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排序方式: 共有422条查询结果,搜索用时 15 毫秒
111.
Dimethyl ether oxidation at elevated temperatures (295-600 K) 总被引:1,自引:0,他引:1
Rosado-Reyes CM Francisco JS Szente JJ Maricq MM Frøsig Østergaard L 《The journal of physical chemistry. A》2005,109(48):10940-10953
Dimethyl ether (DME) has been proposed for use as an alternative fuel or additive in diesel engines and as a potential fuel in solid oxide fuel cells. The oxidation chemistry of DME is a key element in understanding its role in these applications. The reaction between methoxymethyl radicals and O(2) has been examined over the temperature range 295-600 K and at pressures of 20-200 Torr. This reaction has two product pathways. The first produces methoxymethyl peroxy radicals, while the second produces OH radicals and formaldehyde molecules. Real-time kinetic measurements are made by transient infrared spectroscopy to monitor the yield of three main products-formaldehyde, methyl formate, and formic acid-to determine the branching ratio for the CH(3)OCH(2) + O(2) reaction pathways. The temperature and pressure dependence of this reaction is described by a Lindemann and Arrhenius mechanism. The branching ratio is described by f = 1/(1 + A(T)[M]), where A(T) = (1.6(+2.4)(-1.0) x 10(-20)) exp((1800 +/- 400)/T) cm(3) molecule(-1). The temperature dependent rate constant of the methoxymethyl peroxy radical self-reaction is calculated from the kinetics of the formaldehyde and methyl formate product yields, k(4) = (3.0 +/- 2.1) x 10(-13) exp((700 +/- 250)/T) cm(3) molecule(-1) s(-1). The experimental and kinetics modeling results support a strong preference for the thermal decomposition of alkoxy radicals versus their reaction with O(2) under our laboratory conditions. These characteristics of DME oxidation with respect to temperature and pressure might provide insight into optimizing solid oxide fuel cell operating conditions with DME in the presence of O(2) to maximize power outputs. 相似文献
112.
Palladium(II) chloride complexes of o-alkyl substituted phosphanes were prepared in various solvents with the phosphane ligands o-methylphenyldiphenylphosphane, o-ethylphenyldiphenylphosphane, o-isopropylphenyldiphenylphosphane, o-cyclohexylphenyldiphenylphosphane and o-phenylphenyldiphenylphosphane. The structures of the complexes were characterized by 1H NMR and 31P NMR spectroscopy and elemental analysis. The X-ray structures of PdCl2(o-methylphenyldiphenylphosphane)2, PdCl2(o-isopropylphenyldiphenylphosphane)2, PdCl2(o-cyclohexylphenyldiphenylphosphane)2, PdCl2(o-phenylphenyldiphenylphosphane)2, [PdCl2(o-methylphenyldiphenylphosphane)]2, [PdCl2(o-ethylphenyldiphenylphosphane)]2 and [PdCl2(o-cyclohexylphenyldiphenylphosphane)]2 were also determined. We report a systematic, solvent-dependent method to prepare palladium(II) complexes of the aryl phosphines o-methylphenyldiphenylphosphane, o-cyclohexylphenyldiphenylphosphane and o-phenylphenyldiphenylphosphane with a desired nuclearity. We demonstrated that chlorinated solvents promote the formation of dinuclear chlorine-bridged palladium complexes for all five ligands. The ligands preferentially form mononuclear palladium complexes in other solvents where the starting materials are only weakly soluble in the solvent. 相似文献
113.
Luzyanin KV Kukushkin VY Kuznetsov ML Garnovskii DA Haukka M Pombeiro AJ 《Inorganic chemistry》2002,41(11):2981-2986
The reaction between the nitrile complex trans-[PtCl(4)(EtCN)(2)] and benzohydroxamic acids RC(6)H(4)C([double bond]O)NHOH (R = p-MeO, p-Me, H, p-Cl, o-HO) proceeds smoothly in CH(2)Cl(2) at approximately 45 degrees C for 2-3 h (sealed tube) or under focused 300 W microwave irradiation for approximately 15 min at 50 degrees C giving, after workup, good yields of the imino complexes [PtCl(4)[NH[double bond]C(Et)ON[double bond]C(OH)(C(6)H(4)R)](2)] which derived from a novel metalla-Pinner reaction. The complexes [PtCl(4)[NH[double bond]C(Et)ON[double bond]C(OH)(C(6)H(4)R)](2)] were characterized by elemental analyses (C, H, N), FAB mass spectrometry, and IR and (1)H and (13)C[(1)H] spectroscopies, and [PtCl(4)[NH[double bond]C(Et)ON[double bond]C(OH)(Ph)](2)] (as the bis-dimethyl sulfoxide solvate), by X-ray single-crystal diffraction. The latter disclosed its overall trans-configuration with the iminoacyl species in the hydroximic tautomeric form in E-configuration which is held by N[bond]H...N hydrogen bond between the imine [double bond]NH atom and the hydroximic N atom. 相似文献
114.
Tunik SP Khripun VD Haukka M Pakkanen TA 《Dalton transactions (Cambridge, England : 2003)》2004,(11):1775-1782
Reactions between unsaturated [H(2)Os(3)(CO)(9)(PR(3))] clusters (PR(3)= PPh(3), P(4-CF(3)-C(6)H(4))(3), PEt(3)) and 2,4-hexadiyne-1,6-diol have been studied. It was found that the diyne ligand easily reacts with all these complexes to give [HOs(3)(CO)8(PR3)-[mu3, eta1:eta3:eta1)-(CH(3)-C-C=CH-CH=C-O)]] complexes (V, VI and VII, respectively) containing the "Os3C3" pentagonal pyramid cluster framework. This structural pattern is formed through the diyne cyclization, dissociation of a CO ligand and eventual coordination of the cyclized organic moiety to the osmium triangle in the [mu3, eta1:eta3:eta1) manner. In the case of the PEt(3) substituted cluster the second hydride transfer onto the organic fragment occurs to afford the nonhydride [Os(3)(CO)(8)(PR3)[mu3), eta1:eta2:eta1)-(CH(3)-CH-C=CH-CH=C-O)]] cluster, VIII, containing distorted pentagonal pyramid framework with a broken Os-C bond. Heating V, VI of VII and in hexane solutions results in formation of the regioisomers (Va, VIa and VIIa) with the phosphine ligand located at adjacent osmium atoms across the Os-Os bond bridged by the coordinated organic fragment. The most probable mechanism of the isomerization includes reversible phosphine migration between these metal centres. Solid-state structure of V, Va, VI, VIIa and VIII have been established by single crystal X-ray diffraction. A general mechanistic scheme for the diyne ligand cyclization and cluster framework transformations is suggested and discussed. 相似文献
115.
Treatment of trans-[PtCl(4)(RCN)(2)] (R = Me, Et) with ethanol allowed the isolation of trans-[PtCl(4)[E-NH[double bond]C(R)OEt](2)]. The latter were reduced selectively, by the ylide Ph(3)P[double bond]CHCO(2)Me, to trans-[PtCl(2)[E-NH[double bond]C(R)OEt](2)]. The complexed imino esters NH[double bond]C(R)OEt were liberated from the platinum(II) complexes by reaction with 2 equiv of 1,2-bis(diphenylphosphino)ethane (dppe) in chloroform; the cationic complex [Pt(dppe)(2)]Cl(2) precipitates almost quantitatively from the reaction mixture and can be easily separated by filtration to give a solution of NH[double bond]C(R)OEt with a known concentration of the imino ester. The imino esters efficiently couple with the coordinated nitriles in trans-[PtCl(4)(EtCN)(2)] to give, as the dominant product, [PtCl(4)[NH[double bond]C(Et)N[double bond]C(R)OEt](2)] containing a previously unknown linkage, i.e., ligated N-(1-imino-propyl)-alkylimidic acid ethyl esters. In addition to [PtCl(4)[NH[double bond]C(Et)N[double bond]C(Et)OEt](2)], another compound was generated as the minor product, i.e., [PtCl(4)(EtCN)[NH[double bond]C(Et)N[double bond]C(Et)OEt]], which was reduced to [PtCl(2)(EtCN)[NH[double bond]C(Et)N[double bond]C(Et)OEt]], and this complex was characterized by X-ray single-crystal diffraction. The platinum(IV) complexes [PtCl(4)[NH[double bond]C(Et)N[double bond]C(R)OEt](2)] are unstable toward hydrolysis and give EtOH and the acylamidine complexes trans-[PtCl(4)[Z-NH[double bond]C(Et)NHC(R)[double bond]O](2)], where the coordination to the Pt center results in the predominant stabilization of the imino tautomer NH[double bond]C(Et)NHC(R)[double bond]O over the other form, i.e., NH(2)C(Et)[double bond]NC(R)[double bond]O, which is the major one for free acylamidines. The structures of trans-[PtCl(4)[Z-NH[double bond]C(Et)NHC(R)[double bond]O](2)] (R = Me, Et) were determined by X-ray studies. The complexes [PtCl(4)[NH[double bond]C(Et)N[double bond]C(R)OEt](2)] were reduced to the appropriate platinum(II) compounds [PtCl(2)[NH[double bond]C(Et)N[double bond]C(R)OEt](2)], which, similarly to the appropriate Pt(IV) compounds, rapidly hydrolyze to yield the acylamidine complexes [PtCl(2)[NH[double bond]C(Et)NHC(R)[double bond]O](2)] and EtOH. The latter acylamidine compounds were also prepared by an alternative route upon reduction of the corresponding platinum(IV) complexes. Besides the first observation of the platinum(IV)-mediated nitrile-imine ester integration, this work demonstrates that the application of metal complexes gives new opportunities for the generation of a great variety of imines (sometimes unreachable in pure organic chemistry) in metal-mediated conversions of organonitriles, the "storage" of imino species in the complexed form, and their synthetic utilization after liberation. 相似文献
116.
Kallio M Hyötyläinen T Jussila M Hartonen K Palonen S Shimmo M Riekkola ML 《Analytical and bioanalytical chemistry》2003,375(6):725-731
A laboratory-made cryogenic modulator for comprehensive two-dimensional gas chromatography (GCxGC) was constructed and evaluated. Analytes were trapped with carbon dioxide and desorbed with heated GC oven air. The GCxGC system included a non-polar first-dimension column and a semi-polar second-dimension column connected to a flame ionisation detector. A laboratory-written Matlab-based program was used for the data analysis. Peak widths at half height for n-alkanes, obtained with use of new modulator, were at narrowest 60 ms. 相似文献
117.
Ari Lahti Matti Hotokka Kari Neuvonen Gunnar Karlstrm 《International journal of quantum chemistry》1999,72(1):25-37
The photochemical cis/trans isomerization of urocanic acid (UCA, (E)‐3‐(1′H‐imidazol‐4′‐yl)propenoic acid) was investigated using complete active space SCF (CASSCF) ab initio calculations. The singlet ground state and the triplet and the singlet manifolds of the lowest‐lying π→π* (HOMO→LUMO) excitation of the neutral and the anionic UCA were calculated using the 6‐31G* and the 6‐31+G* basis sets, respectively. The torsional barrier of the double bond of the propenoic acid moiety in UCA is observed to be considerably lower in the T1 and S1 excited states of the neutral UCA and in the T1 but not in the S1 excited state of the anionic UCA, as compared to the S0 state of the respective protonation form. The cis‐isomer of both the neutral and the anionic UCA is lower in energy than the trans‐isomer in the S0, T1, and S1 states. This energy difference is larger in the excited states than in the ground state, probably due to strengthening of the intramolecular hydrogen bond of cis‐UCA as the molecule is excited. The results of the calculations, interpreted in terms of the idea that UCA is deprotonated upon electronic excitation, led to construction of a new model for the photoisomerization mechanisms of UCA. According to this model, the trans‐to‐cis isomerization proceeds via both the triplet and the singlet manifolds in the deprotonated form of UCA. This isomerization may occur in the S0 state of the neutral UCA as well. The cis‐to‐trans isomerization is suggested to proceed only in the S0 state of the neutral UCA. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 25–37, 1999 相似文献
118.
Optical Review - Scattering of visible light by micrometer-scale natural wood fibers is usually treated by assuming fibers to be perfect long cylindrical scatterers. In industrial processes,... 相似文献
119.
Determination of platinum and rhodium in dust and plant samples using microwave-assisted sample digestion and ICP-MS 总被引:3,自引:0,他引:3
The platinum group elements (PGEs), particularly platinum, palladium and rhodium, are nowadays increasingly emitted into the environment from automotive catalytic converters. Thus, a method for the determination of PGEs (especially platinum and rhodium) in dust and plant samples was developed. The developed method was based on microwave-assisted sample digestion and inductively coupled plasma mass spectrometric (ICP-MS) determination. Spectral interferences in ICP-MS determination were corrected using mathematical correction equations based on signal ratio measurement. In addition, platinum and rhodium concentrations in the digested dust samples were also determined after Te coprecipitation without correction of the interferences. The results for platinum and rhodium in reference materials (NIST SRM 2557, recycled monolith autocatalyst and BCR-723, road dust) were in good agreement with the certified values. Preliminary results for the anthropogenic platinum and rhodium emissions in Oulu, northern Finland, based on dust and plant samples, indicated a common traffic-related source of these metals. 相似文献
120.
Rantala A Utriainen M Kaushik N Virta M Välimaa AL Karp M 《Analytical and bioanalytical chemistry》2011,400(4):1041-1049
A bacterial biosensor method for the selective determination of a bioavailable organomercurial compound, methylmercury, is
presented. A recombinant luminescent whole-cell bacterial strain responding to total mercury content in samples was used.
The bacterial cells were freeze-dried and used as robust, reagent-like compounds, without batch-to-batch variations. In this
bacteria-based sensing method, luciferase is used as a reporter, which requires no substrate additions, therefore allowing
homogenous, real-time monitoring of the reporter gene expression. A noninducible, constitutively light-producing control bacterial
strain was included in parallel for determining the overall cytotoxicity of the samples. The specificity of the total mercury
sensor Escherichia coli MC1061 (pmerRBlux) bacterial resistance system toward methylmercury is due to a coexpressed specific enzyme, organomercurial lyase. This enzyme
mediates the cleavage of the carbon–mercury bond of methylmercury to yield mercury ions, which induce the reporter genes and
produce a self-luminescent cell. The selective analysis of methylmercury with the total mercury strain is achieved by specifically
chelating the inorganic mercury species from the sample using an optimized concentration of EDTA as a chelating agent. After
the treatment with the chelating agent, a cross-reactivity of 0.2% with ionic mercury was observed at nonphysiological ionic
mercury concentrations (100 nM). The assay was optimized to be performed in 3 h but results can already be read after 1 h
incubation. Total mercury strain E. coli MC1061 (pmerRBlux) has been shown to be highly sensitive and capable of determining methylmercury at a subnanomolar level in optimized assay
conditions with a very high dynamic range of two decades. The limit of detection of 75 ng/l (300 pM) allows measurement of
methylmercury even from natural samples. 相似文献