1,491 results
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2. Enhanced DC Insulation Strength of PMIA Paper by CF 4 /Ar Plasma Treatment.
- Author
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Zhang, Ya-Hui, Ruan, Hao-Ou, Wang, Shuang-Shuang, Zhou, Hua-Hao, Xie, Qing, and Lu, Fang-Cheng
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SURFACE preparation , *INSULATING materials , *SURFACE properties , *FLUORINATION , *ARGON , *POLYHYDRAMNIOS - Abstract
The objective of this article is to enhance the dc insulation strength of poly- ${m}$ -phenylene isophthalamide (PMIA) paper by surface treatment. CF4/Ar plasma is used to modify the surface of PMIA paper by fluorination, and the effects of fluorination on the microstructure, electrical parameters, and insulation properties of the material are investigated, and the optimized treatment parameters of CF4 concentration and treatment time are obtained, and the mechanism is further explained from the perspective of carrier traps. The results show that the moderate CF4/Ar plasma treatment can improve the surface insulation properties of PMIA paper without damaging its overall insulation properties. [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
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3. Halloysite nanotubes with fluorinated cavity: an innovative consolidant for paper treatment.
- Author
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Cavallaro, Giuseppe, Lazzara, Giuseppe, Milioto, Stefana, and Parisi, Filippo
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HALLOYSITE , *FLUORINATION , *PAPER industry , *NANOTUBES , *THERMOGRAVIMETRY , *SCANNING electron microscopy - Abstract
Hybrid material based on halloysite nanotubes (HNTs) and sodium perfluorooctanoate (NaPF8) was used as a consolidant for paper treatment. The consolidation efficiency was determined by thermogravimetry as well as by paper grammage determination. Morphological analysis of the treated paper was performed by means of scanning electron microscopy while the effect of modified HNTs on the thermal behaviour of the cellulose fibres was investigated by differential scanning calorimetry which determined the combustion enthalpy of the paper.Water contact angle measurements were performed to study the paper wettability. The physico-chemical properties investigated (mesoscopic structure, thermal stability and wettability) of the treated paper were correlated successfully with the consolidation loading and, consequently, to the affinity between the fluorinated modified HNTs and the fibrous cellulose structure. This study proposes a new green protocol for paper consolidation based on natural tubular nanoparticles with a flame retardant effect. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
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4. Accelerated Charge Dissipation by Gas-Phase Fluorination on Nomex Paper.
- Author
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Wang, Feipeng, He, Li, Khan, Muhammad Zeeshan, Zhang, Tao, Zhao, Qi, He, Yushuang, Huang, Zhengyong, Zhao, Haisen, and Li, Jian
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SPACE charge ,FLUORINATION ,FOURIER transform infrared spectroscopy ,ELECTRON traps ,SURFACE charges ,ENERGY density - Abstract
The surface charge and space charge accumulation in paper used in oil–paper insulation system may distort electric field distribution and lead to the flashover and breakdown of insulation system. In this paper, the effect of gas-phase fluorination on the surface charge and space charge characteristics of oil-impregnated Nomex paper was investigated. Nomex T410 was fluorinated at 25 °C using F
2 /N2 mixtures with 20% F2 in volume at 0.05 MPa for 15, 30 and 45 min. Fourier Transform Infrared Spectroscopy (FTIR) proved that the molecular chain scission and cleavage occurred during gas-phase fluorination. Furthermore, the surface charge and space charge characteristic of the original and fluorinated oil-impregnated paper were measured using an electrostatic voltmeter and Pulsed Electroacoustic (PEA) equipment respectively. Furthermore, the hole and electron trap distribution of the samples were obtained by Isothermal Surface Potential Decay (ISPD) model. The results showed that both the positive and negative charge decay rates were accelerated by gas-phase fluorination and the hole, electron trap energy and density of the fluorinated samples were reduced by fluorination. It is suggested that the space charge dissipation was also accelerated by fluorination, indicating that gas-phase fluorination is an effective approach to modify the charge dynamics of oil-impregnated Nomex paper. [ABSTRACT FROM AUTHOR]- Published
- 2019
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5. Surface charge accumulation and decay on directfluorinated oil-impregnated paper.
- Author
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Du, B. X., Li, X. L., and Jiang, J. P.
- Subjects
ELECTRICAL insulation contamination ,SURFACE charges ,FLUORINATION ,ELECTRIC fields ,SURFACE properties ,DIELECTRIC materials - Abstract
The oil-impregnated paper, as a vital part in the oil-paper insulation system, serves as the main insulation medium in converter transformer suffering various electric fields. However, the accumulated surface charge on the paper would accelerate the degradation of insulation system and may lead to surface flashover. Direct-fluorination is a method to change the chemical components of polymer matrix thus could affect the surface property of the dielectric material without the alternation of bulk property. This paper presents a method to modify the surface structure of the paper applied in transformers. The paper used in the experiment was treated using the F2/N2 mixture with a volume fraction of 10% for the F2 gas at a pressure of 0.05 MPa in a reaction vessel for 2, 5, 10 and 15 min, respectively. The chemical elements, functional group and physical morphology of the paper before and after modification were measured with energy dispersive X-ray spectroscopy (EDAX), attenuated total reflection infrared (ATR-IR) and scanning electron micrographs (SEM), respectively. Surface and volume resistivity of the fluorinated paper were measured. Furthermore, the surface charge property of the oil-impregnated paper was measured under various positive and negative voltages. Obtained results showed that the fluorination had an obvious influence on the chemical property and surface structure of the paper leading to the reduction of surface and volume resistivity. The treatment was shown to reduce the initial potential and cause acceleration in charge decay process. The trap distribution of the paper surface presented alternation as well. [ABSTRACT FROM PUBLISHER]
- Published
- 2016
- Full Text
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6. Effects of direct fluorination on charge coupling behavior of oil-paper insulation under DC and pulse voltages.
- Author
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Du, B. X., Zhu, W. B., and Li, X. L.
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FLUORINATION , *HALOGENATION , *CHEMICAL reactions , *ELECTRIC potential , *ELECTROSTATICS - Abstract
The oil-impregnated paper, which is the major section in converter transformer, plays a considerable role in the reliability and safety of power grid. However, the insulation degradation will be accelerated by the accumulation of charges that are on the surface of oil-impregnated paper. Therefore, the operating overvoltage occurs and irremediable damage will appear. Direct fluorination is an effective method of modifying the chemical components of polymer matrix so as to have effects on the surface characteristic of the insulating material without reforming the bulk properties. In this research, for studying effects of fluorination on charge behavior on the surface of oil-impregnated paper under the application of DC and impulse voltage, the F2/N2 compound, which the volume fraction for the F2 gas occupied 10 % and the pressure was 0.05 MPa in a reaction kettle for 5, 30 and 60 min respectively, was applied. Meanwhile, the chemical bond groups and the surface morphology of the fluorinated specimen were tested. Besides, the DC voltage amplitude was 4 kV and the applied time was 4 min. The impulse frequency was 500 Hz and the impulse voltage amplitude was 1, 2, 3 and 4 kV, respectively. The charge properties under various situations were investigated. From the research under the application of different fluorination time, impulse voltage amplitudes and polarities, conclusions can be drawn that, fluorination has significant effects on the chemical structure properties and surface characteristic of oil-impregnated paper. Furthermore, the initial potential can be reduced and the decay process of surface charge can be accelerated with different fluorination time increasing from 0 to 30 min. Nevertheless, the tendency is the opposite when the fluorination time continuously extends from 30 to 60 min. The trap distribution also exhibits alternation through the fluorination. [ABSTRACT FROM PUBLISHER]
- Published
- 2017
- Full Text
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7. Method for analysis of 68 organic contaminants in food contact paper using gas and liquid chromatography coupled with tandem mass spectrometry.
- Author
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Vavrouš, Adam, Vápenka, Lukáš, Sosnovcová, Jitka, Kejlová, Kristina, Vrbík, Karel, and Jírová, Dagmar
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FOOD contamination , *TANDEM mass spectrometry , *XENOBIOTICS , *POLYCYCLIC aromatic hydrocarbons , *FLUORINATION - Abstract
Food contact materials (FCMs) have been reported as a source of various xenobiotics. This study investigates the possibility of simultaneous analysis of 68 potential contaminants in paper FCMs, specifically phthalates, polycyclic aromatic hydrocarbons, photoinitiators, bisphenols, and polyfluorinated compounds. Target compounds were co-isolated using a technique based on ultrasonic extraction by mixture of acetonitrile and water followed by QuEChERS-like liquid–liquid partition in the presence of inorganic salts. Resulting extracts were analyzed using gas and high performance liquid chromatography coupled with tandem mass spectrometry (GC–MS/MS, HPLC–MS/MS). Acceptable recoveries (70–120%) and RSDs (<20%) were achieved for most of the analytes at spiking levels of 0.05, 0.2 and 1 mg/kg. LOQs ranged from 0.0013 to 0.22 mg/kg. The proposed method was successfully applied to analysis of 15 real samples. Complex mixtures of contaminants reaching levels up to 48 mg/kg were identified in the samples. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
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8. System Design and the Safety Basis
- Author
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Ellingson, Darrel
- Published
- 2008
9. 8‐1: Distinguished Paper: A Cost‐Effective Fluorination Method for Enhancing the Performance of Metal Oxide Thin‐Film Transistors Using a Fluorinated Planarization Layer.
- Author
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Deng, Sunbin, Zhong, Wei, Dong, Shou-Cheng, Chen, Rongsheng, Li, Guijun, Zhang, Meng, Yeung, Fion Sze Yan, Wong, Man, and Kwok, Hoi-Sing
- Subjects
FLUORINATION ,TRANSISTORS ,INDIUM gallium zinc oxide ,METALLIC oxides ,BUDGET process ,POLYIMIDES ,FLUORINE - Abstract
This work reports a fluorination method for metal oxide thin‐film transistors through a planarization process using fluorinated polyimides. The fluorine diffusion from the planarization layer to the channels enhances device performance and reduces process thermal budget. This method is useful for the cost‐effective production of active‐matrix flat‐panel display panels. [ABSTRACT FROM AUTHOR]
- Published
- 2021
- Full Text
- View/download PDF
10. Contamination, bioaccumulation and toxic effects of perfluorinated chemicals (PFCs) in the water environment: a review paper.
- Author
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Suja, Fatihah, Pramanik, Biplob Kumar, and Zain, Shahrom Md.
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FLUORINATION , *POLLUTANTS , *AQUATIC mammals , *EFFECT of water pollution on aquatic organisms , *CONTAMINATION of drinking water , *BIOACCUMULATION , *BIOCONCENTRATION - Abstract
Perfluorinated compounds such as perfluorooctane sulfonate (PFOS) and perfluorooctane acid (PFOA) have been recognized as emerging environmental pollutants because of their ubiquitous occurrence in the environment, biota and humans. The paper focuses on the distribution, bioaccumulation and toxic effects of PFOS and PFOA in the water. From the available literature, tap and surface water samples in several countries were found to be contaminated with PFOS and PFOA. These compounds were detected globally in the tissues of fish, bird and marine mammals. Their concentrations from relatively more industrialized areas were greater than those from the less populated and remote locations. Blood samples of occupationally exposed people and the general population in various countries were found to contain PFOS and PFOA which suggested a possibility of atmospheric transport of these compounds. There is still a death of information about the environmental pathways of PFOS and PFOA. The presence of these compounds in the tap water, surface water and animal and human tissues indicates their global contamination and bioaccumulative phenomena in the ecosystems. [ABSTRACT FROM AUTHOR]
- Published
- 2009
- Full Text
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11. PAPER CHROMATOGRAPHY OF METAL 2-THENOYLTRIFLUOROACETONE CHELATES
- Author
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McIntyre, R
- Published
- 1954
- Full Text
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12. Chiral bifunctional phase transfer catalysts for asymmetric fluorination of β-keto estersThis article is part of a ChemComm ‘Catalysis in Organic Synthesis’ web-theme issue showcasing high quality research in organic chemistry. Please see our website (http://www.rsc.org/chemcomm/organicwebtheme2009) to access the other papers in this issue.Electronic supplementary information (ESI) available: Experimental details and characterization data for new compounds. See DOI: 10.1039/b920099a
- Author
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Wang, Xisheng, Lan, Quan, Shirakawa, Seiji, and Maruoka, Keiji
- Subjects
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PHASE-transfer catalysis , *CATALYSTS , *FLUORINATION , *ORGANIC synthesis , *CHIRALITY , *PERYLENE , *ENANTIOSELECTIVE catalysis , *ESTERS - Abstract
Chiral bifunctional phase transfer catalysts introducing bis(diarylhydroxymethyl) substituents at 3,3′-positions of the chiral binaphthyl core were successfully applied to asymmetric fluorination of cyclic β-keto esters with high enantioselectivities. [ABSTRACT FROM AUTHOR]
- Published
- 2010
- Full Text
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13. 24‐2: Distinguished Student Paper: Fluorination for Enhancing the Resistance of Indium‐Gallium‐Zinc Oxide Thin‐Film Transistor against Hydrogen‐Induced Degradation.
- Author
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Wang, Sisi, Shi, Runxiao, Li, Jiapeng, Lu, Lei, Xia, Zhihe, Kwok, Hoi Sing, and Wong, Man
- Subjects
INDIUM gallium zinc oxide ,FLUORINATION ,TRANSISTORS ,POLYCRYSTALLINE silicon ,AMORPHOUS silicon ,OXIDES - Abstract
Amorphous indium‐gallium‐zinc oxide (IGZO) thin‐film transistors (TFTs) with or without fluorinated channels were fabricated. The sensitivity of their electrical characteristics to hydrogen exposure was compared. It is shown that those built with fluorinated IGZO exhibit improved intrinsic resistance against hydrogen‐induced degradation. Such improvement correlates well with the reduced incorporation of hydrogen in the fluorinated channels, as revealed by secondary ion‐mass spectrometry. Fluorinated IGZO TFTs are better suited for integration with hydrogen‐containing devices, such as photo‐diodes based on amorphous hydrogenated silicon and TFTs based on low‐temperature polycrystalline silicon. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
- View/download PDF
14. A mechanistic investigation of metal-free allylic fluorination of styrenes for the synthesis of allyl fluoride derivatives using density functional theory.
- Author
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Singh, Harjinder and Saini, Vaneet
- Subjects
DENSITY functional theory ,FLUORINATION ,STYRENE ,ENERGY levels (Quantum mechanics) ,ORGANOFLUORINE compounds - Abstract
The primary objective of this work is to delve into the intricacies of allylic fluorination reactions through the application of density functional theory (DFT) calculations. These reactions hold significant importance in the realm of synthesizing organofluorine compounds. The specific focus lies on comprehending the interaction mechanisms when styrenes, a class of organic molecules, come in contact with an electrophilic fluorinating reagent known as Selectfluor. Notably, this interaction pathway demonstrates remarkable efficiency in yielding allylic fluoride products. The proposed mechanism for this transformation involves a sequential process. To unveil the microcosmic intricacies governing this reaction between the alkene substrate and Selectfluor, advanced computational methodologies are employed. The paper systematically outlines the computational strategies harnessed to probe the minute details of the reaction mechanism. The outcomes of these computations are subsequently subjected to thorough analysis, encompassing crucial facets such as transition states and energy barriers. This analytical depth enhances the fundamental understanding of the reaction mechanism and sheds light on the underlying factors influencing its feasibility and efficiency. In a broader context, the insights garnered from this study carry significant utility. They provide pivotal guidance for the optimization of reaction conditions, facilitating the fine-tuning of experimental setups. Moreover, the elucidated mechanism serves as a platform for the design of even more efficient and selective allylic fluorination reactions. This paper, by amalgamating theoretical insights with practical synthetic objectives, contributes to the broader advancement of organofluorine compound synthesis and allied fields. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
15. Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination
- Author
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Lisa A. Bischoff, Johannes Landmann, Philipp T. Hennig, Nikolai V. Ignat'ev, Michael Drisch, Jan A. P. Sprenger, Michael Hailmann, Maik Finze, Szymon Z. Konieczka, and Raphael Wirthensohn
- Subjects
electrochemical fluorination ,chemistry.chemical_element ,Cyanation ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,Catalysis ,ionic liquids ,chemistry.chemical_compound ,Lewis acids and bases ,Trimethylsilyl cyanide ,Boron trifluoride ,fluoroborates ,Full Paper ,010405 organic chemistry ,Organic Chemistry ,Electrophilic fluorination ,Halogenation ,General Chemistry ,Full Papers ,Electrochemical fluorination ,fluorination ,0104 chemical sciences ,chemistry ,Synthetic Methods | Hot Paper ,ddc:540 ,Fluorine ,cyanoborates - Abstract
Different types of high‐yield, easily scalable syntheses for cyano(fluoro)borates Kt[BFn(CN)4−n] (n=0–2) (Kt=cation), which are versatile building blocks for materials applications and chemical synthesis, have been developed. Tetrafluoroborates react with trimethylsilyl cyanide in the presence of metal‐free Brønsted or Lewis acid catalysts under unprecedentedly mild conditions to give tricyanofluoroborates or tetracyanoborates. Analogously, pentafluoroethyltrifluoroborates are converted into pentafluoroethyltricyanoborates. Boron trifluoride etherate, alkali metal salts, and trimethylsilyl cyanide selectively yield dicyanodifluoroborates or tricyanofluoroborates. Fluorination of cyanohydridoborates is the third reaction type that includes direct fluorination with, for example, elemental fluorine, stepwise halogenation/fluorination reactions, and electrochemical fluorination (ECF) according to the Simons process. In addition, fluorination of [BH(CN)2{OC(O)Et}]− to result in [BF(CN)2{OC(O)Et}]− is described., Three different convenient synthetic routes towards cyano(fluoro)borates, which are versatile building blocks, especially for room temperature ionic liquids, have been developed using easily accessible starting materials.
- Published
- 2020
16. Low friction under ultrahigh contact pressure enabled by self-assembled fluorinated azobenzene layers
- Author
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Xue, Dandan, Xu, Zhi, Guo, Linyuan, Luo, Wendi, Ma, Liran, Tian, Yu, Ma, Ming, Zeng, Qingdao, Deng, Ke, Zhang, Wenjing, Xia, Yichun, Wen, Shizhu, and Luo, Jianbin
- Published
- 2024
- Full Text
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17. Impact of fluorination on interface energetics and growth of pentacene on Ag(111)
- Author
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Steffen Duhm, Antoni Franco-Cañellas, Mengting Chen, Qi Wang, Holger F. Bettinger, Ingo Salzmann, Thomas Geiger, Bin Shen, Frank Schreiber, and Alexander Gerlach
- Subjects
Materials science ,x-ray standing wave technique ,General Physics and Astronomy ,chemistry.chemical_element ,Context (language use) ,02 engineering and technology ,lcsh:Chemical technology ,010402 general chemistry ,medicine.disease_cause ,lcsh:Technology ,01 natural sciences ,Full Research Paper ,decoupling ,Pentacene ,chemistry.chemical_compound ,metal–organic interfaces ,Adsorption ,X-ray photoelectron spectroscopy ,Monolayer ,medicine ,Nanotechnology ,lcsh:TP1-1185 ,General Materials Science ,Electrical and Electronic Engineering ,lcsh:Science ,lcsh:T ,021001 nanoscience & nanotechnology ,fluorination ,lcsh:QC1-999 ,0104 chemical sciences ,organic pi-conjugated molecules ,Nanoscience ,Crystallography ,Electron diffraction ,chemistry ,Fluorine ,lcsh:Q ,0210 nano-technology ,lcsh:Physics ,Ultraviolet - Abstract
We studied the structural and electronic properties of 2,3,9,10-tetrafluoropentacene (F4PEN) on Ag(111) via X-ray standing waves (XSW), low-energy electron diffraction (LEED) as well as ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS). XSW revealed that the adsorption distances of F4PEN in (sub)monolayers on Ag(111) were 3.00 Å for carbon atoms and 3.05 Å for fluorine atoms. The F4PEN monolayer was essentially lying on Ag(111), and multilayers adopted π-stacking. Our study shed light not only on the F4PEN–Ag(111) interface but also on the fundamental adsorption behavior of fluorinated pentacene derivatives on metals in the context of interface energetics and growth mode.
- Published
- 2020
18. Fluorine‐Induced Pseudo ‐Anomeric Effects in Methoxycyclohexanes through Electrostatic 1,3‐Diaxial Interactions
- Author
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David O'Hagan, Bruno Piscelli, Thomas Lebl, Nawaf Al Maharik, Cihang Yu, William Sanders, Rodrigo A. Cormanich, University of St Andrews. School of Chemistry, University of St Andrews. EaSTCHEM, and University of St Andrews. Biomedical Sciences Research Complex
- Subjects
Computational chemistry ,Hydrogen ,Cyclohexane ,Anomeric effect ,T-NDAS ,Ab initio ,chemistry.chemical_element ,Weak interaction ,anomeric effects ,010402 general chemistry ,Ring (chemistry) ,01 natural sciences ,Catalysis ,chemistry.chemical_compound ,medicinal chemistry ,QD ,010405 organic chemistry ,Communication ,Organic Chemistry ,conformational analysis ,General Chemistry ,QD Chemistry ,computational chemistry ,Communications ,fluorination ,0104 chemical sciences ,Crystallography ,Conformational analysis ,chemistry ,Fluorine ,Stereoelectronic effects ,Organofluorine ,Medicinal Chemistry | Hot Paper ,Natural bond orbital - Abstract
We report counter‐intuitive axial preferences in non‐stereochemically biased, selectively fluorinated methoxycyclohexanes. These pseudo‐anomeric effects are apparent when electronegative CF2 groups are placed at the C‐2, C‐4 and C‐6 positions of the cyclohexane ring to render the C‐3/5 axial hydrogen atoms electropositive. The electrostatic interaction between these axial hydrogen atoms and the ‐OMe oxygen is stabilising. The effect is explored using high‐level ab initio and DFT calculations in the framework of NBO, QTAIM and NCI analysis across a range of derivatives, and experimentally (19F{1H}‐NMR at −80 °C) for some illustrative examples. The effect is significant in energy terms for a weak interaction, and illustrates a new stereoelectronic aspect attributed to selective fluorine substitution in organic chemistry., Fluorine chemistry: Selective fluorination in methoxycyclohexanes induces an electrostatic 1,3‐diaxial interaction favouring a counter‐intuitive axial preference.
- Published
- 2020
19. Fluorohydration of alkynes via I(I)/I(III) catalysis
- Author
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Constantin G. Daniliuc, Ryan Gilmour, and Jessica Neufeld
- Subjects
chemistry.chemical_classification ,Organic Chemistry ,Alkyne ,α-fluoroketone ,Combinatorial chemistry ,Full Research Paper ,fluorination ,Catalysis ,lcsh:QD241-441 ,Chemistry ,hypervalent iodine ,lcsh:Organic chemistry ,chemistry ,Organocatalysis ,Substrate specificity ,alkyne ,lcsh:Q ,Amine gas treating ,organocatalysis ,lcsh:Science ,Linker - Abstract
Substrate specificity is ubiquitous in biological catalysis, but less pervasive in the realm of small-molecule catalysis. Herein, we disclose an intriguing example of substrate specificity that was observed whilst exploring catalysis-based routes to generate α-fluoroketones from terminal and internal alkynes under the auspices of I(I)/I(III) catalysis. Utilising p-TolI as an inexpensive organocatalyst with Selectfluor® and amine/HF mixtures, the formation of protected α-fluoroketones from simple alkynes was realised. Whilst the transient p-TolIF2 species generated in situ productively engaged with pentynyl benzoate scaffolds to generate the desired α-fluoroketone motif, augmentation or contraction of the linker suppressed catalysis. The prerequisite for this substructure was established by molecular editing and was complemented with a physical organic investigation of possible determinants.
- Published
- 2020
20. Spatially Resolved Bottom‐Side Fluorination of Graphene by Two‐Dimensional Substrate Patterning
- Author
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Andreas Hirsch, Vincent Lloret, Marcus Halik, Baolin Zhao, Frank Hauke, and Lipiao Bao
- Subjects
Graphene Functionalization | Hot Paper ,Materials science ,Scanning electron microscope ,Band gap ,chemistry.chemical_element ,Nanotechnology ,Substrate (printing) ,Substrate (electronics) ,010402 general chemistry ,01 natural sciences ,Catalysis ,law.invention ,symbols.namesake ,ditopic functionalization ,law ,Spectroscopy ,business.industry ,010405 organic chemistry ,Graphene ,Spatially resolved ,Communication ,graphene ,General Medicine ,General Chemistry ,substrate patterning ,Communications ,fluorination ,0104 chemical sciences ,chemistry ,ddc:540 ,Fluorine ,symbols ,Optoelectronics ,Surface modification ,business ,Raman spectroscopy - Abstract
Patterned functionalization can, on the one hand, open the band gap of graphene and, on the other hand, program demanding designs on graphene. The functionalization technique is essential for graphene‐based nanoarchitectures. A new and highly efficient method was applied to obtain patterned functionalization on graphene by mild fluorination with spatially arranged AgF arrays on the structured substrate. Scanning Raman spectroscopy (SRS) and scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy (SEM‐EDS) were used to characterize the functionalized materials. For the first time, chemical patterning on the bottom side of graphene was realized. The chemical nature of the patterned functionalization was determined to be the ditopic scenario with fluorine atoms occupying the bottom side and moieties, such as oxygen‐containing groups or hydrogen atoms, binding on the top side, which provides information about the mechanism of the fluorination process. Our strategy can be conceptually extended to pattern other functionalities by using other reactants. Bottom‐side patterned functionalization enables utilization of the top side of a material, thereby opening up the possibilities for applications in graphene‐based devices., Bottoms up! Patterned bottom‐side functionalization of graphene was realized using a 2D substrate patterning method. A very high degree of functionalization and patterned fluorination are demonstrated. Ditopic functionalization is observed with fluorine atoms on the bottom side and moieties, such as oxygen‐containing groups or hydrogen atoms, on the top side.
- Published
- 2020
21. Kinetics of electrophilic fluorination of steroids and epimerisation of fluorosteroids
- Author
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Alexander S. Cook, Antal Harsanyi, Ben J. Murray, David R. W. Hodgson, Emily J. Chin, Neshat Rozatian, Alexander S. Hampton, and Graham Sandford
- Subjects
Full Paper ,Chemistry ,Organic Chemistry ,Electrophilic fluorination ,Kinetics ,General Chemistry ,Full Papers ,stereoselectivity ,Enol ,fluorination ,Catalysis ,chemistry.chemical_compound ,Acetic acid ,fluorosteroid ,Reagent ,Electrophile ,Organic chemistry ,Stereoselectivity ,Methanol ,epimerisation - Abstract
Fluorinated steroids, which are synthesised by electrophilic fluorination, form a significant proportion of marketed pharmaceuticals. To gain quantitative information on fluorination at the 6‐position of steroids, kinetics studies were conducted on enol ester derivatives of progesterone, testosterone, cholestenone and hydrocortisone with a series of electrophilic N−F reagents. The stereoselectivities of fluorination reactions of progesterone enol acetate and the kinetic effects of additives, including methanol and water, were investigated. The kinetics of epimerisation of 6β‐fluoroprogesterone to the more pharmacologically active 6α‐fluoroprogesterone isomer in HCl/acetic acid solutions are detailed., Fluorosteroid pharmaceuticals are prepared industrially by electrophilic fluorination. Quantitative insights into the synthesis of 6‐fluorosteroids could lead to more efficient processes. Here, kinetic and analytical studies upon a range of fluorinations of steroid enol esters, and subsequent epimerisation towards the α‐epimer are described. X‐ray crystallography is exploited to deliver unambiguous assignments of absolute configurations.
- Published
- 2020
22. Combining Theory and Experiment to Characterize the Voltammetric Behavior of Nickel Anodes in the Simons Process
- Author
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Gene Senges, Stefan Mattsson, Sebastian Riedel, and Beate Paulus
- Subjects
Inorganic chemistry ,chemistry.chemical_element ,010402 general chemistry ,Electrocatalyst ,01 natural sciences ,Catalysis ,electrocatalysis ,Full Paper ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,nickel fluorides ,quantum-chemical calculations ,General Chemistry ,Full Papers ,Electrochemical fluorination ,Nickel Fluorides | Hot Paper ,cyclic voltammetry ,fluorination ,0104 chemical sciences ,Anode ,Nickel ,Scientific method ,Density functional theory ,Cyclic voltammetry ,500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften ,Layer (electronics) - Abstract
The Simons process, otherwise known as the electrochemical fluorination (ECF) method, is widely used in industry to electrolytically synthesize chemicals for various purposes. Even to this day, the exact mechanism of the ECF reaction remains unknown, but is believed to involve the formation of an anodic nickel fluoride film with highly oxidized nickel centers. In this study, experiments and density functional theory calculations are combined to characterize the initial anodic peak occurring at potentials typically required in an ECF cell. NiF2 is believed to form a passivating layer at low potentials. The calculations show that a potential of +3.1 V is required to oxidize surface Ni2+ centers to Ni3+. This is in good agreement with the measured anodic peak at +3.57 V., Simons says: The fluorinating species in the Simons process is an anodic nickel fluoride film of unknown structure. In this work, complimentary experiments and density functional theory calculations are set up to assign the characteristic anodic peak to the oxidation of Ni2+ to Ni3+.
- Published
- 2020
23. Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.
- Author
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Day, James, Macpherson, Colin, Lowry, David, and Pearson, D.
- Subjects
OXYGEN isotopes ,SECONDARY ion mass spectrometry ,REGOLITH ,FLUORINATION ,OLIVINE ,PERIDOTITE ,PYROXENITE - Abstract
Gurenko et al. (Contrib Mineral Petrol 162:349-363, ) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) O/O datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233-262, ; Day et al. Geology 37:555-558, , Geochim Cosmochim Acta 74:6565-6589, ), these authors find variations in δO (~4.6-6.0 ‰) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231-241, ) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349-363, ) speculate that δO values for La Palma olivine grains measured by LF (Day et al. Geology 37:555-558, , Geochim Cosmochim Acta 74:6565-6589, ) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in δO values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349-363, ) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that δO is weakly correlated ( R = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514-524, ) to describe the estimated weight fraction of pyroxenite-derived melt ( Xpx). With this relationship, end-member δO values for HIMU-peridotite (δO = 5.3 ± 0.3 ‰) and depleted pyroxenite (δO = 5.9 ± 0.3 ‰) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349-363, ) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555-558, , Geochim Cosmochim Acta 74:6565-6589, ) and Day and Hilton (Earth Planet Sci Lett 305:226-234, ), there are significant differences in the predicted δO values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565-6589, ) proposed a mantle source for La Palma lavas with low-δO (<5 ‰), rather than higher-δO (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349-363, ). Here we question the approach of using weakly correlated variations in δO and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques. [ABSTRACT FROM AUTHOR]
- Published
- 2012
- Full Text
- View/download PDF
24. Fluorocyclisation via I(I)/I(III) catalysis: a concise route to fluorinated oxazolines
- Author
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Constantin G. Daniliuc, Felix Scheidt, Ryan Gilmour, Stephanie Meyer, Christian Thiehoff, Gülay Yilmaz, and Gerald Kehr
- Subjects
Stereochemistry ,gauche effect ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Full Research Paper ,Catalysis ,lcsh:QD241-441 ,chemistry.chemical_compound ,lcsh:Organic chemistry ,lcsh:Science ,catalysis ,010405 organic chemistry ,Chemistry ,oxazolines ,Organic Chemistry ,fluorination ,0104 chemical sciences ,cyclisation ,hypervalent iodine ,Fluorine ,lcsh:Q ,Bioisostere ,Brønsted–Lowry acid–base theory ,Vicinal - Abstract
Herein, we describe a catalytic fluorooxygenation of readily accessible N-allylcarboxamides via an I(I)/I(III) manifold to generate 2-oxazolines containing a fluoromethyl group. Catalysis is conditional on the oxidation competence of Selectfluor®, whilst HF serves as both a fluoride source and Brønsted acid activator. The C(sp3)–F bond of the mono-fluoromethyl unit and the C(sp3)–O bond of the ring are aligned in a synclinal relationship thereby engaging in stabilising hyperconjugative interactions with vicinal, electron-rich σ-bonds (σC–C→σ*C–F and σC–H→σ*C–O). This manifestation of the stereoelectronic gauche effect was established by X-ray crystallographic analysis of a representative example. Given the importance of fluorine in drug discovery, its ability to modulate conformation, and the prevalence of the 2-oxazoline scaffold in Nature, this strategy provides a rapid entry into an important bioisostere class.
- Published
- 2018
25. Capacitive Organic Anode Based on Fluorinated-Contorted Hexabenzocoronene: Applicable to Lithium-Ion and Sodium-Ion Storage Cells
- Author
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Seok Ju Kang, Seokhoon Ahn, Sang Kyu Kwak, Jaehyun Park, Cheol Woo Lee, Se Hun Joo, and Ju Hyun Park
- Subjects
Materials science ,General Chemical Engineering ,Capacitive sensing ,General Physics and Astronomy ,Medicine (miscellaneous) ,chemistry.chemical_element ,contorted hexabenzocoronene ,02 engineering and technology ,Electrolyte ,010402 general chemistry ,Electrochemistry ,01 natural sciences ,Biochemistry, Genetics and Molecular Biology (miscellaneous) ,chemistry.chemical_compound ,pseudocapacitors ,General Materials Science ,Conductive polymer ,Full Paper ,General Engineering ,Full Papers ,021001 nanoscience & nanotechnology ,fluorination ,0104 chemical sciences ,Anode ,Hexabenzocoronene ,chemistry ,Chemical engineering ,high current rates ,Pseudocapacitor ,electrochemical capacitors ,Lithium ,0210 nano-technology - Abstract
Conducting polymer‐based organic electrochemical capacitor materials have attracted attention because of their highly conductive nature and highly reversible redox reactions on the surface of electrodes. However, owing to their poor stabilities in aprotic electrolytes, alternative organic electrochemical capacitive electrodes are being actively sought. Here, fluorine atoms are introduced into contorted hexabenzocoronene (cHBC) to achieve the first small‐molecule‐based organic capacitive energy‐storage cells that operate at high current rates with satisfactory specific capacities of ≈160 mA h g−1 and superior cycle capabilities (>400) without changing significantly. This high capacitive behavior in the P21/c crystal phase of fluorinated cHBC (F—cHBC) is caused mainly by the fluorine atoms at the end of each peripheral aromatic ring. Combined Monte Carlo simulations and density functional theory (DFT) calculations show that the most electronegative fluorine atoms accelerate ion diffusion on the surface to promote fast Li+ ion uptake and release by an applied current. Moreover, F—cHBC has potential applications as the capacitive anode in Na‐ion storage cells. The fast dynamics of its capacitive behavior allow it to deliver a specific capacity of 65 mA h g−1 at a high current of 4000 mA g−1.
- Published
- 2018
26. One-pot multistep mechanochemical synthesis of fluorinated pyrazolones
- Author
-
William I. Nicholson, Yerbol Sagatov, Joseph Howard, and Duncan L. Browne
- Subjects
heterocycles ,Heterocycle formation ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,010402 general chemistry ,01 natural sciences ,Combinatorial chemistry ,multistep ,Full Research Paper ,fluorination ,0104 chemical sciences ,Solvent ,lcsh:QD241-441 ,lcsh:Organic chemistry ,Mechanochemistry ,solid-state synthesis ,Pyrazolones ,lcsh:Q ,mechanochemistry ,lcsh:Science - Abstract
Solventless mechanochemical synthesis represents a technique with improved sustainability metrics compared to solvent-based processes. Herein, we describe a methodical process to run one solventless reaction directly into another through multistep mechanochemistry, effectively amplifying the solvent savings. The approach has to consider the solid form of the materials and compatibility of any auxiliary used. This has culminated in the development of a two-step, one-jar protocol for heterocycle formation and subsequent fluorination that has been successfully applied across a range of substrates, resulting in 12 difluorinated pyrazolones in moderate to excellent yields.
- Published
- 2017
27. Theoretical Study on Fluorinated Derivatives of Sulfolane, Cyclopentanone, and Gamma-Butyrolactone.
- Author
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Tshepelevitsh, Sofja, Kütt, Agnes, and Leito, Ivo
- Subjects
BUTYROLACTONES ,PERMITTIVITY ,BOILING-points ,BASICITY ,FLUORINATION ,PROPYLENE carbonate - Abstract
In this paper, fluorinated compounds based on sulfolane, cyclopentanone, and gamma-butyrolactone are studied computationally, focusing on their applicability in electrochemical devices and acid–base-related studies. Candidates for solvents with (1) high polarity, (2) good electrochemical stability, and (3) low basicity were searched for. Some of the compounds are studied here for the first time. Electrochemical stabilities, dielectric constants, boiling points, basicities, and lipophilicities were estimated using DFT and COSMO-RS methods with empirical corrections. The effect of fluorination on these properties as well as the bond parameters was studied. The possible synthesis routes of the proposed compounds are outlined. Some molecules display a combination of estimated properties favorable for a solvent, although none of the studied compounds are expected to surpass acetonitrile and propylene carbonate by the width of the electrochemical stability window. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
28. Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties
- Author
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Martin Heeney, Ji-Seon Kim, Sebastian Wood, Pierre Boufflet, Jessica Wade, and Zhuping Fei
- Subjects
conjugated block-copolymer synthesis ,temperature-dependent Raman spectroscopy ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,0305 Organic Chemistry ,Full Research Paper ,lcsh:QD241-441 ,chemistry.chemical_compound ,symbols.namesake ,lcsh:Organic chemistry ,Block (telecommunications) ,Polymer chemistry ,Copolymer ,Thermal stability ,lcsh:Science ,microphase stabilization ,Organic Chemistry ,021001 nanoscience & nanotechnology ,Microstructure ,polythiophene ,fluorination ,0104 chemical sciences ,Chemistry ,Monomer ,chemistry ,Chemical engineering ,Polymerization ,symbols ,Polythiophene ,lcsh:Q ,0210 nano-technology ,Raman spectroscopy - Abstract
The microstructure of the active blend layer has been shown to be a critically important factor in the performance of organic solar devices. Block copolymers provide a potentially interesting avenue for controlling this active layer microstructure in solar cell blends. Here we explore the impact of backbone fluorination in block copolymers of poly(3-octyl-4-fluorothiophene)s and poly(3-octylthiophene) (F-P3OT-b-P3OT). Two block co-polymers with varying block lengths were prepared via sequential monomer addition under Kumada catalyst transfer polymerisation (KCTP) conditions. We compare the behavior of the block copolymer to that of the corresponding homopolymer blends. In both types of system, we find the fluorinated segments tend to dominate the UV–visible absorption and molecular vibrational spectral features, as well as the thermal behavior. In the block copolymer case, non-fluorinated segments appear to slightly frustrate the aggregation of the more fluorinated block. However, in situ temperature dependent Raman spectroscopy shows that the intramolecular order is more thermally stable in the block copolymer than in the corresponding blend, suggesting that such materials may be interesting for enhanced thermal stability of organic photovoltaic active layers based on similar systems.
- Published
- 2016
29. Organocatalytic asymmetric fluorination of α-chloroaldehydes involving kinetic resolution
- Author
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Akira Narayama, Kazutaka Shibatomi, Takuya Okimi, Seiji Iwasa, Nami Nakamura, and Yoshiyuki Abe
- Subjects
organo-fluorine ,Reaction mechanism ,chlorination ,Chemistry ,Organic Chemistry ,Enantioselective synthesis ,Substrate (chemistry) ,asymmetric catalysis ,Full Research Paper ,fluorination ,Kinetic resolution ,lcsh:QD241-441 ,α-branched aldehyde ,lcsh:Organic chemistry ,Computational chemistry ,Organic chemistry ,lcsh:Q ,lcsh:Science ,organocatalyst - Abstract
In a previous study it was shown that the enantioselective α-fluorination of racemic α-chloroaldehydes with a chiral organocatalyst yielded the corresponding α-chloro-α-fluoroaldehydes with high enantioselectivity. It was also revealed that kinetic resolution of the starting aldehydes was involved in this asymmetric fluorination. This paper describes the determination of the absolute stereochemistry of a resulting α-chloro-α-fluoroaldehyde. Some information about the substrate scope and a possible reaction mechanism are also described which shed more light on the nature of this asymmetric fluorination reaction.
- Published
- 2014
30. Calculations of helium separation via uniform pores of stanene-based membranes
- Author
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Yan Jiao, Yalong Jiao, Liangzhi Kou, Fengxian Ma, Guoping Gao, and Aijun Du
- Subjects
Materials science ,General Physics and Astronomy ,chemistry.chemical_element ,Nanotechnology ,honeycomb lattice ,lcsh:Chemical technology ,lcsh:Technology ,Full Research Paper ,Analytical Chemistry ,Stanene ,General Materials Science ,lcsh:TP1-1185 ,Electrical and Electronic Engineering ,lcsh:Science ,Helium ,lcsh:T ,Noble gas ,fluorination ,lcsh:QC1-999 ,Nanoscience ,Membrane ,gas purification ,Chemical engineering ,chemistry ,Surface modification ,Density functional theory ,lcsh:Q ,Other Chemical Sciences ,Selectivity ,Porous medium ,lcsh:Physics - Abstract
The development of low energy cost membranes to separate He from noble gas mixtures is highly desired. In this work, we studied He purification using recently experimentally realized, two-dimensional stanene (2D Sn) and decorated 2D Sn (SnH and SnF) honeycomb lattices by density functional theory calculations. To increase the permeability of noble gases through pristine 2D Sn at room temperature (298 K), two practical strategies (i.e., the application of strain and functionalization) are proposed. With their high concentration of large pores, 2D Sn-based membrane materials demonstrate excellent helium purification and can serve as a superior membrane over traditionally used, porous materials. In addition, the separation performance of these 2D Sn-based membrane materials can be significantly tuned by application of strain to optimize the He purification properties by taking both diffusion and selectivity into account. Our results are the first calculations of He separation in a defect-free honeycomb lattice, highlighting new interesting materials for helium separation for future experimental validation.
- Published
- 2015
31. Synthesis of new Ln
- Author
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Aritza Wain-Martin, M. I. Arriortua, Peter R. Slater, Aitor Larrañaga, Aroa Morán-Ruiz, María Luisa Sanjuán, Alodia Orera, Eusko Jaurlaritza, Ministerio de Economía, Industria y Competitividad (España), European Commission, Universidad del País Vasco, and Ministerio de Economía y Competitividad (España)
- Subjects
Materials science ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Biochemistry ,03 medical and health sciences ,chemistry.chemical_compound ,symbols.namesake ,X-ray photoelectron spectroscopy ,Fluorination ,poly(vinylidene difluoride) ,General Materials Science ,poly(vinylidene difluoride) ,Poly(vinylidene difluoride) ,Spectroscopy ,030304 developmental biology ,0303 health sciences ,Crystallography ,Difluoride ,Cuspidine-type rare-earth aluminates ,General Chemistry ,Condensed Matter Physics ,Research Papers ,cuspidine-type rare-earth aluminates ,fluorination ,0104 chemical sciences ,X-ray diffraction ,Cuspidine ,chemistry ,QD901-999 ,X-ray crystallography ,Raman spectroscopy ,Fluorine ,symbols ,Fluoride - Abstract
The first fluorination of the cuspidine-related phases of Ln4(Al2O7□)O2 (where Ln = Sm, Eu, Gd) is reported. A low-temperature reaction with poly(vinyl-idene difluoride) lead to the fluorine being substituted in place of oxygen and inserted into the vacant position between the dialuminate groups. X-ray photoelectron spectroscopy shows the presence of the F 1s photoelectron together with an increase in Al 2p and rare-earth 4d binding energies supporting F incorporation. Energy-dispersive X-ray spectroscopy analyses are consistent with the formula Ln4(Al2O6F2)O2, confirming that substitution of one oxygen by two fluoride atoms has been achieved. Rietveld refinements show an expansion in the cell upon fluorination and confirm that the incorporation of fluoride in the Ln4(Al2O7□)O2 structure results in changes in Al coordination from four to five. Thus, the isolated tetrahedral dialuminate Al2O7 groups are converted to chains of distorted square-based pyramids. These structural results are also discussed based on Raman spectra., This research was funded by the Ministerio de Economía, Industria y Competitividad (MAT2016-76739-R) (AEI/FEDER, UE), and Departamento de Educación of the Basque Government (IT-630–13). The authors thank SGIker of UPV/EHU for technical and personnel support. A. Mora´nRuiz thanks UPV/EHU for funding.
- Published
- 2018
32. Physical-chemical features of fluorination of spent fluid catalytic cracking.
- Author
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Puzhel, A. O., Borisov, V. A., and Adeeva, L. N.
- Subjects
CATALYTIC cracking ,FLUORINATION ,CHEMICAL kinetics ,IRON compounds ,ACTIVATION energy ,ALUMINUM forming - Abstract
In this paper, the process of fluoroammonium treatment of a spent fluid catalytic cracking catalyst (FCC catalyst) is studied. The main thermodynamic characteristics for reactions describing the process are calculated. Ammonium fluoride was taken in excess 1 : 1.5. It has been established that the fluorination of silicon in the composition of the catalyst is the most intense. Based on experimental data, a kinetic model for the fluorination reaction of silicon oxide has been determined. The apparent activation energy and the rate constant of the chemical reaction are calculated. Kinetic curves of the fluorination processes of aluminum, iron compounds and for the FCC catalyst are obtained. The residue after fluorination is investigated by IR spectroscopy and SEM. The composition of the residue after fluorination has been established. It is determined that the concentration of REE occurs due to the removal of silicon and partial removal of iron and aluminum compounds in the form of soluble fluoroammonium complexes. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
33. Intramolecular OH⋅⋅⋅Fluorine Hydrogen Bonding in Saturated, Acyclic Fluorohydrins: The γ-Fluoropropanol Motif
- Author
-
Clement Q. Fontenelle, Neil J. Wells, Nicolas Galland, Bruno Linclau, Zhong Wang, Elena Bogdan, Jérôme Graton, Jean-Yves Le Questel, Florent Peron, and Guillaume Compain
- Subjects
Quantum chemical ,chemistry.chemical_classification ,Hydrogen bond ,Chemistry ,Stereochemistry ,Organic Chemistry ,quantum calculations ,Drug design ,chemistry.chemical_element ,General Chemistry ,Nuclear magnetic resonance spectroscopy ,Full Papers ,fluorination ,Catalysis ,NMR spectroscopy ,Computational chemistry ,Intramolecular force ,intramolecular interactions ,hydrogen bonds ,Alkyl substitution ,Fluorine ,Alkyl - Abstract
Fluorination is commonly exercised in compound property optimization. However, the influence of fluorination on hydrogen-bond (HB) properties of adjacent functional groups, as well as the HB-accepting capacity of fluorine itself, is still not completely understood. Although the formation of OH⋅⋅⋅F intramolecular HBs (IMHBs) has been established for conformationally restricted fluorohydrins, such interaction in flexible compounds remained questionable. Herein is demonstrated for the first time-and in contrast to earlier reports-the occurrence of OH⋅⋅⋅F IMHBs in acyclic saturated γ-fluorohydrins, even for the parent 3-fluoropropan-1-ol. The relative stereochemistry is shown to have a crucial influence on the corresponding (h1) JOH⋅⋅⋅F values, as illustrated by syn- and anti-4-fluoropentan-2-ol (6.6 and 1.9 Hz). The magnitude of OH⋅⋅⋅F IMHBs and their strong dependence on the overall molecular conformational profile, fluorination motif, and alkyl substitution level, is rationalized by quantum chemical calculations. For a given alkyl chain, the "rule of shielding" applies to OH⋅⋅⋅F IMHB energies. Surprisingly, the predicted OH⋅⋅⋅F IMHB energies are only moderately weaker than these of the corresponding OH⋅⋅⋅OMe. These results provide new insights of the impact of fluorination of aliphatic alcohols, with attractive perspectives for rational drug design.
- Published
- 2015
34. Enhanced Dyeing of Polypropylene Using Fluorine–Oxygen Gas Mixtures.
- Author
-
Namie, Masanari, Kim, Jae-Ho, and Yonezawa, Susumu
- Subjects
POLYPROPYLENE ,GAS mixtures ,DYES & dyeing ,FLUORINATION ,X-ray photoelectron spectroscopy - Abstract
Surface fluorination with pure F
2 gas can easily make the surface on PP (polypropylene) hydrophobic, and it causes limited dyeability, as reported in a previous paper. In this study, to produce a more hydrophilic surface, surface fluorination of PP was performed at 25 °C, total gas pressure of 13.3 kPa, and reaction time of 1 h using F2 and O2 mixtures with different proportions of F2 gas. The surface roughness of the fluorinated PP samples was about 1.5 times higher than that of the untreated sample (5 nm). Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) results showed that the PP-derived bonds (-C-C- and -CHx ) decreased because they were converted into polar groups (-C–O, -CHF-, and -CFx ), which increased the surface electronegativity of the PP. The variation in the F2 gas proportion in the gas mixture significantly affected the hydrophilicity and surface composition of the PP. At F2 gas proportions of <70%, the hydrophilicity of the fluorinated PP samples was increased. Notably, the hydrophilic and negatively charged PP surface enhanced the dyeing of the polymer with basic methylene blue (MB). In contrast, at F2 gas proportions of >90%, the PP surface became hydrophobic owing to increased numbers of hydrophobic -CF3 bonds. Thus, enhanced PP dyeing can be controlled based on the composition of the F2 and O2 gas mixture. [ABSTRACT FROM AUTHOR]- Published
- 2023
- Full Text
- View/download PDF
35. Effect of the fluorination technique on the surface-fluorination patterning of double-walled carbon nanotubes
- Author
-
Lyubov G. Bulusheva, D.V. Vyalikh, Yuliya V. Fedoseeva, Gregory Van Lier, Victor O. Koroteev, Emmanuel Flahaut, Christopher P. Ewels, Alexander V. Okotrub, Jeremy Rio, Laboratoire de Chimie des Matériaux Inorganiques - LCMI (Toulouse, France), Université Paul Sabatier - Toulouse 3 ( UPS ), Institut des matériaux Jean Rouxel ( IMN ), Université de Nantes ( UN ) -Centre National de la Recherche Scientifique ( CNRS ), Centre National de la Recherche Scientifique - CNRS (FRANCE), Donostia International Physics Center - DIPC (SPAIN), IKERBASQUE (SPAIN), Institut National Polytechnique de Toulouse - INPT (FRANCE), Novosibirsk State University (RUSSIA), Siberian Branch of the Russian Academy of Sciences - SB RAS (RUSSIA), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Université de Nantes (FRANCE), Vrije Universiteit Brussel - VUB (BELGIUM), Centre Interuniversitaire de Recherche et d'Ingénierie des Matériaux - CIRIMAT (Toulouse, France), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Russian Foundation for Basic Research, and European Commission
- Subjects
Double-walled carbon nanotubes ,Quantum-chemical modelin ,General Physics and Astronomy ,02 engineering and technology ,lcsh:Chemical technology ,Photochemistry ,lcsh:Technology ,01 natural sciences ,Full Research Paper ,law.invention ,Fluorination ,law ,Fluorine gas ,Nanotechnology ,Organic chemistry ,lcsh:TP1-1185 ,General Materials Science ,lcsh:Science ,Flurination ,ComputingMilieux_MISCELLANEOUS ,021001 nanoscience & nanotechnology ,lcsh:QC1-999 ,Nanoscience ,Covalent bond ,[PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci] ,symbols ,0210 nano-technology ,Bromine trifluoride ,quantum-chemical modeling ,Materials science ,Selective chemistry of single-walled nanotubes ,[ PHYS.COND.CM-MS ] Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci] ,chemistry.chemical_element ,Carbon nanotube ,010402 general chemistry ,NEXAFS ,symbols.namesake ,CF4 radio-frequency plasma ,Electrical and Electronic Engineering ,lcsh:T ,fluorination ,XANES ,0104 chemical sciences ,chemistry ,Fluorine ,Surface modification ,lcsh:Q ,Mécanique des matériaux ,Raman spectroscopy ,Carbon ,lcsh:Physics - Abstract
Double-walled carbon nanotubes (DWCNTs) are fluorinated using (1) fluorine F2 at 200 °C, (2) gaseous BrF3 at room temperature, and (3) CF4 radio-frequency plasma functionalization. These have been comparatively studied using transmission electron microscopy and infrared, Raman, X-ray photoelectron, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. A formation of covalent C–F bonds and a considerable reduction in the intensity of radial breathing modes from the outer shells of DWCNTs are observed for all samples. Differences in the electronic state of fluorine and the C–F vibrations for three kinds of the fluorinated DWCNTs are attributed to distinct local surroundings of the attached fluorine atoms. Possible fluorine patterns realized through a certain fluorination technique are revealed from comparison of experimental NEXAFS F K-edge spectra with quantum-chemical calculations of various models. It is proposed that fluorination with F2 and BrF3 produces small fully fluorinated areas and short fluorinated chains, respectively, while the treatment with CF4 plasma results in various attached species, including single or paired fluorine atoms and –CF3 groups. The results demonstrate a possibility of different patterning of carbon surfaces through choosing the fluorination method., he work was financially supported by the Russian Foundation for Basic Research (grant 16-53-150003) and the bilateral Program “Russian–German Laboratory at BESSY”. Collaboration between partner institutions was partially supported by the European FP7-PEOPLE-2013-IRSES project 612577.
- Published
- 2017
36. Aminofluorination of 2-alkynylanilines: a Au-catalyzed entry to fluorinated indoles
- Author
-
Antonello Alvino, Antonio Arcadi, Véronique Michelet, and Emanuela Pietropaolo
- Subjects
chemistry.chemical_classification ,Tandem ,Chemistry ,Organic Chemistry ,Gold Catalysis ,Fluorination ,Indoles ,indoles ,Triple bond ,Combinatorial chemistry ,Full Research Paper ,fluorination ,gold catalysis ,Catalysis ,lcsh:QD241-441 ,Cycloisomerization ,lcsh:Organic chemistry ,Cascade reaction ,Organic chemistry ,lcsh:Q ,tandem reactions ,lcsh:Science ,2-alkynylanilines ,Alkyl - Abstract
The scope and limitations of gold-catalyzed tandem cycloisomerization/fluorination reactions of unprotected 2-alkynylanilines to have access to 3,3-difluoro-2-aryl-3H-indoles and 3-fluoro-2-arylindoles are described. An unprecedented aminoauration/oxidation/fluorination cascade reaction of 2-alkynylanilines bearing a linear alkyl group on the terminal triple bond is reported.
- Published
- 2014
37. The difluoromethylene (CF2) group in aliphatic chains: Synthesis and conformational preference of palmitic acids and nonadecane containing CF2 groups
- Author
-
Yi Wang, David O'Hagan, Alexandra M. Z. Slawin, Ricardo Callejo, EPSRC, University of St Andrews. School of Chemistry, University of St Andrews. EaSTCHEM, and University of St Andrews. Biomedical Sciences Research Complex
- Subjects
organo-fluorine ,Nonadecane ,Stereochemistry ,difluoromethylene ,Organic-compounds ,fatty acids ,Full Research Paper ,lcsh:QD241-441 ,Palmitic acid ,chemistry.chemical_compound ,Differential scanning calorimetry ,Organo-fluorine ,lcsh:Organic chemistry ,Fluorination ,Phase (matter) ,palmitic acid ,QD ,Fatty acids ,lcsh:Science ,chemistry.chemical_classification ,Organic fluorine chemistry ,Reagents ,Organofluorine chemistry ,Organic Chemistry ,C-F Bbond ,Difluoromethylene ,organic fluorine chemistry ,QD Chemistry ,fluorination ,Crystallography ,Chemistry ,Hydrocarbon ,chemistry ,Reagent ,Melting point ,Flourine ,lcsh:Q ,Derivatives - Abstract
The syntheses of palmitic acids and a nonadecane are reported with CF2 groups located 1,3 or 1,4 to each other along the aliphatic chain. Specifically 8,8,10,10- and 8,8,11,11-tetrafluorohexadecanoic acids (6b and 6c) are prepared as well as the singly modified analogue 8,8-difluorohexadecanoic acid (6a). Also 8,8,11,11-tetrafluorononadecane (27) is prepared as a pure hydrocarbon containing a 1,4-di-CF2 motif. The modified palmitic acids are characterized by differential scanning calorimetry (DSC) to determine melting points and phase behaviour relative to palmitic acid (62.5 °C). It emerges that 6c, with the CF2 groups placed 1,4- to each other, has a significantly higher melting point (89.9 °C) when compared to the other analogues and palmitic acid itself. It is a crystalline compound and the structure reveals an extended anti-zig-zag chain. Similarly 8,8,11,11-tetrafluorononadecane (27) adopts an extended anti-zig-zag structure. This is rationalized by dipolar relaxation between the two CF2 groups placed 1,4 to each other in the extended anti-zig-zag chain and suggests a design modification for long chain aliphatics which can introduce conformational stability.
- Published
- 2014
38. Flexible fluorinated graphite foils with high contents of the (C2F)n phase for slow neutron reflectors.
- Author
-
Henry, Killian, Colin, Marie, Chambery, Gabin, Vigolo, Brigitte, Cahen, Sébastien, Hérold, Claire, Nesvizhevsky, Valery, Le Floch, Sylvie, Pischedda, Vittoria, Chen, Sam, and Dubois, Marc
- Subjects
GRAPHITE fluorides ,NEUTRONS ,GRAPHENE oxide ,FLUORINATION ,FLUORINE ,GRAPHITE - Abstract
In order to prepare self-standing and flexible slow neutron reflectors made of graphite fluoride (GF) with high contents of (C
2 F)n structural phase, graphite foils of different thicknesses were used as starting materials for gas (F2 )/solid fluorination. The maximal interlayer distance of GF was obtained with this phase thanks to the stacking sequence FCCF/FCCF; this is mandatory for the efficient reflection of slow neutrons. 71 and 77% of the (C2 F)n phase were achieved for graphite foils with thicknesses of 1.0 and 0.1 mm, respectively. The interlayer distances were 8.6 Å as expected. The fluorination conditions (static mode, a long duration of 24 h, annealing in pure F2 gas for 24 h, and temperatures in the 390–460 °C range) were adapted to large pieces of graphite foils (7 × 7 cm2 ) in order to both avoid exfoliation and achieve a homogeneous dispersion of fluorine atoms. This process was also efficient for thinner (0.01 mm thick) graphitized graphene oxide foil. 56% of the (C2 F)n phase and an interlayer of 8.6 Å were achieved for this foil when fluorination was performed at 430 °C. Whatever the nature and the thickness of the foil, their flexibilities are maintained. [ABSTRACT FROM AUTHOR]- Published
- 2024
- Full Text
- View/download PDF
39. Perfluoro(7-methylbicyclo[4.3.0]nonane) Purification from Close-Boiling Impurities by Heteroazeotropic Distillation Method †.
- Author
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Polkovnichenko, Andrei V., Lupachev, Egor V., Kisel', Alexey V., Kvashnin, Sergey Ya., and Kulov, Nikolai N.
- Subjects
PERFLUORO compounds ,PHASE equilibrium ,DISTILLATION ,ELECTROCHEMISTRY ,FLUORINATION ,LIQUID-liquid transformations - Abstract
The purification of perfluoro(7-methylbicyclo[4.3.0]nonane) industrial fractions with a component content above 0.950 in mass fraction is not effective and requires the use of special separation methods. According to experimental data, the separation factor of the initial mixture during distillation with no additional substances is close to 1. At the same time, the addition of acetone (Ac) makes it possible to significantly intensify the process. Ac allowed for obtaining MBCN with a purity higher than 0.998 in mass fraction in one separation cycle, and the degree of recovery was more than 0.85 by weight. The paper presents data on the distribution of components (target product, identified and unidentified impurities of electrochemical fluorination of decalin) between the distillate and bottom product fractions, separation factor, liquid–liquid phase equilibrium in the MBCN-Ac system, and characteristics of the MBCN-Ac heteroazeotrope. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
40. Multigramme synthesis and asymmetric dihydroxylation of a 4-fluorobut-2E-enoate
- Author
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Giuseppe Rinaudo, Jonathan M. Percy, John Parkinson, James A. B. Laurenson, and Ricard Roig
- Subjects
organo-fluorine ,Chemistry ,Radical procedure ,Organic Chemistry ,Diastereomer ,fluorosugars ,Diisopropyl tartrate ,Full Research Paper ,fluorination ,lcsh:QD241-441 ,dihydroxylation ,chemistry.chemical_compound ,lcsh:Organic chemistry ,Dihydroxylation ,Crotonic acid ,asymmetric ,Organic chemistry ,lcsh:Q ,QD ,ee determination ,Enantiomer ,lcsh:Science - Abstract
Esters of crotonic acid were brominated on a multigramme scale using a free radical procedure. A phase transfer catalysed fluorination transformed these species to the 4-fluorobut-2E-enoates reproducibly and at scale (48–53%, ca. 300 mmol). Asymmetric dihydroxylation reactions were then used to transform the butenoate, ultimately into all four diastereoisomers of a versatile fluorinated C4 building block at high enantiomeric-enrichment. The (DHQ)2AQN and (DHQD)2AQN ligands described by Sharpless were the most effective. The development and optimisation of a new and facile method for the determination of ee is also described; 19F{1H} spectra recorded in d-chloroform/diisopropyl tartrate showed distinct baseline separated signals for different enantiomers.
- Published
- 2013
41. Efficient regio- and stereoselective access to novel fluorinated ?-aminocyclohexanecarboxylates
- Author
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Loránd Kiss, Santos Fustero, Melinda Nonn, Ferenc Fülöp, and Reijo Sillanpää
- Subjects
stereoselective reaction ,Double bond ,Stereochemistry ,chemistry.chemical_element ,aminohapot ,Ring (chemistry) ,Full Research Paper ,hydroxylation ,Hydroxylation ,lcsh:QD241-441 ,chemistry.chemical_compound ,lcsh:Organic chemistry ,epoxidation ,lcsh:Science ,ta116 ,chemistry.chemical_classification ,amino acids ,Organic Chemistry ,fluorination ,Amino acid ,Chemistry ,chemistry ,Fluorine ,Stereoselectivity ,lcsh:Q - Abstract
A regio- and stereoselective method has been developed for the synthesis of novel fluorinated 2-aminocyclohexanecarboxylic acid derivatives with the fluorine attached to position 4 of the ring. The synthesis starts from either cis- or trans-β-aminocyclohex-4-enecarboxylic acids and involves regio- and stereoselective transformation of the ring C–C double bond through iodooxazine formation and hydroxylation, followed by hydroxy–fluorine or oxo–fluorine exchange.
- Published
- 2013
42. Improved DC surface insulation performance of epoxy resin by gradient plasma fluorination.
- Author
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LĂĽ, Fang-cheng, LĂĽ, Pin, Ruan, Hao-ou, Wang, Shuang-shuang, Mao, Shuai-tao, Wang, Sheng-hui, and Xie, Qing
- Subjects
FLASHOVER ,SURFACE conductivity ,EPOXY resins ,FLUORINATION ,ELECTRIC potential ,PARTICLE swarm optimization - Abstract
In order to improve the flashover voltage of the disc insulator in gas insulated transmission line under DC voltage, this paper considers reducing the electric field intensity on the surface by adjusting the surface conductivity distribution. Based on the joint simulation of improved particle swarm optimization algorithm and finite element, the surface conductivity gradient partition optimization model is constructed to obtain the optimal surface conductivity distribution sequence. The relationship between conductivity and treatment time is obtained by plasma fluorination, and the gradient distribution of the surface conductivity of the sample is realized by adding different ring polytetrafluoroethylene baffles. Microscopic tests are used to characterize the differences between different regions of the sample surface. The two-dimensional (2D) electric potential distribution, 2D charge density distribution, electric field intensity distribution and flashover voltage on the sample surface under pre-charging conditions are studied and compared with the simulation results. The results show that the maximum field strength of the sample with gradient treatment can be reduced by 71% and the flashover voltage can be increased by 45%. The research in this paper provides a good reference and theoretical support for the surface modification of disc insulators, such as the surface parameters with gradient distribution. [ABSTRACT FROM AUTHOR]
- Published
- 2021
- Full Text
- View/download PDF
43. Modulation mechanism of electron energy dissipation on superlubricity based on fluorinated 2D ZIFs
- Author
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Li, Yuxin, Liu, Lei, Wang, Kunpeng, and Liu, Yuhong
- Published
- 2024
- Full Text
- View/download PDF
44. Insertion of fluorine into a LiFePO4 electrode material by gas-solid fluorination.
- Author
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Kevin, Lemoine, Roméo, Kenmogne-Debah, Léa, Doubtsof, Lawrence, Frezet, Elodie, Petit, Katia, Guerin, Bertrand, Devouard, Moulay-Tahar, Sougrati, Diane, Delbègue, and Pierre, Bonnet
- Subjects
FLUORINATION ,FLUORINE ,NUCLEAR magnetic resonance ,CORE materials ,MOSSBAUER spectroscopy - Abstract
In this study, the insertion of fluorine into LiFePO
4 was carried out under molecular fluorine F2 at different temperatures. The reactivity strongly depends on the applied fluorination temperature, leading to very different products: core delithiation of the material is observed at low temperatures with the formation of a LiF shell around particles, while the material decomposes to gradually form a mixture of α-FeF3 and α-Li3 FeF6 iron fluorides at higher temperatures. A second thermal treatment under N2 leads to the formation of LiFePO4 F in a new way that has not been reported before. Supported by X-ray diffraction, Raman, infrared, Mössbauer spectroscopies,7 Li nuclear magnetic resonance and electrochemical characterization of the different materials, this report demonstrates various fluorination mechanisms for LiFePO4 , from chemical delithiation to the stable pure fluorinated form LiFePO4 F and illustrates an innovative method that can be extended to obtain the triphylite form of NaFePO4 . [ABSTRACT FROM AUTHOR]- Published
- 2024
- Full Text
- View/download PDF
45. Recent Advances in C—F Bond Formation from Carbon‐Centered Radicals.
- Author
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Zhang, Jihua, Wang, Juanjuan, and Cheng, Qiang
- Subjects
- *
RADICALS (Chemistry) , *FLUORINATION , *ORGANIC compounds - Abstract
Comprehensive Summary: Construction of C—F bonds is a direct and efficient method for introducing fluorine into pharmaceuticals, agrochemicals, and materials. Strategies such as nucleophilic, electrophilic, radical, and transition‐metal catalyzed fluorination have been developed to meet the demand of diverse C—F bond formation. Among them, radical fluorination has been witnessed with substantial advancement in a recent decade. Herein, we reviewed methods for formation of C—F bonds with carbon‐centered radicals as key intermediates, especially in recent five years. We introduce in the paper with different fluorinating reagents, strategies for radical generation, and application in late‐stage functionalization and synthesis of PET tracers. We also indicate the current limitations and propose the direction of the field for the future development. Key Scientists: Radical fluorination was recognized as an old and uncontrolled reaction that may date back to the time when element fluorine was first mixed with organic compounds by Henri Moissan in 1891. The development of the field was slow in combination with discovery of new fluorinating reagents. Substantial changes took place in 2012, when the first example of carbon radical fluorination with robust and mild fluorinating reagents, such as NFSI and Selectfluor, was reported by the Sammis group. In the same year, Groves, Lectka, Li, and Boger led the pioneering works on aliphatic C—H fluorination, decarboxylative fluorination, and fluorofunctionalization of alkenes in a radical manner. Photoredox catalysis was introduced to radical fluorination in 2013 by the Chen group, which opens up a new avenue for diverse fluorinative transformations. Most of the previous works focus on radical fluorination to form C(sp3)–F bonds. In 2018, the challenging non‐directed aromatic C—H fluorination was solved by Ritter and coworkers. Direct arene fluorination with fluoride ion was later disclosed by the Nicewicz group in 2019. There are many other scientists that have also made tremendous contribution to the development of radical fluorination, with too limited space to list them all. We only list those with first discoveries that may point to the new direction of radical fluorination. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
46. Selective fluorination of the interlayer surface of layered silicates.
- Author
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Jang, Jeong-Hun, Paek, Seung-Min, and Park, Man
- Subjects
FLUORINATION ,SILICATES ,AMMONIUM fluoride ,X-ray diffraction ,AMMONIUM salts - Abstract
Controllable fluorination of silicate materials has been hardly accomplished mainly due to the high reactivity of fluorinating substances. In this study, the introduction of fluorinating substances into the interlayer space of magadiite in neutral form was attempted to induce an in situ fluorination reaction preferably on the interlayer surface of layered silicates. Two types of fluorinating substances, inorganic ammonium fluoride salts and organic 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride (Floulead), were successfully intercalated into the interlayer space of magadiite without any significant deterioration of the framework. Subsequent in situ fluorination reactions led to the preferred fluorination of the layered silanol groups that was envisioned successfully in the XRD pattern, FT-IR spectrum, TG/DTA curve, and cation exchange capacity. This study demonstrates that the silicate materials could be fluorinated selectively through intercalation and subsequent in situ localized reactions of various fluorinating substances. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
47. The synergistic effect of bulk-surface modification onto the wear resistance of the ultrahigh molecular weight polyethylene.
- Author
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Doronin, Fedor A, Rytikov, Georgy O, Evdokimov, Andrey G, Ruduak, Yury V, and Nazarov, Victor G
- Subjects
ULTRAHIGH molecular weight polyethylene ,WEAR resistance ,POLYETHYLENE ,SCANNING electron microscopes - Abstract
The paper investigates the effect of bulk and surface modification on the adhesive and tribological properties of ultra-high molecular weight polyethylene (UHMWPE) and shows that bulk modification with nano- and micro-sized modifiers (montmorillonite, shungite, exfoliated graphite) mainly reduces the friction coefficient but leads to a decrease in the wear resistance of the corresponding composites. It is found that gas-phase surface fluorination provides an increase in the wear resistance of experimental samples in all cases due to a combination of nanotexturing and chemomorphological transformations of the surface layers of the modified polymers. The significant dependence of the nanotexture on the technique and mode of modification is demonstrated using the original approaches to the quantitative characterization of the experimental samples' surfaces' scanning electron microscopy-images (formed with the scanning electron microscope). It is shown that the surface fluorination not only makes possible to significantly compensate for the increase of the friction coefficient of bulk-modified UHMWPE in comparison with the original one but also provides a nonlinear multiplicative increase in the wear resistance. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
48. NEW TRENDS AND TECHNICAL SOLUTIONS.
- Author
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PACHAI, Alexander Cohr
- Subjects
REFRIGERANTS ,HYDROCARBONS ,FLAMMABILITY ,FLUORINATION ,CARBON dioxide mitigation - Published
- 2024
49. The vicinal difluoro motif : the synthesis and conformation of erythro- and threo-diastereoisomers of 1,2-difluorodiphenylethanes, 2,3-difluorosuccinic acids and their derivatives
- Author
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Martin Schüler, Henry Rzepa, David O'Hagan, Alexandra M. Z. Slawin, University of St Andrews. School of Chemistry, and University of St Andrews. EaSTCHEM
- Subjects
Stereochemistry ,Gauche effect ,COUPLING-CONSTANTS ,Full Research Paper ,Pyrrolidine ,FLUORINATION ,lcsh:QD241-441 ,chemistry.chemical_compound ,lcsh:Organic chemistry ,PYRROLIDINE ,Alkane stereochemistry ,QD ,lcsh:Science ,Alkyl ,chemistry.chemical_classification ,SOLVENT ,STABILITY ,Chemistry ,Organic Chemistry ,Diastereomer ,PEPTIDASE-IV INHIBITORS ,HYDROGEN ,QD Chemistry ,REAGENT ,BIS(2-METHOXYETHYL)AMINOSULFUR TRIFLUORIDE ,Density functional calculation ,lcsh:Q ,Vicinal - Abstract
Background: It is well established that vicinal fluorines (RCHF-CHFR) prefer to adopt a gauche rather than an anti conformation when placed along aliphatic chains. This has been particularly recognised for 1,2-difluoroethane and extends to 2,3-difluorobutane and longer alkyl chains. It follows in these latter cases that if erythro and threo vicinal difluorinated stereoisomers are compared, they will adopt different overall conformations if the fluorines prefer to be gauche in each case. This concept is explored in this paper with erythro- and threo- diastereoisomers of 2,3-difluorosuccinates. Results: A synthetic route to 2,3-difluorosuccinates has been developed through erythro- and threo- 1,2-difluoro-1,2-diphenylethane which involved the oxidation of the aryl rings to generate the corresponding 2,3- difluorosuccinic acids. Ester and amide derivatives of the erythro- and threo- 2,3-difluorosuccinic acids were then prepared. The solid and solution state conformation of these compounds was assessed by X-ray crystallography and NMR. Ab initio calculations were also carried out to model the conformation of erythro- and threo- 1,2-difluoro-1,2-diphenylethane as these differed from the 2,3-difluorosuccinates. Conclusion: In general the overall chain conformations of the 2,3-difluorosuccinates diastereoisomers were found to be influenced by the fluorine gauche effect. The study highlights the prospects of utilising the vicinal difluorine motif (RCHF-CHFR) as a tool for influencing the conformation of performance organic molecules and particularly tuning conformation by selecting specific diastereoisomers (erythro or threo). Publisher PDF
- Published
- 2006
50. A Single‐Atom Cobalt Catalyst for the Fluorination of Acyl Chlorides at Parts‐per‐Million Catalyst Loading.
- Author
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Li, Wen‐Hao, Ye, Bo‐Chao, Yang, Jiarui, Wang, Ye, Yang, Chang‐Jie, Pan, Ying‐Ming, Tang, Hai‐Tao, Wang, Dingsheng, and Li, Yadong
- Subjects
COBALT catalysts ,ACYL chlorides ,FLUORINATION ,STRUCTURE-activity relationships ,CHEMICAL reactions ,ORGANOCATALYSIS - Abstract
Improving the stability of sensitive catalytic systems is an emerging research topic in the catalysis field. However, the current design of heterogeneous catalysts mainly improves their catalytic performance. This paper presents a single‐atom catalyst (SAC) strategy to improve the cobalt‐catalysed fluorination of acyl chlorides. A stable Co−F intermediate can be formed through the oxidative fluorination of Co1−N4@NC SAC, which can replace the unstable high‐valent cobalt catalytic system and avoid the use of phosphine ligands. In the SAC system, KF can be employed as a fluorinating reagent to replace the AgF, which can be applied to various substrates and scale‐up conversion with high turnover numbers (TON=1.58×106). This work also shows that inorganic SACs have tremendous potential for organofluorine chemistry, and it provides a good reference for follow‐up studies on the structure‐activity relationship between catalyst design and chemical reaction mechanisms. [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
- View/download PDF
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