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101.
Fillion E Carson RJ Trépanier VE Goll JM Remorova AA 《Journal of the American Chemical Society》2004,126(47):15354-15355
A one-pot, two-step process that transforms terminal alkynes into ethyl methyl-substituted benzylic quaternary carbon centers is described. (E)-2,2-Disubstituted-1-alkenyldimethylalanes have been shown to participate in 1,2-alkyl migration from aluminum to carbon with concomitant arylation at the 2-position to furnish ethyl methyl-substituted benzylic quaternary carbon centers, when reacted intramolecularly with aryl halides and triflates in the presence of a Pd(0) catalyst. The protocol is initiated with Cp2ZrCl2-catalyzed methylalumination of terminal alkynes followed by palladium-catalyzed intramolecular arylation of the resulting (E)-2,2-disubstituted-1-alkenyldimethylalanes, leading to 1,2-methyl shift from aluminum to carbon. In that sequence, a total of three new C-C single bonds are made, and two of the three alkyl groups on Me3Al transferred to the substrate on vicinal carbons. This method was applied to a variety of substrates, and the mechanism was investigated by deuterium-labeling experiments, which revealed that protodealumination of the final dialkylaluminum triflate or halide intermediates by CH3CN results in the formation of the fourth bond in the course of the transformation. 相似文献
102.
Baeten V von Holst C Garrido A Vancutsem J Michotte Renier A Dardenne P 《Analytical and bioanalytical chemistry》2005,382(1):149-157
In this paper we present an alternative method for detection of meat and bone meal (MBM) in feedstuffs by near-infrared microscopic (NIRM) analysis of the particles in the sediment fraction (dense fraction (d >1.62) from dichloroethylene) of compound feeds. To apply this method the particles of the sediment fraction are spread on a sample holder and presented to the NIR microscope. By using the pointer of the microscope the infrared beam is focussed on each particle and the NIR spectrum (1112–2500 nm) is collected. This method can be used to detect the presence of MBM at concentrations as low as 0.05% mass fraction. When results from the NIRM method were compared with the classical microscopic method, a coefficient of determination (R2) of 0.87 was obtained. The results of this study demonstrated that this method could be proposed as a complementary tool for the detection of banned MBM in feedstuffs by reinforcement of the monitoring of feeds. 相似文献
103.
Christine Bonal Jean-Pierre Morel Nicole Morel-Desrosiers 《Journal of solution chemistry》1998,27(4):361-372
The apparent equilibrium constants and enthalpies of complexation of Nd3+, Sm3+, Eu3+, and Gd3+ by xylitol in aqueous solutions containing NaNO3 at an ionic strength of 2.0 mol-kg–1 have been determined by microcalorimetry at 25°C. Since nitrate anion weakly complexes the lanthanide cations, these values are analyzed in terms of competition between xylitol and NO
3
-
The method leads to the apparent equilibrium constants and enthalpies of complexation of the lanthanide cations by NO
3
-
at this particular ionic strength. Despite the difficulties encountered in characterizing rather weak associations, the results are, whenever comparison is possible, in good agreement with those obtained by direct microcalorimetry. The advantage of this competition method is that it can be used when the enthalpic effects are too weak and insufficiently concentration dependent for direct microcalorimetric determination. In the present case, it allows us to thermodynamically characterize the formation of SmNO
3
2+
and EuNO
3
2+
, processes we have not been able to study directly. 相似文献
104.
Fingering instabilities in films moving along wetted surfaces, dimpling in horizontal liquid films, and the drainage of vertical soap films by marginal regeneration are caused by surface tension gradients along the perimeter of the thin film. These gradients lead to a mechanical instability which involves Marangoni type liquid flow. It is possible to describe the conditions for the onset of marginal regeneration with a critical number of the ratio between the driving force for the Marangoni flow and the friction of film elements that move relative to their surroundings. This ratio is called the Mysels number. A linear stability analysis leads to a scaling relation lambda approximately h(Ca)(-1/3) between the wavelength lambda of the instability and the capillary number Ca (Ca=/etaV(s)/gamma. In experiments with several Marangoni-driven instabilities this scaling relation has been found; it illustrates the general applicability in the understanding of flow phenomena of this type. Copyright 2001 Academic Press. 相似文献
105.
Hou Y Jaffrezic-Renault N Martelet C Tlili C Zhang A Pernollet JC Briand L Gomila G Errachid A Samitier J Salvagnac L Torbiéro B Temple-Boyer P 《Langmuir : the ACS journal of surfaces and colloids》2005,21(9):4058-4065
To make ultrathin films for the fabrication of artificial olfactory systems, odorant biosensors, we have investigated mixed Langmuir and Langmuir-Blodgett films of odorant-binding protein/amphiphile. Under optimized experimental conditions (phosphate buffer solution, pH 7.5, OBP-1F concentration of 4 mg L(-1), target pressure 35 mN m(-1)), the mixed monolayer at the air/water interface is very stable and has been efficiently transferred onto gold supports, which were previously functionalized by self-assembled monolayers (SAMs) with 1-octadecanethiol (ODT). Atomic force microscopy and electrochemical impedance spectroscopy were used to characterize mixed Langmuir-Blodgett (LB) films before and after contact with a specific odorant molecule, isoamyl acetate. AFM phase images show a higher contrast after contact with the odorant molecule due to the new structure of the OBP-1F/ODA LB film. Non-Faradaic electrochemical spectroscopy (EIS) is used to quantify the effect of the odorant based on the electrical properties of the OBP-1F/ODA LB film, as its resistance strongly decreases from 1.18 MOmega (before contact) to 25 kOmega (after contact). 相似文献
106.
Summary The alcoholic portion of avetiver oil (Bourbon), the gas chromatogram of which shows more than 100 components, was analyzed by combined GC-MS with different ionization methods. This enabled us to identify major components. The specificity of the method was improved by using combined gas chromatography-tandem mass spectrometry in the collision-activated-dissociation mode. 相似文献
107.
Biosensors based on enzyme field-effect transistors for determination of some substrates and inhibitors 总被引:3,自引:0,他引:3
Dzyadevych SV Soldatkin AP Korpan YI Arkhypova VN El'skaya AV Chovelon JM Martelet C Jaffrezic-Renault N 《Analytical and bioanalytical chemistry》2003,377(3):496-506
This paper is a review of the authors' publications concerning the development of biosensors based on enzyme field-effect transistors (ENFETs) for direct substrates or inhibitors analysis. Such biosensors were designed by using immobilised enzymes and ion-selective field-effect transistors (ISFETs). Highly specific, sensitive, simple, fast and cheap determination of different substances renders them as promising tools in medicine, biotechnology, environmental control, agriculture and the food industry.The biosensors based on ENFETs and direct enzyme analysis for determination of concentrations of different substrates (glucose, urea, penicillin, formaldehyde, creatinine, etc.) have been developed and their laboratory prototypes were fabricated. Improvement of the analytical characteristics of such biosensors may be achieved by using a differential mode of measurement, working solutions with different buffer concentrations and specific agents, negatively or positively charged additional membranes, or genetically modified enzymes. These approaches allow one to decrease the effect of the buffer capacity influence on the sensor response in an aim to increase the sensitivity of the biosensors and to extend their dynamic ranges.Biosensors for the determination of concentrations of different toxic substances (organophosphorous pesticides, heavy metal ions, hypochlorite, glycoalkaloids, etc.) were designed on the basis of reversible and/or irreversible enzyme inhibition effect(s). The conception of an enzymatic multibiosensor for the determination of different toxic substances based on the enzyme inhibition effect is also described.We will discuss the respective advantages and disadvantages of biosensors based on the ENFETs developed and also demonstrate their practical application. 相似文献
108.
Thermodynamic analysis of the reversed-phase retention behavior of a doxorubicin-peptide conjugate demonstrated that the degree of non-linearity observed in Van't Hoff plots was impacted by mobile phase acetonitrile content over the 25-38% acetonitrile (v/v) range tested. Small decreases in the non-polar surface area of the doxorubicin-peptide conjugate as a function of temperature were estimated from these data using linear solvent strength relationships, suggesting that the retention behavior may be the result of minor analyte conformational changes during the chromatographic experiment. This hypothesis was supported via circular dichroism (CD), Raman and 1H NMR spectroscopic studies of the doxorubicin-peptide conjugate in selected chromatographic mobile phase compositions. The CD and Raman data indicated small changes to the apparent analyte microenvironment as a function of temperature and bulk solvent environment, while 1H NMR studies specifically demonstrated the environmental sensitivity of protons on three non-polar peptide residues and the proximal aromatic region of the analyte. Together, these data suggest that minor changes to the conformational order of the essentially random structure of the doxorubicin-peptide conjugate are sufficient to impact chromatographic performance. 相似文献
109.
Michael Leuck Rubina Giare Matthias Paul Nicole Zien Andreas Wolter 《Tetrahedron letters》2004,45(2):317-320
A novel improved controlled pore glass (CPG) support based on the 2-(hydroxymethyl)-6-nitrobenzoyl (HMNB) protecting group was developed for the synthesis of 3′-aminoalkylated oligonucleotides. The release of oligonucleotides with free 3′-amino groups from the support is complete within 2 h at 55 °C in concentrated ammonia. 相似文献
110.
Paul Müller Nicole Pautex Michael P. Doyle Vahid Bagheri 《Helvetica chimica acta》1990,73(5):1233-1241
The thermocatalytic rearrangements of cyclopropenes 1-4 have been investigated in the presence of Rh(IT) perfiuorobutyrate. 1, 2, 3-Triphenylcyclopropene ( 1a ) undergoes rearrangement lo diphenylindene 5a or, with alkoxycyclopropene derivatives, to α, β-unsaturated ketone 6. Furan formation occurs with 2, 3-diphenylcyclo-propenecarboxylate 2, but the diethyl counterpart 3 rearranges to dienoate 8. 2-Alkylcyclopropenecarboxylates 4 afforded (E)-methylidenecyclopentane derivatives 9 as the only isolable product in yields of ca. 35 %. A mechanism involving regio- and stereospecific cyclopropene ring opening to a Rh-complexed vinylcarbene and insertion of the latter into the C? H bond to give 9 is proposed. An analogous mechanism should account for the rearrangement products of 1 to 3 . 相似文献