio calculations are performed to estimate thermodynamic properties of nine fluorinated ethane compounds (fluoroethane to hexafluoroethane), eight fluoropropane (1-fluoropropane, 1,1- and 1,2- difluoropropane, 1,1,1- and 1,1,2-trifluoropropane, 1,1,1,2- and 1,1,2,2-tetrafluoropropane and 1,1,1,2,2- pentafluoropropane), and 2-fluoro,2-methylpropane. Standard entropies and heat capacities are calculated using the rigid-rotor-harmonic-oscillator approximation with direct integration over energy levels of the intramolecular rotation potential energy curve. Enthalpies of formation are estimated using G2MP2 total energies and isodesmic reactions. Thermodynamic properties for fluorinated carbon groups C/C/F/H2, C/C/F2/H, C/C/F3, C/C2/F/H, C/C2/F2 and C/C3/F for fluorinated alkane compounds, CD/F/H and CD/F2 for fluorinated alkene compounds and CT/F for fluorinated alkyne compounds are estimated. Fluorine-fluorine interaction terms F/F, 2F/F, 3F/F, 2F/2F, 3F/2F and 3F/3F for alkane compounds, F//F, 2F//F and 2F/2F for alkene compounds, and F///F for alkyne compound are also estimated.

Determination of sulfur compounds in hydrotreated transformer base oil by potentiometric titration.

PubMed

Chao, Qiu; Sheng, Han; Cheng, Xingguo; Ren, Tianhui

2005-06-01

A method was developed to analyze the distribution of sulfur compounds in model sulfur compounds by potentiometric titration, and applied to analyze hydrotreated transformer base oil. Model thioethers were oxidized to corresponding sulfoxides by tetrabutylammonium periodate and sodium metaperiodate, respectively, and the sulfoxides were titrated by perchloric acid titrant in acetic anhydride. The contents of aliphatic thioethers and total thioethers were then determined from that of sulfoxides in solution. The method was applied to determine the organic sulfur compounds in hydrotreated transformer base oil.

Chemical bonding and the equilibrium composition of Grignard reagents in ethereal solutions.

PubMed

Henriques, André M; Barbosa, André G H

2011-11-10

A thorough analysis of the electronic structure and thermodynamic aspects of Grignard reagents and its associated equilibrium composition in ethereal solutions is performed. Considering methylmagnesium halides containing fluorine, chlorine, and bromine, we studied the neutral, charged, and radical species associated with their chemical equilibrium in solution. The ethereal solvents considered, tetrahydrofuran (THF) and ethyl ether (Et(2)O), were modeled using the polarizable continuum model (PCM) and also by explicit coordination to the Mg atoms in a cluster. The chemical bonding of the species that constitute the Grignard reagent is analyzed in detail with generalized valence bond (GVB) wave functions. Equilibrium constants were calculated with the DFT/M06 functional and GVB wave functions, yielding similar results. According to our calculations and existing kinetic and electrochemical evidence, the species R(•), R(-), (•)MgX, and RMgX(2)(-) must be present in low concentration in the equilibrium. We conclude that depending on the halogen, a different route must be followed to produce the relevant equilibrium species in each case. Chloride and bromide must preferably follow a "radical-based" pathway, and fluoride must follow a "carbanionic-based" pathway. These different mechanisms are contrasted against the available experimental results and are proven to be consistent with the existing thermodynamic data on the Grignard reagent equilibria.

Serotonergic Neurotoxic Thioether Metabolites of 3,4-Methylenedioxymethamphetamine (MDMA, “Ecstasy”): Synthesis, Isolation and Characterization of Diastereoisomers

PubMed Central

Pizarro, Nieves; de la Torre, Rafael; Joglar, Jesús; Okumura, Noriko; Perfetti, Ximena; Lau, Serrine S.; Monks, Terrence J.

2014-01-01

3,4-Methylenedioxymethamphetamine (MDMA, ecstasy) is a synthetic recreational drug of abuse that produces long-term toxicity associated with the degeneration of serotonergic nerve terminals. In various animal models direct administration of MDMA into the brain fails to reproduce the serotonergic neurotoxicity, implying a requirement for the systemic metabolism and bioactivation of MDMA. Catechol-thioether metabolites of MDMA, formed via oxidation of 3,4-dihydroxymetamphetamine and 3,4-dihydroxyamphetamine (HHMA and HHA) and subsequent conjugation with glutathione (GSH), are selective serotonergic neurotoxicants when administered directly into brain. Moreover, following systemic administration of MDMA, the thioether adducts are present in rat brain dialysate. MDMA contains a stereogenic center, and is consumed as a racemate. Interestingly, different pharmacological properties have been attributed to the two enantiomers, (S)-MDMA being the most active in the central nervous system and responsible for the entactogenic effects, and most likely also for the neurodegeneration. The present study focused on the synthesis and stereochemical analysis of the neurotoxic MDMA thioether metabolites, 5-(glutathion-S-yl)-HHMA, 5-(N-acetylcysteine-S-yl)-HHMA, 2,5-bis-(glutathion-S-yl)-HHMA and 2,5-bis-(N-acetylcysteine-S-yl)-HHMA. Both enzymatic and electrochemical syntheses were explored, and methodologies for analytical and semi-preparative diastereoisomeric separation of MDMA thioether conjugates by HPLC-CEAS and HPLC-UV respectively were developed. Synthesis, diastereoisomeric separation, and unequivocal identification of the thioether conjugates of MDMA provide the chemical tools necessary for appropriate toxicological and metabolic studies on MDMA metabolites contributing to its neurotoxicity. PMID:19548351

Prevention by thioethers of the hepatotoxicity and covalent binding to macromolecules of N-hydroxy-2-acetylaminofluorene and its sulfate ester in rat liver in vivo and in vitro.

PubMed

van den Goorbergh, J A; de Wit, H; Tijdens, R B; Mulder, G J; Meerman, J H

1987-02-01

In order to find potentially effective compounds that could prevent the covalent binding of the carcinogen N-hydroxy-2-acetylaminofluorene (N-OH-AAF) to rat liver macromolecules in vivo, the prevention of the covalent binding to RNA of the sulfate ester of the carcinogen N-OH-AAF by a series of thioethers was investigated in vitro. The most effective thioethers, which inhibited the covalent binding by 70% or more, were studied for their protection against acute hepatotoxicity of N-OH-AAF in the rat in vivo. Three of these thioethers, thiazolidine, methyl 4-(methylthio)benzoate, and 2-(methylthio)benzimidazole significantly decreased the hepatoxicity of N-OH-AAF, by 45, 71 and 83%, respectively. The effects of these thioethers on the covalent binding of N-OH-AAF to cellular macromolecules in vivo were also studied. Methyl 4-(methylthio)benzoate and 2-(methylthio)benzimidazole decreased the adduct formation of N-OH-AAF to DNA by 54 and 44%, respectively, but had no effect on protein adduct formation. Only 2-(methylthio)benzimidazole caused a slight decrease (23%) in the AAF-- protein adduct formation. 2-Acetylaminofluorene (AAF) and methyl 4-(methyl-sulfinyl)benzoate were the main products in the incubation of methyl 4-(methylthio)benzoate with AAF-N-sulfate in vitro. This suggests that the thioether attacks the nitrenium ion which is formed by spontaneous breakdown of AAF-N-sulfate; the formation of a sulfonium--AAF conjugate is postulated which decomposes into AAF and a sulfinyl compound.

Cox-2 inhibitory effects of naturally occurring and modified fatty acids.

PubMed

Ringbom, T; Huss, U; Stenholm , A; Flock, S; Skattebøl, L; Perera, P; Bohlin, L

2001-06-01

In the search for new cyclooxygenase-2 (COX-2) selective inhibitors, the inhibitory effects of naturally occurring fatty acids and some of their structural derivatives on COX-2-catalyzed prostaglandin biosynthesis were investigated. Among these fatty acids, linoleic acid (LA), alpha-linolenic acid (alpha-LNA), myristic acid, and palmitic acid were isolated from a CH(2)Cl(2) extract of the plant Plantago major by bioassay-guided fractionation. Inhibitory effects of other natural, structurally related fatty acids were also investigated: stearic acid, oleic acid, pentadecanoic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA). Further, the inhibitory effects of these compounds on COX-2- and COX-1-catalyzed prostaglandin biosynthesis was compared with the inhibition of some synthesized analogues of EPA and DHA with ether or thioether functions. The most potent COX-2-catalyzed prostaglandin biosynthesis inhibitor was all-(Z)-5-thia-8,11,14,17-eicosatetraenoic acid (2), followed by EPA, DHA, alpha-LNA, LA, (7E,11Z,14Z,17Z)-5-thiaeicosa-7,11,14,17-tetraenoic acid, all-(Z)-3-thia-6,9,12,15-octadecatetraenoic acid, and (5E,9Z,12Z,15Z,18Z)-3-oxaheneicosa-5,9,12,15,18-pentaenoic acid, with IC(50) values ranging from 3.9 to180 microM. The modified compound 2 and alpha-LNA were most selective toward COX-2, with COX-2/COX-1 ratios of 0.2 and 0.1, respectively. This study shows that several of the natural fatty acids as well as all of the semisynthetic thioether-containing fatty acids inhibited COX-2-catalyzed prostaglandin biosynthesis, where alpha-LNA and compound 2 showed selectivity toward COX-2.

The Properties of Fluorine, Oxygen Bifluoride, and Chlorine Trifluoride

DTIC Science & Technology

1949-09-06

they should be of forg€;d steel. Welded joints are excellent provided the welds are slag -free. Cast iron or any ether material containing silica cannot...400°C brilliant light Manganese powder form; 500°C formation of fluoride with glowing Zinc Cadmium powder form; heating glowing and flashing...reaction upon heating Magnesium at first, no reaction; explosive reaction Aluminum after ignition with carbon Zinc TV „ 1X11 Lead Cupfier L

Design, synthesis and evaluation of novel 2,5,6-trisubstituted benzimidazoles targeting FtsZ as antitubercular agents.

PubMed

Park, Bora; Awasthi, Divya; Chowdhury, Soumya R; Melief, Eduard H; Kumar, Kunal; Knudson, Susan E; Slayden, Richard A; Ojima, Iwao

2014-05-01

Filamenting temperature-sensitive protein Z (FtsZ), an essential cell division protein, is a promising target for the drug discovery of new-generation antibacterial agents against various bacterial pathogens. As a part of SAR studies on benzimidazoles, we have synthesized a library of 376 novel 2,5,6-trisubstituted benzimidazoles, bearing ether or thioether linkage at the 6-position. In a preliminary HTP screening against Mtb H37Rv, 108 compounds were identified as hits at a cut off concentration of 5 μg/mL. Among those hits, 10 compounds exhibited MIC values in the range of 0.63-12.5 μg/mL. Light scattering assay and TEM analysis with the most potent compound 5a clearly indicate that its molecular target is Mtb-FtsZ. Also, the Kd of 5a with Mtb-FtsZ was determined to be 1.32 μM. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermomechanical Formation–Structure–Property Relationships in Photopolymerized Copper-Catalyzed Azide–Alkyne (CuAAC) Networks

PubMed Central

Baranek, Austin; Song, Han Byul; McBride, Mathew; Finnegan, Patricia; Bowman, Christopher N.

2016-01-01

Bulk photopolymerization of a library of synthesized multifunctional azides and alkynes was carried out toward developing structure–property relationships for CuAAC-based polymer networks. Multifunctional azides and alkynes were formulated with a copper catalyst and a photoinitiator, cured, and analyzed for their mechanical properties. Material properties such as the glass transition temperatures (Tg) show a strong dependence on monomer structure with Tg values ranging from 41 to 90 °C for the series of CuAAC monomers synthesized in this study. Compared to the triazoles, analogous thioether-based polymer networks exhibit a 45–49 °C lower Tg whereas analogous monomers composed of ethers in place of carbamates exhibit a 40 °C lower Tg. Here, the formation of the triazole moiety during the polymerization represents a critical component in dictating the material properties of the ultimate polymer network where material properties such as the rubbery modulus, cross-link density, and Tg all exhibit strong dependence on polymerization conversion, monomer composition, and structure postgelation. PMID:27867223

Homoallylglycine residues are superior precursors to orthogonally modified thioether containing polypeptides.

PubMed

Perlin, Pesach; Gharakhanian, Eric G; Deming, Timothy J

2018-06-12

Homoallylglycine N-carboxyanhydride, Hag NCA, monomers were synthesized and used to prepare polypeptides containing Hag segments with controllable lengths of up to 245 repeats. Poly(l-homoallylglycine), GHA, was found to adopt an α-helical conformation, which provided good solubility in organic solvents and allowed high yield functionalization of its alkene side-chains via radical promoted addition of thiols. The conformations of these derivatives were shown to be switchable between α-helical and disordered states in aqueous media using thioether alkylation or oxidation reactions. Incorporation of GHA segments into block copolymers with poly(l-methionine), M, segments provided a means to orthogonally modify thioether side-chains different ways in separate copolypeptide domains. This approach allows preparation of functional polypeptides containing discrete domains of oxidized and alkylated thioether containing residues, where chain conformation and functionality of each domain can be independently modified.

Trifluorostyrene containing compounds, and their use in polymer electrolyte membranes

DOEpatents

Choudhury, Biswajit [Kingston, CA; Roelofs, Mark Gerrit [Hockessin, DE; Yang,; Zhen-Yu, [Hockessin, DE

2009-07-21

A fluorinated ion exchange polymer is prepared by grafting a monomer onto a base polymer, wherein the grafting monomer is selected from the group consisting of structure 1a, 1b and mixture thereof; ##STR00001## wherein Y is selected from the group consisting of --R.sub.FSO.sub.2F, --R.sub.FSO.sub.3M, --R.sub.SO.sub.2NH.sub.2 and --R.sub.FSO.sub.2N(M)SO.sub.2R.sup.2.sub.F, where in M is hydrogen, an alkali cation or ammonium; and R.sub.F and R.sup.2.sub.F are perfluorinated or partially fluorinated, and may optionally include ether oxygens; and n is between 1 and 2 for 1a, or n is between 1 and 3 for 1b. These ion exchange polymers are useful is preparing catalyst coated membranes and membrane electrode assemblies for fuel cells.

The Determination of the Smoke Hazards Resulting from the Burning of Shipboard Materials Utilized by the US Navy.

DTIC Science & Technology

1981-08-31

Interior Paairt r’ts RorzotalSapleIeun Forle Tranduer Figure I. Combustion Products Test Chamber. .. 2. *Sold hda 0 Ol~n kb 3’. 8.iIdg IN= W I Vll ue2...hydrocarbons (alkanes, alkenes, and alkynes), alcohols, aldehydes, ketones, ethers, carboxylic acids , aromatic hydrocarbons, polycyclic aromatic hydrocarbons...carboxylic acids , a few nitriles, acetaldehyde, and acetone. A few exotic fluorine containing organic compounds have unusually low refractive indices for

Depletion of mitochondrial coenzyme A and glutathione by 4-dimethylaminophenol and formation of mixed thioethers.

PubMed

Eckert, K G; Elbers, F R; Eyer, P

1989-10-01

4-Dimethylaminophenol (DMAP), an antidote in cyanide poisoning, has been shown to produce kidney lesions in rats, to damage isolated rat kidney tubules and to impair mitochondrial functions as already described for 4-aminophenol. Since DMAP upon oxidation forms bis- and tris-substituted thioethers with GSH, it was anticipated that mitochondrial toxicity of DMAP might result from CoA depletion. In a model reaction DMAP was oxidized by oxyhemoglobin in the presence of CoA and GSH resulting in formation of tris-(CoA-S-yl)-DMAP, tris-(GSH-S-yl)-DMAP and two mixed thioethers, namely, (CoA-S-yl)-bis-(GSH-S-yl)-DMAP and (GSH-S-yl)-bis-(CoA-S-yl)-DMAP. The compounds were isolated by HPLC and identified spectroscopically, by amino acid analysis and Raney-Nickel desulfuration. Rat liver mitochondria (5 mg protein/ml) incubated under state IV conditions with 20 and 50 microM DMAP were depleted of GSH and total coenzyme A with formation of GSSG and the above-mentioned thioethers which were quantified by isotope dilution techniques using [14C]-labelled DMAP and the isolated, inactive thioethers. The results confirm earlier suggestions that part of the cytotoxicity of DMAP may result from depletion of vital mitochondrial thiols, particularly CoA. Since 4-aminophenol reacts analogously, similar cytotoxic effects can be expected from compounds which on (aut)oxidation form quinoid systems capable of 1.4-addition reactions with nucleophilic thiols.

Heavy metal absorbing Thioether-functionalized ligands derived from vegetable oils

USDA-ARS?s Scientific Manuscript database

Sulfur-functionalized vegetable oils containing thioether groups have been shown to effectively remove Ag+ from aqueous solution. Interestingly, the absorption capacity differs depending upon the choice of which vegetable oil precursor is functionalized. In this study, we will provide data for oils ...

Synthesis of the diazonium (perfluoroalkyl) benzenesulfonimide monomer from Nafion monomer for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Mei, Hua; D'Andrea, Dan; Nguyen, Tuyet-Trinh; Nworie, Chima

2014-02-01

One diazonium (perfluoroalkyl) benzenesulfonimide monomer, perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide, has been synthesized from Nafion monomer for the first time. With trifluorovinyl ether and diazonium precursors, the partially-fluorinated diazonium PFSI monomer can be polymerized and will provide chemically bonding with carbon electrode in proton exchange membrane fuel cells. A systematic study of the synthesis and characterization of this diazonium PFSI monomer has been conducted by varying reaction conditions. The optimized synthesis method has been established in the lab.

Effect of lattice-gas atoms on the adsorption behaviour of thioether molecules.

PubMed

Pan, Yi; Yang, Bing; Hulot, Catherine; Blechert, Siegfried; Nilius, Niklas; Freund, Hans-Joachim

2012-08-21

Using STM topographic imaging and spectroscopy, we have investigated the adsorption of two thioether molecules, 1,2-bis(phenylthio)benzene and (bis(3-phenylthio)-phenyl)sulfane, on noble and transition metal surfaces. The two substrates show nearly antipodal behaviour. Whereas complexes with one or two protruding centres are observed on Au(111), only flat and uniform ad-structures are found on NiAl(110). The difference is ascribed to the possibility of the thioethers to form metal-organic complexes by coordinating lattice-gas atoms on the Au(111), while only the pristine molecules adsorb on the alloy surface. The metal coordination in the first case is driven by the formation of strong Au-S bonds and enables the formation of characteristic monomer, dimer and chain-like structures of the thioethers, using the Au atoms as linkers. A similar mechanism is not available on the NiAl, because no lattice gas develops at this surface at room temperature. Our work demonstrates how surface properties, i.e. the availability of mobile ad-species, determine the interaction of organic molecules with metallic substrates.

Nanoengineered Carbon-Based Materials For Reactive Adsorption of Toxic Industrial Compounds

DTIC Science & Technology

2015-01-13

in phenolic, sulfonic, thioethers and pyrrolic groups. 29. Addition of small amount of sulfanilic acid (grafting with acid) to silica-carbons...thioethers and pyrrolic groups. 29. Addition of small amount of sulfanilic acid (grafting with acid) to silica-carbons composites increases NO2

Optimized Structures and Proton Affinities of Fluorinated Dimethyl Ethers: An Ab Initio Study

NASA Technical Reports Server (NTRS)

Orgel, Victoria B.; Ball, David W.; Zehe, Michael J.

1996-01-01

Ab initio methods have been used to investigate the proton affinity and the geometry changes upon protonation for the molecules (CH3)2O, (CH2F)2O, (CHF2)2O, and (CF3)2O. Geometry optimizations were performed at the MP2/3-2 I G level, and the resulting geometries were used for single-point energy MP2/6-31G calculations. The proton affinity calculated for (CH3)2O was 7 Kjoule/mole from the experimental value, within the desired variance of +/- 8Kjoule/mole for G2 theory, suggesting that the methodology used in this study is adequate for energy difference considerations. For (CF3)20, the calculated proton affinity of 602 Kjoule/mole suggests that perfluorinated ether molecules do not act as Lewis bases under normal circumstances; e.g. degradation of commercial lubricants in tribological applications.

Molecular recognition of modified adenine nucleotides by the P2Y(1)-receptor. 1. A synthetic, biochemical, and NMR approach.

PubMed

Halbfinger, E; Major, D T; Ritzmann, M; Ubl, J; Reiser, G; Boyer, J L; Harden, K T; Fischer, B

1999-12-30

The remarkably high potencies of 2-thioether-adenine nucleotides regarding the activation of the P2Y(1)-receptor (P2Y(1)-R) in turkey erythrocyte membranes represent some of the largest substitution-promoted increases in potencies over that of a natural receptor ligand. This paper describes the investigation regarding the origin of the high potency of these P2Y(1)-R ligands over that of ATP. For this study, an integrated approach was employed combining the synthesis of new ATP analogues, their biochemical evaluation, and their SAR analysis involving NMR experiments and theoretical calculations. These experiments and calculations were performed to elucidate the conformation and to evaluate the electronic nature of the investigated P2Y(1)-R ligands. ATP analogues synthesized included derivatives where C2 or C8 positions were substituted with electron-donating groups such as ethers, thioethers, or amines. The compounds were tested for their potency to induce P2Y(1)-R-mediated activation of phospholipase C in turkey erythrocytes and Ca(2+) response in rat astrocytes. 8-Substituted ATP and AMP derivatives had little or no effect on phospholipase C or on calcium levels, whereas the corresponding 2-substituted ATP analogues potently increased the levels of inositol phosphates and ¿Ca(2+)(i). AMP analogues were ineffective except for 2-butylthio-AMP which induced a small Ca(2+) response. P2Y(1)-R activity of these compounds was demonstrated by testing these ligands also on NG108-15 neuroblastoma x glioma hybrid cells. NMR data together with theoretical calculations imply that steric, rather than electronic, effects play a major role in ligand binding to the P2Y(1)-R. Hydrophobic interactions and H-bonds of the C2 substituent appear to be important determinants of a P2Y(1)-R ligand affinity.

Synthesis and Base Hydrolysis of a Cobalt(III) Complex Coordinated by a Thioether Ligand

ERIC Educational Resources Information Center

Roecker, Lee

2008-01-01

A two-week laboratory experiment for students in advanced inorganic chemistry is described. Students prepare and characterize a cobalt(III) complex coordinated by a thioether ligand during the first week of the experiment and then study the kinetics of Co-S bond cleavage in basic solution during the second week. The synthetic portion of the…

High temperature polymers for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Einsla, Brian Russel

Novel proton exchange membranes (PEMs) were investigated that show potential for operating at higher temperatures in both direct methanol (DMFC) and H 2/air PEM fuel cells. The need for thermally stable polymers immediately suggests the possibility of heterocyclic polymers bearing appropriate ion conducting sites. Accordingly, monomers and random disulfonated poly(arylene ether) copolymers containing either naphthalimide, benzoxazole or benzimidazole moieties were synthesized via direct copolymerization. The ion exchange capacity (IEC) was varied by simply changing the ratio of disulfonated monomer to nonsulfonated monomer in the copolymerization step. Water uptake and proton conductivity of cast membranes increased with IEC. The water uptake of these heterocyclic copolymers was lower than that of comparable disulfonated poly(arylene ether) systems, which is a desirable improvement for PEMs. Membrane electrode assemblies were prepared and the initial fuel cell performance of the disulfonated polyimide and polybenzoxazole (PBO) copolymers was very promising at 80°C compared to the state-of-the-art PEM (NafionRTM); nevertheless these membranes became brittle under operating conditions. Several series of poly(arylene ether)s based on disodium-3,3'-disulfonate-4,4 '-dichlorodiphenylsulfone (S-DCDPS) and a benzimidazole-containing bisphenol were synthesized and afforded copolymers with enhanced stability. Selected properties of these membranes were compared to separately prepared miscible blends of disulfonated poly(arylene ether sulfone) copolymers and polybenzimidazole (PBI). Complexation of the sulfonic acid groups with the PBI structure reduced water swelling and proton conductivity. The enhanced proton conductivity of NafionRTM membranes has been proposed to be due to the aggregation of the highly acidic side-chain sulfonic acid sites to form ion channels. A series of side-chain sulfonated poly(arylene ether sulfone) copolymers based on methoxyhydroquinone was synthesized in order to investigate this possible advantage and to couple this with the excellent hydrolytic stability of poly(arylene ether)s. The methoxy groups were deprotected to afford reactive phenolic sites and nucleophilic substitution reactions with functional aryl sulfonates were used to prepare simple aryl or highly acidic fluorinated sulfonated copolymers. The proton conductivity and water sorption of the resulting copolymers increased with the ion exchange capacity, but changing the acidity of the sulfonic acid had no apparent effect.

Novel proton exchange membranes based on structure-optimized poly(ether ether ketone ketone)s and nanocrystalline cellulose

NASA Astrophysics Data System (ADS)

Ni, Chuangjiang; Wei, Yingcong; Zhao, Qi; Liu, Baijun; Sun, Zhaoyan; Gu, Yan; Zhang, Mingyao; Hu, Wei

2018-03-01

Two sulfonated fluorenyl-containing poly(ether ether ketone ketone)s (SFPEEKKs) were synthesized as the matrix of composite proton exchange membranes by directly sulfonating copolymer precursors comprising non-sulfonatable fluorinated segments and sulfonatable fluorenyl-containing segments. Surface-modified nanocrystalline cellulose (NCC) was produced as the "performance-enhancing" filler by treating the microcrystalline cellulose with acid. Two families of SFPEEKK/NCC nanocomposite membranes with various NCC contents were prepared via a solution-casting procedure. Results revealed that the insertion of NCC at a suitable ratio could greatly enhance the proton conductivity of the pristine membranes. For example, the proton conductivity of SFPEEKK-60/NCC-4 (SFPEEKK with 60% fluorenyl segments in the repeating unit, and inserted with 4% NCC) composite membrane was as high as 0.245 S cm-1 at 90 °C, which was 61.2% higher than that of the corresponding pure SFPEEKK-60 membrane. This effect could be attributed to the formation of hydrogen bond networks and proton conduction paths through the interaction between -SO3H/-OH groups on the surface of NCC particles and -SO3H groups on the SFPEEKK backbones. Furthermore, the chemically modified NCC filler and the optimized chemical structure of the SFPEEKK matrix also provided good dimensional stability and mechanical properties of the obtained nanocomposites. In conclusion, these novel nanocomposites can be promising proton exchange membranes for fuel cells at moderate temperatures.

One-pot synthesis of keto thioethers by palladium/gold-catalyzed click and pinacol reactions.

PubMed

Cadu, Alban; Watile, Rahul A; Biswas, Srijit; Orthaber, Andreas; Sjöberg, Per J R; Samec, Joseph S M

2014-11-07

An atom-efficient synthesis of keto thioethers was devised via tandem gold/palladium catalysis. The reaction proceeds through a regioselective thiol attack at the β-position of the alcohol, followed by an alkyl, aryl, or benzyl 1,2-shift. Both acyclic and cyclic systems were studied, in the latter case leading to the ring expansion of cyclic substrates.

Novel imino thioether complexes of platinum(II): synthesis, structural investigation, and biological activity.

PubMed

Sgarbossa, Paolo; Sbovata, Silvia Mazzega; Bertani, Roberta; Mozzon, Mirto; Benetollo, Franco; Marzano, Cristina; Gandin, Valentina; Michelin, Rino A

2013-05-20

The reactions of the nitrile complexes cis- and trans-[PtCl2(NCR)2] (R = Me, Et, CH2Ph, Ph) with an excess of ethanethiol, EtSH, in the presence of a catalytic amount of n-BuLi in tetrahydrofuran (THF), afforded in good yield the bis-imino thioether derivatives cis-[PtCl2{E-N(H)═C(SEt)R}2] (R = Me (1), Et (2), CH2Ph (3), Ph (4)) and trans-[PtCl2{E-N(H)═C(SEt)R}2] (R = Me (5), Et (6), CH2Ph (7), Ph (8)). The imino thioether ligands assumed the E configuration corresponding to a cis addition of the thiol to the nitrile triple bond. The spectroscopic properties of these complexes have been reported along with the molecular structures of 1, 2, and 7 as established by X-ray crystallography which indicated that these compounds exhibit square-planar coordination geometry around the platinum center. Four N-H···Cl intermolecular contacts (N-H···Cl ca. 2.5-2.7 Å) between each chlorine atom and the N-H proton of the imino thioether ligand gave rise to "dimers" Pt2Cl4L4 (L = imino thioether) formed by two PtCl2L2 units. The cytotoxic properties of these new platinum(II) complexes were evaluated against various human cancer cell lines. Among all derivatives, trans-[PtCl2{E-N(H)═C(SEt)CH2Ph}2] showed the greatest in vitro cytotoxic activity being able to decrease cancer cell viability roughly 3-fold more effectively than cisplatin.

In vitro assessment of the structure-activity relationship of tyrosinase-dependent cytotoxicity of a series of substituted phenols.

PubMed

Naish-Byfield, S; Cooksey, C J; Latter, A M; Johnson, C I; Riley, P A

1991-01-01

The rate of oxidation by purified mushroom tyrosinase of 30 compounds was measured by oximetry, and the tyrosinase-dependent cytotoxicity of each estimated in an in vitro assay using exposure of non-melanogenic cells to the agents in the presence and absence of tyrosinase. Cytotoxicity was estimated by immediate inhibition of DNA synthesis; 4-hydroxyanisole was used as the reference material. Compounds that were not oxidized by tyrosinase were found to be non-toxic but there was no direct relationship between the rate of oxidation and the relative cytotoxicity of those materials that acted as substrates for the enzyme. Thioethers were found to be more cytotoxic than the corresponding phenoxyethers. This was partly due to their greater rate of oxidation by tyrosinase and, in the case of propylthiophenol, the consequence of higher effective toxicity of the lipophilic species. The optimum chain length for the side chain of the oxyethers was three saturated carbon atoms and the toxicity appeared to be influenced by the lipophilicity of the compounds, possibly reflecting the relative lipid solubility of the putative toxic ortho-quinones generated from them. The maximum tyrosinase-dependent toxicity observed was in the range 5-6 times the relative toxicity of 4-hydroxyanisole. Sulphinyl and sulphonyl derivatives were inactive. In addition to oxyethers and thioethers, esters and glycosides of oxyethers were also examined and were found to be toxic in the presence of tyrosinase when hydrolysed. The succinates were found to be oxidized and toxic in our test system, suggesting that they rapidly underwent spontaneous hydrolysis. Oximetry data suggest that slight spontaneous hydrolysis of the other compounds occurs but they were not toxic in our assay. Ring-methylated phenoxyethers were oxidized relatively slowly and were non-toxic. Fluorine-substituted phenoxyethers were oxidized slightly more rapidly and exhibited clear toxicity in our system. Sesamol was oxidized to a black pigment but was non-toxic in our assay. A water-soluble vitamin E derivative was not oxidized and was non-toxic. Allyl hydroquinone was not oxidized but exhibited significant direct toxicity.

Fluorinated reduced graphene oxide as a protective layer on the metallic lithium for application in the high energy batteries.

PubMed

Bobnar, Jernej; Lozinšek, Matic; Kapun, Gregor; Njel, Christian; Dedryvère, Rémi; Genorio, Boštjan; Dominko, Robert

2018-04-11

Metallic lithium is considered to be one of the most promising anode materials since it offers high volumetric and gravimetric energy densities when combined with high-voltage or high-capacity cathodes. However, the main impediment to the practical applications of metallic lithium is its unstable solid electrolyte interface (SEI), which results in constant lithium consumption for the formation of fresh SEI, together with lithium dendritic growth during electrochemical cycling. Here we present the electrochemical performance of a fluorinated reduced graphene oxide interlayer (FGI) on the metallic lithium surface, tested in lithium symmetrical cells and in combination with two different cathode materials. The FGI on the metallic lithium exhibit two roles, firstly it acts as a Li-ion conductive layer and electronic insulator and secondly, it effectively suppresses the formation of high surface area lithium (HSAL). An enhanced electrochemical performance of the full cell battery system with two different types of cathodes was shown in the carbonate or in the ether based electrolytes. The presented results indicate a potential application in future secondary Li-metal batteries.

Assessment of genotoxic exposure in Swedish coke-oven work by different methods of biological monitoring.

PubMed

Reuterwall, C; Aringer, L; Elinder, C G; Rannug, A; Levin, J O; Juringe, L; Onfelt, A

1991-04-01

This study evaluated the results of several biological methods used simultaneously to monitor coke-oven work. Blood samples from 44 male coke-oven workers and 48 male referents, matched for age and smoking/snuff consumption, were examined for cytogenetic damage in lymphocytes. Urinary thioether excretion was determined for 62, and urine mutagenicity for 31, of the subjects, who followed a standardized diet during the urine sampling. Exposure to polycyclic aromatic hydrocarbons varied with work task, the ambient air levels of benzo[a]pyrene sometimes exceeding 5 micrograms/m3. Cytogenetic damage, urine mutagenicity, and thioether excretion did not differ between the groups. The smokers, however, had significantly higher sister chromatid exchange frequencies, urine mutagenicity, and thioether excretion than the nonsmokers. The absence of biological indications of genotoxic exposure was unexpected and indicates that the studied methods are not adequate to assess the carcinogenic risks of Swedish coke-oven workers.

Design of multimodal degradable hydrogels for controlled therapeutic delivery

NASA Astrophysics Data System (ADS)

Kharkar, Prathamesh Madhav

Hydrogels are of growing interest for the delivery of therapeutics to specific sites in the body. For localized drug delivery, hydrophilic polymeric precursors often are laden with bioactive moieties and then directly injected to the site of interest for in situ gel formation. The release of physically entrapped cargo is dictated by Fickian diffusion, degradation of the drug carrier, or a combination of both. The goal of this work was to design and characterize degradable hydrogel formulations that are responsive to multiple biologically relevant stimuli for degradation-mediated delivery of cargo molecules such as therapeutic proteins, growth factors, and immunomodulatory agents. We began by demonstrating the use of cleavable click linkages formed by Michael-type addition reactions in conjunction with hydrolytically cleavable functionalities for the degradation of injectable hydrogels by endogenous stimuli for controlled protein release. Specifically, the reaction between maleimides and thiols was utilized for hydrogel formation, where thiol selection dictates the degradability of the resulting linkage under thiol-rich reducing conditions. Relevant microenvironments where degradation would occur in vivo include those rich in glutathione (GSH), a tripeptide that is found at elevated concentrations in carcinoma tissues. Degradation of the hydrogels was monitored with rheometry and volumetric swelling measurements. Arylthiol-based thioether succinimide linkages underwent degradation via click cleavage and thiol exchange reaction in the presence of GSH and via ester hydrolysis, whereas alkylthiol-based thioether succinimide linkages only undergo degradation by only ester hydrolysis. The resulting control over the degradation rate within a reducing microenvironment resulted in 2.5 fold differences in the release profile of the model protein, a fluorescently-labeled bovine serum albumin, from dually degradable hydrogels compared to non-degradable hydrogels, where the thiol exchange reaction facilitated rapid and responsive protein release in the presence of GSH. A photolabile o-nitrobenzyl ether group (o-NB) was subsequently incorporated within the PEG-based, gel-forming monomers to demonstrate cargo release triggered by exogenous stimuli for patient-specific therapies. Upon the application of cytocompatible doses of light, the photolabile o-NB linkage underwent irreversible cleavage yielding ketone and carboxylic acid-based cleavage products. Hydrogel degradation kinetics was characterized in response to externally applied cytocompatible light or GSH in aqueous microenvironments. By incorporating a photodegradable o-nitrobenzyl ether group, a thiol-sensitive succinimide thioether linkage, and ester linkages within the hydrogels, we demonstrated unique control over degradation via surface erosion or bulk degradation mechanisms, respectively, with degradation rate constants ranging from 10-1 min-1 to 10-4 min-1. As a proof of concept, the controlled release of nanobeads from the hydrogel was demonstrated in a preprogrammed and stimuli-responsive fashion. The multimodal degradable hydrogels were then investigated for the local controlled release of small molecular weight proteins, which are of interest for regulating various cellular functions and fates in vivo. Low molecular weight heparin, a highly sulfated polysaccharide was incorporated within the hydrogel network by Michael-type reaction due to its affinity with biologics such as growth factors and immunomodulatory proteins. Incorporation of reduction-sensitive linkages resulted in 2.3 fold differences in the release profile of fibroblast growth factor-2 (FGF-2) in the presence of GSH compared to non-reducing microenvironment. Bioactivity of released FGF-2 was comparable to pristine FGF-2, indicating the ability of the hydrogel to retain bioactivity of cargo molecules during encapsulation and release. Further, preliminary in vivo studies demonstrated control over hydrogel degradation by varying % degradable contents. Collectively, this research developed injectable hydrogels that are responsive to various endogenous and exogenous stimuli, establishing a platform for stimuli-responsive drug delivery carriers.

Extending antigen release from particulate vaccines results in enhanced antitumor immune response.

PubMed

Kapadia, Chintan H; Tian, Shaomin; Perry, Jillian L; Sailer, David; Christopher Luft, J; DeSimone, Joseph M

2018-01-10

Tumor-specific CD8 + cytotoxic T lymphocytes (CTLs) play a critical role in an anti-tumor immune response. However, vaccination intended to elicit a potent CD8 + T cell responses employing tumor-associated peptide antigens, are typically ineffective due to poor immunogenicity. Previously, we engineered a polyethylene glycol (PEG) hydrogel-based subunit vaccine for the delivery of an antigenic peptide and CpG (adjuvant) to elicit potent CTLs. In this study, we further examined the effect of antigen release kinetics on their induced immune responses. A CD8 + T cell epitope peptide from OVA (CSIINFEKL) and CpG were co-conjugated to nanoparticles utilizing either a disulfide or a thioether linkage. Subsequent studies comparing peptide release rates as a function of linker, determined that the thioether linkage provided sustained release of peptide over 72h. Ability to control the release of peptide resulted in both higher and prolonged antigen presentation when compared to disulfide-linked peptide. Both NP vaccine formulations resulted in activation and maturation of bone marrow derived dendritic cells (BMDCs) and induced potent CD8 + T cell responses when compared to soluble antigen and soluble CpG. Immunization with either disulfide or thioether linked vaccine constructs effectively inhibited EG7-OVA tumor growth in mice, however only treatment with the thioether linked vaccine construct resulted in enhanced survival. Copyright © 2017. Published by Elsevier B.V.

Application of Thioether for Vapor Phase Lubrication

NASA Technical Reports Server (NTRS)

Graham, E. Earl

1997-01-01

The objective of these studies was to identify the optimal conditions for vapor phase lubrication using Thioether for both sliding and rolling wear. The important variable include; (1) The component materials including M50 steel, monel and silicon nitride. (2) The vapor concentration and flow rate. (3) The temperature in the range of 600 F to 1500 F. (4) The loads and rolling and/or sliding speeds.

Design, synthesis and activity as acid ceramidase inhibitors of 2-oxooctanoyl and N-oleoylethanolamine analogues.

PubMed

Grijalvo, Santiago; Bedia, Carmen; Triola, Gemma; Casas, Josefina; Llebaria, Amadeu; Teixidó, Jordi; Rabal, Obdulia; Levade, Thierry; Delgado, Antonio; Fabriàs, Gemma

2006-10-01

The synthesis of novel N-acylethanolamines and their use as inhibitors of the aCDase is reported here. The compounds are either 2-oxooctanamides or oleamides of sphingosine analogs featuring a 3-hydroxy-4,5-hexadecenyl tail replaced by ether or thioether moieties. It appears that, within the 2-oxooctanamide family, the C3-OH group of the sphingosine molecule is required for inhibition both in vitro and in cultured cells. Furthermore, although the (E)-4 double bond is not essential for inhibitory activity, the (E) configuration is required, since the analogue with a (Z)-4 unsaturation was not inhibitory. None of the oleamides inhibited the aCDase in vitro. Conversely, with the exception of N-oleoylethanolamine and its analogs with S-decyl and S-hexadecyl substituents, all the synthesized oleamides inhibited the aCDase in cultured cells, although with a relatively low potency. We conclude that novel aCDase inhibitors can evolve from N-acylation of sphingoid bases with electron deficient-acyl groups. In contrast, chemical modification of the N-oleoylsphingosine backbone does not seem to offer an appropriate strategy to obtain aCDase inhibitors.

1,5-(H, RO, RS) shift/6π-electrocyclic ring closure tandem processes on N-[(α-heterosubstituted)-2-tolyl]ketenimines: a case study of relative migratory aptitudes and activating effects.

PubMed

Alajarín, Mateo; Bonillo, Baltasar; Orenes, Raúl-Angel; Ortín, María-Mar; Vidal, Angel

2012-12-28

A number of N-aryl ketenimines, substituted at the ortho position either with different non-cyclic acetalic functions (acetals, monothioacetals, dithioacetals) or with only one alkoxymethyl or (alkylthio)methyl group, have been prepared and submitted to thermal treatment in toluene solution. Under smooth heating the ketenimines bearing non-cyclic acetals converted into 3,4-dihydroquinolines following two competitive tandem sequences that involve the alternative 1,5 migration of a hydride or alkoxy group as the first mechanistic step, followed by subsequent 6π electrocyclic ring closure. The heterocumulenes bearing acyclic monothioacetal and dithioacetal functions converted via a unique consecutive process involving the selective migration of the alkanethiolate group. Ketenimines bearing only one ether or thioether group transformed exclusively by the tandem sequence initiated by a 1,5 hydride shift. All these transformations provided as final reaction products a variety of quinoline derivatives with a range of substitution patterns. From these experiments the following order of propensity to migration can be extracted: RS > RO > H. It was also possible to estimate the following order of relative activating activities: RO > RS > H.

Novel dengue virus NS2B/NS3 protease inhibitors.

PubMed

Wu, Hongmei; Bock, Stefanie; Snitko, Mariya; Berger, Thilo; Weidner, Thomas; Holloway, Steven; Kanitz, Manuel; Diederich, Wibke E; Steuber, Holger; Walter, Christof; Hofmann, Daniela; Weißbrich, Benedikt; Spannaus, Ralf; Acosta, Eliana G; Bartenschlager, Ralf; Engels, Bernd; Schirmeister, Tanja; Bodem, Jochen

2015-02-01

Dengue fever is a severe, widespread, and neglected disease with more than 2 million diagnosed infections per year. The dengue virus NS2B/NS3 protease (PR) represents a prime target for rational drug design. At the moment, there are no clinical PR inhibitors (PIs) available. We have identified diaryl (thio)ethers as candidates for a novel class of PIs. Here, we report the selective and noncompetitive inhibition of the serotype 2 and 3 dengue virus PR in vitro and in cells by benzothiazole derivatives exhibiting 50% inhibitory concentrations (IC50s) in the low-micromolar range. Inhibition of replication of DENV serotypes 1 to 3 was specific, since all substances influenced neither hepatitis C virus (HCV) nor HIV-1 replication. Molecular docking suggests binding at a specific allosteric binding site. In addition to the in vitro assays, a cell-based PR assay was developed to test these substances in a replication-independent way. The new compounds inhibited the DENV PR with IC50s in the low-micromolar or submicromolar range in cells. Furthermore, these novel PIs inhibit viral replication at submicromolar concentrations. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Bioorthogonal Metabolic DNA Labelling using Vinyl Thioether-Modified Thymidine and o-Quinolinone Quinone Methide.

PubMed

Gubu, Amu; Li, Long; Ning, Yan; Zhang, Xiaoyun; Lee, Seonghyun; Feng, Mengke; Li, Qiang; Lei, Xiaoguang; Jo, Kyubong; Tang, Xinjing

2018-04-17

Bioorthogonal metabolic DNA labeling with fluorochromes is a powerful strategy to visualize DNA molecules and their functions. Here, we report the development of a new DNA metabolic labeling strategy enabled by the catalyst-free bioorthogonal ligation using vinyl thioether modified thymidine and o-quinolinone quinone methide. With the newly designed vinyl thioether-modified thymidine (VTdT), we added labeling tags on cellular DNA, which could further be linked to fluorochromes in cells. Therefore, we successfully visualized the DNA localization within cells as well as single DNA molecules without other staining reagents. In addition, we further characterized this bioorthogonal DNA metabolic labeling using DNase I digestion, MS characterization of VTdT as well as VTdT-oQQF conjugate in cell nuclei or mitochondria. This technique provides a powerful strategy to study DNA in cells, which paves the way to achieve future spatiotemporal deciphering of DNA synthesis and functions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural characterization of thioether-bridged bacteriocins.

PubMed

Lohans, Christopher T; Vederas, John C

2014-01-01

Bacteriocins are a group of ribosomally synthesized antimicrobial peptides produced by bacteria, some of which are extensively post-translationally modified. Some bacteriocins, namely the lantibiotics and sactibiotics, contain one or more thioether bridges. However, these modifications complicate the structural elucidation of these bacteriocins using conventional techniques. This review will discuss the techniques and strategies that have been applied to determine the primary structures of lantibiotics and sactibiotics. A major challenge is to identify the topology of thioether bridges in these peptides (i.e., which amino-acid residues are involved in which bridges). Edman degradation, NMR spectroscopy and tandem MS have all been commonly applied to characterize these bacteriocins, but can be incompatible with the post-translational modifications present. Chemical modifications to the modified residues, such as desulfurization and reduction, make the treated bacteriocins more compatible to analysis by these standard peptide analytical techniques. Despite their differences in structure, similar strategies have proved useful to study the structures of both lantibiotics and sactibiotics.

Toward the development of the direct and selective detection of nitrates by a bioinspired Mo-Cu system.

PubMed

Marom, Hanit; Popowski, Yanay; Antonov, Svetlana; Gozin, Michael

2011-10-21

The development of a new platform for the direct and selective detection of nitrates is described. Two thioether-based chemosensors and the corresponding sulfoxides and sulfones were prepared, and their photophysical properties were evaluated. Upon selective sulfoxidation of these thioethers with nitrates via an oxygen-transfer reaction promoted by a bioinspired Mo-Cu system, significant fluorescence shifts were measured. A selective response of these systems, discriminating between nitrate salts and H(2)O(2), was also shown. © 2011 American Chemical Society

Rate and Selectivity Control in Thioether and Alkene Oxidation with H 2 O 2 over Phosphonate-Modified Niobium(V)-Silica Catalysts

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

Thornburg, Nicholas E.; Notestein, Justin M.

Supported metal oxide catalysts are versatile materials for liquid-phase oxidations, including alkene epoxidation and thioether sulfoxidation with H2O2. Periodic trends in H2O2 activation was recently demonstrated for alkene epoxidation, highlighting Nb-SiO2 as a more active and selective catalyst than Ti-SiO2. Three representative catalysts are studied consisting of NbV, TiIV, and ZrIV on silica, each made through a molecular precursor approach that yields highly dispersed oxide sites, for thioanisole oxidation by H2O2. Initial rates trend Nb>Ti>>Zr, as for epoxidation, and Nb outperforms Ti for a number of other thioethers. In contrast, selectivity to sulfoxide vs. sulfone trends Ti>Nb>>Zr at all conversions.more » Modifying the Nb-SiO2 catalyst with phenylphosphonic acid does not completely remove sulfoxidation reactivity, as it did for photooxidation and epoxidation, and results in an unusual material active for sulfoxidation but neither epoxidation nor overoxidation to the sulfone.« less

Identification of cytochrome P450 2E1 as the predominant enzyme catalyzing human liver microsomal defluorination of sevoflurane, isoflurane, and methoxyflurane.

PubMed

Kharasch, E D; Thummel, K E

1993-10-01

Renal and hepatic toxicity of the fluorinated ether volatile anesthetics is caused by biotransformation to toxic metabolites. Metabolism also contributes significantly to the elimination pharmacokinetics of some volatile agents. Although innumerable studies have explored anesthetic metabolism in animals, there is little information on human volatile anesthetic metabolism with respect to comparative rates or the identity of the enzymes responsible for defluorination. The first purpose of this investigation was to compare the metabolism of the fluorinated ether anesthetics by human liver microsomes. The second purpose was to test the hypothesis that cytochrome P450 2E1 is the specific P450 isoform responsible for volatile anesthetic defluorination in humans. Microsomes were prepared from human livers. Anesthetic metabolism in microsomal incubations was measured by fluoride production. The strategy for evaluating the role of P450 2E1 in anesthetic defluorination involved three approaches: for a series of 12 human livers, correlation of microsomal defluorination rate with microsomal P450 2E1 content (measured by Western blot analysis), correlation of defluorination rate with microsomal P450 2E1 catalytic activity using marker substrates (para-nitrophenol hydroxylation and chlorzoxazone 6-hydroxylation), and chemical inhibition by P450 isoform-selective inhibitors. The rank order of anesthetic metabolism, assessed by fluoride production at saturating substrate concentrations, was methoxyflurane > sevoflurane > enflurane > isoflurane > desflurane > 0. There was a significant linear correlation of sevoflurane and methoxyflurane defluorination with antigenic P450 2E1 content (r = 0.98 and r = 0.72, respectively), but not with either P450 1A2 or P450 3A3/4. Comparison of anesthetic defluorination with either para-nitrophenol or chlorzoxazone hydroxylation showed a significant correlation for sevoflurane (r = 0.93, r = 0.95) and methoxyflurane (r = 0.78, r = 0.66). Sevoflurane defluorination was also highly correlated with that of enflurane (r = 0.93), which is known to be metabolized by human P450 2E1. Diethyldithiocarbamate, a selective inhibitor of P450 2E1, produced a concentration-dependent inhibition of sevoflurane, methoxyflurane, and isoflurane defluorination. No other isoform-selective inhibitor diminished the defluorination of sevoflurane, whereas methoxyflurane defluorination was inhibited by the selective P450 inhibitors furafylline (P450 1A2), sulfaphenazole (P450 2C9/10), and quinidine (P450 2D6) but to a much lesser extent than by diethyldithiocarbamate. These results demonstrate that cytochrome P450 2E1 is the principal, if not sole human liver microsomal enzyme catalyzing the defluorination of sevoflurane. P450 2E1 is the principal, but not exclusive enzyme responsible for the metabolism of methoxyflurane, which also appears to be catalyzed by P450s 1A2, 2C9/10, and 2D6. The data also suggest that P450 2E1 is responsible for a significant fraction of isoflurane metabolism. Identification of P450 2E1 as the major anesthetic metabolizing enzyme in humans provides a mechanistic understanding of clinical fluorinated ether anesthetic metabolism and toxicity.

Synthesis and biological studies of positron-emitting radiopharmaceuticals

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

Dischino, D.D.

The development and clinical evaluation of two-positron emitting radiopharmaceuticals designed to image myelin in humans is reported. Carbon-11-labeled benzyl methyl ether was synthesized by the reaction of carbon-11-labeled methanol and benzyl chloride in dimethyl sulfoxide containing powdered potassium hydroxide in a radiochemical yield of 43% and a synthesis and purification time of 40 minutes. Carbon-11-labeled diphenylmethanol was synthesized by the reaction of carbon-11-labeled carbon dioxide and phenyllithium followed by the reduction of the carbon-11-labeled intermediate to diphenylmethanol via lithium aluminum hydride in a radiochemical yield of 71% and a synthesis and purification time of 38 minutes. Carbon-11-labeled benzyl methyl ethermore » and diphenylmethanol were each evaluated as myelin imaging agents in three patients with multiple sclerosis via positron-emission tomography. In two out of three patients studied with carbon-11-labeled benzyl methyl ether, the distribution of activity in the brain was not consistent with local lipid content. A new synthesis of carbon-11-labeled-DL-phenylalanine labeled in the benzylic position and the synthesis of fluorine-18-labeled 1-(2-nitro-1-imidazolyl)-3-fluoro-2-propanol, a potential in vivo marker of hypoxic tissue, are reported.« less

Copper-catalyzed aerobic oxidative N-S bond functionalization for C-S bond formation: regio- and stereoselective synthesis of sulfones and thioethers.

PubMed

Li, Xianwei; Xu, Yanli; Wu, Wanqing; Jiang, Chang; Qi, Chaorong; Jiang, Huanfeng

2014-06-23

A regio- and stereoselective synthesis of sulfones and thioethers by means of Cu(I)-catalyzed aerobic oxidative N-S bond cleavage of sulfonyl hydrazides, followed by cross-coupling reactions with alkenes and aromatic compounds to form the C sp 2-S bond, is described herein. N2 and H2O are the byproducts of this transformation, thus offering an environmentally benign process with a wide range of potential applications in organic synthesis and medicinal chemistry. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of a thioether lubricant by infrared Fourier microemission spectrophotometry

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.; Morales, W.; Lauer, J. L.

1986-01-01

An infrared Fourier microemission spectrophotometer is used to obtain spectra (wavenumber range, 630 to 1230 0.1 cm) from microgram quantities of thioether lubricant samples deposited on aluminum foil. Infrared bands in the spectra are reproducible and could be identified as originating from aromatic species (1,3-disubstituted benzenes). Spectra from all samples (neat and formulated, used and unused) are very similar. Additives (an acid and a phosphinate) present in low concentration (0.10 percent) in the formulated fluid are not detected. This instrument appears to be a viable tool in helping to identify lubricant components separated by liquid chromatography.

Isolation and structures of sulfonium salts derived from thioethers: [{o-C(6)H(4)(CH(2)SMe)(2)}H][NbF(6)] and [{[9]aneS(3)}H][NbF(6)].

PubMed

Jura, Marek; Levason, William; Reid, Gillian; Webster, Michael

2009-10-07

Two very unusual sulfonium salts, [{o-C(6)H(4)(CH(2)SMe)(2)}H][NbF(6)] and [{[9]aneS(3)}H][NbF(6)], obtained from reaction of the thioethers with NbF(5) in CH(2)Cl(2) solution, are reported and their structures described; the eight-coordinate tetrafluoro Nb(v) cation of the dithioether is obtained from the same reaction.

Thioether coordination to divalent selenium halide acceptors--synthesis, properties and structures.

PubMed

Jolleys, Andrew; Levason, William; Reid, Gillian

2013-02-28

The tetravalent SeCl(4) and SeBr(4) are reduced in the presence of thioether ligands L (SMe(2), tht) or L-L (MeS(CH(2))(n)SMe (n = 2 or 3), o-C(6)H(4)(SMe)(2)) in MeCN solution at 0 °C, forming Se(II) thioether complexes, including the crystallographically characterised halo-bridged chain polymers [SeX(2)(SMe(2))] (X = Cl or Br), molecular trans-[SeX(2)(tht)(2)], cis-[SeBr(2){MeS(CH(2))(2)SMe}] and the thioether-bridged polymer [SeBr(2){MeS(CH(2))(3)SMe}], as the main products, together with halogenated ligand. The [SeX(2)(L)(2)] and [SeX(2)(L-L)] complexes are all based upon distorted square planar coordination, with two Se-based lone pairs assumed to occupy the (vacant) axial sites, and Se-S bond distances of ca. 2.4-2.6 Å. The 1:1 species [SeX(2)(SMe(2))] are T-shaped with trans X groups and weak intermolecular SeX contacts. The SeCl(2)-thioether complexes are less stable than the bromides, both in solution in CH(2)Cl(2) and as solids at ambient temperature. Reaction of SeBr(4) with o-C(6)H(4)(SMe(2))(2) leads to the red complex cis-[SeBr(2){κ(1)-o-C(6)H(4)(SMe)(2)}(2)] as the major product; together with a minor (yellow) product formed via bromination of the aromatic ring, [SeBr(2){4-Br-1,2-(SMe)(2)-C(6)H(3)}(2)]. The crystal structure confirms a V-shaped SeBr(2) unit with long (weak) κ(1)-interactions to one S donor (meta to the Br) from two brominated ligands--an extremely rare coordination mode for an o-phenylene dithioether. Similar reaction of o-C(6)H(4)(SMe(2))(2) with SeCl(4) leads to several species, including monosulfonium cation, [1](+) formed by coupling of one thioether group to the C4-position of the phenylene backbone in an adjacent molecule, confirmed crystallographically. Carbon-sulfur coupling is also evident in the reaction of SeX(4) with o-C(6)H(4)(CH(2)SMe)(2), leading to two related cyclic sulfonium species, [2](+) and [3](+), which were structurally characterised as [SeBr(4)](2-) and [Se(2)Cl(6)](2-) salts respectively. Reaction of SeX(4) with SeMe(2) leads to halogenation of the ligand to form Me(2)SeX(2) and reduction of the SeX(4) to elemental selenium.

Transmutation of a heme protein.

PubMed Central

Barker, P D; Ferrer, J C; Mylrajan, M; Loehr, T M; Feng, R; Konishi, Y; Funk, W D; MacGillivray, R T; Mauk, A G

1993-01-01

Residue Asn57 of bovine liver cytochrome b5 has been replaced with a cysteine residue, and the resulting variant has been isolated from recombinant Escherichia coli as a mixture of four major species: A, BI, BII, and C. A combination of electronic spectroscopy, 1H NMR spectroscopy, resonance Raman spectroscopy, electrospray mass spectrometry, and direct electrochemistry has been used to characterize these four major cytochrome derivatives. The red form A (E(m) = -19 mV) is found to possess a heme group bound covalently through a thioether linkage involving Cys57 and the alpha carbon of the heme 4-vinyl group. Form BI has a covalently bound heme group coupled through a thioether linkage involving the beta carbon of the heme 4-vinyl group. Form BII is similar to BI except that the sulfur involved in the thioether linkage is oxidized to a sulfoxide. The green form C (E(m) = 175 mV) possesses a noncovalently bound prosthetic group with spectroscopic properties characteristic of a chlorin. A mechanism is proposed for the generation of these derivatives, and the implications of these observations for the biosynthesis of cytochrome c and naturally occurring chlorin prosthetic groups are discussed. PMID:8341666

Alternative mass reference standards for direct analysis in real time mass spectrometry.

PubMed

Cody, Robert B; Dane, A John

2016-05-30

Mass spectra were acquired with the Direct Analysis in Real Time (DART®) ion source for an amine-terminated polyether used as positive-ion mass reference standards and for several fluorinated materials commonly used as negative-ion reference standards for mass spectrometry. A commercial time-of-flight mass spectrometer equipped with a DART ion source was used for all measurements. Mass reference standards deposited onto the sealed end of a glass melting point tube were suspended in the DART gas stream for analysis. A polyetheramine (Jeffamine® M-600) produced intense peaks corresponding to protonated molecules. Perfluorotributylamine (PFTBA), and perfluorotripentylamine, gave useful reference spectra for different m/z ranges. DART mass spectra of Ultramark 1621® resembled those previously reported for Fast Atom Bombardment (FAB) and Electrospray Ionization (ESI). Fomblin®Y, a fluorinated ether, was the most useful negative-ion reference standard of the materials tested. The material is commercially available, inexpensive, and provides reference peaks covering the m/z range 85 to >3000. Jeffamine-M600 was found to be a convenient alternative to polyethers such as polyethylene glycol (PEG) for DART positive-ion mass calibration. Fomblin Y was suitable for use as a negative-ion reference standard. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Distribution, bioaccumulation and trophic transfer of chlorinated polyfluoroalkyl ether sulfonic acids in the marine food web of Bohai, China.

PubMed

Chen, Hong; Han, Jianbo; Cheng, Jiayi; Sun, Ruijun; Wang, Xiaomeng; Han, Gengchen; Yang, Wenchao; He, Xin

2018-06-04

Chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs) caused great concerns recently as novel fluorinated alternatives. However, information on their bioconcentration, bioaccumulation and biomagnification in marine ecosystems is limited. In this study, 152 biological samples including invertebrates, fishes, seabirds and mammals collected from Bohai Sea of China were analyzed to investigate the residual level, spatial distribution, bioaccumulation and biomagnification of Cl-PFESAs. 6:2 Cl-PFESA was found in concentrations ranging from

Thioether-functionalized mesoporous fiber membranes: sol-gel combined electrospun fabrication and their applications for Hg2+ removal.

PubMed

Teng, Minmin; Wang, Hongtao; Li, Fengting; Zhang, Bingru

2011-03-01

Mesoporous polyvinylpyrrolidone (PVP)/SiO(2) composite nanofiber membranes functionalized with thioether groups have been fabricated by a combination method of sol-gel process and electrospinning. The precursor sol was synthesized by one-step co-condensation of tetraethyl orthosilicate (TEOS) and 1,4-bis(triethoxysilyl)propane tetrasulfide (BTESPTS, (CH(3)CH(2)O)(3)Si(CH(2))(3)S-S-S-S(CH(2))(3)Si-(OCH(2)CH(3))(3)), with the triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (P123, EO(20)PO(70)EO(20)) as template. After the addition of PVP, nanofiber membranes were prepared by electrospinning. The membranes were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) images, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), N(2) adsorption-desorption isotherms, and an Elementar Vario EL analyzer. The composites were used as highly selective adsorbents for Hg(2+) due to the modification with thioether groups (-S-), and were conveniently separated from the waste water. The composite could be regenerated through acidification. Copyright © 2010 Elsevier Inc. All rights reserved.

Biocatalytic trifluoromethylation of unprotected phenols

NASA Astrophysics Data System (ADS)

Simon, Robert C.; Busto, Eduardo; Richter, Nina; Resch, Verena; Houk, Kendall N.; Kroutil, Wolfgang

2016-11-01

Organofluorine compounds have become important building blocks for a broad range of advanced materials, polymers, agrochemicals, and increasingly for pharmaceuticals. Despite tremendous progress within the area of fluorination chemistry, methods for the direct introduction of fluoroalkyl-groups into organic molecules without prefunctionalization are still highly desired. Here we present a concept for the introduction of the trifluoromethyl group into unprotected phenols by employing a biocatalyst (laccase), tBuOOH, and either the Langlois' reagent or Baran's zinc sulfinate. The method relies on the recombination of two radical species, namely, the phenol radical cation generated directly by the laccase and the CF3-radical. Various functional groups such as ketone, ester, aldehyde, ether and nitrile are tolerated. This laccase-catalysed trifluoromethylation proceeds under mild conditions and allows accessing trifluoromethyl-substituted phenols that were not available by classical methods.

[Desflurane (I 653) and sevoflurane: halogenated anesthetics of the future?].

PubMed

Debaene, B; Lienhart, A

1992-01-01

Sevoflurane is an halogenated methyl isopropyl ether. It is potent, non explosive and non flammable. It reacts with soda lime to form traces of a related ether which has not been shown to have any toxic effect on animals chronically exposed to it in a closed system. Induction of anaesthesia with sevoflurane is rapid and smooth, as predicted by a blood/gas partition coefficient of about 0.6 and an acceptable odour which allows the use of concentrations of up to 10%. Its MAC has been reported to vary between 1.7 and 2.3 vol %. Sevoflurane causes dose-dependent cardiovascular and respiratory depression. Its effect on the cerebral circulation is similar to that of isoflurane. The extent of biotransformation is similar to that of enflurane, but its low solubility and rapid elimination confine this to the period of inhalation. No toxic effects on the kidneys, liver and haematopoietic system have been found. Desflurane is a fluorinated methyl ether, structurally very similar to isoflurane. It is non flammable and non explosive at clinical concentrations. It is more stable in the presence of soda lime than any of the volatile anaesthetic agents available. This agent must be delivered with a thermostated vaporizer within a closed circle system, as its boiling point is 23.5 degrees C. Desflurane is less potent than isoflurane. Its MAC has been estimated to be about 7.2 vol % in man. Desflurane did not lead to any liver, lung or kidney injury in laboratory rats, even during hypoxia and enzyme induction. Desflurane undergoes little biotransformation, although the presence of volatile metabolites or covalent tissue-bound products cannot be excluded.(ABSTRACT TRUNCATED AT 250 WORDS)

Chemisorbed monolayers of corannulene penta-thioethers on gold.

PubMed

Angelova, Polina; Solel, Ephrath; Parvari, Galit; Turchanin, Andrey; Botoshansky, Mark; Gölzhäuser, Armin; Keinan, Ehud

2013-02-19

Penta(tert-butylthio)corannulene and penta(4-dimethylaminophenylthio)corannulene form highly stable monolayers on gold surfaces, as indicated by X-ray photoelectron spectroscopy (XPS). Formation of these homogeneous monolayers involves multivalent coordination of the five sulfur atoms to gold with the peripheral alkyl or aryl substituents pointing away from the surface. No dissociation of C-S bonds upon binding could be observed at room temperature. Yet, the XPS experiments reveal strong chemical bonding between the thioether groups and gold. Temperature-dependent XPS study shows that the thermal stability of the monolayers is higher than the typical stability of self-assembled monolayers (SAMs) of thiolates on gold.

Design and study of advanced photoresist materials: Positive tone photoresists with reduced environmental impact and materials for 157 nm lithography

NASA Astrophysics Data System (ADS)

Yamada, Shintaro

Concern about using organic solvents in semiconductor manufacturing led us to consider a photoresist system that can be fully processed with aqueous media. A series of new polymers were designed and prepared that demonstrate fully aqueous processable positive tone imaging. Positive tone imaging requires two solubility switches, and this has been accomplished by two different methods. In both cases, a post application baking step was utilized to render the water soluble polymer insoluble in water, and photo-induced acid catalyzed reactions regenerated aqueous solubility only in the exposed areas. The first system is based on the reaction of vinyl ethers. When the film is baked after casting from water, the vinyl ethers incorporated into the photoresist react with acidic hydroxyl groups on the matrix polymer to form acetal cross-linkages. The acetal linkages of the exposed areas are hydrolyzed by photo-acids to create positive tone imaging with pure water development. Although these systems provided positive tone imaging and were successfully cast from and developed with pure water, there are some shortcomings to this design approach such as poor dry etch resistance and short shelf life. The second system was designed to address these shortcomings. Various polystyrene-based polymers bearing ammonium salts of malonic acid monoesters were prepared and studied. The ammonium salts render the styrenic polymers soluble in water. Upon baking, ammonia is volatilized, and the resulting malonic acid monoester undergoes decarboxylation that results in formation of a base insoluble polymer. Studies on the selection of acid labile ester protecting groups, kinetics of decarboxylation and imaging are presented. Lithography with 157 nm exposure is the most promising candidate for post-193 nm lithography, and this technology is expected to provide the resolution required for the next generation of microelectronic devices. Designing photoresists for 157 nm imaging is a challenge because air, water and even the simplest hydrocarbon polymers such as polyethylene absorb strongly at this wavelength. Incorporation of fluorine atoms into matrix polymers is the key to reducing their absorbance at 157 nm. Studies on the metal-catalyzed polymerization of fluorine-containing norbornene derivatives for this application are also presented.

Stable trifluorostyrene containing compounds grafted to base polymers, and their use as polymer electrolyte membranes

DOEpatents

Yang, Zhen-Yu; Roelofs, Mark Gerrit

2010-11-09

A fluorinated ion exchange polymer prepared by grafting at least one grafting monomer on to at least one base polymer, wherein the grafting monomer comprises structure 1a or 1b: wherein Z comprises S, SO.sub.2, or POR wherein R comprises a linear or branched perfluoroalkyl group of 1 to 14 carbon atoms optionally containing oxygen or chlorine, an alkyl group of 1 to 8 carbon atoms, an aryl group of 6 to 12 carbon atoms or a substituted aryl group of 6 to 12 carbon atoms; RF comprises a linear or branched perfluoroalkene group of 1 to 20 carbon atoms, optionally containing oxygen or chlorine; Q is chosen from F, --OM, NH.sub.2, --N(M)SO.sub.2R.sup.2.sub.F, and C(M)(SO.sub.2R.sup.2.sub.F).sub.2, wherein M comprises H, an alkali cation, or ammonium; R.sup.2.sub.F groups comprises alkyl of 1 to 14 carbon atoms which may optionally include ether oxygens or aryl of 6 to 12 carbon atoms where the alkyl or aryl groups may be perfluorinated or partially fluorinated; and n is 1 or 2 for 1a, and n is 1, 2, or 3 for 1b. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.

Stable trifluorostyrene containing compounds grafted to base polymers, and their use as polymer electrolyte membranes

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

Yang, Zhen-Yu; Roelofs, Mark Gerrit

2010-11-09

A fluorinated ion exchange polymer prepared by grafting at least one grafting monomer on to at least one base polymer, wherein the grafting monomer comprises structure 1a or 1b: wherein Z comprises S, SO.sub.2, or POR wherein R comprises a linear or branched perfluoroalkyl group of 1 to 14 carbon atoms optionally containing oxygen or chlorine, an alkyl group of 1 to 8 carbon atoms, an aryl group of 6 to 12 carbon atoms or a substituted aryl group of 6 to 12 carbon atoms; RF comprises a linear or branched perfluoroalkene group of 1 to 20 carbon atoms, optionallymore » containing oxygen or chlorine; Q is chosen from F, --OM, NH.sub.2, --N(M)SO.sub.2R.sup.2.sub.F, and C(M)(SO.sub.2R.sup.2.sub.F).sub.2, wherein M comprises H, an alkali cation, or ammonium; R.sup.2.sub.F groups comprises alkyl of 1 to 14 carbon atoms which may optionally include ether oxygens or aryl of 6 to 12 carbon atoms where the alkyl or aryl groups may be perfluorinated or partially fluorinated; and n is 1 or 2 for 1a, and n is 1, 2, or 3 for 1b. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.« less

Exposure of Polymer Film Thermal Control Materials on the Materials International Space Station Experiment (MISSE)

NASA Technical Reports Server (NTRS)

Dever, Joyce; Miller, Sharon; Messer, Russell; Sechkar, Edward; Tollis, Greg

2002-01-01

Seventy-nine samples of polymer film thermal control (PFTC) materials have been provided by the National Aeronautics and Space Administration (NASA) Glenn Research Center (GRC) for exposure to the low Earth orbit environment on the exterior of the International Space Station (ISS) as part of the Materials International Space Station Experiment (MISSE). MISSE is a materials flight experiment sponsored by the Air Force Research Lab/Materials Lab and NASA. This paper will describe background, objectives, and configurations for the GRC PFTC samples for MISSE. These samples include polyimides, fluorinated polyimides, and Teflon fluorinated ethylene propylene (FEP) with and without second-surface metallizing layers and/or surface coatings. Also included are polyphenylene benzobisoxazole (PBO) and a polyarylene ether benzimidazole (TOR-LM). On August 16, 2001, astronauts installed passive experiment carriers (PECs) on the exterior of the ISS in which were located twenty-eight of the GRC PFTC samples for 1-year space exposure. MISSE PECs for 3-year exposure, which will contain fifty-one GRC PFTC samples, will be installed on the ISS at a later date. Once returned from the ISS, MISSE GRC PFTC samples will be examined for changes in optical and mechanical properties and atomic oxygen (AO) erosion. Additional sapphire witness samples located on the AO exposed trays will be examined for deposition of contaminants.

19F spin-lattice relaxation of perfluoropolyethers: Dependence on temperature and magnetic field strength (7.0-14.1 T)

NASA Astrophysics Data System (ADS)

Kadayakkara, Deepak K.; Damodaran, Krishnan; Hitchens, T. Kevin; Bulte, Jeff W. M.; Ahrens, Eric T.

2014-05-01

Fluorine (19F) MRI of perfluorocarbon-labeled cells has become a powerful technique to track the migration and accumulation of cells in living organisms. It is common to label cells for 19F MRI with nanoemulsions of perfluoropolyethers that contain a large number of chemically equivalent fluorine atoms. Understanding the mechanisms of 19F nuclear relaxation, and in particular the spin-lattice relaxation of these molecules, is critical to improving experimental sensitivity. To date, the temperature and magnetic field strength dependence of spin-lattice relaxation rate constant (R1) for perfluoropolyethers has not been described in detail. In this study, we evaluated the R1 of linear perfluoropolyether (PFPE) and cyclic perfluoro-15-crown-5 ether (PCE) at three magnetic field strengths (7.0, 9.4, and 14.1 T) and at temperatures ranging from 256-323 K. Our results show that R1 of perfluoropolyethers is dominated by dipole-dipole interactions and chemical shift anisotropy. R1 increased with magnetic field strength for both PCE and PFPE. In the temperature range studied, PCE was in the fast motion regime (ωτc < 1) at all field strengths, but for PFPE, R1 passed through a maximum, from which the rotational correlation time was estimated. The importance of these measurements for the rational design of new 19F MRI agents and methods is discussed.

19F Spin-lattice Relaxation of Perfluoropolyethers: Dependence on Temperature and Magnetic Field Strength (7.0-14.1T)

PubMed Central

Kadayakkara, Deepak K.; Damodaran, Krishnan; Hitchens, T. Kevin; Bulte, Jeff W.M.; Ahrens, Eric T.

2014-01-01

Fluorine (19F) MRI of perfluorocarbon labeled cells has become a powerful technique to track the migration and accumulation of cells in living organisms. It is common to label cells for 19F MRI with nanoemulsions of perfluoropolyethers that contain a large number of chemically equivalent fluorine atoms. Understanding the mechanisms of 19F nuclear relaxation, and in particular the spin-lattice relaxation of these molecules, is critical to improving experimental sensitivity. To date, the temperature and magnetic field strength dependence of spin-lattice relaxation rate constant (R1) for perfluoropolyethers has not been described in detail. In this study, we evaluated R1 of linear perfluoropolyether (PFPE) and cyclic perfluoro-15-crown-5 ether (PCE) at three magnetic field strengths (7.0, 9.4, and 14.1 T) and at temperatures ranging from 256-323K. Our results show that R1 of perfluoropolyethers is dominated by dipole-dipole interactions and chemical shift anisotropy. R1 increased with magnetic field strength for both PCE and PFPE. In the temperature range studied, PCE was in the fast motion regime (ωτc < 1) at all field strengths, but for PFPE, R1 passed through a maximum, from which the rotational correlation time was estimated. The importance of these measurements for the rational design of new 19F MRI agents and methods is discussed. PMID:24594752

Biocatalytic trifluoromethylation of unprotected phenols

PubMed Central

Simon, Robert C.; Busto, Eduardo; Richter, Nina; Resch, Verena; Houk, Kendall N.; Kroutil, Wolfgang

2016-01-01

Organofluorine compounds have become important building blocks for a broad range of advanced materials, polymers, agrochemicals, and increasingly for pharmaceuticals. Despite tremendous progress within the area of fluorination chemistry, methods for the direct introduction of fluoroalkyl-groups into organic molecules without prefunctionalization are still highly desired. Here we present a concept for the introduction of the trifluoromethyl group into unprotected phenols by employing a biocatalyst (laccase), tBuOOH, and either the Langlois' reagent or Baran's zinc sulfinate. The method relies on the recombination of two radical species, namely, the phenol radical cation generated directly by the laccase and the CF3-radical. Various functional groups such as ketone, ester, aldehyde, ether and nitrile are tolerated. This laccase-catalysed trifluoromethylation proceeds under mild conditions and allows accessing trifluoromethyl-substituted phenols that were not available by classical methods. PMID:27834376

New Fluorinated Polymers

NASA Technical Reports Server (NTRS)

Fitch, John W., III

1997-01-01

This report summarizes progress during 1996 in our research effort along with a description of additional results associated with a TAG supplement to this grant (items 2 and 5 below). Progress is reported in five areas: 1) Polyamides Derived from [(p-HOOCC6H4)](sub 2)C(CF3)X (X= -CF3, OCH3, Cl); 2) Phosphorus-containing '12F-PEK' - Effect of Systematic Replacement of [(p-FC6H4COC6H4)](sub 2)C[(CF3)](sub 2) Monomer by [(p-FC6H4)](sub 2)(C6H5)PO; 3) Poly(ether ketone)s Derived from [(p-FC6H4COC6H4)](sub 2)(C6H5)PO; 4) New CF3-containing Organosilane Monomers and; 5) New Monomers for 12F-PEK Analogues with Improved Processability and Solubility.

Acidic attack of perfluorinated alkyl ether lubricant molecules by metal oxide surfaces

NASA Technical Reports Server (NTRS)

Zehe, Michael J.; Faut, Owen D.

1990-01-01

The reactions of linear perfluoropolyalkylether (PFAE) lubricants with alpha-Fe203 and Fe203-based solid superacids were studied. The reaction with alpha-Fe203 proceeds in two stages. The first stage is an initial slow catalytic decomposition of the fluid. This reaction releases reactive gaseous products which attach the metal oxide and convert it to FeF3. The second stage is a more rapid decomposition of the fluid, effected by the surface FeF3. A study of the initial breakdown step was performed using alpha-Fe203, alpha-Fe203 preconverted to FeF3, and sulfate-promoted alpha-Fe203 superacids. The results indicate that the breakdown reaction involves acidic attack at fluorine atoms on acetal carbons in the linear PFAE. Possible approaches to combat the problem are outlined.

Thiol Reactivity of Curcumin and Its Oxidation Products.

PubMed

Luis, Paula B; Boeglin, William E; Schneider, Claus

2018-04-16

The polypharmacological effects of the turmeric compound curcumin may be partly mediated by covalent adduction to cellular protein. Covalent binding to small molecule and protein thiols is thought to occur through a Michael-type addition at the enone moiety of the heptadienedione chain connecting the two methoxyphenol rings of curcumin. Here we show that curcumin forms the predicted thiol-Michael adducts with three model thiols, glutathione, N-acetylcysteine, and β-mercaptoethanol. More abundant, however, are respective thiol adducts of the dioxygenated spiroepoxide intermediate of curcumin autoxidation. Two electrophilic sites at the quinone-like ring of the spiroepoxide are identified. Addition of β-mercaptoethanol at the 5'-position of the ring gives a 1,7-dihydroxycyclopentadione-5' thioether, and addition at the 1'-position results in cleavage of the aromatic ring from the molecule, forming methoxyphenol-thioether and a tentatively identified cyclopentadione aldehyde. The curcuminoids demethoxy- and bisdemethoxycurcumin do not form all of the possible thioether adducts, corresponding with their increased stability toward autoxidation. RAW264.7 macrophage-like cells activated with phorbol ester form curcumin-glutathionyl and the 1,7-dihydroxycyclopentadione-5'-glutathionyl adducts. These studies indicate that the enone of the parent compound is not the only functional electrophile in curcumin, and that its oxidation products provide additional electrophilic sites. This suggests that protein binding by curcumin may involve oxidative activation into reactive quinone methide and spiroepoxide electrophiles.

Synthesis of new high performance lubricants and solid lubricants

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

Lagow, Richard J.

1993-04-08

In our second year of funding we began the testing phase of a number of new classes of lubricants. Three different testing collaborations have already begun and a fourth one is In the works with Dr. Stephen Hsu of the National Institute of Standards and Technology. Dr. Hsu also plans to test some of the same materials for us that Shell Development is studying. With Dr. Bill Jones of NASA, we are studying the effects of branching an high temperature lubricant properties in perfluoropolyethers, Initially Bill Jones is comparing the lubrication and physical properties of perfluorotetraglyme and the following twomore » spherical perfluoropolyethers, Note that one contains a fluorocarbon chain and the other one contains a fluorocarbon ether chain. The synthesis of these was reported in the last progress report. With Professor Patricia Thiel of Iowa State University, we are working on studies of perfluoromethylene oxide ethers and have prepared a series of four of these polyethers to study in collaboration with her research group. These perfluoromethylene oxide ethers have the best low temperature properties of any known lubricants. Thiel's group is studying their interactions with metals under extreme conditions. Thirdly, we have also begun an Interaction with W. August Birke of Shell Development Company in Houston for whom we have already prepared samples of the chlorine-substituted fluorocarbon polyether lubricants whose structures appear on page 54 of our research proposal. Each of these four structures is thought to have potential as lubricant additives to motor oils. We also have underway syntheses of other fluorine-containing branched ether lubricants. These new materials which are also promising as antifriction additives for motor oils appear ahead of the perfluoro additives as Appendix I to the progress report. Additionally for Birke and Shell Development we have at their request prepared the novel compound perfluoro salicylic acid. This synthesis was suggested by the Shell staff who thought that esters of perfluoro salicylic acid might be an excellent antifriction additive for motor oil fuels. One of the best additives currently used in motor oils is the hydrocarbon ester of salicylic acid.« less

Synthesis and dopamine transporter imaging in rhesus monkeys with fluorine-18 labeled FECT

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

Keil, R.; Hoffman, J.M.; Eschima, D.

1996-05-01

Parkinson`s patients have been shown to suffer a 60-80% loss of dopamine transporters in the substantia nigra and striatum. Dopamine transporter ligands labeled with fluorine-18 (t {1/2}=110 min) are attractive probes for measuring the density of dopamine transporter sites n the striatum for the diagnosis and evaluation of Parkinson`s patients by PET. We have synthesized (Ki = 32 nM vs RTI-55), fluorine-18 labeled 2{beta}-carbomethoxy-3{beta}(4-chlorophenyl)-8-(3-fluoropropyl)nortropane (FECT), with favorable kinetics as a potential dopamine transporter PET imaging agent. Treatment of 2{beta}-carbomethoxy-3{beta}-(4-chlorophenyl)nortropane (1) with 1-bromo-2-fluoroethane (2) in CH3CN at 80{degrees}C gave FECT (3). [F-18]FECT (3) was prepared by treating 1,2-ditosyloxyethane (4) with NCAmore » K[F-18]/K222 (365 mCi) for 5 min in CH3CN at 85{degrees}C to give [F-18] 1-fluoro-2-tosyloxyethane (5) (175 mCi)in 59% E.O.B. yield. Coupling of [F-18] 5 with 1 in DMF at 135 {degrees}C for 45 min gave [F-18]FECT (41 mCi) in 25% yield E.O.B. following HPLC purification in a total synthesis time of 122 min. [F-18] 5 was >99% radiochemically pure with a specific activity of 5 Ci/{mu}mole. Following intravenous administration to a rhesus monkey [F-18]FECT (8.13 mCi) showed a peak uptake at 30 min in the striatum (S) followed by a slow clearance and a rapid washout from the cerebellum to afford a high S/C ratio = 11.0 at 125 min. Radio-HPLC analysis of the ether extracts form plasma samples for radioactive metabolites detected only the presence of [F-18]FECT. These results suggest that FECT is an Research supported by DOE.« less

Legacy and Emerging Perfluoroalkyl Substances Are ...

EPA Pesticide Factsheets

Long-chain per- and polyfluoroalkyl substances (PFASs) are being replaced by short-chain PFASs and fluorinated alternatives. For ten legacy PFASs and seven recently discovered perfluoroalkyl ether carboxylic acids (PFECAs), we report (1) their occurrence in the Cape Fear River (CFR) watershed, (2) their fate in water treatment processes, and (3) their adsorbability on powdered activated carbon (PAC). In the headwater region of the CFR basin, PFECAs were not detected in raw water of a drinking water treatment plant (DWTP), but concentrations of legacy PFASs were high. The U.S. Environmental Protection Agency’s lifetime health advisory level (70 ng/L) for perfluorooctanesulfonic acid and perfluorooctanoic acid (PFOA) was exceeded on 57 of 127 sampling days. In raw water of a DWTP downstream of a PFAS manufacturer, the mean concentration of perfluoro-2-propoxypropanoic acid (PFPrOPrA), a replacement for PFOA, was 631 ng/L (n = 37). Six other PFECAs were detected, with three exhibiting chromatographic peak areas up to 15 times that of PFPrOPrA. At this DWTP, PFECA removal by coagulation, ozonation, biofiltration, and disinfection was negligible. The adsorbability of PFASs on PAC increased with increasing chain length. Replacing one CF2 group with an ether oxygen decreased the affinity of PFASs for PAC, while replacing additional CF2 groups did not lead to further affinity changes. The USEPA’s recently completed Unregulated Contaminant Monitoring Rule 3 (UCMR3) p

Photo-cross-linked poly(thioether-co-carbonate) networks derived from the natural product quinic acid.

PubMed

Link, Lauren A; Lonnecker, Alexander T; Hearon, Keith; Maher, Cameron A; Raymond, Jeffery E; Wooley, Karen L

2014-10-22

Polycarbonate networks derived from the natural product quinic acid that can potentially return to their natural building blocks upon hydrolytic degradation are described herein. Solvent-free thiol-ene chemistry was utilized in the copolymerization of tris(alloc)quinic acid and a variety of multifunctional thiol monomers to obtain poly(thioether-co-carbonate) networks with a wide range of achievable thermomechanical properties including glass transition temperatures from -18 to +65 °C and rubbery moduli from 3.8 to 20 MPa. The network containing 1,2-ethanedithiol expressed an average toughness at 25 and 63 °C of 1.08 and 2.35 MJ/m(3), respectively, and an order-of-magnitude increase in the average toughness at 37 °C of 15.56 MJ/m(3).

NisT, the transporter of the lantibiotic nisin, can transport fully modified, dehydrated, and unmodified prenisin and fusions of the leader peptide with non-lantibiotic peptides.

PubMed

Kuipers, Anneke; de Boef, Esther; Rink, Rick; Fekken, Susan; Kluskens, Leon D; Driessen, Arnold J M; Leenhouts, Kees; Kuipers, Oscar P; Moll, Gert N

2004-05-21

Lantibiotics are lanthionine-containing peptide antibiotics. Nisin, encoded by nisA, is a pentacyclic lantibiotic produced by some Lactococcus lactis strains. Its thioether rings are posttranslationally introduced by a membrane-bound enzyme complex. This complex is composed of three enzymes: NisB, which dehydrates serines and threonines; NisC, which couples these dehydrated residues to cysteines, thus forming thioether rings; and the transporter NisT. We followed the activity of various combinations of the nisin enzymes by measuring export of secreted peptides using antibodies against the leader peptide and mass spectroscopy for detection. L. lactis expressing the nisABTC genes efficiently produced fully posttranslationally modified prenisin. Strikingly, L. lactis expressing the nisBT genes could produce dehydrated prenisin without thioether rings and a dehydrated form of a non-lantibiotic peptide. In the absence of the biosynthetic NisBC enzymes, the NisT transporter was capable of excreting unmodified prenisin and fusions of the leader peptide with non-lantibiotic peptides. Our data show that NisT specifies a broad spectrum (poly)peptide transporter that can function either in conjunction with or independently from the biosynthetic genes. NisT secretes both unmodified and partially or fully posttranslationally modified forms of prenisin and non-lantibiotic peptides. These results open the way for efficient production of a wide range of peptides with increased stability or novel bioactivities.

Structure, Bonding, and Stability of Mercury Complexes with Thiolate and Thioether Ligands from High-Resolution XANES Spectroscopy and First-Principles Calculations.

PubMed

Manceau, Alain; Lemouchi, Cyprien; Rovezzi, Mauro; Lanson, Martine; Glatzel, Pieter; Nagy, Kathryn L; Gautier-Luneau, Isabelle; Joly, Yves; Enescu, Mironel

2015-12-21

We present results obtained from high energy-resolution L3-edge XANES spectroscopy and first-principles calculations for the structure, bonding, and stability of mercury(II) complexes with thiolate and thioether ligands in crystalline compounds, aqueous solution, and macromolecular natural organic matter (NOM). Core-to-valence XANES features that vary in intensity differentiate with unprecedented sensitivity the number and identity of Hg ligands and the geometry of the ligand environment. Post-Hartree-Fock XANES calculations, coupled with natural population analysis, performed on MP2-optimized Hg[(SR)2···(RSR)n] complexes show that the shape, position, and number of electronic transitions observed at high energy-resolution are directly correlated to the Hg and S (l,m)-projected empty densities of states and occupations of the hybridized Hg 6s and 5d valence orbitals. Linear two-coordination, the most common coordination geometry in mercury chemistry, yields a sharp 2p to 6s + 5d electronic transition. This transition varies in intensity for Hg bonded to thiol groups in macromolecular NOM. The intensity variation is explained by contributions from next-nearest, low-charge, thioether-type RSR ligands at 3.0-3.3 Å from Hg. Thus, Hg in NOM has two strong bonds to thiol S and k additional weak Hg···S contacts, or 2 + k coordination. The calculated stabilization energy is -5 kcal/mol per RSR ligand. Detection of distant ligands beyond the first coordination shell requires precise measurement of, and comparison to, spectra of reference compounds as well as accurate calculation of spectra for representative molecular models. The combined experimental and theoretical approaches described here for Hg can be applied to other closed-shell atoms, such as Ag(I) and Au(I). To facilitate further calculation of XANES spectra, experimental data, a new crystallographic structure of a key mercury thioether complex, Cartesian coordinates of the computed models, and examples of input files are provided as Supporting Information .

Method for separating metal chelates from other materials based on solubilities in supercritical fluids

DOEpatents

Wai, Chien M.; Smart, Neil G.; Phelps, Cindy

2001-01-01

A method for separating a desired metal or metalloi from impurities using a supercritical extraction process based on solubility differences between the components, as well as the ability to vary the solvent power of the supercritical fluid, is described. The use of adduct-forming agents, such as phosphorous-containing ligands, to separate metal or metalloid chelates in such processes is further disclosed. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones; phosphine oxides, such as trialkylphosphine oxides, triarylphosphine oxides and alkylarylphosphine oxides; phosphinic acids; carboxylic acids; phosphates, such as trialkylphosphates, triarylphosphates and alkylarylphosphates; crown ethers; dithiocarbamates; phosphine sulfides; phosphorothioic acids; thiophosphinic acids; halogenated analogs of these chelating agents; and mixtures of these chelating agents. In especially preferred embodiments, at least one of the chelating agents is fluorinated.

Towards Enhanced Gas Sensor Performance with Fluoropolymer Membranes

PubMed Central

Graunke, Thorsten; Schmitt, Katrin; Raible, Stefan; Wöllenstein, Jürgen

2016-01-01

In this paper we report on how to increase the selectivity of gas sensors by using fluoropolymer membranes. The mass transport of polar and non-polar gases through a polymer membrane matrix was studied by systematic selection of polymers with different degrees of fluorination, as well as polymers whose monomers have ether groups (-O-) in addition to fluorine groups (-F). For the study, a set of application-relevant gases including H2, CO, CO2, NO2, methane, ethanol, acetone, and acetaldehyde as well as various concentrations of relative humidity were used. These gases have different functional groups and polarities, yet have a similar kinetic diameter and are therefore typically difficult to separate. The concentrations of the gases were chosen according to international indicative limit values (TWA, STEL). To measure the concentration in the feed and permeate, we used tin-dioxide-based metal oxide gas sensors with palladium catalyst (SnO2:Pd), catalytic sensors (also SnO2:Pd-based) and thermal conductivity sensors. This allows a close examination of the interdependence of diffusion and physicochemical operating principle of the sensor. Our goal is to increase the selectivity of gas sensors by using inexpensive fluoropolymer membranes. The measurements showed that through membranes with low polarity, preferably non-polar gases are transported. Furthermore, the degree of crystallization influences the permeability and selectivity of a polymer membrane. Basically the polar polymers showed a higher permeability to water vapor and polar substances than non-polar polymer membranes. PMID:27690045

Acidic attack of perfluorinated alkyl ether lubricant molecules by metal oxide surfaces

NASA Technical Reports Server (NTRS)

Zehe, Michael J.; Faut, Owen D.

1989-01-01

The reactions of linear perfluoropolyalkylether (PFAE) lubricants with alpha-Fe2O3 and Fe2O3-based solid superacids were studied. The reaction with alpha-Fe2O3 proceeds in two stages. The first stage is an initial slow catalytic decomposition of the fluid. This reaction releases reactive gaseous products which attach the metal oxide and convert it to FeF3. The second stage is a more rapid decomposition of the fluid, effected by the surface FeF3. A study of the inital breakdown step was performed using alpha-Fe2O3, alpha-Fe2O3 preconverted to FeF3, and sulfate-promoted alpha-Fe2O3 superacids. The results indicate that the breakdown reaction involves acidic attack at fluorine atoms on acetal carbons in the linear PFAE. Possible approaches to combat the problem are outlined.

Synthesis of a zinc(II) complex with hexadentate N4S2 donor thioether ligand: X-ray structure, DNA binding study and DFT computation

NASA Astrophysics Data System (ADS)

Mondal, Apurba Sau; Jana, Mahendra Sekhar; Manna, Chandan Kumar; Naskar, Rahul; Mondal, Tapan Kumar

2018-07-01

A new zinc(II) complex, [Zn(L)](ClO4) with hexadentate N4S2 donor azo-thioether ligand (HL) was synthesized and characterized by several spectroscopic techniques. The structure was confirmed by single crystal X-ray analysis. The interaction of the complex with CT DNA was investigated by UV-vis method and binding constant is found to be 6.6 × 104 M-1. Competitive binding titration with ethidium bromide (EB) by fluorescence titration method reveals that the complex efficiently displaces EB from EB-DNA system and the Stern-Volmer dynamic quenching constant, Ksv is found to be 2.6 × 104 M-1. DFT and TDDFT calculations were carried out to interpret the electronic structure and electronic spectra of the complex.

PERFLUORINATED AROMATIC COMPOUNDS

DTIC Science & Technology

decafluorodiphenylamine, 3,3’,4,4’-tetra substituted- hexafluorobiphenyls, tetrafluororesorcinol, perfluoroaromatic thioethers, and dithiols. These...and other perfluorinated aromatic compounds are the intermediates employed in the synthesis of perfluorinated model compounds and polymers.

Wholly Aromatic Ether-Imides as n-Type Semiconductors

NASA Technical Reports Server (NTRS)

Weiser, Erik; St. Clair, Terry L.; Dingemans, Theo J.; Samulski, Edward T.; Irene, Gene

2006-01-01

Some wholly aromatic ether-imides consisting of rod-shaped, relatively-low-mass molecules that can form liquid crystals have been investigated for potential utility as electron-donor-type (ntype) organic semiconductors. It is envisioned that after further research to improve understanding of their physical and chemical properties, compounds of this type would be used to make thin film semiconductor devices (e.g., photovoltaic cells and field-effect transistors) on flexible electronic-circuit substrates. This investigation was inspired by several prior developments: Poly(ether-imides) [PEIs] are a class of engineering plastics that have been used extensively in the form of films in a variety of electronic applications, including insulating layers, circuit boards, and low-permittivity coatings. Wholly aromatic PEIs containing naphthalene and perylene moieties have been shown to be useful as electrochromic polymers. More recently, low-molecular-weight imides comprising naphthalene-based molecules with terminal fluorinated tails were shown to be useful as n-type organic semiconductors in such devices as field-effect transistors and Schottky diodes. Poly(etherimide)s as structural resins have been extensively investigated at NASA Langley Research Center for over 30 years. More recently, the need for multi-functional materials has become increasingly important. This n-type semiconductor illustrates the scope of current work towards new families of PEIs that not only can be used as structural resins for carbon-fiber reinforced composites, but also can function as sensors. Such a multi-functional material would permit so-called in-situ health monitoring of composite structures during service. The work presented here demonstrates that parts of the PEI backbone can be used as an n-type semiconductor with such materials being sensitive to damage, temperature, stress, and pressure. In the near future, multi-functional or "smart" composite structures are envisioned to be able to communicate such important parameters to the flight crew and provide vital information with respect to the operational status of their aircraft.

Identification of Novel Perfluoroalkyl Ether Carboxylic Acids (PFECAs) and Sulfonic Acids (PFESAs) in Natural Waters Using Accurate Mass Time-of-Flight Mass Spectrometry (TOFMS).

PubMed

Strynar, Mark; Dagnino, Sonia; McMahen, Rebecca; Liang, Shuang; Lindstrom, Andrew; Andersen, Erik; McMillan, Larry; Thurman, Michael; Ferrer, Imma; Ball, Carol

2015-10-06

Recent scientific scrutiny and concerns over exposure, toxicity, and risk have led to international regulatory efforts resulting in the reduction or elimination of certain perfluorinated compounds from various products and waste streams. Some manufacturers have started producing shorter chain per- and polyfluorinated compounds to try to reduce the potential for bioaccumulation in humans and wildlife. Some of these new compounds contain central ether oxygens or other minor modifications of traditional perfluorinated structures. At present, there has been very limited information published on these "replacement chemistries" in the peer-reviewed literature. In this study we used a time-of-flight mass spectrometry detector (LC-ESI-TOFMS) to identify fluorinated compounds in natural waters collected from locations with historical perfluorinated compound contamination. Our workflow for discovery of chemicals included sequential sampling of surface water for identification of potential sources, nontargeted TOFMS analysis, molecular feature extraction (MFE) of samples, and evaluation of features unique to the sample with source inputs. Specifically, compounds were tentatively identified by (1) accurate mass determination of parent and/or related adducts and fragments from in-source collision-induced dissociation (CID), (2) in-depth evaluation of in-source adducts formed during analysis, and (3) confirmation with authentic standards when available. We observed groups of compounds in homologous series that differed by multiples of CF2 (m/z 49.9968) or CF2O (m/z 65.9917). Compounds in each series were chromatographically separated and had comparable fragments and adducts produced during analysis. We detected 12 novel perfluoroalkyl ether carboxylic and sulfonic acids in surface water in North Carolina, USA using this approach. A key piece of evidence was the discovery of accurate mass in-source n-mer formation (H(+) and Na(+)) differing by m/z 21.9819, corresponding to the mass difference between the protonated and sodiated dimers.

Oxygen Sensing with Perfluorocarbon-Loaded Ultraporous Mesostructured Silica Nanoparticles.

PubMed

Lee, Amani L; Gee, Clifford T; Weegman, Bradley P; Einstein, Samuel A; Juelfs, Adam R; Ring, Hattie L; Hurley, Katie R; Egger, Sam M; Swindlehurst, Garrett; Garwood, Michael; Pomerantz, William C K; Haynes, Christy L

2017-06-27

Oxygen homeostasis is important in the regulation of biological function. Disease progression can be monitored by measuring oxygen levels, thus producing information for the design of therapeutic treatments. Noninvasive measurements of tissue oxygenation require the development of tools with minimal adverse effects and facile detection of features of interest. Fluorine magnetic resonance imaging ( 19 F MRI) exploits the intrinsic properties of perfluorocarbon (PFC) liquids for anatomical imaging, cell tracking, and oxygen sensing. However, the highly hydrophobic and lipophobic properties of perfluorocarbons require the formation of emulsions for biological studies, though stabilizing these emulsions has been challenging. To enhance the stability and biological loading of perfluorocarbons, one option is to incorporate perfluorocarbon liquids into the internal space of biocompatible mesoporous silica nanoparticles. Here, we developed perfluorocarbon-loaded ultraporous mesostructured silica nanoparticles (PERFUMNs) as 19 F MRI detectable oxygen-sensing probes. Ultraporous mesostructured silica nanoparticles (UMNs) have large internal cavities (average = 1.8 cm 3 g -1 ), facilitating an average 17% loading efficiency of PFCs, meeting the threshold fluorine concentrations needed for imaging studies. Perfluoro-15-crown-5-ether PERFUMNs have the highest equivalent nuclei per PFC molecule and a spin-lattice (T 1 ) relaxation-based oxygen sensitivity of 0.0032 mmHg -1 s -1 at 16.4 T. The option of loading PFCs after synthesizing UMNs, rather than traditional in situ core-shell syntheses, allows for use of a broad range of PFC liquids from a single material. The biocompatible and tunable chemistry of UMNs combined with the intrinsic properties of PFCs makes PERFUMNs a MRI sensor with potential for anatomical imaging, cell tracking, and metabolic spectroscopy with improved stability.

Enabling electrolyte compositions for columnar silicon anodes in high energy secondary batteries

NASA Astrophysics Data System (ADS)

Piwko, Markus; Thieme, Sören; Weller, Christine; Althues, Holger; Kaskel, Stefan

2017-09-01

Columnar silicon structures are proven as high performance anodes for high energy batteries paired with low (sulfur) or high (nickel-cobalt-aluminum oxide, NCA) voltage cathodes. The introduction of a fluorinated ether/sulfolane solvent mixture drastically improves the capacity retention for both battery types due to an improved solid electrolyte interface (SEI) on the surface of the silicon electrode which reduces irreversible reactions normally causing lithium loss and rapid capacity fading. For the lithium silicide/sulfur battery cycling stability is significantly improved as compared to a frequently used reference electrolyte (DME/DOL) reaching a constant coulombic efficiency (CE) as high as 98%. For the silicon/NCA battery with higher voltage, the addition of only small amounts of fluoroethylene carbonate (FEC) to the novel electrolyte leads to a stable capacity over at least 50 cycles and a CE as high as 99.9%. A high volumetric energy density close to 1000 Wh l-1 was achieved with the new electrolyte taking all inactive components of the stack into account for the estimation.

Docking model of the nicotinic acetylcholine receptor and nitromethylene neonicotinoid derivatives with a longer chiral substituent and their biological activities.

PubMed

Nagaoka, Hikaru; Nishiwaki, Hisashi; Kubo, Takuya; Akamatsu, Miki; Yamauchi, Satoshi; Shuto, Yoshihiro

2015-02-15

In the present study, nitromethylene neonicotinoid derivatives possessing substituents that contain a sulfur atom, oxygen atom or aromatic ring at position 5 on the imidazolidine ring were synthesized to evaluate their affinity for the nicotinic acetylcholine receptor (nAChR) and their insecticidal activity against adult female houseflies. Comparing the receptor affinity of the alkylated derivative with the receptor affinity of compounds possessing either ether or thioether groups revealed that conversion of the carbon atom to a sulfur atom did not influence the receptor affinity, whereas conversion to an oxygen atom was disadvantageous for the receptor affinity. The receptor affinity of compounds possessing a benzyl or phenyl group was lower than that of the unsubstituted compound. Analysis of the three-dimensional quantitative structure-activity relationship using comparative molecular field analysis demonstrated that steric hindrance of the receptor should exist around the C3 of an n-butyl group attached at position 5 on the imidazolidine ring. A docking study of the nAChR-ligand model suggested that the ligand-binding region expands as the length of the substituent increases by brushing against the amino acids that form the binding region. The insecticidal activity of the compounds was positively correlated with the receptor affinity by considering logP and the number of heteroatoms, including sulfur and oxygen atoms, in the substituents, suggesting that the insecticidal activity is influenced by the receptor affinity, hydrophobicity, and metabolic stability of the compounds. Copyright © 2015 Elsevier Ltd. All rights reserved.

Perfluorocarbon Particle Size Influences Magnetic Resonance Signal and Immunological Properties of Dendritic Cells

PubMed Central

Waiczies, Helmar; Lepore, Stefano; Janitzek, Nicole; Hagen, Ulrike; Seifert, Frank; Ittermann, Bernd; Purfürst, Bettina; Pezzutto, Antonio; Paul, Friedemann; Niendorf, Thoralf; Waiczies, Sonia

2011-01-01

The development of cellular tracking by fluorine (19F) magnetic resonance imaging (MRI) has introduced a number of advantages for following immune cell therapies in vivo. These include improved signal selectivity and a possibility to correlate cells labeled with fluorine-rich particles with conventional anatomic proton (1H) imaging. While the optimization of the cellular labeling method is clearly important, the impact of labeling on cellular dynamics should be kept in mind. We show by 19F MR spectroscopy (MRS) that the efficiency in labeling cells of the murine immune system (dendritic cells) by perfluoro-15-crown-5-ether (PFCE) particles increases with increasing particle size (560>365>245>130 nm). Dendritic cells (DC) are professional antigen presenting cells and with respect to impact of PFCE particles on DC function, we observed that markers of maturation for these cells (CD80, CD86) were also significantly elevated following labeling with larger PFCE particles (560 nm). When labeled with these larger particles that also gave an optimal signal in MRS, DC presented whole antigen more robustly to CD8+ T cells than control cells. Our data suggest that increasing particle size is one important feature for optimizing cell labeling by PFCE particles, but may also present possible pitfalls such as alteration of the immunological status of these cells. Therefore depending on the clinical scenario in which the 19F-labeled cellular vaccines will be applied (cancer, autoimmune disease, transplantation), it will be interesting to monitor the fate of these cells in vivo in the relevant preclinical mouse models. PMID:21811551

One-Bead-Two-Compound Thioether Bridged Macrocyclic γ-AApeptide Screening Library against EphA2.

PubMed

Shi, Yan; Challa, Sridevi; Sang, Peng; She, Fengyu; Li, Chunpu; Gray, Geoffrey M; Nimmagadda, Alekhya; Teng, Peng; Odom, Timothy; Wang, Yan; van der Vaart, Arjan; Li, Qi; Cai, Jianfeng

2017-11-22

Identification of molecular ligands that recognize peptides or proteins is significant but poses a fundamental challenge in chemical biology and biomedical sciences. Development of cyclic peptidomimetic library is scarce, and thus discovery of cyclic peptidomimetic ligands for protein targets is rare. Herein we report the unprecedented one-bead-two-compound (OBTC) combinatorial library based on a novel class of the macrocyclic peptidomimetics γ-AApeptides. In the library, we utilized the coding peptide tags synthesized with Dde-protected α-amino acids, which were orthogonal to solid phase synthesis of γ-AApeptides. Employing the thioether linkage, the desired macrocyclic γ-AApeptides were found to be effective for ligand identification. Screening the library against the receptor tyrosine kinase EphA2 led to the discovery of one lead compound that tightly bound to EphA2 (K d = 81 nM) and potently antagonized EphA2-mediated signaling. This new approach of macrocyclic peptidomimetic library may lead to a novel platform for biomacromolecular surface recognition and function modulation.

Solution- and solid-phase parallel synthesis of 4-alkoxy-substituted pyrimidines with high molecular diversity.

PubMed

Font, David; Heras, Montserrat; Villalgordo, José M

2003-01-01

A simple and straightforward methodology toward the synthesis of novel 2,6-disubstituted-4-alkoxypyrimidine derivatives of type 16 and 19 has been developed. This methodology, initially developed in solution, can be perfectly adapted to the solid support under analogous conditions, taking full advantage of automated parallel synthesis systems. This successful methodology benefits from the key role played by the thioether linkage placed at the 2-position in 3, 9, or 13 in a double manner: on one side, the steric effect exerted by the thioether linkage is likely to be responsible for the very high observed selectivity toward the formation of the O-alkylation products. On the other side, this sulfur linkage can serve not only as a robust point of attachment for the heterocycle, stable to a number of reaction conditions, but also as a means of introducing a new element of diversity through activation to the corresponding sulfone (safety-catch linker concept) and subsequent ipso-substitution reaction with a variety of different N-nucleophiles.

A Boiling-Water-Stable, Tunable White-Emitting Metal-Organic Framework from Soft-Imprint Synthesis.

PubMed

He, Jun; Huang, Jian; He, Yonghe; Cao, Peng; Zeller, Matthias; Hunter, Allen D; Xu, Zhengtao

2016-01-26

A new avenue for making porous frameworks has been developed by borrowing an idea from molecularly imprinted polymers (MIPs). In lieu of the small molecules commonly used as templates in MIPs, soft metal components, such as CuI, are used to orient the molecular linker and to leverage the formation of the network. Specifically, a linear dicarboxylate linker with thioether side groups reacted simultaneously with Ln(3+) ions and CuI, leading to a bimetallic net featuring strong, chemically hard Eu(3+) -carboxylate links, as well as soft, thioether-bound Cu2 I2 clusters. The CuI block imparts water stability to the host; with the tunable luminescence from the lanthanide ions, this creates the first white-emitting MOF that is stable in boiling water. The Cu2 I2 block also readily reacts with H2 S, and enables sensitive colorimetric detection while the host net remains intact. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for fluorinating coal

DOEpatents

Huston, John L.; Scott, Robert G.; Studier, Martin H.

1978-01-01

Coal is fluorinated by contact with fluorine gas at low pressure. After pial fluorination, when the reaction rate has slowed, the pressure is slowly increased until fluorination is complete, forming a solid fluorinated coal of approximate composition CF.sub.1.55 H.sub.0.15. The fluorinated coal and a solid distillate resulting from vacuum pyrolysis of the fluorinated coal are useful as an internal standard for mass spectrometric unit mass assignments from about 100 to over 1500.

Handling and Use of Fluorine and Fluorine - Oxygen Mixtures in Rocket Systems,

DTIC Science & Technology

1967-01-01

with nitroso rubber, which could normally be expected to burn when exposed to the flow of liquid fluorine. The materials tested included (1) Nitroso...the system free of contamination. Most common metals of construction are compatible for use in a fluorine environment. Metals can burn with fluorine...conditions of contact), fluorinated compounds in their highest state of oxidation, and a few fluorinated polymers. Even these polymers may burn in fluorine

Mechanisms of Mitochondrial Holocytochrome c Synthase and the Key Roles Played by Cysteines and Histidine of the Heme Attachment Site, Cys-XX-Cys-His*

PubMed Central

Babbitt, Shalon E.; San Francisco, Brian; Mendez, Deanna L.; Lukat-Rodgers, Gudrun S.; Rodgers, Kenton R.; Bretsnyder, Eric C.; Kranz, Robert G.

2014-01-01

Mitochondrial cytochrome c assembly requires the covalent attachment of heme by thioether bonds between heme vinyl groups and a conserved CXXCH motif of cytochrome c/c1. The enzyme holocytochrome c synthase (HCCS) binds heme and apocytochrome c substrate to catalyze this attachment, subsequently releasing holocytochrome c for proper folding to its native structure. We address mechanisms of assembly using a functional Escherichia coli recombinant system expressing human HCCS. Human cytochrome c variants with individual cysteine, histidine, double cysteine, and triple cysteine/histidine substitutions (of CXXCH) were co-purified with HCCS. Single and double mutants form a complex with HCCS but not the triple mutant. Resonance Raman and UV-visible spectroscopy support the proposal that heme puckering induced by both thioether bonds facilitate release of holocytochrome c from the complex. His-19 (of CXXCH) supplies the second axial ligand to heme in the complex, the first axial ligand was previously shown to be from HCCS residue His-154. Substitutions of His-19 in cytochrome c to seven other residues (Gly, Ala, Met, Arg, Lys, Cys, and Tyr) were used with various approaches to establish other roles played by His-19. Three roles for His-19 in HCCS-mediated assembly are suggested: (i) to provide the second axial ligand to the heme iron in preparation for covalent attachment; (ii) to spatially position the two cysteinyl sulfurs adjacent to the two heme vinyl groups for thioether formation; and (iii) to aid in release of the holocytochrome c from the HCCS active site. Only H19M is able to carry out these three roles, albeit at lower efficiencies than the natural His-19. PMID:25170082

Interaction of d(10) metal ions with thioether ligands: a thermodynamic and theoretical study.

PubMed

Melchior, Andrea; Peralta, Elena; Valiente, Manuel; Tavagnacco, Claudio; Endrizzi, Francesco; Tolazzi, Marilena

2013-05-07

Thermodynamic parameters of complex formation between d(10) metal ions, such as Zn(2+), Cd(2+), Hg(2+) and Ag(+), and the macrocyclic thioether 1,4,7-trithiacyclononane ([9]AneS3) or the monodentate diethylsulfide (Et(2)S), in acetonitrile (AN) at 298.15 K, were studied by a systematic methodology including potentiometry, calorimetry and polarography. [9]AneS3 is able to form complexes with all the target cations, Et(2)S only reacts with Hg(2+) and Ag(+). Mononuclear ML(j) (j = 1, 2) complexes are formed with all the metal ions investigated, where the affinity order is Hg(2+) > Ag(+) > Cd(2+) ≈ Zn(2+) when L = [9]AneS3 and Hg(2+) > Ag(+) when L = Et(2)S. Enthalpy and entropy values are generally negative, as a consequence of both metal ion interactions with neutral ligands, the reagents' loss of degrees of freedom and the release of solvating molecules. DFT calculations on the complexes formed with [9]AneS3 in vacuum and in AN are also carried out, to correlate experimental and theoretical thermodynamic values and to highlight the interplay between the direct metal-thioether interaction and the solvation effects. Trends obtained for the stability constants and enthalpies of the 1 : 1 and 1 : 2 complexes in solvent well reproduce the experimental ones for all the divalent metal ion complexes with [9]AneS3 and indicate the release of 3 AN molecules in the formation of each consecutive octahedral complex. In addition, calculated and experimental values for Ag(+) complex formation in solution suggest that in AgL(2) species [9]AneS3 ligands are not both tridentate.

Structure-activity relationships of fluorinated dendrimers in DNA and siRNA delivery.

PubMed

Wang, Mingming; Cheng, Yiyun

2016-12-01

Fluorinated dendrimers have shown great promise in gene delivery due to their high transfection efficacy and low cytotoxicity, however, the structure-activity relationships of these polymers still remain unknown. Herein, we synthesized a library of fluorinated dendrimers with different dendrimer generations and fluorination degrees and investigated their behaviors in both DNA and siRNA delivery. The results show that fluorination significantly improves the transfection efficacy of G4-G7 polyamidoamine dendrimers in DNA and siRNA delivery. Fluorination on generation 5 dendrimer yields the most efficient polymers in gene delivery, and the transfection efficacy of fluorinated dendrimers depends on fluorination degree. All the fluorinated dendrimers cause minimal toxicity on the transfected cells at their optimal transfection conditions. This study provides a general and facile strategy to prepare high efficient and low cytotoxic gene carriers based on fluorinated polymers. The structure-activity relationships of fluorinated dendrimers in gene delivery is still unknown and the behavior of fluorinated dendrimers in siRNA delivery has not yet been investigated. Herein, we synthesized a library of fluorinated PAMAM dendrimers with different dendrimer generations and fluorination degrees and investigated their behaviors in both DNA and siRNA delivery. The results clearly indicate that fluorination significantly improves the transfection efficacy of dendrimers in both DNA and siRNA delivery without causing additional toxicity. G5 PAMAM dendrimer is best scaffold to synthesize fluorinated dendrimers and the transfection efficacy of fluorinated dendrimers depends on fluorination degree. This systematic study provides a general and facile strategy to prepare high efficient and low cytotoxic gene carriers based on fluorinated polymers. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Mechanistic Understanding of Lanthipeptide Biosynthetic Enzymes

PubMed Central

2017-01-01

Lanthipeptides are ribosomally synthesized and post-translationally modified peptides (RiPPs) that display a wide variety of biological activities, from antimicrobial to antiallodynic. Lanthipeptides that display antimicrobial activity are called lantibiotics. The post-translational modification reactions of lanthipeptides include dehydration of Ser and Thr residues to dehydroalanine and dehydrobutyrine, a transformation that is carried out in three unique ways in different classes of lanthipeptides. In a cyclization process, Cys residues then attack the dehydrated residues to generate the lanthionine and methyllanthionine thioether cross-linked amino acids from which lanthipeptides derive their name. The resulting polycyclic peptides have constrained conformations that confer their biological activities. After installation of the characteristic thioether cross-links, tailoring enzymes introduce additional post-translational modifications that are unique to each lanthipeptide and that fine-tune their activities and/or stability. This review focuses on studies published over the past decade that have provided much insight into the mechanisms of the enzymes that carry out the post-translational modifications. PMID:28135077

Low Temperature Fluorination of Aerosol and Condensed Phase Sol Suspensions of Hydrocarbons Utilizing Elemental Fluorine.

DTIC Science & Technology

1980-10-01

NEOPENTANE FLUORINATIONS Ref. No. Structure Name NA F-C(CF3)3 perfluoroisobutane NB C (CF3)4. perfluoroneopentane 14 ,3 2 NC CFH-C(CF3)3...Photochemical Fluorination Fluorination Perfluorination El~mental Fluorine 20. APOWACT (Continue on rover** aide It necessary and identify by block...aerosol fluorinator capable of achieving high yields of perfluorinated hydrocarbons via a photo- chemical fluorination stage. The aerosol system also

Synthesis and characterization of a new zinc(II) complex with tetradentate azo-thioether ligand: X-ray structure, DNA binding study and DFT calculation

NASA Astrophysics Data System (ADS)

Mondal, Apurba Sau; Pramanik, Ajoy Kumar; Patra, Lakshman; Manna, Chandan Kumar; Mondal, Tapan Kumar

2017-10-01

A new zinc(II) complex, [Zn(L)(H2O)](ClO4) (1) with azo-thioether containing NSNO donor ligand, 3-(2-(2-((pyridin-2-ylmethyl)thio)phenyl)hydrazono)pentane-2,4-dione (HL) is synthesized and characterized by several spectroscopic techniques. The distorted square based pyramidal (DSBP) geometry is confirmed by single crystal X-ray structure. The ability of the complex to bind with CT DNA is investigated by UV-vis method and the binding constant is found to be 4.16 × 104 M-1. Competitive binding study with ethidium bromide (EB) by fluorescence method suggests that the zinc(II) complex efficiently displaces EB from EB-DNA. The Stern-Volmer dynamic quenching constant, Ksv is found to be 1.2 × 104 M-1. Theoretical calculations by DFT and TDDFT/CPCM methods are used to interpret the electronic structure and UV-vis spectrum of the complex.

Space charge characteristics of fluorinated polyethylene: Different effects of fluorine and oxygen

NASA Astrophysics Data System (ADS)

Zhao, Ni; Nie, Yongjie; Li, Shengtao

2018-04-01

Direct fluorination are proved having obvious effect on space charge characteristics of polyethylene. It is believed that fluorine has a positive effect on suppressing space charge injection while oxygen impurity has a negative effect. However, the mechanism for the opposite effect of fluorine and oxygen is still not clear. In this paper, the different effects of fluorine and oxygen on space charge characteristics of fluorinated low density polyethylene (LDPE) are investigated on the basis of dielectric property, chemical constitutes and trap performance of surface fluorinated layers. The results show that direct fluorination has obvious effect on chemical constitutes and dielectric properties of surface fluorinated layer. Introduced fluorine is the main factor for suppressing charge injection from the electrodes, because it seriously changes the chemical constitutes and further the trap properties of the surface fluorinated layer. While introduction of oxygen results in heterocharges and makes space charge distribution complex, due to the ionization of generated small groups like C=O containing groups. Moreover, direct fluorination will result in cleavage of some LDPE molecules whatever there is oxygen impurity or not.

Temperature- and Pressure-Dependent Kinetics Studies of Atomic Chlorine Reactions with Some Fluorinated Olefins and Ethers

NASA Astrophysics Data System (ADS)

Nicovich, J. M.; Wine, P. H.; Mazumder, S.; Hatzis, G. P.; Jiang, M.

2016-12-01

Laser flash photolysis of Cl2CO/N2/CO2/X mixtures (X = CF3CH=CH2, E-CF3CH=CHCl, E-CF3CH=CHF, (CF3)2CHOCH3, and CF3CF2CH2OCH3), has been coupled with time-resolved detection of Cl atoms by atomic resonance fluorescence spectroscopy to study the kinetics of Cl + X reactions as a function of temperature (T) and pressure (P). The Cl + X reactions were chosen for study because (1) the compounds X are potentially useful substitutes for ozone depleting substances in practical applications, (2) literature results demonstrate that Cl + X reactions are 60-120 times faster than the corresponding OH + X reactions at ambient T and P, suggesting that reaction with Cl is a significant atmospheric loss process for the compounds X, and (3) to our knowledge, Cl + X kinetics have not previously been studied as functions of T and P. For the Cl + olefin reactions, falloff curves are measured over the approximate T ranges 220-300 K. At elevated temperatures, equilibrium constants are determined for Cl + olefin association/dissociation, thus allowing C-Cl bond strengths in the product haloalkyl radicals to be evaluated. Arrhenius expressions are determined for the (P-independent) Cl + ether reactions over the approximate range of T 200-500K. The Cl + CF3CF2CH2OCH3 reaction is quite fast and its rate coefficient is nearly independent of T. The Cl + (CF3)2CHOCH3 reaction is somewhat slower and has a non-Arrhenius T dependence.

Hexafluorobenzene in comparison with perfluoro-15-crown-5-ether for repeated monitoring of oxygenation using 19F MRI in a mouse model.

PubMed

Mignion, Lionel; Magat, Julie; Schakman, Olivier; Marbaix, Etienne; Gallez, Bernard; Jordan, Bénédicte F

2013-01-01

Hexafluorobenzene (HFB) and perfluoro-15-crown-5-ether (15C5) were compared as fluorine reporter probes of tissue oxygenation using (19)F MRI for dynamic assessment of muscle oxygenation, with special focus on muscle tissue toxicity of the probes, and consecutive alteration of animal behavior. The latter were also compared in terms of sensitivity to changes in oxygenation as well as of signal-to-noise ratio for accurate pO(2) measurements. For that purpose, mouse muscles were imaged at 11.7 T, at 2- and 36-h after intramuscular injection of HFB or 15C5. Histological analysis of the muscle tissue revealed a lack of toxicity for 15C5 from 2 up to 36-h postinjection, whereas HFB induced tissue necrosis, blood clots and thrombosis as soon as 24-h postinjection. This muscle toxicity led to a limitation in mice mobility 24-h after injection of HFB as evidenced by behavioral testing (open-field, grip strength, and catwalk tests), which was not the case after 15C5 intramuscular injection. Finally, pO(2) measurements assessed 2-h postinjection showed consistent values with both probes, evidencing cross-validation of the (19)F MRI oximetry technique for acute measurements. However, the measurement at 36-h was hampered for HFB, which showed significant lower values of muscle pO(2), whereas 15C5 was able to reliably assess muscle pO(2) at 36-h postinjection. Copyright © 2012 Wiley Periodicals, Inc.

Improving Photoconductance of Fluorinated Donors with Fluorinated Acceptors

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

Garner, Logan E.; Larson, Bryon; Oosterhout, Stefan

2016-11-21

This work investigates the influence of fluorination of both donor and acceptor materials on the generation of free charge carriers in small molecule donor/fullerene acceptor BHJ OPV active layers. A fluorinated and non-fluorinated small molecule analogue were synthesized and their optoelectronic properties characterized. The intrinsic photoconductance of blends of these small molecule donors was investigated using time-resolved microwave conductivity. Blends of the two donor molecules with a traditional non-fluorinated fullerene (PC70BM) as well as a fluorinated fullerene (C60(CF3)2-1) were investigated using 5% and 50% fullerene loading. We demonstrate for the first time that photoconductance in a 50:50 donor:acceptor BHJ blendmore » using a fluorinated fullerene can actually be improved relative to a traditional non-fluorinated fullerene by fluorinating the donor molecule as well.« less

Fluorine-fixing efficiency on calcium-based briquette: pilot experiment, demonstration and promotion.

PubMed

Yang, Jiao-lan; Chen, Dong-qing; Li, Shu-min; Yue, Yin-ling; Jin, Xin; Zhao, Bing-cheng; Ying, Bo

2010-02-05

The fluorosis derived from coal burning is a very serious problem in China. By using fluorine-fixing technology during coal burning we are able to reduce the release of fluorides in coal at the source in order to reduce pollution to the surrounding environment by coal burning pollutants as well as decrease the intake and accumulating amounts of fluorine in the human body. The aim of this study was to conduct a pilot experiment on calcium-based fluorine-fixing material efficiency during coal burning to demonstrate and promote the technology based on laboratory research. A proper amount of calcium-based fluorine sorbent was added into high-fluorine coal to form briquettes so that the fluorine in high-fluorine coal can be fixed in coal slag and its release into atmosphere reduced. We determined figures on various components in briquettes and fluorine in coal slag as well as the concentrations of indoor air pollutants, including fluoride, sulfur dioxide and respirable particulate matter (RPM), and evaluated the fluorine-fixing efficiency of calcium-based fluorine sorbents and the levels of indoor air pollutants. Pilot experiments on fluorine-fixing efficiency during coal burning as well as its demonstration and promotion were carried out separately in Guiding and Longli Counties of Guizhou Province, two areas with coal burning fluorosis problems. If the calcium-based fluorine sorbent mixed coal was made into honeycomb briquettes the average fluorine-fixing ratio in the pilot experiment was 71.8%. If the burning calcium-based fluorine-fixing bitumite was made into a coalball, the average of fluorine-fixing ratio was 77.3%. The concentration of fluoride, sulfur dioxide and PM10 of indoor air were decreased significantly. There was a 10% increase in the cost of briquettes due to the addition of calcium-based fluorine sorbent. The preparation process of calcium-based fluorine-fixing briquette is simple yet highly flammable and it is applicable to regions with abundant bitumite coal. As a small scale application, villagers may make fluorine-fixing coalballs or briquettes by themselves, achieving the optimum fluorine-fixing efficiency and reducing indoor air pollutants providing environmental and social benefits.

An antimicrobial bicyclic peptide from chemical space against multidrug resistant Gram-negative bacteria.

PubMed

Di Bonaventura, Ivan; Baeriswyl, Stéphane; Capecchi, Alice; Gan, Bee-Ha; Jin, Xian; Siriwardena, Thissa N; He, Runze; Köhler, Thilo; Pompilio, Arianna; Di Bonaventura, Giovanni; van Delden, Christian; Javor, Sacha; Reymond, Jean-Louis

2018-05-15

We used the concept of chemical space to explore a virtual library of bicyclic peptides formed by double thioether cyclization of a precursor linear peptide, and identified an antimicrobial bicyclic peptide (AMBP) with remarkable activity against several MDR strains of Acinetobacter baumannii and Pseudomonas aeruginosa.

Electrolytes including fluorinated solvents for use in electrochemical cells

DOEpatents

Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan

2015-07-07

Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include ion-supplying salts and fluorinated solvents capable of maintaining single phase solutions with the salts at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and increase safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Fluorinated salts, such as fluoroalkyl-substituted LiPF.sub.6, fluoroalkyl-substituted LiBF.sub.4 salts, linear and cyclic imide salts as well as methide salts including fluorinated alkyl groups, may be used due to their solubility in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene or, more specifically, a cyclic phosphazene and/or one or more ionic liquids.

Molecular Grafting of Fluorinated and Nonfluorinated Alkylsiloxanes on Various Ceramic Membrane Surfaces for the Removal of Volatile Organic Compounds Applying Vacuum Membrane Distillation.

PubMed

Kujawa, Joanna; Al-Gharabli, Samer; Kujawski, Wojciech; Knozowska, Katarzyna

2017-02-22

Four main tasks were presented: (i) ceramic membrane functionalization (TiO 2 5 kDa and 300 kDa), (ii) extended material characterization (physicochemistry and tribology) of pristine and modified ceramic samples, (iii) evaluation of chemical and mechanical stability, and finally (iv) assessment of membrane efficiency in vacuum membrane distillation applied for volatile organic compounds (VOCs) removal from water. Highly efficient molecular grafting with four types of perfluoroalkylsilanes and one nonfluorinated agent was developed. Materials with controllable tribological and physicochemical properties were achieved. The most meaningful finding is associated with the applicability of fluorinated and nonfluorinated grafting agents. The results of contact angle, hysteresis of contact angle, sliding angle, and critical surface tension as well as Young's modulus, nanohardness, and adhesion force for grafting by these two modifiers are comparable. This provides insight into the potential applicability of environmental friendly hydrophobic and superhydrophobic surfaces. The achieved hydrophobic membranes were very effective in the removal of VOCs (butanol, methyl-tert-butyl ether, and ethyl acetate) from binary aqueous solutions in vacuum membrane distillation. The correlation between membrane effectiveness and separated solvent polarity was compared in terms of material properties and resistance to the wetting (kinetics of wetting and in-depth liquid penetration). Material properties were interpreted considering Zisman theory and using Kao diagram. The significant influence of surface chemistry on the membrane performance was noticed (5 kDa, influence of hydrophobic nanolayer and separation controlled by solution-diffusion model; 300 kDa, no impact of surface chemistry and separation controlled by liquid-vapor equilibrium).

Fluorine, fluorite, and fluorspar in central Colorado

USGS Publications Warehouse

Wallace, Alan R.

2010-01-01

Fluorine (F) is a widespread element that was deposited in a variety of rocks, minerals, and geologic environments in central Colorado. It occurs as a trace element, as a major component of the mineral fluorite (CaFs), and as a major economic source of fluorine in fluorspar deposits, which are massive concentrations of fluorite. This study has compiled available geochemical analyses of rocks, both unmineralized and mineralized, to determine the distribution of fluorine in specific age-lithologic categories, ranging from 1.8-giga-annum (Ga) metamorphic rocks to modern soils, throughout central Colorado. It also draws upon field studies of fluorine-rich mineral deposits, including fluorspar deposits, to decipher the nearly two-billion-year-long geologic history of fluorine in the study area, with implications for mineral-resource evaluations and exploration. The resulting compilation provides an important inventory of the naturally occurring levels and sources of fluorine that ultimately weather, erode, and become part of surface waters that are used for domestic water supplies in densely populated areas along the Colorado Front Range. Most commonly, fluorine is a trace element in virtually all rocks in the region. In the 3,798 unmineralized rocks that were analyzed for fluorine in the study area, the average fluorine content was 1,550 parts per million (ppm). The median was 640 ppm, nearly identical to the average crustal abundance of 650 ppm, and some high-fluorine rocks in the Pikes Peak area skewed the average to a value much greater than the median. Most unmineralized age-lithologic rock suites, including Proterozoic metamorphic rocks, 1.7- and 1.4-Ga granitic batholiths, Cambrian igneous rocks, Phanerozoic sedimentary rocks, and Laramide and Tertiary igneous rocks, had median fluorine values of 400 to 740 ppm fluorine. In all suites, however, a small number of analyzed samples contained more than 1 percent (10,000 ppm) fluorine. The 1.1-Ga plutonic rocks related to the Pikes Peak batholith had a mean fluorine content of 1,700 ppm, and primary magmatic fluorite and fluorite-bearing pegmatites are common throughout that igneous mass. Fluorine was deposited in many types of economic mineral deposits in central Colorado, and it currently is a significant trace element in some thermal springs. In the fluorspar deposits, fluorine contents were as high as 37 percent. Some fluorine-rich porphyry systems, such as Jamestown, had fluorine values that ranged from 200 ppm to nearly 37 percent fluorine, and veins in other deposits contained hydrothermal fluorite, although it was not ubiquitous. For the 495 samples from non-fluorspar mining districts (and excluding Jamestown), however, the median fluorine content was 990 ppm. This is above the crustal average but still relatively modest compared to the fluorspar deposits, and it indicates that the majority of the mineralizing systems in central Colorado did not deposit large amounts of fluorine. Nevertheless, the fluorine- and fluorite-rich mineral deposits could be used as guides for the evaluation and discovery of related but concealed porphyry and epithermal base- and precious-metal deposits. The Cenozoic geologic history of central Colorado included multiple periods during which fluorine-bearing rocks and mineral deposits were exposed, weathered, and eroded. This protracted history has released fluorine into soils and regoliths, and modern rainfall and snowmelt interact with these substrates to add fluorine to the hydrosphere. This study did not evaluate the fluorine contents of water or make any predictions about what areas might be major sources for dissolved fluorine. However, the abundant data that are available on fluorine in surface water and ground water can be coupled with the results of this study to provide additional insight into natural sources of fluorine in domestic drinking water.

Heterogeneous catalytic esterification of omega-sulfhydryl fatty acids: Avoidance of thioethers, thioesters, and disulfides

USDA-ARS?s Scientific Manuscript database

Two mesoporous silicas functionalized with propylsulfonic (SBA-15-PSA) and arenesulfonic (SBA-15-ASA) acid groups, and a highly acidic, functionalized styrene divinylbenzene copolymer ion exchange resin (Amberlyst-15) were examined for their ability to catalyze the ethanolic esterification of the N-...

Dental caries in fluorine exposure areas in China.

PubMed

Binbin, Wang; Baoshan, Zheng; Hongying, Wang; Yakun, Ping; Yuehua, Tao

2005-12-01

In this study, fluorine concentrations in drinking water and in urine of residents from a fluorine exposure area in China were tested. DMFT (average number of decayed, missing and filled teeth) of local residents in four age groups were also determined. The results of the study indicate that in fluorine exposure areas, there is a strictly positive correlation between fluorine content in urine and the fluorine content in drinking water. Effect of dental caries by high fluorine content drinking water is different for the different age groups. High fluorine content drinking water is more dangerous for 15-and 18-year-old groups than 5- and 12-year-old groups.

RECOVERY OF Pu VALUES BY FLUORINATION AND FRACTIONATION

DOEpatents

Brown, H.S.; Webster, D.S.

1959-01-20

A method is presented for the concentration and recovery of plutonium by fluorination and fractionation. A metallic mass containing uranium and plutonium is heated to 250 C and contacted with a stream of elemental fluorine. After fluorination of the metallic mass, the rcaction products are withdrawn and subjected to a distillation treatment to separate the fluorination products of uranium and to obtain a residue containing the fluorination products of plutonium.

Comparison of the tribological properties of fluorinated cokes and graphites

NASA Technical Reports Server (NTRS)

Fusaro, Robert L.

1988-01-01

The friction, wear, endurance life, and surface morphology of rubbed (burnished) fluorinated graphite and fluorinated coke materials were studied. Two different coke powders, a graphitic carbon powder, and a graphite powder were fluorinated and then tribologically investigated. In addition, one of the coke powders was reduced in size before fluorinating to evaluate the effect of a finer particle size on the tribological properties. For comparison, graphite and coke powders which were not fluorinated were also tribologically evaluated. Elemental analysis by emission spectroscopy was performed on each sample to determine the impurity content and X-ray diffraction analysis was performed to determine the crystallinity. Coke was found to have very little lubricating ability, but fluorinated coke did possess good lubricating properties. However, the fluorinated graphite and fluorinated graphitic carbon (which gave equivalent results) gave superior results to those obtained with the fluorinated cokes. No tribological benefit was found for using small versus a larger particle size of coke, at least when evaluated as a rubbed film.

Comparison of the tribological properties of fluorinated cokes and graphites

NASA Technical Reports Server (NTRS)

Fusaro, Robert L.

1987-01-01

The friction, wear, endurance life, and surface morphology of rubbed (burnished) fluorinated graphite and fluorinated coke materials were studied. Two different coke powders, a graphitic carbon powder, and a graphite powder were fluorinated and then tribologically investigated. In addition, one of the coke powders was reduced in size before fluorinating to evaluate the effect of a finer particle size on the tribological properties. For comparison, graphite and coke powders which were not fluorinated were also tribologically evaluated. Elemental analysis by emission spectroscopy was performed on each sample to determine the impurity content and X-ray diffraction analysis was performed to determine the crystallinity. Coke was found to have very little lubricating ability, but fluorinated coke did possess good lubricating properties. However, the fluorinated graphite and fluorinated graphitic carbon (which gave equivalent results) gave superior results to those obtained with the fluorinated cokes. No tribological benefit was found for using small versus a larger particle size of coke, at least when evaluated as a rubbed film.

Photomodulation of the nucleating activity of a photocleavable crosslinked actin dimer.

PubMed

Marriott, G; Miyata, H; Kinosita, K

1992-04-01

The ability to generate substrate concentration jumps through photo-deprotection of amine, carboxyl and phosphate groups has been an important development for investigations of protein activity in complex systems. To broaden the versatility and applications of photo-deprotection techniques for the photomodulation of protein activity we describe the synthesis and characterisation of a reagent for generating free thiol from thioether groups and a related photocleavable, heterobifunctional crosslinking reagent. Chemical and spectroscopic studies of a model thiol protected derivative were used to show some features of thiol group photodeprotection. To demonstrate how the photocleavable crosslinking reagent may be used to modulate the activity of proteins we investigated the effect of light on the nucleating activity of crosslinked actin dimer; thus following near-ultraviolet irradiation of the actin dimer the crosslink was cleaved, presumeably at the thioether bond, resulting in the concomitant dissociation of dimer, loss of nucleating activity and creation of a concentration jump of polymerisable G-actin monomer. On the basis of this initial study we discuss applications and limitations of these reagents for the photomodulation of protein activity in vitro and in vivo.

Fluorination utilizing thermodynamically unstable fluorides and fluoride salts thereof

DOEpatents

Bartlett, Neil; Whalen, J. Marc; Chacon, Lisa

2000-12-12

A method for fluorinating a carbon compound or cationic carbon compound utilizes a fluorination agent selected from thermodynamically unstable nickel fluorides and salts thereof in liquid anhydrous hydrogen fluoride. The desired carbon compound or cationic organic compound to undergo fluorination is selected and reacted with the fluorination agent by contacting the selected organic or cationic organic compound and the chosen fluorination agent in a reaction vessel for a desired reaction time period at room temperature or less.

Isolated single-molecule magnets on native gold.

PubMed

Zobbi, Laura; Mannini, Matteo; Pacchioni, Mirko; Chastanet, Guillaume; Bonacchi, Daniele; Zanardi, Chiara; Biagi, Roberto; Del Pennino, Umberto; Gatteschi, Dante; Cornia, Andrea; Sessoli, Roberta

2005-03-28

The incorporation of thioether groups in the structure of a Mn12 single-molecule magnet, [Mn12(O12)(L)16(H2O)4] with L = 4-(methylthio)benzoate, is a successful route to the deposition of well-separated clusters on native gold surfaces and to the addressing of individual molecules by scanning tunnelling microscopy.

Cysteine Racemization on IgG Heavy and Light Chains

PubMed Central

Zhang, Qingchun; Flynn, Gregory C.

2013-01-01

Under basic pH conditions, the heavy chain 220-light chain 214 (H220-L214) disulfide bond, found in the flexible hinge region of an IgG1, can convert to a thioether. Similar conditions also result in racemization of the H220 cysteine. Here, we report that racemization occurs on both H220 and L214 on an IgG1 with a λ light chain (IgG1λ) but almost entirely on H220 of an IgGl with a κ light chain (IgG1κ) under similar conditions. Likewise, racemization was detected at significant levels on H220 and L214 on endogenous human IgG1λ but only at the H220 position on IgG1κ. Low but measurable levels of d-cysteines were found on IgG2 cysteines in the hinge region, both with monoclonal antibodies incubated under basic pH conditions and on antibodies isolated from human serum. A simplified reaction mechanism involving reversible β-elimination on the cysteine is presented that accounts for both base-catalyzed racemization and thioether formation at the hinge disulfide. PMID:24142697

Molecular evidence for biodegradation of geomacromolecules

NASA Astrophysics Data System (ADS)

Jenisch-Anton, A.; Adam, P.; Michaelis, W.; Connan, J.; Herrmann, D.; Rohmer, M.; Albrecht, P.

2000-10-01

The biodegradability of macromolecular organic structures of geological origin was investigated by performing in vitro studies. Cultures of the common Nocardioides simplex were grown, first, on a high molecular weight, asymmetric thioether (1-(phytanylsulfanyl)-octadecane 1) and then on macromolecular fractions isolated from a sulfur-rich oil. Gross data indicate that bacteria convert macromolecular substances to material of higher polarity by oxidizing the abundant thioethers to sulfones and sulfoxides and by introducing new functionalities, such as carboxylic acid, keto or hydroxyl groups. Furthermore, bacteria remineralize the macromolecular structures. Bacterially induced alterations were also studied on a molecular level after chemical desulfurization of the macromolecular structure. Thus, it could be established that the amounts of linear hydrocarbons in the macromolecular structure are decreased relative to branched and cyclic structures due to a preferential bacterial attack of the linear moieties bound to the macromolecules. This is further supported by the detection of S-bound fatty acids resulting from the bacterial oxidation of S-bound n-alkanes. Moreover, N. simplex also degraded sulfur-bound steranes by oxidation of the steroid side-chain leading to S-bound steroid acids.

A Novel Action of the Proton Pump Inhibitor Rabeprazole and Its Thioether Derivative against the Motility of Helicobacter pylori

PubMed Central

Tsutsui, Nanako; Taneike, Ikue; Ohara, Tatsuki; Goshi, Satoshi; Kojio, Seiichi; Iwakura, Nobuhiro; Matsumaru, Hiroyuki; Wakisaka-Saito, Noriko; Zhang, Hui-Min; Yamamoto, Tatsuo

2000-01-01

The motility of Helicobacter pylori was maximum at 37°C and at pH 6. A newly developed proton pump inhibitor, rabeprazole (RPZ), and its thioether derivative (RPZ-TH) markedly inhibited the motility of H. pylori. The concentrations of the drug necessary to inhibit 50% of the motility were 0.25, 16, 16, and >64 μg/ml for RPZ-TH, RPZ, lansoprazole, and omeprazole, respectively. No such inhibitory effects were observed with H2 blockers or anti-H. pylori agents. The motilities of Campylobacter jejuni and C. coli—but not those of Vibrio cholerae O1 and O139, Vibrio parahaemolyticus, Salmonella enterica serovar Typhimurium, and Proteus mirabilis—were also inhibited. Prolonged incubation with RPZ or RPZ-TH inhibited bacterial growth of only H. pylori, except for a turbid colony mutant. The results indicate that RPZ and RPZ-TH have a characteristic inhibitory effect against the motility of H. pylori (spiral-shaped bacteria), which is distinguished from that against bacterial growth. PMID:11036024

Fluorinated graphenes as advanced biosensors - effect of fluorine coverage on electron transfer properties and adsorption of biomolecules

NASA Astrophysics Data System (ADS)

Urbanová, Veronika; Karlický, František; Matěj, Adam; Šembera, Filip; Janoušek, Zbyněk; Perman, Jason A.; Ranc, Václav; Čépe, Klára; Michl, Josef; Otyepka, Michal; Zbořil, Radek

2016-06-01

Graphene derivatives are promising materials for the electrochemical sensing of diverse biomolecules and development of new biosensors owing to their improved electron transfer kinetics compared to pristine graphene. Here, we report complex electrochemical behavior and electrocatalytic performance of variously fluorinated graphene derivatives prepared by reaction of graphene with a nitrogen-fluorine mixture at 2 bars pressure. The fluorine content was simply controlled by varying the reaction time and temperature. The studies revealed that electron transfer kinetics and electrocatalytic activity of CFx strongly depend on the degree of fluorination. The versatility of fluorinated graphene as a biosensor platform was demonstrated by cyclic voltammetry for different biomolecules essential in physiological processes, i.e. NADH, ascorbic acid and dopamine. Importantly, the highest electrochemical performance, even higher than pristine graphene, was obtained for fluorinated graphene with the lowest fluorine content (CF0.084) due to its high conductivity and enhanced adsorption properties combining π-π stacking interaction with graphene regions with hydrogen-bonding interaction with fluorine atoms.Graphene derivatives are promising materials for the electrochemical sensing of diverse biomolecules and development of new biosensors owing to their improved electron transfer kinetics compared to pristine graphene. Here, we report complex electrochemical behavior and electrocatalytic performance of variously fluorinated graphene derivatives prepared by reaction of graphene with a nitrogen-fluorine mixture at 2 bars pressure. The fluorine content was simply controlled by varying the reaction time and temperature. The studies revealed that electron transfer kinetics and electrocatalytic activity of CFx strongly depend on the degree of fluorination. The versatility of fluorinated graphene as a biosensor platform was demonstrated by cyclic voltammetry for different biomolecules essential in physiological processes, i.e. NADH, ascorbic acid and dopamine. Importantly, the highest electrochemical performance, even higher than pristine graphene, was obtained for fluorinated graphene with the lowest fluorine content (CF0.084) due to its high conductivity and enhanced adsorption properties combining π-π stacking interaction with graphene regions with hydrogen-bonding interaction with fluorine atoms. Electronic supplementary information (ESI) available: SEM, HRTEM, and AFM images the sheet in pristine graphene sample, survey XPS spectrum, high resolution C 1s XPS spectrum, and Raman spectrum of pristine graphene precursor used for controlled fluorination, survey and high resolution F 1s XPS spectra of the CF0.084, CF0.158, and CF0.218 samples, EDS chemical mapping of fluorine in CF0.158, contact angle measurement of CF0.084, CF0.158, CF0.218, and HOPG, and additional electrochemical data. See DOI: 10.1039/c6nr00353b

Mono- and Dinuclear Manganese Carbonyls Supported by 1,8-Disubstituted (L = Py, SMe, SH) Anthracene Ligand Scaffolds.

PubMed

Manes, Taylor A; Rose, Michael J

2016-06-06

Presented herein is a synthetic scheme to generate symmetric and asymmetric ligands based on a 1,8-disubstituted anthracene scaffold. The metal-binding scaffolds were prepared by aryl chloride activation of 1,8-dichloroanthracene using Suzuki-type couplings facilitated by [Pd(dba)2] as a Pd source; the choice of cocatalyst (XPhos or SPhos) yielded symmetrically or asymmetrically substituted scaffolds (respectively): namely, Anth-SMe2 (3), Anth-N2 (4), and Anth-NSMe (6). The ligands exhibit a nonplanar geometry in the solid state (X-ray), owing to steric hindrance between the anthracene scaffold and the coupled aryl units. To determine the flexibility and binding characteristics of the anthracene-based ligands, the symmetric scaffolds were complexed with [Mn(CO)5Br] to afford the mononuclear species [(Anth-SMe2)Mn(CO)3Br] (8) and [(Anth-N2)Mn(CO)3Br] (9), in which the donor moieties chelate the Mn center in a cis fashion. The asymmetric ligand Anth-NSMe (6) binds preferentially through the py moieties, affording the bis-ligated complex [(Anth-NSMe)2Mn(CO)3Br] (10), wherein the thioether-S donors remain unbound. Alternatively, deprotection of the thioether in 6 affords the free thiol ligand Anth-NSH (7), which more readily binds the Mn center. Complexation of 7 ultimately affords the mixed-valence Mn(I)/Mn(II) dimer of formula [(Anth-NS)3Mn2(CO)3] (11), which exhibits a fac-{Mn(CO)3} unit supported by a triad of bridging thiolates, which are in turn ligated to a supporting Mn(II) center (EPR: |D| = 0.053 cm(-1), E/|D| = 0.3, Aiso = -150 MHz). All of the metal complexes have been characterized by single-crystal X-ray diffraction, IR spectroscopy and NMR/EPR measurements-all of which demonstrate that the meta-linked, anthracene-based ligand scaffold is a viable approach for the coordination of metal carbonyls.

Time-of-flight mass spectrometry assessment of fluconazole and climbazole UV and UV/H2O2 degradability: Kinetics study and transformation products elucidation.

PubMed

Castro, Gabriela; Casado, Jorge; Rodríguez, Isaac; Ramil, María; Ferradás, Aida; Cela, Rafael

2016-01-01

The efficiency of UV irradiation for the removal of the antimycotic drugs fluconazole (FCZ) and climbazole (CBZ) from water samples is evaluated. Degradation experiments, at laboratory scale, were carried out with spiked aliquots of ultrapure water solutions and treated wastewater samples using low-pressure mercury lamps emitting at 254 nm. Time course of precursor pollutants and identification of arising transformation products (TPs) was performed by injection of different reaction time aliquots in a liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) system. Chemical structures of identified TPs were proposed from their full-product ion spectra, acquired using different collision energies. During UV irradiation experiments, the half-lives (t1/2) of FCZ and CBZ were similar in ultrapure water solutions and wastewater samples; however, the first species was more recalcitrant than the second one. Four TPs were identified in case of FCZ resulting from substitution of fluorine atoms by hydroxyl moieties and intramolecular cyclization with fluorine removal. CBZ interacted with UV radiation through reductive dechlorination, hydroxylation and cleavage of the ether bond; moreover, five additional primary TPs, with the same empirical formula as CBZ, were also noticed. Given the relatively long t1/2 of FCZ under direct photolysis (ca. 42 min), UV irradiation was combined with H2O2 addition to promote formation of reactive hydroxyl radicals. Under such conditions, the degradation rate of FCZ was enhanced significantly and no TPs were detected. These latter conditions allowed also the effective removal of CBZ TPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Occurrence and seasonal variations of per- and polyfluoroalkyl substances (PFASs) including fluorinated alternatives in rivers, drain outlets and the receiving Bohai Sea of China.

PubMed

Chen, Hong; Han, Jianbo; Zhang, Can; Cheng, Jiayi; Sun, Ruijun; Wang, Xiaomeng; Han, Gengchen; Yang, Wenchao; He, Xin

2017-12-01

A simultaneous sampling campaign was undertaken to study the pollution by 21 per- and polyfluoroalkyl substances (PFASs) in rivers, drain outlets and their receiving Bohai Sea of China. Chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs) are being used as fluorinated alternatives and they were included in this study. In comparison with other regions and countries, high concentrations of ∑ 21 PFASs in seawater samples from the Bohai Sea, ranging from 5.03 to 41 700 ng/L (median: 64.8 ng/L), were observed. The spatial distribution of PFAS levels in this sea area was in the ranking of Laizhou Bay > Liaodong Bay > Bohai Bay > other sea areas. By comparing the levels and composition profiles of PFASs in the seawater and their sources (rivers and drain outlets), it was concluded that rivers and drain outlets are the primary sources of PFAS contamination to the Bohai Sea. These PFAS levels varied seasonally among the rivers and drain outlets, but statistically significant changes were not observed. Levels of 6:2 and 8:2 Cl-PFESAs in rivers, drain outlets and receiving sea were firstly reported in the present study. Relatively high concentrations of 6:2 Cl-PFESA were found in drain outlets, ranging from below method limits of quantification (MLQ) to 7600 ng/L, but 8:2 Cl-PFAES detection was infrequent and all median concentration below MLQ. Mass discharges to the sea of 6:2 Cl-PFESA from rivers and drain outlets to the sea were estimated to be 37 and 17 kg/y, respectively. Copyright © 2017. Published by Elsevier Ltd.

Enhanced Proton Conductivity of Sulfonated Hybrid Poly(arylene ether ketone) Membranes by Incorporating an Amino-Sulfo Bifunctionalized Metal-Organic Framework for Direct Methanol Fuel Cells.

PubMed

Ru, Chunyu; Li, Zhenhua; Zhao, Chengji; Duan, Yuting; Zhuang, Zhuang; Bu, Fanzhe; Na, Hui

2018-03-07

Novel side-chain-type sulfonated poly(arylene ether ketone) (SNF-PAEK) containing naphthalene and fluorine moieties on the main chain was prepared in this work, and a new amino-sulfo-bifunctionalized metal-organic framework (MNS, short for MIL-101-NH 2 -SO 3 H) was synthesized via a hydrothermal technology and postmodification. Then, MNS was incorporated into a SNF-PAEK matrix as an inorganic nanofiller to prepare a series of organic-inorganic hybrid membranes (MNS@SNF-PAEK-XX). The mechanical property, methanol resistance, electrochemistry, and other properties of MNS@SNF-PAEK-XX hybrid membranes were characterized in detail. We found that the mechanical strength and methanol resistances of these hybrid membranes were improved by the formation of an ionic cross-linking structure between -NH 2 of MNS and -SO 3 H on the side chain of SNF-PAEK. Particularly, the proton conductivity of these hybrid membranes increased obviously after the addition of MNS. MNS@SNF-PAEK-3% exhibited the proton conductivity of 0.192 S·cm -1 , which was much higher than those of the pristine membrane (0.145 S·cm -1 ) and recast Nafion (0.134 S·cm -1 ) at 80 °C. This result indicated that bifunctionalized MNS rearranged the microstructure of hybrid membranes, which could accelerate the transfer of protons. The hybrid membrane (MNS@SNF-PAEK-3%) showed a better direct methanol fuel cell performance with a higher peak power density of 125.7 mW/cm 2 at 80 °C and a higher open-circuit voltage (0.839 V) than the pristine membrane.

Plasma cystathionine and risk of acute myocardial infarction among patients with coronary heart disease: Results from two independent cohorts.

PubMed

Dhar, Indu; Svingen, Gard F T; Pedersen, Eva R; DeRatt, Barbara; Ulvik, Arve; Strand, Elin; Ueland, Per M; Bønaa, Kaare H; Gregory, Jesse F; Nygård, Ottar K

2018-04-21

Cystathionine is a thio-ether and a metabolite formed from homocysteine during transsulfuration. Elevated plasma cystathionine levels are reported in patients with cardiovascular disease; however prospective relationships with acute myocardial infarction (AMI) are unknown. We investigated associations between plasma cystathionine and AMI among patients with suspected and/or verified coronary heart disease (CHD). Subjects from two independent cohort studies, the Western Norway Coronary Angiography Cohort (WECAC) (3033 patients with stable angina pectoris; 263 events within 4.8 years of median follow-up) and the Norwegian Vitamin Trial (NORVIT) (3670 patients with AMI; 683 events within 3.2 years of median follow-up) were included. In both cohorts, plasma cystathionine was associated with several traditional CHD risk factors (P < 0.001). Comparing the cystathionine quartile 4 to 1, age and gender adjusted hazard ratios (95% confidence intervals) for AMI were 2.08 (1.43-3.03) and 1.41 (1.12-1.76) in WECAC and NORVIT, respectively. Additional adjustment for traditional risk factors slightly attenuated the risk estimates, which were generally stronger in both cohorts among non-smokers, patients with higher age, and lower BMI or PLP status (P-interaction ≤ 0.04). Risk associations also tended to be stronger in patients not treated with B-vitamins. Additionally, in a subset of 80 WECAC patients, plasma cystathionine associated strongly negatively with glutathione, an important antioxidant and positively with lanthionine, a marker of H 2 S production (P < 0.001). Plasma cystathionine is associated with increased risk of AMI among patients with either suspected or verified coronary heart disease, and is possibly related to altered redox homeostasis. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Electrochemical fluorination of trichloroethylene and N, N-dimethyltrifluoroacetamide

NASA Technical Reports Server (NTRS)

Hsu, L. C.

1979-01-01

Fluorination of trichloroethylene and N, N-dimethyltrifluoroacetamide was carried out on a laboratory scale in an advanced Simons type electrochemical apparatus which could be operated automatically from ambient to 50 psi pressure. A variety of fluorine-substituted products are formed, depending upon electrolysis conditions and concentrations of reactant relative to the NaF, KF, HF electrolyte. A new reaction mechanism of electrochemical fluorination of trichloroethylene is proposed. The solvency-to-fluorine content relationship of fluorinated N, N-dimethyltrifluoroacetamide is described.

The storage capacity of fluorine in olivine and pyroxene under upper mantle conditions

NASA Astrophysics Data System (ADS)

Grützner, Tobias; Kohn, Simon C.; Bromiley, David W.; Rohrbach, Arno; Berndt, Jasper; Klemme, Stephan

2017-07-01

We present new experimental results on the fluorine storage capacity of olivine and orthopyroxene in the Earth's mantle. Experiments were performed in the system MgO-SiO2 + MgF2 at temperatures between 1350 °C and 1700 °C and pressures up to 17 GPa. Electron microprobe measurements show that fluorine concentrations in olivine reach up to 5100 μg/g. The storage capacity of fluorine in olivine shows only a small pressure dependence but a strong temperature dependence with a positive correlation between increasing temperature and fluorine storage capacity. Fluorine concentrations found in enstatite are one order of magnitude smaller and reach up to 670 μg/g. Our data show that concentrations of fluorine in fluorine-saturated olivine are in the same range as water concentrations in olivine. Nevertheless, fluorine and water solubility in olivine show opposing behavior with increasing pressure and temperature. The fluorine solubility in olivine increases with increasing temperature but is not much affected by pressure. In contrast, water solubility in olivine has previously been shown to decrease with increasing temperature and increase with increasing pressure. Our experiments show that nominally fluorine-free minerals like forsterite and enstatite are capable of storing the entire fluorine budget of the upper mantle, without the need to invoke accessory phases such as apatite or amphibole.

Catalysis for Fluorination and Trifluoromethylation

PubMed Central

Furuya, Takeru; Kamlet, Adam S.; Ritter, Tobias

2011-01-01

Preface Recent advances in catalysis have made the incorporation of fluorine into complex organic molecules easier than ever before, but selective, general, and practical fluorination reactions remain sought after. Fluorination of molecules often imparts desirable properties such as metabolic and thermal stability, and fluorinated molecules are therefore frequently used as pharmaceuticals or materials. Even with the latest advances in chemistry, carbon–fluorine bond formation in complex molecules is still a significant challenge. Within the last few years, new reactions to make organofluorides have emerged and exemplify how to overcome some of the intricate challenges associated with fluorination. PMID:21614074

Fluorine compounds for doping conductive oxide thin films

DOEpatents

Gessert, Tim; Li, Xiaonan; Barnes, Teresa M; Torres, Jr., Robert; Wyse, Carrie L

2013-04-23

Methods of forming a conductive fluorine-doped metal oxide layer on a substrate by chemical vapor deposition are described. The methods may include heating the substrate in a processing chamber, and introducing a metal-containing precursor and a fluorine-containing precursor to the processing chamber. The methods may also include adding an oxygen-containing precursor to the processing chamber. The precursors are reacted to deposit the fluorine-doped metal oxide layer on the substrate. Methods may also include forming the conductive fluorine-doped metal oxide layer by plasma-assisted chemical vapor deposition. These methods may include providing the substrate in a processing chamber, and introducing a metal-containing precursor, and a fluorine-containing precursor to the processing chamber. A plasma may be formed that includes species from the metal-containing precursor and the fluorine-containing precursor. The species may react to deposit the fluorine-doped metal oxide layer on the substrate.

Recent advances in fluorination techniques and their anticipated impact on drug metabolism and toxicity.

PubMed

Murphy, Cormac D; Sandford, Graham

2015-04-01

Fluorine's unique physicochemical properties make it a key element for incorporation into pharmacologically active compounds. Its presence in a drug can alter a number of characteristics that affect ADME-Tox, which has prompted efforts at improving synthetic fluorination procedures. This review describes the influence of fluorine on attributes such as potency, lipophilicity, metabolic stability and bioavailablility and how the effects observed are related to the physicochemical characteristics of the element. Examples of more recently used larger scale synthetic methods for introduction of fluorine into drug leads are detailed and the potential for using biological systems for fluorinated drug production is discussed. The synthetic procedures for carbon-fluorine bond formation largely still rely on decades-old technology for the manufacturing scale and new reagents and methods are required to meet the demands for the preparation of structurally more complex drugs. The improvement of in vitro and computational methods should make fluorinated drug design more efficient and place less emphasis on approaches such as fluorine scanning and animal studies. The introduction of new fluorinated drugs, and in particular those that have novel fluorinated functional groups, should be accompanied by rigorous environmental assessment to determine the nature of transformation products that may cause ecological damage.

Fluorine separation and generation device

DOEpatents

The Regents of the University of California

2008-12-23

A process and apparatus for the electrolytic separation of fluorine from a mixture of gases is disclosed. Also described is the process and apparatus for the generation of fluorine from fluorine/fluoride containing solids, liquids or gases.

Biodegradability of fluorinated fire-fighting foams in water.

PubMed

Bourgeois, A; Bergendahl, J; Rangwala, A

2015-07-01

Fluorinated fire-fighting foams may be released into the environment during fire-fighting activities, raising concerns due to the potential environmental and health impacts for some fluorinated organics. The current study investigated (1) the biodegradability of three fluorinated fire-fighting foams, and (2) the applicability of current standard measures used to assess biodegradability of fluorinated fire-fighting foams. The biodegradability of three fluorinated fire-fighting foams was evaluated using a 28-day dissolved organic carbon (DOC) Die-Away Test. It was found that all three materials, diluted in water, achieved 77-96% biodegradability, meeting the criteria for "ready biodegradability". Defluorination of the fluorinated organics in the foam during biodegradation was measured using ion chromatography. It was found that the fluorine liberated was 1-2 orders of magnitude less than the estimated initial amount, indicating incomplete degradation of fluorinated organics, and incomplete CF bond breakage. Published biodegradability data may utilize biochemical oxygen demand (BOD), chemical oxygen demand (COD), and total organic carbon (TOC) metrics to quantify organics. COD and TOC of four fluorinated compounds were measured and compared to the calculated carbon content or theoretical oxygen demand. It was found that the standard dichromate-based COD test did not provide an accurate measure of fluorinated organic content. Thus published biodegradability data using COD for fluorinated organics quantification must be critically evaluated for validity. The TOC measurements correlated to an average of 91% of carbon content for the four fluorinated test substances, and TOC is recommended for use as an analytical parameter in fluorinated organics biodegradability tests. Copyright © 2015 Elsevier Ltd. All rights reserved.

FLUORINE IN THE SOLAR NEIGHBORHOOD: NO EVIDENCE FOR THE NEUTRINO PROCESS

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

Jönsson, H.; Ryde, N.; Spitoni, E.

Asymptotic giant branch (AGB) stars are known to produce “cosmic” fluorine, but it is uncertain whether these stars are the main producers of fluorine in the solar neighborhood or if any of the other proposed formation sites, Type II supernovae (SNe II) and/or Wolf-Rayet (W-R) stars, are more important. Recent articles have proposed both AGB stars and SNe II as the dominant sources of fluorine in the solar neighborhood. In this paper we set out to determine the fluorine abundance in a sample of 49 nearby, bright K giants for which we previously have determined the stellar parameters, as wellmore » as alpha abundances homogeneously from optical high-resolution spectra. The fluorine abundance is determined from a 2.3 μ m HF molecular line observed with the spectrometer Phoenix. We compare the fluorine abundances with those of alpha-elements mainly produced in SNe II and find that fluorine and the alpha-elements do not evolve in lockstep, ruling out SNe II as the dominating producers of fluorine in the solar neighborhood. Furthermore, we find a secondary behavior of fluorine with respect to oxygen, which is another evidence against the SNe II playing a large role in the production of fluorine in the solar neighborhood. This secondary behavior of fluorine will put new constraints on stellar models of the other two suggested production sites: AGB stars and W-R stars.« less

Electrochemical fluorination of trichloroethylene and N, N-dimethyltrifluoroacetamide

NASA Technical Reports Server (NTRS)

Hsu, L.-C.

1979-01-01

The paper presents the results of experiments concerning the fluorination of trichloroethylene and N, N-dimethyltrifluoroacetamide carried out on a laboratory scale in an advanced 'Simons' type electrochemical apparatus which could be operated automatically from ambient to 50 psi pressure. It is shown that a variety of fluorine-substituted products are formed, depending upon electrolysis conditions and concentrations of reactant relative to the NaF, KF, HF electrolyte. A new reaction mechanism of electrochemical fluorination of trichloroethylene is proposed. Finally, the solvency-to-fluorine content relationship of fluorinated N, N-dimethyltrifluoroacetamide is described.

Nonmetallic Material Compatibility with Liquid Fluorine

NASA Technical Reports Server (NTRS)

Price, Harold G , Jr; Douglass, Howard W

1957-01-01

Static tests were made on the compatibility of liquid fluorine with several nonmetallic materials at -3200 F and at pressures of 0 and 1500 pounds per square inch gage. The results are compared with those from previous work with gaseous fluorine at the same pressures, but at atmospheric temperature. In general, although environmental effects were not always consistent, reactivity was least with the low-temperature, low-pressure liquid fluorine. Reactivity was greatest with the warm, high-pressure gaseous fluorine. None of the liquids and greases tested was found to be entirely suitable for use in fluorine systems. Polytrifluorochloroethylene and N-43, the formula for which is (C4F9)3N, did not react with liquid fluorine at atmospheric pressure or 1500 pounds per square inch gage under static conditions, but they did react when injected into liquid fluorine at 1500 pounds per square inch gage; they also reacted with gaseous fluorine at 1500 pounds per square inch gage. While water did not react with liquid fluorine at 1500 pounds per square inch gage, it is known to react violently with fluorine under other conditions. The pipe-thread lubricant Q-Seal did not react with liquid fluorine, but did react with gaseous fluorine at 1500 pounds per square inch gage. Of the solids, ruby (Al2O3) and Teflon did not react under the test conditions. The results show that the compatibility of fluorine with nonmetals depends on the state of the fluorine and the system design.

Plasma fluorination of vertically aligned carbon nanotubes: functionalization and thermal stability.

PubMed

Struzzi, Claudia; Scardamaglia, Mattia; Hemberg, Axel; Petaccia, Luca; Colomer, Jean-François; Snyders, Rony; Bittencourt, Carla

2015-01-01

Grafting of fluorine species on carbon nanostructures has attracted interest due to the effective modification of physical and chemical properties of the starting materials. Various techniques have been employed to achieve a controlled fluorination yield; however, the effect of contaminants is rarely discussed, although they are often present. In the present work, the fluorination of vertically aligned multiwalled carbon nanotubes was performed using plasma treatment in a magnetron sputtering chamber with fluorine diluted in an argon atmosphere with an Ar/F2 ratio of 95:5. The effect of heavily diluted fluorine in the precursor gas mixture is investigated by evaluating the modifications in the nanotube structure and the electronic properties upon plasma treatment. The existence of oxygen-based grafted species is associated with background oxygen species present in the plasma chamber in addition to fluorine. The thermal stability and desorption process of the fluorine species grafted on the carbon nanotubes during the fluorine plasma treatment were evaluated by combining different spectroscopic techniques.

Radiosyntheses using Fluorine-18: the Art and Science of Late Stage Fluorination

PubMed Central

Cole, Erin L.; Stewart, Megan N.; Littich, Ryan; Hoareau, Raphael; Scott, Peter J. H.

2014-01-01

Positron (β+) emission tomography (PE) is a powerful, noninvasive tool for the in vivo, three-dimensional imaging of physiological structures and biochemical pathways. The continued growth of PET imaging relies on a corresponding increase in access to radiopharmaceuticals (biologically active molecules labeled with short-lived radionuclides such as fluorine-18). This unique need to incorporate the short-lived fluorine-18 atom (t1/2 = 109.77 min) as late in the synthetic pathway as possible has made development of methodologies that enable rapid and efficient late stage fluorination an area of research within its own right. In this review we describe strategies for radiolabeling with fluorine-18, including classical fluorine-18 radiochemistry and emerging techniques for late stage fluorination reactions, as well as labeling technologies such as microfluidics and solid-phase radiochemistry. The utility of fluorine-18 labeled radiopharmaceuticals is showcased through recent applications of PET imaging in the healthcare, personalized medicine and drug discovery settings. PMID:24484425

Atmospheric chlorinated polyfluorinated ether sulfonate and ionic perfluoroalkyl acids in 2006 to 2014 in Dalian, China.

PubMed

Liu, Wei; Qin, Hui; Li, Jingwen; Zhang, Qian; Zhang, Huanhuan; Wang, Zaoshi; He, Xin

2017-10-01

Chlorinated polyfluorinated ether sulfonate (Cl-PFESA; trade name F-53B) is an alternative product for perfluorooctane sulfonate (PFOS) used in metal plating; little is known about its levels in the environment and its risks. To our knowledge, the present study constitutes the first report of Cl-PFESA in the atmosphere. In 2006 to 2014, C8 Cl-PFESA, along with ionic perfluoroalkyl acids (PFAAs), was detected in atmospheric particulate matter in Dalian, China. Concentrations of C8 Cl-PFESA increased from 140 pg/m 3 in 2007 to 722 pg/m 3 in 2014. Levels of 11 (total) ionic PFAAs increased in 2006 to 2008 and decreased afterward, with a range of 35.7 to 860 pg/m 3 . The PFAAs in the particulate matter were dominated by perfluorocarboxylates, with perfluorooctanoate detected at the highest concentration at a mean level of 71.7 pg/m 3 , followed by perfluoroheptanoate and perfluorohexanoate. Perfluorosulfonates were detected at lower levels, with mean concentrations of PFOS, perfluorobutanesulfonate, and perfluorohexane sulfonate of 5.73, 1.64, and 1.24 pg/m 3 , respectively. Back-trajectory analysis suggested that the air mass approaching Dalian during the sampling originated from the northwest, where fluorochemical industry parks and metal plating industries are densely located. No significant correlation was observed between Cl-PFESA and the ionic PFAAs. The relatively high Cl-PFESA concentrations suggested that it possibly contributed largely to the previously reported exposure to undefined organic fluorine compounds, for which further research on emission and environmental risks is needed. Environ Toxicol Chem 2017;36:2581-2586. © 2017 SETAC. © 2017 SETAC.

[Risk and prevention of teeth fluorosis in infants by feeding pattern changes].

PubMed

Borinskaia, E Iu; Davydov, B N; Kushnir, S M; Borinskiĭ, Iu N; Mikin, V M

2013-01-01

Effect of fluorides in drinking water on fluorine content in breast milk, the food for infants of the 1-sty year of life, was investigated. On determining fluorine concentration in urine and its excretion, fluorine intake by the infants was calculated under various alternatives (breast, mixed and artificial) of feeding. It has been found the in mixed and especially in artificial feeding, fluorine intake by the infants acquires uncontrollable character exceeding several times the dose of fluorine intake with breast milk under natural feeding. That was predominantly fluorine of drinking water. Mathematical formula for calculation of fluorine content in the food cooked for feeding of infants was elaborated. A computer program was formed be means of which calculation, control and management of fluorine intake are carried out in feeding alteration.

The surface chemical properties of multi-walled carbon nanotubes modified by thermal fluorination for electric double-layer capacitor

NASA Astrophysics Data System (ADS)

Jung, Min-Jung; Jeong, Euigyung; Lee, Young-Seak

2015-08-01

The surfaces of multi-walled carbon nanotubes (MWCNTs) were thermally fluorinated at various temperatures to enhance the electrochemical properties of the MWCNTs for use as electric double-layer capacitor (EDLC) electrodes. The fluorine functional groups were added to the surfaces of the MWCNTs via thermal fluorination. The thermal fluorination exposed the Fe catalyst on MWCNTs, and the specific surface area increased due to etching during the fluorination. The specific capacitances of the thermally fluorinated at 100 °C, MWCNT based electrode increased from 57 to 94 F/g at current densities of 0.2 A/g, respectively. This enhancement in capacitance can be attributed to increased polarization of the thermally fluorinated MWCNT surface, which increased the affinity between the electrode surface and the electrolyte ions.

Biological effect of fluoride on plants

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

Collet, G.F.

1969-10-01

The action of several fluorine compounds was studied by means of hydroponics. Seedlings of several species were used. In leaves of Prunus armeniaca, a good correlation between the extent of necrosis and the leaf's total fluorine content was noted. Boron plays a spectacular role as it enhances the expected fluorine accumulation. Similar results were obtained with other plant material, an observation which suggests that this phenomenon is universal in plant life. Fluorine accumulation and leaf damage due to fluorine depend upon the chemical nature of the fluorine compound. 11 references, 3 figures, 2 tables.

Measurement of S-nitrosylated Proteins in Tissues of Rats Fed Diets with Differing Levels of Nitrite

DTIC Science & Technology

2011-12-01

project could be substantial. Excluding immediate deaths, 50 % of all battlefield deaths (KIAs) occur within 5 minutes of injury, prior to the...exists for quantitation of DMPO thioethers. Furthermore, DMPO exhibits low cytotoxicity. In spin trapping experiments, cells tolerate this nitrone in

Fluorination process using catalyst

DOEpatents

Hochel, Robert C.; Saturday, Kathy A.

1985-01-01

A process for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3, AgF.sub.2 and NiF.sub.2, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3 and AgF.sub.2, whereby the fluorination is significantly enhanced.

Fluorination process using catalysts

DOEpatents

Hochel, R.C.; Saturday, K.A.

1983-08-25

A process is given for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/, AgF/sub 2/ and NiF/sub 2/, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/ and AgF/sub 2/, whereby the fluorination is significantly enhanced.

Palladium-catalysed electrophilic aromatic C-H fluorination

NASA Astrophysics Data System (ADS)

Yamamoto, Kumiko; Li, Jiakun; Garber, Jeffrey A. O.; Rolfes, Julian D.; Boursalian, Gregory B.; Borghs, Jannik C.; Genicot, Christophe; Jacq, Jérôme; van Gastel, Maurice; Neese, Frank; Ritter, Tobias

2018-02-01

Aryl fluorides are widely used in the pharmaceutical and agrochemical industries, and recent advances have enabled their synthesis through the conversion of various functional groups. However, there is a lack of general methods for direct aromatic carbon-hydrogen (C-H) fluorination. Conventional methods require the use of either strong fluorinating reagents, which are often unselective and difficult to handle, such as elemental fluorine, or less reactive reagents that attack only the most activated arenes, which reduces the substrate scope. A method for the direct fluorination of aromatic C-H bonds could facilitate access to fluorinated derivatives of functional molecules that would otherwise be difficult to produce. For example, drug candidates with improved properties, such as increased metabolic stability or better blood-brain-barrier penetration, may become available. Here we describe an approach to catalysis and the resulting development of an undirected, palladium-catalysed method for aromatic C-H fluorination using mild electrophilic fluorinating reagents. The reaction involves a mode of catalysis that is unusual in aromatic C-H functionalization because no organometallic intermediate is formed; instead, a reactive transition-metal-fluoride electrophile is generated catalytically for the fluorination of arenes that do not otherwise react with mild fluorinating reagents. The scope and functional-group tolerance of this reaction could provide access to functional fluorinated molecules in pharmaceutical and agrochemical development that would otherwise not be readily accessible.

Combinations of fluorinated solvents with imide salts or methide salts for electrolytes

DOEpatents

Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan; Lei, Norman; Guerrero-Zavala, Guillermo; Kwong, Kristie W

2015-11-10

Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include imide salts and/or methide salts as well as fluorinated solvents capable of maintaining single phase solutions at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and improve safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Linear and cyclic imide salts, such as LiN(SO.sub.2CF.sub.2CF.sub.3).sub.2, and LiN(SO.sub.2CF.sub.3).sub.2, as well as methide salts, such as LiC(SO.sub.2CF.sub.3).sub.3 and LiC(SO.sub.2CF.sub.2CF.sub.3).sub.3, may be used in these electrolytes. Fluorinated alkyl groups enhance solubility of these salts in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene, and/or one or more ionic liquids.

Fluorine follows water: Effect on electrical conductivity of silicate minerals by experimental constraints from phlogopite

NASA Astrophysics Data System (ADS)

Li, Yan; Jiang, Haotian; Yang, Xiaozhi

2017-11-01

Fluorine and hydroxyl groups are minor constituents of silicate minerals, and share a lot of similarities concerning their physical and chemical properties. Hydroxyl groups significantly enhance the electrical conductivity of many silicate minerals, and it is expected that fluorine would have a comparable effect. This, however, has never been documented quantitatively. Here we present experimental approaches on this issue, by investigating the electrical conductivity of phlogopite with a wide range of fluorine content (but with broadly similar contents for other major elements). Electrical conductivities of gem-quality single crystal phlogopites, with samples prepared along the same orientation (normal to the (0 0 1) plane), were determined at 1 GPa and 200-650 °C using an end-loaded piston cylinder apparatus and a Solartron-1260 Impedance/Gain Phase Analyzer over the frequency range of 106 to 0.1 Hz. The complex spectra usually show an arc in the high frequency range and a short tail in the low frequency range, which are caused by lattice conduction and electrode effects, respectively. The electrical conductivity increases with increasing fluorine content, and the main charge carriers are fluorine. The activation enthalpies are ∼180 to 200 kJ/mol, nearly independent of fluorine content. The conductivity is linearly proportional to the content of fluorine, with an exponent factor of ∼1. The results demonstrate that conduction by fluorine leads to very high electrical conductivity at high temperatures. The influence of fluorine on electrical conductivity may be compared to that of hydrogen in nominally anhydrous minerals. This, along with the close association of fluorine and hydroxyl groups in silicate minerals and their similar crystal-chemical behaviors, suggests a more general role of fluorine in enhancing the electrical conductivity of many silicate minerals. Fluorine-rich assemblages, e.g., phlogopite and amphibole, could be locally enriched in the upper mantle, and if they form connected networks as observed for some natural samples, regionally high electrical conductivities could be produced. It has been recently proposed that the transition zone is probably a major reservoir for fluorine in the mantle, due to the significant dissolution of fluorine in wadsleyite and ringwoodite and the coupled incorporation with hydroxyl groups. As such, geophysically-resolved high electrical conductivities in the transition zone may be accounted for by fluorine in the dominant minerals, rather than by hydroxyl groups. The results of this work would stimulate a wide scope of future studies on the deep fluorine cycle, the deep water cycle and the geodynamical properties of the mantle.

Fluorine in the UK environment.

PubMed

Fuge, R; Andrews, M J

1988-12-01

Relatively low concentrations of fluorine in drinking water (≤ 1 mg F/l) have been shown to significantly reduce the degree of dental caries in children and fluorine would also appear to have a beneficial effect on bone formation in both humans and farm animals. However, it is apparent that elevated levels of fluorine in the diet have sometimes resulted in problems of increased dental caries and of the development of bone deformities. Much of the fluorine in rocks and soils occurs in apatite and hydroxysilicate minerals, fluorite being the only relatively common rock forming mineral containing fluorine as an essential constituent.Little systematic data are available on fluorine concentrations in soils, plants and natural waters in the UK. General background soil concentrations lie in the range 200 - 400 mg F/kg. For waters the average fluorine content is low, <0.1 mg F/l.In the British Isles there are several areas where there are enhanced levels of fluorine. In the northern Pennines, Derbyshire, northeast Wales and Cornwall, fluorite occurs as a significant component of mineralisation and much fluorine has been added to the environment from mining waste dumps. Soils in northeast Wales contain up to 3,650 mg F/kg and in the northern Pennines up to 20,000 mg F/kg. Waters contain up to 2.3 mg F/l. In southwest England, the granites are generally fluorine-rich with the fluorite granites of the St Austell pluton containing as much as 1 percent fluorine. These rocks are frequently kaolinised and intensively worked as a source of china clay. Soils in the vicinity of the waste tips contain up to 3,300 mg F/kg and grasses up to 2,950 mg F/kg. Surface waters in the St Austell area contain up to 1.25 mg F/l.Atmospheric fluorine pollution around brickworks in the Peterborough and Bedford areas has resulted in fluorosis in farm animals. Other sources of atmospheric fluorine pollution are aluminium smelters, steelworks and fossil fuel burning.

Polyfluorides and Neat Fluorine as Host Material in Matrix-Isolation Experiments.

PubMed

Brosi, Felix; Vent-Schmidt, Thomas; Kieninger, Stefanie; Schlöder, Tobias; Beckers, Helmut; Riedel, Sebastian

2015-11-09

The use of neat fluorine in matrix isolation is reported, as well as the formation of polyfluoride monoanions under cryogenic conditions. Purification procedures and spectroscopic data of fluorine are described, and matrix shifts of selected molecules and impurities in solid fluorine are compared to those of common matrix gases (Ar, Kr, N2 , Ne). The reaction of neat fluorine and IR-laser ablated metal atoms to yield fluorides of chromium (CrF5 ), palladium (PdF2 ), gold (AuF5 ), and praseodymium (PrF4 ) has been investigated. The fluorides have been characterized in solid fluorine by IR spectroscopy at 5 K. Also the fluorination of Kr and the photo-dismutation of XeO4 have been studied by using IR spectroscopy in neat fluorine. Formation of the [F5 ](-) ion was obtained by IR-laser ablation of platinum in the presence of fluorine and proven in a Ne matrix at 5 K by two characteristic vibrational bands of [F5 ](-) at $\\tilde \

Fluorine interaction with defects on graphite surface by a first-principles study

NASA Astrophysics Data System (ADS)

Wang, Song; Xuezhi, Ke; Zhang, Wei; Gong, Wenbin; Huai, Ping; Zhang, Wenqing; Zhu, Zhiyuan

2014-02-01

The interaction between fluorine atom and graphite surface has been investigated in the framework of density functional theory. Due to the consideration of molten salt reactor system, only carbon adatoms and vacancies are chemical reactive for fluorine atoms. Fluorine adsorption on carbon adatom will enhance the mobility of carbon adatom. Carbon adatom can also be removed easily from graphite surface in form of CF2 molecule, explaining the formation mechanism of CF2 molecule in previous experiment. For the interaction between fluorine and vacancy, we find that fluorine atoms which adsorb at vacancy can hardly escape. Both pristine surface and vacancy are impossible for fluorine to penetrate due to the high penetration barrier. We believe our result is helpful to understand the compatibility between graphite and fluorine molten salt in molten salt reactor system.

Space charge dynamics Of CF4 fluorinated LDPE samples from different fluorination conditions and their DC conductivities

NASA Astrophysics Data System (ADS)

Liu, Ning; Li, Ziyun; Chen, George; Chen, Qiang; Li, Shengtao

2017-07-01

Taking advantage of plasma technology using mixing gas CF4/H2, a fluorination process was performed on LDPE samples in the present paper. Different exposure times and discharge voltage levels were applied to produce four different types of samples. It has been found that after fluorination, space charge injection is obviously suppressed. And with longer fluorination times and higher discharge voltage, injected homocharges are reduced. By employing x-ray photoelectron spectroscopy, new chemical groups of C-F bindings are confirmed to be introduced by fluorination process of the plasma treatment. The charge suppression effect can be explained as: surface traps introduced by fluorination will reduce the interface field at both electrodes. Moreover, for fluorinated samples, heterocharge emerges obviously under 30 kV \\text{m}{{\\text{m}}-1} , which are considered as charges ionized from degradation products of etching and/or lower weight molecular specifies. Through the conductivity measurements also performed at 30 kV \\text{m}{{\\text{m}}-1} , it is found that, for the fluorinated samples with the better charge blocking effect, the conductivity is lowered. However, the conductivity of the fluorinated sample with the lightest degree of fluorination is found to be higher than that of normal samples.

The Curious Case of Fluorination of Conjugated Polymers for Solar Cells.

PubMed

Zhang, Qianqian; Kelly, Mary Allison; Bauer, Nicole; You, Wei

2017-09-19

Organic solar cells (OSCs) have been a rising star in the field of renewable energy since the introduction of the bulk heterojunction (BHJ) in 1992. Recent advances have pushed the efficiencies of OSCs to over 13%, an impressive accomplishment via collaborative efforts in rational materials design and synthesis, careful device engineering, and fundamental understanding of device physics. Throughout these endeavors, several design principles for the conjugated donor polymers used in such solar cells have emerged, including optimizing the conjugated backbone with judicious selection of building blocks, side-chain engineering, and substituents. Among all of the substituents, fluorine is probably the most popular one; improved device characteristics with fluorination have frequently been reported for a wide range of conjugated polymers, in particular, donor-acceptor (D-A)-type polymers. Herein we examine the effect of fluorination on the device performance of solar cells as a function of the position of fluorination (on the acceptor unit or on the donor unit), aiming to outline a clear understanding of the benefits of this curious substituent. As fluorination of the acceptor unit is the most adopted strategy for D-A polymers, we first discuss the effect of fluorination of the acceptor units, highlighting the five most widely utilized acceptor units. While improved device efficiency has been widely observed with fluorinated acceptor units, the underlying reasons vary from case to case and highly depend on the chemical structure of the polymer. Second, the effect of fluorination of the donor unit is addressed. Here we focus on four donor units that have been most studied with fluorination. While device-performance-enhancing effects by fluorination of the donor units have also been observed, it is less clear that fluorine will always benefit the efficiency of the OSC, as there are several cases where the efficiency drops, in particular with "over-fluorination", i.e., when too many fluorine substituents are incorporated. Finally, while this Account focuses on studies in which the polymer is paired with fullerene derivatives as the electron accepting materials, non-fullerene acceptors (NFAs) are quickly becoming key players in the field of OSCs. The effect of fluorination of the polymers on the device performance may be different when NFAs are used as the electron-accepting materials, which remains to be investigated. However, the design of fluorinated polymers may provide guidelines for the design of more efficient NFAs. Indeed, the current highest-performing OSC (∼13%) features fluorination on both the donor polymer and the non-fullerene acceptor.

Grafted functional groups on expanded tetrafluoroethylene (ePTFE) support for fuel cell and water transport membranes

DOEpatents

Fuller, Timothy J.; Jiang, Ruichun

2017-01-24

A method for forming a modified solid polymer includes a step of contacting a solid fluorinated polymer with a sodium sodium-naphthalenide solution to form a treated fluorinated solid polymer. The treated fluorinated solid polymer is contacted with carbon dioxide, sulfur dioxide, or sulfur trioxide to form a solid grafted fluorinated polymer. Characteristically, the grafted fluorinated polymer includes appended CO.sub.2H or SO.sub.2H or SO.sub.3H groups. The solid grafted fluorinated polymer is advantageously incorporated into a fuel cell as part of the ion-conducting membrane or a water transport membrane in a humidifier.

Can Csbnd H⋯Fsbnd C hydrogen bonds alter crystal packing features in the presence of Nsbnd H⋯Odbnd C hydrogen bond?

NASA Astrophysics Data System (ADS)

Yadav, Hare Ram; Choudhury, Angshuman Roy

2017-12-01

Intermolecular interactions involving organic fluorine have been the contemporary field of research in the area of organic solid state chemistry. While a group of researchers had refuted the importance of "organic fluorine" in guiding crystal structures, others have provided evidences for in favor of fluorine mediated interactions in the solid state. Many systematic studies have indicated that the "organic fluorine" is capable of offering weak hydrogen bonds through various supramolecular synthons, mostly in the absence of other stronger hydrogen bonds. Analysis of fluorine mediated interaction in the presence of strong hydrogen bonds has not been highlighted in detail. Hence a thorough structural investigation is needed to understand the role of "organic fluorine" in crystal engineering of small organic fluorinated molecules having the possibility of strong hydrogen bond formation in the solution and in the solid state. To fulfil this aim, we have synthesized a series of fluorinated amides using 3-methoxyphenylacetic acid and fluorinated anilines and studied their structural properties through single crystal and powder X-ray diffraction methods. Our results indicated that the "organic fluorine" plays a significant role in altering the packing characteristics of the molecule in building specific crystal lattices even in the presence of strong hydrogen bond.

Improved stability of highly fluorinated phospholipid-based vesicles in the presence of bile salts.

PubMed

Gadras, C; Santaella, C; Vierling, P

1999-01-04

The stability of fluorinated phospholipid-based vesicles in terms of detergent-induced release of encapsulated carboxyfluorescein has been evaluated. The fluorinated liposomes are substantially more resistant towards the lytic action of sodium taurocholate than conventional DSPC or even DSPC/CH 1/1 liposomes. Concerning structure/permeability relationships, the larger the fluorination degree of the membrane, the higher the resistance of the fluorinated liposomes to their destruction by the detergent. These results show that fluorinated liposomes have a promising potential as drug carrier and delivery systems for oral administration.

Quantitative Assessment of the Impact of Fluorine Substitution on P-Glycoprotein (P-gp) Mediated Efflux, Permeability, Lipophilicity, and Metabolic Stability.

PubMed

Pettersson, Martin; Hou, Xinjun; Kuhn, Max; Wager, Travis T; Kauffman, Gregory W; Verhoest, Patrick R

2016-06-09

Strategic replacement of one or more hydrogen atoms with fluorine atom(s) is a common tactic to improve potency at a given target and/or to modulate parameters such as metabolic stability and pKa. Molecular weight (MW) is a key parameter in design, and incorporation of fluorine is associated with a disproportionate increase in MW considering the van der Waals radius of fluorine versus hydrogen. Herein we examine a large compound data set to understand the effect of introducing fluorine on the risk of encountering P-glycoprotein mediated efflux (as measured by MDR efflux ratio), passive permeability, lipophilicity, and metabolic stability. Statistical modeling of the MDR ER data demonstrated that an increase in MW as a result of introducing fluorine atoms does not lead to higher risk of P-gp mediated efflux. Fluorine-corrected molecular weight (MWFC), where the molecular weight of fluorine has been subtracted, was found to be a more relevant descriptor.

Nephelometric determination of fluorine

USGS Publications Warehouse

Stevens, R.E.

1936-01-01

Fluorine in minerals may be determined with the nephelometer to about 1 per cent of the fluorine. The determination is made on an aliquot of the sodium chloride solution of the fluorine, obtained by the Berzelius method of extraction. The fluorine is precipitated as colloidal calcium fluoride in alcoholic solution, gelatin serving as a protective colloid. Arsenates, sulfates, and phosphates, which interfere with the determination, must be removed.

Synthesis of Fluorinated Graphene/CoAl-Layered Double Hydroxide Composites as Electrode Materials for Supercapacitors.

PubMed

Peng, Weijun; Li, Hongqiang; Song, Shaoxian

2017-02-15

CoAl-layered double hydroxide/fluorinated graphene (CoAl-LDH/FGN) composites were fabricated via a two-step hydrothermal method. The synthesized CoAl-LDH/FGN composites have been characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), and electrochemical measurements. The results indicated that the fluorinated carbon with various configuration forms were grafted onto the framework of graphene, and the C-F bond configuration and fluorine content could be tuned by the fluorination time. Most of semi-ionic C-F bonds were formed at an appropriate fluorination time and, then, converted into fluorine rich surface groups (such as CF 2 , CF 3 , etc.) which were electrochemically inactive as the fluorination time prolonged. Moreover, the CoAl-LDH/FGN composites prepared at the optimal fluorination time exhibited the highest specific capacitance (1222 F/g at 1 A/g), the best rate capability, and the most stable capacitance retention, which offered great promise as electrode materials for supercapacitors.

Finding the perfect spot for fluorine: improving potency up to 40-fold during a rational fluorine scan of a Bruton's Tyrosine Kinase (BTK) inhibitor scaffold.

PubMed

Lou, Yan; Sweeney, Zachary K; Kuglstatter, Andreas; Davis, Dana; Goldstein, David M; Han, Xiaochun; Hong, Junbae; Kocer, Buelent; Kondru, Rama K; Litman, Renee; McIntosh, Joel; Sarma, Keshab; Suh, Judy; Taygerly, Joshua; Owens, Timothy D

2015-01-15

A rational fluorine scan based on co-crystal structures was explored to increase the potency of a series of selective BTK inhibitors. While fluorine substitution on a saturated bicyclic ring system yields no apparent benefit, the same operation on an unsaturated bicyclic ring can increase HWB activity by up to 40-fold. Comparison of co-crystal structures of parent molecules and fluorinated counterparts revealed the importance of placing fluorine at the optimal position to achieve favorable interactions with protein side chains. Copyright © 2014 Elsevier Ltd. All rights reserved.

PRODUCTION OF FLUORINE-CONTAINING HYDROCARBON

DOEpatents

Sarsfield, N.F.

1949-08-01

This patent relates to improvements in the production of fluorine- containing hydrocarbon derivatives. The process for increasing the degree of fluorination of a fluorochlorohydrocarbon comprises subjecting a highly fluorinated fluorochlorohydrocarbon to the action of a dehydrochlorinating agent, and treating the resulting unsaturated body with fluorine, cobalt trifluoride, or silver difluoride. A number of reagents are known as dehydrochlorinaling agents, including, for example, the caustic alkalies, either in an anhydrous condition or dissolved in water or a lower aliphatic alcohol.

Human Lamin B Contains a Farnesylated Cysteine Residue*

PubMed Central

Farnsworth, Christopher C.; Wolda, Sharon L.; Gelb, Michael H.; Glomset, John A.

2012-01-01

We recently showed that HeLa cell lamin B is modified by a mevalonic acid derivative. Here we identified the modified amino acid, determined its mode of link-age to the mevalonic acid derivative, and established the derivative’s structure. A cysteine residue is modified because experiments with lamin B that had been biosynthetically labeled with [3H] mevalonic acid or [35S] cysteine and then extensively digested with proteases yielded 3H- or 35S-labeled products that co-chromatographed in five successive systems. A thioether linkage rather than a thioester linkage is involved because the mevalonic acid derivative could be released from the 3H-labeled products in a pentane-extractable form by treatment with Raney nickel but not with methanolic KOH. The derivative is a farnesyl moiety because the Raney nickel-released material was identified as 2,6,10-trimethyl-2,6,10-dodecatriene by a combination of gas chromatography and mass spectrometry. The thioether-modified cysteine residue appears to be located near the carboxyl end of lamin B because treatment of 3H-labeled lamin B with cyanogen bromide yielded a single labeled polypeptide that mapped toward this end of the cDNA-inferred sequence of human lamin B. PMID:2684976

Fluorinated Alq3 derivatives with tunable optical properties.

PubMed

Shi, Yue-Wen; Shi, Min-Min; Huang, Jia-Chi; Chen, Hong-Zheng; Wang, Mang; Liu, Xiao-Dong; Ma, Yu-Guang; Xu, Hai; Yang, Bing

2006-05-14

This communication reports that not only the emission colour but also the photoluminescence quantum yield of Alq3 can be tuned by introducing fluorine atoms at different positions; with fluorination at C-5 the emission is red-shifted with a tremendously decreased intensity, fluorination at C-6 causes a blue-shift with a significantly increased intensity, and fluorination at C-7 has a minor effect on both the colour and intensity of Alq3's emission.

Synthesis of antifungal vaccines by conjugation of β-1,2 trimannosides with T-cell peptides and covalent anchoring of neoglycopeptide to tetanus toxoid.

PubMed

Cartmell, Jonathan; Paszkiewicz, Eugenia; Dziadek, Sebastian; Tam, Pui-Hang; Luu, Thanh; Sarkar, Susmita; Lipinski, Tomasz; Bundle, David R

2015-02-11

Selective strategies for the construction of novel three component glycoconjugate vaccines presenting Candida albicans cell wall glycan (β-1,2 mannoside) and polypeptide fragments on a tetanus toxoid carrier are described. The first of two conjugation strategies employed peptides bearing an N-terminal thiopropionyl residue for conjugation to a trisaccharide equipped with an acrylate linker and a C-terminal S-acetyl thioglycolyl moiety for subsequent linking of neoglycopeptide to bromoacetylated tetanus toxoid. Michael addition of acrylate trisaccharides to peptide thiol under mildly basic conditions gave a mixture of N- and C- terminal glyco-peptide thioethers. An adaptation of this strategy coordinated S-acyl protection with anticipated thioester exchange equilibria. This furnished a single chemically defined fully synthetic neoglycopeptide conjugate that could be anchored to a tetanus toxoid carrier and avoids the introduction of exogenous antigenic groups. The second strategy retained the N-terminal thiopropionyl residue but replaced the C-terminal S-acetate functionality with an azido group that allowed efficient, selective formation of neoglycopeptide thioethers and subsequent conjugation of these with propargylated tetanus toxoid, but introduced potentially antigenic triazole linkages. Copyright © 2014 Elsevier Ltd. All rights reserved.

[Fluorine speciation and its distribution characteristics in selected agricultural soils of North China Plain].

PubMed

Yi, Chun-Yao; Wang, Bing-Guo; Jin, Meng-Gui

2013-08-01

The objectives of this study were to study fluorine speciation and its distribution characteristics in the cultivated soils of wheat-corn fields at the typical areas, the North China Plain. The fluorine contents in cultivated soils and profile soils were measured by consecutive extraction. The results showed that the soil total fluorine (T-F) content at typical areas in the North China Plain ranged from 338.31 mg x kg(-1) to 781.67 mg x kg(-1), with a mean of 430.46 mg x kg(-1). The soil fluorine speciation with the highest content was Residual-Fluorine (Res-F), with a mean of 402.73 mg x kg(-1). The average content of Water soluble Fluorine (Ws-F) was 14.39 mg x kg(-1). The result indicated that the cultivated soil in the study area was at a relatively high fluoride pollution level, which may be harmful to human health and the ecological environment. The contents of Organic Fluorine (Or-F) and Fe/Mn Oxide-Fluorine (Fe/ Mn-F) were also quite high, with a mean of 8.90 mg x kg(-1) and 4.10 mg x kg(-1), respectively. The exchangeable fluorine (Ex-F) only had a very small amount of 0.33 mg x kg(-1). Soil Ws-F was positively correlated with soil pH and CEC, while it was negatively correlated with the percentage of soil clay. The content of soil Fe/Mn-F was positively correlated with soil pH, CEC and the sand grain content percentage, while it was negatively correlated with the clay grain content percentage. The soil pH value had the most significant influence on the water soluble fluorine (Ws-F) and Fe/Mn Oxide-Fluorine (Fe/Mn-F), and the soil CEC had the most significant influence on the soil total fluorine (T-F) and residual-Fluorine (Res-F) by stepwise regression analysis. In the soil profiles, the T-F content appeared as peaks and valleys representing the change of the soil lithology in the vadose zone. The Ws-F in the soil profiles mainly changed in the depth of 0-100 cm near the surface soil and was little influenced by the soil lithology. But it was strongly influenced by the soil pH, and was positively correlated with the soil pH. This study can provide a scientific evidence for soil fluorine pollution, prevention and a theoretical basis for soil fluorine mobility and its influence on ecology and environment.

Negative Hyperconjugation versus Electronegativity: Vibrational Spectra of Free Fluorinated Alkoxide Ions in the Gas Phase.

PubMed

Oomens, Jos; Berden, Giel; Morton, Thomas Hellman

2015-06-22

CO stretching frequencies of free, gaseous, fluorinated alkoxide ions shift substantially to the blue, relative to those of corresponding alcohols complexed with ammonia. Free α-fluorinated ions, pentafluoroethoxide and heptafluoroisopropoxide anions, display further blue shifts relative to cases with only β-fluorination, providing experimental evidence for fluorine negative hyperconjugation. DFT analysis with the atoms in molecules (AIM) method confirms an increase in CO bond order for the α-fluorinated ions, demonstrating an increase in carbonyl character for the free ions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Deciphering the Fluorine Code-The Many Hats Fluorine Wears in a Protein Environment.

PubMed

Berger, Allison Ann; Völler, Jan-Stefan; Budisa, Nediljko; Koksch, Beate

2017-09-19

Deciphering the fluorine code is how we describe not only the focus of this Account, but also the systematic approach to studying the impact of fluorine's incorporation on the properties of peptides and proteins used by our groups and others. The introduction of fluorine has been shown to impart favorable, but seldom predictable, properties to peptides and proteins, but up until about two decades ago the outcomes of fluorine modification of peptides and proteins were largely left to chance. Driven by the motivation to extend the application of the unique properties of the element fluorine from medicinal and agro chemistry to peptide and protein engineering we have established extensive research programs that enable the systematic investigation of effects that accompany the introduction of fluorine into this class of biopolymers. The introduction of fluorine into amino acids offers a universe of options for modifications with regard to number and position of fluorine substituents in the amino acid side chain. Moreover, it is important to emphasize that the consequences of incorporating the C-F bond into a biopolymer can be attributed to two distinct yet related phenomena: (i) the fluorine substituent can directly engage in intermolecular interactions with its environment and/or (ii) the other functional groups present in the molecule can be influenced by the electron withdrawing nature of this element (intramolecular) and in turn interact differently with their immediate environment (intermolecular). Based on our studies, we have shown that a change in number and/or position of as subtle as one single fluorine substituent has the power to considerably modify key properties of amino acids such as hydrophobicity, polarity, and secondary structure propensity. These properties are crucial factors in peptide and protein engineering, and thus, fluorinated amino acids can be applied to fine-tune properties such as protein folding, proteolytic stability, and protein-protein interactions provided we understand and become able to predict the outcome of a fluorine substitution in this context. With this Account, we attempt to analyze information we gained from our recent projects on how the nature of the fluorine atom and C-F bond influence four key properties of peptides and proteins: peptide folding, protein-protein interactions, ribosomal translation, and protease stability. These results impressively show why the introduction of fluorine creates a new class of amino acids with a repertoire of functionalities that is unique to the world of proteins and in some cases orthogonal to the set of canonical and natural amino acids. Our concluding statements aim to offer a few conserved design principles that have emerged from systematic studies over the last two decades; in this way, we hope to advance the field of peptide and protein engineering based on the judicious introduction of fluorinated building blocks.

Antioxidant activity of amino acids in soybean oil at frying temperature: Structural effects and synergism with tocopherols

USDA-ARS?s Scientific Manuscript database

The purpose of this study was to evaluate amino acids as natural antioxidants for frying. Twenty amino acids were added to soybean oil heated to 180 ºC, and the effects of amino acid structure on the antioxidant activity were investigated. Amino acids containing a thiol, a thioether, or an extra ami...

Decarboxylative Fluorination Strategies for Accessing Medicinally-relevant Products

PubMed Central

Qiao, Yupu; Zhu, Lingui; Ambler, Brett R.

2014-01-01

Fluorinated organic compounds have a long history in medicinal chemistry, and synthetic methods to access target fluorinated compounds are undergoing a revolution. One powerful strategy for the installation of fluorine-containing functional groups includes decarboxylative reactions. Benefits of decarboxylative approaches potentially include: 1) readily available substrates or reagents 2) mild reaction conditions; 3) simplified purification. This focus review highlights the applications of decarboxylation strategies for fluorination reactions to access compounds with biomedical potential. The manuscript highlights on two general strategies, fluorination by decarboxylative reagents and by decarboxylation of substrates. Where relevant, examples of medicinally useful compounds that can be accessed using these strategies are highlighted. PMID:24484421

Tris(thioimidazolyl)borate-zinc-thiolate complexes for the modeling of biological thiolate alkylations.

PubMed

Ibrahim, Mohamed M; Seebacher, Jan; Steinfeld, Gunther; Vahrenkamp, Heinrich

2005-11-14

The S3Zn-SR coordination of thiolate-alkylating enzymes such as the Ada DNA repair protein was reproduced in tris(thioimidazolyl)borate-zinc-thiolate complexes Tti(R)Zn-SR'. Four different Tti(R) ligands and nine different thiolates were employed, yielding a total of 12 new complexes. In addition, one Tti(R)Zn-SH complex and two thiolate-bridged [Tti(R)-SEt-Tti(R)]+ complexes were obtained. A selection of six thiolate complexes was converted with methyl iodide to the corresponding methyl thioethers and Tti(R)Zn-I. According to a kinetic analysis these reactions are second-order processes, which implies that the alkylations are likely to occur at the zinc-bound thiolates. They are much faster than the alkylations of zinc thiolates with N3 or N2S tripod ligands. The most reactive thiolate, Tti(Xyl)Zn-SEt, reacts slowly with trimethyl phosphate in a nonpolar medium at room temperature, yielding methyl-ethyl-thioether and Tti(Xyl)Zn-OPO(OMe)2 which can be converted back to the thiolate complex with NaSEt. This is the closest reproduction of the Ada repair process so far.

Fluorinated graphite fibers as a new engineering material: Promises and challenges

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh; Long, Martin

1989-01-01

Pitch based graphitized carbon fibers with electrical resistivity of 300 micro-Ohm/cm were brominated and partially debrominated to 18 percent bromine at room temperature, and then fluorinated at 300 to 450 C, either continuously or intermittently for several cycles. In addition, on fluorine and titanium fluoride intercalated fiber sample was fluorinated at 270 C from the same fiber source. The mass and conductivity of the brominated-debrominated then fluorinated fibers (with fluorine-to-carbon atom ratio of 0.54 or higher) stabilized at room temperature air in a few days. However, at 200 C, these values decreased rapidly and then more slowly, throughout a 2-week test period. The electrically insulative or semiconductive fibers were found to be compatible with epoxy and have the fluorine-to-carbon atom ratio of 0.65 to 0.68, thermal conductivity of 5 to 24 W/m-K, electrical resistivity of 10(exp 4) to 10(exp 11) Ohm/cm, tensile strength of 70 to 150 ksi, Young's modulus of 20 to 30 msi, and CTE (coefficient of thermal expansion) values of 7 ppm/deg C. Data of these physical property values are preliminary. However, it is concluded that these physical properties can be tailor-made. They depend largely on the fluorine content of the final products and the intercalant in the fibers before fluorination, and, to a smaller extent, on the fluorination temperature histogram.

40 CFR 721.10146 - Partially fluorinated condensation polymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Partially fluorinated condensation... Specific Chemical Substances § 721.10146 Partially fluorinated condensation polymer (generic). (a) Chemical... as partially fluorinated condensation polymer (PMN P-07-87) is subject to reporting under this...

40 CFR 721.10146 - Partially fluorinated condensation polymer (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Partially fluorinated condensation... Specific Chemical Substances § 721.10146 Partially fluorinated condensation polymer (generic). (a) Chemical... as partially fluorinated condensation polymer (PMN P-07-87) is subject to reporting under this...

40 CFR 721.10146 - Partially fluorinated condensation polymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Partially fluorinated condensation... Specific Chemical Substances § 721.10146 Partially fluorinated condensation polymer (generic). (a) Chemical... as partially fluorinated condensation polymer (PMN P-07-87) is subject to reporting under this...

40 CFR 721.10146 - Partially fluorinated condensation polymer (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Partially fluorinated condensation... Specific Chemical Substances § 721.10146 Partially fluorinated condensation polymer (generic). (a) Chemical... as partially fluorinated condensation polymer (PMN P-07-87) is subject to reporting under this...

Enantioselective Organocatalytic α-Fluorination of Cyclic Ketones

PubMed Central

Kwiatkowski, Piotr; Beeson, Teresa D.; Conrad, Jay C.

2011-01-01

The first highly enantioselective α-fluorination of ketones using organocatalysis has been accomplished. The long-standing problem of enantioselective ketone α-fluorination via enamine activation has been overcome via high-throughput evaluation of a new library of amine catalysts. The optimal system, a primary amine functionalized Cinchona alkaloid, allows the direct and asymmetric α-fluorination of a variety of carbo- and heterocyclic substrates. Furthermore, this protocol also provides diastereo-, regio- and chemoselective catalyst control in fluorinations involving complex carbonyl systems. PMID:21247133

Chemistry, Biochemistry, Pharmacology, and Toxicology of CS and Synthesis of Its Novel Analogs

DTIC Science & Technology

2007-10-01

fluorine and fluorine -containing groups have been synthesized using microwave irradiation and novel catalysts. The structures and physical properties and...safe, and biologically more potent CS analogs. To this end, the synthesis of a novel group of CS-agents incorporating fluorine and fluorine ...CONCLUSION The new CS-analogs are expected to be more potent than CS. This observation is based on the following considerations. First, fluorine is

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.

Method for directly recovering fluorine from gas streams

DOEpatents

Orlett, Michael J.; Saraceno, Anthony J.

1981-01-01

This invention is a process for the direct recovery of gaseous fluorine from waste-gas streams or the like. The process comprises passing the gas stream through a bed of anhydrous K.sub.3 NiF.sub.6 pellets to fluorinate the same to K.sub.3 NiF.sub.7 and subsequently desorbing the fluorine by heating the K.sub.3 NiF.sub.7 pellets to a temperature re-converting them to K.sub.3 NiF.sub.6. The efficiency of the fluorine-absorption step is maximized by operating in a selected and conveniently low temperature. The desorbed fluorine is highly pure and is at a pressure of several atmospheres. Preferably, the K.sub.3 NiF.sub.6 pellets are prepared by a method including the steps of forming agglomerates of hydrated K.sub.3 NiF.sub.5, sintering the agglomerates to form K.sub.3 NiF.sub.5 pellets of enhanced reactivity with respect to fluorine, and fluorinating the sintered pellets to K.sub.3 NiF.sub.6.

Tuning the tunneling magnetoresistance by using fluorinated graphene in graphene based magnetic junctions

NASA Astrophysics Data System (ADS)

Meena, Shweta; Choudhary, Sudhanshu

2017-12-01

Spin polarized properties of fluorinated graphene as tunnel barrier with CrO2 as two HMF electrodes are studied using first principle methods based on density functional theory. Fluorinated graphene with different fluorine coverages is explored as tunnel barriers in magnetic tunnel junctions. Density functional computation for different fluorine coverages imply that with increase in fluorine coverages, there is increase in band gap (Eg) of graphene, Eg ˜ 3.466 e V was observed when graphene sheet is fluorine adsorbed on both-side with 100% coverage (CF). The results of CF graphene are compared with C4F (fluorination on one-side of graphene sheet with 25% coverage) and out-of-plane graphene based magnetic tunnel junctions. On comparison of the results it is observed that CF graphene based structure offers high TMR ˜100%, and the transport of carrier is through tunneling as there are no transmission states near Fermi level. This suggests that graphene sheet with both-side fluorination with 100% coverages acts as a perfect insulator and hence a better barrier to the carriers which is due to negligible spin down current (I ↓ ) in both Parallel Configuration (PC) and Antiparallel Configuration (APC).

Improved retention of phosphorus donors in germanium using a non-amorphizing fluorine co-implantation technique

NASA Astrophysics Data System (ADS)

Monmeyran, Corentin; Crowe, Iain F.; Gwilliam, Russell M.; Heidelberger, Christopher; Napolitani, Enrico; Pastor, David; Gandhi, Hemi H.; Mazur, Eric; Michel, Jürgen; Agarwal, Anuradha M.; Kimerling, Lionel C.

2018-04-01

Co-doping with fluorine is a potentially promising method for defect passivation to increase the donor electrical activation in highly doped n-type germanium. However, regular high dose donor-fluorine co-implants, followed by conventional thermal treatment of the germanium, typically result in a dramatic loss of the fluorine, as a result of the extremely large diffusivity at elevated temperatures, partly mediated by the solid phase epitaxial regrowth. To circumvent this problem, we propose and experimentally demonstrate two non-amorphizing co-implantation methods; one involving consecutive, low dose fluorine implants, intertwined with rapid thermal annealing and the second, involving heating of the target wafer during implantation. Our study confirms that the fluorine solubility in germanium is defect-mediated and we reveal the extent to which both of these strategies can be effective in retaining large fractions of both the implanted fluorine and, critically, phosphorus donors.

Low temperature preparation of highly fluorinated multiwalled carbon nanotubes activated by Fe3O4 towards enhanced microwave absorbing property.

PubMed

Liu, Yang; Zhang, Yichun; Zhang, Cheng; Huang, Benyuan; Li, Yulong; Lai, Wenchuan; Wang, Xu; Liu, Xiangyang

2018-06-11

Conventional approach to preparation highly fluorinated multiwalled carbon nanotubes (MWCNTs) always need high temperature. This paper presents a catalytic tactic realizing effective fluorination of MWNCTs at room temperature (RT). Fe3O4@MWCNTs composites with Fe3O4 loaded on MWCNTs were firstly prepared through solvothermal method, which is followed by fluorination treatment at RT. The attachment of Fe3O4 changes the charge distribution and dramatically improves the fluorination activity of MWCNTs. Consequently, the fluorine content of fluorinated Fe3O4@MWCNTs (F-Fe3O4@MWCNTs) can reach up to 17.13 at% (almost 6 times that of the unloaded sample) only after room temperature of fluorination, which lead to obvious decrease of permittivity. Besides, the partial fluorination of Fe3O4 brings about abnormal enhanced permeability due to strengthened exchange resonance. Benefiting from the lower permittivity and higher permeability, F-Fe3O4@CNTs composite exhibit increased impedance matching. As a result, F-Fe3O4@CNTs behave good microwave absorption property with minimal reflection loss -45 dB at 2.61 mm when filler content is 13 wt%. The efficient absorption bandwidth (<-10 dB) reaches 4.1 GHz when the thickness is 2.5 mm. This work illustrates a novel catalytic approach to prepare highly fluorinated MWCNTs as promising microwave absorbers, and the design concept can also be extended to the fluorination of other carbon materials. © 2018 IOP Publishing Ltd.

Industrial Applications of Graphite Fluoride Fibers

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh; Kucera, Donald

1991-01-01

Based on fluorination technology developed during 1934 to 1959, and the fiber technology developed during the 1970s, a new process was developed to produce graphite fluoride fibers. In the process, pitch based graphitized carbon fibers are at first intercalated and deintercalated several times by bromine and iodine, followed by several cycles of nitrogen heating and fluorination at 350 to 370 C. Electrical, mechanical, and thermal properties of this fiber depend on the fluorination process and the fluorine content of the graphite fluoride product. However, these properties are between those of graphite and those of PTFE (Teflon). Therefore, it is considered to be a semiplastic. The physical properties suggest that this new material may have many new and unexplored applications. For example, it can be a thermally conductive electrical insulator. Its coefficient of thermal expansion (CTE) can be adjusted to match that of silicon, and therefore, it can be a heat sinking printed circuit board which is CTE compatible with silicon. Using these fibers in printed circuit boards may provide improved electrical performance and reliability of the electronics on the board over existing designs. Also, since it releases fluorine at 300 C or higher, it can be used as a material to store fluorine and to conduct fluorination. This application may simplify the fluorination process and reduce the risk of handling fluorine.

Fluorine-Rich Planetary Environments as Possible Habitats for Life

PubMed Central

Budisa, Nediljko; Kubyshkin, Vladimir; Schulze-Makuch, Dirk

2014-01-01

In polar aprotic organic solvents, fluorine might be an element of choice for life that uses selected fluorinated building blocks as monomers of choice for self-assembling of its catalytic polymers. Organofluorine compounds are extremely rare in the chemistry of life as we know it. Biomolecules, when fluorinated such as peptides or proteins, exhibit a “fluorous effect”, i.e., they are fluorophilic (neither hydrophilic nor lipophilic). Such polymers, capable of creating self-sorting assemblies, resist denaturation by organic solvents by exclusion of fluorocarbon side chains from the organic phase. Fluorous cores consist of a compact interior, which is shielded from the surrounding solvent. Thus, we can anticipate that fluorine-containing “teflon”-like or “non-sticking” building blocks might be monomers of choice for the synthesis of organized polymeric structures in fluorine-rich planetary environments. Although no fluorine-rich planetary environment is known, theoretical considerations might help us to define chemistries that might support life in such environments. For example, one scenario is that all molecular oxygen may be used up by oxidation reactions on a planetary surface and fluorine gas could be released from F-rich magma later in the history of a planetary body to result in a fluorine-rich planetary environment. PMID:25370378

Solid sampling determination of total fluorine in baby food samples by high-resolution continuum source graphite furnace molecular absorption spectrometry.

PubMed

Ozbek, Nil; Akman, Suleyman

2016-11-15

This study describes the applicability of solid sampling technique for the determination of fluorine in various baby foods via molecular absorption of calcium monofluoride generated in a graphite furnace of high-resolution continuum source atomic absorption spectrometry. Fluorine was determined at CaF wavelength, 606.440nm in a graphite tube applying a pyrolysis temperature of 1000°C and a molecule forming temperature of 2200°C. The limit of detection and characteristic mass of the method were 0.20ng and 0.17ng of fluorine, respectively. The fluorine concentrations determined in standard reference sample (bush branches and leaves) were in good agreement with the certified values. By applying the optimized parameters, the concentration of fluorine in various baby foods were determined. The fluorine concentrations were ranged from

Method of preparing pure fluorine gas

DOEpatents

Asprey, Larned B.

1976-01-01

A simple, inexpensive system for purifying and storing pure fluorine is described. The method utilizes alkali metal-nickel fluorides to absorb tank fluorine by forming nickel complex salts and leaving the gaseous impurities which are pumped away. The complex nickel fluoride is then heated to evolve back pure gaseous fluorine.

Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

DOEpatents

Marks, Tobin J.; Chen, You-Xian

2001-01-01

Organo-Lewis acids of the formula BR'R".sub.2 wherein B is boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

DOEpatents

Marks, Tobin J.; Chen, You-Xian

2002-01-01

Organo-Lewis acids of the formula BR'R".sub.2 wherein B is boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

Self-formation of a nanonet of fluorinated carbon nanowires on the Si surface by combined etching in fluorine-containing plasma

NASA Astrophysics Data System (ADS)

Amirov, I. I.; Gorlachev, E. S.; Mazaletskiy, L. A.; Izyumov, M. O.; Alov, N. V.

2018-03-01

In this work, we report a technique of the self-formation of a nanonet of fluorinated carbon nanowires on the Si surface using a combined etching in fluorine-containing C4F8/Ar and SF6 plasmas. Using scanning electron microscopy, atomic force microscopy and x-ray photoelectron spectroscopy, we show that after the etching of Si in the C4F8/Ar plasma, a fluorinated carbon film of nanometer-scale thickness is formed on its surface and its formation accelerates at elevated temperatures. After a subsequent short-term etching in the SF6 plasma, the film is modified into a nanonet of self-formed fluorinated carbon nanowires.

Experimental study of electrochemical fluorination of trichloroethylene

NASA Technical Reports Server (NTRS)

Polisena, C.; Liu, C. C.; Savinell, R. F.

1982-01-01

The electrochemical fluorination of trichloroethylene in anhydrous hydrogen fluoride at 0 C and at constant cell potential was investigated. A microprocessor-aided electrochemical fluorination reactor system that yields highly reproducible results was utilized. The following major two-carbon-chain products were observed: CHCl2-CCl2F, CHCl2-CClF2, CHClF-CCl2F, and CCl2F-CClF2. The first step in the reaction sequence was determined to be fluorine addition to the double bond, followed by replacement of first hydrogen and then chlorine by fluorine. Polymerization reactions yielded higher molecular weight or possible ring-type chlorofluorohydrocarbons. A comparison of the reaction products of electrochemical and chemical fluorinations of trichloroethylene is also discussed.

Quantitative Determination of Fluorinated Alkyl Substances by Large-Volume-Injection LC/MS/MS—Characterization of Municipal Wastewaters

PubMed Central

Schultz, Melissa M.; Barofsky, Douglas F.; Field, Jennifer A.

2008-01-01

A quantitative method was developed for the determination of fluorinated alkyl substances in municipal wastewater influents and effluents. The method consisted of centrifugation followed by large-volume injection (500 μL) of the supernatant onto a liquid chromatograph with a reverse-phase column and detection by electrospray ionization, and tandem mass spectrometry (LC/MS/MS). The fluorinated analytes studied include perfluoroalkyl sulfonates, fluorotelomer sulfonates, perfluorocarboxylates, and select fluorinated alkyl sulfonamides. Recoveries of the fluorinated analytes from wastewater treatment plant (WWTP) raw influents and final effluent ranged from 77% – 96% and 80% – 99%, respectively. The lower limit of quantitation ranged from 0.5 to 3.0 ng/L depending on the analyte. The method was applied to flow-proportional composites of raw influent and final effluent collected over a 24 hr period from ten WWTPs nationwide. Fluorinated alkyl substances were observed in wastewater at all treatment plants and each plant exhibited unique distributions of fluorinated alkyl substances despite similarities in treatment processes. In nine out of the ten plants sampled, at least one class of fluorinated alkyl substances exhibited increased concentrations in the effluent as compared to the influent concentrations. In some instances, decreases in certain fluorinated analyte concentrations were observed and attributed to sorption to sludge. PMID:16433363

Synthesis, characterization and cell behavior of fluoridated hydroxyapatite

NASA Astrophysics Data System (ADS)

Qu, Haibo

Fluorine-containing hydroxyapatite (Ca5(PO4) 3(OH)1-xFx FHA), where F- partially replaces OH- in hydroxyapatite (HA), is recognized as a possible biomaterial for bone and tooth implants and gaining attention in the last several years as a possible alternative to HA. In this study, FHA powders were synthesized through a pH-cycling method. It was discovered that fluorine incorporation increased with the fluorine content in the initial solution and the number of pH cycles employed. A relatively low fluorine incorporation efficiency, ˜60%, was attained for most of the FHA samples. The short time of stay at each pH cycle and the limited number of cycles used are believed to be the main reasons of the low fluorine incorporation into the apatite structure. It was also revealed that the FHA particles produced by the pH-cycling method were inhomogeneous. They were a mixture of hydroxyapatite and F-rich apatite (or FA) particles. The mechanisms of incorporation of fluorine ions into hydroxyapatite by a pH cyclicing method were studied using TEM, XRD and fluorine measurement. Instead of forming laminated structures as reported by other research groups, a mixture of nano-sized F-rich apatite (FHA) and hydroxyapatite (HA) particles were obtained using the pH-cyclicing method. After calcination, these FHA particles were homogenized and became single phased FHA. The effect of fluorine content, preparing method, and sintering temperature on both the bulk density and biaxial flexural strength of sintered FHA was studied. Both uniaxially pressed un-milled (UPU) and cold isostatically pressed milled (IPM) FHA discs were sintered at temperatures between 1200˜400°C at an interval of 100°C. It was found that the fluorine content had a significant impact on the sintering behavior, densification, and mechanical properties of FHA discs. A close correlation between the sintered density and biaxial flexural strength of the specimens was revealed, where the biaxial flexural strength increased exponentially with the sintered density. FHA discs with various fluorine contents have been used to investigate the effect of fluorine content on osteoblastic cell behaviors. Rat osteosarcoma (ROS 17/28) cells were cultured on FHA discs for appropriate times. The osteoblastic cell behaviors were examined in terms of cell attachment, proliferation, morphology and differentiation. The fluorine content in FHA strongly affected the cell activities. More cell attachment and proliferation were observed on the fluorine-containing FHA than pure HA. Fluorine content also affected the differentiation behaviors of osteoblastic cells. Cells on fluorine-containing FHA had higher alkaline phosphatase (ALP) activity than pure HA in 2 weeks. The morphology of the cells showed that it took less time for cells to cover the surface of fluorine-containing samples than that of pure HA. These results suggested that fluorine ions had a significant impact on osteoblastic cell behaviors.

Diastereocontrolled Electrophilic Fluorinations of 2-Deoxyribonolactone: Syntheses of All Corresponding 2-Deoxy-2-fluoro-lactones and 2’-Deoxy-2’-fluoro-NAD+s

PubMed Central

Cen, Yana; Sauve, Anthony A.

2009-01-01

Methods to construct 2’-deoxy-2’-fluoro-nucleosides have undergone limited improvement in the last twenty years in spite of substantially increased value of these compounds as pharmaceuticals and as tools for studying biological processes. We herein describe a consolidated approach to synthesize precursors to these commercially and scientifically valuable compounds via diastereocontrolled fluorination of the readily available precursor 2-deoxy-d-ribonolactone. With employment of appropriate sterically bulky silyl protecting groups at 3 and 5 positions, controlled electrophilic fluorination of the Li-ribonolactone enolate by N-fluorodibenezenesulfonamide yielded the corresponding 2-deoxy-2-fluoro-arabino-lactone in high isolated yield (72 %). The protected 2-deoxy-2, 2-difluoro-ribonolactone was obtained similarly in high yield from a second round of electrophilic fluorination (2 steps, 51% from protected ribonolactone starting material). Accomplishment of the difficult ribo-fluorination of the lactone was achieved by the directive effects of a diastereoselectively installed α-trimethylsilyl group. Electrophilic fluorination of a protected 2-deoxy-2-trimethylsilyl-arabino-lactone via enolate generation provided the protected 2-deoxy-2-fluoro-ribo-lactone as the exclusive fluorinated product. The reaction also yielded the starting material, the desilylated protected 2-deoxy-ribonolactone, which was recycled to provide a 38% chemical yield of the fluorinated product (versus initial protected ribonolactone) after consecutive silylation and fluorination cycles. Using our fluorinated sugar precursors we prepared the 2’-fluoro-arabino-, 2’-fluoro-ribo- and 2’,2’-difluoro-nicotinamide adenine dinucleotides (NAD+) of potential biological interest. These syntheses provide the most consolidated and efficient methods for production of sugar precursors of 2’-deoxy-2’-fluoronucleosides and have the advantage of utilizing an air-stable electrophilic fluorinating agent. The fluorinated NAD+s are anticipated to be useful for studying a variety of cellular metabolic and signaling processes. PMID:19958035

Relationship between fluorine in drinking water and dental health of residents in some large cities in China.

PubMed

Wang, Binbin; Zheng, Baoshan; Zhai, Cheng; Yu, Guangqian; Liu, Xiaojing

2004-10-01

In this project, the relationship between fluorine content in drinking water and dental health of residents in some large cities in China was evaluated. The concentration of fluorine in tap water and in urine of local subjects of 28 cities and 4 high fluorine villages in China shows a strong positive correlation (r(2)=0.96, S.E.=0.9881). Our studies indicate that drinking water is the most important source of fluorine intake for Chinese people, and in more than 90% of urban cities, fluorine concentrations in drinking water are below levels recommended by the WHO (approximately 0.5-1.0 mg/l). A 1995 investigation by The National Committee on Oral Health of China (NCOH) shows the relationship between average number of decayed, missing and filled teeth (DMFT) of urban residents and fluorine concentration in drinking water to be negatively correlated but not forming a good linear relationship. Our results, together with the previous study, suggest that: (1) dental caries of the study population can be reduced by drinking water fluoridation and that (2) other factors such as economic level, weather, lifestyle, food habits, living condition, etc., of a city can also affect the incidence of dental caries that cannot be predicted by fluoridation alone. Research on the relation between index of fluorosis (IF) and the fluorine concentration in drinking water for the four high fluorine villages showed that the recommended concentration of fluorine in drinking water can protect from dental fluorosis.

Fluorinated Compounds in US Fast Food Packaging | Science ...

EPA Pesticide Factsheets

Per- and polyfluoroalkyl substances (PFASs) are highly persistent synthetic chemicals, some of which have been associated with cancer, developmental toxicity, immunotoxicity, and other health effects. PFASs in grease-resistant food packaging can leach into food and increase dietary exposure. We collected ∼400 samples of food contact papers, paperboard containers, and beverage containers from fast food restaurants throughout the United States and measured total fluorine using particle-induced γ-ray emission (PIGE) spectroscopy. PIGE can rapidly and inexpensively measure total fluorine in solid-phase samples. We found that 46% of food contact papers and 20% of paperboard samples contained detectable fluorine (>16 nmol/cm2). Liquid chromatography/high-resolution mass spectrometry analysis of a subset of 20 samples found perfluorocarboxylates, perfluorosulfonates, and other known PFASs and/or unidentified polyfluorinated compounds (based on nontargeted analysis). The total peak area for PFASs was higher in 70% of samples (10 of 14) with a total fluorine level of >200 nmol/cm2 compared to six samples with a total fluorine level of <16 nmol/cm2. Samples with high total fluorine levels but low levels of measured PFASs may contain volatile PFASs, PFAS polymers, newer replacement PFASs, or other fluorinated compounds. The prevalence of fluorinated chemicals in fast food packaging demonstrates their potentially significant contribution to dietary PFAS exposure and envi

Effect of Partially Fluorinated N-Alkyl-Substituted Piperidine-2-carboxamides on Pharmacologically Relevant Properties.

PubMed

Vorberg, Raffael; Trapp, Nils; Zimmerli, Daniel; Wagner, Björn; Fischer, Holger; Kratochwil, Nicole A; Kansy, Manfred; Carreira, Erick M; Müller, Klaus

2016-10-06

The modulation of pharmacologically relevant properties of N-alkyl-piperidine-2-carboxamides was studied by selective introduction of 1-3 fluorine atoms into the n-propyl and n-butyl side chains of the local anesthetics ropivacaine and levobupivacaine. The basicity modulation by nearby fluorine substituents is essentially additive and exhibits an exponential attenuation as a function of topological distance between fluorine and the basic center. The intrinsic lipophilicity of the neutral piperidine derivatives displays the characteristic response noted for partially fluorinated alkyl groups attached to neutral heteroaryl systems. However, basicity decrease by nearby fluorine substituents affects lipophilicities at neutral pH, so that all partially fluorinated derivatives are of similar or higher lipophilicity than their non-fluorinated parents. Aqueous solubilities were found to correlate inversely with lipophilicity with a significant contribution from crystal packing energies, as indicated by variations in melting point temperatures. All fluorinated derivatives were found to be somewhat more readily oxidized in human liver microsomes, the rates of degradation correlating with increasing lipophilicity. Because the piperidine-2-carboxamide core is chiral, pairs with enantiomeric N-alkyl groups are diastereomeric. While little response to such stereoisomerism was observed for basicity or lipophilicity, more pronounced variations were observed for melting point temperatures and oxidative degradation. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of fluorine addition to the vanguard first stage

NASA Technical Reports Server (NTRS)

Tomazic, William A; Schmidt, Harold W; Tischler, Adelbert O

1957-01-01

The effect of adding fluorine to the Vanguard first-stage oxidant was anlyzed. An increase in specific impulse of 5.74 percent may be obtained with 30 percent fluorine. This increase, coupled with increased mass ratio due to greater oxidant density, gave up to 24.6-percent increase in first-stage burnout energy with 30 percent fluorine added. However, a change in tank configuration is required to accommodate the higher oxidant-fuel ratio necessary for peak specific impulse with fluorine addition.

Synthesis and use of (polyfluoroaryl)fluoroanions of aluminum, gallium and indium

DOEpatents

Marks, Tobin J.; Chen, You-Xian

2000-01-01

Salts of (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium are described. The (polyfluoroaryl)fluoroanions have the formula [ER'R"R'"F].sup..crclbar. wherein E is aluminum, gallium, or indium, wherein F is fluorine, and wherein R', R", and R'" is each a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic group.

21 CFR 170.45 - Fluorine-containing compounds.

Code of Federal Regulations, 2010 CFR

2010-04-01

... § 170.45 Fluorine-containing compounds. The Commissioner of Food and Drugs has concluded that it is in the interest of the public health to limit the addition of fluorine compounds to foods (a) to that... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Fluorine-containing compounds. 170.45 Section 170...

Site-selective local fluorination of graphene induced by focused ion beam irradiation.

PubMed

Li, Hu; Daukiya, Lakshya; Haldar, Soumyajyoti; Lindblad, Andreas; Sanyal, Biplab; Eriksson, Olle; Aubel, Dominique; Hajjar-Garreau, Samar; Simon, Laurent; Leifer, Klaus

2016-01-29

The functionalization of graphene remains an important challenge for numerous applications expected by this fascinating material. To keep advantageous properties of graphene after modification or functionalization of its structure, local approaches are a promising road. A novel technique is reported here that allows precise site-selective fluorination of graphene. The basic idea of this approach consists in the local radicalization of graphene by focused ion beam (FIB) irradiation and simultaneous introduction of XeF2 gas. A systematic series of experiments were carried out to outline the relation between inserted defect creation and the fluorination process. Based on a subsequent X-ray photoelectron spectroscopy (XPS) analysis, a 6-fold increase of the fluorine concentration on graphene under simultaneous irradiation was observed when compared to fluorination under normal conditions. The fluorine atoms are predominately localized at the defects as indicated from scanning tunneling microscopy (STM). The experimental findings are confirmed by density functional theory which predicts a strong increase of the binding energy of fluorine atoms when bound to the defect sites. The developed technique allows for local fluorination of graphene without using resists and has potential to be a general enabler of site-selective functionalization of graphene using a wide range of gases.

Site-selective local fluorination of graphene induced by focused ion beam irradiation

NASA Astrophysics Data System (ADS)

Li, Hu; Daukiya, Lakshya; Haldar, Soumyajyoti; Lindblad, Andreas; Sanyal, Biplab; Eriksson, Olle; Aubel, Dominique; Hajjar-Garreau, Samar; Simon, Laurent; Leifer, Klaus

2016-01-01

The functionalization of graphene remains an important challenge for numerous applications expected by this fascinating material. To keep advantageous properties of graphene after modification or functionalization of its structure, local approaches are a promising road. A novel technique is reported here that allows precise site-selective fluorination of graphene. The basic idea of this approach consists in the local radicalization of graphene by focused ion beam (FIB) irradiation and simultaneous introduction of XeF2 gas. A systematic series of experiments were carried out to outline the relation between inserted defect creation and the fluorination process. Based on a subsequent X-ray photoelectron spectroscopy (XPS) analysis, a 6-fold increase of the fluorine concentration on graphene under simultaneous irradiation was observed when compared to fluorination under normal conditions. The fluorine atoms are predominately localized at the defects as indicated from scanning tunneling microscopy (STM). The experimental findings are confirmed by density functional theory which predicts a strong increase of the binding energy of fluorine atoms when bound to the defect sites. The developed technique allows for local fluorination of graphene without using resists and has potential to be a general enabler of site-selective functionalization of graphene using a wide range of gases.

Effect of soil contamination with fluorine on the yield and content of nitrogen forms in the biomass of crops.

PubMed

Szostek, Radosław; Ciećko, Zdzisław

2017-03-01

The research was based on a pot experiment, in which the response of eight species of crops to soil contamination with fluorine was investigated. In parallel, some inactivating substances were tested in terms of their potential use for the neutralization of the harmful influence of fluorine on plants. The response of crops to soil contamination with fluorine was assessed according to the volume of biomass produced by aerial organs and roots as well as their content of N-total, N-protein, and N-NO 3 - . The following crops were tested: maize, yellow lupine, winter oilseed rape, spring triticale, narrow-leaf lupine, black radish, phacelia, and lucerne. In most cases, soil pollution with fluorine stimulated the volume of biomass produced by the plants. The exceptions included grain and straw of spring triticale, maize roots, and aerial parts of lucerne, where the volume of harvested biomass was smaller in treatments with fluorine-polluted soil. Among the eight plant species, lucerne was most sensitive to the pollution despite smaller doses of fluorine in treatments with this plant. The other species were more tolerant to elevated concentrations of fluorine in soil. In most of the tested plants, the analyzed organs contained more total nitrogen, especially aerial organs and roots of black radish, grain and straw of spring triticale, and aerial biomass of lucerne. A decrease in the total nitrogen content due to soil contamination with fluorine was detected only in the aerial mass of yellow lupine. With respect to protein nitrogen, its increase in response to fluorine as a soil pollutant was found in grain of spring triticale and roots of black radish, whereas the aerial biomass of winter oilseed rape contained less of this nutrient. Among the analyzed neutralizing substances, lime most effectively alleviated the negative effect of soil pollution with fluorine. The second most effective substance was loam, while charcoal was the least effective in this respect. Our results showed the effect of soil contamination with fluorine on the yield and chemical composition of fluorine depended on the species and organ of a tested plant, on the rate of the xenobotic element and on the substance added to soil in order to neutralize fluorine.

Molecular Packing of Functionalized Fluorinated Lipids in Langmuir Monolayers

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

Landsberg, Michael J.; Ruggles, Jeremy L.; Hussein, Waleed M.

2012-01-20

Fluorinated amphipaths are a fascinating class of compounds, which, despite significant challenges associated with their syntheses, have found use across a number of areas of biotechnology. Applications range from the in vitro stabilization of membrane proteins to the development of enhanced stability intravenous drug and gene delivery systems. More recently, monolayer-forming fluorinated lipids have found use in the 2D crystallization of detergent-solubilized hydrophobic or partially hydrophobic proteins at the air-water interface. In this study, we investigate the surface properties of a novel suite of monolayer forming, partially fluorinated lipids. These modular lipid structures contain a densely fluorinated insertion in themore » hydrocarbon tail and a synthetically modifiable headgroup. Analyses of surface-pressure area isotherms and X-ray reflectometry profiles reveal that the lipids spread into fluid monolayers and are more compressible than their non-fluorinated counterparts. Furthermore, the data support a model whereby the partially fluorinated chains of the lipid tails form a film which is fundamentally incompatible with detergents and other destabilizing amphipaths.« less

Two‐Dimensional Fluorinated Graphene: Synthesis, Structures, Properties and Applications

PubMed Central

Long, Peng; Feng, Yiyu; Li, Yu

2016-01-01

Fluorinated graphene, an up‐rising member of the graphene family, combines a two‐dimensional layer‐structure, a wide bandgap, and high stability and attracts significant attention because of its unique nanostructure and carbon–fluorine bonds. Here, we give an extensive review of recent progress on synthetic methods and C–F bonding; additionally, we present the optical, electrical and electronic properties of fluorinated graphene and its electrochemical/biological applications. Fluorinated graphene exhibits various types of C–F bonds (covalent, semi‐ionic, and ionic bonds), tunable F/C ratios, and different configurations controlled by synthetic methods including direct fluorination and exfoliation methods. The relationship between the types/amounts of C–F bonds and specific properties, such as opened bandgap, high thermal and chemical stability, dispersibility, semiconducting/insulating nature, magnetic, self‐lubricating and mechanical properties and thermal conductivity, is discussed comprehensively. By optimizing the C–F bonding character and F/C ratios, fluorinated graphene can be utilized for energy conversion and storage devices, bioapplications, electrochemical sensors and amphiphobicity. Based on current progress, we propose potential problems of fluorinated graphene as well as the future challenge on the synthetic methods and C‐F bonding character. This review will provide guidance for controlling C–F bonds, developing fluorine‐related effects and promoting the application of fluorinated graphene. PMID:27981018

Quasi-particle energies and optical excitations of hydrogenated and fluorinated germanene.

PubMed

Shu, Huabing; Li, Yunhai; Wang, Shudong; Wang, Jinlan

2015-02-14

Using density functional theory, the G0W0 method and Bethe-Salpeter equation calculations, we systematically explore the structural, electronic and optical properties of hydrogenated and fluorinated germanene. The hydrogenated/fluorinated germanene tends to form chair and zigzag-line configurations and its electronic and optical properties show close geometry dependence. The chair hydrogenated/fluorinated and zigzag-line fluorinated germanene are direct band-gap semiconductors, while the zigzag-line hydrogenated germanene owns an indirect band-gap. Moreover, the quasi-particle corrections are significant and strong excitonic effects with large exciton binding energies are observed. Moreover, the zigzag-line hydrogenated/fluorinated germanene shows highly anisotropic optical responses, which may be used as a good optical linear polarizer.

Electrochemical fluorination of La(2)CuO(4): a mild "chimie douce" route to superconducting oxyfluoride materials.

PubMed

Delville, M H; Barbut, D; Wattiaux, A; Bassat, J M; Ménétrier, M; Labrugère, C; Grenier, J C; Etourneau, J

2009-08-17

The fluorination of La(2)CuO(4) was achieved for the first time under normal conditions of pressure and temperature (1 MPa and 298 K) via electrochemical insertion in organic fluorinated electrolytes and led to lanthanum oxyfluorides of general formula La(2)CuO(4)F(x). Analyses showed that, underneath a very thin layer of LaF(3) (a few atomic layers), fluorine is effectively inserted in the material's structure. The fluorination strongly modifies the lanthanum environment, whereas very little modification is observed on copper, suggesting an insertion in the La(2)O(2) blocks of the structure. In all cases, fluorine insertion breaks the translation symmetry and introduces a long-distance disorder, as shown by electron spin resonance. These results highlight the efficiency of electrochemistry as a new "chimie douce" type fluorination technique for solid-state materials. Performed at room temperature, it additionally does not require any specific experimental care. The choice of the electrolytic medium is crucial with regard to the fluorine insertion rate as well as the material deterioration. Successful application of this technique to the well-known La(2)CuO(4) material provides a basis for further syntheses from other oxides.

Fluorinated precursors of superconducting ceramics, and methods of making the same

DOEpatents

Wiesmann, Harold; Solovyov, Vyacheslav

2014-02-18

This invention provides a method of making a fluorinated precursor of a superconducting ceramic. The method comprises providing a solution comprising a rare earth salt, an alkaline earth metal salt and a copper salt; spraying the solution onto a substrate to provide a film-covered substrate; and heating the film-covered substrate in an atmosphere containing fluorinated gas to provide the fluorinated precursor.

Fluorinated precursors of superconducting ceramics, and methods of making the same

DOEpatents

Wiesmann, Harold [Stony Brook, NY; Solovyov, Vyacheslav [Rocky Point, NY

2008-04-22

This invention provides a method of making a fluorinated precursor of a superconducting ceramic. The method comprises providing a solution comprising a rare earth salt, an alkaline earth metal salt and a copper salt; spraying the solution onto a substrate to provide a film-covered substrate; and heating the film-covered substrate in an atmosphere containing fluorinated gas to provide the fluorinated precursor.

Fluorinated precursors of superconducting ceramics, and methods of making the same

DOEpatents

Wiesmann, Harold [Stony Brook, NY; Solovyov, Vyacheslav [Rocky Point, NY

2012-07-10

This invention provides a method of making a fluorinated precursor of a superconducting ceramic. The method comprises providing a solution comprising a rare earth salt, an alkaline earth metal salt and a copper salt; spraying the solution onto a substrate to provide a film-covered substrate; and heating the film-covered substrate in an atmosphere containing fluorinated gas to provide the fluorinated precursor.

The rare fluorinated natural products and biotechnological prospects for fluorine enzymology.

PubMed

Chan, K K Jason; O'Hagan, David

2012-01-01

Nature has hardly evolved a biochemistry of fluorine although there is a low-level occurrence of fluoroacetate found in selected tropical and subtropical plants. This compound, which is generally produced in low concentrations, has been identified in the plants due to its high toxicity, although to date the biosynthesis of fluoroacetate in plants remains unknown. After that, fluorinated entities in nature are extremely rare, and despite increasingly sophisticated screening and analytical methods applied to natural product extraction, it has been 25 years since the last bona fide fluorinated natural product was identified from an organism. This was the reported isolation of the antibiotic 4-fluorothreonine and the toxin fluoroacetate in 1986 from Streptomyces cattleya. This bacterium has proven amenable to biochemical investigation, the fluorination enzyme (fluorinase) has been isolated and characterized, and the biosynthetic pathway to these bacterial metabolites has been elucidated. Also the fluorinase gene has been cloned into a host bacterium (Salinispora tropica), and this has enabled the de novo production of a bioactive fluorinated metabolite from fluoride ion, by genetic engineering. Biotechnological manipulation of the fluorinase offers the prospects for the assembly of novel fluorinated metabolites by fermentation technology. This is particularly attractive, given the backdrop that about 15-20% of pharmaceuticals licensed each year (new chemical entities) contain a fluorine atom. Copyright © 2012 Elsevier Inc. All rights reserved.

Experience with fluorine and its safe use as a propellant

NASA Technical Reports Server (NTRS)

Bond, D. L.; Guenther, M. E.; Stimpson, L. D.; Toth, L. R.; Young, D. L.

1979-01-01

The industrial and the propulsion experience with fluorine and its derivatives is surveyed. The hazardous qualities of fluorine and safe handling procedures for the substance are emphasized. Procedures which fulfill the safety requirements during ground operations for handling fluorinated propulsion systems are discussed. Procedures to be implemented for use onboard the Space Transportation System are included.

40 CFR Table I-2 to Subpart I - Examples of Fluorinated GHGs and Fluorinated Heat Transfer Fluids Used by the Electronics Industry

Code of Federal Regulations, 2012 CFR

2012-07-01

... Fluorinated Heat Transfer Fluids Used by the Electronics Industry I Table I-2 to Subpart I Protection of... REPORTING Electronics Manufacturing Pt. 98, Subpt. I, Table I-2 Table I-2 to Subpart I—Examples of Fluorinated GHGs and Fluorinated Heat Transfer Fluids Used by the Electronics Industry Product type...

Removal of fluorine from contaminated soil by electrokinetic treatment driven by solar energy.

PubMed

Zhou, Ming; Zhu, Shufa; Liu, Yana; Wang, Xuejian

2013-08-01

Instead of direct current power supply, a series of electrokinetic remediation experiments driven by solar energy on fluorine-contaminated soil were conducted in a self-made electrolyzer, in order to reduce energy expenditure of electrokinetic remediation. After the 12-day electrokinetic remediation driven by solar energy, the removal efficiency of fluorine was 22.3%, and electrokinetic treatment had an impact on changes in partitioning of fluorine in soil. It proved that the combination of electrokinetics and solar energy was feasible and effective to some extent for the remediation of fluorine-contaminated soil. Meanwhile, the experimental results also indicated that the electromigration was a more dominant transport mechanism for the removal of fluorine from contaminated soil than electroosmosis, and the weather condition was the important factor in affecting the removal efficiency.

Method for producing fluorinated diamond-like carbon films

DOEpatents

Hakovirta, Marko J.; Nastasi, Michael A.; Lee, Deok-Hyung; He, Xiao-Ming

2003-06-03

Fluorinated, diamond-like carbon (F-DLC) films are produced by a pulsed, glow-discharge plasma immersion ion processing procedure. The pulsed, glow-discharge plasma was generated at a pressure of 1 Pa from an acetylene (C.sub.2 H.sub.2) and hexafluoroethane (C.sub.2 F.sub.6) gas mixture, and the fluorinated, diamond-like carbon films were deposited on silicon <100>substrates. The film hardness and wear resistance were found to be strongly dependent on the fluorine content incorporated into the coatings. The hardness of the F-DLC films was found to decrease considerably when the fluorine content in the coatings reached about 20%. The contact angle of water on the F-DLC coatings was found to increase with increasing film fluorine content and to saturate at a level characteristic of polytetrafluoroethylene.

Generation of highly N-type, defect passivated transition metal oxides using plasma fluorine insertion

DOEpatents

Baker, L. Robert; Seo, Hyungtak; Hervier, Antoine; Somorjai, Gabor A.

2016-04-12

A new composition of matter is disclosed wherein oxygen vacancies in a semiconducting transition metal oxide such as titanium dioxide are filled with a halogen such as Fluorine, whereby the conductivity of the composition is greatly enhanced, while at the same time the chemical stability of the composition is greatly improved. Stoichiometric titanium dioxide having less than 3 % oxygen vacancies is subject to fluorine insertion such that oxygen vacancies are filled, limited amounts of fluorine replace additional oxygen atoms and fluorine interstitially inserts into the body of the TiO.sub.2 composition.

Fluorine Scan of Inhibitors of the Cysteine Protease Human Cathepsin L: Dipolar and Quadrupolar Effects in the π-Stacking of Fluorinated Phenyl Rings on Peptide Amide Bonds.

PubMed

Giroud, Maude; Harder, Michael; Kuhn, Bernd; Haap, Wolfgang; Trapp, Nils; Schweizer, W Bernd; Schirmeister, Tanja; Diederich, François

2016-05-19

The π-stacking of fluorinated benzene rings on protein backbone amide groups was investigated, using a dual approach comprising enzyme-ligand binding studies complemented by high-level quantum chemical calculations. In the experimental study, the phenyl substituent of triazine nitrile inhibitors of human cathepsin L (hCatL), which stacks onto the peptide amide bond Gly67-Gly68 at the entrance of the S3 pocket, was systematically fluorinated, and differences in inhibitory potency were measured in a fluorimetric assay. Binding affinity is influenced by lipophilicity (clog P), the dipole and quadrupole moments of the fluorinated rings, but also by additional interactions of the introduced fluorine atoms with the local environment of the pocket. Generally, the higher the degree of fluorination, the better the binding affinities. Gas phase calculations strongly support the contributions of the molecular quadrupole moments of the fluorinated phenyl rings to the π-stacking interaction with the peptide bond. These findings provide useful guidelines for enhancing π-stacking on protein amide fragments. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorine distribution in aquatic environment and its health effect in the Western Region of the Songnen Plain, Northeast China.

PubMed

Zhang, Bo; Hong, Mei; Zhang, Bai; Zhang, Xue-lin; Zhao, Yong-sheng

2007-10-01

Endemic fluorosis was investigated and studied in the west region of the Songnen plain, Northeast China in 2001-2002. The results showed that the fluorine distribution in aquatic environment was that the fluorine concentrations in the lake water and unconfined ground water were higher than that in the river water and confined ground water. The lake water (Alkali lake) is connected with unconfined ground water. In unconfined ground water, from the east and southeast areas to the west and the northwest areas of the plain, fluorine concentration fluctuated with high and low alternatively. The fluorine in the water comes from the weathering of rocks and minerals in the mountains and hills around the Songnen Plain. The main influence factors of the fluorine distribution in aquatic environment are discussed. Unconfined ground water containing high fluorine is used as drinking water. In this region, the fluorine concentration in drinking water is evidently correlated to the morbidity of dental and skeletal fluorosis. High fluorine concentration in drinking water has endangered human health.

Pulsed glow discharge enables direct mass spectrometric measurement of fluorine in crystal materials - Fluorine quantification and depth profiling in fluorine doped potassium titanyl phosphate

NASA Astrophysics Data System (ADS)

Bodnar, Victoria; Ganeev, Alexander; Gubal, Anna; Solovyev, Nikolay; Glumov, Oleg; Yakobson, Viktor; Murin, Igor

2018-07-01

A pulsed direct current glow discharge time-of-flight mass spectrometry (GD TOF MS) method for the quantification of fluorine in insoluble crystal materials with fluorine doped potassium titanyl phosphate (KTP) KTiOPO4:KF as an example has been proposed. The following parameters were optimized: repelling pulse delay, discharge duration, discharge voltage, and pressure in the discharge cell. Effective ionization of fluorine in the space between sampler and skimmer under short repelling pulse delay, related to the high-energy electron impact at the discharge front, has been demonstrated. A combination of instrumental and mathematical correction approaches was used to cope for the interferences of 38Ar2+ and 1H316O + on 19F+. To maintain surface conductivity in the dielectric KTP crystals and insure its effective sputtering in combined hollow cathode cell, silver suspension applied by the dip-coating method was employed. Fluorine quantification was performed using relative sensitivity factors. The analysis of a reference material and scanning electron microscope-energy dispersive X-ray spectroscopy was used for validation. Fluorine limit of detection by pulsed direct current GD TOF MS was 0.01 mass%. Real sample analysis showed that fluorine seems to be inhomogeneously distributed in the crystals. That is why depth profiling of F, K, O, and P was performed to evaluate the crystals' non-stoichiometry. The approaches designed allow for fluorine quantification in insoluble dielectric materials with minimal sample preparation and destructivity as well as performing depth profiling to assess crystal non-stoichiometry.

Selection of Environmentally Friendly Solvents for the Extravehicular Mobility Unit Secondary Oxygen Pack Cold Trap Testing

NASA Technical Reports Server (NTRS)

Steele, John; Chullen, Cinda; Morenz, Jesse; Stephenson, Curtis

2010-01-01

Freon-113(TradeMark) has been used as a chemistry lab sampling solvent at NASA/JSC for EMU (extravehicular Mobility Unit) SOP (Secondary Oxygen Pack) oxygen testing Cold Traps utilized at the USA (United Space Alliance) Houston facility. Similar testing has occurred at the HSWL (Hamilton Sundstrand Windsor Locks) facility. A NASA Executive Order bans the procurement of all ODS (ozone depleting substances), including Freon-113 by the end of 2009. In order to comply with NASA direction, HSWL began evaluating viable solvents to replace Freon-113 . The study and testing effort to find Freon-113 replacements used for Cold Trap sampling is the subject of this paper. Test results have shown HFE-7100 (a 3M fluorinated ether) to be an adequate replacement for Freon-113 as a solvent to remove and measure the non-volatile residue collected in a Cold Trap during oxygen testing. Furthermore, S-316 (a Horiba Instruments Inc. high molecular weight, non-ODS chlorofluorocarbon) was found to be an adequate replacement for Freon-113 as a solvent to reconstitute non-volatile residue removed from a Cold Trap during oxygen testing for subsequent HC (hydrocarbon) analysis via FTIR (Fourier Transform Infrared Spectroscopy).

Electrolytes for Low-Temperature Operation of Li-CFx Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Whitacre, Jay F.; Bugga, Ratnakumar V.; Prakash, G. K. Surya; Bhalla, Pooja; Smith, Kiah

2009-01-01

A report describes a study of electrolyte compositions selected as candidates for improving the low-temperature performances of primary electrochemical cells that contain lithium anodes and fluorinated carbonaceous (CFx) cathodes. This study complements the developments reported in Additive for Low-Temperature Operation of Li-(CF)n Cells (NPO- 43579) and Li/CFx Cells Optimized for Low-Temperature Operation (NPO- 43585), which appear elsewhere in this issue of NASA Tech Briefs. Similar to lithium-based electrolytes described in several previous NASA Tech Briefs articles, each of these electrolytes consisted of a lithium salt dissolved in a nonaqueous solvent mixture. Each such mixture consisted of two or more of the following ingredients: propylene carbonate (PC); 1,2-dimethoxyethane (DME); trifluoropropylene carbonate; bis(2,2,2-trifluoroethyl) ether; diethyl carbonate; dimethyl carbonate; and ethyl methyl carbonate. The report describes the physical and chemical principles underlying the selection of the compositions (which were not optimized) and presents results of preliminary tests made to determine effects of the compositions upon the low-temperature capabilities of Li-CFx cells, relative to a baseline composition of LiBF4 at a concentration of 1.0 M in a solvent comprising equal volume parts of PC and DME.

In vivo quantification of bone-fluorine by delayed neutron activation analysis: a pilot study of hand-bone-fluorine levels in a Canadian population.

PubMed

Chamberlain, Mike; Gräfe, James L; Aslam; Byun, Soo-Hyun; Chettle, David R; Egden, Lesley M; Webber, Colin E; McNeill, Fiona E

2012-03-01

Humans can be exposed to fluorine (F) through their diet, occupation, environment and oral dental care products. Fluorine, at proper dosages, is believed to have positive effects by reducing the incidence of dental caries, but fluorine toxicity can occur when people are exposed to excessive quantities of fluorine. In this paper we present the results of a small pilot in vivo study on 33 participants living in Southwestern Ontario, Canada. The mean age of participants was 45 ± 18 years with a range of 20-87 years. The observed calcium normalized hand-bone-fluorine concentrations in this small pilot study ranged from 1.1 to 8.8 mg F/g Ca. Every person measured in this study had levels of fluorine in bone above the detection limit of the system. The average fluorine concentration in bone was found to be 3.5 ± 0.4 mg F/g Ca. No difference was observed in average concentration for men and women. In addition, a significant correlation (r(2) = 0.55, p < 0.001) was observed between hand-bone-fluorine content and age. The amount of fluorine was found to increase at a rate of 0.084 ± 0.014 mg F/g Ca per year. There was no significant difference observed in this small group of subjects between the accumulation rates in men and women. To the best of our knowledge, this is the first time data from in vivo measurement of fluorine content in humans by neutron activation analysis have been presented. The data determined by this technique were found to be consistent with results from ex vivo studies from other countries. We suggest that the data demonstrate that this low risk non-invasive diagnostic technique will permit the routine assessment of bone-fluorine content with potential application in the study of clinical bone-related diseases. This small study demonstrated that people in Southern Ontario are exposed to fluoride in measureable quantities, and that fluoride can be seen to accumulate in bone with age. However, all volunteers were found to have levels below those expected with clinical fluorosis, and only one older subject was found to have levels comparable with preclinical exposure.

Enantioselective Cobalt-Catalyzed Sequential Nazarov Cyclization/Electrophilic Fluorination: Access to Chiral α-Fluorocyclopentenones.

PubMed

Zhang, Heyi; Cheng, Biao; Lu, Zhan

2018-06-20

A newly designed thiazoline iminopyridine ligand for enantioselective cobalt-catalyzed sequential Nazarov cyclization/electrophilic fluorination was developed. Various chiral α-fluorocyclopentenones were prepared with good yields and diastereo- and enantioselectivities. Further derivatizations could be easily carried out to provide chiral cyclopentenols with three contiguous stereocenters. Furthermore, a direct deesterification of fluorinated products could afford chiral α-single fluorine-substituted cyclopentenones.

40 CFR Table I-2 to Subpart I of... - Examples of Fluorinated GHGs and Fluorinated Heat Transfer Fluids Used by the Electronics Industry

Code of Federal Regulations, 2013 CFR

2013-07-01

... Fluorinated Heat Transfer Fluids Used by the Electronics Industry I Table I-2 to Subpart I of Part 98... GREENHOUSE GAS REPORTING Electronics Manufacturing Pt. 98, Subpt. I, Table I-2 Table I-2 to Subpart I of Part 98—Examples of Fluorinated GHGs and Fluorinated Heat Transfer Fluids Used by the Electronics Industry...

The effect of fluorine substitutions on the refractive index properties for π-conjugated calamitic nematic materials

NASA Astrophysics Data System (ADS)

Arakawa, Yuki; Tsuji, Hideto

2017-06-01

In order to reveal the effect of fluorine substitutions on the refractive index properties for calamitic nematic materials, we carried out a comparative study with respect to non-fluorinated and two types of laterally fluorinated 1,4-bis[4-(hexyloxy)phenyl]ethynylbenzene molecules. Phase transition behaviours were investigated by differential scanning calorimetry and polarised optical microscopy. Additionally, extraordinary and ordinary refractive index and birefringence were evaluated from each single component system. All the analogues exhibited high birefringence values beyond 0.3 at 550 nm, of which an analogue with a fluorine substitution at the central benzene ring showed the highest Δn-value of 0.43. With respect to an analogue with the highest level of fluorination, Δn as well as ne and no values were declined due to decreased order parameter and diluted molecular density. Not only the mesomorphic behaviours but also optical properties strongly relied on the manner of fluorine substitution including the number and position.

Aldolase-catalysed stereoselective synthesis of fluorinated small molecules.

PubMed

Windle, Claire L; Berry, Alan; Nelson, Adam

2017-04-01

The introduction of fluorine has been widely exploited to tune the biological functions of small molecules. Indeed, around 20% of leading drugs contain at least one fluorine atom. Yet, despite profound effects of fluorination on conformation, there is only a limited toolkit of reactions that enable stereoselective synthesis of fluorinated compounds. Aldolases are useful catalysts for the stereoselective synthesis of bioactive small molecules; however, despite fluoropyruvate being a viable nucleophile for some aldolases, the potential of aldolases to control the formation of fluorine-bearing stereocentres has largely been untapped. Very recently, it has been shown that aldolase-catalysed stereoselective carboncarbon bond formation with fluoropyruvate as nucleophile enable the synthesis of many α-fluoro β-hydroxy carboxyl derivatives. Furthermore, an understanding of the structural basis for the stereocontrol observed in these reactions is beginning to emerge. Here, we review the application of aldolase catalysis in the stereocontrolled synthesis of chiral fluorinated small molecules, and highlight likely areas for future developments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemoselective Aliphatic C–H Bond Oxidation Enabled by Polarity Reversal

PubMed Central

2017-01-01

Methods for selective oxidation of aliphatic C–H bonds are called on to revolutionize organic synthesis by providing novel and more efficient paths. Realization of this goal requires the discovery of mechanisms that can alter in a predictable manner the innate reactivity of these bonds. Ideally, these mechanisms need to make oxidation of aliphatic C–H bonds, which are recognized as relatively inert, compatible with the presence of electron rich functional groups that are highly susceptible to oxidation. Furthermore, predictable modification of the relative reactivity of different C–H bonds within a molecule would enable rapid diversification of the resulting oxidation products. Herein we show that by engaging in hydrogen bonding, fluorinated alcohols exert a polarity reversal on electron rich functional groups, directing iron and manganese catalyzed oxidation toward a priori stronger and unactivated C–H bonds. As a result, selective hydroxylation of methylenic sites in hydrocarbons and remote aliphatic C–H oxidation of otherwise sensitive alcohol, ether, amide, and amine substrates is achieved employing aqueous hydrogen peroxide as oxidant. Oxidations occur in a predictable manner, with outstanding levels of product chemoselectivity, preserving the first-formed hydroxylation product, thus representing an extremely valuable tool for synthetic planning and development. PMID:29296677

Chemoselective Aliphatic C-H Bond Oxidation Enabled by Polarity Reversal.

PubMed

Dantignana, Valeria; Milan, Michela; Cussó, Olaf; Company, Anna; Bietti, Massimo; Costas, Miquel

2017-12-27

Methods for selective oxidation of aliphatic C-H bonds are called on to revolutionize organic synthesis by providing novel and more efficient paths. Realization of this goal requires the discovery of mechanisms that can alter in a predictable manner the innate reactivity of these bonds. Ideally, these mechanisms need to make oxidation of aliphatic C-H bonds, which are recognized as relatively inert, compatible with the presence of electron rich functional groups that are highly susceptible to oxidation. Furthermore, predictable modification of the relative reactivity of different C-H bonds within a molecule would enable rapid diversification of the resulting oxidation products. Herein we show that by engaging in hydrogen bonding, fluorinated alcohols exert a polarity reversal on electron rich functional groups, directing iron and manganese catalyzed oxidation toward a priori stronger and unactivated C-H bonds. As a result, selective hydroxylation of methylenic sites in hydrocarbons and remote aliphatic C-H oxidation of otherwise sensitive alcohol, ether, amide, and amine substrates is achieved employing aqueous hydrogen peroxide as oxidant. Oxidations occur in a predictable manner, with outstanding levels of product chemoselectivity, preserving the first-formed hydroxylation product, thus representing an extremely valuable tool for synthetic planning and development.

Clinical perspectives of hybrid proton-fluorine magnetic resonance imaging and spectroscopy.

PubMed

Wolters, Martijn; Mohades, Seyede G; Hackeng, Tilman M; Post, Mark J; Kooi, Marianne E; Backes, Walter H

2013-05-01

The number of applications of fluorine 19 (19F) magnetic resonance (MR) imaging and spectroscopy in biomedical and clinical research is steadily growing. The 100% natural abundance of fluorine and its relatively high sensitivity for MR (83% to that of protons) make it an interesting nucleus for a wide range of MR applications. Fluorinated contrast media have a number of advantages over the conventionally used gadolinium-based or iron-based contrast agents. The absence of an endogenous fluorine background intensity in the human body facilitates reliable quantification of fluorinated contrast medium or drugs. Anatomy can be visualized separately with proton MR imaging, creating the application of hybrid hydrogen 1 (1H)/19F MR imaging. The availability of 2 channels (ie, the 1H and 19F channels) enables dual-targeted molecular imaging. Recently, novel developments have emerged on fluorine-based contrast media in preclinical studies and imaging techniques. The developments in fluorine MR seem promising for clinical applications, with contributions in therapy monitoring, assessment of lung function, angiography, and molecular imaging. This review outlines the translation from recent advances in preclinical MR imaging and spectroscopy to future perspectives of clinical hybrid 1H/19/F MR imaging applications.

Site-selective local fluorination of graphene induced by focused ion beam irradiation

PubMed Central

Li, Hu; Daukiya, Lakshya; Haldar, Soumyajyoti; Lindblad, Andreas; Sanyal, Biplab; Eriksson, Olle; Aubel, Dominique; Hajjar-Garreau, Samar; Simon, Laurent; Leifer, Klaus

2016-01-01

The functionalization of graphene remains an important challenge for numerous applications expected by this fascinating material. To keep advantageous properties of graphene after modification or functionalization of its structure, local approaches are a promising road. A novel technique is reported here that allows precise site-selective fluorination of graphene. The basic idea of this approach consists in the local radicalization of graphene by focused ion beam (FIB) irradiation and simultaneous introduction of XeF2 gas. A systematic series of experiments were carried out to outline the relation between inserted defect creation and the fluorination process. Based on a subsequent X-ray photoelectron spectroscopy (XPS) analysis, a 6-fold increase of the fluorine concentration on graphene under simultaneous irradiation was observed when compared to fluorination under normal conditions. The fluorine atoms are predominately localized at the defects as indicated from scanning tunneling microscopy (STM). The experimental findings are confirmed by density functional theory which predicts a strong increase of the binding energy of fluorine atoms when bound to the defect sites. The developed technique allows for local fluorination of graphene without using resists and has potential to be a general enabler of site-selective functionalization of graphene using a wide range of gases. PMID:26822900

Plasma membranes modified by plasma treatment or deposition as solid electrolytes for potential application in solid alkaline fuel cells.

PubMed

Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

2012-07-30

In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane.

Plasma Membranes Modified by Plasma Treatment or Deposition as Solid Electrolytes for Potential Application in Solid Alkaline Fuel Cells

PubMed Central

Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

2012-01-01

In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane. PMID:24958295

40 CFR 98.90 - Definition of the source category.

Code of Federal Regulations, 2012 CFR

2012-07-01

... uses plasma-generated fluorine atoms and other reactive fluorine-containing fragments, that chemically... thin films are cleaned periodically using plasma-generated fluorine atoms and other reactive fluorine-containing fragments. (3) Any electronics production process in which wafers are cleaned using plasma...

40 CFR 98.90 - Definition of the source category.

Code of Federal Regulations, 2011 CFR

2011-07-01

... uses plasma-generated fluorine atoms and other reactive fluorine-containing fragments, that chemically... thin films are cleaned periodically using plasma-generated fluorine atoms and other reactive fluorine-containing fragments. (3) Any electronics production process in which wafers are cleaned using plasma...

40 CFR 98.90 - Definition of the source category.

Code of Federal Regulations, 2013 CFR

2013-07-01

... uses plasma-generated fluorine atoms and other reactive fluorine-containing fragments, that chemically... thin films are cleaned periodically using plasma-generated fluorine atoms and other reactive fluorine-containing fragments. (3) Any electronics production process in which wafers are cleaned using plasma...

40 CFR 98.90 - Definition of the source category.

Code of Federal Regulations, 2014 CFR

2014-07-01

... uses plasma-generated fluorine atoms and other reactive fluorine-containing fragments, that chemically... thin films are cleaned periodically using plasma-generated fluorine atoms and other reactive fluorine-containing fragments. (3) Any electronics production process in which wafers are cleaned using plasma...

Electronic Structures, Bonding Configurations, and Band-Gap-Opening Properties of Graphene Binding with Low-Concentration Fluorine

DOE PAGES

Duan, Yuhua; Stinespring, Charter D.; Chorpening, Benjamin

2015-06-18

To better understand the effects of low-level fluorine in graphene-based sensors, first-principles density functional theory (DFT) with van der Waals dispersion interactions has been employed to investigate the structure and impact of fluorine defects on the electrical properties of single-layer graphene films. The results show that both graphite-2H and graphene have zero band gaps. When fluorine bonds to a carbon atom, the carbon atom is pulled slightly above the graphene plane, creating what is referred to as a CF defect. The lowest-binding energy state is found to correspond to two CF defects on nearest neighbor sites, with one fluorine abovemore » the carbon plane and the other below the plane. Overall this has the effect of buckling the graphene. The results further show that the addition of fluorine to graphene leads to the formation of an energy band (BF) near the Fermi level, contributed mainly from the 2p orbitals of fluorine with a small contribution from the porbitals of the carbon. Among the 11 binding configurations studied, our results show that only in two cases does the BF serve as a conduction band and open a band gap of 0.37 eV and 0.24 eV respectively. The binding energy decreases with decreasing fluorine concentration due to the interaction between neighboring fluorine atoms. The obtained results are useful for sensor development and nanoelectronics.« less

Comprehensive analysis of the green-to-blue photoconversion of full-length Cyanobacteriochrome Tlr0924.

PubMed

Hardman, Samantha J O; Hauck, Anna F E; Clark, Ian P; Heyes, Derren J; Scrutton, Nigel S

2014-11-04

Cyanobacteriochromes are members of the phytochrome superfamily of photoreceptors and are of central importance in biological light-activated signaling mechanisms. These photoreceptors are known to reversibly convert between two states in a photoinitiated process that involves a basic E/Z isomerization of the bilin chromophore and, in certain cases, the breakage of a thioether linkage to a conserved cysteine residue in the bulk protein structure. The exact details and timescales of the reactions involved in these photoconversions have not been conclusively shown. The cyanobacteriochrome Tlr0924 contains phycocyanobilin and phycoviolobilin chromophores, both of which photoconvert between two species: blue-absorbing and green-absorbing, and blue-absorbing and red-absorbing, respectively. Here, we followed the complete green-to-blue photoconversion process of the phycoviolobilin chromophore in the full-length form of Tlr0924 over timescales ranging from femtoseconds to seconds. Using a combination of time-resolved visible and mid-infrared transient absorption spectroscopy and cryotrapping techniques, we showed that after photoisomerization, which occurs with a lifetime of 3.6 ps, the phycoviolobilin twists or distorts slightly with a lifetime of 5.3 ?s. The final step, the formation of the thioether linkage with the protein, occurs with a lifetime of 23.6 ms.

Fluorine (19F) MRS and MRI in biomedicine

PubMed Central

Ruiz-Cabello, Jesús; Barnett, Brad P.; Bottomley, Paul A.; Bulte, Jeff W.M.

2011-01-01

Shortly after the introduction of 1H MRI, fluorinated molecules were tested as MR-detectable tracers or contrast agents. Many fluorinated compounds, which are nontoxic and chemically inert, are now being used in a broad range of biomedical applications, including anesthetics, chemotherapeutic agents, and molecules with high oxygen solubility for respiration and blood substitution. These compounds can be monitored by fluorine (19F) MRI and/or MRS, providing a noninvasive means to interrogate associated functions in biological systems. As a result of the lack of endogenous fluorine in living organisms, 19F MRI of ‘hotspots’ of targeted fluorinated contrast agents has recently opened up new research avenues in molecular and cellular imaging. This includes the specific targeting and imaging of cellular surface epitopes, as well as MRI cell tracking of endogenous macrophages, injected immune cells and stem cell transplants. PMID:20842758

Temporal and fluoride control of secondary metabolism regulates cellular organofluorine biosynthesis

PubMed Central

Walker, Mark C.; Wen, Miao; Weeks, Amy M.; Chang, Michelle C. Y.

2018-01-01

Elucidating mechanisms of natural organofluorine biosynthesis is essential for a basic understanding of fluorine biochemistry in living systems as well as for expanding biological methods for fluorine incorporation into probe or therapeutic molecules. To meet this goal we have combined massively parallel sequencing technologies, genetic knockout, and in vitro biochemical approaches to investigate the fluoride response of the only known genetic host of an organofluorine producing pathway, Streptomyces cattleya. Interestingly, we have discovered that the major mode of S. cattleya’s resistance to the fluorinated toxin it produces, fluoroacetate, may be due to temporal control of production rather than the ability of the host’s metabolic machinery to discriminate between fluorinated and non–fluorinated molecules. Indeed, neither the acetate kinase/phosphotransacetylase acetate assimilation pathway nor the TCA cycle enzymes (citrate synthase and aconitase) exclude fluorinated substrates based on in vitro biochemical characterization. Furthermore, disruption of the fluoroacetate resistance gene encoding a fluoroacetyl–CoA thioesterase (FlK) does not appear to lead to an observable growth defect related to organofluorine production. By showing that a switch in central metabolism can mediate and control molecular fluorine incorporation, our findings reveal a new potential strategy toward diversifying simple fluorinated building blocks into more complex products. PMID:22769062

Investigation of Fluorination on Donor Moiety of Donor-Acceptor 4,7-Dithienylbenzothiadiazole-Based Conjugated Polymers toward Enhanced Photovoltaic Efficiency.

PubMed

Li, Yonghai; Wang, Junyi; Liu, Yan; Qiu, Meng; Wen, Shuguang; Bao, Xichang; Wang, Ning; Sun, Mingliang; Yang, Renqiang

2016-10-05

It is known that fluorination on π-conjugated donor-acceptor (D-A) polymers can significantly affect the optoelectronic properties and fluorination on A moiety has been well established for design of efficient photovoltaic materials. For example, polymers based on 4,7-dithienyl-5,6-difluorobenzothiadiazole (DTffBT) have been intensively investigated and exhibited excellent performance, but the corresponding DTBT-based polymers without fluorine often display an unfavorable efficiency. With the purpose of improving photovoltaic efficiency of DTBT-based D-A polymers, we design three polymers PDTBT-TxfBT (x = 0, 1, 2) with fluorination on D moiety (TxfBT) and systematically investigate fluorination on the photophysical/electrochemical and photovoltaic properties. The results show that polymer solar cells (PSCs) based on PDTBT-TBT exhibit moderate power conversion efficiency (PCE) of 5.84%. However, the bis-fluorination on TffBT moiety (PDTBT-TffBT) can greatly enhance the molecular planarity and intermolecular interaction, improve the charge transport and heterojunction morphology, and further suppress the charge recombination losses. PSCs based on PDTBT-TffBT demonstrate obviously improved photovoltaic efficiency with the best PCE up to 7.53% without any processing additives, which ranks among the top DTBT-based PSCs. However, it should be noted that unsymmetrical fluorination on TfBT moiety (PDTBT-TfBT) impairs the regularity of polymer backbone and intermolecular interaction, increases the recombination losses, and seriously reduces the short-circuit current density and efficiency (5.44%). The results exhibit that fluorination on D moiety is a helpful strategy for design high-performance photovoltaic materials and the regularity of fluorination is crucial to improving efficiencies.

Room-Temperature Fluorine-Induced Decrease in the Stability of Bromine and Iodine Intercalated Carbon Fibers

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1995-01-01

Upon exposure to room-temperature fluorine, intercalated carbon fibers (containing either bromine alone or iodine and bromine together) become heavier and less stable. For Amoco P-100 graphitized carbon fibers, which were intercalated with 18 wt percent bromine, 1 hour of fluorine exposure resulted in a large weight increase but caused only a small decrease in thermal stability. An additional 89 hours of fluorine exposure time resulted in small additional increases in fiber weight, but significant further decreases in fiber thermal stability. Such phenomena of weight increase and stability decrease do not occur if the intercalated fibers are exposed to 250 C fluorine. These observations suggest that, at room temperature, fluorine is absorbed quickly by the intercalated fibers and is intercalated slowly into the fibers. Most of the original intercalates are replaced by fluorine in the process of fluorine intercalation. In an inert environment, the bromine intercalated fibers are much more thermally stable. After 800 C vacuum heating for 2 weeks, the brominated fibers lost about 45% of their bromine, and their resistivity increased from 64 mu(Omega)-cm to a range of 95-170 mu(Omega)-cm. This is still much lower than the value of 300 mu(Omega)-cm for pristine P-100. For practical purposes, to preserve their thermal stability, brominated fibers need to be protected from exposure to fluorine at room temperature or to any intercalate at a temperature where, upon direct contact with graphite, an intercalation compound can easily be formed.

Synthesis, physical and chemical properties, and potential applications of graphite fluoride fibers

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh; Long, Martin; Stahl, Mark

1987-01-01

Graphite fluoride fibers can be produced by fluorinating pristine or intercalated graphite fibers. The higher the degree of graphitization of the fibers, the higher the temperature needed to reach the same degree of fluorination. Pitched based fibers were fluorinated to flourine-to-carbon atom rations between 0 and 1. The graphite fluoride fibers with a fluorine-to-carbon atom ration near 1 have extensive visible structural damage. On the other hand, fluorination of fibers pretreated with bromine or fluorine and bromine result in fibers with a fluorine-to-carbon atom ratio nearly equal to 0.5 with no visible structural damage. The electrical resistivity of the fibers is dependent upon the fluorine to carbon atom ratio and ranged from .01 to 10 to the 11th ohm/cm. The thermal conductivity of these fibers ranged from 5 to 73 W/m-k, which is much larger than the thermal conductivity of glass, which is the regular filler in epoxy composites. If graphite fluoride fibers are used as a filler in epoxy or PTFE, the resulting composite may be a high thermal conductivity material with an electrical resistivity in either the insulator or semiconductor range. The electrically insulating product may provide heat transfer with lower temperature gradients than many current electrical insulators. Potential applications are presented.

Fluorine and Fluorinated Motifs in the Design and Application of Bioisosteres for Drug Design.

PubMed

Meanwell, Nicholas A

2018-02-05

The electronic properties and relatively small size of fluorine endow it with considerable versatility as a bioisostere and it has found application as a substitute for lone pairs of electrons, the hydrogen atom, and the methyl group while also acting as a functional mimetic of the carbonyl, carbinol, and nitrile moieties. In this context, fluorine substitution can influence the potency, conformation, metabolism, membrane permeability, and P-gp recognition of a molecule and temper inhibition of the hERG channel by basic amines. However, as a consequence of the unique properties of fluorine, it features prominently in the design of higher order structural metaphors that are more esoteric in their conception and which reflect a more sophisticated molecular construction that broadens biological mimesis. In this Perspective, applications of fluorine in the construction of bioisosteric elements designed to enhance the in vitro and in vivo properties of a molecule are summarized.

How Stress Treatments Influence the Performance of Biodegradable Poly(Butylene Succinate)-Based Copolymers with Thioether Linkages for Food Packaging Applications

PubMed Central

Genovese, Laura

2017-01-01

Biodegradable poly(butylene succinate) (PBS)-based random copolymers containing thioether linkages (P(BSxTDGSy)) of various compositions have been investigated and characterized from the gas barrier, thermal, and mechanical point of view, after food contact simulants or thermal and photoaging processes. Each stress treatment was performed on thin films and the results obtained have been compared to the same untreated film, used as a standard. Barrier properties with different gases (O2 and CO2) were evaluated, showing that the polymer chemical composition strongly influenced the permeability behavior. The relationships between the diffusion coefficients (D) and solubility (S) with polymer composition were also investigated. The results highlighted a correlation between polymer chemical structure and treatment. Gas transmission rate (GTR) mainly depending on the performed treatment, as GTR increased with the increase of TDGS co-unit amount. Thermal and mechanical tests allowed for the recording of variations in the degree of crystallinity and in the tensile properties. An increase in the crystallinity degree was recorded after contact with simulant liquids and aging treatments, together with a molecular weight decrease, a slight enhancement of the elastic modulus and a decrement of the elongation at break, proportional to the TDGS co-unit content. PMID:28867806

How Stress Treatments Influence the Performance of Biodegradable Poly(Butylene Succinate)-Based Copolymers with Thioether Linkages for Food Packaging Applications.

PubMed

Siracusa, Valentina; Genovese, Laura; Munari, Andrea; Lotti, Nadia

2017-08-30

Biodegradable poly(butylene succinate) (PBS)-based random copolymers containing thioether linkages (P(BSxTDGSy)) of various compositions have been investigated and characterized from the gas barrier, thermal, and mechanical point of view, after food contact simulants or thermal and photoaging processes. Each stress treatment was performed on thin films and the results obtained have been compared to the same untreated film, used as a standard. Barrier properties with different gases (O₂ and CO₂) were evaluated, showing that the polymer chemical composition strongly influenced the permeability behavior. The relationships between the diffusion coefficients ( D ) and solubility ( S ) with polymer composition were also investigated. The results highlighted a correlation between polymer chemical structure and treatment. Gas transmission rate ( GTR ) mainly depending on the performed treatment, as GTR increased with the increase of TDGS co-unit amount. Thermal and mechanical tests allowed for the recording of variations in the degree of crystallinity and in the tensile properties. An increase in the crystallinity degree was recorded after contact with simulant liquids and aging treatments, together with a molecular weight decrease, a slight enhancement of the elastic modulus and a decrement of the elongation at break, proportional to the TDGS co-unit content.

Biodegradation of fluorinated alkyl substances.

PubMed

Frömel, Tobias; Knepper, Thomas P

2010-01-01

The incorporation of fluorine into organic molecules entails both positive and adverse effects. Although fluorine imparts positive and unique properties such as water-and oil-repellency and chemical stability, adverse effects often pervade members of this compound class. A striking property of long perfluoroalkyl chains is their very pronounced environmental persistence. The present review is the first one designed to summarize recent accomplishments in the field of biodegradation of fluorine-containing surfactants, their metabolites, and structural analogs. The pronounced scientific and public interest in these chemicals has given impetus to undertake numerous degradation studies to assess the sources and origins of different fluorinated analog chemical known to exist in the environment. It was shown that biodegradation plays an important role in understanding how fluorinated substances reach the environment and, once they do, what their fate is. Today, PFOS and PFOA are ubiquitously detected as environmental contaminants. Their prominence as contaminants is mainly due to their extreme persistence, which is linked to their perfluoroalkyl chain length. It appears that desulfonation of a highly fluorinated surfactants can be achieved if an α-situated H atom, in relation to the sulfonate group, is present, at least under sulfur-limiting conditions. Molecules that are less heavily fluorinated can show very complex metabolic behavior, as is the case for fluorotelomer alcohols. These compounds are degraded via different but simultaneous pathways, which produce different stable metabolites, one of which is the respective perfluoroalkanoate (8:2-FTOH is transformed to PFOA). Preliminary screening tests indicate that fluorinated functional groups, such as the trifluoromethoxy group and the p-(trifluoromethyl)phenoxy group, may be useful implementations in novel, environmentally benign fluorosurfactants. More specifically, trifluoromethoxy groups constitute a substitute for those that have been used in the past; this functionality is degradable when it appears in structures that are normally subject to biodegradation. Other compounds tested did not meet this criterion. Interdisciplinary investigations on fluorinated surfactants are still very much needed and will certainly continue during the next many years. For instance, the role of fluorinated polymers in contributing small fluorinated molecules to the environmental burden still has not been fully understood.

Flow microreactor synthesis in organo-fluorine chemistry

PubMed Central

Nagaki, Aiichiro

2013-01-01

Summary Organo-fluorine compounds are the substances of considerable interest in various industrial fields due to their unique physical and chemical properties. Despite increased demand in wide fields of science, synthesis of fluoro-organic compounds is still often faced with problems such as the difficulties in handling of fluorinating reagents and in controlling of chemical reactions. Recently, flow microreactor synthesis has emerged as a new methodology for producing chemical substances with high efficiency. This review outlines the successful examples of synthesis and reactions of fluorine-containing molecules by the use of flow microreactor systems to overcome long-standing problems in fluorine chemistry. PMID:24367443

Flow microreactor synthesis in organo-fluorine chemistry.

PubMed

Amii, Hideki; Nagaki, Aiichiro; Yoshida, Jun-Ichi

2013-12-05

Organo-fluorine compounds are the substances of considerable interest in various industrial fields due to their unique physical and chemical properties. Despite increased demand in wide fields of science, synthesis of fluoro-organic compounds is still often faced with problems such as the difficulties in handling of fluorinating reagents and in controlling of chemical reactions. Recently, flow microreactor synthesis has emerged as a new methodology for producing chemical substances with high efficiency. This review outlines the successful examples of synthesis and reactions of fluorine-containing molecules by the use of flow microreactor systems to overcome long-standing problems in fluorine chemistry.

Formation of anodic layers on InAs (111)III. Study of the chemical composition

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

Valisheva, N. A., E-mail: valisheva@thermo.isp.nsc.ru; Tereshchenko, O. E.; Prosvirin, I. P.

2012-04-15

The chemical composition of {approx}20-nm-thick anodic layers grown on InAs (111)III in alkaline and acid electrolytes containing or not containing NH{sub 4}F is studied by X-ray photoelectron spectroscopy. It is shown that the composition of fluorinated layers is controlled by the relation between the concentrations of fluorine and hydroxide ions in the electrolyte and by diffusion processes in the growing layer. Fluorine accumulates at the (anodic layer)/InAs interface. Oxidation of InAs in an acid electrolyte with a low oxygen content and a high NH{sub 4}F content brings about the formation of anodic layers with a high content of fluorine andmore » elemental arsenic and the formation of an oxygen-free InF{sub x}/InAs interface. Fluorinated layers grown in an alkaline electrolyte with a high content of O{sup 2-} and/or OH{sup -} groups contain approximately three times less fluorine and consist of indium and arsenic oxyfluorides. No distinction between the compositions of the layers grown in both types of fluorine-free electrolytes is established.« less

Synthesis of polymeric fluorinated sol-gel precursor for fabrication of superhydrophobic coating

NASA Astrophysics Data System (ADS)

Li, Qianqian; Yan, Yuheng; Yu, Miao; Song, Botao; Shi, Suqing; Gong, Yongkuan

2016-03-01

A fluorinated polymeric sol-gel precursor (PFT) is synthesized by copolymerization of 2,3,4,5,5,5-hexafluoro-2,4-bis(trifluorinated methyl)pentyl methacrylate (FMA) and 3-methacryloxypropyltrimethoxysilane (TSMA) to replace the expensive long chain fluorinated alkylsilanes. The fluorinated silica sol is prepared by introducing PFT as co-precursor of tetraethyl orthosilicate (TEOS) in the sol-gel process with ammonium hydroxide as catalyst, which is then used to fabricate superhydrophobic coating on glass substrate through a simple dip-coating method. The effects of PFT concentrations on the chemical structure of the formed fluorinated silica, the surface chemical composition, surface morphology, wetting and self-cleaning properties of the resultant fluorinated silica coatings were studied by using X-ray powder diffraction (XRD), Fourier transform infrared spectrometer (FTIR), X-ray photoelectron spectrophotometer (XPS), scanning electron microscopy (SEM) and water contact angle measurements (WCA). The results show that the fluorinated silica sols are successfully obtained. The size and size distribution of the fluorinated silica particles are found greatly dependent on the concentration of PFT, which play a crucial role in the surface morphology of the corresponding fluorinated silica coatings. The suitable PFT concentration added in the sol-gel stage, i.e. for F-sol-1 and F-sol-2, is helpful to achieve both the low surface energy and multi-scaled microstructures, leading to the formation of the superhydrophobic coatings with bio-mimicking self-cleaning property similar to lotus leaves.

Molecular Recognition of Fluorine Impacts Substrate Selectivity in the Fluoroacetyl-CoA Thioesterase FlK

PubMed Central

2015-01-01

The fluoroacetate-producing bacterium Streptomyces cattleya has evolved a fluoroacetyl-CoA thioesterase (FlK) that exhibits a remarkably high level of discrimination for its cognate substrate compared to the cellularly abundant analogue acetyl-CoA, which differs only by the absence of the fluorine substitution. A major determinant of FlK specificity derives from its ability to take advantage of the unique properties of fluorine to enhance the reaction rate, allowing fluorine discrimination under physiological conditions where both substrates are likely to be present at saturating concentrations. Using a combination of pH–rate profiles, pre-steady-state kinetic experiments, and Taft analysis of wild-type and mutant FlKs with a set of substrate analogues, we explore the role of fluorine in controlling the enzyme acylation and deacylation steps. Further analysis of chiral (R)- and (S)-[2H1]fluoroacetyl-CoA substrates demonstrates that a kinetic isotope effect (1.7 ± 0.2) is observed for only the (R)-2H1 isomer, indicating that deacylation requires recognition of the prochiral fluoromethyl group to position the α-carbon for proton abstraction. Taken together, the selectivity for the fluoroacetyl-CoA substrate appears to rely not only on the enhanced polarization provided by the electronegative fluorine substitution but also on molecular recognition of fluorine in both formation and breakdown of the acyl-enzyme intermediate to control active site reactivity. These studies provide insights into the basis of fluorine selectivity in a naturally occurring enzyme–substrate pair, with implications for drug design and the development of fluorine-selective biocatalysts. PMID:24635371

Geminal difunctionalization of α-diazo arylmethylphosphonates: synthesis of fluorinated phosphonates.

PubMed

Zhou, Yujing; Zhang, Yan; Wang, Jianbo

2016-11-08

A general approach towards diverse fluorinated phosphonates via geminal difunctionalization reactions of α-diazo arylmethylphosphonates is described. The diazo functionality (RR'C[double bond, length as m-dash]N 2 ) is successfully converted to RR'CF 2 , RR'CHF, RR'CFBr or RR'CFNR'' 2 groups by employing different fluorination reagents. A variety of fluorinated organophosphorus compounds were readily accessed in good to excellent yields from a common type of precursor.

Fluorination effect of activated carbons on performance of asymmetric capacitive deionization

NASA Astrophysics Data System (ADS)

Jo, Hanjoo; Kim, Kyung Hoon; Jung, Min-Jung; Park, Jae Hyun; Lee, Young-Seak

2017-07-01

Activated carbons (ACs) were fluorinated and fabricated into electrodes to investigate the effect of fluorination on asymmetric capacitive deionization (CDI). Fluorine functional groups were introduced on the AC surfaces via fluorination. The specific capacitance of the fluorinated AC (Fsbnd AC) electrode increased drastically from 261 to 337 F/g compared with the untreated AC (Rsbnd AC) electrode at a scan rate of 5 mV/s, despite a decrease in the specific surface area and total pore volume after fluorination. The desalination behavior of asymmetric CDI cells assembled with an Rsbnd AC electrode as the counter electrode and an Fsbnd AC electrode as the cathode (R || F-) or anode (R || F +) was studied. For R || F-, the salt adsorption capacity and charge efficiency increased from 10.6 mg/g and 0.58-12.4 mg/g and 0.75, respectively, compared with the CDI cell assembled with identical Rsbnd AC electrodes at 1 V. This CDI cell exhibited consistently better salt adsorption capacity and charge efficiency at different applied voltages because Fsbnd AC electrodes have a cation attractive effect originating from the partially negatively charged fluorine functional groups on the AC surface. Therefore, co-ion expulsion in the Fsbnd AC electrode as the cathode is effectively diminished, leading to enhanced CDI performance.

The Electrochemical Fluorination of Organosilicon Compounds

NASA Technical Reports Server (NTRS)

Seaver, Robert E.

1961-01-01

The electrochemical fluorination of tetramethylsilane, hexamethyl-disiloxane, diethyldichlorosilane, amyltrichlorosilane, and phenyltri-chlorosilane was conducted in an Inconel cell equipped with nickel electrodes. A potential of approximately 5.0 volts and a current of approximately 1.0 ampere were used for the electrolysis reaction. In all cases the fluorinations resulted in considerable scission of the carbon-silicon bonds yielding hydrogen and the various fluorinated decomposition products; no fluoroorganosilicon compounds were identified. The main decomposition products were silicon tetrafluoride, the corresponding fluorinated carbon compounds, and the various organofluorosilanes. It is suggested that this is due to the nucleophilic attack of the fluoride ion (or complex fluoride ion) on the carbon-silicon bond.

Novel pleuromutilin derivatives with excellent antibacterial activity against Staphylococcus aureus.

PubMed

Xu, Peng; Zhang, Yuan-Yuan; Sun, Yong-Xue; Liu, Jian-Hua; Yang, Bing; Wang, Yu-Zhong; Wang, Yu-Liang

2009-06-01

Ten novel pleuromutilin derivatives with thioether moiety and heterocyclic carboxamide or chloroformate group in the side chain were synthesized and confirmed by (1)H NMR, IR and HRMS. The results of the antibacterial activity showed that the title compounds had excellent antibacterial activity against Staphylococcus aureus, among which the MIC of 5f reached 0.03125 microg/mL.

[Concentrations of fluorine, aluminum and magnesium in some structures of the central nervous system of rats exposed to aluminum and fluorine in drinking water].

PubMed

Lubkowska, Anna; Chlubek, Dariusz; Machoy-Mokrzyńska, Anna; Noceń, Iwona; Zyluk, Beata; Nowacki, Przemysław

2004-01-01

Fluorine and aluminum are able to pass through the blood-brain barrier and accumulate in the central nervous system (CNS) of exposed animals. Chronic intoxication is accompanied by behavioral disorders, degenerative changes, and abnormalities of aerobic metabolism of the neurons. Awareness of the role of aluminum in Alzheimer's disease stems from epidemiological studies demonstrating increased prevalence of this condition in areas with relatively high content of aluminum in drinking water. The uptake of aluminum in the gastrointestinal tract is decreased in the presence of iron, calcium, magnesium, phosphate, or fluoride. Many magnesium-containing enzymes are affected by aluminum, which is able to replace magnesium and thus reduce their activity. The purpose of this study was to determine the concentrations of fluorine, aluminum, and magnesium in some structures of the CNS of rats exposed to fluorine and aluminum in water. Our material consisted of 64 Wistar rats divided into eight equal groups. Groups I, II and III were female rats exposed, respectively, to 100 ppm fluorine ions, 300 ppm aluminum ions or both at same doses alternating every second day. Groups IA, IIA and IIIA consisted of male rats exposed like the respective female groups. Control groups K1--females and K2--males received distilled water ad libitum. Exposure lasted 31 days whereupon the animals were anesthetized with ketamine and sacrificed. The brain was collected and the cerebellum, brain cortex, and hippocampus were isolated. Concentrations of fluorine, aluminum, and magnesium were measured with prior mineralization of wet tissues in a microwave oven. Fluorine concentrations were determined with a potentiometric method and ion-selective electrode. Aluminum was measured with ICP (inductively coupled plasma) and magnesium with ASA (atomic absorption spectrometry). The highest concentrations of fluorine were observed in rats exposed to fluorine only. The same pattern was true for aluminum. Groups exposed alternatively to both elements demonstrated lower accumulation of fluorine whereas accumulation of aluminum did not change significantly. Apparently, aluminum reduced the availability of fluorine but there was no reciprocal effect. No significant changes in the concentrations of magnesium were noted, regardless of the brain structure or group. It can thus be concluded that exposure to fluorine, aluminum or both has little effect on the concentration of magnesium in the CNS of rats.

Fluorine (19F) MRS and MRI in biomedicine.

PubMed

Ruiz-Cabello, Jesús; Barnett, Brad P; Bottomley, Paul A; Bulte, Jeff W M

2011-02-01

Shortly after the introduction of (1)H MRI, fluorinated molecules were tested as MR-detectable tracers or contrast agents. Many fluorinated compounds, which are nontoxic and chemically inert, are now being used in a broad range of biomedical applications, including anesthetics, chemotherapeutic agents, and molecules with high oxygen solubility for respiration and blood substitution. These compounds can be monitored by fluorine ((19)F) MRI and/or MRS, providing a noninvasive means to interrogate associated functions in biological systems. As a result of the lack of endogenous fluorine in living organisms, (19)F MRI of 'hotspots' of targeted fluorinated contrast agents has recently opened up new research avenues in molecular and cellular imaging. This includes the specific targeting and imaging of cellular surface epitopes, as well as MRI cell tracking of endogenous macrophages, injected immune cells and stem cell transplants. Copyright © 2010 John Wiley & Sons, Ltd.

Exploration of fluorine chemistry at the multidisciplinary interface of chemistry and biology.

PubMed

Ojima, Iwao

2013-07-05

Over the last three decades, my engagement in "fluorine chemistry" has evolved substantially because of the multidisciplinary nature of the research programs. I began my research career as a synthetic chemist in organometallic chemistry and homogeneous catalysis directed toward organic synthesis. Then, I was brought into a very unique world of "fluorine chemistry" in the end of 1970s. I started exploring the interface of fluorine chemistry and transition metal homogeneous catalysis first, which was followed by amino acids, peptides, and peptidomimetics for medicinal chemistry. Since then, I have been exploring the interfaces of fluorine chemistry and multidisciplinary fields of research involving medicinal chemistry, chemical biology, cancer biology, and molecular imaging. This perspective intends to cover my fruitful endeavor in the exploration of fluorine chemistry at the multidisciplinary interface of chemistry and biology in a chronological order to show the evolution of my research interest and strategy.

Exploration of Fluorine Chemistry at the Multidisciplinary Interface of Chemistry and Biology

PubMed Central

Ojima, Iwao

2013-01-01

Over the last three decades, my engagement in “fluorine chemistry” has evolved substantially, because of the multidisciplinary nature of the research programs. I began my research career as a synthetic chemist in organometallic chemistry and homogeneous catalysis directed toward organic synthesis. Then, I was brought into a very unique world of “fluorine chemistry” in the end of 1970s. I started exploring the interface of fluorine chemistry and transition metal homogeneous catalysis first, which was followed by amino acids, peptides, and peptidomimetics for medicinal chemistry. Since then, I have been exploring the interfaces of fluorine chemistry and multidisciplinary fields of research involving medicinal chemistry, chemical biology, cancer biology and molecular imaging. This perspective intends to cover my fruitful endeavor in the exploration of fluorine chemistry at the multidisciplinary interface of chemistry and biology in a chronological order to show the evolution of my research interest and strategy. PMID:23614876

Determination of small and large amounts of fluorine in rocks

USGS Publications Warehouse

Grimaldi, F.S.; Ingram, B.; Cuttitta, F.

1955-01-01

Gelatinous silica and aluminum ions retard the distillation of fluorine in the Willard and Winter distillation method. A generally applicable, simple method for the determination of fluorine in rocks containing aluminum or silicon or both as major constituents was desired. In the procedure developed, the sample is fused with a mixture of sodium carbonate and zinc oxide, leached with water, and filtered. The residue is granular and retains nearly all of the silica. The fluorine in the filtrate is distilled directly from a perchloric acid-phosphoric acid mixture. Phosphoric acid permits the quantitative distillation of fluorine in the presence of much aluminum at the usual distillation temperature and without the collection of large volumes of distillate. The fluorine is determined either by microtitration with thorium nitrate or colorimetrically with thoron. The procedure is rapid and has yielded excellent results on silicate rocks and on samples from the aluminum phosphate (leached) zone of the Florida phosphate deposits.

Transition Metal-Mediated and -Catalyzed C-F Bond Activation via Fluorine Elimination.

PubMed

Fujita, Takeshi; Fuchibe, Kohei; Ichikawa, Junji

2018-06-28

Activation of carbon-fluorine (C-F) bonds is an important topic in synthetic organic chemistry recently. Among the methods for C-F bond cleavage, metal mediated and catalyzed β- or α-fluorine elimination proceeds under mild conditions compared with oxidative addition of C-F bond. The β- or α-fluorine elimination is initiated from organometallic intermediates having fluorine substituents on carbon atoms β or α to metal centers, respectively. Transformations via these elimination processes (C-F bond cleavage), which are typically preceded by carbon-carbon (or carbon-heteroatom) bond formation, have been remarkably developed as C-F bond activation methods in the past five years. In this minireview, we summarize the applications of transition metal-mediated and -catalyzed fluorine elimination to synthetic organic chemistry from a historical perspective for early studies and from a systematic perspective for recent studies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Compendium of fluorine data

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

Detamore, J.A.

1983-04-16

Research was conducted to locate information about fluorine. This information includes chemical and physical properties of fluorine, physiological effects produced by the material, first-aid, personnel and facility protection, and materials of construction required when handling fluorine in piping and process vessels. The results of this research have been compiled in this report.

Aerosol Direct Fluorination. Syntheses of the Perfluoroalkyl Orthocarbonates, F-Tetramethyl and F-Ethylene Orthocarbonates.

DTIC Science & Technology

1984-03-30

ff AD-AFRU9 98? AEROSOL DIRECT FLUORINATION SYNTHESES OF THE / 1 PERFLUOROALKYL ORTHOCRBONAT.-(U) TENNESSEE UNIY KNOXVILLE DEPT OF CHEMISTRY J L...SYNTHESES OF THE PERFLUOROALKYL ORTHOCARBONATES, F-TETRAMETHYL AND F-ETHYLENE ORTHOCARBONATES by James L. Adcock* and Mark L. Robin Department of...number) Aerosol, Direct Fluorination, Elemental Fluorine, Perfluoroalkyl % orthocarbonates 211,A’!S RACY (Contiue en reverse aide it neessary and

Incorporating fluorinated moieties in fully conjugated donor-acceptor block copolymers

NASA Astrophysics Data System (ADS)

Lee, Youngmin; Wang, Qing; Gomez, Enrique D.

Fully conjugated donor-acceptor block copolymers are promising candidates for photovoltaics due to their ability to microphase separate at length scales commensurate with exciton diffusion lengths. These materials can also serve as model systems to study the relationship between molecular structure, microstructure, and optoelectronic properties of conjugated polymers. The development of new donor-acceptor block copolymers relies on the manipulation of the chemical structure to fine tune properties and improve overall performance when employed in photovoltaic devices. To this end, we have demonstrated the incorporation of fluorinated moieties in conjugated block copolymers. The introduction of fluorine, a strong electron withdrawing element, is known to influence phase separation and the bandgap, and as a result, optoelectronic properties. Fluorine was introduced to the acceptor block of poly(3-hexylthiophene-2,5-diyl)-block-poly((9,9-bis(2-octyl)fluorene-2,7-diyl)-alt-(4,7-di(thiophene-2-yl)-2,1,3-benzothiadiazole)-5 ',5?-diyl) (P3HT- b-PFTBT). PFTBTs were prepared with di-fluorinated and mono-fluorinated TBT. We find that fluorination impacts the bandgap, morphology and performance in devices.

Molecular beam epitaxy growth of SmFeAs(O,F) films with Tc = 55 K using the new fluorine source FeF3

NASA Astrophysics Data System (ADS)

Sakoda, Masahito; Ishii, Akihiro; Takinaka, Kenji; Naito, Michio

2017-07-01

REFeAs(O,F) (RE: rare-earth element) has the highest-Tc (˜58 K) among the iron-based superconductors, but a thin-film growth of REFeAs(O,F) is difficult. This is because it is not only a complex compound consisting of five elements but also requires doping of highly reactive fluorine to achieve superconductivity. We have reported in our previous article that fluorine can be supplied to a film by subliming solid-state fluorides such as FeF2 or SmF3. In this article, we report on the growth of SmFeAs(O,F) using FeF3 as an alternative fluorine source. FeF3 is solid at ambient temperatures and decomposes at temperatures as low as 100-200 °C, and releases fluorine-containing gas during the thermal decomposition. With this alternative fluorine source, we have grown SmFeAs(O,F) films with Tc as high as 55 K. This achievement demonstrates that FeF3 has potential as a fluorine source that can be employed ubiquitously for a thin-film growth of any fluorine containing compounds. One problem specific to FeF3 is that the compound is highly hydroscopic and contains a substantial amount of water even in its anhydrous form. In this article, we describe how to overcome this specific problem.

Fluorination of vertically aligned carbon nanotubes: from CF4 plasma chemistry to surface functionalization.

PubMed

Struzzi, Claudia; Scardamaglia, Mattia; Colomer, Jean-François; Verdini, Alberto; Floreano, Luca; Snyders, Rony; Bittencourt, Carla

2017-01-01

The surface chemistry of plasma fluorinated vertically aligned carbon nanotubes (vCNT) is correlated to the CF 4 plasma chemical composition. The results obtained via FTIR and mass spectrometry are combined with the XPS and Raman analysis of the sample surface showing the dependence on different plasma parameters (power, time and distance from the plasma region) on the resulting fluorination. Photoemission and absorption spectroscopies are used to investigate the evolution of the electronic properties as a function of the fluorine content at the vCNT surface. The samples suffer a limited ageing effect, with a small loss of fluorine functionalities after two weeks in ambient conditions.

Fluorination of vertically aligned carbon nanotubes: from CF4 plasma chemistry to surface functionalization

PubMed Central

Scardamaglia, Mattia; Colomer, Jean-François; Verdini, Alberto; Floreano, Luca; Snyders, Rony; Bittencourt, Carla

2017-01-01

The surface chemistry of plasma fluorinated vertically aligned carbon nanotubes (vCNT) is correlated to the CF4 plasma chemical composition. The results obtained via FTIR and mass spectrometry are combined with the XPS and Raman analysis of the sample surface showing the dependence on different plasma parameters (power, time and distance from the plasma region) on the resulting fluorination. Photoemission and absorption spectroscopies are used to investigate the evolution of the electronic properties as a function of the fluorine content at the vCNT surface. The samples suffer a limited ageing effect, with a small loss of fluorine functionalities after two weeks in ambient conditions. PMID:28904833

Photochemistry of fluorinated 4-iodophenylnitrenes: matrix isolation and spectroscopic characterization of phenylnitrene-4-yls.

PubMed

Grote, Dirk; Sander, Wolfram

2009-10-02

The photochemistry of a series of fluorinated p-iodophenyl azides 2 has been investigated using matrix isolation IR and EPR spectroscopy. In all cases, the corresponding phenylnitrenes 1 were formed as primary photoproducts. Further irradiation of the nitrenes 1 resulted in the formation of azirines 3, ketenimines 4, and nitreno radicals 5. The yield of 5 depends on the number of ortho fluorine substituents: with two ortho fluorine atoms the highest yield is observed, whereas without fluorine atoms the yield is too low for IR spectroscopic detection. The interconversion between the isomers 1, 3, and 4 proved to be rather complex. If the fluorine atoms are distributed unsymmetrically, two isomers of azirines 3 and ketenimines 4 can be formed. The yields of these isomers depend critically on the irradiation conditions.

Development of the titanium–TADDOLate-catalyzed asymmetric fluorination of β-ketoesters

PubMed Central

Hintermann, Lukas; Perseghini, Mauro

2011-01-01

Summary Titanium-based Lewis acids catalyze the α-fluorination of β-ketoesters by electrophilic N–F-fluorinating reagents. Asymmetric catalysis with TADDOLato–titanium(IV) dichloride (TADDOL = α,α,α',α'-tetraaryl-(1,3-dioxolane-4,5-diyl)-dimethanol) Lewis acids produces enantiomerically enriched α-fluorinated β-ketoesters in up to 91% enantiomeric excess, with either F–TEDA (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)) in acetonitrile solution or NFSI (N-fluorobenzenesulfonimide) in dichloromethane solution as fluorinating reagents. The effects of various reaction parameters and of the TADDOL ligand structure on the catalytic activity and enantioselectivity were investigated. The absolute configuration of several fluorination products was assigned through correlation. Evidence for ionization of the catalyst complex by chloride dissociation, followed by generation of titanium β-ketoenolates as key reaction intermediates, was obtained. Based on the experimental findings, a general mechanistic sketch and a steric model of induction are proposed. PMID:22043253

Xenon fluorides show potential as fluorinating agents

NASA Technical Reports Server (NTRS)

Chernick, C. L.; Shieh, T. C.; Yang, N. C.

1967-01-01

Xenon fluorides permit the controlled addition of fluorine across an olefinic double bond. They provide a series of fluorinating agents that permit ready separation from the product at a high purity. The reactions may be carried out in the vapor phase.

Fluorinated elastomeric materials

DOEpatents

Lagow, Richard J.; Dumitru, Earl T.

1986-11-04

This invention relates to a method of making perfluorinated elastomeric materials, and to materials made by such methods. In the full synthetic scheme, a partially fluorinated polymeric compound, with moieties to prevent crystallization, is created. It is then crosslinked to a desired degree, then perfluorinated. Various intermediate materials, such as partially fluorinated crosslinked polymers, have useful properties, and are or may become commercially available. One embodiment of this invention therefore relates to perfluorination of a selected partially fluorinated, crosslinked material, which is one step of the full synthetic scheme.

Fluorinated elastomeric materials

DOEpatents

Lagow, Richard J.; Dumitru, Earl T.

1990-02-13

This invention relates to a method of making perfluorinated elastomeric materials, and to materials made by such methods. In the full synthetic scheme, a partially fluorinated polymeric compound, with moieties to prevent crystallization, is created. It is then crosslinked to a desired degree, then perfluorinated. Various intermediate materials, such as partially fluorinated crosslinked polymers, have useful properties, and are or may become commercially available. One embodiment of this invention therefore relates to perfluorination of a selected partially fluorinated, crosslinked material, which is one step of the full synthetic scheme.

Effects of fluorine on crops, soil exoenzyme activities, and earthworms in terrestrial ecosystems.

PubMed

Chae, Yooeun; Kim, Dokyung; An, Youn-Joo

2018-04-30

Fluorine can flow into the environment after leakage or spill accidents and these excessive amounts can cause adverse effects on terrestrial ecosystems. Using three media (filter paper, soil, and filter-paper-on-soil), we investigated the toxic effects of fluorine on the germination and growth of crops (barley, mung bean, sorghum, and wheat), on the activities of soil exoenzymes (acid phosphatase, arylsulfatase, fluorescein diacetate hydrolase, and urease) and on the survival, abnormality, and cytotoxicity of Eisenia andrei earthworms. The germination and growth of crops were affected by fluorine as exposure concentration increased. The activities of the four enzymes after 0-, 3-, 10-, and 20-day periods varied as exposure concentration increased. According to in vivo and in vitro earthworm assays, E. andrei mortality, abnormality, and cytotoxicity increased with increasing fluorine concentration. Overall, fluorine significantly affected each tested species in the concentration ranges used in this study. The activities of soil exoenzymes were also affected by soil fluorine concentration, although in an inconsistent manner. Albeit the abnormally high concentrations of fluorine in soil compared to that observed under natural conditions, its toxicity was much restrained possibly due to the adsorption of fluorine on soil particles and its combination with soil cations. Copyright © 2017 Elsevier Inc. All rights reserved.

Synthetic Aspects and Electro-Optical Properties of Fluorinated Arylenevinylenes for Luminescence and Photovoltaics

PubMed Central

Martinelli, Carmela; Farinola, Gianluca M.; Pinto, Vita; Cardone, Antonio

2013-01-01

In this review, the main synthetic aspects and properties of fluorinated arylenevinylene compounds, both oligomers and polymers, are summarized and analyzed. Starting from vinyl organotin derivatives and aryl halides, the Stille cross-coupling reaction has been successfully applied as a versatile synthetic protocol to prepare a wide series of π-conjugated compounds, selectively fluorinated on the aromatic and/or vinylene units. The impact of fluoro-functionalization on properties, the solid state organization and intermolecular interactions of the synthesized compounds are discussed, also in comparison with the non-fluorinated counterparts. Luminescent and photovoltaic applications are also discussed, highlighting the role of fluorine on the performance of devices. PMID:28809206

Oxidatively stable fluorinated sulfone electrolytes for high voltage high energy lithium-ion batteries

DOE PAGES

Su, Chi -Cheung; He, Meinan; Redfern, Paul C.; ...

2017-03-16

New fluorinated sulfones were synthesized and evaluated in high voltage lithium-ion batteries using LiNi 0.5Mn 1.5O 4 (LNMO) cathode. Fluorinated sulfones with an α-trifluoromethyl group exhibit enhanced oxidation stability, reduced viscosity and superior separator wettability as compared to their non-fluorinated counterparts. Finally, the improved performance in high voltage cells makes it a promising high voltage electrolyte for 5-V lithium-ion chemistry.

40 CFR Table 6 to Subpart Jj of... - VHAP of Potential Concern

Code of Federal Regulations, 2011 CFR

2011-07-01

... glycol butyl ether, ethylene glycol ethyl ether (2-ethoxy ethanol), ethylene glycol hexyl ether, ethylene..., ethylene glycol mono-2-ethylhexyl ether, diethylene glycol butyl ether, diethylene glycol ethyl ether... glycol propyl ether, triethylene glycol butyl ether, triethylene glycol ethyl ether, triethylene glycol...

Distribution and formation of high-fluorine groundwater in China

NASA Astrophysics Data System (ADS)

Fuhong, Ren; Shuqin, Jiao

1988-08-01

In China, high-fluorine groundwater, which contains more than 1.0 mg/l fluorine, is mainly distributed in shallow aquifers of unconsolidated deposits in some arid and semiarid areas, deep aquifers of unconsolidated deposits in semiarid areas, as well as in hot springs of bed rock mountainous area and aquifers of fluorite-mine area. Its formation is controlled by regional climate factors, seepage conditions of groundwater, as well as the hydrogeochemical environment. The physicochemical properties of soil mass of the aeration zone play an important role in fluorine concentration in shallow groundwater. In the coastal plain areas, where groundwater is mainly recharged and discharged vertically, and its regime type belongs to the type of infiltration—evaporation, the grain size of soil mass of aeration zone directly influences the amount of fluorine transferred from solid medium into water; and the chemical constituents of the soil mass of aeration zone controls the chemical characteristics of the shallow groundwater, consequently influencing the concentration condition of fluorine in water. Fluorine ion in groundwater continuously migrates and concentrates under the comprehensive influence of many factors. High-fluorine groundwater exceeding the sanitary standard (1.0 mg/l) has an obvious zonality in regional distribution in China. Based on current statistics, there are roughly 50 million people (Zheng Qifu 1986) who have consumed water which exceeds standards in China. In highfluorine groundwater areas, endemic fluorine-poisoning often arises to different extents, affecting human health seriously. At the end of 1983, over 20 million patients were suffering from fluorine-poisoning diseases in China (Xu Guozhang, unpublished data). Therefore, research of the distribution feature and formation mechanism of fluorine ion in groundwater has become an important task.

Measurement of Fluorine Atom Concentrations and Reaction Rates in Chemical Laser Systems.

DTIC Science & Technology

1981-09-01

AD-A1RA 070 AERODYNEERESEARCHUINC BEDFORDM MA F/6_20/5 MEASURE MENT OF FLUORINE ATOM CONCENTRATIONS AND REACTION RATFS -ETC(U) SEP_ A A C STANT ON...0772 LEVELIg 00 ~ARI-RR-272 cO0 MEASUREMENT OF FLUORINE ATOM CONCENTRATIONS AND REACTION RATES IN CHEMICAL LASER SYSTEMS ANNUAL TECHNICAL REPORT by...MEASUREMENT OF FLUORINE ATOM CONCENTRATIONS AND Annual Report REACTION RATES IN CHEMICAL LASER SYSTEMS 23 July 1980 - 23 July 1981 S. PERFORMING ORG. REPORT

Process for preparing fluorine-18

DOEpatents

Winchell, Harry S.; Wells, Dale K.; Lamb, James F.; Beaudry, Samuel B.

1976-09-21

An improved process for preparation of fluorine-18 by a neon (deuteron, alpha particle) fluorine-18 nuclear reaction in a non-reactive enclosed reaction zone wherein a ultrapure product is recovered by heating the reaction zone to a high temperature and removing the product with an inert gas.

A new microwave acid digestion bomb method for the determination of total fluorine.

PubMed

Grobler, S R; Louw, A J

1998-01-01

A new microwave acid digestion method for total fluorine analysis was compared to the reliable reverse-extraction technique. The commercially available Parr bombs which are compatible with microwave heating were modified for this purpose. The Mann-Whitney statistical test did not show any significant differences (p > 0.05) in the determinations of total fluorine in various samples between the two above-mentioned methods. The microwave method also gave high fluorine recoveries (> 97%) when fluoride was added to different samples. The great advantage of the microwave acid digestion bomb method is that the digestion under pressure is so aggressive that only a few minutes is needed for complete digestion (also of covalently bonded fluorine), which reduces the time for fluorine analysis dramatically, while no loss of fluorine or contamination from extraneous sources could take place during the ashing procedure. The digestion solution was made up of 300 microliter of concentrated nitric acid plus 537 microliter of water. After digestion 675 microliter of approximately 8.5 M sodium hydroxide plus 643 microliter of citrate/TISAB buffer was added resulting in an alkaline solution (pH approximately 12) which was finally adjusted to a pH of approximately 5.3 for fluoride determination.

[Current trends in fluorine research].

PubMed

Machoy-Mokrzyńska, Anna; Machoy, Zygmunt

2006-01-01

Current topics in fluorine research are presented with emphasis on findings by researchers in Szczecin and Poland, as well as in the world. Reports are cited on the distribution of fluorine compounds in the environment, routes of penetration into living organisms, and analytical methods for the quantitative determinations of fluorine content in air, water, soil, and foods. Important contributions have been made by Polish researchers on the role and patterns of fluorides in body fluids, soft and hard tissues, which remain in direct relationship to accumulation and elimination of fluorine. So far, comprehensive studies on mutagenic effects of fluorine and its potential role in bone neoplasms, Down syndrome, and other genetic disorders have not been carried out in Poland. Worthy of mention are reports on mechanisms of action of fluorine compounds on the cellular and subcellular level. Finally, two achievements of recent years in the field of fluorine research are discussed briefly. The first is concerned with the use in dentistry of chemical analysis for studying mineral reconstruction of teeth throughout the lifetime of an individual. The second is in the field of medicine where molecular modeling has been applied to explain the mechanism of action of aluminofluoride complexes (AlFx) as a messenger of false information during protein biosynthesis and their apparent role in the etiology of Alzheimer's disease.

Radiolabeled cholesteryl ethers: A need to analyze for biological stability before use.

PubMed

Manual Kollareth, Denny Joseph; Chang, Chuchun L; Hansen, Inge H; Deckelbaum, Richard J

2018-03-01

Radiolabeled cholesteryl ethers are widely used as non-metabolizable tracers for lipoproteins and lipid emulsions in a variety of in vitro and in vivo experiments. Since cholesteryl ethers do not leave cells after uptake and are not hydrolyzed by mammalian cellular enzymes, these compounds can act as markers for cumulative cell uptakes of labeled particles. We have employed [ 3 H]cholesteryl oleoyl ether to study the uptake and distribution of triglyceride-rich emulsion particles on animal models. However, questionable unexpected results compelled us to analyze the stability of these ethers. We tested the stability of two commercially available radiolabeled cholesteryl ethers - [ 3 H]cholesteryl oleoyl ether and [ 3 H]cholesteryl hexadecyl ether from different suppliers, employing in vitro , in vivo and chemical model systems. Our results show that, among the two cholesteryl ethers tested, one ether was hydrolyzed to free cholesterol in vitro , in vivo and chemically under alkaline hydrolyzing agent. Free cholesterol, unlike cholesteryl ether, can then re-enter the circulation leading to confounding results. The other ether was not hydrolyzed to free cholesterol and remained as a stable ether. Hence, radiolabeled cholesteryl ethers should be analyzed for biological stability before utilizing them for in vitro or in vivo experiments.

Superhydrophobicity of electrospray-synthesized fluorinated silica layers.

PubMed

Kim, Eun-Kyeong; Lee, Chul-Sung; Kim, Sang Sub

2012-02-15

The preparation of superhydrophobic SiO(2) layers through a combination of a nanoscale surface roughness and a fluorination treatment is reported. Electrospraying SiO(2) precursor solutions that had been prepared by a sol-gel chemical route produced very rough SiO(2) layers. Subsequent fluorination treatment with a solution containing trichloro(1H,1H,2H,2H-perfluorooctyl)silane resulted in highly rough, fluorinated SiO(2) layers. The fluorinated rough SiO(2) layers exhibited excellent repellency toward various liquid droplets. In particular, water repellency of 168° was observed. On the bases of Cassie-Baxter and Young-Dupre equations, the surface fraction and the work of adhesion of the rough, fluorinated SiO(2) layers were respectively estimated. In light of the durability in water, ultraviolet resistance, and thermal stability, the superhydrophobic SiO(2) layers prepared in this work hold promise in a range of practical applications. Copyright © 2011 Elsevier Inc. All rights reserved.

Altering the Polymorphic Accessibility of Polycyclic Aromatic Hydrocarbons with Fluorination

DOE PAGES

Hiszpanski, Anna M.; Woll, Arthur R.; Kim, Bumjung; ...

2017-04-25

Here, substituting hydrogen with fluorine is an extensively employed strategy to improve the macroscopic properties of compounds for use in fields as diverse as pharmaceutics and optoelectronics. The role fluorine substitution plays on polymorphism—the ability of a compound to adopt more than one crystal structure—has not been previously studied. Yet, this understanding is important as different polymorphs of the same compound can result in drastically different bulk properties (e.g., solubility, absorptivity, and conductivity). Strategies to either promote or suppress the crystallization of particular polymorphs are thus desired. Here, we show that substituting hydrogen with fluorine affects the polymorphic behavior ofmore » contorted hexabenzocoronene (cHBC). A polycyclic aromatic hydrocarbon and molecular semiconductor, cHBC exhibits two polymorphs (i.e., P2 1/c crystal structure which we refer to as polymorph I and a triclinic crystal structure which we refer to as polymorph II) that are accessible through postdeposition processing of amorphous films. While the same two polymorphs remain accessible in fluorinated derivatives of cHBC, fluorination appears to favor the formation of polymorph I, with progressively smaller energy barrier for transformation from polymorph II to polymorph I with fluorination.« less

Altering the Polymorphic Accessibility of Polycyclic Aromatic Hydrocarbons with Fluorination

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

Hiszpanski, Anna M.; Woll, Arthur R.; Kim, Bumjung

Here, substituting hydrogen with fluorine is an extensively employed strategy to improve the macroscopic properties of compounds for use in fields as diverse as pharmaceutics and optoelectronics. The role fluorine substitution plays on polymorphism—the ability of a compound to adopt more than one crystal structure—has not been previously studied. Yet, this understanding is important as different polymorphs of the same compound can result in drastically different bulk properties (e.g., solubility, absorptivity, and conductivity). Strategies to either promote or suppress the crystallization of particular polymorphs are thus desired. Here, we show that substituting hydrogen with fluorine affects the polymorphic behavior ofmore » contorted hexabenzocoronene (cHBC). A polycyclic aromatic hydrocarbon and molecular semiconductor, cHBC exhibits two polymorphs (i.e., P2 1/c crystal structure which we refer to as polymorph I and a triclinic crystal structure which we refer to as polymorph II) that are accessible through postdeposition processing of amorphous films. While the same two polymorphs remain accessible in fluorinated derivatives of cHBC, fluorination appears to favor the formation of polymorph I, with progressively smaller energy barrier for transformation from polymorph II to polymorph I with fluorination.« less

Decarboxylative Fluorination of Aliphatic Carboxylic Acids via Photoredox Catalysis.

PubMed

Ventre, Sandrine; Petronijevic, Filip R; MacMillan, David W C

2015-05-06

The direct conversion of aliphatic carboxylic acids to the corresponding alkyl fluorides has been achieved via visible light-promoted photoredox catalysis. This operationally simple, redox-neutral fluorination method is amenable to a wide variety of carboxylic acids. Photon-induced oxidation of carboxylates leads to the formation of carboxyl radicals, which upon rapid CO2-extrusion and F(•) transfer from a fluorinating reagent yield the desired fluoroalkanes with high efficiency. Experimental evidence indicates that an oxidative quenching pathway is operable in this broadly applicable fluorination protocol.

Correlation of Calculated Halonium Ion Structures with Experimental Product Distributions from Terminal Alkenes: The Effect of Electron-Withdrawing Fluorine Substituents on the Structure and Charge Localization of Halonium Ions (PREPRINT)

DTIC Science & Technology

2006-04-03

2) Substituting a vinyl hydrogen with a fluorine presents an interesting situation for electrophilic reactions. The π-bond is less...reactive toward electrophiles due to the electron-withdrawing effect of the vinyl fluorine . Therefore, carbocations or radical cations are destabilized...NUMBER Distributions from Terminal Alkenes: The Effect of Electron-Withdrawing Fluorine Substituents on the Structure and Charge Localization of

40 CFR 721.10524 - Fluorinated alkylsulfonamidol urethane polymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... polymer (generic). 721.10524 Section 721.10524 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10524 Fluorinated alkylsulfonamidol urethane polymer (generic). (a... generically as fluorinated alkylsulfonamidol urethane polymer (PMN P-11-384) is subject to reporting under...

40 CFR 721.10524 - Fluorinated alkylsulfonamidol urethane polymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... polymer (generic). 721.10524 Section 721.10524 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10524 Fluorinated alkylsulfonamidol urethane polymer (generic). (a... generically as fluorinated alkylsulfonamidol urethane polymer (PMN P-11-384) is subject to reporting under...

[Caries and fluorine: role of water factor, problems and solutions].

PubMed

Rakhmanin, Iu A; Kir'ianova, L F; Mikhaĭlova, R I; Sevost'ianova, E M

2001-01-01

The epidemiological studies of the severity and spread of caries of deciduous and permanent teeth in Moscow schoolchildren (n = > 20,000) aged 7-17 years in relation to the content of fluoride in the drinking water, to the use of fluorine-containing tablets and varnishes have provided evidence for the high efficiency of drinking water fluorination for the primary prevention of caries as compared with other preventive alternatives. Based on sanitary studies, two main lines are now under way in solving the problem connected with low dietary fluoride intake: the introduction of routine water-purifying fluorine generators (based on a new technology of fluorination of limited water volumes for drinking and cooking) and the setting-up of plants manufacturing bottled drinking waters containing the optimum or higher fluorine levels for provision of different population groups, primarily children and pregnant women in particular.

Kα X-Ray Emission Spectra and K X-Ray Absorption-Edge Structures of Fluorine in 3d Transition-Metal Difluorides

NASA Astrophysics Data System (ADS)

Sugiura, Chikara

1991-08-01

The fluorine Kα emission spectra in fluorescence from a series of 3d transition-metal difluorides MF2 (M=Mn, Fe, Co, Ni, Cu and Zn) have been measured with a high-resolution two-crystal vacuum spectrometer. It is shown that the observed FWHM of the Kα1,2 emission band is closely related to the difference in the electronegativity between the metal and fluorine atoms. The measured emission spectra are presented along with the UPS or XPS spectra of the valence bands and the fluorine K absorption spectra of the metal difluorides, reported previously. The structures at the fluorine K absorption edges are interpreted in terms of a molecular orbital (MO) model.

Substrate Material for Holographic Emulsions Utilizing Fluorinated Polyimide Film

NASA Technical Reports Server (NTRS)

Gierow, Paul A. (Inventor); Clayton, William R. (Inventor); St.Clair, Anne K. (Inventor)

1999-01-01

A new holographic substrate utilizing flexible. optically transparent fluorinated polyimides. Said substrates have 0 extremely low birefringence which results in a high signal to noise ratio in subsequent holograms. Specific examples of said fluorinated polyimides include 6FDA+APB and 6FDA+4BDAF.

Synthetic biology approaches to fluorinated polyketides

PubMed Central

Thuronyi, Benjamin W.; Chang, Michelle C. Y.

2016-01-01

Conspectus The catalytic diversity of living systems offers a broad range of opportunities for developing new methods to produce small molecule targets such as fuels, materials, and pharmaceuticals. In addition to providing cost-effective and renewable methods for large-scale commercial processes, the exploration of the unusual chemical phenotypes found in living organisms can also enable the expansion of chemical space for discovery of novel function by combining orthogonal attributes from both synthetic and biological chemistry. In this context, we have focused on the development of new fluorine chemistry using synthetic biology approaches. While fluorine has become an important feature in compounds of synthetic origin, the scope of biological fluorine chemistry in living systems is limited, with fewer than 20 organofluorine natural products identified to date. In order to expand the diversity of biosynthetically accessible organofluorines, we have begun to develop methods for the site-selective introduction of fluorine into complex natural products by engineering biosynthetic machinery to incorporate fluorinated building blocks. To gain insight into how both enzyme active sites and metabolic pathways can be evolved to manage and select for fluorinated compounds, we have studied one of the only characterized natural hosts for organofluorine biosynthesis, the soil microbe Streptomyces cattleya. This information provides a template for designing engineered organofluorine enzymes, pathways, and hosts and has allowed us to initiate construction of enzymatic and cellular pathways for the production of fluorinated polyketides. PMID:25719427

Supercritical temperature synthesis of fluorine-doped VO2(M) nanoparticle with improved thermochromic property

NASA Astrophysics Data System (ADS)

Riapanitra, Anung; Asakura, Yusuke; Cao, Wenbin; Noda, Yasuto; Yin, Shu

2018-06-01

Fluorine-doped VO2(M) nanoparticles have been successfully synthesized using the hydrothermal method at a supercritical temperature of 490 °C. The pristine VO2(M) has the critical phase transformation temperature of 64 °C. The morphology and homogeneity of the monoclinic structure VO2(M) were adopted by the fluorine-doped system. The obtained particle size of the samples is smaller at the higher concentration of anion doping. The best reduction of critical temperature was achieved by fluorine doping of 0.13% up to 48 °C. The thin films of the fluorine-doped VO2(M) showed pronounced thermochromic property and therefore are suitable for smart window applications.

A method to remove intercalates from bromine and iodine intercalated carbon fibers

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1993-01-01

Upon exposure to room-temperature fluorine, intercalated carbon fibers (containing either bromine alone or iodine and bromine together) become heavier and less stable. For Amoco P-100 graphitized carbon fibers which were intercalated with 18 percent bromine by weight, 1 hr of fluorine exposure results in a large weight increase, but causes only a small decrease in thermal stability. More than l hr of fluorine exposure time results in small additional increases in fiber weight, but significant further decreases in fiber thermal stability. Such phenomena do not occur if the fluorine exposure is at 250 C. These observations suggest the mechanism that at room temperature, fluorine is absorbed quickly by the intercalated fibers and intercalated slowly into the fibers. Most of the original intercalates are replaced by fluorine in the process of fluorine intercalation. Under an inert environment, the bromine intercalated fibers are much more thermally stable. After 800 C vacuum heating for two weeks, the brominated fibers lost about 45 percent of their bromine, and their resistivity increased from 64 omega-cm to a range of 95 to 170 micro omega-cm. This is still much lower than the 300 micro omega-cm value for pristine P-100. For practical purposes, in order to preserve their thermal stability, brominated fibers need to be protected from exposure to fluorine at room temperature, or to any intercalate at a temperature where, upon direct contact to graphite, an intercalation compound can easily be formed.

40 CFR 721.10146 - Partially fluorinated condensation polymer (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... polymer (generic). 721.10146 Section 721.10146 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10146 Partially fluorinated condensation polymer (generic). (a) Chemical... as partially fluorinated condensation polymer (PMN P-07-87) is subject to reporting under this...

Theoretical investigation of structural and optical properties of semi-fluorinated bilayer graphene

NASA Astrophysics Data System (ADS)

Xiao-Jiao, San; Bai, Han; Jing-Geng, Zhao

2016-03-01

We have studied the structural and optical properties of semi-fluorinated bilayer graphene using density functional theory. When the interlayer distance is 1.62 Å, the two graphene layers in AA stacking can form strong chemical bonds. Under an in-plane stress of 6.8 GPa, this semi-fluorinated bilayer graphene becomes the energy minimum. Our calculations indicate that the semi-fluorinated bilayer graphene with the AA stacking sequence and rectangular fluorinated configuration is a nonmagnetic semiconductor (direct gap of 3.46 eV). The electronic behavior at the vicinity of the Fermi level is mainly contributed by the p electrons of carbon atoms forming C=C double bonds. We compare the optical properties of the semi-fluorinated bilayer graphene with those of bilayer graphene stacked in the AA sequence and find that the semi-fluorinated bilayer graphene is anisotropic for the polarization vector on the basal plane of graphene and a red shift occurs in the [010] polarization, which makes the peak at the low-frequency region located within visible light. This investigation is useful to design polarization-dependence optoelectronic devices. Project supported by the Program of Educational Commission of Heilongjiang Province, China (Grant No. 12541131).

Advanced clay nanocomposites based on in situ photopolymerization utilizing novel polymerizable organoclays

NASA Astrophysics Data System (ADS)

Kim, Soon Ki

Polymer nanocomposite technology has had significant impact on material design. With the environmental advantages of photopolymerization, a research has recently focused on producing nanocomposites utilizing inexpensive clay particles based on in situ photopolymerization. In this research, novel polymerizable organoclays and thiol-ene photopolymerization have been utilized to develop advanced photopolymer clay nanocomposites and to overcome several limitations in conventional free radical photopolymers. To this end, factors important in nanocomposite processes such as monomer composition, clay dispersion, and photopolymerization behavior in combination with the evolution of ultimate nanocomposite properties have been investigated. For monomer-organoclay compositions, higher chemical compatibility of components induces enhanced clay exfoliation, resulting in photopolymerization rate increases due to an amplified clay template effect. Additionally, by affecting the stoichiometric ratio between thiol and acrylate double bond in the clay gallery, thiolated organoclays enhance thiol-ene copolymerization with increased final thiol conversion while acrylated organoclays encourage acrylate homopolymerization. In accordance with the reaction behavior, incorporation of thiolated organoclays makes polymer chains more flexible with decreased glass transition temperature due to higher formation of thio-ether linkages while adding acrylated organoclays significantly increases the modulus. Photopolymer nanocomposites also help overcome two major drawbacks in conventional free radical photopolymerization, namely severe polymerization shrinkage and oxygen inhibition during polymerization. With addition of a low level of thiol monomers, the oxygen inhibition in various acrylate systems can be overcome by addition of only 5wt% thiolated organoclay. The same amount of polymerizable organoclay also induces up to 90% decreases in the shrinkage stress for acrylate or thiol-acrylate systems. However, nonreactive clays do not reduce the stress substantially and even decreases the polymerization rate in air. Additionally, the clay morphology and polymerization behavior are closely related with evolution of ultimate nanocomposite performance. Use of polymerizable organoclay significantly improves overall toughness of nanocomposites by increasing either modulus or elongation at break based on the type of polymerizable organoclay, which demonstrates the promise of this technology as a modulation and/or optimization tool for nanocomposite properties.

Method of forming fluorine-bearing diamond layer on substrates, including tool substrates

DOEpatents

Chang, R. P. H.; Grannen, Kevin J.

2002-01-01

A method of forming a fluorine-bearing diamond layer on non-diamond substrates, especially on tool substrates comprising a metal matrix and hard particles, such as tungsten carbide particles, in the metal matrix. The substrate and a fluorine-bearing plasma or other gas are then contacted under temperature and pressure conditions effective to nucleate fluorine-bearing diamond on the substrate. A tool insert substrate is treated prior to the diamond nucleation and growth operation by etching both the metal matrix and the hard particles using suitable etchants.

Sulfonimide-containing poly(arylene ether)s and poly(arylene ether sulfone)s, methods for producing the same, and uses thereof

DOEpatents

Hofmann, Michael A.

2006-11-14

The present invention is directed to sulfonimide-containing polymers, specifically sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, and processes for making the sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, for use conductive membranes and fuel cells.

A study of the degree of fluorination in regioregular poly(3-hexylthiophene)

DOE PAGES

Blaskovits, J. Terence; Bura, Thomas; Beaupre, Serge; ...

2016-12-27

Here, we systematically varied the degree of fluorination along the backbone of a series of highly regioregular 3-hexylthiophene-based polymers, P3HT-50F, P3HT-33F and P3HT-25F, in which 50%, 33% and 25% of the thiophene units within the polymer chain contain fluorine atoms in the available 4-position. These materials were homopolymerized using the Kumada catalyst transfer polycondensation method from a set of mono-fluorinated bi-, ter- and quarterthiophenes, to ensure high polymer regioregularity and evenly-spaced fluorine atoms along the conjugated thiophene backbone. The monomers were obtained from a synthetic route consisting of iterative Migita-Stille couplings of fluorinated and non-fluorinated 3- hexylthiophenes. The effect ofmore » the fluorine atoms on both polymer structure and properties is presented, with supporting quantum mechanical calculations that rationalize the intrinsic conformation preferences of the three P3HT derivatives. P3HT-50F (M¯ n = 34 kg/mol, 98.5% rr), P3HT-33F (M¯ n = 46 kg/mol, 98% rr) and P3HT-25F (M¯ n = 53 kg/mol, 95% rr) displayed HOMO levels of -5.34, -5.26 and -5.24 eV, bandgaps of 1.98, 1.98 and 1.97 eV, and average field-effect transistor hole mobilities of 4.5 × 10 -3, 2.7 × 10 -2, and 1.2 × 10 -2 cm 2 V -1s -1, respectively.« less

Boron compounds as anion binding agents for nonaqueous battery electrolytes

DOEpatents

Lee, Hung Sui; Yang, Xia-Oing; McBreen, James; Xiang, Caili

2000-02-08

Novel fluorinated boron-based compounds which act as anion receptors in non-aqueous battery electrolytes are provided. When added to non-aqueous battery electrolytes, the fluorinated boron-based compounds of the invention enhance ionic conductivity and cation transference number of non-aqueous electrolytes. The fluorinated boron-based anion receptors include borane and borate compounds bearing different fluorinated alkyl and aryl groups.

Phenyl boron-based compounds as anion receptors for non-aqueous battery electrolytes

DOEpatents

Lee, Hung Sui; Yang, Xiao-Qing; McBreen, James; Sun, Xuehui

2002-01-01

Novel fluorinated boronate-based compounds which act as anion receptors in non-aqueous battery electrolytes are provided. When added to non-aqueous battery electrolytes, the fluorinated boronate-based compounds of the invention enhance ionic conductivity and cation transference number of non-aqueous electrolytes. The fluorinated boronate-based anion receptors include different fluorinated alkyl and aryl groups.

Fluorine-18 patents (2009–2015). Part 2: new radiochemistry

PubMed Central

Mossine, Andrew V; Thompson, Stephen; Brooks, Allen F; Sowa, Alexandra R; Miller, Jason M; Scott, Peter JH

2016-01-01

Fluorine-18 (18F) is one of the most common positron-emitting radionuclides used in the synthesis of positron emission tomography radiotracers due to its ready availability, convenient half-life and outstanding imaging properties. In Part 1 of this review, we presented the first analysis of patents issued for novel radiotracers labeled with fluorine-18. In Part 2, we follow-up with a focus on patents issued for new radiochemistry methodology using fluorine-18 issued between January 2009 and December 2015. PMID:27610753

Method to synthesize lanthanide fluoride materials from lanthanide fluorinated alkoxides

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

Boyle, Timothy J.

Lanthanide fluorinated alkoxide derivatives can be synthesized from the alcoholysis reaction of the lanthanide bis-trimethylsilyl amide and an excess amount of hexafluoro iso-propanol. Nanoparticles can be formed from the lanthanide fluorinated alkoxide derivatives by a solvothermal or solution precipitation process.

Suppression of Sclerostin and Dickkopf-1 levels in patients with fluorine bone injury.

PubMed

Wang, Wenpeng; Xu, Jian; Liu, Kejian; Liu, Xiaoli; Li, Changcheng; Cui, Caiyan; Zhang, Yuzeng; Li, Huabing

2013-05-01

Evidence has been accumulating for the role of Sclerostin and Dickkopf-1 as the antagonists of Wnt/β-Catenin signaling pathway, which suppresses bone formation through inhibiting osteoblastic function. To get deep-inside information about the expression of the antagonists in patients with fluorine bone injury, a case-control study was conducted in two counties in Hubei Province. Urinary and serum fluoride were significantly higher in patients with fluorine bone injury than in healthy controls. Additionally, patients with fluorine bone injury had significantly lower serum Sclerostin and Dickkopf-1 levels compared with healthy controls (P<0.001). Serum Sclerostin and Dickkopf-1 levels were significantly correlated with serum fluoride in all studied subjects (n=186). Low Sclerostin and Dickkopf-1 levels were associated with a significantly increased risk of fluorine bone injury. In conclusion, serum Sclerostin and Dickkopf-1 might be used as important markers of bone metabolism change and potential therapeutic targets to treat fluorine bone injury. Copyright © 2013 Elsevier B.V. All rights reserved.

Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks

NASA Astrophysics Data System (ADS)

Byun, Jeehye; Patel, Hasmukh A.; Thirion, Damien; Yavuz, Cafer T.

2016-11-01

Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow.

Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks

PubMed Central

Byun, Jeehye; Patel, Hasmukh A.; Thirion, Damien; Yavuz, Cafer T.

2016-01-01

Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow. PMID:27830697

Oxidative aliphatic C-H fluorination with manganese catalysts and fluoride ion

PubMed Central

Liu, Wei; Huang, Xiongyi; Groves, John T

2014-01-01

Fluorination is a reaction that is useful in improving the chemical stability and changing the binding affinity of biologically active compounds. The protocol described here can be used to replace aliphatic, C(sp3)-H hydrogen in small molecules with fluorine. Notably, isolated methylene groups and unactivated benzylic sites are accessible. The method uses readily available manganese porphyrin and manganese salen catalysts and various fluoride ion reagents, including silver fluoride (AgF), tetrabutylammonium fluoride and triethylamine trihydrofluoride (TREAT·HF), as the source of fluorine. Typically, the reactions afford 50–70% yield of mono-fluorinated products in one step. Two representative examples, the fragrance component celestolide and the nonsteroidal anti-inflammatory drug ibuprofen, are described; they produced useful isolated quantities (250–300 mg, ~50% yield) of fluorinated material over periods of 1–8 h. The procedures are performed in a typical fume hood using ordinary laboratory glassware. No special precautions to rigorously exclude water are required. PMID:24177292

Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe 2O 3–FeF 3 Conversion Compounds by Direct Fluorination

DOE PAGES

Zhou, Hui; Ruther, Rose E.; Adcock, Jamie; ...

2015-02-22

In this paper, we report a direct fluorination method under fluorine gas atmosphere using a fluidized bed reactor for converting nanophase iron oxide (n-Fe 2O 3) to an electrochemically stable and higher energy density iron oxyfluoride/fluoride phase. Interestingly, no noticeable bulk iron oxyfluoride phase (FeOF) phase was observed even at fluorination temperature close to 300 °C. Instead, at fluorination temperatures below 250 °C, scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) and X-ray photoelectron spectroscopy (XPS) analysis showed surface fluorination with nominal composition, Fe 2O 3-xF 2x (x < 1). At fluorination temperatures of 275 °C, STEM-EELSmore » results showed porous interconnected nanodomains of FeF 3 and Fe 2O 3 coexisting within the same particle, and overall the particles become less dense after fluorination. We performed potentiometric intermittent titration and electrochemical impedance spectroscopy studies to understand the lithium diffusion (or apparent diffusion) in both the oxyfluoride and mixed phase FeF 3 + Fe 2O 3 composition, and correlate the results to their electrochemical performance. Finally and further, we analyze from a thermodynamical perspective, the observed formation of the majority fluoride phase (77% FeF 3) and the absence of the expected oxyfluoride phase based on the relative formation energies of oxide, fluoride, and oxyfluorides.« less

Coordination chemistry of highly hemilabile bidentate sulfoxide N-heterocyclic carbenes with palladium(II).

PubMed

Yu, Kuo-Hsuan; Wang, Chia-Ching; Chang, I-Hsin; Liu, Yi-Hung; Wang, Yu; Elsevier, Cornelis J; Liu, Shiuh-Tzung; Chen, Jwu-Ting

2014-12-01

Imidazolium salts, [RS(O)-CH2 (C3 H3 N2 )Mes]Cl (R=Me (L1a), Ph (L1b)); Mes=mesityl), make convenient carbene precursors. Palladation of L1a affords the monodentate dinuclear complex, [(PdCl2 {MeS(O)CH2 (C3 H2 N2 )Mes})2 ] (2a), which is converted into trans-[PdCl2 (NHC)2] (trans-4a; N-heterocyclic carbene) with two rotamers in anti and syn configurations. Complex trans-4a can isomerize into cis-4a(anti) at reflux in acetonitrile. Abstraction of chlorides from 4a or 4b leads to the formation of a new dication: trans-[Pd{RS(O)CH2(C3H2N2)Mes}2](PF6)2 (R=Me (5a), Ph (5b)). The X-ray structure of 5a provides evidence that the two bidentate SO-NHC ligands at palladium(II) are in square-planar geometry. Two sulfoxides are sulfur- and oxygen-bound, and constitute five- and six-membered chelate rings with the metal center, respectively. In acetonitrile, complexes 5a or 5b spontaneously transform into cis-[Pd(NHC)2(NCMe)2](PF6)2. Similar studies of thioether-NHCs have also been examined for comparison. The results indicate that sulfoxides are more labile than thioethers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorine determination in human healthy and carious teeth using the PIGE technique

NASA Astrophysics Data System (ADS)

Carvalho, M. L.; Karydas, A. G.; Casaca, C.; Zarkadas, Ch; Paradellis, Th; Kokkoris, M.; Nsouli, B.; Cunha, A. S.

2001-09-01

The purpose of this study is to determine and compare the fluorine concentration in human teeth from two different populations, living in the Portuguese quite isolated islands of Açores: S. Miguel and Terceira. Both populations have similar dietary habits, similar occupational activities, mostly rural, and the age of both populations is more or less the same, around 40 years. No chronic diseases were registered in any of the donors. The two groups are exposed to different levels of fluorine in drinking water. Terceira island has moderate fluorine concentration levels (1-2 μg g -1) while S. Miguel island is known for the high fluorine concentration levels in its water (>3 μg g -1), especially in one area known as Furnas. Thirty-three teeth, 17 healthy and 16 carious without restoration (14 incisors and canines, 7 premolars and 12 molars), were collected and analyzed for the determination of fluorine concentration in the dentine region, using the nuclear reaction 19F( p, αγ) 16O. The teeth were cross-sectioned along the vertical plane and polished, in order to obtain a smooth and plane surface of about 1 mm thickness. In this work an association between caries prevalence and fluorine content of drinking water is discussed and the variation of fluorine concentration among different types of teeth (canines and incisors, premolars, molars) and physical state (carious and non-carious) is examined.

Decarboxylative Fluorination of Aliphatic Carboxylic Acids via Photoredox Catalysis

PubMed Central

Ventre, Sandrine; Petronijevic, Filip R.; MacMillan, David W. C.

2016-01-01

The direct conversion of aliphatic carboxylic acids to the corresponding alkyl fluorides has been achieved via visible light-promoted photoredox catalysis. This operationally simple, redox-neutral fluorination method is amenable to a wide variety of carboxylic acids. Photon-induced oxidation of carboxylates leads to the formation of carboxyl radicals, which upon rapid CO2-extrusion and F• transfer from a fluorinating reagent yield the desired fluoroalkanes with high efficiency. Experimental evidence indicates that an oxidative quenching pathway is operable in this broadly applicable fluorination protocol. PMID:25881929

40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

Code of Federal Regulations, 2011 CFR

2011-07-01

... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under this...

40 CFR 721.9075 - Quaternary ammonium salt of fluorinated alkylaryl amide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... fluorinated alkylaryl amide. 721.9075 Section 721.9075 Protection of Environment ENVIRONMENTAL PROTECTION... amide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as quaternary ammonium salt of fluorinated alkylaryl amide (PMN No. P-92-688) is...

Low Temperature Fluorination of Aerosol Suspensions of Hydrocarbons Utilizing Elemental Fluorine.

DTIC Science & Technology

1982-09-01

admitting boron trifluoride into the aerosol direct florination of neopentane. The aerosol direct fluorination of ketones indicates the carbonyl group...fluorination of molecules with primary, secondary and tertiary hydro- gens is also included as is the effect of admitting boron trifluoride into the...significantly different physical and chemical properties than either of their components. For example, both ammonia and boron trifluoride are low

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

Kim, Eun-Kyeong; Yeong Kim, Ji; Sub Kim, Sang, E-mail: sangsub@inha.ac.kr

We describe the preparation of superhydrophobic SiO{sub 2} layers through a combination of surface roughness and fluorination. Electrospraying SiO{sub 2} precursor solutions that were prepared by a sol-gel route and included trichloro(1H,1H,2H,2H-perfluorooctyl)silane as a fluorination source produced highly rough, fluorinated SiO{sub 2} layers. In sharp contrast to the fluorinated flat SiO{sub 2} layer, the fluorinated rough SiO{sub 2} layer showed much enhanced repellency toward liquid droplets of different surface tensions. The surface fraction and the work of adhesion of the superhydrophobic SiO{sub 2} layers were determined, respectively, based on Cassie-Baxter and Young-Dupre equations. The satisfactory long-term stability for 30 days,more » the ultraviolet resistance and the thermal stability up to 400 {sup o}C of the superhydrophobic SiO{sub 2} layers prepared in this work confirm a promising practical application. - Graphical abstract: A schematic illustration of the electrospray deposition used for preparing SiO{sub 2} layers. Shapes of liquid droplets of water, glycerol, coffee, juice and milk created on the fluorinated rough SiO{sub 2} layer deposited on a silicon wafer. Highlights: Black-Right-Pointing-Pointer Superhydrophobic SiO{sub 2} layers are realized by a combination of surface roughness and fluorination. Black-Right-Pointing-Pointer The fluorinated rough SiO{sub 2} layer shows enhanced repellency toward various liquid droplets. Black-Right-Pointing-Pointer The wetting behavior is explained based on Cassie-Baxter and Young-Dupre equations. Black-Right-Pointing-Pointer The superhydrophobic SiO{sub 2} layers confirm a promising practical application.« less

Revisited study of fluorine implantation impact on negative bias temperature instability for input/output device of automotive micro controller unit

NASA Astrophysics Data System (ADS)

Yoshida, Tetsuya; Maekawa, Keiichi; Tsuda, Shibun; Shimizu, Tatsuo; Ogasawara, Makoto; Aono, Hideki; Yamaguchi, Yasuo

2018-04-01

We investigate the effect of fluorine implanted in the polycrystalline silicon (poly-Si) gate and source/drain (S/D) region on negative bias temperature instability (NBTI) improvement. It is found that there is a trade-off implantation energy dependence of NBTI between fluorine in the poly-Si gate and that in the S/D region. Fluorine implanted in the poly-Si gate contributes to NBTI improvement under low energy implantation. On the other hand, NBTI is improved by fluorine implanted in the S/D region under high energy. We propose that the two-step implantation process with high and low energy is the optimum condition for NBTI improvement.

Graphite fluoride lubrication: The effect of fluorine content, atmosphere, and burnishing technique

NASA Technical Reports Server (NTRS)

Fusaro, R. L.

1975-01-01

Eight different graphite fluoride compounds with fluorine to carbon ratios varying from x = 0.25 to 1.1 were evaluated as burnished films in order to determine the effect of fluorine content on the solid lubricant properties of graphite fluoride. For comparison, similar experiments were conducted on graphite burnished films. It was found that even a small amount of fluorine in graphite fluoride (CF sub 0.25) sub n improved the lubricating properties of graphite. Such factors as burnishing atmosphere, burnishing technique, test atmosphere, and specimen temperature affected the results as much as varying the fluorine to carbon ratio of the compound. Best life was found for films that were machine-burnished in moist air and tested in moist air.

Facing the rain after the phase out: Performance evaluation of alternative fluorinated and non-fluorinated durable water repellents for outdoor fabrics.

PubMed

Schellenberger, S; Gillgard, P; Stare, A; Hanning, A; Levenstam, O; Roos, S; Cousins, I T

2018-02-01

Fluorinated durable water repellent (DWR) agents are used to obtain water and stain repellent textiles. Due to the on-going phase-out of DWRs based on side-chain fluorinated polymers (SFP) with "long" perfluoroalkyl chains, the textile industry lacks suitable alternatives with comparable material characteristics. The constant development and optimization of SFPs for textile applications initiated more than half a century ago has resulted in a robust and very efficient DWR-technology and textiles with exceptional hydro- and oleo-phobic properties. The industry is now in the predicament that the long-chain SFPs with the best technical performance have undesirable toxicological and environmental behaviour. This study provides a comprehensive overview of the technical performance of presently available fluorinated and non-fluorinated DWRs as part of a chemical alternatives assessment (CAA). The results are based on a study with synthetic outdoor fabrics treated with alternative DWRs and tested for repellency using industrial standard and complementary methods. Using this approach, the complex structure-property relationships of DWR-polymers could be explained on a molecular level. Both short-chain SFPs and non-fluorinated DWRs showed excellent water repellency and durability in some cases while short-chain SFPs were the more robust of the alternatives to long-chain SFPs. A strong decline in oil repellency and durability with perfluoroalkyl chain length was shown for SFP DWRs. Non-fluorinated alternatives were unable to repel oil, which might limit their potential for substitution in textile application that require repellency towards non-polar liquids. Copyright © 2017. Published by Elsevier Ltd.

From toothpaste to topological insulators and materials for valleytronics: The journeys of fluorinated tin

NASA Astrophysics Data System (ADS)

Barraza-Lopez, Salvador; Rivero, Pablo; Yan, Jia-An; Garcia-Suarez, Victor Manuel; Ferrer, Jaime

2015-03-01

Tin fluoride has a vast literature. This material is stable in bulk form at room temperature and has commercial applications that include fluorinated toothpaste. Bulk tin fluoride has a pair of fluorine atoms bridging two tin atoms. In the recent past the electronic properties of 2D tin with honeycomb structure have been discussed thus generating a wealth of literature that emphasizes its non-topologically-trivial electronic properties due to the combination of a Dirac-like dispersion and a strong spin-orbit coupling given its large atomic mass. Nevertheless the stability of such freestanding structures has been contested recently. As it turns out, the most stable form of fluorinated tin does not possess a graphane-like structure either. In the most stable phase to be discussed here, fluorine atoms tilt away from (graphane-like) positions over/below tin atoms; in an atomistic arrangement similar to the one seen on their parent bulk structure. Electronic properties depend on atomistic coordination, and the most stable form of fluorinated tin does not possess non-trivial topological properties. Nevertheless it represents a new paradigm for valleytronics in 2D.

Quantification of fluorine traces in solid samples using CaF molecular emission bands in atmospheric air Laser-Induced Breakdown Spectroscopy

NASA Astrophysics Data System (ADS)

Alvarez-Llamas, C.; Pisonero, J.; Bordel, N.

2016-09-01

Direct solid determination of trace amounts of fluorine using Laser-Induced Breakdown Spectroscopy (LIBS) is a challenging task due to the low excitation efficiency of this element. Several strategies have been developed to improve the detection capabilities, including the use of LIBS in a He atmosphere to enhance the signal to background ratios of F atomic emission lines. An alternative method is based on the detection of the molecular compounds that are formed with fluorine in the LIBS plasma. In this work, the detection of CaF molecular emission bands is investigated to improve the analytical capabilities of atmospheric air LIBS for the determination of fluorine traces in solid samples. In particular, Cu matrix samples containing different fluorine concentration (between 50 and 600 μg/g), and variable amounts of Ca, are used to demonstrate the linear relationships between CaF emission signal and F concentration. Limits of detection for fluorine are improved by more than 1 order of magnitude using CaF emission bands versus F atomic lines, in atmospheric-air LIBS. Furthermore, a toothpaste powder sample is used to validate this analytical method. Good agreement is observed between the nominal and the predicted fluorine mass-content.

Chemical vapor deposition of fluorine-doped zinc oxide

DOEpatents

Gordon, Roy G.; Kramer, Keith; Liang, Haifan

2000-06-06

Fims of fluorine-doped zinc oxide are deposited from vaporized precursor compounds comprising a chelate of a dialkylzinc, such as an amine chelate, an oxygen source, and a fluorine source. The coatings are highly electrically conductive, transparent to visible light, reflective to infrared radiation, absorbing to ultraviolet light, and free of carbon impurity.

Modern Approaches for Asymmetric Construction of Carbon-Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs.

PubMed

Zhu, Yi; Han, Jianlin; Wang, Jiandong; Shibata, Norio; Sodeoka, Mikiko; Soloshonok, Vadim A; Coelho, Jaime A S; Toste, F Dean

2018-04-11

New methods for preparation of tailor-made fluorine-containing compounds are in extremely high demand in nearly every sector of chemical industry. The asymmetric construction of quaternary C-F stereogenic centers is the most synthetically challenging and, consequently, the least developed area of research. As a reflection of this apparent methodological deficit, pharmaceutical drugs featuring C-F stereogenic centers constitute less than 1% of all fluorine-containing medicines currently on the market or in clinical development. Here we provide a comprehensive review of current research activity in this area, including such general directions as asymmetric electrophilic fluorination via organocatalytic and transition-metal catalyzed reactions, asymmetric elaboration of fluorine-containing substrates via alkylations, Mannich, Michael, and aldol additions, cross-coupling reactions, and biocatalytic approaches.

Probing plasma fluorinated graphene via spectromicroscopy.

PubMed

Struzzi, C; Scardamaglia, M; Reckinger, N; Sezen, H; Amati, M; Gregoratti, L; Colomer, J-F; Ewels, C; Snyders, R; Bittencourt, C

2017-11-29

Plasma fluorination of graphene is studied using a combination of spectroscopy and microscopy techniques, giving insight into the yield and fluorination mechanism for functionalization of supported graphene with both CF 4 and SF 6 gas precursors. Ion acceleration during fluorination is used to probe the effect on grafting functionalities. Adatom clustering, which occurs with CF 4 plasma treatment, is suppressed when higher kinetic energy is supplied to the ions. During SF 6 plasma functionalization, the sulfur atoms tend to bond to bare copper areas instead of affecting the graphene chemistry, except when the kinetic energy of the ions is restricted. Using scanning photoelectron microscopy, with a 100 nm spatial resolution, the chemical bonding environment is evaluated in the fluorinated carbon network at selected regions and the functionalization homogeneity is controlled in individual graphene flakes.

Novel Synthesis of Slightly Fluorinated Graphene Quantum Dots with Luminescent and Paramagnetic Properties through Thermal Cutting of Fluorinated Graphene

PubMed Central

Feng, Qian; Xiao, Wenqing; Zheng, Yongping; Lin, Yuda; Li, Jiaxin; Ye, Qingying; Huang, Zhigao

2018-01-01

A novel approach has been developed to synthesize slightly fluorinated graphene quantum dots (GQDs-F) through thermal cutting of highly fluorinated graphene. The fluorinated graphene with substantial structure defects is fragile and is readily attacked. The direct evaporation of abundant CFn (n = 2, 3) groups near structure defects lead to the loss of adjacent skelton C atoms, and the fluorinated graphene can be thermally cut into GQDs-F with a relatively uniform nanosize in pyrolysis at 810 K. The GQDs-F with a low F/C atomic ratio of ca. 0.03 exhibit excitation wavelength-dependent properties with multicolor photoluminescence (PL) from blue to green. At the same time, F adatoms that are most likely located at the edges of GQDs-F have a high efficiency of introducing paramagnetic centres, and GQDs-F show a strong paramagnetism because of sp3-type defects and magnetic zigzag edges. The graphene quantum dots with such multimodal capabilities should have great applied value in material science. PMID:29316730

40 CFR 721.10413 - Fluorinated dialkyl ketone (generic) (P-10-135).

Code of Federal Regulations, 2012 CFR

2012-07-01

...) (P-10-135). 721.10413 Section 721.10413 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10413 Fluorinated dialkyl ketone (generic) (P-10-135). (a) Chemical... as fluorinated dialkyl ketone (PMN P-10-135) is subject to reporting under this section for the...

40 CFR 721.10413 - Fluorinated dialkyl ketone (generic) (P-10-135).

Code of Federal Regulations, 2014 CFR

2014-07-01

...) (P-10-135). 721.10413 Section 721.10413 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10413 Fluorinated dialkyl ketone (generic) (P-10-135). (a) Chemical... as fluorinated dialkyl ketone (PMN P-10-135) is subject to reporting under this section for the...

40 CFR 721.10413 - Fluorinated dialkyl ketone (generic) (P-10-135).

Code of Federal Regulations, 2013 CFR

2013-07-01

...) (P-10-135). 721.10413 Section 721.10413 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10413 Fluorinated dialkyl ketone (generic) (P-10-135). (a) Chemical... as fluorinated dialkyl ketone (PMN P-10-135) is subject to reporting under this section for the...

40 CFR 98.92 - GHGs to report.

Code of Federal Regulations, 2011 CFR

2011-07-01

... GREENHOUSE GAS REPORTING Electronics Manufacturing § 98.92 GHGs to report. (a) You must report emissions of fluorinated GHGs (as defined in § 98.6) and N2O. The fluorinated GHGs that are emitted from electronics... emitted from chemical vapor deposition and other electronics manufacturing processes. (5) Fluorinated GHGs...

[Study on the calcium-based sorbent for removal fluorine during coal combustion].

PubMed

Li, Shu-ling; Qi, Qing-jie; Liu, Jian-zhong; Cao, Xin-yu; Zhou, Jun-hu; Cen, Ke-fa

2004-03-01

In the paper, the reaction of CaO-HF and fluorine removal mechanics at high temperature by blending calcium-based sorbents with coal during coal combustion were discussed, and test results about fluorine retention during coal combustion in fluidized bed and chain-grate furnace were reported. The results identified that lime and calcium-based sorbets developed can restratin the emission of fluorine during coal combustion. The efficiency of fluorine removal can reach 66.7%-70.0% at Ca/F 60-70 by blending lime with coal in fluidized bed combustion, and the efficiency of fluorine removal are between 57.32% and 75.19% by blending calcium-based sorbets with coal in chain-grate furnace combustion. Blending CaO or lime with coal during coal combustion can remove SO2 and HF simultaneously.

Highly sensitive and selective determination of fluorine ion by graphene oxide/nanogold resonance Rayleigh scattering-energy transfer analytical platform.

PubMed

Liang, Aihui; Peng, Jing; Liu, Qingye; Wen, Guiqing; Lu, Zhujun; Jiang, Zhiliang

2015-08-15

In pH 4.0 acetate buffer solution, fluorine ions react with fluorine reagent (FR) and La(III) to generate blue ternary complex that exhibited strong absorption at about 370 nm. Upon addition of graphene oxide/nanogold (GO/NG) as resonance Rayleigh scattering (RRS) spectral probe with strong RRS peak at 370 nm, the color changed to gray, and the RRS intensity decreased with the increase of fluorine ion concentration due to the RRS energy transfer (RRSET) from GO/NG to the complex. Under the selected condition, the decreased RRS peak ΔI370 nm was linear to fluorine ion concentration in the range of 6.0 × 10(-8)-1.3 × 10(-5)mol/L, with a detection limit of 3.0 × 10(-8)mol/L F(-). This RRSET method was applied to the analysis of fluorine in toothpaste and water samples, with satisfactory results. Copyright © 2015 Elsevier Ltd. All rights reserved.

Development of Selective Colorimetric Probes for Hydrogen Sulfide Based on Nucleophilic Aromatic Substitution

PubMed Central

Montoya, Leticia A.; Pearce, Taylor F.; Hansen, Ryan J.; Zakharov, Lev N.; Pluth, Michael D.

2013-01-01

Hydrogen sulfide is an important biological signalling molecule and an important environmental target for detection. A major challenge in developing H2S detection methods is separating the often similar reactivity of thiols and other nucleophiles from H2S. To address this need, the nucleophilic aromatic substitution (SNAr) reaction of H2S with electron-poor aromatic electrophiles was developed as a strategy to separate H2S and thiol reactivity. Treatment of aqueous solutions of nitrobenzofurazan (7-nitro-1,2,3-benzoxadiazole, NBD) thioethers with H2S resulted in thiol extrusion and formation of nitrobenzofurazan thiol (λmax = 534 nm). This reactivity allows for unwanted thioether products to be converted to the desired nitrobenzofurazan thiol upon reaction with H2S. The scope of the reaction was investigated using a Hammett linear free energy relationship study, and the determined ρ = +0.34 is consistent with the proposed SN2Ar reaction mechanism. The efficacy of the developed probes was demonstrated in buffer and in serum with associated sub-micromolar detection limits as low as 190 nM (buffer) and 380 nM (serum). Furthermore, the sigmoidal response of nitrobenzofurazan electrophiles with H2S can be fit to accurately quantify H2S. The developed detection strategy offers a manifold for H2S detection that we foresee being applied in various future applications. PMID:23735055

Protein-protein conjugate nanoparticles for malaria antigen delivery and enhanced immunogenicity

PubMed Central

Scaria, Puthupparampil V.; Jones, David S.; Barnafo, Emma; Fischer, Elizabeth R.; Anderson, Charles; MacDonald, Nicholas J.; Lambert, Lynn; Rausch, Kelly M.; Narum, David L.

2017-01-01

Chemical conjugation of polysaccharide to carrier proteins has been a successful strategy to generate potent vaccines against bacterial pathogens. We developed a similar approach for poorly immunogenic malaria protein antigens. Our lead candidates in clinical trials are the malaria transmission blocking vaccine antigens, Pfs25 and Pfs230D1, individually conjugated to the carrier protein Exoprotein A (EPA) through thioether chemistry. These conjugates form nanoparticles that show enhanced immunogenicity compared to unconjugated antigens. In this study, we examined the broad applicability of this technology as a vaccine development platform, by comparing the immunogenicity of conjugates prepared by four different chemistries using different malaria antigens (PfCSP, Pfs25 and Pfs230D1), and carriers such as EPA, TT and CRM197. Several conjugates were synthesized using thioether, amide, ADH and glutaraldehyde chemistries, characterized for average molecular weight and molecular weight distribution, and evaluated in mice for humoral immunogenicity. Conjugates made with the different chemistries, or with different carriers, showed no significant difference in immunogenicity towards the conjugated antigens. Since particle size can influence immunogenicity, we tested conjugates with different average size in the range of 16–73 nm diameter, and observed greater immunogenicity of smaller particles, with significant differences between 16 and 73 nm particles. These results demonstrate the multiple options with respect to carriers and chemistries that are available for protein-protein conjugate vaccine development. PMID:29281708

Development of selective colorimetric probes for hydrogen sulfide based on nucleophilic aromatic substitution.

PubMed

Montoya, Leticia A; Pearce, Taylor F; Hansen, Ryan J; Zakharov, Lev N; Pluth, Michael D

2013-07-05

Hydrogen sulfide is an important biological signaling molecule and an important environmental target for detection. A major challenge in developing H2S detection methods is separating the often similar reactivity of thiols and other nucleophiles from H2S. To address this need, the nucleophilic aromatic substitution (SNAr) reaction of H2S with electron-poor aromatic electrophiles was developed as a strategy to separate H2S and thiol reactivity. Treatment of aqueous solutions of nitrobenzofurazan (7-nitro-1,2,3-benzoxadiazole, NBD) thioethers with H2S resulted in thiol extrusion and formation of nitrobenzofurazan thiol (λmax = 534 nm). This reactivity allows for unwanted thioether products to be converted to the desired nitrobenzofurazan thiol upon reaction with H2S. The scope of the reaction was investigated using a Hammett linear free energy relationship study, and the determined ρ = +0.34 is consistent with the proposed SN2Ar reaction mechanism. The efficacy of the developed probes was demonstrated in buffer and in serum with associated submicromolar detection limits as low as 190 nM (buffer) and 380 nM (serum). Furthermore, the sigmoidal response of nitrobenzofurazan electrophiles with H2S can be fit to accurately quantify H2S. The developed detection strategy offers a manifold for H2S detection that we foresee being applied in various future applications.

Catalytic Enantioselective Cyclization and C3-Fluorination of Polyenes

PubMed Central

Cochrane, Nikki A.; Nguyen, Ha; Gagne, Michel R.

2013-01-01

(xylyl-phanephos)Pt2+ in combination with XeF2 mediates the consecutive diastereoselective cation-olefin cyclization/fluorination of polyene substrates. Isolated yields were typically in the 60s while enantioselectivies reached as high as 87%. The data are consistent with a stereoretentive fluorination of a P2Pt-alkyl cation intermediate. PMID:23282101

THE PHASE BEHAVIOR OF FLUORINATED DIOLS, DIVINYL ADIPATE, AND A FLUORINATED POLYESTER IN SUPERCRITICAL CARBON DIOXIDE. (R828131)

EPA Science Inventory

The use of supercritical carbon dioxide as a reaction medium for polyester synthesis is hindered by the low solubility of diols in CO₂. However, it has been previously demonstrated that fluorinated compounds can exhibit greater miscibility with carbon dioxide than t...

Total fluorine, extractable organic fluorine, perfluorooctane sulfonate and other related fluorochemicals in liver of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) from South China.

PubMed

Yeung, L W Y; Miyake, Y; Wang, Y; Taniyasu, S; Yamashita, N; Lam, P K S

2009-01-01

The concentrations of 10 PFCs (perfluorinated compounds: PFOS, PFHxS, PFOSA, N-EtFOSA, PFDoDA, PFUnDA, PFDA, PFNA, PFOA, and PFHpA) were measured in liver samples of Indo-Pacific humpback dolphins (Sousa chinensis) (n=10) and finless porpoises (Neophocaena phocaenoides) (n=10) stranded in Hong Kong between 2003 and 2007. PFOS was the dominant PFC in the tissues at concentrations ranging at 26-693 ng/g ww in dolphins and 51.3-262 ng/g ww in porpoises. A newly developed combustion ion chromatography for fluorine was applied to measure total fluorine (TF) and extractable organic fluorine (EOF) in these liver samples to understand PFC contamination using the concept of mass balance analysis. Comparisons between the amounts of known PFCs and EOF in the livers showed that a large proportion (approximately 70%) of the organic fluorine in both species is of unknown origin. These investigations are critical for a comprehensive assessment of the risks of these compounds to humans and other receptors.

Negative differential resistance in partially fluorinated graphene films

NASA Astrophysics Data System (ADS)

Antonova, I. V.; Shojaei, S.; Sattari-Esfahlan, S. M.; Kurkina, Irina I.

2017-07-01

Partially fluorinated graphene films were created by chemical functionalization of graphene layers in an aqueous solution of hydrofluoric acid. The formation of graphene islands or graphene quantum dots (GQDs) and a fluorinated graphene network is demonstrated in such films. Negative differential resistance (NDR) resulting from the formation of the potential barrier system in the films was observed for different fluorination degrees of suspension. The origin of the NDR varies with an increase in the fluorination degree of the suspension. Numerical calculations were performed to elucidate the tunneling between adjacent energy levels and creation of NDR. It was found that in the case of films with smaller flake and smaller GQD sizes, multi-peak NDR appears in the I-V curve. We predict that the NDR peak position shifts towards lower voltage with a decrease in the GQD size. Surprisingly, we observed a negative step-like valley for positive biases in the I-V curve of samples. Our findings with detailed analysis shed light on understanding the mechanisms of the NDR phenomenon in a partially fluorinated graphene system.

X-ray photoelectron spectroscopy as detection tool for coordinated or uncoordinated fluorine atoms demonstrated on fluoride systems NaF, K2TaF7, K3TaF8, K2ZrF6, Na7Zr6F31 and K3ZrF7

NASA Astrophysics Data System (ADS)

Boča, Miroslav; Barborík, Peter; Mičušík, Matej; Omastová, Mária

2012-07-01

While systems K3TaF8 and K3ZrF7 were prepared by modified molten salt method modified wet pathway was used for reproducible preparation of Na7Zr6F31. Its congruently melting character was demonstrated on simultaneous TG/DSC measurements and XRD patterns. X-ray photoelectron spectroscopy was applied for identification of differently bonded fluorine atoms in series of compounds NaF, K2TaF7, K3TaF8, K2ZrF6, Na7Zr6F31 and K3ZrF7. Three different types of fluorine atoms were described qualitatively and quantitatively. Uncoordinated fluorine atoms (F-) provide signals at lowest binding energies, followed by signals from terminally coordinated fluorine atoms (M-F) and then bridging fluorine atoms (M-F-M) at highest energy. Based on XPS F 1s signals assigned to fluorine atoms in compounds with correctly determined structure it was suggested that fluorine atoms in K3ZrF7 have partially bridging character.

Fluorine in the solar neighborhood: Chemical evolution models

NASA Astrophysics Data System (ADS)

Spitoni, E.; Matteucci, F.; Jönsson, H.; Ryde, N.; Romano, D.

2018-04-01

Context. In light of new observational data related to fluorine abundances in solar neighborhood stars, we present chemical evolution models testing various fluorine nucleosynthesis prescriptions with the aim to best fit those new data. Aim. We consider chemical evolution models in the solar neighborhood testing various nucleosynthesis prescriptions for fluorine production with the aim of reproducing the observed abundance ratios [F/O] versus [O/H] and [F/Fe] versus [Fe/H]. We study in detail the effects of various stellar yields on fluorine production. Methods: We adopted two chemical evolution models: the classical two-infall model, which follows the chemical evolution of halo-thick disk and thin disk phases; and the one-infall model, which is designed only for thin disk evolution. We tested the effects on the predicted fluorine abundance ratios of various nucleosynthesis yield sources, that is, asymptotic giant branch (AGB) stars, Wolf-Rayet (W-R) stars, Type II and Type Ia supernovae, and novae. Results: The fluorine production is dominated by AGB stars but the W-R stars are required to reproduce the trend of the observed data in the solar neighborhood with our chemical evolution models. In particular, the best model both for the two-infall and one-infall cases requires an increase by a factor of 2 of the W-R yields. We also show that the novae, even if their yields are still uncertain, could help to better reproduce the secondary behavior of F in the [F/O] versus [O/H] relation. Conclusions: The inclusion of the fluorine production by W-R stars seems to be essential to reproduce the new observed ratio [F/O] versus [O/H] in the solar neighborhood. Moreover, the inclusion of novae helps to reproduce the observed fluorine secondary behavior substantially.

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

NASA Astrophysics Data System (ADS)

Li, Lijie; Cocker, David R.

2018-05-01

Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA formation.

Defeating Leishmania resistance to miltefosine (hexadecylphosphocholine) by peptide-mediated drug smuggling: a proof of mechanism for trypanosomatid chemotherapy.

PubMed

Luque-Ortega, Juan Román; de la Torre, Beatriz G; Hornillos, Valentín; Bart, Jean-Mathieu; Rueda, Cristina; Navarro, Miguel; Amat-Guerri, Francisco; Acuña, A Ulises; Andreu, David; Rivas, Luis

2012-08-10

Miltefosine (hexadecylphosphocholine, HePC), the first orally active drug successful against leishmaniasis, is especially active on the visceral form of the disease. Resistance mechanisms are almost exclusively associated to dysfunction in HePC uptake systems. In order to evade the requirements of its cognate receptor/translocator, HePC-resistant Leishmania donovani parasites (R40 strain) were challenged with constructs consisting of an ω-thiol-functionalized HePC analogue conjugated to the cell-penetrating peptide (CPP) Tat(48-60), either through a disulfide or a thioether bond. The conjugates enter and kill both promastigote and intracellular amastigote forms of the R40 strain. Intracellular release of HePC by reduction of the disulfide-based conjugate was confirmed by means of double tagging at both the CPP (Quasar 670) and HePC (BODIPY) moieties. Scission of the conjugate, however, is not mandatory, as the metabolically more stable thioether conjugate retained substantial activity. The disulfide conjugate is highly active on the bloodstream form of Trypanosoma b. brucei, naturally resistant to HePC. Our results provide proof-of-mechanism for the use of CPP conjugates to avert drug resistance by faulty drug accumulation in parasites, as well as the possibility to extend chemotherapy into other parasites intrinsically devoid of membrane translocation systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Domino-Fluorination-Protodefluorination Enables Decarboxylative Cross-Coupling of α-Oxocarboxylic Acids with Styrene via Photoredox Catalysis.

PubMed

Zhang, Muliang; Xi, Junwei; Ruzi, Rehanguli; Li, Nan; Wu, Zhongkai; Li, Weipeng; Zhu, Chengjian

2017-09-15

Domino-fluorination-protodefluorination decarboxylative cross-coupling of α-keto acids with styrene has been developed via photoredox catalysis. The critical part of this strategy is the formation of the carbon-fluorine (C-F) bond by the capture of a carbon-centered radical intermediate, which will overcome side reactions during the styrene radical functionalization process. Experimental studies have provided evidence indicating a domino-fluorination-protodefluorination pathway with α-keto acid initiating the photoredox cycle. The present catalytic protocol also affords a novel approach for the construction of α,β-unsaturated ketones under mild conditions.

Catalytic oxidation of dimethyl ether

DOEpatents

Zelenay, Piotr; Wu, Gang; Johnston, Christina M.; Li, Qing

2016-05-10

A composition for oxidizing dimethyl ether includes an alloy supported on carbon, the alloy being of platinum, ruthenium, and palladium. A process for oxidizing dimethyl ether involves exposing dimethyl ether to a carbon-supported alloy of platinum, ruthenium, and palladium under conditions sufficient to electrochemically oxidize the dimethyl ether.

Isolation and characterization of an ether-type polyurethane-degrading micro-organism and analysis of degradation mechanism by Alternaria sp.

PubMed

Matsumiya, Y; Murata, N; Tanabe, E; Kubota, K; Kubo, M

2010-06-01

To degrade ether-type polyurethane (ether-PUR), ether-PUR-degrading micro-organism was isolated. Moreover, ether-PUR-degrading mechanisms were analysed using model compounds of ether-PUR. A fungus designated as strain PURDK2, capable of changing the configuration of ether-PUR, has been isolated. This isolated fungus was identified as Alternaria sp. Using a scanning electron microscope, the grid structure of ether-PUR was shown to be melted and disrupted by the fungus. The degradation of ether-PUR by the fungus was analysed, and the ether-PUR was degraded by the fungus by about 27.5%. To analyse the urethane-bond degradation by the fungus, a degraded product of ethylphenylcarbamate was analysed using GC/MS. Aniline and ethanol were detected by degradation with the supernatant, indicating that the fungus secreted urethane-bond-degrading enzyme(s). PURDK2 also degraded urea bonds when diphenylmethane-4,4'-dibutylurea was used as a substrate. The enzyme(s) from PURDK2 degraded urethane and urea bonds to convert the high molecular weight structure of ether-PUR to small molecules; and then the fungus seems to use the small molecules as an energy source. Ether-PUR-degrading fungus, strain PURDK2, was isolated, and the urethane- and urea-bonds-degrading enzymes from strain PURDK2 could contribute to the material recycling of ether-PUR.

A new route to synthesize aryl acetates from carbonylation of aryl methyl ethers

PubMed Central

Yang, Youdi; Li, Shaopeng; Han, Buxing

2018-01-01

Ether bond activation is very interesting because the synthesis of many valuable compounds involves conversion of ethers. Moreover, C–O bond cleavage is also very important for the transformation of biomass, especially lignin, which abundantly contains ether bonds. Developing efficient methods to activate aromatic ether bonds has attracted much attention. However, this is a challenge because of the inertness of aryl ether bonds. We proposed a new route to activate aryl methyl ether bonds and synthesize aryl acetates by carbonylation of aryl methyl ethers. The reaction could proceed over RhCl3 in the presence of LiI and LiBF4, and moderate to high yields of aryl acetates could be obtained from transformation of various aryl methyl ethers with different substituents. It was found that LiBF4 could assist LiI to cleave aryl methyl ether bonds effectively. The reaction mechanism was proposed by a combination of experimental and theoretical studies. PMID:29795781

Molecular Dynamics Pinpoint the Global Fluorine Effect in Balanoid Binding to PKCε and PKA.

PubMed

Hardianto, Ari; Liu, Fei; Ranganathan, Shoba

2018-02-26

(-)-Balanol is an adenosine triphosphate mimic that inhibits protein kinase C (PKC) isozymes and cAMP-dependent protein kinase (PKA) with limited selectivity. While PKA is known as a tumor promoter, PKC isozymes can be tumor promoters or suppressors. In particular, PKCε is frequently involved in tumorigenesis and a potential target for anticancer drugs. We recently reported that stereospecific fluorination of balanol yielded a balanoid with enhanced selectivity for PKCε over other PKC isozymes and PKA, although the global fluorine effect behind the selectivity enhancement is not fully understood. Interestingly, in contrast to PKA, PKCε is more sensitive to this fluorine effect. Here we investigate the global fluorine effect on the different binding responses of PKCε and PKA to balanoids using molecular dynamics (MD) simulations. For the first time to the best of our knowledge, we found that a structurally equivalent residue in each kinase, Thr184 in PKA and Ala549 in PKCε, is essential for the different binding responses. Furthermore, the study revealed that the invariant Lys, Lys73 in PKA and Lys437 in PKCε, already known to have a crucial role in the catalytic activity of kinases, serves as the main anchor for balanol binding. Overall, while Thr184 in PKA attenuates the effect of fluorination, Ala549 permits remote response of PKCε to fluorine substitution, with implications for rational design of future balanol-based PKCε inhibitors.

Effects of Interfacial Fluorination on Performance Enhancement of High-k-Based Charge Trap Flash Memory

NASA Astrophysics Data System (ADS)

Wang, Chenjie; Huo, Zongliang; Liu, Ziyu; Liu, Yu; Cui, Yanxiang; Wang, Yumei; Li, Fanghua; Liu, Ming

2013-07-01

The effects of interfacial fluorination on the metal/Al2O3/HfO2/SiO2/Si (MAHOS) memory structure have been investigated. By comparing MAHOS memories with and without interfacial fluorination, it was identified that the deterioration of the performance and reliability of MAHOS memories is mainly due to the formation of an interfacial layer that generates excess oxygen vacancies at the interface. Interfacial fluorination suppresses the growth of the interfacial layer, which is confirmed by X-ray photoelectron spectroscopy depth profile analysis, increases enhanced program/erase efficiency, and improves data retention characteristics. Moreover, it was observed that fluorination at the SiO-HfO interface achieves a more effective performance enhancement than that at the HfO-AlO interface.

Compilation of Requirements for Safe Handling of Fluorine and Fluorine-Containing Products of Uranium Hexafluoride Conversion

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

Ferrada, J.J.

2000-04-03

Public Law (PL) 105-204 requires the U.S. Department of Energy to develop a plan for inclusion in the fiscal year 2000 budget for conversion of the Department's stockpile of depleted uranium hexafluoride (DUF{sub 6}) to a more stable form over an extended period. The conversion process into a more stable form will produce fluorine compounds (e.g., elemental fluorine or hydrofluoric acid) that need to be handled safely. This document compiles the requirements necessary to handle these materials within health and safety standards, which may apply in order to ensure protection of the environment and the safety and health of workersmore » and the public. Fluorine is a pale-yellow gas with a pungent, irritating odor. It is the most reactive nonmetal and will react vigorously with most oxidizable substances at room temperature, frequently with ignition. Fluorine is a severe irritant of the eyes, mucous membranes, skin, and lungs. In humans, the inhalation of high concentrations causes laryngeal spasm and broncospasms, followed by the delayed onset of pulmonary edema. At sublethal levels, severe local irritation and laryngeal spasm will preclude voluntary exposure to high concentrations, unless the individual is trapped or incapacitated. A blast of fluorine gas on the shaved skin of a rabbit causes a second degree burn. Lower concentrations cause severe burns of insidious onset, resulting in ulceration, similar to the effects produced by hydrogen fluoride. Hydrofluoric acid is a colorless, fuming liquid or gas with a pungent odor. It is soluble in water with release of heat. Ingestion of an estimated 1.5 grams produced sudden death without gross pathological damage. Repeated ingestion of small amounts resulted in moderately advanced hardening of the bones. Contact of skin with anhydrous liquid produces severe burns. Inhalation of AHA or aqueous hydrofluoric acid mist or vapors can cause severe respiratory tract irritation that may be fatal. Based on the extreme chemical properties of these chemicals as noted above, fluorine or fluorine compounds must be handled appropriately within the boundaries of many safety requirements for the protection of the environment and the public. This report analyzes the safety requirements that regulatory agencies have issued to handle fluorine or fluorine compounds and lists them in Table 1. Table 1 lists the source of the requirements, the specific section of the source document, and a brief description of the requirements.« less

Low-Absorption Liquid Crystals for Infrared Beam Steering

DTIC Science & Technology

2013-10-22

Low absorption, MWIR, chlorinated liquid crystals, fluorination, FTIR, eutectic mixture, deuteration, nematic phase, birefringence, overtone...absorption compounds for LWIR and SWIR are also investigated. Key words: Low absorption, MWIR, chlorinated liquid crystals, fluorination, FTIR, eutectic ...the melting point significantly. We did careful investigation and formed a eutectic mixture consisting of five fluorinated compounds without any

Volcanogenic fluorine in rainwater around active degassing volcanoes: Mt. Etna and Stromboli Island, Italy.

PubMed

Bellomo, S; D'Alessandro, W; Longo, M

2003-01-01

Many studies have assessed the strong influence of volcanic activity on the surrounding environment. This is particularly true for strong gas emitters such as Mt. Etna and Stromboli volcanoes. Among volcanic gases, fluorine compounds are potentially very harmful. Fluorine cycling through rainwater in the above volcanic areas was studied analysing more than 400 monthly bulk samples. Data indicate that only approximately 1% of fluorine emission through the plume is deposited on the two volcanic areas by meteoric precipitations. Although measured bulk rainwater fluorine fluxes are comparable to and sometimes higher than in heavily polluted areas, their influence on the surrounding vegetation is limited. Only annual crops, in fact, show some damage that could be an effect of fluorine deposition, indicating that long-living endemic plant species or varieties have developed some kind of resistance. Copyright 2002 Elsevier Science B.V.

Photoemission studies of fluorine functionalized porous graphitic carbon

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

Ganegoda, Hasitha; Olive, Daniel; Cheng, Lidens

2012-03-01

Porous graphitic carbon (PGC) has unique properties desirable for liquid chromatography applications when used as a stationary phase. The polar retention effect on graphite (PREG) allows efficient separation of polar and non-polar solutes. Perfluorinated hydrocarbons however lack polarizabilty and display strong lipo- and hydrophobicity, hence common lipophilic and hydrophilic analytes have low partition coefficiency in fluorinated stationary phases. Attractive interaction between fluorinated stationary phase and fluorinated analytes results in strong retention compared to non-fluorinated analytes. In order to change the selectivities of PGC, it is necessary to develop a bonded PGC stationary phase. In this study, we have synthesized perfluorinated,more » PGC using hepatadecafluoro-1-iodooctane, under different temperature conditions. Surface functionalization of the raw material was studied using photoelectron spectroscopy (PES). Results indicate the existence of fluorine containing functional groups, -CF, -CF{sub 2} along with an intercalated electron donor species. Multiple oxygen functional groups were also observed, likely due to the presence of oxygen in the starting material. These oxygen species may be responsible for significant modifications to planer and tetrahedral carbon ratios.« less

Hypervalent iodine-promoted α-fluorination of acetophenone derivatives with a triethylamine·HF complex.

PubMed

Kitamura, Tsugio; Muta, Kensuke; Muta, Kazutaka

2014-06-20

The direct fluorination reaction of acetophenone using iodosylarenes and TEA·5HF was conducted under mild conditions except for use of a HF reagent. The fluorination reaction was applied to acetophenone derivatives, acetonaphthones, benzyl phenyl ketone, propiophenone, butyrophenone, 1-indanone, and phenacyl chloride, giving selectively the corresponding α-fluoroketone derivatives in good yields.

Graphite fluoride fibers and their applications in the space industry

NASA Technical Reports Server (NTRS)

Hung, Ching-Chen; Long, Martin; Dever, Therese

1990-01-01

Characterization and potential space applications of graphite fluoride fibers from commercially available graphitized carbon fibers are presented. Graphite fluoride fibers with fluorine to carbon ratios of 0.65 and 0.68 were found to have electrical resistivity values of 10(exp 4) and 10(exp 11) Ohms-cm, respectively, and thermal conductivity values of 24 and 5 W/m-K, respectively. At this fluorine content range, the fibers have tensile strength of 0.25 + or - 0.10 GPa (36 + or - 14 ksi), Young's modulus of 170 + or - 30 GPa (25 + or - 5 Msi). The coefficient of thermal expansion value of a sample with fluorine to carbon ratio of 0.61 was found to be 7 ppm/C. These properties change and approach the graphite value as the fluorine content approach 0. Electrically insulative graphite fluoride fiber is at least five times more thermally conductive than fiberglass. Therefore, it can be used as a heat sinking printed circuit board material for low temperature, long life power electronics in spacecraft. Also, partially fluorinated fiber with tailor-made physical properties to meet the requirements of certain engineering design can be produced. For example, a partially fluorinated fiber could have a predetermined CTE value in -1.5 to 7 ppm/C range and would be suitable for use in solar concentrators in solar dynamic power systems. It could also have a predetermined electrical resistivity value suitable for use as a low observable material. Experimental data indicate that slightly fluorinated graphite fibers are more durable in the atomic oxygen environment than pristine graphite. Therefore, fluorination of graphite used in the construction of spacecraft that would be exposed to the low Earth orbit atomic oxygen may protect defect sites in atomic oxygen protective coatings and therefore decrease the rate of degradation of graphite.

Radionuclide-binding compound, a radionuclide delivery system, a method of making a radium complexing compound, a method of extracting a radionuclide, and a method of delivering a radionuclide

DOEpatents

Fisher, Darrell R.; Wai, Chien M.; Chen, Xiaoyuan

2000-01-01

The invention pertains to compounds which specifically bind radionuclides, and to methods of making radionuclide complexing compounds. In one aspect, the invention includes a radionuclide delivery system comprising: a) a calix[n]arene-crown-[m]-ether compound, wherein n is an integer greater than 3, and wherein m is an integer greater than 3, the calix[n]arene-crown-[m]-ether compound comprising at least two ionizable groups; and b) an antibody attached to the calix[n]arene-crown-[m]-ether compound. In another aspect, the invention includes a method of making a radium complexing compound, comprising: a) providing a calix[n]arene compound, wherein n is an integer greater than 3, the calix[n]arene compound comprising n phenolic hydroxyl groups; b) providing a crown ether precursor, the crown ether precursor comprising a pair of tosylated ends; c) reacting the pair of tosylated ends with a pair of the phenolic hydroxyl groups to convert said pair of phenolic hydroxyl groups to ether linkages, the ether linkages connecting the crown ether precursor to the calix[n]arene to form a calix[n]arene-crown-[m]-ether compound, wherein m is an integer greater than 3; d) converting remaining phenolic hydroxyl groups to esters; e) converting the esters to acids, the acids being proximate a crown-[m]-ether portion of the calix[n]arene-crown-[m]-ether compound; and f) providing a Ra.sup.2+ ion within the crown-[m]-ether portion of the calix[n]arene-crown-[m]-ether compound.

Systems and methods for treating material

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

Scheele, Randall D; McNamara, Bruce K

Systems for treating material are provided that can include a vessel defining a volume, at least one conduit coupled to the vessel and in fluid communication with the vessel, material within the vessel, and NF.sub.3 material within the conduit. Methods for fluorinating material are provided that can include exposing the material to NF.sub.3 to fluorinate at least a portion of the material. Methods for separating components of material are also provided that can include exposing the material to NF.sub.3 to at least partially fluorinate a portion of the material, and separating at least one fluorinated component of the fluorinated portionmore » from the material. The materials exposed to the NF.sub.3 material can include but are not limited to one or more of U, Ru, Rh, Mo, Tc, Np, Pu, Sb, Ag, Am, Sn, Zr, Cs, Th, and/or Rb.« less

Assessment of arsenic and fluorine in surface soil to determine environmental and health risk factors in the Comarca Lagunera, Mexico.

PubMed

Sariñana-Ruiz, Yareli A; Vazquez-Arenas, Jorge; Sosa-Rodríguez, Fabiola S; Labastida, Israel; Armienta, Ma Aurora; Aragón-Piña, Antonio; Escobedo-Bretado, Miguel A; González-Valdez, Laura S; Ponce-Peña, Patricia; Ramírez-Aldaba, Hugo; Lara, René H

2017-07-01

Total, bioaccessible and mobile concentrations of arsenic and fluorine are determined in polluted surface soil within the Comarca Lagunera region using standardized protocols to obtain a full description of the environmental behavior for these elements. The composition of mineral phases associated with them is evaluated with microscopic and spectroscopic techniques. Mineralogical characterizations indicate that ultra-fine particles (<1-5 μm) including mimetite-vanadite (Pb 5 (AsO 4 ) 3 Cl, Pb 5 (AsO 4 , VO 4 ) 3 Cl)-like, lead arseniate (Pb 3 (AsO 4 ) 2 )-like and complex arsenic-bearing compounds are main arsenic-bearing phases, while fluorite (CaF 2 ) is the only fluorine-bearing phase. Total fluorine and arsenic concentrations in surface soil range from 89.75 to 926.63 and 2.7-78.6 mg kg -1 , respectively, exceeding in many points a typical baseline value for fluorine (321 mg kg -1 ), and trigger level criterion for arsenic soil remediation (20 mg kg -1 ); whereas fluoride and arsenic concentrations in groundwater vary from 0.24 to 1.8 mg L -1 and 0.12-0.650 mg L -1 , respectively. The main bioaccessible percentages of soil in the gastric phase (SBRC-G) are estimated for arsenic from 1 to 63%, and this parameter in the intestinal phase (SBRC-I) fluorine from 2 to 46%, suggesting human health risks for this region. While a negligible/low mobility is found in soil for arsenic (0.1-11%), an important mobility is determined for fluorine (2-39%), indicating environmental risk related to potential fluorine release. The environmental and health risks connected to arsenic and fluorine are discussed based on experimental data. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetic Monte Carlo simulations of fluorine and vacancies concentration at the CeO2(111) surface

NASA Astrophysics Data System (ADS)

Mattiello, S.; Kolling, S.; Heiliger, C.

2017-09-01

Recently, a new identification of the experimental depressions of scanning tunnelling microscopy images on the {{CeO}}2(111) surface as fluorine impurities has been proposed in Kullgren et al (2014 Phys. Rev. Lett. 112 156102). In particular, the high immobility of the depressions seems to be in contradiction with the low diffusion barrier for the oxygen vacancies. Consequently, the oxygen vacancies concentration has to disappear. The first aim of this paper is to confirm dynamically the recent interpretation of the experimental finding. For this purpose, we investigate the competition between fluorine and oxygen vacancies using two dimensional kinetic Monte Carlo simulations (kMC) as compared to an appropriate Langmuir model. We calculate the concentration of the vacancies and of the fluorine for the surface (111) of {{CeO}}2 for a UHV condition as a function of the fluorine-oxygen mixture in the gas phase as well as of the binding energies of fluorine and oxygen. We found that at a temperature of T=573 {{K}}, at which the experimental measurements were conducted, vacancies cannot exist. This confirms the possibility of fluorine impurities in Kullgren et al (2014 Phys. Rev. Lett. 112 156102). The second aim of the present paper is to perform a first dynamical estimation of the fluorine binding energy value {E}{Fl} that allows one to describe the experimental data in Pieper et al (2012 Phys. Chem. Chem. Phys. 14 15361). Using 2D-kMC simulations, we found {E}{Fl}\\in [-5.53,-5.27] {eV} which can be used for comparison to density functional theory calculations in further works.

Experiments shed new light on nickel-fluorine reactions

NASA Technical Reports Server (NTRS)

Fischer, J.; Gunther, W.; Jarry, R. L.

1967-01-01

Isotopic tracer experiments and scale-impingement experiments show fluorine to be the migrating species through the nickel fluoride scale formed during the fluorination of nickel. This is in contrast to nickel oxide scales, where nickel is the migrating species.

Poly(arylene ether)s containing pendent ethynyl groups

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Jensen, Brian J. (Inventor)

1996-01-01

Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350.degree. C. to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

Poly(arylene ether)s containing pendent ethynyl groups

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Jensen, Brian J. (Inventor)

1994-01-01

Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350 C to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

19F DOSY NMR analysis for spin systems with nJFF couplings.

PubMed

Dal Poggetto, Guilherme; Favaro, Denize C; Nilsson, Mathias; Morris, Gareth A; Tormena, Cláudio F

2014-04-01

NMR is a powerful method for identification and quantification of drug components and contaminations. These problems present themselves as mixtures, and here, one of the most powerful tools is DOSY. DOSY works best when there is no spectral overlap between components, so drugs containing fluorine substituents are well-suited for DOSY analysis as (19)F spectra are typically very sparse. Here, we demonstrate the use of a modified (19)F DOSY experiment (on the basis of the Oneshot sequences) for various fluorinated benzenes. For compounds with significant (n) JFF coupling constants, as is common, the undesirable J-modulation can be efficiently suppressed using the Oneshot45 pulse sequence. This investigation highlights (19)F DOSY as a valuable and robust method for analysis of molecular systems containing fluorine atoms even where there are large fluorine-fluorine couplings. Copyright © 2014 John Wiley & Sons, Ltd.

Fluorination-enabled optimal morphology leads to over 11% efficiency for inverted small-molecule organic solar cells

PubMed Central

Deng, Dan; Zhang, Yajie; Zhang, Jianqi; Wang, Zaiyu; Zhu, Lingyun; Fang, Jin; Xia, Benzheng; Wang, Zhen; Lu, Kun; Ma, Wei; Wei, Zhixiang

2016-01-01

Solution-processable small molecules for organic solar cells have attracted intense attention for their advantages of definite molecular structures compared with their polymer counterparts. However, the device efficiencies based on small molecules are still lower than those of polymers, especially for inverted devices, the highest efficiency of which is <9%. Here we report three novel solution-processable small molecules, which contain π-bridges with gradient-decreased electron density and end acceptors substituted with various fluorine atoms (0F, 1F and 2F, respectively). Fluorination leads to an optimal active layer morphology, including an enhanced domain purity, the formation of hierarchical domain size and a directional vertical phase gradation. The optimal morphology balances charge separation and transfer, and facilitates charge collection. As a consequence, fluorinated molecules exhibit excellent inverted device performance, and an average power conversion efficiency of 11.08% is achieved for a two-fluorine atom substituted molecule. PMID:27991486

HPLC-Based Mass Spectrometry Characterizes the Phospholipid Alterations in Ether-Linked Lipid Deficiency Models Following Oxidative Stress

PubMed Central

Drechsler, Robin; Chen, Shaw-Wen; Dancy, Blair C. R.; Mehrabkhani, Lena

2016-01-01

Despite the fact that the discovery of ether-linked phospholipids occurred nearly a century ago, many unanswered questions remain concerning these unique lipids. Here, we characterize the ether-linked lipids of the nematode with HPLC-MS/MS and find that more than half of the phosphoethanolamine-containing lipids are ether-linked, a distribution similar to that found in mammalian membranes. To explore the biological role of ether lipids in vivo, we target fatty acyl-CoA reductase (fard-1), an essential enzyme in ether lipid synthesis, with two distinct RNAi strategies. First, when fard-1 RNAi is initiated at the start of development, the treated animals have severely reduced ether lipid abundance, resulting in a shift in the phosphatidylethanolamine lipid population to include more saturated fatty acid chains. Thus, the absence of ether lipids during development drives a significant remodeling of the membrane landscape. A later initiation of fard-1 RNAi in adulthood results in a dramatic reduction of new ether lipid synthesis as quantified with 15N-tracers; however, there is only a slight decrease in total ether lipid abundance with this adult-only fard-1 RNAi. The two RNAi strategies permit the examination of synthesis and ether lipid abundance to reveal a relationship between the amount of ether lipids and stress survival. We tested whether these species function as sacrificial antioxidants by directly examining the phospholipid population with HPLC-MS/MS after oxidative stress treatment. While there are significant changes in other phospholipids, including polyunsaturated fatty acid-containing species, we did not find any change in ether-linked lipids, suggesting that the role of ether lipids in stress resistance is not through their general consumption as free radical sinks. Our work shows that the nematode will be a useful model for future interrogation of ether lipid biosynthesis and the characterization of phospholipid changes in various stress conditions. PMID:27893806

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

Not Available

Phillips Petroleum Co. is poised to license its high conversion process to produce fuel ethers for blending in reformulated gasolines. The technology has been proven in a Phillips semiworks at Bartlesville, Okla. The process can produce methyl tertiary butyl ether, ethyl tertiary butyl ether, tertiary amyl methyl ether, or tertiary amyl ethyl ether with typical refinery process equipment and techniques. Phillips said it can achieve conversion levels of 92-99%, depending on the ether. The ether produced is determined by which hydrocarbon fraction is used for feedstock and which alcohol is chosen for reaction. The process is described.

Ultrahydrophobic Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS) (Preprint)

DTIC Science & Technology

2007-01-25

From - To) 25-01-2007 Journal Article 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Ultrahydrophobic Fluorinated Polyhedral Oligomeric Silsesquioxanes...Ultrahydrophobic Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS) Joseph M. Mabry,* Ashwani Vij,* Scott T. Iacono, and Brent D. Viers Recently...there exists a demand to construct ultrahydrophobic materials inspired by nature that are easy to prepare on a large scale. Polyhedral oligomeric

Method for fluorination of uranium oxide

DOEpatents

Petit, George S.

1987-01-01

Highly pure uranium hexafluoride is made from uranium oxide and fluorine. The uranium oxide, which includes UO.sub.3, UO.sub.2, U.sub.3 O.sub.8 and mixtures thereof, is introduced together with a small amount of a fluorine-reactive substance, selected from alkali chlorides, silicon dioxide, silicic acid, ferric oxide, and bromine, into a constant volume reaction zone. Sufficient fluorine is charged into the zone at a temperature below approximately 0.degree. C. to provide an initial pressure of at least approximately 600 lbs/sq. in. at the ambient atmospheric temperature. The temperature is then allowed to rise in the reaction zone until reaction occurs.

Examination of fluorination effect on physical properties of saturated long-chain alcohols by DSC and Langmuir monolayer.

PubMed

Nakahara, Hiromichi; Nakamura, Shohei; Okahashi, Yoshinori; Kitaguchi, Daisuke; Kawabata, Noritake; Sakamoto, Seiichi; Shibata, Osamu

2013-02-01

Partially fluorinated long-chain alcohols have been newly synthesized from a radical reaction, which is followed by a reductive reaction. The fluorinated alcohols have been investigated by differential scanning calorimetry (DSC) and compression isotherms in a Langmuir monolayer state. Their melting points increase with an increase in chain length due to elongation of methylene groups. However, the melting points for the alcohols containing shorter fluorinated moieties are lower than those for the typical hydrogenated fatty alcohols. Using the Langmuir monolayer technique, surface pressure (π)-molecular area (A) and surface potential (ΔV)-A isotherms of monolayers of the fluorinated alcohols have been measured in the temperature range from 281.2 to 303.2K. In addition, a compressibility modulus (Cs(-1)) is calculated from the π-A isotherms. Four kinds of the alcohol monolayers show a phase transition (π(eq)) from a disordered to an ordered state upon lateral compression. The π(eq) values increase linearly with increasing temperatures. A slope of π(eq) against temperature for the alcohols with shorter fluorocarbons is unexpectedly larger than that for the corresponding fatty alcohols. Generally, fluorinated amphiphiles have a greater thermal stability (or resistance), which is a characteristic of highly fluorinated or perfluorinated compounds. Herein, however, the alcohols containing perfluorobutylated and perfluorohexylated chains show the irregular thermal behavior in both the solid and monolayer states. Copyright © 2012 Elsevier B.V. All rights reserved.

Rational Design of Orthogonal Multipolar Interactions with Fluorine in Protein–Ligand Complexes

DOE PAGES

Pollock, Jonathan; Borkin, Dmitry; Lund, George; ...

2015-08-19

Multipolar interactions involving fluorine and the protein backbone have been frequently observed in protein–ligand complexes. Such fluorine–backbone interactions may substantially contribute to the high affinity of small molecule inhibitors. Here we found that introduction of trifluoromethyl groups into two different sites in the thienopyrimidine class of menin–MLL inhibitors considerably improved their inhibitory activity. In both cases, trifluoromethyl groups are engaged in short interactions with the backbone of menin. In order to understand the effect of fluorine, we synthesized a series of analogues by systematically changing the number of fluorine atoms, and we determined high-resolution crystal structures of the complexes withmore » menin. Here, we found that introduction of fluorine at favorable geometry for interactions with backbone carbonyls may improve the activity of menin–MLL inhibitors as much as 5- to 10-fold. In order to facilitate the design of multipolar fluorine–backbone interactions in protein–ligand complexes, we developed a computational algorithm named FMAP, which calculates fluorophilic sites in proximity to the protein backbone. We demonstrated that FMAP could be used to rationalize improvement in the activity of known protein inhibitors upon introduction of fluorine. Furthermore, FMAP may also represent a valuable tool for designing new fluorine substitutions and support ligand optimization in drug discovery projects. Analysis of the menin–MLL inhibitor complexes revealed that the backbone in secondary structures is particularly accessible to the interactions with fluorine. Lastly, considering that secondary structure elements are frequently exposed at protein interfaces, we postulate that multipolar fluorine–backbone interactions may represent a particularly attractive approach to improve inhibitors of protein–protein interactions.« less

Radiation Durability of Candidate Polymer Films for the Next Generation Space Telescope Sunshield

NASA Technical Reports Server (NTRS)

Dever, Joyce; Semmel, Charles; Edwards, David; Messer, Russell; Peters, Wanda; Carter, Amani; Puckett, David

2002-01-01

The Next Generation Space Telescope (NGST), anticipated to be launched in 2009 for a 10-year mission, will make observations in the infrared portion of the spectrum to examine the origins and evolution of our universe. Because it must operate at cold temperatures in order to make these sensitive measurements, it will use a large, lightweight, deployable sunshield, comprised of several polymer film layers, to block heat and stray light. This paper describes laboratory radiation durability testing of candidate NGST sunshield polymer film materials. Samples of fluorinated polyimides CP1 and CP2, and a polvarylene ether benzimidazole. TOR-LM(TM), were exposed to 40 keV electron and 40 keV proton radiation followed by exposure to vacuum ultraviolet (VUV) radiation in the 115 to 200 nm wavelength range. Samples of these materials were also exposed to VUV without prior electron and proton exposure. Samples of polyimides Kapton HN, Kapton E, and Upilex-S were exposed to electrons and protons only, due to limited available exposure area in the VUV facility. Exposed samples were evaluated for changes in solar absorptance and thermal emittance and mechanical properties of ultimate tensile strength and elongation at failure. Data obtained are compared with previously published data for radiation durability testing of these polymer film materials.

Effects of Aqueous Film-Forming Foams (AFFFs) on Trichloroethene (TCE) Dechlorination by a Dehalococcoides mccartyi-Containing Microbial Community.

PubMed

Harding-Marjanovic, Katie C; Yi, Shan; Weathers, Tess S; Sharp, Jonathan O; Sedlak, David L; Alvarez-Cohen, Lisa

2016-04-05

The application of aqueous film-forming foams (AFFFs) to extinguish chlorinated solvent-fueled fires has led to the co-contamination of poly- and perfluoroalkyl substances (PFASs) and trichloroethene (TCE) in groundwater and soil. Although reductive dechlorination of TCE by Dehalococcoides mccartyi is a frequently used remediation strategy, the effects of AFFF and PFASs on TCE dechlorination are not well-understood. Various AFFF formulations, PFASs, and ethylene glycols were amended to the growth medium of a D. mccartyi-containing enrichment culture to determine the impact on dechlorination, fermentation, and methanogenesis. The community was capable of fermenting organics (e.g., diethylene glycol butyl ether) in all AFFF formulations to hydrogen and acetate, but the product concentrations varied significantly according to formulation. TCE was dechlorinated in the presence of an AFFF formulation manufactured by 3M but was not dechlorinated in the presence of formulations from two other manufacturers. Experiments amended with AFFF-derived PFASs and perfluoroalkyl acids (PFAAs) indicated that dechlorination could be inhibited by PFASs but that the inhibition depends on surfactant concentration and structure. This study revealed that the fermentable components of AFFF can stimulate TCE dechlorination, while some of the fluorinated compounds in certain AFFF formulations can inhibit dechlorination.

Fluorine incorporation in solution-processed poly-siloxane passivation for highly reliable a-InGaZnO thin-film transistors

NASA Astrophysics Data System (ADS)

Yoshida, Naofumi; Bermundo, Juan Paolo; Ishikawa, Yasuaki; Nonaka, Toshiaki; Taniguchi, Katsuto; Uraoka, Yukiharu

2018-03-01

We investigated a fluorine-containing polysiloxane (Poly-SX) passivation layer fabricated by solution process for amorphous InGaZnO (a-IGZO) thin-film transistors (TFT). This passivation layer greatly improved the stability of the a-IGZO device even after being subjected to positive bias stress (PBS) and negative bias stress (NBS). The mobility (µ) of TFTs passivated by fluorine-containing Poly-SX increased by 31%-56% (10.50-12.54 cm2 V-1 s-1) compared with TFTs passivated by non-fluorinated Poly-SX (8.04 cm2 V-1 s-1). Increasing the amount of fluorine additives led to a higher µ in passivated TFTs. Aside from enhancing the performance, these passivation layers could increase the reliability of a-IGZO TFTs under PBS and NBS with a minimal threshold voltage shift (ΔV th) of up to  +0.2 V and  -0.1 V, respectively. Additionally, all TFTs passivated by the fluorinated passivation materials did not exhibit a hump effect after NBS. We also showed that fluorinated photosensitive Poly-SX, which can be fabricated without any dry etching process, had an effective passivation property. In this report, we demonstrated the photolithography of Poly-SX, and electrical properties of Poly-SX passivated TFTs, and analyzed the state of the a-IGZO layer to show the large potential of Poly-SX as an effective solution-processed passivation material.

Diastereoselective Diels-Alder reactions of alpha-fluorinated alpha,beta-unsaturated carbonyl compounds: chemical consequences of fluorine substitution. 2.

PubMed

Essers, Michael; Mück-Lichtenfeld, Christian; Haufe, Günter

2002-07-12

Two alpha-fluoro alpha,beta-unsaturated carbonyl compounds, i.e., benzyl 2-fluoroacrylate (3) and 2-fluorooct-1-en-3-one (4), as well as the corresponding nonfluorinated parent compounds, were synthesized and subjected to Diels-Alder reactions with cyclopentadiene. The cycloadditions were conducted thermally, microwave-assisted, and Lewis acid-mediated (TiCl(4)). The fluorinated dienophiles exhibited a lower reactivity and exo diastereoselectivity, while the corresponding nonfluorinated parent compounds reacted endo selectively. DFT calculations suggest that kinetic effects of fluorine determine the stereoselectivity rather than higher thermodynamic stability of the exo products.

Provenance and geochemical behavior of fluorine in the soils of an endemic fluorosis belt, central Iran

NASA Astrophysics Data System (ADS)

Dehbandi, Reza; Moore, Farid; Keshavarzi, Behnam

2017-05-01

The concentration of fluorine, major, trace and rare earth elements (REEs) were used to estimate the probable sources and provenance of fluorine in the soils of an endemic fluorosis belt in central Iran. Total fluorine (TF) in soils varied from 146 to 406 mg/kg with a mean of 277.5 mg/kg. Calculated enrichment factor (EF) and single factor pollution index (SFPI) revealed that the majority of soil samples were moderately contaminated by fluorine. The very strong positive correlation of TF with weathering indices and soil's fine sized fractions indicated that chemical weathering and alteration of parent rocks/soils are the main controlling factors of fluorine behavior in soils. Fluorine affinity to immobile transition trace elements and REEs suggested the role of heavy minerals as the potential F host phases. Modal mineralogy along with SEM-EDX analysis indicated that apatite, fluorapophyllite, epidote, biotite, muscovite and chlorite, as well as, clay minerals are the main F-bearing minerals in the studied soils. Discriminant, bivariate and ternary diagrams of elemental compositions displayed similar geochemical signature of soils to intermediate-acidic rocks and local shales. Based on the weathering indices, soils were immature and showed a non-steady state weathering trend from upper continental crust (UCC), acidic and intermediate igneous source rocks towards shale composition possibly due to mixing of moderately weathered and un-weathered sources of different primary compositions.

Crystallization-induced dynamic resolution of Fox chiral auxiliary and application to the diastereoselective electrophilic fluorination of amide enolates.

PubMed

Lubin, Hodney; Dupuis, Christophe; Pytkowicz, Julien; Brigaud, Thierry

2013-04-05

A highly efficient crystallization-induced dynamic resolution (CIDR) of trans-Fox (fluorinated oxazolidine) chiral auxiliary is reported. This chiral auxiliary was used for highly diastereoselective (>98% de) electrophilic fluorination of amide enolates. After removal of the chiral auxiliary, highly valuable enantiopure α-fluorocarboxylic acids and β-fluoroalcohols are obtained.

Preparation, characterization, physical testing and performance of flurocarbon membranes and separators

NASA Technical Reports Server (NTRS)

Lagow, R. J.; Dumitru, E. T.

1983-01-01

The direct fluorination method of converting carefully selected hydrocarbon substrates to fluorinated membranes was successfully applied to produce promising, novel membranes for electrochemical devices. A family of polymer blends was identified which permits wide latitude in the concentration of both crosslinks and carboxyl groups in hydrocarbon membranes. The membranes of paragraph two were successfully fluorinated.

Vanadium-Catalyzed C(sp3)–H Fluorination Reactions†

PubMed Central

Xia, Ji-Bao; Ma, Yuyong; Chen, Chuo

2014-01-01

Vanadium(III) oxide catalyzes the direct fluorination of C(sp3)–H groups with Selectfluor. This reaction is operationally simple. The catalyst and the reaction byproduct can be removed easily by filtration. Using this method, a fluorine atom can be introduced to the tertiary position of 1,4-cineole and L-menthone selectively. PMID:24976971

How Cinchona Alkaloid-Derived Primary Amines Control Asymmetric Electrophilic Fluorination of Cyclic Ketones

PubMed Central

2015-01-01

The origin of selectivity in the α-fluorination of cyclic ketones catalyzed by cinchona alkaloid-derived primary amines is determined with density functional calculations. The chair preference of a seven-membered ring at the fluorine transfer transition state is key in determining the sense and level of enantiofacial selectivity. PMID:24967514

The Insulation of Copper Wire by the Electrostatic Coating Process.

DTIC Science & Technology

1983-06-30

fluorinated ethylene propylene), ECFTE (ethylene- chlorotrifluoro ethylene), and PFA (perfluoroalkoxy resin). Another material of interest with good...Fluoroplastics - Fluoroplastics are a family of polymers with the general paraffin structure that have some or all of the hydrogen replaced by fluorine ...ETFE (ethylene-tetrafluoroethylene copolymer), PFA (perfluoroalkoxy resin), ECTFE (ethylene-chlorotrifluoroethylene), and FEP ( fluorinated ethylene

Stabilization of coiled-coil peptide domains by introduction of trifluoroleucine.

PubMed

Tang, Y; Ghirlanda, G; Vaidehi, N; Kua, J; Mainz, D T; Goddard III, W A; DeGrado, W F; Tirrell, D A

2001-03-06

Substitution of leucine residues by 5,5,5-trifluoroleucine at the d-positions of the leucine zipper peptide GCN4-p1d increases the thermal stability of the coiled-coil structure. The midpoint thermal unfolding temperature of the fluorinated peptide is elevated by 13 degrees C at 30 microM peptide concentration. The modified peptide is more resistant to chaotropic denaturants, and the free energy of folding of the fluorinated peptide is 0.5-1.2 kcal/mol larger than that of the hydrogenated form. A similarly fluorinated form of the DNA-binding peptide GCN4-bZip binds to target DNA sequences with affinity and specificity identical to those of the hydrogenated form, while demonstrating enhanced thermal stability. Molecular dynamics simulation on the fluorinated GCN4-p1d peptide using the Surface Generalized Born implicit solvation model revealed that the coiled-coil binding energy is 55% more favorable upon fluorination. These results suggest that fluorination of hydrophobic substructures in peptides and proteins may provide new means of increasing protein stability, enhancing protein assembly, and strengthening receptor-ligand interactions.

Catalytic stereoselective synthesis of highly substituted indanones via tandem Nazarov cyclization and electrophilic fluorination trapping.

PubMed

Nie, Jing; Zhu, Hong-Wei; Cui, Han-Feng; Hua, Ming-Qing; Ma, Jun-An

2007-08-02

A new catalytic stereoselective tandem transformation via Nazarov cyclization/electrophilic fluorination has been accomplished. This sequence is efficiently catalyzed by a Cu(II) complex to afford fluorine-containing 1-indanone derivatives with two new stereocenters with high diastereoselectivity (trans/cis up to 49/1). Three examples of catalytic enantioselective tandem transformation are presented.

A Highly Stretchable and Robust Non-fluorinated Superhydrophobic Surface.

PubMed

Ju, Jie; Yao, Xi; Hou, Xu; Liu, Qihan; Zhang, Yu Shrike; Khademhosseini, Ali

2017-08-21

Superhydrophobic surface simultaneously possessing exceptional stretchability, robustness, and non-fluorination is highly desirable in applications ranging from wearable devices to artificial skins. While conventional superhydrophobic surfaces typically feature stretchability, robustness, or non-fluorination individually, co-existence of all these features still remains a great challenge. Here we report a multi-performance superhydrophobic surface achieved through incorporating hydrophilic micro-sized particles with pre-stretched silicone elastomer. The commercial silicone elastomer (Ecoflex) endowed the resulting surface with high stretchability; the densely packed micro-sized particles in multi-layers contributed to the preservation of the large surface roughness even under large strains; and the physical encapsulation of the microparticles by silicone elastomer due to the capillary dragging effect and the chemical interaction between the hydrophilic silica and the elastomer gave rise to the robust and non-fluorinated superhydrophobicity. It was demonstrated that the as-prepared fluorine-free surface could preserve the superhydrophobicity under repeated stretching-relaxing cycles. Most importantly, the surface's superhydrophobicity can be well maintained after severe rubbing process, indicating wear-resistance. Our novel superhydrophobic surface integrating multiple key properties, i.e. stretchability, robustness, and non-fluorination, is expected to provide unique advantages for a wide range of applications in biomedicine, energy, and electronics.

Mechanisms of fenthion activation in rainbow trout (Oncorhynchus mykiss) acclimated to hypersaline environments

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

Lavado, Ramon; Rimoldi, John M.; Schlenk, Daniel

2009-03-01

Previous studies in rainbow trout have shown that acclimation to hypersaline environments enhances the toxicity to thioether organophosphate and carbamate pesticides. In order to determine the role of biotransformation in this process, the metabolism of the thioether organophosphate biocide, fenthion was evaluated in microsomes from gills, liver and olfactory tissues in rainbow trout (Oncorhynchus mykiss) acclimated to freshwater and 17 per mille salinity. Hypersalinity acclimation increased the formation of fenoxon and fenoxon sulfoxide from fenthion in liver microsomes from rainbow trout, but not in gills or in olfactory tissues. NADPH-dependent and independent hydrolysis was observed in all tissues, but onlymore » NADPH-dependent fenthion cleavage was differentially modulated by hypersalinity in liver (inhibited) and gills (induced). Enantiomers of fenthion sulfoxide (65% and 35% R- and S-fenthion sulfoxide, respectively) were formed in liver and gills. The predominant pathway of fenthion activation in freshwater appears to be initiated through initial formation of fenoxon which may be subsequently converted to the most toxic metabolite fenoxon R-sulfoxide. However, in hypersaline conditions both fenoxon and fenthion sulfoxide formation may precede fenoxon sulfoxide formation. Stereochemical evaluation of sulfoxide formation, cytochrome P450 inhibition studies with ketoconazole and immunoblots indicated that CYP3A27 was primarily involved in the enhancement of fenthion activation in hypersaline-acclimated fish with limited contribution of FMO to initial sulfoxidation.« less

Enantioselective aldol reactions with masked fluoroacetates

NASA Astrophysics Data System (ADS)

Saadi, Jakub; Wennemers, Helma

2016-03-01

Despite the growing importance of organofluorines as pharmaceuticals and agrochemicals, the stereoselective introduction of fluorine into many prominent classes of natural products and chemotherapeutic agents is difficult. One long-standing unsolved challenge is the enantioselective aldol reaction of fluoroacetate to enable access to fluorinated analogues of medicinally relevant acetate-derived compounds, such as polyketides and statins. Herein we present fluoromalonic acid halfthioesters as biomimetic surrogates of fluoroacetate and demonstrate their use in highly stereoselective aldol reactions that proceed under mild organocatalytic conditions. We also show that the methodology can be extended to formal aldol reactions with fluoroacetaldehyde and consecutive aldol reactions. The synthetic utility of the fluorinated aldol products is illustrated by the synthesis of a fluorinated derivative of the top-selling drug atorvastatin. The results show the prospects of the method for the enantioselective introduction of fluoroacetate to access a wide variety of highly functionalized fluorinated compounds.

[Effect of fluorine, selenium and cadmium on anti-oxidase and microelements in rat's body].

PubMed

Mou, Suhua; Qin, Si; Hu, Qituo; Duan, Xianyu

2004-03-01

To study the effect of fluorine, selenium and cadmium on lipid peroxide(LPO), the activity of glutathione peroxidase (GSH-Px) and microelements such as cadmium, selenium and zinc in rats. Measurement of the contents of LPO, GSH-Px and microelements such as cadmium, selenium and zinc in SD rats after killing that have drunk water containing fluorine, selenium and cadmium eight-week ago. The contents of GSH-Px in the serum, liver and kidney of rats that were contaminated with fluorine, selenium and cadmium respectively remarkably reduced and the content of LPO noticeably increased in comparison with those of rats without being contaminated. The contents of GSH-Px noticeably increased and LPO remarkably reduced in those contaminated with the combination of any two of the three elements when compared with those in the rats contaminated with any one element of them, while the contents of GSH-Px in those contaminated with the combination of the three elements increased even more. Excessive selenium or cadmium led to the increase of selenium content in kidney and cadmium content in liver by several times. Excessive fluorine or cadmium gave rise to the lack of selenium and zinc. Selenium brought out universal increase of zinc in liver and kidney. The combination of fluorine and selenium or the combination of cadmium and selenium or that of fluorine, selenium and cadmium produced remarkable decrease of the accumulation of selenium in kidney and cadmium in liver. They also lowed the loss of zinc caused by fluorine or cadmium. Excessive fluorine, selenium or cadmium could inhabit the activity of GSH-Px in rats, which could diminish the antioxidation ability of the body. But when two or three of the chemical elements coexisted, they reduced the inhabitation of each of them on the activity of GSH-Px and in the meantime decreased the accumulation of cadmium and selenium and diminished the loss of zinc caused by fluorine and cadmium.

Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

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

Wang, Meng; Gutiérrez, Oliver Y.; Camaioni, Donald M.

Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

Super-hydrophobic fluorine containing aerogels

DOEpatents

Coronado, Paul R [Livermore, CA; Poco, John F [Livermore, CA; Hrubesh, Lawrence W [Pleasanton, CA

2007-05-01

An aerogel material with surfaces containing fluorine atoms which exhibits exceptional hydrophobicity, or the ability to repel liquid water. Hydrophobic aerogels are efficient absorbers of solvents from water. Solvents miscible with water are separated from it because the solvents are more volatile than water and they enter the porous aerogel as a vapor across the liquid water/solid interface. Solvents that are immisicble with water are separated from it by selectively wetting the aerogel. The hydrophobic property is achieved by formulating the aerogel using fluorine containing molecules either directly by addition in the sol-gel process, or by treating a standard dried aerogel using the vapor of fluorine containing molecules.

The influences of fluorine and process variations on polysilicon film stress and MOSFET hot carrier effects

NASA Technical Reports Server (NTRS)

Lowry, Lynn E.; Macwilliams, Kenneth P.; Isaac, Mary

1991-01-01

The use of fluorinated gate oxides may provide an improvement in nMOSFET reliability by enhancing hot carrier resistance. In order to clarify the mechanisms by which polysilicon processing and fluorination influence the oxide behavior, a matrix of nMOSFET structures was prepared using various processing, doping, and implantation strategies. These structures were evaluated for crystalline morphology and chemical element distribution. Mechanical stress measurements were taken on the polysilicon films from room temperature to cryogenic temperature. These examinations showed that fluorination of a structure with randomly oriented polysilicon can reduce residual mechanical stress and improve hot carrier resistance at room temperature.

Gallium (III) triflate catalyzed efficient Strecker reaction of ketones and their fluorinated analogs

PubMed Central

Prakash, G. K. Surya; Mathew, Thomas; Panja, Chiradeep; Alconcel, Steevens; Vaghoo, Habiba; Do, Clement; Olah, George A.

2007-01-01

The synthesis of α-aminonitriles and their fluorinated analogs has been carried out in high yield and purity by the Strecker reaction from the corresponding ketones and amines with trimethylsilyl cyanide using gallium triflate in dichloromethane. Monofluoro-, difluro-, or trifluoromethyl groups can be incorporated into the α-aminonitrile product by varying the nature of the fluorinated ketones. Study with various fluorinated and nonfluorinated ketones reveals that the choice of proper catalyst and the solvent system (suitable metal triflates as a catalyst and dichloromethane as a solvent) plays the key role in the direct Strecker reactions of ketones. PMID:17360416

Name that compound: The numbers game for CFCs, HFCs, HCFCs, and Halons

DOE Data Explorer

Blasing, T. J.; Jones, Sonja

2012-02-01

Chlorofluorocarbons (CFCs) contain Carbon and some combination of Fluorine and Chlorine atoms. Hydrofluorocarbons (HFCs) contain Hydrogen, Fluorine, and Carbon (no chlorine). Hydrochlorofluorocarbons (HCFCs) contain Hydrogen, Chlorine, Fluorine, and Carbon atoms. Hydrobromofluorocarbons (HBFCs) contain Hydrogen, Bromine, Fluorine, and Carbon atoms. Perfluorocarbons contain Fluorine, Carbon, and Bromine atoms, and some contain Chlorine and/or Hydrogen atoms. These compounds are often designated by a combination of letters and numbers (e.g., CFC-11, HCFC-142b). In the latter example, the lower-case b refers to an isomer, which has no relationship to the chemical formula (C2H3F2Cl), but designates a particular structural arrangement of the atoms included. For example, HCFC-142b identifies the isomer in which all three hydrogen atoms are attached to the same carbon atom, and the structural formula is written as CH3CF2Cl. By contrast, HCFC-142 (without the b) refers to an arrangement in which one carbon atom is attached to two hydrogen atoms and one chlorine atom, while the other carbon atom is attached to the third hydrogen atom and two fluorine atoms. Hence, it has a different structural formula (CH2ClCHF2).

The influence of fluorine on phase relations and REE enrichment in alkaline magmas

NASA Astrophysics Data System (ADS)

Beard, C. D.; van Hinsberg, V.; Stix, J.; Wilke, M.

2017-12-01

Fluorine is a minor element in most magmas, but higher concentrations to wt% levels have been reported in alkaline systems, including those which host economic deposits of REE + HFSE1. Despite low abundance in most natural melts, fluorine has received great attention from the experimental community because it has a strong influence on melt structure, lowering melting points and drastically reducing viscosity. The effect of fluorine on element speciation has important implications for phase relations and the partitioning of trace elements between minerals and melts, thus metal enrichment processes in alkaline magmas. We have experimentally investigated the impact of fluorine on phase relations and partitioning of rare metals, the REE in particular, in evolved alkaline melts. Synthetic glasses of tephriphonolite to phonolite composition were doped with a wide range of elements at trace levels, and fluorine contents were varied from fluorine-free to 2.5 wt%. Experiments were performed water-saturated in an internally heated pressure vessel at 200 MPa with log fO2 at ca. QFM+1, which represents the intrinsic redox conditions of the setup. Charges were heated to super-liquidus conditions for 16 hours, cooled slowly (1˚C/min) to run temperature and subsequently equilibrated for at least 40 hours. Run products were analysed by EPMA and LA-ICP-MS. The experiments produce an equilibrium assemblage of sodic pyroxene, biotite, Fe-oxide, melt, fluid, ±K-feldspar, ±titanite, ±fluorite. Addition of fluorine markedly increases the mode of biotite, which initially buffers melt F content at low levels (< 0.2 wt%). Only in experiments with more than 0.6 wt% F do we observe a significant increase in the melt F-content. Here, fluorine decreases pyroxene/melt partitioning coefficients equally for all REE where pyroxene composition and P-T conditions are equivalent (ca. 1/2 with 0.6% F). We suggest that the formation of REE-F complexes in the melt2 lowers the availability of metals for incorporation into solid phases. An increasing fluorine content of the melt will thus make the REE progressively more incompatible and available for residual enrichment. 1. Vasyukova, O. & Williams-Jones, A. E. Geochim. Cosmochim. Acta 139, 110-130 (2014). 2. Ponader, C. W. & Brown Jr., G. E. Geochim. Cosmochim. Acta 53, 2905-2914 (1989).

Highly fluorinated polyurethanes

NASA Technical Reports Server (NTRS)

Stump, E. C., Jr.; Rochow, S. E. (Inventor)

1972-01-01

New polyurethanes containing a high degree of fluorine atoms are reported. The presence of the fluorine atoms in the polyurethane resins provides material having good thermal stability and chemical resistance. These polyurethanes are derived from a new hydroxy-terminated perfluoro polyether. The hydroxy terminated material is reacted with a diisocyanate to produce the polyurethanes. The polyurethanes can be used to form seals, coatings, potting material, hoses and the like.

Low Temperature Fluorination of Aerosol Suspensions of Hydrocarbons Utilizing Elemental Fluorine. Aerosol Direct Fluorination-Syntheses of Perfluoroketones.

DTIC Science & Technology

1983-03-01

81.16 ppm (in) 3 *CF 2 - -126.31 ppm (an) 2 *CF2 - -118.66 ppm (an) 2 (a) See Ref. 11. (b) A. L. Renne and Win. C. Francis, 3. Amr. Cbes. Sat...Knoxville’>Tennessee 37916 1 Professor R. Neilson Dr. A. Cowley Department of Chemistry Department of Chemistry Texas Christian University University

A Rapid Deposition of Fluorine Doped Zinc Oxide Using the Atmospheric Pressure Chemical Vapour Deposition Method

NASA Astrophysics Data System (ADS)

Najafi, Navid; Rozati, S. M.

2018-03-01

Fluorine-doped zinc oxide (FZO) (ZnO:F) thin films were manufactured by atmospheric pressure chemical vapor deposition (APCVD) on glass substrates using zinc acetate dihydrate [C4H6O4Zn·2H2O, ZnAc] and ammonium fluoride (NH4F) as the source of fluorine with deposition duration of only 120 s for each sample. The effects of different amounts of fluorine as the dopant on the structural, electrical and optical properties of FZO thin films were investigated. The results show a polycrystalline structure at higher temperatures compared to amorphous structure at lower temperatures. The x-ray diffraction patterns of the polycrystalline films were identified as a hexagonal wurtzite structure of zinc oxide (ZnO) with the (002) preferred orientation. Also, the sheet resistance decreased from 17.8 MΩ/□ to 28.9 KΩ/□ for temperatures 325°C to 450°C, respectively. In order to further decrease the sheet resistance of the undoped ZnO thin films, fluorine was added using NH4F as the precursor, and again a drastic change in sheet resistance of only 17.7 Ω/□ was obtained. Based on the field emission scanning electron microscopy images, the fluorine concentration in CVD source is an important factor affecting the grain size and modifies electrical parameters. Ultraviolet-visible measurements revealed reduction of transparency of the layers with increasing fluorine as the dopant.

Studies on nitrile rubber degradation in zinc bromide completion fluid and its prevention by surface fluorination

NASA Astrophysics Data System (ADS)

Vega-Cantu, Yadira Itzel

Poly(acrylonitrile-co-butadiene) or nitrile-butadiene rubber (NBR) is frequently used as an O-ring material in the oil extraction industry due to its excellent chemical properties and resistance to oil. However, degradation of NBR gaskets is known to occur during the well completion and oil extraction process where packers are exposed to completion fluids such as ZnBr2 brine. Under these conditions NBR exhibits accelerated chemical degradation resulting in embrittlement and cracking. Samples of NBR, poly(acrylonitrile) (PAN) and poly(butadiene) (PB) have been exposed to ZnBr2 based completion fluid, and analyzed by ATR and diffuse reflectance IR. Analysis shows the ZnBr2 based completion fluid promotes hydrolysis of the nitrile group to form amides and carboxylic groups. Analysis also shows that carbon-carbon double bonds in NBR are unaffected after short exposure to zinc bromide based completion fluid, but are quickly hydrolyzed in acidic bromide mixtures. Although fluoropolymers have excellent chemical resistance, their strength is less than nitrile rubber and replacing the usual gasket materials with fluoroelastomers is expensive. However, a fluoropolymer surface on a nitrile elastomer can provide the needed chemical resistance while retaining their strength. In this study, we have shown that this can be achieved by direct fluorination, a rather easy and inexpensive process. Samples of NBR O-rings have been fluorinated by exposure to F2 and F2/HF mixtures at various temperatures. Fluorination with F 2 produces the desired fluoropolymer layer; however, fluorination by F2/HF mixtures gave a smoother fluorinated layer at lower temperatures and shorter times. Fluorinated samples were exposed to ZnBr2 drilling fluid and solvents. Elemental analysis shows that the fluorinated layer eliminates ZnBr2 diffusion into the NBR polymeric matrix. It was also found that surface fluorination significantly retards the loss of mechanical properties such as elasticity, tensile strength, toughness and compression set of nitrile rubber when exposed to zinc bromide fluid. This surface fluorination can be applied to extend the useful life of O-rings and packers in the field during oil extraction. The extended life can save millions of dollars by limiting the downtime of the well.

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms.

PubMed

Díaz-de-Mera, Yolanda; Aranda, Alfonso; Bravo, Iván; Rodríguez, Diana; Rodríguez, Ana; Moreno, Elena

2008-10-01

The adverse environmental impacts of chlorinated hydrocarbons on the Earth's ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C-F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF(3)CF(2)CF(2)OCH(3)) (1) and its isomer CF(3)CF(2)CF(2)CH(2)OH (2). Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube-mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266-333 and 298-353 K for reactions of HFE-7000 and CF(3)CF(2)CF(2)CH(2)OH, respectively. The measured room temperature rate constants were k(Cl+CF(3)CF(2)CF(2)OCH(3)) = (1.24 +/- 0.28) x 10(-13) cm(3) molecule(-1) s(-1)and k(Cl+CF(3)CF(2)CF(2)CH(2)OH) = (8.35 +/- 1.63) x 10(-13) cm(3) molecule(-1) s(-1) (errors are 2sigma + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k (1)(266-333 K) = (6.1 +/- 3.8) x 10(-13)exp[-(445 +/- 186)/T] cm(3) molecule(-1) s(-1) and k (2)(298-353 K) = (1.9 +/- 0.7) x 10(-12)exp[-(244 +/- 125)/T] cm(3) molecule(-1) s(-1) (errors are 2sigma). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 +/- 0.38 and 0.97 +/- 0.16 (errors are 2sigma) were obtained for CF(3)CF(2)CF(2)OCH(3) and CF(3)CF(2)CF(2)CH(2)OH, respectively. The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k (1) and k (2), HFE-7000 is significantly less reactive than its isomer C(3)F(7)CH(2)OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of -CF(2)- in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of -CF(2)- without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C(3)H(7)CH(2)OH, respectively. The studied CFCs' substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, tau (Cl) values as low as 2.5 and 0.4 years for HFE-7000 and C(3)H(7)CH(2)OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF(3)CF(2)CF(2)OCH(3), significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure-reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.

Aromatic fluorine compounds. II. 1,2,4,5-Tetrafluorobenzene and related compounds

USGS Publications Warehouse

Finger, G.C.; Reed, F.H.; Burness, D.M.; Fort, D.M.; Blough, R.R.

1951-01-01

The synthesis and properties of 1,2,4,5-tetrafluorobenzene and a group of bromofluoro and chlorofluorobenzenes with a predominating 1,2,4,5-structure are described. Flash point and surface tension data for the fluorinated benzenes and the influence of chlorine substitution upon these values were studied. Under nitration conditions, 1,2,4,5-tetrafluorobenzene will not form a nitro derivative, but will undergo a preferential 1,4-fluorine displacement-oxidation mechanism to give 2,5-difluoro-1,4-benzoquinone. Diazotization reactions on 2-nitro-3,4,6-trifluoroaniline reveal that the nitro group or a fluorine atom in the 4- or 6-position may become labilized, under certain conditions, and undergo replacement.

Mutasynthesis of fluorinated pactamycin analogues and their antimalarial activity.

PubMed

Almabruk, Khaled H; Lu, Wanli; Li, Yuexin; Abugreen, Mostafa; Kelly, Jane X; Mahmud, Taifo

2013-04-05

A mutasynthetic strategy has been used to generate fluorinated TM-025 and TM-026, two biosynthetically engineered pactamycin analogues produced by Streptomyces pactum ATCC 27456. The fluorinated compounds maintain excellent activity and selectivity toward chloroquine-sensitive and multidrug-resistant strains of malarial parasites as the parent compounds. The results also provide insights into the biosynthesis of 3-aminobenzoic acid in S. pactum.

Self-Cleaning Coatings

DTIC Science & Technology

2014-06-01

Canada), telle que representee par le ministre de la Defense nationale, 2014 i Abstract Under certain conditions, military coatings...μm Particle C: a compound of fluorinated polymer and polypropylene , mean particle size 9 μm Due to the fact that all three types of particles have...functional particles, which are either pure fluorinated polymer or compound of fluorinated polymer and polypropylene , possessing certain degrees of

On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin-Spin Coupling Constants

NASA Astrophysics Data System (ADS)

Sanchez, Marina; Provasi, Patricio F.; Aucar, Gustavo A.; Sauer, Stephan P. A.

Locally dense basis sets (

Prediction of Quantum Anomalous Hall Insulator in half-fluorinated GaBi Honeycomb

PubMed Central

Chen, Sung-Ping; Huang, Zhi-Quan; Crisostomo, Christian P.; Hsu, Chia-Hsiu; Chuang, Feng-Chuan; Lin, Hsin; Bansil, Arun

2016-01-01

Using first-principles electronic structure calculations, we predict half-fluorinated GaBi honeycomb under tensile strain to harbor a quantum anomalous Hall (QAH) insulator phase. We show that this QAH phase is driven by a single inversion in the band structure at the Γ point. Moreover, we have computed the electronic spectrum of a half-fluorinated GaBi nanoribbon with zigzag edges, which shows that only one edge band crosses the Fermi level within the band gap. Our results suggest that half-fluorination of the GaBi honeycomb under tensile strain could provide a new platform for developing novel spintronics devices based on the QAH effect. PMID:27507248

Prediction of Quantum Anomalous Hall Insulator in half-fluorinated GaBi Honeycomb

DOE PAGES

Chen, Sung-Ping; Huang, Zhi-Quan; Crisostomo, Christian P.; ...

2016-08-10

Using first-principles electronic structure calculations, we predict half-fluorinated GaBi honeycomb under tensile strain to harbor a quantum anomalous Hall (QAH) insulator phase. We show that this QAH phase is driven by a single inversion in the band structure at the Γ point. Moreover, we have computed the electronic spectrum of a half-fluorinated GaBi nanoribbon with zigzag edges, which shows that only one edge band crosses the Fermi level within the band gap. In conclusion, our results suggest that half-fluorination of the GaBi honeycomb under tensile strain could provide a new platform for developing novel spintronics devices based on the QAHmore » effect.« less

Thermal NF3 fluorination/oxidation of cobalt, yttrium, zirconium, and selected lanthanide oxides

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

Scheele, Randall D.; McNamara, Bruce K.; Casella, Andrew M.

2013-02-01

This paper presents results of our continuing investigation on the use of nitrogen trifluoride as a fluorination or fluorination/oxidation agent for separating valuable constituents from used nuclear fuels by exploiting the different volatilities of the constituent fission product and actinide fluorides. This article focuses on fission products that do not have volatile fluorides or oxyfluorides at expected operations temperatures. Our thermodynamic calculations show that nitrogen trifluoride has the potential to completely fluorinate fission product oxides to their fluorides. Simultaneous thermogravimetric and differential thermal analyses show that the oxides of cobalt, zirconium, and the lanthanides are fluorinated but do not formmore » volatile fluorides when treated with nitrogen trifluoride at temperatures up to 550°C. Our studies of gadolinium-doped commercial nuclear fuel indicate that nitrogen trifluoride can extract uranium from the non-volatile gadolinium.« less

40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Monomethyl Ether *Dimer Acids Dioxane Ethane Ethylene Glycol Monophenyl Ether *Ethoxylates, Misc. Ethylene Glycol Dimethyl Ether Ethylene Glycol Monobutyl Ether Ethylene Glycol Monoethyl Ether Ethylene Glycol...

Decreased IgA+ B cells population and IgA, IgG, IgM contents of the cecal tonsil induced by dietary high fluorine in broilers.

PubMed

Liu, Juan; Cui, Hengmin; Peng, Xi; Fang, Jing; Zuo, Zhicai; Deng, Junliang; Wang, Hesong; Wu, Bangyuan; Deng, Yuanxin; Wang, Kangping

2013-05-02

Fluoride is an environmental and industrial pollutant that affects various organs in humans and animals. The cecal tonsil is an important component of the mucosal immune system and performs important and unique immune functions. In the present study, we investigated the effects of dietary high fluorine on the quantities of IgA+ B cells in the cecal tonsil by immunohistochemistry, and the immunoglobulin A (IgA), immunoglobulin G (IgG) and immunoglobulin M (IgM) contents in the cecal tonsil by ELISA. A total of 280 one-day-old avian broilers were divided into four groups and fed on a corn-soybean basal diet as control diet (fluorine 22.6 mg/kg) or the same diet supplemented with 400, 800 and 1,200 mg/kg fluorine (high fluorine groups I, II and III) in the form of sodium fluoride, respectively, throughout a 42-day experimental period. The results showed that the quantities of IgA+ B cells were lower (p < 0.05 or p < 0.01) and the IgA, IgG, and IgM contents were decreased (p < 0.05 or p < 0.01) in high fluorine groups II and III in comparison with those of control group. It was concluded that dietary fluorine, in the 800-1,200 mg/kg range, could reduce the numbers of the IgA+ B cells and immunoglobulin contents in the cecal tonsil, implying the local mucosal immune function was ultimately impacted in broilers.

Decreased IgA+ B Cells Population and IgA, IgG, IgM Contents of the Cecal Tonsil Induced by Dietary High Fluorine in Broilers

PubMed Central

Liu, Juan; Cui, Hengmin; Peng, Xi; Fang, Jing; Zuo, Zhicai; Deng, Junliang; Wang, Hesong; Wu, Bangyuan; Deng, Yuanxin; Wang, Kangping

2013-01-01

Fluoride is an environmental and industrial pollutant that affects various organs in humans and animals. The cecal tonsil is an important component of the mucosal immune system and performs important and unique immune functions. In the present study, we investigated the effects of dietary high fluorine on the quantities of IgA+ B cells in the cecal tonsil by immunohistochemistry, and the immunoglobulin A (IgA), immunoglobulin G (IgG) and immunoglobulin M (IgM) contents in the cecal tonsil by ELISA. A total of 280 one-day-old avian broilers were divided into four groups and fed on a corn-soybean basal diet as control diet (fluorine 22.6 mg/kg) or the same diet supplemented with 400, 800 and 1,200 mg/kg fluorine (high fluorine groups I, II and III) in the form of sodium fluoride, respectively, throughout a 42-day experimental period. The results showed that the quantities of IgA+ B cells were lower (p < 0.05 or p < 0.01) and the IgA, IgG, and IgM contents were decreased (p < 0.05 or p < 0.01) in high fluorine groups II and III in comparison with those of control group. It was concluded that dietary fluorine, in the 800–1,200 mg/kg range, could reduce the numbers of the IgA+ B cells and immunoglobulin contents in the cecal tonsil, implying the local mucosal immune function was ultimately impacted in broilers. PMID:23644827

Materials Refining for Solar Array Production on the Moon

NASA Technical Reports Server (NTRS)

Landis, Geoffrey A.

2005-01-01

Silicon, aluminum, and glass are the primary raw materials that will be required for production of solar arrays on the moon. A process sequence is proposed for producing these materials from lunar regolith, consisting of separating the required materials from lunar rock with fluorine. The fluorine is brought to the moon in the form of potassium fluoride, and is liberated from the salt by electrolysis in a eutectic salt melt. Tetrafluorosilane produced by this process is reduced to silicon by a plasma reduction stage; the fluorine salts are reduced to metals by reaction with metallic potassium. Fluorine is recovered from residual MgF and CaF2 by reaction with K2O.

Materials refining on the Moon

NASA Astrophysics Data System (ADS)

Landis, Geoffrey A.

2007-05-01

Oxygen, metals, silicon, and glass are raw materials that will be required for long-term habitation and production of structural materials and solar arrays on the Moon. A process sequence is proposed for refining these materials from lunar regolith, consisting of separating the required materials from lunar rock with fluorine. The fluorine is brought to the Moon in the form of potassium fluoride, and is liberated from the salt by electrolysis in a eutectic salt melt. Tetrafluorosilane produced by this process is reduced to silicon by a plasma reduction stage; the fluorine salts are reduced to metals by reaction with metallic potassium. Fluorine is recovered from residual MgF and CaF2 by reaction with K2O.

Determination of fluorine in organic compounds: Microcombustion method

USGS Publications Warehouse

Clark, H.S.

1951-01-01

A reliable and widely applicable means of determining fluorine in organic compounds has long been needed. Increased interest in this field of research in recent years has intensified the need. Fluorine in organic combinations may be determined by combustion at 900?? C. in a quartz tube with a platinum catalyst, followed by an acid-base titration of the combustion products. Certain necessary precautions and known limitations are discussed in some detail. Milligram samples suffice, and the accuracy of the method is about that usually associated with the other halogen determinations. Use of this method has facilitated the work upon organic fluorine compounds in this laboratory and it should prove to be equally valuable to others.

Two-photon-excited fluorescence spectroscopy of atomic fluorine at 170 nm

NASA Technical Reports Server (NTRS)

Herring, G. C.; Dyer, Mark J.; Jusinski, Leonard E.; Bischel, William K.

1988-01-01

Two-photon-excited fluorescence spectroscopy of atomic fluorine is reported. A doubled dye laser at 286-nm is Raman shifted in H2 to 170 nm (sixth anti-Stokes order) to excite ground-state 2P(0)J fluorine atoms to the 2D(0)J level. The fluorine atoms are detected by one of two methods: observing the fluorescence decay to the 2PJ level or observing F(+) production through the absorption of an additional photon by the excited atoms. Relative two-photon absorption cross sections to and the radiative lifetimes of the 2D(0)J states are measured.

Defect pair formation in fluorine and nitrogen codoped TiO2

NASA Astrophysics Data System (ADS)

Kordatos, A.; Kelaidis, N.; Chroneos, A.

2018-04-01

Titanium oxide is extensively investigated because of its high chemical stability and its photocatalytic properties; nevertheless, the large band gap limits its activity to a small portion of the solar spectrum. Nitrogen and fluorine codoping is an efficient defect engineering strategy to increase the photocatalytic activity of titanium oxide. In the present study, we apply density functional theory to investigate the interaction of nitrogen with fluorine and the formation of defect pairs. We show that in fluorine and nitrogen codoped titanium oxide, the FiNi, FONi, and FiNTi defects can form. Their impact on the electronic structure of titanium oxide is discussed.

Vapor intrusion risk of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME) and ethyl tert-butyl ether (ETBE): A modeling study.

PubMed

Ma, Jie; Xiong, Desen; Li, Haiyan; Ding, Yi; Xia, Xiangcheng; Yang, Yongqi

2017-06-15

Vapor intrusion of synthetic fuel additives represents a critical yet still neglected problem at sites contaminated by petroleum fuel releases. This study used an advanced numerical model to investigate the vapor intrusion potential of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), and ethyl tert-butyl ether (ETBE). Simulated indoor air concentration of these compounds can exceed USEPA indoor air screening level for MTBE (110μg/m 3 ). Our results also reveal that MTBE has much higher chance to cause vapor intrusion problems than TAME and ETBE. This study supports the statements made by USEPA in the Petroleum Vapor Intrusion (PVI) Guidance that the vertical screening criteria for petroleum hydrocarbons may not provide sufficient protectiveness for fuel additives, and ether oxygenates in particular. In addition to adverse impacts on human health, ether oxygenate vapor intrusion may also cause aesthetic problems (i.e., odour and flavour). Overall, this study points out that ether oxygenates can cause vapor intrusion problems. We recommend that USEPA consider including the field measurement data of synthetic fuel additives in the existing PVI database and possibly revising the PVI Guidance as necessary. Copyright © 2017 Elsevier B.V. All rights reserved.

78 FR 69337 - Greenhouse Gas Reporting Program: Amendments and Confidentiality Determinations for Fluorinated...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-19

... Classification System NF 3 nitrogen trifluoride NODA notice of data availability NTTAA National Technology... Previously Produced Fluorinated GHGs and From Venting of Residual Fluorinated GHGs From Containers 7... emissions from production and transformation processes; emissions from venting of container heels and...

21 CFR 170.45 - Fluorine-containing compounds.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Fluorine-containing compounds. 170.45 Section 170.45 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD ADDITIVES Specific Administrative Rulings and Decisions § 170.45 Fluorine-containing compounds...

Surface fluorination of zirconia: adhesive bond strength comparison to commercial primers.

PubMed

Piascik, Jeffrey R; Swift, Edward J; Braswell, Krista; Stoner, Brian R

2012-06-01

This study evaluated contact angle and shear bond strength of three commercial zirconia primers and compared them to a recently developed fluorination pre-treatment. Earlier investigations reported that plasma fluorinated zirconia modifies the chemical bonding structure creating a more reactive surface. Yttria-stabilized zirconia (LAVA, 3M ESPE) plates were highly polished using 3μm diamond paste (R(a) ∼200nm) prior to pretreatments. After primer and fluorination treatment, contact angles were measured to quantify surface hydrophobicity before and after ethanol clean. Additionally, simple shear bond tests were performed to measure the adhesion strength to a composite resin. Plasma fluorination produced the lowest contact angle (7.8°) and the highest shear bond strength (37.3MPa) suggesting this pretreatment facilitates a more "chemically" active surface for adhesive bonding. It is hypothesized that plasma fluorination increase hydroxylation at the surface, making it more reactive, thus allowing for covalent bonding between zirconia surface and resin cement. A strong correlation was observed between contact angle and adhesion strength for all specimens; a relationship which may help understand the frequency and modes of failures, clinically. It is also believed that this surface treatment can increase long-term viability of zirconia restorations over other adhesive techniques. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Janus dendrimersomes coassembled from fluorinated, hydrogenated, and hybrid Janus dendrimers as models for cell fusion and fission.

PubMed

Xiao, Qi; Sherman, Samuel E; Wilner, Samantha E; Zhou, Xuhao; Dazen, Cody; Baumgart, Tobias; Reed, Ellen H; Hammer, Daniel A; Shinoda, Wataru; Klein, Michael L; Percec, Virgil

2017-08-22

A three-component system of Janus dendrimers (JDs) including hydrogenated, fluorinated, and hybrid hydrogenated-fluorinated JDs are reported to coassemble by film hydration at specific ratios into an unprecedented class of supramolecular Janus particles (JPs) denoted Janus dendrimersomes (JDSs). They consist of a dumbbell-shaped structure composed of an onion-like hydrogenated vesicle and an onion-like fluorinated vesicle tethered together. The synthesis of dye-tagged analogs of each JD component enabled characterization of JDS architectures with confocal fluorescence microscopy. Additionally, a simple injection method was used to prepare submicron JDSs, which were imaged with cryogenic transmission electron microscopy (cryo-TEM). As reported previously, different ratios of the same three-component system yielded a variety of structures including homogenous onion-like vesicles, core-shell structures, and completely self-sorted hydrogenated and fluorinated vesicles. Taken together with the JDSs reported herein, a self-sorting pathway is revealed as a function of the relative concentration of the hybrid JD, which may serve to stabilize the interface between hydrogenated and fluorinated bilayers. The fission-like pathway suggests the possibility of fusion and fission processes in biological systems that do not require the assistance of proteins but instead may result from alterations in the ratios of membrane composition.

Analysis of Rocket, Ram-Jet, and Turbojet Engines for Supersonic Propulsion of Long-Range Missles. II - Rocket Missile Performance

NASA Technical Reports Server (NTRS)

Huff, Vearl N.; Kerrebrock, Jack

1954-01-01

The theoretical performance of a two-stage ballistic rocket mis having a centerbody and two parallel boosters was investigated for J oxygen and ammonia-fluorine propellants. Both power-plant and missi parameters were optimized to give minimum cost on-the basis of the analysis for a range of 5500 nautical miles. After optimum values were found, each parameter was varied independently to determine its effect on performance of the missile. The missile using the ammonia-fluorine propellant weighs about one half as much as a missile using JP4-oxygen. Based on an expected unit cost of fluorine in quantity production, the ammonia-fluorine missile has a substantially lower relative cost than a JP4-oxygen missile. Optimum chamber pressures for both propellant systems and for both the centerbody and boosters were between 450 and 600 pounds per square inch. High design altitudes for the exhaust nozzle are desirable for both the centerbody and boosters. For the centerbody, the design altitude should be between 45,000 and 60,000 feet, with the value for ammonia-fluorine lower than that for JP4-oxygen. For the boosters, the design altitude should be 20,000 to 30,000 feet, with the value for the ammonia-fluorine. missile higher.

Synthesis of three novel fluorine-18 labeled analogues of L-deprenyl for positron emission tomography (PET) studies of monoamine oxidase B (MAO-B).

PubMed

Nag, Sangram; Lehmann, Lutz; Heinrich, Tobias; Thiele, Andrea; Kettschau, Georg; Nakao, Ryuji; Gulyás, Balázs; Halldin, Christer

2011-10-27

The aim in this project was to synthesize and to study fluorine-18 labeled analogues of l-deprenyl which bind selectively to the enzyme monoamine oxidase B (MAO-B). Three fluorinated l-deprenyl analogues have been generated in multistep organic syntheses. The most promising fluorine-18 compound N-[(2S)-1-[(18)F]fluoro-3-phenylpropan-2-yl]-N-methylprop-2-yn-1-amine (4c) was synthesized by a one-step fluorine-18 nucleophilic substitution reaction. Autoradiography on human brain tissue sections demonstrated specific binding for compound 4c to brain regions known to have a high content of MAO-B. In addition, the corresponding nonradioactive fluorine-19 compound (13) inhibited recombinant human MAO-B with an IC(50) of 170.5 ± 29 nM but did not inhibit recombinant human MAO-A (IC(50) > 2000 nM), demonstrating its specificity. Biodistribution of 4c in mice showed high initial brain uptake leveling at 5.2 ± 0.04%ID/g after 2 min post injection. In conclusion, compound 4c is a specific inhibitor of MAO-B with high initial brain uptake in mice and is, therefore, a candidate for further investigation in PET.

[The effect of alternating administration of aluminum chloride and sodium fluoride in drinking water on the concentration of fluoride in serum and its content in bones of rats].

PubMed

Lubkowska, Anna; Chlubek, Dariusz; Machoy-Mokrzyniska, Anna

2006-01-01

Fluorine and aluminum remain a very interesting research topic due to equivocal and relatively unknown toxic action, role in the etiology of various diseases, and interactions of both elements. Fluorine and aluminum compounds are absorbed by organisms through the gastric and respiratory systems, although the latter route operates only at very high concentrations in air. Chronic exposure to fluorine and aluminum leads to accumulation of both elements, especially in bones and teeth, but also in lung, brain, kidney, and liver. Organisms excrete these elements with urine, faeces, and to a minor extent with sweat and bile. In the light of reports suggesting that aluminum has protective properties against fluorine toxicity during exposure to both elements, we decided to examine the effect of alternating doses of aluminum fluoride and sodium fluoride in drinking water on rats. Four female groups received: I--100 ppm fluorine ions during one month; II--100 ppm fluorine ions alternating every two days with 300 ppm aluminum ions during one month; III--100 ppm fluoride ions during four months; IV--100 ppm fluorine ions alternating every two days with 300 ppm aluminum ions during four months. The respective male groups called IA, IIA, IIIA, and IVA were treated identically. Subsequently, the animals were anesthetized and sacrificed. Blood was sampled from the heart and the right femur was removed for fluorine determination. Fluorine content in the femur and serum was determined with an ion-selective electrode (Orion). The results were analyzed statistically (Statistica 6). We observed higher fluoride concentrations in serum as compared with control values in all groups of female and male rats exposed to sodium fluoride only. Longer exposure time (4 months) did not result in further increase in serum fluoride concentration. However, longer exposure increased fluoride accumulation in the femur (p < 0.001). All groups exposed to NaF had significantly higher fluoride concentration in the femur as compared with control animals. Groups receiving NaF and AlCl3 showed lower fluoride concentration in serum and femur compared with those exposed to NaF only and higher in comparison with controls. Fluorine content in the femur of rats exposed to NaF and AlCI3 for four months was similar to the results obtained after one month of exposure.

40 CFR Table I-2 to Subpart I of... - Examples of Fluorinated GHGs Used by the Electronics Industry

Code of Federal Regulations, 2014 CFR

2014-07-01

... the Electronics Industry I Table I-2 to Subpart I of Part 98 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Electronics... the Electronics Industry Product type Fluorinated GHGs and fluorinated heat transfer fluids used...

Improved Thermal Stability of Lithium-Rich Layered Oxide by Fluorine Doping.

PubMed

Kapylou, Andrei; Song, Jay Hyok; Missiul, Aleksandr; Ham, Dong Jin; Kim, Dong Han; Moon, San; Park, Jin Hwan

2018-01-05

The thermal stability of lithium-rich layered oxide with the composition Li(Li 1/6 Ni 1/6 Co 1/6 Mn 1/2 )O 2-x F x (x=0.00 and 0.05) is evaluated for use as a cathode material in lithium-ion batteries. Thermogravimetric analysis, evolved gas analysis, and differential scanning calorimetry show that, upon fluorine doping, degradation of the lithium-rich layered oxides commences at higher temperatures and the exothermic reaction is suppressed. Hot box tests also reveal that the prismatic cell with the fluorine-doped powder does not explode, whereas that with the undoped one explodes at about 135 °C with a sudden temperature increase. XRD analysis indicates that fluorine doping imparts the lithium-rich layered oxide with better thermal stability by mitigating oxygen release at elevated temperatures that cause an exothermic reaction with the electrolyte. The origin of the reduced oxygen release from the fluorinated lithium-rich layered oxide is also discussed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controllable preparation of fluorine-containing fullerene-like carbon film

NASA Astrophysics Data System (ADS)

Wang, Jia; Liang, Aimin; Wang, Fuguo; Xu, Longhua; Zhang, Junyan

2016-05-01

Fluorine-containing fullerene-like carbon (F-FLC) films were prepared by high frequency unipolar pulse plasma-enhanced chemical vapor deposition. The microstructures, mechanical properties as well as the tribological properties of the films were investigated. The results indicate that fullerene-like microstructures appear in amorphous carbon matrix and increase greatly with the increase of bias voltage from -600 to -1600 V. And the fluorine contents in F-FLC films also show a minor rise. In addition, the hardness enhances with the bias voltage and the outstanding elastic recovery maintains because of the formation of fullerene-like microstructures in the F-FLC films. Undoubtedly, the F-FLC film deposited under high bias voltage owns a superiorly low friction, which combines the merits of fluorinated carbon film and fullerene-like carbon film. Moreover, the film also shows a remarkable wear resistance, which is mainly attributed to the excellent mechanical properties. This study provides new insights for us to prepare fluorine-containing FLC films with good mechanical and tribological properties.

.sup.18 F-4-Fluoroantipyrine

DOEpatents

Shiue, Chyng-Yann; Wolf, Alfred P.

1984-03-13

The novel radioactive compound .sup.18 F-4-fluoroantipyrine having high specific activity which can be used in nuclear medicine in diagnostic applications, prepared by the direct fluorination of antipyrine in acetic acid with radioactive fluorine at room temperature and purifying said radioactive compound by means of gel chromatography with ethyl acetate as eluent is disclosed. The non-radioactive 4-fluoroantipyrine can also be prepared by the direct fluorination of antipyrine in acetic acid with molecular fluorine at room temperature and purified by means of gel chromotography with ethyl acetate eluent.

Ozone Depleting Chemical (ODC) Replacement - Alternative Cleaning Solvents and Lubricants.

DTIC Science & Technology

1995-02-01

surface. This phenomenon helps to explain why some aqueous based cleaners (such as Daraclean®) can effectively remove fluorinated greases (such as...structurally similar to hydrocarbon oils, waxes, and greases it removes. In some fluorinated greases such as Krytox®, only solvents identically similar to...the contaminant (such as Tribolube®, a fluorinated solvent) effectively dissolves them. Hexane and methanol, being members of different chemical

Fabrication of hydrophobic fluorinated silica-polyamide thin film nanocomposite reverse osmosis membranes with dramatically improved salt rejection.

PubMed

Pang, Ruizhi; Zhang, Kaisong

2018-01-15

Thin film nanocomposite reverse osmosis (TFN RO) membranes incorporated with hydrophilic nanoparticles show a potential problem that the salt rejection can not be improved significantly. In this study, novel TFN RO membranes incorporated with hydrophobic fluorinated silica nanoparticles were fabricated to improve the salt rejection. Fluorinated silica nanoparticles were well dispersed in organic phase during the interfacial polymerization (IP) process. The TFN RO membranes were characterized with attenuated total reflectance infra-red, field emission scanning electron microscopy, atomic force microscopy and water contact angle measurements. The preparation conditions of TFN RO membranes, including IP reaction time, organic solvent removal time, and fluorinated silica loading, were optimized by characterizing desalination performance using 2000ppm NaCl aqueous solution at 1.55MPa and 25°C. The salt rejection increased significantly from 96.0% without fluorinated silica nanoparticles to 98.6% with the optimal 0.12% (w/v) fluorinated silica nanoparticles, while the water flux decreased slightly from 0.99m 3 /m 2 /day to 0.93m 3 /m 2 /day. This study demonstrated the potential use of hydrophobic nanoparticles in high-performance TFN RO membranes. Copyright © 2017 Elsevier Inc. All rights reserved.

Sinterable Ceramic Powders from Laser-Heated Gases.

DTIC Science & Technology

1988-02-01

ether . carboxylic acid. and aldehyde clases: water is also included.Acrigto William and Goodman.’ a single crystalline sili- The single-crstalline...represent commonly available organic families, Including aliphatic and aromatic hydrocarbons, chlorides, ethers , ketones , esters, alcohols, aldehydes...Hydrocarbons Ketone Amine Chlorides Low-alcohols 8f . Ether Ester - _Aldehyde Ether Ketones High-alcohols 04 Carboxylic Ester I acid Ether o . Nitrile

[Assessment of Soil Fluorine Pollution in Jinhua Fluorite Ore Areas].

PubMed

Ye, Qun-feng; Zhou, Xiao-ling

2015-07-01

The contents of. soil total fluorine (TF) and water-soluble fluorine (WF) were measured in fluorite ore areas located in Jinhua City. The single factor index, geoaccumulation index and health risk assessment were used to evaluate fluorine pollution in soil in four fluorite ore areas and one non-ore area, respectively. The results showed that the TF contents in soils were 28. 36-56 052. 39 mg.kg-1 with an arithmetic mean value of 8 325.90 mg.kg-1, a geometric mean of 1 555. 94 mg.kg-1, and a median of 812. 98 mg.kg-1. The variation coefficient of TF was 172. 07% . The soil WF contents ranged from 0. 83 to 74. 63 mg.kg-1 with an arithmetic mean value of 16. 94 mg.kg-1, a geometric mean of 10. 59 mg.kg-1, and a median of 10. 17 mg.kg-1. The variation coefficient of WF was 100. 10%. The soil TF and WF contents were far higher than the national average level of the local fluorine epidemic occurrence area. The fluoride pollution in soil was significantly affected by human factors. Soil fluorine pollution in Yangjia, Lengshuikeng and Huajie fluorite ore areas was the most serious, followed by Daren fluorite ore area, and in non-ore area there was almost no fluorine pollution. Oral ingestion of soils was the main exposure route. Sensitivity analysis of model parameters showed that children's weight exerted the largest influence over hazard quotient. Furthermore, a significant positive correlation was found among the three kinds of evaluation methods.