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191.
Alexandre?Ioan?RomoscanuEmail author Mahir?Behar?Sayir Klaus?H?usler Adam?Stewart?Burbidge 《Rheologica Acta》2003,42(5):462-476
In this work an instrument is described which measures the complex shear viscosity of liquids in the kHz frequency range. The instrument is driven electromagnetically and operates in resonant mode. The measurement of the primary data, from which the rheological properties of the fluid sample are inferred, does not include any deflection amplitude measuring step and is purely digital. Models allowing the interpretation of the probe primary data in terms of fluid complex viscosity are presented. The theoretically predicted mechanical behaviour of the probe is compared with the measured one and the rheometric ability of the device is discussed. 相似文献
192.
Copper‐Mediated Formation of Aryl,Heteroaryl, Vinyl and Alkynyl Difluoromethylphosphonates: A General Approach to Fluorinated Phosphate Mimics
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Maria V. Ivanova Dr. Alexandre Bayle Dr. Tatiana Besset Dr. Thomas Poisson Prof. Dr. Xavier Pannecoucke 《Angewandte Chemie (International ed. in English)》2015,54(45):13406-13410
A general and efficient access to aryl, heteroaryl, vinyl and alkynyl difluoromethylphosphonates is described. The developed methodology using TMSCF2PO(OEt)2, iodonium salts and a copper salt provided a straightforward manifold to reach these highly relevant products. The reaction proved to be highly functional group tolerant and proceeded under mild conditions, giving the corresponding products in good to excellent yields. This method represents the first general synthetic route to this important class of fluorinated scaffolds, which are well‐recognized as in vivo stable phosphate surrogates. 相似文献
193.
Electrolytic Macrocyclizations: Scalable Synthesis of a Diazonamide‐Based Drug Development Candidate
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Dr. Hui Ding Patrick L. DeRoy Christian Perreault Dr. Alexandre Larivée Dr. Arshad Siddiqui Dr. Charles G. Caldwell Susan Harran Prof. Dr. Patrick G. Harran 《Angewandte Chemie (International ed. in English)》2015,54(16):4818-4822
An electrochemical method to synthesize the core macrolactam of diazonamides is described. Large ring‐forming dehydrogenation is initiated by anodic oxidation at a graphite surface. The reaction requires no tailoring of the substrate and occurs at ambient temperature in aqueous DMF in an undivided cell open to air. This unique chemistry has enabled a concise, scalable preparation of DZ‐2384; a refined analog of diazonamide A slated for clinical development as a cancer therapeutic. 相似文献
194.
Vianney O. Santos Isabela R. Leite Alexandre G. Brolo Joel C. Rubim 《Journal of Raman spectroscopy : JRS》2016,47(6):674-680
The electrochemical conversion of CO2 into value‐added products using room temperature ionic liquids as solvent/electrolyte has been proposed as an alternative to minimize the environmental effects of CO2 emissions. A key issue in the design of electrochemical systems for the reduction of CO2 is the in situ identification of intermediate surface species as well as reaction products. Copper electrodes, besides being used as cathodes in the electrochemical reduction of CO2, present surface‐enhanced Raman scattering (SERS) when properly activated. In this sense, the electrochemical reduction of CO2 over a copper electrode in the room temperature ionic liquids 1‐n‐butyl‐3‐methyl imidazolium tetrafluoroborate (BMI.BF4) was investigated by cyclic voltammetry and by in situ SERS. The cyclic voltammetries have shown that the presence of CO2 on the BMI.BF4 anticipates the reduction of BMI+ to the corresponding carbene. Fourier‐transform‐SERS spectra excited at 1064 nm and SERS spectra excited at 632.8 nm have shown vibrational signals from adsorbed CO. These SERS results indicated that CO adsorbs on the copper surface at two different surface sites. The observation of a 2275 cm−1 vibration in the SERS spectra also confirmed the presence of chemically adsorbed CO2. Other products of CO2 reduction in BMI.BF4, besides CO, were identified, including BMI carbene and the BMI‐CO2 adduct. The SERS results also suggest that the presence of a thin film of Cu2O on the copper surface anticipates the reduction of CO2 to CO, an important component of syngas. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
195.
Alexandre Westermann Christophe Geantet Philippe Vernoux Stphane Loridant 《Journal of Raman spectroscopy : JRS》2016,47(10):1276-1279
In this work, the origin of the Raman defects band at 570 cm−1 of praseodymium‐doped ceria was revisited from in situ spectra using six different exciting lines between 458 and 785 nm at low temperatures after oxidizing or reducing treatment. The observation of overtones and the fast change of relative intensity with excitation wavelength were explained by a resonance effect around 514 nm, which involved a Pr4+ containing defect stabilized at the oxidized state leading to an absorption band around 530 nm. The reduction of Pr4+ cations contained in such defects modifies the electronic properties of praseodymium doped ceria inhibiting the resonance effect. Additionally, the number of D1 defects that involved Pr3+ cations and oxygen vacancies increased allowing them to be distinguished. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
196.
Patricia Regal Alexandre Lamas Cristina A. Fente Carlos M. Franco Alberto Cepeda 《液相色谱法及相关技术杂志》2017,40(11):541-548
Growth hormone (GH) or somatotropin (ST) is a species-specific polypeptide hormone produced in the pituitary gland of vertebrates. When administered exogenously to dairy cattle, it has galactopoietic effects and is capable of increasing the milk yield. The beginning of the commercial production of recombinant variants of bovine somatotropin (rbST), by the end of the 20th century, had a major economic impact in the dairy industry. Recombinant bST enabled large-scale applications in farms, enhancing significantly milk production. While it is banned in the European Union (EU), several countries permit the trade and use of recombinant somatotropins in animal husbandry. Also, rbST-free dairy products can be frequently found in the market of those countries, even though these labels are not actually verified in a laboratory. In this context, effective analytical methods are needed for residue control to avoid an illegal use of rbST but also to prevent fraudulent labeling in some cases. The present review includes studies published in the last 5 years (from 2012 to 2017) to monitor rbST in bovine animals, using liquid-based applications. It is then intended to serve as a practical guide to help those laboratories interested in developing analytical methods to detect rbST use and abuse. 相似文献
197.
In order to describe the basic phenomenon of miscible grout propagation during the injection in a saturated and deformable porous medium, a general mathematical model was proposed, which accounts for the existing coupling between the fluid flow analysis, the miscible grout transport, and the solid skeleton deformation, leading to a realistic prediction of the injected zone. The development of the model was made concurrently with laboratory experiments to determine the model parameters. This paper describes the determination of the longitudinal dispersivity during the transport of a micro-cement grout injected in a one-dimensional soil column, by relying on image processing analysis. The application concerned here is the injection of soils for improving their properties, that is, to reduce permeability, increase mechanical strength or reduce the deformability. The longitudinal dispersion coefficient is an essential parameter governing the mixing process and the evolution of the transition zone, and thus the injection efficiency. Finally, the comparison between simulated results from the developed model and experimental data, essential to validate the model from a phenomenological standpoint, is made. 相似文献
198.
The local and global nonlinear dynamics of a two-degrees-of-freedom model system conveying fluid is studied. The undeflected model consistsof an inverted T formed by three rigid rods, with the tips of the twohorizontal rods resting on the viscous foundation. The foundationexhibits a visco-elasto-plastic response, including the Bauschingereffect. The vertical rigid rod of an annular cross-section is subjectedto a conservative (dead) force. Also, it conveys fluid having bothstatic and pulsation components. First, the method of multiple scales isused for the analysis of the local dynamics of the system withvisco-elastic response. Attention is focused on modal interactionphenomena in weak excitation at primary resonance and on hardsub-harmonic excitation. Two different asymptotic expansions areutilised to get a structural response for typical ranges of excitationparameters. Numerical integration of the governing equations is thenperformed to validate the results of asymptotic analysis in each case. Afull global nonlinear dynamics analysis of the visco-elasto-plasticsystem is performed. The role of plastic deformations in thedestabilisation of the system is discussed. Large-amplitude nonlinearoscillations of the visco-elasto-plastic system are studied, includingthe influence of material hardening and of static and periodiccomponents of pulsating fluid. Chaotic regimes of motion with andwithout plastic effects are considered. The results of the analysis maybe used in devices composed of a rather short tube connected to a notcompletely fixed foundation resting on the soil exhibitingelasto-plastic behaviour. 相似文献
199.
Alexandre Ragouilliaux Benjamin Herzhaft François Bertrand Philippe Coussot 《Rheologica Acta》2006,46(2):261-271
To have a better knowledge of problems occurring with drilling fluids in complex wells, we carried out a detailed rheological analysis of a typical drilling mud at low shear rates using both conventional rheometry and MRI velocimetry. We show the existence of a viscosity bifurcation effect: Below a critical stress value, the mud tends to completely stop flowing, whereas beyond this critical stress, it reaches an apparent shear rate larger than a finite (critical) value, and no stable flows can be obtained between this critical shear rate value and zero. These results are confirmed by MRI velocity profiles, which exhibit a slope break at the interface between the solid and the liquid phases inside the Couette geometry. Moreover, this viscosity bifurcation is a transient phenomenon, the progressive development of which can be observed by MRI. A further examination of MRI data shows that, in the transient regime, the shear rate does not vary monotonously in the rheometer gap and is particularly large along the outer (rough) cylinder, which might be at the origin of the development of a region of constant shear rate in the apparent flow curve. 相似文献
200.
Facile Synthesis and Structural Characterization by NMR,ESI–MS/MS and DFT Calculations of New (E)‐6‐[2‐Ferrocenylalkylidenehydrazino]nicotinic Hydrazides and Their (E)‐Ferrocenyl‐pyrazolyl‐pyridine Heterocyclic System
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Liliane M. F. Porte Gisele R. Paim Thiago G. Schwanz Alexandre R. Meyer Helio G. Bonacorso Marcos A. P. Martins Nilo Zanatta 《Journal of heterocyclic chemistry》2014,51(5):1333-1339
This paper reports a facile and convenient access by a conventional thermal procedure in ethanol as solvent to a new examples of (E)‐6‐[2‐ferrocenylalkylidenehydrazino]nicotinic hydrazides ( 3 ) (53–72%) from the quimioselective reactions of 6‐hydrazinonicotinc hydrazide ( 1 ) with acylferrocenes ( 2 ), where acyl = formyl and acetyl. Subsequently, cyclocondensation reactions of ferrocenylalkylidene hydrazones ( 3 ) with 4‐R1‐4‐alkoxy‐1,1,1‐trifluoroalk‐3‐en‐2‐ones ( 4 ), where R1 = Me, Ph, 2‐Furyl, to obtain new six heterocyclic derivatives as (E)‐pyrazolyl‐pyridinohydrazones ( 5 ) (58–63%), are also presented. The structures of these new heterocyclic compounds 5 containing an organometallic unit were characterized and studied by NMR, ESI–MS/MS techniques. DFT calculations were also employed to assign the E configuration for compounds 3 and 5 . 相似文献