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121.
We used a continuum model to investigate the isochoric radial expansion of a right circular cylindrical specimen composed of a nematic elastomer that is crosslinked in a uniaxial state and then annealed. Numerical solutions show that, above a certain radial expansion, the material has a definitive energetic preference for a state involving a disclination of strength +1 along the cylinder axis. Surrounding such a disclination is a core with radial dimension on the order of 10?2 μm, which coincides with observations in conventional liquid‐crystal melts. Examination of the normal‐stress differences indicates that the first of these differences depends nonmonotically on the extent of radial expansion and possesses a local minimum at the point where a disclination becomes energetically preferred. This suggests a practical experimental method for testing the predictions of our model. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2098–2106, 2002 相似文献
122.
Le Bailly de Tilleghem C Beck B Boulanger B Govaerts B 《Journal of chemical information and modeling》2005,45(3):758-767
Combinatorial chemistry is widely used in drug discovery. Once a lead compound has been identified, a series of R-groups and reagents can be selected and combined to generate new potential drugs. The combinatorial nature of this problem leads to chemical libraries containing usually a very large number of virtual compounds, far too large to permit their chemical synthesis. Therefore, one often wants to select a subset of "good" reagents for each R-group of reagents and synthesize all their possible combinations. In this research, one encounters some difficulties. First, the selection of reagents has to be done such that the compounds of the resulting sublibrary simultaneously optimize a series of chemical properties. For each compound, a desirability index, a concept proposed by Harrington,(20) is used to summarize those properties in one fitness value. Then a loss function is used as objective criteria to globally quantify the quality of a sublibrary. Second, there are a huge number of possible sublibraries, and the solutions space has to be explored as fast as possible. The WEALD algorithm proposed in this paper starts with a random solution and iterates by applying exchanges, a simple method proposed by Fedorov(13) and often used in the generation of optimal designs. Those exchanges are guided by a weighting of the reagents adapted recursively as the solutions space is explored. The algorithm is applied on a real database and reveals to converge rapidly. It is compared to results given by two other algorithms presented in the combinatorial chemistry literature: the Ultrafast algorithm of D. Agrafiotis and V. Lobanov and the Piccolo algorithm of W. Zheng et al. 相似文献
123.
Rozet E Dewé W Morello R Chiap P Lecomte F Ziemons E Boos KS Boulanger B Crommen J Hubert P 《Journal of chromatography. A》2008,1189(1-2):32-41
The transfer of analytical methods from a sending laboratory to a receiving one requires to guarantee that this last laboratory will obtain accurate results. Undeniably method transfer is the ultimate step before routine implementation of the method at the receiving site. The conventional statistical approaches generally used in this domain which analyze separately the trueness and precision characteristics of the receiver do not achieve this. Therefore, this paper aims first at demonstrating the applicability of two recent statistical approaches using total error-based criterion and taking into account the uncertainty of the true value estimate of the sending laboratory, to the transfer of bioanalytical methods. To achieve this, they were successfully applied to the transfer of two fully automated liquid chromatographic method coupled on-line to solid-phase extraction. The first one was dedicated to the determination of three catecholamines in human urine using electrochemical detection, and the second one to the quantitation of N-methyl-laudanosine in plasma using fluorescence detection. Secondly, a risk-based evaluation is made in order to understand why classical statistical approaches are not sufficient to provide the guarantees that the analytical method will give most of the time accurate results during its routine use. Finally, some recommendations for the transfer studies are proposed. 相似文献
124.
CuO nanospheres, synthesized by a simple one‐step hydrothermal method, have been applied to modify the glassy carbon (GC) electrode for sensitive nonenzymatic glucose detection. The CuO nanospheres modified electrode, compared to the Nafion modified GC electrode, exhibits an enhanced electrocatalytic property for direct glucose oxidation and shows a fast response and a high sensitivity for the amperometric detection of glucose. It has been determined that the dissolved oxygen is not involved in glucose oxidation and the high concentration of NaCl does not poison the electrode. These results also indicate that CuO nanospheres have great potential application in electrochemical detection. 相似文献
125.
Boulanger AM Rennie EE Holland DM Shaw DA Mayer PM 《The journal of physical chemistry. A》2008,112(5):866-879
The unimolecular dissociation reactions of the methylhydrazine (MH) and tetramethylhydrazine (TMH) radical cations have been investigated using tandem mass spectrometry and threshold photoelectron photoion coincidence spectroscopy in the photon energy ranges 9.60-31.95 eV (for the MH ion) and 7.74-29.94 eV (for the TMH ion). Methylhydrazine ions (CH3NHNH2(+*)) have three low-energy dissociation channels: hydrogen atom loss to form CH2NHNH2(+) (m/z 45), loss of a methyl radical to form NHNH2(+) (m/z 31), and loss of methane to form the fragment ion m/z 30, N2H2(+*). Tetramethylhydrazine ions only exhibit two dissociation reactions near threshold: that of methyl radical loss to form (CH3)2NNCH3(+) (m/z 73) and of methane loss to form the fragment ion m/z 72 with the empirical formula C3H8N2(+*). The experimental breakdown curves were modeled with Rice-Ramsperger-Kassel-Marcus theory, and it was found that, particularly for methyl radical loss, variational transition state theory was needed to obtain satisfactory fits to the data. The 0 K enthalpies of formation (delta(f)H0) for all fragment ions (m/z 73, m/z 72, m/z 45, m/z 31, and m/z 30) have been determined from the 0 K activation energies (E0) obtained from the fitting procedure: delta(f)H0[(CH3)2NNCH3(+)] = 833 +/- 5 kJ mol(-1), delta(f)H0 [C3H8N2(+*)] = 1064 +/- 5 kJ mol(-1), delta(f)H0[CH2NHNH2(+)] = 862 +/- 5 kJ mol(-1), delta(f)H0[NHNH2(+)] = 959 +/- 5 kJ mol(-1), and delta(f)H0[N2H2(+*)] = 1155 +/- 5 kJ mol(-1). The breakdown curves have been measured from threshold up to h nu approximately 32 eV for both hydrazine ions. As the photon energy increases, other dissociation products are observed and their appearance energies are reported. 相似文献
126.
127.
Eliot Fried 《Archive for Rational Mechanics and Analysis》2008,190(2):227-265
We develop a sharp-interface theory for phase transformations between the isotropic and uniaxial nematic phases of a flowing
liquid crystal. Aside from conventional evolution equations for the bulk phases and corresponding interface conditions, the
theory includes a supplemental interface condition expressing the balance of configurational momentum. As an idealized illustrative
application of the theory, we consider the problem of an evolving spherical droplet of the isotropic phase surrounded by the
nematic phase in a radially-oriented state. For this problem, the bulk and interfacial equations collapse to a single nonlinear
second-order ordinary differential equation for the radius of the droplet—an equation which, in essence, expresses the balance
of configurational momentum on the interface. This droplet evolution equation, which closely resembles a previously derived
and extensively studied equation for the expansion of contraction of a spherical gas bubble in an incompressible viscous liquid,
includes terms accounting for the curvature elasticity and viscosity of the nematic phase, interfacial energy, interfacial
viscosity, and the ordering kinetics of the phase transformation. We determine the equilibria of this equation and study their
stability. Additionally, we find that motion of the interface generates a backflow, without director reorientation, in the
nematic phase. Our analysis indicates that a backflow measurement has the potential to provide an independent means to determine
the density difference between the isotropic and uniaxial nematic phases. 相似文献
128.
S. Seghir C. Boulanger S. Diliberto J.M. Lecuire V. Bouquet M. Potel M. Guilloux-Viry 《Electrochemistry communications》2010,12(12):1734-1737
Electrochemical transfer junctions (ETJs) were synthesized via a physical or chemical covering method onto a porous ceramic substrate (mullite and alumina). The Mo6S8 layer thickness ranged from 10 to 100 μm. The ETJ composites placed between two tanks lead to a cobalt transfer by applying a current density between electrodes placed in both tanks. The thickness decrease compared to a hot pressed junction allows imposing current densities equal to 7 or 9 mA cm?2 inducing 4–6 fold faster Co2+ fluxes (1.3.10?4 and 1.7.10?4 mol h?1 cm?2 for physical and chemical covering respectively, versus 2.9.10?5 mol h?1 cm?2 for hot pressed junctions). 相似文献
129.
Boulanger AM Holland DM Shaw DA Mayer PM 《Journal of the American Society for Mass Spectrometry》2009,20(1):20-24
Threshold photoelectron photoion coincidence (TPEPICO) experiments have shown that o-, m-, and p-difluorobenzene ions dissociate via a common, ring-opened intermediate and not via ionized p-difluorobenzene. Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental breakdown curves yields activation energies for the initial isomerization of 4.48 +/- 0.05, 4.55 +/- 0.05, and 4.68 +/- 0.05 eV for o-, m-, and p-difluorobenzene, respectively. These values place each ion at a similar absolute energy and thus similar transition states. A large positive DeltaS(double dagger) for each ion (ca 100 J K(-1) mol(-1)) suggests a ring-opened structure for these transition states. 相似文献
130.
Isabelle Maraval Kemal Sen Chantal Menut Renaud Boulanger Christian Mestres 《Analytica chimica acta》2010,675(2):148-155
A new and convenient synthesis of 2-acetyl-1-pyrroline (2AP), a potent flavor compound in rice, and its ring-deuterated analog, 2-acetyl-1-d2-pyrroline (2AP-d2), was reported. A stable isotope dilution assay (SIDA), involving headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-positive chemical ionization-ion trap-tandem mass spectrometry (GC-PCI-IT-MS-MS), was developed for 2AP quantification. A divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was used for HS-SPME procedure and parameters affecting analytes recovery, such as extraction time and temperature, pH and salt, were studied. The repeatability of the method (n = 10) expressed as relative standard deviation (RSD) was 11.6%. A good linearity was observed from 5.9 to 779 ng of 2AP (r2 = 0.9989). Limits of detection (LOD) and quantification (LOQ) for 2AP were 0.1 and 0.4 ng g−1 of rice, respectively. The recovery of spiked 2AP from rice matrix was almost complete. The developed method was applied to the quantification of 2AP in aerial parts and grains of scented and non-scented rice cultivars. 相似文献