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1.
Gandelman M Naing KM Rybtchinski B Poverenov E Ben-David Y Ashkenazi N Gauvin RM Milstein D 《Journal of the American Chemical Society》2005,127(43):15265-15272
A new general, synthetically simple, and safe method for the preparation of metal carbene complexes, which is based on diphenyl sulfonium salts as carbenoid precursors, has been developed, and its scope and applications were studied. In general, deprotonation of a sulfonium salt with a base results in a sulfur ylide, which, in turn, reacts with an appropriate metal precursor to give the corresponding metal carbene complex. Thus, starting from benzyldiphenylsulfonium salt, the complexes (PCX)Rh=CHPh (X = P, N) were prepared in quantitative yield. Syntheses of Grubbs' catalyst, (PCy(3))(2)Cl(2)Ru=CHPh, and of Werner's carbene, [Os(=CHPh)HCl(CO)(P(i)Pr(3))(2)], were achieved by this method. Novel trans-bisphosphine Rh and Ir carbenes, ((i)Pr(3)P)(2)(Cl)M=CHPh, which could not be prepared by other known methods, were synthesized by the sulfur ylide approach. The method is not limited to metal benzylidenes, as demonstrated by the preparation of the Ru vinyl-alkylidene, (PCy(3))(2)Cl(2)Ru=CH-CH=CH(2), methoxycarbonyl-alkylidene, (PCy(3))(2)Cl(2)Ru=CH(CO(2)Me), and alkylidene (PCy(3))(2)Cl(2)Ru=CH(CH(3)), (PCy(3))(2)Cl(2)Ru=CH(2) compounds. The problem of recycling of starting materials as well as the issue of facile purification of the product metal carbene complex were addressed by the synthesis of a polymer-supported diarylsulfide, the carrier of the carbenoid unit in the process. Based on the sulfur ylide route, a methodology for the synthesis of metallocarbenes anchored to a polymer via the carbene ligand, using a commercial Merrifield resin, was developed. 相似文献
2.
Filipe Belarmino de Lima Gessenildo Pereira Rodrigues Juracy Regis de Lucena Júnior Elizete Ventura Rui Fausto Igor Reva Silmar Andrade do Monte 《International journal of quantum chemistry》2020,120(16):e26263
Multi-reference configuration interaction, MR-CI (including extensivity corrections, named +Q), calculations were performed on the S0–S3 states of cyclohexa-2,4-diene-1-thione (thione 24 ) and cyclohexa-2,5-diene-1-thione (thione 25 ), which are thione isomers of thiophenol. Several types of uncontracted MR-CIS and MR-CISD wavefunctions were employed, comprising MR-CI expansions as large as ~365 × 106 configuration state functions. The nature of the studied excited states was characterized. Vertical excitation energies (ΔE) and oscillator strengths (f) were computed. The most intense transitions (S0 → S2 for 24 and S0 → S3 for 25 ) did not change with the wavefunction, although a variation as large as ~1 eV was obtained for the S3 state of 24 , at the highest (MR-CI+Q) level. On the other hand, ΔE changed at most by ~0.56 eV for 25 as the wavefunction changes, at the same level. The S1 state of both thiones was found to have nπ* character and is in the visible region. For 24 , S2 and S3 are ππ* and nπ* states, respectively, while for 25 the reverse order is obtained. S2 and S3 are in the range ~3.5 to 5.2 eV, again at the highest level. It is the first time that the excited states of the title molecules are studied. The computed results agree with the experimental onset of photoreactions of thiones 24 and 25 found by Reva et al (Phys. Chem. Chem. Phys., 2015 , 17, 4888). 相似文献
3.
Regis Guyonnet 《Journal of statistical physics》1991,65(1-2):269-289
The NMR properties of nuclei linked to long linear polymer molecules are sensitive to the influence of hard walls. In this context, the residual energy of tensorial spin-spin interactions is calculated using a path integral approach. Several thermodynamic quantities of the polymer system (free energy, equation of state,...) are also expressed, taking chain stiffness effects and the presence of two repulsive walls into consideration. 相似文献
4.
Regis D. Gougeon Dr. Marianna Lucio Arnaud De Boel Moritz Frommberger Dr. Norbert Hertkorn Dr. Dominique Peyron Dr. David Chassagne Dr. François Feuillat Dr. Philippe Cayot Prof. Andrée Voilley Prof. Istvan Gebefügi Dr. Philippe Schmitt‐Kopplin Priv.‐Doz. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(3):600-611
A non‐targeted, ultra‐high‐resolution mass spectrometric, direct analysis of oak‐wood extracts from two species (Quercus robur L. and Quercus petraea Liebl.) from three French forests, and of a wine aged in barrels derived therefrom has been performed to identify families of metabolites that could discriminate both the species and the geographical origin of woods. From 12 T ultra‐high‐resolution Fourier transform ion cyclotron resonance mass spectra of wood extracts, hundreds of mass signals were identified as possible significant biomarkers of the two species, with phenolic and carbohydrate moieties leading the differentiation between Q. robur and Q. petraea, respectively, as corroborated by both FTMS and NMR data. For the first time, it is shown that oak woods can also be discriminated on the basis of hundreds of forest‐related compounds, and particular emphasis is put on sessile oaks from the Tronçais forest, for which sugars are significantly discriminant. Despite the higher complexity and diversity of wine metabolites, forest‐related compounds can also be detected in wines aged in related barrels. It is only by using these non‐targeted analyses that such innovative results, which reveal specific chemodiversities of natural materials, can be obtained. 相似文献
5.
The ARCADE 2 Collaboration has recently measured an isotropic radio emission which is significantly brighter than the expected contributions from known extra-galactic sources. The simplest explanation of such excess involves a "new" population of unresolved sources which become the most numerous at very low (observationally unreached) brightness. We investigate this scenario in terms of synchrotron radiation induced by weakly interacting massive particle (WIMP) annihilations or decays in extra-galactic halos. Intriguingly, for light-mass WIMPs with a thermal annihilation cross section, the level of expected radio emission matches the ARCADE observations. 相似文献
6.
7.
We introduce a master–worker framework for parallel global optimization of computationally expensive functions using response surface models. In particular, we parallelize two radial basis function (RBF) methods for global optimization, namely, the RBF method by Gutmann [Gutmann, H.M., 2001a. A radial basis function method for global optimization. Journal of Global Optimization 19(3), 201–227] (Gutmann-RBF) and the RBF method by Regis and Shoemaker [Regis, R.G., Shoemaker, C.A., 2005. Constrained global optimization of expensive black box functions using radial basis functions, Journal of Global Optimization 31, 153–171] (CORS-RBF). We modify these algorithms so that they can generate multiple points for simultaneous evaluation in parallel. We compare the performance of the two parallel RBF methods with a parallel multistart derivative-based algorithm, a parallel multistart derivative-free trust-region algorithm, and a parallel evolutionary algorithm on eleven test problems and on a 6-dimensional groundwater bioremediation application. The results indicate that the two parallel RBF algorithms are generally better than the other three alternatives on most of the test problems. Moreover, the two parallel RBF algorithms have comparable performances on the test problems considered. Finally, we report good speedups for both parallel RBF algorithms when using a small number of processors. 相似文献
8.
Non‐Invasive Salivary Electrochemical Quantification of Paraquat Poisoning Using Boron Doped Diamond Electrode 下载免费PDF全文
Thiago Matheus Guimarães Selva William Reis de Araujo Thiago Regis Longo Cesar da Paixão 《Electroanalysis》2015,27(7):1642-1648
The present work describes the first electrochemical method for quantifying paraquat herbicide poisoning in human saliva samples. Paraquat shows two couples of well‐defined peaks in aqueous solution using a boron doped diamond (BDD) electrode. By using square wave voltammetry (SWV) technique under optimum experimental conditions, a linear analytical curve was obtained for paraquat concentrations ranging from 0.800 to 167 µmol L?1, with a detection limit of 70 nmol L?1. This method was applied to quantify paraquat spikes in human saliva samples and in two different water samples (tap and river). The recovery values obtained ranged from 83.0 to 104 % and 99.1 to 105 %, respectively, which highlight the accuracy of the proposed method. 相似文献
9.
Accelerating flames in tubes—an analysis 总被引:1,自引:0,他引:1
C. Regis L. Bauwens Luc Bauwens Ida Wierzba 《Proceedings of the Combustion Institute》2007,31(2):2381-2388
Flame acceleration in tubes is studied. A tube filled with flammable mixture is closed at one end and open to the atmosphere at its second end. When ignition takes place near the closed end, it is well-known from experiments that the flame may accelerate, oscillate and eventually reach considerable speeds. A one-dimensional analysis is presented, based upon the assumption that the flame front propagates at a speed that is small compared to the speed of sound. The analysis leads to a construction of the complete unsteady solution. Results from the analysis and from a numerical simulation are compared. They are similar enough to validate the analysis. The tube acoustics are set in motion by the expansion of the fluid due to ignition at the closed end. Subsequently, both spectrum and amplitude evolve because of the motion of the temperature interface, and because of forcing by the flame front, which the analysis precisely quantifies. Oscillations in the front position are strong enough to result in flow reversal. In addition, the induced periodic acoustic acceleration of the temperature and density interface will periodically make the flame front Rayleigh–Taylor unstable, which should result in the dramatic increase in the propagation speed seen in experiments. 相似文献
10.
Santos Regis C. Maia José R. da S. Abras Anuar Filgueiras Carlos A. L. 《Hyperfine Interactions》2002,142(3-4):495-501
Several novel tin(IV) adducts of amidines, [SnClPh3L], [SnCl2Ph2L] and [SnBr4L] {L=N,N-diphenylacetamidine (Hdpac) or N,N-diphenylbenzamidine (Hdpba)}, were prepared and investigated by Mössbauer spectroscopy which was an important tool for the elucidation of bonding and structural features. The resulting Mössbauer data also led to the conclusion that the tin(IV) centre for the adduct [SnClPh3L] is pentacoordinated in a trigonal bipyramidal arrangement and hexacoordinated for [SnCl2Ph2L] and [SnBr4L] in a geometric patterns of an octahedral. The amidines act as monodentate ligands to the metal centre for the former and bidentate for the latter. 相似文献