- Reductive electrochemical decomposition of chloroform on metal electrodes
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The electrochemical reductive decomposition of chloroform was carried out using 15 kinds of metal electrodes. The efficiency of the decomposition and the main product of reaction largely depended on the metal electrodes. The hydrogenation of chloroform by Ag, Zn, Pd and Cu electrodes proceeded in about 100% efficiency. These electrodes produced methane mainly. Pb electrode produced dichloromethane selectively.
- Sonoyama, Noriyuki,Hara, Kohjiro,Sakata, Tadayoshi
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Read Online
- Kinetics and mechanism of the gas phase reaction of atomic chlorine with CH2ICl at 206-432 K
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The title reaction was studied using two different experimental techniques: laser flash photolysis with resonance fluorescence detection of Cl atoms and continuous photolysis with FTIR detection of end products. Over the temperature range 206-432 K the rate constant for reaction of Cl atoms with CH2ICl is given (to within ±15%) by the Arrhenius expression k1 = 4.4 × 10-11 exp(195/T) cm3 molecule-1 s-1, which gives k1 = 8.5 × 10-11 cm3 molecule-1 s-1 at 298 K. Variation of the total pressure of N2 diluent over the range 5-700 Torr at 295 K had no discernible (2 the reaction proceeds via iodine transfer to give CH2Cl radicals. As part of this work the rate constant k(CH2Cl+O2+M) was measured at 295 K in the presence of 1-800 Torr of N2 diluent. The results were well described by the Troe expression with a broadening factor Fc of 0.6 and limiting low- and high-pressure rate constants of k0 = (1.8 ± 0.1) × 10-30 cm6 molecule-2 s-1 and k∞ = (3.3 ± 0.3) × 10-12 cm3 molecule-1 s-1. The results are discussed with respect to the available literature for reactions of Cl atoms with halogenated organic compounds and the potential role of the title reaction in atmospheric chemistry.
- Bilde,Sehested,Nielsen,Wallington,Meagher,McIntosh,Piety,Nicovich,Wine
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Read Online
- Redox-active porous coordination polymers prepared by trinuclear heterometallic pivalate linking with the redox-active nickel(II) complex: Synthesis, structure, magnetic and redox properties, and electrocatalytic activity in organic compound dehalogenation in heterogeneous medium
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Linking of the trinuclear pivalate fragment Fe2CoO(Piv) 6 by the redox-active bridge Ni(L)2 (compound 1; LH is Schiff base from hydrazide of 4-pyridinecarboxylic acid and 2- pyridinecarbaldehyde, Piv- = pivalate) led to formation of a new porous coordination polymer (PCP) {Fe2CoO(Piv)6}{Ni(L) 2}1.5 (2). X-ray structures of 1 and 2 were determined. A crystal lattice of compound 2 is built from stacked 2D layers; the Ni(L) 2 units can be considered as bridges, which bind two Fe 2CoO(Piv)6 units. In desolvated form, 2 possesses a porous crystal lattice (SBET = 50 m2 g-1, V DR = 0.017 cm3 g-1 estimated from N2 sorption at 78 K). At 298 K, 2 absorbed a significant quantity of methanol (up to 0.3 cm3 g-1) and chloroform. Temperature dependence of molar magnetic susceptibility of 2 could be fitted as superposition of X MT of Fe2CoO(Piv)6 and Ni(L)2 units, possible interactions between them were taken into account using molecular field model. In turn, magnetic properties of the Fe2CoO(Piv) 6 unit were fitted using two models, one of which directly took into account a spin-orbit coupling of CoII, and in the second model the spin-orbit coupling of CoII was approximated as zero-field splitting. Electrochemical and electrocatalytic properties of 2 were studied by cyclic voltammetry in suspension and compared with electrochemical and electrocatalytic properties of a soluble analogue 1. A catalytic effect was determined by analysis of the catalytic current dependency on concentrations of the substrate. Compound 1 possessed electrocatalytic activity in organic halide dehalogenation, and such activity was preserved for the Ni(L)2 units, incorporated into the framework of 2. In addition, a new property occurred in the case of 2: the catalytic activity of PCP depended on its sorption capacity with respect to the substrate. In contrast to homogeneous catalysts, usage of solid PCPs may allow selectivity due to porous structure and simplify separation of product.
- Lytvynenko,Kolotilov,Kiskin,Cador,Golhen,Aleksandrov,Mishura,Titov,Ouahab,Eremenko,Novotortsev
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- Chlorodefluorination of Fluoromethanes and Fluoroolefins at a Lewis Acidic Aluminum Fluoride
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Chlorodefluorination reactions of fluoromethanes and fluoroolefins catalysed by the highly Lewis acidic nanoscopic aluminum chlorofluoride (ACF, AlClxF3?x, x≈0.05–0.3) in the presence of ClSiEt3 were studied. Both fluoromethanes and fluoroolefins convert under mild reaction conditions by fluorine-chlorine exchange steps into chlorinated fluoro derivatives. MAS NMR studies provided information on the interaction of silanes and hexafluoropropene with the ACF surface.
- Braun, Thomas,Pan, Xinzi,Scholz, Gudrun,Talavera, Maria
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- CROSSLINKED ARTIFICIAL NUCLEIC ACID ALNA
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The present invention provides a novel bridged artificial nucleic acid and an oligomer containing the same as a monomer. The present invention provides specifically a compound represented by general formula (I) (wherein each symbol is the same as defined in the specification) or salts thereof; as well as an oligonucleotide compound represented by general formula (I′) (wherein each symbol is the same as defined in the specification) or salts thereof.
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- Method of Converting a Brominated Hydrocarbon to a Chlorinated Hydrocarbon
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The present invention provides a method of converting a brominated hydrocarbon to a chlorinated hydrocarbon that involves contacting together the brominated hydrocarbon and a chlorinated ion exchange resin that has a water content of less than or equal to 30 percent by weight, based on the total weight of the chlorinated ion exchange resin and the water. The brominated hydrocarbon includes at least one replaceable bromo group, where each replaceable bromo group is independently covalently bonded to an sp3 hybridized carbon. Contact between the brominated hydrocarbon and the chlorinated ion exchange resin results in replacement of at least one replaceable bromo group of the brominated hydrocarbon with a chloro group, and correspondingly conversion of at least a portion of the brominated hydrocarbon to the chlorinated hydrocarbon.
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Paragraph 0183-0186
(2021/02/19)
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- A new strategy to improve catalytic activity for chlorinated volatile organic compounds oxidation over cobalt oxide: Introduction of strontium carbonate
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Co3O4–SrCO3 catalysts with various Sr/Co ratios were synthesized by the coprecipitation method, and their properties were tuned by adjusting the Sr/Co molar ratio. Furthermore, the catalytic combustion of vinyl chloride (VC) was used to evaluate the catalytic activity of the Co3O4–SrCO3 catalysts. The physicochemical properties of the catalysts were studied by X-ray diffraction (XRD), infrared spectroscopy (IR), N2 sorption, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), H2 temperature-programmed reduction (H2-TPR) and VC temperature-programmed desorption (VC-TPD). The results showed that the Co3O4–SrCO3 catalysts exhibited composite phases of Co3O4 and SrCO3 and the presence of interactions between them. As a result, the crystallization of the Co3O4 phase for the Co3O4–SrCO3 catalysts was restrained, and the state of Co on the catalyst surface was adjusted. Furthermore, the reducibility and VC adsorption capacity of the Co3O4–SrCO3 catalysts with Sr/Co molar ratios of 0.2 and 0.4 were enhanced compared with those of the Co3O4 catalyst. Otherwise, catalyst SrCo-0.4 exhibited excellent catalytic performance, accompanied by the highest reaction rate and the lowest apparent activation energy. More importantly, the optimized SrCO3–Co3O4 catalyst showed superior catalytic performance compared with other transition metal oxides in previous literature. These results brought a new idea for promoting the activity of transition metal catalysts for the deep oxidation of chlorinated volatile organic compounds (CVOCs) by introducing alkaline-earth metal salts.
- Liu, Hao,Shen, Kai,Zhao, Hailin,Jiang, Yongjun,Guo, Yanglong,Guo, Yun,Wang, Li,Zhan, Wangcheng
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- A process of preparing methyl chloride using multistage reaction
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The present invention relates to a method of producing methyl chloride by multistage reactions. The method of the present invention comprises: a) a chlorination step for sufficiently increasing the conversion rate of methane, which is an initial reactant; and b) a subsequent reaction step for actively utilizing hydrogen chloride (HCl), which is a hazardous byproduct of chlorination, efficiently treating harmful hydrogen chloride, and at the same time, improving the overall production of methyl chloride.COPYRIGHT KIPO 2020
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Paragraph 0092-0100; 0112
(2020/06/10)
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- Control of methane chlorination with molecular chlorine gas using zeolite catalysts: Effects of Si/Al ratio and framework type
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CH4 chlorination with Cl2 gas is used for the production of chlorinated products via C–H bond activation in CH4. Due to the high reactivity of Cl2, this reaction can occur spontaneously under UV irradiation or with mild thermal energy even in the absence of a catalyst via a free radical-mediated chain reaction mechanism that undesirably causes excessive chlorination of the CH4 and is thus non-selective. In this work, CH4 chlorination is investigated using HY and MFI zeolites with various Si/Al ratios, by which the reaction is catalytically controlled for selective production of the mono-chlorinated product (CH3Cl). Depending on the framework type, Si/Al ratio of the zeolites, and reaction conditions, different degrees of CH4 conversion, CH3Cl selectivity, and hence CH3Cl yield were achieved, by which systematic relationships between the catalyst properties and performance were discovered. A high aluminum content facilitated the production of CH3Cl with up to ~20 % yield at a high gas hourly space velocity of 2400 cm3gcat?1 h?1 with a CH4/Cl2 ratio of 1 at 350 °C. HY zeolites generally furnished a slightly higher CH3Cl yield than MFI zeolites, which can be attributed to the larger micropores of the HY zeolites that support facile molecular diffusion. With various flow rates and ratios of CH4 and Cl2, the CH4 conversion and CH3Cl selectivity changed simultaneously, with a trade-off relationship. Unfortunately, all zeolite catalysts suffered from framework dealumination due to the HCl produced during the reaction, but it was less pronounced for the zeolites having a low aluminum content. The results shed light on the detailed roles of zeolites as solid-acid catalysts in enhancing CH3Cl production during electrophilic CH4 chlorination.
- Kwon, Seungdon,Chae, Ho-Jeong,Na, Kyungsu
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p. 111 - 117
(2020/01/31)
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- METHOD OF CONVERTING ALKANES TO ALCOHOLS, OLEFINS AND AROMATICS
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A cost-effective and energy-efficient process is disclosed for converting a methane-containing gas to a methane sulfonyl halide comprising reacting the methane-containing gas, under illumination by a light emitting diode (LED) source, with a sulfuryl halide or a halogen in the presence of sulfur dioxide, whereby the methane sulfonyl halide is obtained for isolation or further reactions. The further reactions may sequentially include, in order, contacting the methane sulfonyl halide with a catalyst complex to form a methane monohalide; catalytically converting the methane monohalide to a value-added chemical such as an alcohol, an olefin, an aromatic, derivatives thereof, or mixtures thereof; releasing any hydrogen halide formed in the process; and converting the hydrogen halide to a halogen and recycling it for re-use.
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Paragraph 0054-0055
(2019/08/08)
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- Experimental Study and Kinetic Modeling of Chloroform Decomposition in Aqueous Solutions under the Action of γ-Radiation
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Abstract: The radiolysis of aqueous chloroform solutions (10–3–10–2 M) in the presence of dissolved oxygen is studied to establish a chain mode for the decomposition of chloroform. CO2, H2, H2O2 and chlorinated hydrocarbons-dichloromethane and dichloroethane are identified as products of the radiolysis of aqueous chloroform solutions. Changes in the pH and COD from the absorbed dose for the radiolysis of an aqueous chloroform solution with a concentration of 4.2 × 10?2 M are studied. It is found that as the dose is increased, the pH index and COD fall, indicating the decomposition of organic compounds and the formation of acids. It is shown that the radiation-chemical yields of chloroform decomposition depend on its initial concentration. At ≥4.2 × 10?2 M, they lie in the range of 52–245 molec./100 eV. A formal kinetic scheme of the processes that occur during the γ-radiolysis of aqueous chloroform solutions is compiled using the obtained data and allowing for the available literature values of the rate constants of elementary reactions.
- Iskenderova,Kurbanov
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p. 102 - 105
(2019/04/25)
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- DICHLOROMETHANE REDUCTION FROM A METHANE OXYCHLORINATION PRODUCT STREAM
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A chemical reactor system includes: a feed; a methane oxychlorination catalyst, wherein a product of an oxychlorination reaction is dichloromethane; and a dichloromethane conversion catalyst, wherein the dichloromethane conversion catalyst provides a product stream having a dichloromethane selectivity less than 5%. The addition of the dichloromethane conversion catalyst to the reactor bed can decrease the amount of dichloromethane produced and increase the amount of monochloromethane produced. Accordingly, dichloromethane does not have to be separated from the product stream and the monochloromethane can then be used to produce other products, such as olefins.
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Paragraph 0027-0039
(2018/08/25)
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- Nature's hydrides: rapid reduction of halocarbons by folate model compounds
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Halocarbons R-X are reduced to hydrocarbons R-H by folate model compounds under biomimetic conditions. The reactions correspond to a halide-hydride exchange with the methylenetetrahydrofolate (MTHF) models acting as hydride donors. The MTHF models are also functional equivalents of dehalohydrogenases but, unlike these enzymes, do not require a metal cofactor. The reactions suggest that halocarbons have the potential to act as endocrinological disruptors of biochemical pathways involving MTHF. As a case in point, we observe the rapid reaction of the MTHF models with the inhalation anaesthetic halothane. The ready synthetic accessibility of the MTHF models as well as their dehalogenation activity in the presence of air and moisture allow for the remediation of toxic, halogenated hydrocarbons.
- Denk, Michael K.,Milutinovi?, Nicholas S.,Marczenko, Katherine M.,Sadowski, Natalie M.,Paschos, Athanasios
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p. 1883 - 1887
(2017/03/09)
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- Selective reduction of a C–Cl bond in halomethanes with Et3GeH at nanoscopic Lewis acidic Aluminium fluoride
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The selective activation of C–Cl bonds of hydrochlorofluoromethanes and chloromethanes at moderate reaction conditions using ACF in a combination with Et3GeH is presented. The reactions of the chloromethanes (CH3Cl, CH2Cl2, CHCl3 and CCl4) in the presence of Et3GeH and ACF as catalyst led to the activation of only one C–Cl bond resulting in the hydrodechlorination. Friedel-Crafts reactions with benzene as solvent are suppressed by Et3GeH. A selective hydrodechlorination of hydrochlorofluoromethanes was achieved, because a transformation of a C–F bond into a C–H bond by the combination of ACF with Et3GeH did not occur. Supporting PulseTA experiments illustrated the interaction between the solid catalyst and Et3GeH, the solvent benzene or CH2Cl2.
- Mei?ner, Gisa,Feist, Michael,Braun, Thomas,Kemnitz, Erhard
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p. 234 - 241
(2017/09/12)
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- Dehalogenation of organic halides in aqueous media by hydrogen transfer from formate catalyzed by water-soluble Ru(II)-N-heterocyclic carbene complexes
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Water-soluble [RuCl(NHC)(L)(η6-arene)] complexes (NHC?=?bmim?=?1-butyl-3-methyl-imidazole-2-ylidene;?L?=?tertiary phosphine, such as mtppms, mtppts, pta, pta-Me and pta-Bn; η6-arene?=?η6-p-cymene) were succesfully applied for the first time as catalysts in hydrodehalogenation of organic halides by hydrogen transfer from aqueous Na-formate with turnover frequencies up to TOF?=?112?h?1 at 80?°C. Simultaneous to hydrodehalogenation, aqueous formate was also decomposed to H2 and HCO3?. In case of [RuCl(bmim)(pta)(η6-p-cymene)]Cl (pta?=?1,3,5-triaza-7-phosphaadamantane) a reaction mechanism is suggested on basis of kinetic and NMR measurements which accounts for both hydrodehalogenation and formate dehydrogenation and involves [RuH(bmim)(pta)(η6-p-cymene)]+ as the key catalytic species for both cycles.
- Marozsán, Natália,Horváth, Henrietta,Erdei, Anikó,Joó, Ferenc
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p. 103 - 109
(2016/10/09)
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- Low-temperature catalytic oxidation of vinyl chloride over Ru modified Co3O4 catalysts
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Ruthenium modified cobalt oxides were prepared by (1) impregnating ruthenium chloride hydrate on cobalt oxides, Ru-supported catalysts (Ru/Co3O4), and (2) Ru-doped catalysts (Ru-Co3O4) where the ruthenium ions were added to the precursor solution, by a one-step sol-gel method with cobalt nitrate. The physicochemical properties of the catalysts were characterized by ICP, BET, XRD, HR-TEM, TPR, and XPS analysis. The effects of ruthenium were studied for the total oxidation of vinyl chloride. This Ru modifier was observed to enhance oxygenate formation. The different preparation methods made contributions to the different amounts of Ru4+ on the surfaces of the catalysts while Ru4+ would be in synergy with Co2+ concentration, and this also changed the chemical coordination of oxygen on the surface. Dispersion of Ru oxides on the cobalt oxides surface could not only improve the catalytic activity and stability on steam, but also decrease the amount of chlorinated by-products and increase HCl selectivity.
- Wang, Chao,Zhang, Chuanhui,Hua, Wenchao,Guo, Yanglong,Lu, Guanzhong,Gil, Sonia,Giroir-Fendler, Anne
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p. 99577 - 99585
(2016/11/02)
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- Implementing thermally-excited-catalytic course solely using ambient heat motivation for efficient abatement of water pollutants
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Interest in photocatalysis has been fascinated by the realization that solar light is effectively an inexhaustible energy resource. Nevertheless, the necessity for high-energy ultraviolet irradiation and excessive recombination of photogenerated electrons
- Luo, Xuegang,Zhang, Sizhao,Ding, Feng,Lin, Xiaoyan
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p. 18040 - 18051
(2016/03/01)
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- Onion-Like Graphene Carbon Nanospheres as Stable Catalysts for Carbon Monoxide and Methane Chlorination
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Thermal treatment induces a modification in the nanostructure of carbon nanospheres that generates ordered hemi-fullerene-type graphene shells arranged in a concentric onion-type structure. The catalytic reactivity of these structures is studied in comparison with that of the parent carbon material. The change in the surface reactivity induced by the transformation of the nanostructure, characterized by TEM, XRD, X-ray photoelectron spectroscopy (XPS), Raman, and porosity measurements, is investigated by multipulses of Cl2 in inert gas or in the presence of CH4 or CO. The strained C-C bonds (sp2-type) in the hemi-fullerene-type graphene shells induce unusually strong, but reversible, chemisorption of Cl2 in molecular form. The active species in CH4 and CO chlorination is probably in the radical-like form. Highly strained C-C bonds in the parent carbon materials react irreversibly with Cl2, inhibiting further reaction with CO. In addition, the higher presence of sp3-type defect sites promotes the formation of HCl with deactivation of the reactive C-C sites. The nano-ordering of the hemi-fullerene-type graphene thus reduces the presence of defects and transforms strained C-C bonds, resulting in irreversible chemisorption of Cl2 to catalytic sites able to perform selective chlorination. Tidy up the carbon! CO and CH4 chlorination over hemi-fullerene-type graphene is described. The surface nano-ordering, induced by thermal treatment, transforms strained C-C bond sites resulting in irreversible Cl2 chemisorption to catalytic sites that are able to selectively chlorinate CO and CH4.
- Centi, Gabriele,Barbera, Katia,Perathoner, Siglinda,Gupta, Navneet K.,Ember, Erika E.,Lercher, Johannes A.
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p. 3036 - 3046
(2015/09/22)
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- Hydrodechlorination of CCl4 over carbon-supported palladium-gold catalysts prepared by the reverse "water-in-oil" microemulsion method
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Two series of carbon-supported Pd-Au catalysts were prepared by the reverse "water-in-oil, W/O" method, characterized by various techniques and investigated in the reaction of tetrachloromethane with hydrogen at 423K. The synthesized nanoparticles were reasonably monodispersed having an average diameter of 4-6nm (Pd/C and Pd-Au/C) and 9nm (Au/C). Monometallic palladium catalysts quickly deactivated during the hydrodehalogenation of CCl4. Palladium-gold catalysts with molar ratio Pd:Au=90:10 and 85:15 were stable and much more active than the monometallic palladium and Au-richer Pd-Au catalysts. The selectivity toward chlorine-free hydrocarbons (especially for C2+ hydrocarbons) was increased upon introducing small amounts of gold to palladium. Simultaneously, for the most active Pd-Au catalysts, the selectivity for undesired dimers C2HxCly, which are considered as coke precursors, was much lower than for monometallic Pd catalysts. Reasons for synergistic effects are discussed. During CCl4 hydrodechlorination the Pd/C and Pd-Au/C catalysts were subjected to bulk carbiding.
- Bonarowska, Magdalena,Karpiński, Zbigniew,Kosydar, Robert,Szume?da, Tomasz,Drelinkiewicz, Alicja
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p. 1143 - 1151
(2015/11/11)
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- METHOD FOR DECHLORINATING CARBON TETRACHLORIDE AND METHOD FOR PRODUCING DECHLORINATED MATERIAL
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PROBLEM TO BE SOLVED: To provide a method for dechlorinating carbon tetrachloride and a method for producing dechlorinated material, which neither need high temperature and high pressure conditions nor need to use corrosive, inflammable, volatile, or highly toxic chemicals. SOLUTION: Provided is a method for producing a dechlorinated material by using carbon tetrachloride as a raw material and dechlorinating the carbon tetrachloride by the dechlorinating method, where an ionic liquid represented by the formula (1) is reacted to carbon tetrachloride. (In the formula, R1 to R4 each independently represent an alkyl group or an aryl group, a part of whose hydrogen atoms may be substituted; and A represents a phosphorus atom or a nitrogen atom.) COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0045-0046
(2017/01/05)
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- Active carbon-supported nickel-palladium catalysts for hydrodechlorination of 1,2-dichloroethane and 1,1,2-trichloroethene
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Norit active carbon-supported Ni-Pd catalysts were prepared, by incipient wetness impregnation, from the metal chlorides NiCl2.6H2O and PdCl2. The catalysts were characterized by temperature-programmed reduction, X-ray diffraction, and scanning electron microscopy, and by temperature-programmed hydrogenation (TPH) of the catalysts after use. When the catalysts were used for gasphase hydrodechlorination (HDC) of 1,2-dichloroethane (1,2-DCA) and 1,1,2-trichloroethene (TCE), very high activity and stability at a relatively low reaction temperature (503 K) were observed. Hydrodechlorination of TCE led to formation of hydrocarbons as the main products. Use of Ni and Ni-Pd catalysts for hydrodechlorination of 1,2-DCA resulted in very high (~100 %) selectivity for ethene. TPH of the catalysts after use for HDC of 1,2-DCA and TCE revealed the presence of carbon and chlorine-containing deposits on the surfaces of the catalysts. Formation of the NiCx fcc phase and the Ni3C hcp carbide phase were detected for the monometallic nickel and Ni95Pd05 catalysts.
- Kamińska,?r?bowata
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p. 9267 - 9280
(2015/03/14)
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- PROCESS FOR THE PRODUCTION OF 1,1,1,2,2-PENTAFLUORO- 3-CHLOROPROPANE
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A process for the manufacture of CF3CF2CH2Cl comprising contacting CH2ClF with CF2=CF2 in the presence of a catalytically effective amount of an aluminum halide composition having a bulk formula of AlClxBryF3-x-y wherein the average value of x is 0 to 3, the average value of y is 0 to 3-x, provided that the average values of x and y are not both 0, to produce CF3CF2CH2Cl with a selectivity of at least 70%.
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Page/Page column 7; 8
(2015/11/09)
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- BIFUNCTIONAL CYTOTOXIC AGENTS
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Cytotoxic dimers comprising CBI-based and/or CPI-based sub-units, antibody drug conjugates comprising such dimers, and to methods for using the same to treat cancer and other conditions.
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Page/Page column
(2015/08/04)
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- Semiconducting polymers
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Novel semiconducting photovoltaic polymers with conjugated units that provide improved solar conversion efficiency that can be used in electro-optical and electric devices. The polymers exhibit increased solar conversion efficiency in solar devices.
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(2015/05/26)
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- DAPTOMYCIN ANALOGUES AND A METHOD FOR THE PREPARATION OF DAPTOMYCIN OR A DAPTOMYCIN ANALOGUE
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A method for the synthesis of daptomycin or a daptomycin analogue is carried out on a resin to form a linear precursor followed by a serine ligation macrocyclization in solution. Daptomycin analogues can differ from daptomycin by substitution of amino acids residues and/or deletion or addition of amino acid residues. Daptomycin analogues can include a different fatty acid in the side arm of the daptomycin analogue.
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(2015/05/13)
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- Design of a bimetallic Au/Ag system for dechlorination of organochlorides: Experimental and theoretical evidence for the role of the cluster effect
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The experimental study of dechlorination activity of a Au/Ag bimetallic system has shown formation of a variety of chlorinated bimetallic Au/Ag clusters with well-defined Au:Ag ratios from 1:1 to 4:1. It is the formation of the Au/Ag cluster species that mediated C-Cl bond breakage, since neither Au nor Ag species alone exhibited a comparable activity. The nature of the products and the mechanism of dechlorination were investigated by ESI-MS, GC-MS, NMR, and quantum chemical calculations at the M06/6-311G(d)&SDD level of theory. It was revealed that formation of bimetallic clusters facilitated dechlorination activity due to the thermodynamic factor: C-Cl bond breakage by metal clusters was thermodynamically favored and resulted in the formation of chlorinated bimetallic species. An appropriate Au:Ag ratio for an efficient hydrodechlorination process was determined in a joint experimental and theoretical study carried out in the present work. This mechanistic finding was followed by synthesis of molecular bimetallic clusters, which were successfully involved in the hydrodechlorination of CCl4 as a low molecular weight environment pollutant and in the dechlorination of dichlorodiphenyltrichloroethane (DDT) as an eco-toxic insecticide. High activity of the designed bimetallic system made it possible to carry out a dechlorination process under mild conditions at room temperature.
- Romashov, Leonid V.,Khemchyan, Levon L.,Gordeev, Evgeniy G.,Koshevoy, Igor O.,Tunik, Sergey P.,Ananikov, Valentine P.
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p. 6003 - 6012
(2015/02/19)
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- Catalytic dechlorination of carbon tetrachloride in liquid phase with methanol as H-donor over AG/C catalyst
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Catalytic hydrodechlorination of carbon tetrachloride (CCl4) is an effective measure to remove CCl4due to its pollutant character. The dechlorination of CCl4to dichloromethane (CH2Cl2) and chloroform (CHCl3) with a molar ratio of 3:2 was catalyzed by carbon-supported silver (Ag/C) catalyst in methanol solution. It was proposed from the catalytic results and characterization (X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy) data that, the chloride ion is abstracted from adsorbed CCl4by Ag to form CCl3and CCl2radicals and silver chloride (AgCl), and meanwhile the dehydrogenation of methanol over Ag domains intrigues initial active Ag-H species and formaldehyde (HCHO): then the CCl3and CCl2radicals are combined with Ag-H to generate reaction products (CHCl3, and CH2Cl2) and Ag, and the dehydrogenated product HCHO facilitates the regeneration of formed AgCl to Ag with formation of carbon monoxide and hydrogen chloride. The catalyst can be recovered and recycled, and there was no significant decrease in catalytic activity and selectivity after 4threcycling. Copyright
- Lu, Mohong,Li, Xuebing,Chen, Bo,Li, Mingshi,Xin, Hongchuan,Song, Liang
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p. 7315 - 7318
(2015/01/09)
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- Photocatalysis of Chloroform Decomposition by Tetrachlorocuprate (II) on Dowex 2-X8
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Heterogenized on a polystyrene anion exchange resin and in the presence of oxygen, CuCl24 catalyzes the photodecomposition of chloroform at wavelengths above 345 nm with greater efficiency than an equivalent amount in homogeneous solution. The reaction is proposed to proceed in two stages, the first stage yielding CCl4 and HO2 as products, the second consisting of a chain reaction resulting from the CuCl2 4-catalyzed photodissociation of CCl4, yielding phosgene with CCl3 radicals as chain carriers. Photodecomposition is retarded by added Cl, CH3CN, C6H12 or C2H5OH, which is ascribed to the displacement of CHCl3 molecules from the vicinity of the copper by attraction to the polystyrene matrix or to the alkylammonium cation sites.
- Harvey, Brent M.,Hoggard, Patrick E.
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p. 1234 - 1242
(2015/02/18)
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- NON COVALENT MOLECULAR STRUCTURE, COMPRISING A PYRENE BASED GLYCOCONJUGATE, DEVICE COMPRISING THE SAME AND ITS USE FOR DETECTION OF LECTIN
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The present invention relates to a non covalent molecular structure comprising a carbon nanostructure and a pyrene based glycoconjugate (I) which is linked to the said carbon nanostructure by a non covalent link, the said glycoconjugate (I) having the formula: wherein B is a group which is present on any of the ten carbon atoms of the pyrene structure represented in (I) susceptible to bear a substituent, and is represented by the following group: —(CH2)n-CO—NH-A, wherein n is an integer from 1 to 9, A is a group of formula: The present invention also relates to an electronic device comprising the said non covalent molecular structure, and to the use of this device for the detection of a lectin involved in bacterial or viral infections. Thus the invention also relates to a method for detecting the presence of a lectin in a sample to be analysed.
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(2014/06/11)
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- METHOD OF PREPARING HALOGENATED SILAHYDROCARBYLENES
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A method comprises separate and consecutive steps (i) and (ii). Step (i) includes contacting a copper catalyst with hydrogen gas and a halogenated silane monomer at a temperature of 500 °C to 1400 °C to form a silicon-containing copper catalyst comprising at least 0.1 % (w/w) of silicon. Step (ii) includes contacting the silicon-containing copper catalyst with an organohalide at a temperature of 100°C to 600 °C to form a reaction product. The organohalide has formula HaCbXc, where X is a halogen atom, subscript a is an integer of 0 or more, subscript b is an integer of 1 or more, and subscript c is an integer of 2 or more. The method produces a reaction product. The reaction product includes a halogenated silahydrocarbylene.
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Paragraph 0040
(2014/05/07)
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- Evaluation of decomposition products of EMImCl·1.5AlCl3 during aluminium electrodeposition with different analytical methods
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Ionic liquids are of great importance for electrodeposition of metals, which can't be deposited from aqueous electrolytes due to their negative standard potentials. In this paper non-woven polymers were coated with aluminium by electrodeposition from 1-et
- Poetz, Sandra,Handel, Patricia,Fauler, Gisela,Fuchsbichler, Bernd,Schmuck, Martin,Koller, Stefan
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p. 6685 - 6690
(2014/02/14)
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- A 1,4,5-TRISUBSTITUTED1,2,3-TRIAZOLE MIMETIC OF RGD and/or OGP10-14, PROCESS TO OBTAIN IT AND USES THEREOF
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The present invention relates to nonpeptide compounds of formula (I) which are mimetics of RGD (Arg-Gly-Asp) and/or, OGP10-14 (Tyr-Gly-Phe-Gly-Gly), osteogenic peptides, containing a central 1,4,5-trisubstituted 1,2,3-triazole core and a reactive appendage appropriate to form covalent click bonds on the surface of materials functionalized with reactive groups including: azide, terminal alkyne, cyclooctalkyne, thiol, maleimide or thiolacid groups and to a process for the preparation of RGD and OGP10-14 mimetics containing a 1,4,5-trisubstituted 1,2,3-triazole core. These nonpeptide mimetics are particularly useful for medical devices, in particular implants and tissue engineering and cell culture matrices.
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Page/Page column
(2014/07/09)
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- MCR DENDRIMERS
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The invention relates to a method for producing peptoidic, peptidic and chimeric peptidic-peptoidic dendrimers by multiple iterative multi-component reactions (MCR), in particular Ugi or Passerini multi-component reactions, to compounds produced in this way and to the use thereof.
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Page/Page column
(2013/08/15)
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- Transformation of methane to propylene: A two-step reaction route catalyzed by modified CeO2 nanocrystals and zeolites
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Propylene from methane: The transformation of methane to propylene has been realized in a two-step route via CH3Cl or CH3Br. CeO 2 serves as an efficient and stable catalyst for the oxidative chlorination and bromination of methane to CH3Cl and CH 3Br. In the second step, a modified zeolite is highly a selective and stable catalyst for the conversion of CH3Cl or CH3Br into propylene. Copyright
- He, Jieli,Xu, Ting,Wang, Zhihui,Zhang, Qinghong,Deng, Weiping,Wang, Ye
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supporting information; experimental part
p. 2438 - 2442
(2012/04/23)
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- COMPOSITIONS AND METHODS FOR IMAGING TISSUES, ORGANS AND TUMORS
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The present invention relates to compounds and related technetium and rhenium complexes thereof which are suitable for imaging or therapeutic treatment of tissues, organs, or tumors. In another embodiment, the invention relates to methods of imaging tissues, organs, or tumors using radiolabeled metal complexes, particularly tissues, organs, or tumors which express certain receptors to which the compounds or complexes of the invention have an affinity. The present invention also relates to methods of treating cancer, particularly those cancer lines which express certain receptors to which the compounds or complexes of the invention have an affinity. In yet another embodiment, the present invention provides methods of imaging and/or inhibiting receptors or neuroreceptors using compounds or complexes of the invention which have an affinity for the receptor or neuroreceptor to be imaged and/or inhibited.
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- SYNTHESIS AND USE OF RADIOLABELLED INSULIN ANALOGUES
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A radiolabelled insulin analogue is provided. The analogue comprises a radiolabel linked to an insulin analogue at an amino acid at the terminal end of the B chain of the insulin analogue.
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- Hydrodechlorination of chloromethanes with a highly stable Pt on activated carbon catalyst
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A platinum catalyst with activated carbon-support (Pt/C) was prepared and showed a high activity for the deep gas-phase hydrodechlorination (HDC) of dichloromethane (DCM) and chloroform (TCM), with conversions of up to 70% and 100%, respectively (operating conditions: atmospheric pressure, reaction temperatures of 150-250 °C, and space-times of 0.08-1.7 kg h mol -1). The catalyst was highly selective to methane (the only non-chlorinated product) with selectivities of up to 85% for HDC of DCM and 93% for HDC of TCM. The catalyst showed exceptional stability with no loss of activity after 26 days on stream in the HDC of DCM. This can be ascribed to its high resistance to poisoning by organic compounds compared to Pd/C catalysts previously studied. This can be attributed to re-dispersion of Pt during the reaction and to the high proportion of metal in the zero-valent state (Pt 0) which disfavors the stabilization of chlorocarbon compounds at the active centers of the catalyst.
- Alvarez-Montero,Gomez-Sainero,Mayoral,Diaz,Baker,Rodriguez
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scheme or table
p. 389 - 396
(2011/06/17)
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- COMPOSITIONS FOR TREATMENT OF CYSTIC FIBROSIS AND OTHER CHRONIC DISEASES
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The present invention relates to pharmaceutical compositions comprising an inhibitor of epithelial sodium channel activity in combination with at least one ABC Transporter modulator compound of Formula A, Formula B, Formula C, or Formula D. The invention also relates to pharmaceutical formulations thereof, and to methods of using such compositions in the treatment of CFTR mediated diseases, particularly cystic fibrosis using the pharmaceutical combination compositions.
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- Novel antimalarial 3-azabicyclo[3.2.2]nonane derivatives
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The present invention relates to novel 3-azabicyclo[3.2.2]nonane derivatives of the general formula (I) or a pharmaceutically acceptable salt thereof wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are as defined in the specification. The novel 3-azabicyclo[3.2.2]nonane derivatives are particularly useful for treatment and prevention of malaria and trypanosomiasis.
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- BENT-CORE LC DECORATED GOLD NANOCLUSTERS
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Novel thiol-terminated bent-core liquid crystals (LCs) are used to decorate gold nanoparticles. Thioacetate or xanthate/xanthogenate functional groups are used to effect the attachment of the LCs to the gold nanoparticles. Such bent-core decorated nanoparticles may be dissolved in bent-core liquid crystal host media to provide polarizable systems which respond quickly to applied electric fields and exhibit other interesting and useful optical and electro-optic behaviour.
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- NOVEL GHRELIN ANALOGUES
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Ghrelin analogues having high affinity for a target receptor in diseased cells are provided, as well as methods of diagnosis and treatment utilizing such analogues.
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- IMAGING DENDRIMER NANOPROBES AND USES THEREOF
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This invention relates to imaging nanoprobe and methods of use thereof. Specifically, the invention relates to long-lived oxygen-insensitive nanoprobe comprising a lumisescent moeity with a long excited state lifetime, embedded in a dendrimer, wherein said dendrimer is internally cross-linked and has hydrophilic peripheral layer.
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- Kinetic and theoretical study of the hydrodechlorination of CH 4- xClx (x = 1-4) compounds on palladium
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The reaction kinetics of hydrodechlorination (HDCl) for a series of CH 4-xClx (x = 1-4) compounds were measured on a Pd/carbon catalyst. The rate of HDCl correlated with the C-Cl bond energy, suggesting scission of this bond in the molecularly adsorbed molecule is rate-determining. The measured reaction kinetics of the CH4-xClx compounds support a previously proposed Langmuir-Hinshelwood type reaction mechanism. Kinetic and isotope exchange experiments demonstrated the following: gas phase H2 and HCl are in equilibrium with surface H and Cl; adsorbed Cl is the most abundant surface intermediate; and irreversible scission of the first C-Cl bond is rate-determining. The overall hydrodechlorination reaction rate can be written as kKR-Cl[R-Cl]/(1 + KHCl[HCl]/KH2 1/2[H2]1/2). The activation energy of the rate-determining step was related linearly to the dissociation energy of the first C-Cl bond broken in a Broensted-Evans-Polanyi relationship. This behavior is in agreement with a previous study of CF3CF 3-xClx compounds. During the reaction of CH3Cl, CH2Cl2, and CHCl3 with deuterium, H-D exchange occurred in only 2%, 6%, and 9% of products, respectively. The increasing H-D exchange with Cl content suggests the steps which determine selectivity in these multipath, parallel reactions. The density functional theory (DFT)-calculated activation energies for the dissociation of the first C-Cl bond in the family of chlorinated methane compounds are in good agreement with the values extracted from kinetic modeling, suggesting that parameters estimated from DFT calculations may be used to estimate the reactivity of a particular chlorinated compound within a family of chlorocarbons.
- Chen, Nan,Rioux, Robert M.,Barbosa, Luis A. M. M.,Ribeiro, Fabio H.
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experimental part
p. 16615 - 16624
(2011/10/30)
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- Kinetics of the reactions of CH2Cl, CH3CHCl, and CH3CCl2 Radicals with Cl2 in the Temperature Range 191-363 K
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The kinetics of three chlorinated free radical reactions with Cl 2 have been studied in direct time-resolved measurements. Radicals were produced in low initial concentrations by pulsed laser photolysis at 193 nm, and the subsequent decays of the radical concentrations were measured under pseudo-first-order conditions using photoionization mass spectrometer (PIMS). The bimolecular rate coefficients of the CH3CHCl + Cl2 reaction obtained from the current measurements exhibit negative temperature dependence and can be expressed by the equation k(CH3CHCl + Cl 2) =(3.02 ± 0.14) × 10-12)(T/300 K) -1.89±0.19 cm3 molecule-1 s-1 (1.7-5.4 Torr, 191-363 K). For the CH3CCl2 + Cl 2 reaction the current results could be fitted with the equation k(CH3CCl2 + Cl2) =(1.23 ± 0.02) × 10-13)(T/300 K)-0.26±0.10 cm3 molecule-1 s-1 (3.9-5.1 Torr, 240-363 K). The measured rate coefficients for the CH2Cl + Cl2 reaction plotted as a function of temperature show a minimum at about T ) 240 K: first decreasing with increasing temperature and then, above the limit, increasing with temperature. The determined reaction rate coefficients can be expressed as k(CH2Cl + Cl2) = (2.11 ± 1.29) × 10 -14) exp(773 ±183 K/T)(T/300 K)3.26±0.67 cm3 molecule-1 s-1 (4.0-5.6 Torr, 201-363 K). The rate coefficients for the CH3CCl2 + Cl2 and CH2Cl + Cl2 reactions can be combined with previous results to obtain: kcombined(CH3CCl2 + Cl 2) =(4.72 kcombined 1.66) × 10-15) exp(971 ± 106 K/T)(T/300 K)3.07 ±0.23 cm3 molecule -1 s-1 (3.1-7.4 Torr, 240-873 K) and k combined(CH2Cl + Cl2) =(5.18 ± 1.06) ± 10-14) exp(525 ±63 K/T)(T/300 K) 2.52±0.13 cm3 molecule-1 s-1 (1.8-5.6 Torr, 201-873 K). All the uncertainties given refer only to the 1θ statistical uncertainties obtained from the fitting, and the estimated overall uncertainty in the determined bimolecular rate coefficients is about ± 15%. Copyright
- Rissanen, Matti P.,Eskola, Arkke J.,Timonen, Raimo S.
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scheme or table
p. 4805 - 4810
(2011/01/10)
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- OXIDATIVE MONO-HALOGENATION OF METHANE
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Oxidatively halogenate methane by placing a feedstream that comprises methane, a source of halogen, a source of oxygen and, optionally, a source of diluent gas in contact with a first catalyst (e.g. a solid super acid or a solid super base) that has greater selectivity to methyl halide and carbon monoxide than to methylene halide, trihalomethane or carbon tetrahalide. Improve overall selectivity to methyl halide by using a second catalyst that converts at least part of the feedstream to a mixture of methyl halide, methylene halide, trihalomethane, carbon tetrahalide and unreacted oxygen, and placing that mixture in contact with the first catalyst which converts at least a portion of the methylene halide, trihalomethane and carbon tetrahalide to carbon monoxide, hydrogen halide and water.
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Page/Page column 12
(2010/06/17)
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- PROCESS FOR PREPARING FLUORINE-CONTAINING PROPANE
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The present invention provides a process for preparing a fluorine-containing propane represented by the formula: CF2XCF2CH3 wherein X is F or Cl, the process including reacting tetrafluoroethylene and methyl chloride in the presence of an antimony halide represented by the formula: SbFxC5-x wherein x is a value of 0 to 5. According to the present invention, the fluorine-containing propane represented by the formula: CF2XCF2CH3 wherein X is F or Cl, which is useful as a starting material of 2,3,3,3-tetrafluoropropene (1234yf), can be obtained by a simple process, using relatively inexpensive starting materials.
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Page/Page column 9-10
(2010/12/17)
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- METHODS OF TREATING DRUG-RESISTANT CANCERS
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Methods of treating a refractory or drug resistant cancer, cell proliferative disorder and tumor cells are provided.
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- Photocatalysis of chloroform decomposition by hexachloroosmate(IV)
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Hexachloroosmate(IV) effectively catalyzes the photodecomposition of chloroform in aerated solutions. The decomposition products are consistent with a mechanism in which excited state OsCl62- reduces chloroform, rather than one involving photodissociation of chlorine atoms. Trace amounts of ethanol or water in the chloroform lead to photosubstitution to form OsCl5(EtOH)- or OsCl5(H2O) -, neither of which is photocatalytically active.
- Pena, Laura A.,Hoggard, Patrick E.
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body text
p. 467 - 470
(2010/10/19)
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- POLY(METH)ACRYLAMIDES AND POLY(METH)ACRYLATES CONTAINING FLUORINATED AMIDE
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A composition comprising a copolymer having repeating units in any sequence of Formula I wherein Rf is a straight or branched perfluoroalkyl group having from about 1 to about 20 carbon atoms, or a mixture thereof, which is optionally interrupted by at least one oxygen atom,X3 is oxygen or X1,each X1 is independently an organic divalent linking group having from about 1 to about 20 carbon atoms, optionally containing an oxygen, nitrogen, or sulfur, or a combination thereof,G is F or CF3,A is an amide,j is zero or positive integer,X2 is an organic linking group,Y is O, N or S,h is zero when Y is N, and h is one when Y is O or S,Z is H, a straight or branched alkyl group having from about 1 to about 4 carbon atoms, or halide,B is H or wherein Rf, X1, X3, G, A, and j are as defined above, provided that when B is H, j is a positive integer,m is a positive integer,q is zero or a positive integer when Y is O, and q is a positive integer when Y is N or S,p is zero or a positive integer when Y is O, and p is a positive integer when Y is N or S,each W is independently various copolymer units.
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- Antibody drug conjugate metabolites
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Methods of treating a refractory or drug resistant cancer, cell proliferative disorder and tumor cells are provided. Also provided are antibody drug conjugate metabolites.
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- METHOD FOR PREPARING CHLORINATED COMPOUND FROM SATURATED HYDROCARBON
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The present invention relates to a method for preparing chlorinated compounds from saturated hydrocarbon. More particularly, the present invention relates to the method for preparing chlorinated compounds by conducting alternately an oxidation reaction of a catalyst under oxygen and hydrogen chloride, and a chlorination reaction for converting the saturated hydrocarbon into the chlorinated compounds by using the catalyst. The present invention has the advantages that the conversion rate of the saturated hydrocarbon may be enhanced; there is no need to consider erexplosion hazards; unreacted hydrogen chloride and corrosion of reactor may be reduced; a separate device for separating COx in exhaust gases may not be required since CO or CO2 is not produced in a combustion reaction; by-product may not be generated; and the durability of a catalyst may be remarkably enhanced.
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Page/Page column 12-18
(2009/04/25)
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- Nanoparticles and Method to Control Nanoparticle Spacing
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Disclosed herein are novel nanoparticles, particularly metal nanoparticles, such as gold nanoparticles. According to one embodiment of a method disclosed herein nanoparticles are functionalized via ligand exchange reactions. Also disclosed is a method for controlling nanoparticle spacing to produce nanoparticle arrays having defined spacing. Such nanoparticles and arrays thereof are particularly useful in nanoelectronics, nanophotonics, catalysis, sensors, and biotaggents.
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